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2-----------------------[ (c) 1996 Swedish Infomania ]---------------------
3
4              Secrets of Methamphetamine Manufacture (3rd ed.)
5                              by Uncle Fester
6                   Published by Loompanics Unlimited 1994
7                Converted to ASCII by Swedish Infomania 1996
8
9--------------------------------------------------------------------------
10
11                                INTRODUCTION
12    
13    This book is the result of six years experience in the field of 
14manufacturing methamphetamine. It contains virtually everything I know
15about the subject. There are a lot of secrets in this area, hence the title
16Secrets of Methamphetamine Manufacture.
17    
18    A thorough review of the scientific literature on this subject will 
19show that the descriptions of this process are, at best, vague and
20imprecise, at worst, downright wrong. The Russian journals are especially
21unreliable.
22    
23    There are two reasons for this. First of all, the companies holding 
24patents on the processes want to keep their trade secrets secure, so they
25disclose no more than is absolutely necessary to obtain their patents.
26Secondly, the articles written by university scientists cover the making of
27large numbers of compounds and so do not delve deeply into the details of
28making any particular one.
29    
30    This book fills the glaring gap in published scientific literature. The 
31reader receives the benefit of my lengthy scientific education at expensive
32and prestigious universities and detailed knowledge of these processes that
33would otherwise be available only through tedious and expensive
34experiments. There is no magic involved, only good chemistry, and I show
35how underground chemists manufacture illegal drugs and get away with it.
36    
37    Skilled and successful underground chemists have usually taken a 
38college level Organic Chemistry course, with lab, for at least one
39semester. In this lab, they get practice in distillation, extraction, and
40other skills involved in making methamphetamine. At the very least, they
41will go to a college bookstore and purchase the lab manual for the Organic
42Chemistry class. That book goes into some detail on how to distill, reflux,
43etc.
44    
45    While this book is not meant to encourage anyone to break the law, it
46does point out the ultimate futility of government prohibition of 
47"controlled substances" by showing just how easily these substances can be
48manufactured.
49    
50    Underground drug manufacturers sometimes enjoy chipping into their own
51product. If there is one product which underground chemists can make, and
52also enjoy themselves, it is methamphetamine, the fuel that powered the
53Third Reich. They need have no fear of messing up their batches while under
54the influence of methamphetamine, unlike chemical garbage such as PCP.
55    
56    Legal methamphetamine is sold under such trade names as Desoxyn,
57Methedrine, etc. It is closely related both in structure and effects to
58regular amphetamine, called benzedrine and dexedrine.
59    
60    The difference between methedrine and benzedrine is that meth is more
61potent and its effect lasts a longer time. Meth is a potent stimulant
62similar in effect to cocaine, but much longer lasting. Where I come from,
63if people have a choice between coke and meth, they will choose meth,
64unless it's 2 AM. This is because meth is a much better bargain and can
65keep a man rolling through a hard day's work or a long night of play, or
66both. It sharpens the mind, allowing great amounts of mental work to be
67done quickly and error-free. It also sharpens one's reflexes to previously
68unknown levels, perfect for football. If you are planning to get into a
69fight, there is nothing better. It's not banned from boxing for nothing.
70    
71    The effects of meth on sexual function is a crap shoot. One day you
72will be a sexual athlete, the likes of which has never been seen this side
73of the porno flicks, the next you will be a complete failure. The odds in
74favor of athleticism are about 3 to 1, but can be improved by moderate
75alcohol consumption, and worsened by heavy drinking or immoderate use of
76meth. Poorly purified meth also has this drawback. The product should be
77distilled carefully.
78    
79    On the street, methamphetamine is known by such names as meth, crystal
80meth, crystal, speed, crank or wire. Most of the stuff on the street shows
81the telltale signs of sloppy lab work: yellow crystals, sticky crystals, or
82a tendency to soak up water from the air and melt.
83    
84    Back in the 60s, meth got a bad name because fools were shooting the
85stuff up constantly, starving themselves to death or getting hepatitis.
86This is how the slogan "speed kills" got started. If you do not have
87suicidal tendencies, accept the fact that your sinus cavities are close
88enough to your brain. You must also control your intake of meth. I would
89recommend no more than 50 milligrams (1/20 gram), no more than three times a
90week. Any more than this, and bad effects begin to appear, such as
91difficulty in thinking clearly, paranoid behavior and excessive weight loss
92leading finally to amphetamine psychosis, which quickly fades upon stopping
93consumption of amphetamine. Meth is not physically addicting, but since
94good effective stimulation is so enjoyable, it is habit-forming. People
95have been known to take extremely large doses, over a gram, and survive
96with no after effects, so overdoses are not a problem unless you have some
97underlying problem like a bad heart or hard arteries.
98    
99    I have some recommendations for underground chemists who consume their
100own product. First of all, they must eat well whether they feel like eating
101or not. Most people can stand to lose 10 pounds or so, but beyond that,
102forget it. It has been my experience that a few beers is usually all it
103takes to get a speed demon in the mood to eat. They'll probably need a few
104beers to get to sleep anyway, so they might as well take care of both
105things at once. I also recommend a 1/2 gram of phenylalanine per day. This
106is because meth works by releasing stores of norepinephrine from the brain,
107charging it up to new levels of activity. The amino acid phenylalanine is
108the starting material for making more norepinephrine, and a good supply of
109it will help refill spent stocks. They should also take a good
110mega-multi-vitamin with the minerals, selenium and zinc. They must not take
111methamphetamine closer than 6-8 hours before bedtime, or they will have to
112drink the bar dry to get to sleep.
113
114--------------------------------------------------------------------------
115                          CHEMICALS AND EQUIPMENT
116--------------------------------------------------------------------------
117    
118    The heart of the chemical laboratory is the set of glassware 
119collectively called "the kit." It consists of several round bottom flasks,
120a claisen adapter, a still head with thermometer holder, a thermometer, a
121condenser, a vacuum adapter and a separatory funnel (sep funnel, for
122short). These pieces each have ground glass joints of the same size, so
123that the set can be put together in a variety of ways, depending on the
124process being done. For the production of quarter to third of a pound
125batches, 24/40 size ground glass joints are used. Also necessary are one
126each of the following sizes of round bottom flasks: 3000 ml, 2000 ml and
127500 ml; and two each of 1000 ml and 250 ml. Two condensers are also
128required, both of the straight central tube variety, one about 35 cm in
129length, the other about 50 cm in length.
130    
131    Other glassware used are several 500 ml Erlenmeyer flasks, about 5
132pieces of plain (not Pyrex) glass tubing about three feet long, and a
133Buchner filtering funnel with the filtering flask it fits into.
134    
135    All this glassware costs in the range of $600-$700, and is available at
136many scientific supply houses on a cash-and-carry basis. The best equipment
137supply house in the Midwest is Sargent-Welch in Skokie. Illinois.
138    
139    Another necessary piece of equipment is a source of vacuum for vacuum
140distillation and filtering the crystal product. Here there are two choices.
141each with its advantages and disadvantages.
142    
143    One choice is the aspirator, also called a water pump. It works by 
144running tap water through it under good pressure, producing a vacuum in the
145side arm theoretically equal to the vapor pressure of the water being run
146through it (see Figure 1). For this reason, the best vacuum is obtained
147with cold water, since it has a lower vapor pressure. The vacuum is brought
148from the side arm to the glassware by an automotive type vacuum hose such
149as can be purchased at an auto parts store. The vacuum adapter and
150filtering flask each have nipples to which the other end of the hose is
151attached, making it possible to produce a vacuum inside the glassware. The
152top end of the aspirator is threaded so it can be threaded into the water
153source. Alternatively, the threaded head can be pushed inside a section of
154garden house and secured by a pipe clamp. The hose can then be attached to
155a cold water faucet. The bottom end of the aspirator, where the water comes
156out, is rippled and can also be pushed and clamped inside a section of
157garden hose leading to the drain. The aspirator is kept in an upright
158position and at a lower level than the glassware it serves. This is because
159water has a habit of finding its wav into the vacuum hose and running into
160the batch. Keeping the aspirator lower forces the water to run uphill to
161get into the glassware. The aspirator has the disadvantage that it requires
162constant water pressure flowing through it, or the vacuum inside the
163glassware draws water from it inside to make a mess of the batch. For this
164reason, only city water is used. And, unless the vacuum line is
165disconnected from the glassware before the water flow through the aspirator
166is turned off, the same thing will happen. The aspirator has these
167advantages: it flushes fumes from the chemicals down with the water flow,
168costs only about $10, and produces no sparks. A well-working aspirator
169produces a vacuum of 10 to 20 torr (2 to 3% of normal air pressure)(The
170unit "torr" means one milliliter of Mercury pressure. Normal air pressure
171is 760 torr.).
172    
173    The other choice for a source of vacuum is an electric vacuum pump,
174which costs about $200, not including the electric motor, purchased
175separately. To avoid the danger of sparks, the motor must be properly
176grounded. The pump has the advantage that it can be used in the country,
177where steady water pressure is not available. It also produces a better
178vacuum than the aspirator, about 5 torr, for faster and lower temperature
179distillation. It has the disadvantage of exhausting the chemical fumes it
180pumps into the room air, unless provision is made to pump them outside. The
181oil inside the pump also tends to absorb the vapors of ether or benzene it
182is pumping, thereby ruining the vacuum it can produce and making it
183necessary to change the oil.
184    
185    Another necessary piece of equipment is a single-burner-element buffet
186range with infinite temperature control. It is perfect for every heating
187operation and only costs about $20 at a department store. Finally, a couple
188of ringstands with a few Fisher clamps are used to hold the glassware in
189position.
190    
191    A number of troublesome yet futile laws have been enacted since the
192publication of the first edition of this book. On the federal level, 
193phenylacetic acid and phenylacetronitrile are now restricted chemicals. See
194Federal Register, Section 1310.02 Section A, "listed precursor chemicals."
195This means that clandestine operators wishing to use these materials will
196either have to smuggle them in from abroad, or make them from simpler,
197noncontrolled materials. For this last option, see Organic Syntheses,
198Collective Volumes I, II, and III. Check the table of contents to find
199directions for making the desired substance.
200    
201    An even more noxious, yet similarly futile law has been enacted in 
202California. Since this is bound to be the model for similar laws enacted
203throughout the country, let's examine it more closely.
204    
205    The most easily defeated part of the law concems the sale of chem lab
206equipment and chemicals. The law states that purchasers of equipment and/or
207chemicals in excess of $100 must present proper ID, and that the seller
208must save the bill of sale for inspection by officers of the law. Since
209most individual pieces of chem lab equipment go for less than $100, this
210law is gotten around by keeping one's equipment purchases under $100, and
211splitting up one's business between various suppliers. The five finger
212discount method while attending college chem lab courses is another option.
213Similarly, transfers between friends, and the old fashioned heist from
214well-stocked labs are other ways around this law.
215    
216    The most stringent section of the law is aimed primarily at production
217of meth, LSD, MDA and MDMA, PCP, and the barbiturates. Of those chemicals
218relevant to this book, it lists: phenylacetone, methylamine, phenylacetic
219acid, ephedrine, pseudoephedrine, norpseudoephedrine, phenylpropanolamine,
220isosafrole, safrole, piperonal, benzyl cyanide, chlorephedrine, thionyl
221chloride, and N-methyl derivatives of ephedrine.
222    
223    This section of the law states that anyone wishing to purchase these
224chemicals must obtain a permit. Anyone wishing to obtain such a permit must
225submit two sets of his ten fingerprints to the authorities. It is
226interesting to note here that the over-the-counter stimulants which contain
227ephedrine sulfate or phenylpropanolamine hydrochloride are exempt from
228these restrictions. Dexatrim, and those mail order white crosses, have not
229been made illegal. The determined experimenter can easily extract the
230needed starting material out of the legal "stimulant" pills.
231    
232    A third, and less restricted, class of chemicals deals mainly with 
233meth, and PCP. The chemicals of interest here are: sodium and potassium
234cyanide, bromobenzene, magnesium turnings (the last two also have PCP
235implications), mercuric chloride, sodium metal, palladium black, and acetic
236anhydride. For this class of chemicals, the law requires presentation of
237proper ID (i.e., state-issued photo ID) and calls for the seller to record
238said ID. The obvious ways around this section of the law are to do business
239in less nosy states, or to obtain false identification.
240    
241    Clandestine operators also need to know that the law allows the central
242scrutinizers to add chemicals to the lists without waming or approval. So
243the new precursors mentioned in this book could go on the lists of
244restricted chemicals at any time.
245    
246--------------------------------------------------------------------------
247                THE LEUCKARDT-WALLACH REACTION: AN OVERVIEW
248--------------------------------------------------------------------------
249    
250    The best way to produce batches of up to one-half pound in size is by
251the Leuckardt-Wallach reaction. It is one of the touchiest reactions there
252is, right up there with the Grignard reaction.
253    
254    The Leuckardt-Wallach reaction involves reacting a ketone with two
255molecules of a formamide to produce the formyl derivative of an amine,
256which is then hydrolyzed with hydrochloric acid to produce the desired
257amine. In this case, the reaction is shown on page 14.
258    
259    There are several reviews of this reaction in the scientific 
260literature, the best of them Crossley and More in the Journal of Chemistry
261(1949).
262    
263    The conditions which favor the production of high yields of fine 
264quality products are as follows. There should be a small amount of formic
265acid in the reaction mixture, because it acts as a catalyst. It should be
266buffered by the presence of some free methylamine, to prevent the pH of the
267reaction mixture from falling too low (becoming too acidic). The presence
268of water in the reaction mixture is to be avoided at all costs, because
269this really messes up the reaction. It prevents the phenylacetone from
270dissolving in the N-methylformamide, leading to low yields of
271purple-colored crystal. The directions I give in a later chapter for making
272N-methylformamide give a product which is perfect for this reaction.
273    
274    It is also important that the reaction be done at the lowest 
275temperature at which it will proceed smoothly, and that the heating be
276continued for as long as the reaction is still going. In this way nearly
277all the phenylacetone is converted to methamphetamine.
278
279    There is one stumbling block in the path of underground chemists: in
2801979, the DEA made phenylacetone illegal to purchase or possess. 
281N-methylformamide is also risky to obtain, although it is not illegal and
282is used in industry as a solvent.
283    
284    However, they are both easy to make. And, because of these 
285restrictions, the price of methamphetamine has gone above $100 per gram,
286while it costs only $1 or $2 per gram to make. 
287    
288--------------------------------------------------------------------------
289                        PREPARATION OF PHENYLACETONE
290--------------------------------------------------------------------------
291    
292    Phenylacetone, also known as methyl benzyl ketone, or 
2931-phenyl2-propanone, is easy but tedious to make. In this reaction,
294phenylacetic acid reacts with acetic anhydride with pyridine catalysts to
295produce phenylacetone plus carbon dioxide and water. In chemical writing:
296    
297[Deleted]
298    
299    A Russian journal tells of using sodium acetate instead of pyridine, 
300which would be great if it worked, because sodium acetate is much cheaper
301than pyridine. However, I have tried it and the results are unsatisfactory.
302Typical of those lying Commies.
303    
304    The reaction is done as follows: Into a clean, dry 3000 ml round bottom
305flask is placed 200 grams of phenylacetic acid, 740 ml of acetic anhydride
306and 740 nil of pyridine. This is done on a table covered with a sheet of
307newspaper, because phenylacetic acid, once it is exposed to the air, smells
308like cat urine, and the smell is next to impossible to get rid of. Pyridine
309also smells awful. The pyridine and acetic anhydride are measured out in a
310large glass measuring cup.
311    
312    The flask is then gently swirled until the phenylacetic acid is 
313dissolved. The flask is then assembled with the 50 cm condensa and the
314vacuum adapter, as shown in Figure 2a. Before assembly, the joints are
315lightly greased with silicone based stop cock grease. This prevents the
316pieces from getting stuck together. All pieces should be clean and dry. The
317vacuum nipple of the vacuum adapter is plugged with a piece of tape. In the
318rounded section of the vacuum adapter is a plug of cotton, then about two
319teaspoons of Drierite (anhydrous calcium sulfate), then another plug of
320cotton. This makes a bed of Drierite which is prevented from falling into
321the flask by a ball of cotton. The purpose of this is to keep moisture from
322the air away from the reaction.
323    
324    Now the underground chemist is ready to begin heating the flask. Notice
325that in Figure 2b, the flask is in a large pan which sits on the buffet
326range. The pan is filled about half-full of cooking oil (Wesson works
327fine). This is so that the flask is heated evenly. The heat is turned about
328half-way to maximum, and the flow of cold water through the condenser is
329begun. A length of plastic or rubber tubing runs from the cold water faucet
330to the lower water inlet of the condenser. The cold water runs through the
331condenser and out of the top water exit, through another length of tubing
332to the drain. In this way, the rising vapors from the boiling pyridine are
333condensed and returned to the flask. A rate of water flow of about one
334gallon per minute is good.
335    
336    Within a half hour, the flask is hot enough to begin boiling. The heat
337is then turned down to stabilize the flask at a gentle rate of boiling.
338This is called a reflux. The boiling is allowed to continue for 7 hours.
339During this time, the reaction mixture turns from clear to brownish-red in
340color. Periodically, the rate of water flow coming out of the condenser is
341checked, because faucet washers tend to swell after a while and slow down
342the rate of water flow.
343    
344    After 7 hours, the heat is turned off. Twenty minutes after the boiling
345stops, the glassware is set up as shown in Figure 3. The cotton and
346Drierite are removed from the vacuum adapter. Then 4 pea-sized pieces are
347broken off a pumice foot stone (purchased at the local pharmacy). These are
348called boiling chips, because they cause liquids to boil faster and more
349evenly. They are added to the flask with the reaction mixture in it. But
350they are not added until 20 minutes after the boiling stops; otherwise they
351could produce a geyser of hot chemicals.
352    
353    Now the heat is turned back on, a little hotter than when refluxing the
354reaction mixture. Water flow to the condenser is resumed. The mixture soon
355begins boiling again and the vapors condense in the condenser and flow to
356the collecting round bottom flask. What is being boiled off is a mixture of
357pyridine and acetic anhydride. The phenylacetone remains behind in the
358distilling round bottom flask, because its boiling point is about 100
359degrees Celsius higher than the pyridine and acetic anhydride. This process
360is called simple distillation. Distillation continues until 1300 ml has
361been collected in the collecting round bottom flask, then the heat is
362turned off. The 1300 ml is poured into a clean dry glass jug about one
363gallon in size which is then stoppered with a cork. At the end of this
364chapter, I will describe a process by which this pyridine is recycled for
365future use. Since pyridine is so expensive, this cuts production costs
366considerably.
367    
368    What is left in the distilling round bottom flask is a mixture of 
369phenylacetone, some acetic anhydride and pyridine, and a
370high-molecular-weight, tarry polymer which is reddish-brown in color. The
371next step is to isolate and purify the phenylacetone.
372    
373    The flask is taken out of the hot oil and allowed to cool down. 
374Three-quarters of a gallon of 10% sodium hydroxide solution (NaOH) is
375needed. So a gallon-size glass jug is filled three-quarters full of cold 
376water and about 10 ounces of sodium hydroxide pellets are added to it. A
377good quality lye, such as Red Devil or Hi-Test, is a substitute that saves
378a good deal of money and works fine. Eye protection is always worn when
379mixing this up. It is mixed thoroughly by swirling, or by stirring with a
380clean, wooden stick. The dissolution of NaOH in water produces a great deal
381of heat. It is allowed to cool off before the chemist proceeds.
382    
383    About 500 ml of the 10% NaOH is put in a 1000 ml sep funnel, then the
384crude phenylacetone mixture from the round bottom flask is poured in the
385sep funnel also. The top of the sep funnel is stoppered and mixed by
386swirling. When the funnel gets hot, it is allowed to set for a while. Then
387the mixing is continued, with the underground chemist working his way up to
388shaking the sep funnel, with his finger holding in the stopper. What he is
389doing is removing and destroying the acetic anhydride. Acetic anhydride
390reacts with the sodium hydroxide solution to prodbce sodium acetate, which
391stays dissolved in the water, never to be seen again. Some of the pyridine
392and red-colored tar also go into the water. The destruction of the acetic
393anhydride is what produces the heat.
394    
395    After it has cooled down, about 100 ml of benzene is added to the sep
396funnel and shaken vigorously for about 15 seconds. The sep funnel is
397unstoppered and allowed to sit in an upright position for about one minute.
398The liquid in the funnel will now have separated into two layers. On top is
399a mixture of benzene, phenylacetone, and red tar. On the bottom is the
400water layer, which has some phenylacetone in it. Pyridine is in both
401layers.
402    
403    Two 500 ml Erlenmeyer flasks are placed on the table, one marked "A,"
404the other marked "B." The stop cock on the sep funnel is opened, and the
405water layer is drained into B. The top layer is poured into A. B is poured
406back into the sep funnel, and 50 ml of benzene is added. The funnel is
407shaken for lS seconds, then the water layer is drained back into B. The top
408layer is poured into A. The purpose of this is to get the phenylacetone out
409of the water. Once again the water in B is put in the sep funnel. 50 ml of
410benzene is added, and shaken. The water is drained into B and the benzene
411layer poured into A. The water in B is poured down the drain and the
412contents of A put into the sep funnel along with 400 ml of 10% NaOH
413solution from the jug. After shaking, the water layer is drained into B and
414the benzene layer poured into A. The contents of B are put back in the sep
415funnel and 50 ml of benzene added. After shaking, the chemist drains the
416water layer into B and pours it down the drain. The contents of A are added
417to the funnel again, along with 400 ml of 10% NaOH solution; the funnel is
418shaken again. The water layer is drained into B and the benzene layer
419poured into A. The contents of B are returned to the sep funnel, along with
42050 ml benzene, and shaken again. The water layer is poured into B and
421poured down the drain. The benzene layer is poured into A. The sep funnel
422is washed out with hot water.
423    
424    Now the last traces of pyridine are removed from the phenylacetone. For
425this purpose, some hydrochloric acid is needed. Hardware stores usually
426have the 28% strength sometimes called muriatic acid. A bottle in which the
427acid seems clear-colored is used; the ones with a green tint have been
428sifflng around too long.
429    
430    The contents of A are returned to the clean sep funnel. Then 10 ml of
431hydrochloric acid, mixed with 10 ml of water, is added to the sep funnel
432and shaken for 30 seconds. The stopper is pulled out to check whether or
433not the odor of pyridine has disappeared. If not, another 20 ml of the
434acid-water mix is added and shaken. The odor should now be gone, but if it
435is not, some more of the mix is added and shaken. Now 200 rnl of water is
436added and shaken. Flask A is rinsed out with hot water; the water layer is
437drained into B and poured down the drain. The benzene layer is poured into
438A. What has just been done is to convert the pyridine into pyridine
439hydrochloride, which dissolves in water, but not in benzene. It is now down
440the drain.
441    
442    Finally, for one last time, the contents of A are returned to the sep 
443funnel, along with 200 ml of the 10% NaOH solution. This is shaken and the
444water layer drained into B. The benzene layer is allowed to stay in the sep
445funnel for the time being; more water will slowly fall out to the area of
446the stop cock, where it can be drained out. It is now ready to be
447distilled, and stray water must be removed beforehand.
448    
449    The glassware is set up as shown in Figure 4. Figure 4 shows a 
450glass-packed fractionating column which an underground chemist can make
451himself. The claisen adapter is checked to make sure it is clean and dry. A
452clear glass beer bottle is washed out with hot water, then smashed on the
453cement floor. A few pieces are picked out that are small enough to fit in
454the lower opening of the claisen, yet big enough that they will not fall
455out of the bottom opening of the claisen adapter. Pieces of the broken
456bottle are dropped in the lower opening until that section of the claisen
457adapter is filled to about the level shown in the drawing. The chemist
458tries to get it to land in a jumbled pattern, as shown in the drawing. Then
459more similarly-sized pieces of glass are dropped in the upper opening of
460the claisen adapter until it is filled to the level shown. Again a jumbled
461pattern is striven for. The lower opening is then stoppered with the proper
462size of glass or rubber stopper. Finally, the outside is wrapped with a
463layer or two of aluminum foil, except for the ground glass joint.
464    
465    The underground chemist is now ready to distill the phenylacetone.
466First, here is some information on the process to be performed. The crude
467phenylacetone the underground chemist has is a mixture of benzene,
468phenylacetone, red tarry polymer, some water and maybe some dibenzyl
469ketone. These substances all have very different boiling temperatures. By
470distilling this mixture through a fractionating column, the chemist can
471separate them very effectively and get a highpurity product. The way it
472works is easy to understand. The vapors from the boiling mixture in the
473distilling flask rise up into the fractionating column and come into
474contact with the pieces of glass inside. Here the vapors are separated
475according to boiling point. The substance in the mixture with the lowest
476boiling point is able to pass on through, while the other substances are
477condensed and flow back into the distilling flask. This is why the pieces
478of glass in the column can't be tightly packed, as that would interfere
479with the return flow, leading to a condition called flooding. Once all of
480the lowest-boiling substance has been distilled, the substance with the
481next higher boiling point can come through the fractionating column. In the
482distillation process to be described, the order is as follows: benzenewater
483azeotrope, 68øC; benzene, 80-ø C; phenylacetone, 120-130-ø C (under a
484vacuum of about 20 torr).
485    
486    Why must the phenylacetone be distilled under a vacuum? Because its
487boiling point at normal pressure is 216ø C, which is much too hot.
488Distilling it at that temperature would ruin the product. By distilling it
489under a vacuum, it boils at a much lower temperature. The exact temperature
490depends on how strong the vacuum is; the stronger the vacuum, the lower the
491temperature. For example, at a vacuum of 13 torr, the boiling point goes
492down to about 105ø C.
493    
494    The glassware is set up as shown in Figure 5. The distilling flask is
495no more than 2/3 full. If the underground chemist has more crude 
496phenylacetone than that, he has to wait until some of the benzene has
497distilled off, then turns off the heat, waits until the boiling stops and
498adds the rest of it to the distilling flask.
499    
500    The glassware should be clean and dry. A faster way of drying glassware
501after washing is to put it in the oven at 400øF for 20 minutes. Rubber
502stoppers do not go in the oven. Water tends to stay inside round bottom
503flasks dried in this way. SO, while they are still hot, the chemist takes a
504piece of glass tubing and puts it inside the flask. He sucks the moist air
505out of the flask with the glass tubing before it has a chance to cool down
506and condense. For the distillation, two 250 ml round bottom flasks are
507needed, one to collect the benzene in, the other to collect the
508phenylacetone in. Five boiling chips are put in the distilling flask.
509    
510    The heat source is turned on, to the low range, about 1/4 maximum.
511Water must be flowing through the shorter condenser at about one gallon per
512minute. When the mixture has begun boiling, the heat is adjusted so that
513about one or two drops per second drip into the collecting flask. The
514temperature on the thermometer should say about 68øC. For accurate
515temperature readings, the tip of the thermometer extends into the stillhead
516to the depth shown in Figure 6. 
517    
518    The material distilling at 68øC is the benzene-water azeotrope. It is 
519about 95% benzene and 5% water. It is milky white from suspended droplets
520of water. Once the water is all gone, pure benzene is distilled at about
52180øC. It is clear in color. If the liquid in the collecting flask is not
522clear or white in color, then undistilled material is being carried over
523from the distilling flask. This is caused either by having the distilling
524flask too full or by having the heat turned too high. In either case, the
525chemist must correct accordingly and redistill it. Once the temperature
526reaches 85øC on the thermometer, or the rate of benzene appearing in the
527collecting flask slows to a crawl, the heat is turned off because the
528chemist is ready to vacuum distill the phenylacetone.
529    
530    There is a problem that is sometimes encountered while distilling off
531the benzene. Sometimes the benzene in the distilling flask will foam up in
532the distilling flask instead of boiling nicely. These bubbles refuse to
533break and they carry undistilled material along with them to the collecting
534flask, leaving a red liquid over there. This cannot be allowed to happen.
535One effective method of dealing with this is to turn on the water supply to
536the aspirator at a slow rate so that a weak vacuum is produced. Then the
537vacuum hose is attached to the vacuum adapter and a weak vacuum produced
538inside the glassware. This causes the bubbles to break. Every few seconds,
539the vacuum hose is removed, then reattached. In a while, the benzene begins
540to boil normally and the vacuum can be left off.
541    
542    After it has cooled off, the collected distilled benzene is poured into
543a labeled glass bottle. It can be used again in later batches of 
544phenylacetone. The same 250 ml round bottom flask is reattached to the
545collecting side, and the vacuum hose attached to the vacuum adapter. The
546vacuum source is turned on. If an aspirator is being used, the water is
547turned all the way on. All the pieces of glassware must be fitted snugly
548together. A strong vacuum quickly develops inside the glassware. The heat
549is turned on to about i/3 maximum. The boiling begins again. At first, what
550distills over are the last remnants of benzene and water left in the
551distilling flask. Then the temperature shown on the thermometer begins to
552climb. The phenylacetone begins to distill. When the thermometer reaches
5531009 C, the vacuum hose is removed and the collecting 250 ml flask is
554replaced with the clean, dry 250 ml flask, then the vacuum hose is
555reattached. If a good vacuum pump is being used, the flasks are changed at
556about 809 C. This flask changing is done as fast as possible to prevent the
557material in the distilling flask from getting too hot during the change
558over. If it gets too hot, it distills too rapidly when the vacuum is
559reapplied, resulting in some red tar being carried over along with it.
560    
561    So the vacuum is reapplied, and the phenylacetone is collected. With a
562properly working aspirator, the phenylacetone will all be collected once
563the temperature on the thermometer reaches 140-1SOQ C. With a good vacuum
564pump, it will all come over by the time the temperature reaches 110-llSQ C.
565Once it is all collected, the heat is turned off, the vacuum hose is
566removed from the vacuum adapter and the vacuum source is turned off.
567    
568    The yield is about 100 ml of phenylacetone. It should be clear to pale
569yellow in color. It has a unique but not unpleasant smell. The flask
570holding this product is stoppered and stored upright in a safe place.
571Although phenylacetone can be stored in a freezer, to keep it fresh, the
572chemist now proceeds to making N-methylformamide.
573    
574    Once the distilling flask has cooled down, the glassware is taken apart
575and cleaned. The red tar left in the distilling flask and the fractionating
576column is rinsed out with rubbing alcohol. Then hot soapy water is used on
577all pieces. A long, narrow brush comes in handy for this.
578    
579    One last word about vacuum distillation. To keep the vacuum strong, the
580vacuum hose is no more than three feet long. This forces the chemist to do
581the distilling close to the source of the vacuum.
582    
583    Now for that pyridine recycling process I mentioned earlier in this 
584chapter. After the underground chemist has made a few batches of
585phenylacetone, he will have accumulated a fair amount of pyridineacetic
586anhydride mixture in the gallon-sized glass jug. He will now fractionally
587distill it to recover the pyridine from it. The clean dry glassware is set
588up as shown in Figure 7. It has a long-column fractionating column instead
589of the short type just used. This is because pyridine and acetic anhydride
590are harder to separate, so a longer column is needed to do the job.
591    
592    The distilling flask is a 3000 ml round bottom flask with 5 boiling 
593chips in it. The chemist pours 2000 ml of the acetic anhydride-pyridine
594mixture into it. The heat is turned on to about 1/3 maximum and the cold
595water is started flowing slowly through the condenser. Within a half hour,
596the mixture will begin to boil. A couple of minutes later, the vapors will
597have worked their way through the fractionating column and hegin appearing
598in the 2000 ml collecting flask. The heat source is adjusted so that it is
599collecting at the rate of one or two drops per second. Distilling is
600continued until 1000 ml have accumulated in the collecting flask. If the
601temperature reading on the thermometer goes above 135øC, the heat is turned
602down a little to slow the rate of distillation.
603    
604    Once 1000 ml has been collected, the heat is turned off and it is 
605allowed to cool down. After it is cool, the distilling flask is removed and
606its contents (mainly acetic anhydride) poured down the drain. The contents
607of the collecting flask (mainly pyridine) are poured into a clean, dry 2000
608ml round bottom flask with 5 boiling chips, or 5 boiling chips are simply
609added to the 2000 ml round bottom flask that the pyridine collected in and
610that flask is put on the distilling side in place of the 3000 ml flask. A
611clean, dry 1000 ml round bottom flask is put on the collecting side. The
612heat is turned back on and in a while the distilling begins again. As
613before, the rate of distillation is adjusted to one or two drops per
614second. The distillation is continued until 750 ml of pyridine has been
615collected. Sometimes it does not keep well, but so long as it is used to
616make another batch of phenylacetone within a few hours after it is made,
617this pyridine works just as well as new pyridine. 
618    
619--------------------------------------------------------------------------
620                      PREPARATION OF N-METHYLFORMAMIDE
621--------------------------------------------------------------------------
622    
623    N-methylformamide is best made by the reaction of methylamine with
624formic acid. The reaction proceeds like this:
625    
626    [SNiP]
627
628    The methylamine (a base) reacts with formic acid to form the 
629methylamine salt of formic acid. The heat that this reaction builds up then
630causes this intermediate salt to lose a molecule of water and form
631N-methylformamide. Since water is a product of this reaction, the
632underground chemist warts to keep water out of his starting materials as
633far as is possible. That is because having less water in them will shift
634the equilibrium of the reaction in favor of producing more 
635N-methylformamide.
636    
637    Both of the starting materials have water in them. The usual grade of
638formic acid is 88% pure and 12% water. It cannot be made any purer by
639distilling. The chemist can put up with the 12% water, but if a higher
640purity formic acid is available, it is worth the extra cost. The usual
641grade of methylamine is 40% by weight in water. The majority of this water
642can be removed by using the apparatus shown in Figure 8. Methylamine may
643also be obtained as a gas in a cylinder. In that case, the methylamine can
644be piped directly into the formic acid.
645    
646    The glassware is set up as shown in Figure 8. The 40% methylamine is in
647a 1000 ml round bottom flask attached to a long condenser. In the top of
648this condenser is a one-hole stopper. A bent piece of glass tubing is
649pushed all the way through this stopper so that the end of the piece of
650tubing extends about one or two millimeters below the bottom of the
651stopper. This bent piece of tubing then extends down through the center of
652the other condenser into the flask containing the formic acid. It should
653extend below the surface of the formic acid and end about one centimeter
654above the bottom of the flask containing the formic acid. The idea here is
655simple. The 40% methylamine is heated, causing methylamine gas to be boiled
656out along with some water vapor. These gases then travel up the condenser,
657where the water is condensed out, allowing nearly pure methylamine gas to
658be forced by pressure through the glass tubing into the formic acid.
659    
660    The bent tubing has to be bent by the chemist himself from a 
6613-foot-long piece of glass tubing. Its outer diameter should be about 1/4
662inch. The glassware is set up as shown in Figure 8 and he decides about
663where the tubing should be bent. If necessary, he will consult the chapter
664on bending glass in an Organic Chemistry lab manual. With a little
665practice, it is easy. A good source of flame to soften up the glass is a
666propane torch with the flame spreader attachment. After it is bent, he will
667blow through the tubing to make sure he did not melt it shut.
668    
669    He is now ready to proceed. All pieces of glassware are clean and dry.
670Into the round bottom 1000 ml flask sitting on the heat source is placed
671500 grams (about 500 ml) of 40% methylamine in water, along with 3 or 4
672boiling chips. Into the other 1000 ml round bottom flask is placed 250 ml
673of 88% formic acid. Water flow is begun through the longer condenser. It is
674advantageous to use ice cold water in this condenser, because it will then
675do a better job of removing water vapor from the methylamine. A good way to
676get ice cold water for the condenser is to get a couple of 5-gallon pails.
677One of them is filled with ice cubes no bigger than a fist and topped off
678with water. Then the section of plastic tubing that runs to the lower water
679inlet of the condenser is placed in the pail. Its end is weighted to keep
680it on the bottom of the pail. This pail is placed on the table along with
681the glassware. The other pail is placed on the floor and the plastic tubing
682from the upper water exit of the condenser is run to this pail. By sucking
683on the end of the water exit tubing, the ice cold water can be siphoned
684from the pail on the table, through the condenser, to the pail on the
685floor. The rate of water flow can be regulated to about one gallon per
686minute by putting a clamp on the tubing to slow its flow. When the pail on
687the table is about empty, the water that has flowed to the pail on the
688floor is returned to the table.
689    
690    The heat on the methylamine is turned on to about i/4 maximum. Soon the
691methylamine begins boiling out and moving through the tubing into the
692formic acid. The underground chemist checks for gas leaks in the system by
693sniffing for the smell of escaping methylamine. If such a leak is detected,
694the joint it is escaping from is tightened up.
695    
696    The methylamine bubbling into the formic acid produces a cloud of white
697gas inside the flask containing the formic acid. It makes its way up to the
698condenser, then returns to the flask as a liquid. For this condenser, tap
699water flow is fine. The rate of methylamine boiling is adjusted so that the
700white gas does not escape out the top of the condenser. As more methylamine
701is boiled out, a higher heat setting is required to maintain the same rate
702of methylamine flow.
703    
704    In this process, the formic acid gets very hot. It must get hot to 
705produce good yields of N-methylformamide. It sometimes gets hot enough to
706boil a little bit (105øC), but this is no problem. As the chemist continues
707bubbling methylamine into the formic acid, its volume increases until it is
708double its starting volume, about 500 ml. At about this time, the cloud of
709white gas thins and then disappears. This white gas is formed by the fumes
710of formic acid reacting with methylamine above the surface of the liquid
711formic acid. It disappears because there is no longer much formic acid
712left. The chemist now begins checking to see if the reaction is complete.
713He pulls out one of the stoppers from the 3-necked flask that contains the
714N-methylformamide and sniffs the escaping fumes for the odor of
715methylamine. He does this periodically until he smells methylamine. Once he
716smells it, he turns off the heat on the methylamine. When the methylamine
717stops bubbling into the N-methylformamide, he immediately lowers the level
718of the 3-necked flask so that the bent glass tubing is above the surface of
719the N-methylformamide. This is done because, as the methylamine cools, it
720will contract and create a vacuum which would suck the N-methylformamide
721over into the other flask in a flash, ruining his work.
722    
723    Both flasks are allowed to cool down. The methylamine is almost gone,
724so it can be poured down the drain. The next step is to fractionally
725distill the N-methylformamide. The glass-packed claisen adapter is used as
726the fractionating column. The glassware is set up as shown in Figure 5,
727back in Chapter 3. The distilling flask is a 1000 ml round bottom flask
728with 5 boiling chips in it. The collecting flask is a 250 ml round bottom
729flask. Unlike the distillation of phenylacetone, in this case the
730distillation is done under a vacuum from the beginning. The ice water
731siphoning system is used for the condenser, because N-methylformamide has a
732very high latent heat of vaporization, and, without this precaution, it may
733collect very hot in the collecting flask.
734    
735    The underground chemist is now ready to distill the N-methylformamide.
736All of the crude product is put in the 1000 ml round bottom flask. It will
737fill it about half full. The vacuum is applied at full strength, and the
738heat source is turned on to 1/3 to 1/2 maximum. The water in the mixture
739begins distilling. The temperature shown on the thermometer will show a
740steady climb during the process.
741    
742    In a while, the temperature rises high enough that the chemist can 
743begin collecting the distilled liquid as suspected N-methylformamide. If he
744is using an aspirator, he begins collecting in a clean, dry 250 ml round
745bottom flask when the temperature reaches 95-100øC. If he is using a good
746vacuum pump, he begins saving the distilled material at about gSQ C As the
747N-methylformamide distills, the temperature rises a little bit above the
748temperature at which he first began collecting the N-methylformamide, then
749holds steady. This temperature is noted. Distilling is continued until he
750has collected 100 ml. Then the heat is turned off. When the boiling stops,
751the vacuum hose is disconnected from the glassware.
752    
753    During the distillation process, a fair amount of methylamine was lost,
754leaving the N-methylformamide with too much formic acid. The next step is
755to correct this problem.
756    
757    The 100 ml of N-methylformamide that has been distilled is poured back
758in the distilling flask with the undistilled material. The distilled
759material is clear, while the undistilled material has turned yellow from
760the heat of distilling. The glassware is set up again as shown in Figure 8.
761This time, the round bottom flask holding the methylamine is a 500 ml
762flask. It has 100 ml of fresh 40% methylamine in water in it. The bent
763glass tubing leads into the flask containing the N-methylformamide. This
764flask does not need to have a condenser on it.
765    
766    The heat is turned on the methylamine and the flow of ice water through
767its condenser is begun. Soon the methylamine gas is bubbling into the
768N-methylformamide, reacting with the excess formic acid in it. Within about
76910 seconds, the odor of methylamine can be detected above the
770N-methylformamide. The heat is turned off, and when the bubbling stops, the
771level of the N-methylformamide is lowered so that it is not sucked into the
772other flask. Once the methylamine has cooled off, it can be poured back in
773with the good me~ylamine, because it is not exhausted. Once a bottle of
774methylamine has been opened, it should be reclosed tightly and the cap
775sealed with vinyl electrical tape in order to hold in the methylamine gas.
776    
777    Now the N-methylformamide is to be distilled again. The glassware is
778set up again for fractional distillation as shown in Figure 5. The
779distilling flask is a 500 ml round bottom flask, while the collecting flask
780is 250 ml. All pieces are clean and dry.
781    
782    The N-methylformamide is placed inside the distilling flask with 5 
783boiling chips. (Fresh chips are used every time.) The vacuum is reapplied
784and the heat is turned on again to 1/3 to 1/2 maximum. A little bit of
785water is again distilled. The temperature shown on the thermometer climbs
786as before. When it reaches a temperature 7øC below the temperature at which
787it leveled off the first time around, the chemist begins collecting in a
788clean dry 250 ml flask. The distilling continues until it has almost all
789distilled over. About 10 or 1S ml is left in the distilling flask. If he is
790using an aspirator, the chemist makes sure that no water is backing into
791the product from the vacuum line. The yield is about 250 ml
792N-methylformamide. If he gets a little more, it won't all fit in the 250 ml
793collecting flask. If that happens, he pours what has collected into a clean
794dry Erlenmeyer flask and continues distilling. N-methylformamide is a clear
795liquid with no odor.
796    
797    The N-methylformamide the underground chemist has just made is perfect
798for the Leuckardt-Wallach reaction. Because he began collecting it 7
799degrees below the leveling off temperature, it contains a mixture of
800N-methylformamide, formic acid and methylamine. To get good results, he
801uses it within a few hours after distilling it.
802    
803                                 References
804    
805Journal of the American Chemical Society, Volume 53, page 1879 (1931).
806    
807    
808--------------------------------------------------------------------------
809                           MAKING METHAMPHETAMINE
810--------------------------------------------------------------------------
811    
812    I explained the general theory behind this reaction in Chapter 2. Now,
813after doing the reactions described in the previous two chapters, the
814underground chemist has phenylacetone and N-methylformamide suitable for
815making methamphetamine. He will want to get going before the chemicals get
816stale.
817    
818    The first thing he does is test the chemicals. He puts 5 ml of 
819phenylacetone and 10 ml of N-methylformamide in a clean dry test tube or
820similar small glass container. Within a few seconds they should mix
821together entirely. At this point, he may offer a prayer to the chemical
822god, praising his limitless chemical power and asking that some of this
823power be allowed to flow through him, the god's High Priest. He may also
824ask to be delivered from the red tar that can be the result of this
825reaction. If they do not mix, there is water in the Nmethylformamide. In
826this case, he must distill it again, being more careful this time.
827    
828    Having tested the chemicals, he is ready to proceed with the batch.
829(However, if the underground chemist was reckless enough to obtain
830N-methylformamide ready made, he will have to distill it under a vacuum
831before it can be used in this reaction.) The phenylacetone he made (about
832100 ml) is mixed with the N-methylformamide. The best amount of
833N-methylformamide to use is about 250 ml, but any amount from 200 to 300 ml
834will work fine. With 200 ml of N-methylformamide, there are about four
835molecules of N-methylformamide to one of phenylacetone. This is the bare
836minimum. With 300 ml, the ratio is nearly six to one. Any more than this is
837a waste of N-methylformamide. The best flask for mixing them is a 500 ml
838round bottom flask. After they are mixed, this flask is set up as shown in
839Figure 9. The flask is sitting in an oil bath, to supply even heating to
840the flask. The oil (once again, Wesson is a good choice) should extend
841about 2/3 of the way up the side of the flask. A metal bowl makes a good
842container for this oil bath. This is better than a pan, because it will be
843important to see into the flask. The fact that the oil will expand when
844heated is kept in mind when filling the bowl with oil. A thermometer is
845also needed in the oil bath to follow its temperature.
846    
847    The test material is added to the flask. The heat source to the flask
848is turned on. A low heat setting is used so that the rise in temperature
849can be closely controlled. The thermometer used in the distillations is
850placed (clean and dry) inside the flask.
851    
852    The rise in temperature of both the oil bath and the flask is 
853monitored. The contents of the flask are stirred regularly with the
854thermometer. The temperature of the oil bath is brought to lOOQ C over the
855course of about 45 minutes. Once it reaches this level, the heat is turned
856back down a little bit to stabilize it in this area. The chemist must
857closely control every degree of temperature increase from here on. The
858temperature of the contents of the flask is worked up to 105g C. The
859contents of the flask are stirred every 15 minutes. At about lOSQ C, the
860reaction kicks in, although sometimes the heat must go as high as 110g C
861before it starts. When the reaction starts, the contents of the flask begin
862to bubble, sort of like beer, except that a head does not develop. A trick
863to get this reaction going at a nice low temperature is to gently scrape
864the thermometer along the bottom of the flask. Although I have never had
865the sophisticated equipment to prove it, it is a pet theory of mine that
866this is because ultrasonic waves are generated, producing a condition of
867resonance with the reactants that causes the reaction to start.
868    
869    The chemist wants to keep the temperature down at the same level at
870which the reaction first kicked in for as long as the reaction will
871continue at that level. Generally, it can go for a couple of hours at this
872level before the reaction dies down and an increase in temperature is
873necessary. The reaction mixture has the same color as beer and gently
874bubbles. The bubbles rise up from the bottom of the flask, come to the
875surface, and then head for where the thermometer breaks the surface. Here
876they collect to form bubbles about 1 centimeter in size before they break.
877This may look like boiling, but it is not. Everything inside the flask has
878a much higher boiling point than the temperatures being used. These are
879actually bubbles of carbon dioxide gas being formed as by-products of the
880reaction. The chemist can tell how well the reaction is going by the amount
881of bubbling going on.
882    
883    When the rate of bubbling slows down to almost stopping, it is time to
884raise the temperature. It should only be raised about 3g C. This requires
885turning up the heat only slightly. The highest yield of product is obtained
886when the lowest possible temperature is used. For the duration of the
887reaction, the contents of the flask are stirred with the thermometer every
888half hour. 
889    
890    And so the reaction is continued. As the reaction dies down at one
891temperature setting, the temperature is raised a few degrees to get it
892going again. It will be able to stay in the 1209 to 130Q C range for a long
893time. The reaction has a lot of staying power in this range. Finally, after
89424 to 36 hours, 140Q or 145Q C is reached. The reaction stops. The chemist
895takes his time working up to this temperature because the amount and
896quality of the product depends on it.
897    
898    Once 140ø to 145ø C is reached and the reaction stops, the heat is
899turned off and the contents allowed to cool down. It should still look like
900beer. A reddish tint means that his prayer failed and he was not delivered
901from the tar. Even so, there's still lots of good product in it.
902    
903    While it is cooling down, the underground chemist gets ready for the
904next step in the process. He is going to recover the unused methylamine for
905use in the next batch. This cuts his consumption of methylamine to about
906half of what it would be without this technique. What he is going to do is
907react the unused N-methylformamide with a strong solution of sodium
908hydroxide. The N-methylformamide is hydrolyzed to form methylamine gas and
909the sodium salt of formic acid (sodium formate). In chemical writing, this
910reaction is as follows:
911    
912    [SNiP]
913    
914    The methylamine gas produced is piped into formic acid to make 
915N-methylformamide for use in the next batch.
916    
917    First, 6 ounces (about 180 grams) of sodium hydroxide pellets are added
918to 450 ml of water. A good quality lye is an acceptable substitute. Eye
919protection is worn. Once the solution has cooled down, it is poured in a
9202000 ml round bottom flask with 5 boiling chips. Then all of the
921methamphetamine reaction mixture is poured into the flask along with it. It
922is swirled around a little bit to try to get some of the N-methylformamide
923dissolved into the water. This does not accomplish much, however, as the
924reaction mixture floats on the sodium hydroxide solution. The glassware is
925set up as shown in Figure 8 in Chapter 4. The 2000 ml flask containing the
926NaOH solution and the methamphetamine reaction mixture sits on the heat
927source. The bent piece of glass tubing once again leads to a 1000 ml round
928bottom flask equipped with a condenser. The 1000 ml flask once again
929contains 250 ml of 88% formic acid.
930    
931    The heat source is turned on to about 1/3 maximum. The flow of ice
932water through the long condenser is begun. In a while, the boiling chips
933float up to the interface of the sodium hydroxide solution and the reaction
934mixture, and some bubbling and frothing of the reaction mixture begins. The
935heat is turned down some, since the temperature of the mixture should rise
936slowly from now on. That is because the hydrolysis reaction forming
937methylamine tends to kick in all at once, if this precaution is not taken,
938leaving the chemist in a dangerous situation with a runaway reaction.
939    
940    After the first rush of the reaction has subsided and the bubbling of
941the methylamine into the formic acid has slowed down, the heat applied to
942the 2000 ml flask is increased to maintain a good rate of methylamine flow
943to the formic acid. Eventually, all the methylamine will be boiled out.
944This will be when methylamine no longer flows evenly into the formic acid.
945The flask must not be heated so strongly that water is forced through the
946bent glass tubing.
947    
948    The heat is turned off and the level of the flask containing formic 
949acid is lowered so that the acid is not sucked back into the other flask.
950This formic acid is about half reacted with methylamine. When it has cooled
951down, it is poured in a tall glass bottle and kept in the freezer until the
952next batch is made, when it is used for the production of Nmethylformamide.
953Since it is already half reacted, the amount of methylamine used is reduced
954accordingly.
955    
956    Meanwhile, back in the 2000 ml flask, the methamphetamine reaction
957mixture is about 100 ml in volume and has a red color. It floats above the
958sodium hydroxide solution. Once it has cooled down, the contents of this
959flask are poured into a 1000 ml sep funnel. The sodium hydroxide solution
960is drained out and thrown away. The red methamphetamine formyl amide is
961poured into a 500 ml round bottom flask with 3 boiling chips. 200 ml of
962hydrochloric acid is measured out. (The 28% hardware store variety is fine
963for this purpose.) It is poured into the sep funnel and swirled around to
964dissolve any product left behind in the sep funnel. Then it is poured into
965the 500 ml flask with the product. When swirled around, they mix easily.
966    
967    The glassware is set up as shown in Figure 2b in Chapter 3. Tap water
968flow is proper for use in the condenser. The heat is turned on to the 500
969ml flask, and a gentle rate of boiling is maintained for 2 hours. The
970mixture quickly turns black. The reaction going on here is metharnphetamine
971formyl amide reacting w~th hydrochloric acid to produce methamphetamine
972hydrochloride and formic acid. This is a hydrolysis reaction.
973    
974    After the two hours have passed, the heat to the flask is turned off.
975While the flask is cooling down, 80 grams of sodium hydroxide and 250 ml of
976water are mixed in a 1000 ml round bottom flask. Once again, a good quality
977lye is acceptable. If the 35% laboratory grade of hydrochloric acid was
978used in the last step, then 100 grams of sodium hydroxide is mixed with 300
979ml of water.
980    
981    When both flasks have cooled down, the black reaction mixture is 
982cautiously added to the sodium hydroxide solution. It is added in small
983portions, then swirled around to mix it. They react together quite
984violently. The reaction here is sodium hydroxide reacting with hydrochloric
985acid to produce table salt, with formic acid to produce sodium formate, and
986with methamphetamine hydrochloride to produce methamphetamine free base.
987When the sodium hydroxide solution gets very hot, the chemist stops adding
988the reaction mixture to it until it cools down again.
989    
990    After all the black reaction mixture has been added to the sodium 
991hydroxide solution, there is a brown liquid layer floating above the sodium
992hydroxide solution. This brown layer is methamphetamine free base. It also
993has a good deal of unreacted methamphetamine hydrochloride dissolved in it.
994This latter has to be neutralized because it will not distill in its
995present form. The 1000 ml flask is stoppered and shaken vigorously for 5
996minutes. This gets the methamphetamine hydrochloride into contact with the
997sodium hydroxide so it can react.
998    
999    The bottom of the flask is full of salt crystals that cannot dissolve 
1000in the water because the water is already holding all the salt it can.
1001
1002    The chemist adds 100 ml of water to the flask and swirls it around for 
1003a few minutes. If that does not dissolve it all, he adds another 100 ml of
1004water.
1005    
1006    After the flask has cooled down, it is poured into a 1000 ml sep 
1007funnel, and 100 ml of benzene is added. The sep funnel is stoppered and
1008shaken for 15 seconds. It is allowed to stand for a couple of minutes, then
1009the lower water layer is drained into a glass container. The brown
1010methamphetamine-benzene layer is poured into a clean, dry 500 ml round
1011bottom flask. The water layer is extracted once more with 100 ml benzene,
1012then thrown away. The benzene layer is poured into the 500 ml flask along
1013with the rest of the methamphetamine.
1014    
1015    The chemist is now ready to distill the methamphetamine. He adds three
1016boiling chips to the 500 ml round bottom flask and sets up the glassware
1017for fractional distillation as shown in Figure 5. The 500 ml flask sits
1018directly on the heat source. The glass-packed claisen adapter is the proper
1019fractionating column. The collecting flask is a 250 ml round bottom flask.
1020Tap water is used in the condenser.
1021    
1022    The heat source is turned on to 1/4 to 1/3 maximum. Soon the mixture
1023begins boiling. The first thing that distills is benzene water azeotrope at
102468ø C. Then pure benzene comes over at 80øC. Once again, as in the
1025distillation of phenylacetone, foaming can sometimes be a problem. In that
1026case, it is dealt with in the same way as described in Chapter 3.
1027    
1028    When the temperature reaches 85øC, or the rate of benzene collecting
1029slows to a crawl, the heat is turned off and the flask allowed to cool
1030down. The collected benzene is poured into a bottle. It can be used again
1031the next time this process is done. The same 250 ml flask is put on the
1032collecting side.
1033    
1034    The distilling flask is now cool, so vacuum is applied to the glassware
1035at full strength. The last remnants of benzene begin to boil, and the heat
1036is turned back on to 1/3 maximum. The temperature begins to climb. If an
1037aspirator is being used, when the temperature reaches 80-ø C, the chemist
1038quickly removes the vacuum hose and replaces the 250 ml flask with a clean
1039dry one. If he is using a good vacuum pump, he makes this change at about
104070øC. The flask change is done quickly to avoid overheating in the
1041distilling flask. 
1042    
1043    The methamphetamine distills over. With an aspirator, the chemist 
1044collects from 80øC to about 140ø or 150ø C, depending on how strong the
1045vacuum is. With a vacuum pump, he collects to about 120ø or 130øC. Once it
1046has distilled, the heat is turned off and the vacuum hose disconnected.
1047    
1048    The product is about 90 ml of clear to pale yellow methamphetamine. If
1049the chemist is feeling tired now, he may take out a drop on a glass rod and
1050lick it off. It tastes truly awful and has a distinctive odor, somewhat
1051biting to the nostrils.
1052    
1053    He is now ready to make his liquid methamphetamine free base into
1054crystalline methamphetamine hydrochloride. Half of the product is put into
1055each of two clean dry 500 ml Erlenmeyer flasks.
1056    
1057    The chemist now has a choice to make. He can use either benzene or
1058ethyl ether as the solvent to make the crystals in. Benzene is cheaper, and
1059less of it is needed because it evaporates more slowly during the filtering
1060process. Ether is more expensive, and flammable. But since it evaporates
1061more quickly, the crystals are easier to dry off. If ether is used, it is
1062anhydrous (contains no water).
1063    
1064    A third choice is also possible for use as a crystallization solvent. 
1065This is mineral spirits available from hardware stores in the paint
1066department. Mineral spirits are roughly equivalent to the petroleum ether
1067or ligroin commonly seen in chem labs. Those brands which boast of low odor
1068are the best choice. Before using this material it is best to fractionally
1069distill it, and collect the lowest boiling point half of the product. This
1070speeds crystal drying. Since the choice of mineral spirits eliminates ether
1071from the supply loop, the clandestine operator may well go this route.
1072Toluene is also an acceptable solvent.
1073    
1074    With the solvent of his choice, the chemist rinses the insides of the 
1075condenser, vacuum adapter and 250 ml flask to get out the methamphetamine
1076clinging to the glass. This rinse is poured in with the product. Solvent is
1077added to each of the Erlenmeyer flasks until the volume of liquid is 300
1078ml. They are mixed by swirling.
1079    
1080    A source of anhydrous hydrogen chloride gas is now needed. The chemist
1081will generate his own. The glassware is set up as in Figure 10. He will
1082have to bend another piece of glass tubing to the shape shown. It should
1083start out about 18 inches long. One end of it should be pushed through a
1084one-hole stopper. A 125 ml sep funnel is the best size. The stoppers and
1085joints must be tight, since pressure must develop inside this flask to
1086force the hydrogen chloride gas out through the tubing as it is generated.
1087    
1088    Into the 1000 ml, three-necked flask is placed 200 grams of table salt.
1089Then 35% concentrated hydrochloric acid is added to this flask until it
1090reaches the level shown in the figure. The hydrochloric acid must be of
1091laboratory grade.
1092    
1093    Some concentrated sulfuric acid (99-98%) is put into the sep funnel and
1094the spigot turned so that 1 ml of concentrated sulfuric acid flows into the
1095flask. It dehydrates the hydrochloric acid and produces hydrogen chloride
1096gas. This gas is then forced by pressure through the glass tubing.
1097    
1098    One of the Erlenmeyer flasks containing methamphetamine in solvent is
1099placed so that the glass tubing extends into the methamphetamine, almost
1100reaching the bottom of the flask. Dripping in more sulfuric acid as needed
1101keeps the flow of gas going to the methamphetamine. If the flow of gas is
1102not maintained, the methamphetamine may solidify inside the glass tubing,
1103plugging it up.
1104    
1105    Within a minute of bubbling, white crystals begin to appear in the 
1106solution. More and more of them appear as the process continues. It is an
1107awe-inspiring sight. In a few minutes, the solution becomes as thick as
1108watery oatmeal.
1109    
1110    It is now time to filter out the crystals, which is a two-man job. The
1111flask with the crystals in it is removed from the HC1 source and 
1112temporarily set aside. The three-necked flask is swirled a little to spread
1113around the sulfuric acid and then the other Erlenmeyer flask is subjected
1114to a bubbling with HC1. While this flask is being buWled, the crystals
1115already in the other flask are filtered out.
1116    
1117    The filtering flask and Buchner funnel are set up as shown in Figure
111811. The drain stem of the Buchner funnel extends all the way through the
1119rubber stopper, because methamphetamine has a nasty tendency to dissolve
1120rubber stoppers. This would color the product black. A piece of filter
1121paper covers the flat bottom of the Buchner funnel. The vacuum is turned on
1122and the hose attached to the vacuum nipple. Then the crystals are poured
1123into the Buchner funnel. The solvent and the uncrystallized methamphetamine
1124pass through the filter paper and the crystals stay in the Buchner funnel
1125as a solid cake. About 15 ml of solvent is poured into the Erlenmeyer
1126flask. The top of the flask is covered with a palm and it is shaken to
1127suspend the crystals left clinging to the sides. This is also poured into
1128the Buchner funnel. Finally, another 15 ml of solvent is poured over the
1129top of the filter cake.
1130    
1131    Now the vacuum hose is disconnected and the Buchner funnel, stopper and
1132all, is pulled from the filtering flask. All of the filtered solvent is
1133poured back into the Erlenmeyer flask it came from. It is returned to the
1134HC1 source for more bubbling. The Buchner funnel is put back into the top
1135of the filtering flask. It still contains the filter cake of
1136methamphetamine crystals. It will now be dried out a little bit. The vacuum
1137is turned back on, the vacuum hose is attached to the filtering flask, and
1138the top of the Buchner funnel is covered with the palm or a section of
1139latex rubber glove. The vacuum builds and removes most of the solvent from
1140the filter cake. This takes about 60 seconds. The filter cake can now be
1141dumped out onto a glass or China plate (not plastic) by tipping the Buchner
1142funnel upside-down and tapping it gently on the plate.
1143    
1144    And so, the filtering process continues, one flask being filtered while
1145the other one is being bubbled with HC1. Solvent is added to the Erlenmeyer
1146flask to keep their volumes at 300 ml. Eventually, after each flask has
1147been bubbled for about seven times, no more crystal will come out and the
1148underground chemist is finished.
1149    
1150    If ether was used as the solvent, the filter cakes on the plates will 
1151be nearly dry now. With a knife from the silverware drawer, the cakes are
1152cut into eighths. They are allowed to dry out some more then chopped up
1153into powder. If benzene was used, this process takes longer. Heat lamps may
1154be used to speed up this drying, but no stronger heat source.
1155    
1156    The yield of product is about 100 grams of nearly pure product. It 
1157should be white and should not get wet, except in the most humid weather.
1158It is suitable for any purpose. It can be cut in half and the underground
1159chemists will still have a better product than their competition. But they
1160will not cut it until a few days have passed, so that their options are not
1161limited should one of the problems described in the next few paragraphs
1162arise.
1163    
1164    Here are some of the common problems that arise with the crystals, and
1165how they are dealt with. To spot these possible problems, the crystals are
1166first left on the plate to dry out, and then transferred to glass jars or
1167plastic baggies.
1168    
1169    Yellow Crystals. This is caused by not properly rinsing off the 
1170crystals while in the Buchner funnel, or not using enough solvent to
1171dissolve the methamphetamine in the Erlenmeyer flasks. To whiten them up,
1172they are allowed to soak in some ether in a glass jar, then filtered again.
1173    
1174    Yellow Stinky Crystals. The smell takes a few days to develop fully.
1175They are left alone for 5 days, then soaked in ether and filtered again.
1176The smell should not return. (The problem is caused by heating the reaction
1177mixture above the 145øC upper limit.)
1178
1179    Crystals Refuse To Dry. This can especially be a problem using benzene
1180as a solvent. It can also be a problem on very humid days. The crystals are
1181placed in the clean, dry filtering flask, the top is stoppered and vacuum
1182applied at full strength for 15 minutes. Warming the outside of the
1183filtering flask with hot water while it is under vacuum speeds the process.
1184    
1185    Crystals Melt. Here the crystals soak up water from the air and melt.
1186This is usually caused by raising the temperature of the reaction too
1187rapidly, or by collecting too much high boiling material during the 
1188distillation. First, they are put into the filtering flask and a vacuum
1189applied to dry them out. They are soaked in ether and filtered. If this
1190doesn't cure the problem, cutting the material to 50% purity should take
1191care of it.
1192
1193    Crystals Are Sticky. Here the crystals seem covered by a thin layer of
1194oily material, causing them to stick to razor blades, etc. The problem is
1195dealt with in the same way as melting crystals.
1196    
1197    Crystals Fail to Form. This problem occurs during the process of 
1198bubbling HCl into the methamphetamine. Instead of forming crystals, an oil
1199settles to the bottom of the flask. This is generally caused by incomplete
1200hydrolysis of the formyl amide. Perhaps it didn't mix with the hydrochloric
1201acid. It is put in a flask and the solvent boiled off under a vacuum. Then
1202200 ml of hydrochloric acid is added and the process is repeated, starting
1203from the hydrolysis of the formyl amide of methamphetamine. The 35%
1204laboratory grade of hydrochloric acid is used.
1205    
1206    In the event of melting or sticky crystals, cutting is first tried on a 
1207small sample of the crystals to see if that will solve the problem. If it
1208does not, then a recrystallization must be resorted to. This is done by
1209dissolving the crystals in the smallest amount of warm alcohol that will
1210dissolve them. 190-proof grain alcohol, 95% denatured alcohol, or absolute
1211alcohol may be used. Then 20 times that volume of ether is added. After
1212vigorous shaking for three minutes, the crystals reappear. If not, more
1213ether is added, followed by more shaking. After being filtered, the
1214crystals should be in good shape.
1215    
1216    A technique which may be used in especially stubborn cases is to 
1217dissolve the crystals in dilute hydrochloric acid solution, extract out the
1218oily impurities with benzene, and then isolate the methamphetamine. This is
1219done as follows:
1220    
1221    For every 100 grams of crystal, 200 ml of 10% hydrochloric acid is
1222prepared by mixing 60 ml of 35% hydrochloric acid with 140 ml of water. The
1223crystals are dissolved in the acid solution by stirring or shaking in the
1224sep funnel. 100 ml of benzene is added to the solution in the sep funnel,
1225which is then shaken vigorously for about 2 minutes. The lower layer is
1226drained out into a clean beaker. It contains the methamphetamine. The
1227benzene layer is thrown out. It contains the oil grunge which was polluting
1228the crystals.
1229    
1230    The acid solution is returned to the sep funnel and the acid 
1231neutralized by pouring in a solution of 70 grams of sodium hydroxide in 250
1232ml of water. After it has cooled down, the mixture is shaken for 3 minutes
1233to make sure that all the methamphetamine hydrochloride has been converted
1234to free base. Then 100 ml of benzene is added and the mixture shaken again.
1235The lower water layer is drained out and thrown away. The
1236benzene-methamphetamine solution is distilled as described earlier in this
1237chapter. Then, as described earlier in this chapter, dry hydrogen chloride
1238gas is bubbled through it to obtain clean crystals. (Hydrogen chloride gas
1239must be made in a well-ventilated area; otherwise, it will get into the
1240chemist's lungs and do real damage.)
1241    
1242    There is an alternative method for converting amphetamine free base
1243into the crystalline hydrochloride. It is based on the method that South
1244American cocaine manufacturers use to turn coca paste into cocaine
1245hydrochloride. This method does not give the really high quality crystals
1246that the bubble through method gives, but its use is justified when really
1247big batches are being handled.
1248    
1249    In this alternative procedure, the free base is dissolved in two or 
1250three volumes of acetone. Concentrated hydrochloric acid (37%) is then
1251added to the acetone while stirring until the mixture becomes acid to
1252litmus paper. Indicating pH paper should show a pH of 4 or lower. The
1253hydrochloride is then precipitated from solution by slowly adding ether
1254with stirring. It will take the addition of 10 to 20 volumes of ether to
1255fully precipitate the hydrochloride. Toluene or mineral spirits may be
1256substituted for the ether. Then the crystals are filtered out using a
1257Buchner funnel as described before, and set aside to dry. The filtrate
1258should be tested for completeness of precipitation by adding some more
1259ether to it.
1260    
1261                                 References
1262    
1263    Journal of Organic Chemistry, Volume 14, page 559 (1949).  
1264    Journal of the American Chemical Society, Volume 58, page 1808  
1265    (1936); Volume 61, page 520 (1939); Volume 63, page 3132 (1941).  
1266    Organic Syntheses, Collective Volume II, page 503. 
1267    
1268--------------------------------------------------------------------------
1269                        INDUSTRIAL-SCALE PRODUCTION
1270--------------------------------------------------------------------------
1271    
1272    In the previous five chapters, I described a process by which 
1273underground chemists make smaller amounts of methamphetamine, up to about
1274one-half pound of pure methamphetamine. The process takes about three days
1275with two people working in shifts around the clock. Thus, the maximum
1276production level is stuck at one pound per week.
1277    
1278    There is a way to break through this production limit, which is to 
1279produce phenylacetone and turn it into methamphetamine by different
1280methods. These methods produce more in less time, and they are cheaper. Two
1281of them, the tube fumace and the hydrogenation bomb, are major engineering
1282projects. But they are no problem for those with a Mr. Handyman streak.
1283    
1284    However, underground chemists will not move up to industrialscale
1285production until they are sure that they are going to be able to sell it
1286without having to deal with strangersðunless, of course, they want to get
1287busted.
1288    
1289    One major difference in the logistics of a large-scale operation versus
1290a smaller one is that a different source of chemicals is required. An
1291outlet that specializes in pints and quarts of chemicals is not going to be
1292much help when multi-gallons are needed. Here a factor comes into play
1293which cannot be taken advantage of at lower levels of production. Most
1294chemical suppliers will not deal with individuals, only with corporations
1295and companies.
1296    
1297    Now the underground chemist can turn this situation to his advantage by
1298means of subterfuge. First he develops a false identity. He gets some of
1299the books on false ID andðAbracadabra!ðhe's Joe Schmoe. He uses this
1300identity to form several companies. If he wants to be official, he consults
1301the book, How to Forrn Your Own Corporation For Under 50 Dollars, available
1302in most libraries. Otherwise, he just has some invoice-order forms printed
1303up for his company. He may also open a checking account for his company to
1304pay for chemicals. He uses checks with high numbers on them so that they
1305don't think that he just appeared out of thin air. As an alternative, he
1306may pay with certified checks from the bank.
1307    
1308    The next step is to rent some space as his company headquarters and
1309chemical depot. Indeed, he'll probably rent a couple such depots to house
1310hisvarious companies. Now he starts contacting chemical dealers, ordering
1311enough of one or two chemicals to last for a couple of years. Then he
1312contacts another dealer and orders a similar quantity of one or two other
1313chemicals under a different company name. He continues this process until
1314he has everything he needs. He offers to pick them up so that they do not
1315see the dump he's rented as his headquarters. As a precaution, he equips
1316these dumps with a phone and answering machine so that they can call him
1317back. If he doesn't live in a large city, he does business out of town.
1318That way they won't be surprised that they never heard of him. But he does
1319not do business too far away from home base, so they won't wonder why he
1320came so far.
1321    
1322    There is a better strategy to follow in getting the equipment and 
1323chemicals needed for clandestine meth production. The best method to use is
1324to first order the equipment and a couple of the most suspicion arousing
1325chemicals. Then the underground operator lays low for a while. The narco
1326swine have a habit of going off half-cocked on their search warrants. If
1327the initial purchases caught their eyes, they will likely swoop right in,
1328planning on finding an operating lab, or at least enough to make a
1329conspiracy charge stick. If they move now, the meth meister will not be
1330prosecutable, so long as he does not admit guilt. An alternative narco
1331swine strategy would be for them to initiate intense surveillance upon Joe
1332Schmoe. So long as Joe is not brain dead, this will be pretty obvious after
1333awhile. If surveillance is noticed, it is time to put the plan into a deep
1334freeze, and consider the initial purchases a long term investment rather
1335than a quick payoff. If Joe is able to get the most sensitive materials
1336unnoticed, it is then time to quickly get the more mundane items needed and
1337immediately turn to the production end of the operation.
1338    
1339    When it is time for the underground chemist to pick up the chemicals,
1340he uses a pick-up or van registered in Joe Schmoe's name. As a precaution,
1341he equips his vehicle with a radio scanner. He buys the book, U.S.
1342Government Radio Frequencies, and tunes the scanner to pick up the FBI, the
1343DEA, the state and local police. He picks up the chemicals and returns with
1344them to his headquarters and depot. He takes a roundabout route to make
1345sure he isn't being followed. Two tricks he may use to detect a tail are to
1346turn into a dead-end street and to drive either too fast or too slow. He
1347leaves Joe's vehicle at the depot and takes a roundabout route home. He
1348stops at a few bars and leaves by the back exit.
1349    
1350    A very common, and quite stale trick is for the narco swine to place a
1351radio tracing device in the packing materials surrounding jugs of chemicals
1352purchased by suspected drug manufacturers. All items purchased should be
1353carefully inspected during the drive away from the point of purchase. If
1354such a device is found, it is cause for clear thinking action, rather than
1355panic. While using such a device, the heat will usually lay quite far back
1356on their pursuit to avoid being noticed. They will rely on the transmitter
1357to tell them where you are going. It is best not to smash such a
1358transmitter, but rather keep it in hand, and toss it into the back of
1359another pickup truck at a stoplight. This is then followed by putting the
1360plan into a deep freeze until the heat grows bored with you.
1361    
1362    The next thing the underground chemist needs is a laboratory location.
1363A country location makes any surveillance very obvious and keeps chemical
1364smells out of the way of nosy neighbors. Electricity and running water are
1365absolutely necessary. Now he loads the chemicals onto Joe's wheels and
1366heads for the laboratory in a very roundabout manner, keeping an eye open
1367for any tail and paying close attention to the scanner. He leaves the
1368scanner at the lab for entertainment in the long hours ahead.
1369    
1370    A nice addition to any underground laboratory is a self-destruct 
1371device. This consists of a few sticks of dynamite armed with a blasting
1372cap, held inside an easily opened metal can. The purpose of the metal can
1373is to prevent small accidental fires from initiating the self-destruct 
1374sequence. If Johnny Law pays an uninvited visit to his lab, the underground
1375chemist lights the fuse and dives out the window. The resulting blast will
1376shatter all the glass chemical containers and set the chemicals on fire.
1377This fire will destroy all the evidence. He keeps his mouth shut and lets
1378his lying lawyer explain why the blast happened to come at the same time as
1379the raid. He has no reason to fear the state crime lab putting the pieces
1380of his lab back together. These guys learned their chemistry in school and
1381are truly ignorant when it comes to the particulars of a well-designed lab.
1382    
1383    The feds, on the other hand, have a higher grade of chemist working for
1384them, but they are tiny individuals who are haunted by nagging self doubt,
1385wondering why after obtaining a Ph.D., they are just faceless cogs in a
1386machine. To compensate for this, they will claim to make great discoveries
1387of the obvious. Case in point is an article published in the Journal of
1388Forensic Sciences. This is a petty journal published by Johnny Law where
1389the aforementioned tiny individuals can stroke their egos by getting
1390published. In an article covering the lithium in ammonia reduction of
1391ephedrine to meth production method featured in this third edition of my
1392book, the unnamed tiny, frustrated chemists trumpeted "we found that a
1393nitrogen atmosphere to protect the reaction was unnecessary, contrary to
1394the claims of the authors who said it was essential."
1395    
1396    The authors to which they refer here are Gary Small and Arlene 
1397Minnella, legitimate scientists who were published in a legitimate
1398scientific journal, the Journal of Organic Chemistry. In their article
1399covering the lithium in ammonia reduction of benzyl alcohols, they used
1400really tiny batches that might actually need a nitrogen atmosphere to
1401protect them, and in no place claimed that it was essential. See the
1402Journal of Organic Chemistry article cited in Chapter 15 of this book. It
1403was obvious that the steady boiling away of liquid am monia would form its
1404own protective gas blanket when done on a scale corresponding to real meth
1405production.
1406    
1407    They further went on to nitpick the purification procedure used by the
1408real scientists, claiming it was unnecessary. Everyone who reads the
1409journals knows that it is unnecessary. This is just the protocol that has
1410been followed by research scientists for the past god-knows-howmany ages.
1411They just do this so that if they get unexpected results in their research,
1412they will know that it is not due to impurities in the reaction mix. To
1413make a great discovery out of finding that these rigorous purification
1414schemes are not needed for practical production methods just shows how
1415shallow these people are.
1416    
1417    
1418--------------------------------------------------------------------------
1419                      PHENYLACETONE FROM B-KETO ESTERS
1420--------------------------------------------------------------------------
1421    
1422    In this chapter, I will cover two separate but similar methods of 
1423making phenylacetone. Neither of them is actually suitable for
1424industrial-scale production, but they have the advantage of not using
1425phenylacetic acid. This allows an underground chemist to diversify the
1426chemicals used, and enables him to defeat a blockade on his phenylacetic
1427acid supply. Neither of these reactions is foolproof; both require a
1428certain amount of laboratory skill. The chemicals must be weighed and
1429measured fairly exactly. This is unlike the method described in Chapter 3,
1430where anything within a ballpark range will work. These methods require a
1431reliable scale.
1432    
1433    Both of these reactions use sodium metal, which is some nasty stuff. It
1434reacts violently with water to produce sodium hydroxide and hydrogen. It
1435will also react with air. The chemist never touches it intentionally; if he
1436does touch it, he washes it off with warm water. Sodium metal comes in a
1437can, covered with a bath of petroleum distillate. This is to protect it
1438from water and air. As long as it stays covered, it causes the chemist no
1439problems.
1440    
1441    In this reaction, sodium metal is reacted with absolute alcohol to make
1442sodium ethoxide (NaOCH2CH3). Ethyl acetoacetate and bromobenzene are then
1443added to this to produce a beta keto ester. Reaction with acid then
1444produces phenylacetone. 
1445    
1446    A side reaction which sometimes becomes a problem is bromobenzene
1447reacting with beta keto ester to produce di-phenylacetone. This can be
1448controlled by not using too much bromobenzene, adding it slowly and
1449stirring it well.
1450    
1451    Figure 12 shows the glassware used. The glassware must be very dry, so
1452it is dried out in the oven for an hour or so. If the sep funnel has a
1453plastic valve, the valve is taken out before the sep funnel is put in the
1454oven. The magnetic stirring bar does not go in the oven either. It is
1455coated with Teflon, so it does not have any water on it. A magnetic stirrer
1456is necessary to do this reaction, because good stirring is very important.
1457An extra claisen adapter is needed for this reaction; one is filled with
1458broken pieces of glass for use as a fractionating column, the other is kept
1459as is for use in the Figure 12 apparatus.
1460    
1461    To begin, the underground chemist puts a bed of Drierite in the vacuum
1462adapter as shown in Figure 2a, being sure to plug up the vacuum nipple. The
1463water lines are attached to the condenser and cold water started flowing
1464through it. But if it is humid, the water flow is not started until the
1465glassware is assembled.
1466    
1467    The can of sodium is opened. A chunk about the size of a medium egg is
1468needed. The chemist selects a convenient corner of the block of sodium to
1469work on. With a clean, sharp knife, he scrapes off any discolored skin
1470there might be in the area he plans to use. Good clean sodium has a bright
1471metallic look. He keeps the block under the petroleum as he scrapes the
1472discolored skin.
1473    
1474    Now he must weigh the sodium. A 100 ml beaker is filled halffull of the
1475petroleum distillate from the can of sodium, or with xylene. He puts it on
1476the scale and weighs it. He needs 34.5 grams of sodium metal, so with a
1477clean sharp knife. he cuts off a chunk of sodium, transfers it to the
1478beaker and weighs it. If it is not quite 34.5 grams, he cuts a little more
1479sodium and adds it to the beaker. This is done quickly, so that evaporation
1480of the petroleum does not throw the measurement off. Then another 100 ml
1481beaker is filled half-full of anhydrous ethyl ether. The sodium metal is
1482transferred to it with a spoon. The petroleum is poured back in with the
1483block of sodium and the can sealed up so that it does not evaporate. With a
1484clean sharp knife, the sodium is cut up into little pieces about 1/2 the
1485size of a pea.
1486
1487    The sodium is kept under the ether while this is being done. Eye 
1488protection is always worn when working with sodium.
1489    
1490    After the sodium is cut up, the magnetic stirring bar is put in the 
14912000 ml flask. Then the sodium metal pieces are scooped out with a spoon
1492and put in the 2000 ml flask. The glassware is immediately assembled as
1493shown in Figure 12. One liter (1000 ml) of absolute ethyl alcohol is
1494measured out. Absolute alcohol absorbs water out of air, so this is done
1495rapidly. Here's how. The chemist gets a quart beer bottle, marks on the
1496outside how full one liter is, and bakes the bottle in the oven to dry it
1497out. When he takes it out of the oven, he sucks the hot, moist air out of
1498it with a section of glass tubing. Once it has cooled down, he fills it
1499with one liter of absolute alcohol and stoppers it to keep it dry. He wants
1500to get the alcohol in with the sodium before the ether on it evaporates,
1501and this saves him the time of measuring it out.
1502    
1503    About 200 ml of the absolute alcohol is put in the sep funnel and the
1504valve opened to allow the alcohol to flow down onto the sodium metal. Cold
1505water should be flowing through the condenser. Magnetic stirring is not
1506necessary at this time, but the 2000 ml flask is sitting in a large pan. A
1507pail of cold water and a towel are kept handy. Sodium and alcohol react
1508together vigorously, and the alcohol boils like crazy. The condenser is
1509checked to see how far up the alcohol vapors are reaching. The chemist does
1510not want the alcohol vapors to escape out the top of the condenser. If the
1511vapors are making it more than halfway up the condenser, cold water is
1512poured from the pail into the pan the flask is sitting in. That cools it
1513off and slows down the boiling. But if that does not do enough, the wet
1514towel is put on top of the flask. When the boiling slows down, the towel
1515and the pan of water are removed, then more alcohol is added to the sep
1516funnel. A fresh ball of cotton is put in the top of the sep funnel to
1517protect the alcohol from water in the air. The alcohol is added to the
1518flask at such a Mte that the boiling of the alcohol continues at a nice
1519Mte. When all of the original one liter of absolute alcohol has been added
1520to the flask, the flask is gently heated on the hot plate to keep the
1521alcohol boiling until the little pieces of sodium are dissolved. If the
1522chemist has done a very good job, the result is a clear solution. If not,
1523it will be milkycolored.
1524    
1525    The magnetic stirring is now begun, and 195 grams (190 ml) of 
1526ethylacetoacetate is put in the sep funnel over the next 15 minutes. The
1527solution is heated to a gentle boiling. As it is boiling and stirring, 236
1528grams of bromobenzene is put in the sep funnel and dripped into it over a
1529period of an hour. The boiling and stirring is continued for 8 hours.
1530    
1531    Then the stirring is stopped and the solution allowed to cool down. A
1532good amount of sodium bromide crystals settle to the bottom of the flask.
1533When they have settled to the bottom, the glassware is taken apart and as
1534much of the alcohol solution as possible is poured into a 3000 ml flask.
1535The last of the product is rinsed off the sodium bromide crystals by adding
1536about 50 ml of absolute alcohol to them, swirling around the mixture, then
1537filtering it. This alcohol is added to the alcohol in the 3000 ml flask.
1538    
1539    The glassware is set up as shown in Figure 3 in Chapter 3. A 1000 ml
1540flask is used as the collecting flask. The alcohol in the 3000 ml flask is
1541heated. The oil in the pan is not heated above 115ø C. The distillation is
1542continued until the chemist has collected over 900 ml of alcohol in the
1543collecting flask.
1544    
1545    When the alcohol has been boiled out, the heat is turned off and the
1546flask removed from the pan of oil. As it is cooling off, 1500 ml of 5%
1547sodium hydroxide solution is mixed. To do this, 75 grams of sodium
1548hydroxide is put in a flask and 1400 ml of water added. (Lye may be used as
1549a sodium hydroxide substitute.) When both the sodium hydroxide solution and
1550the reaction mixture near room temperature, the sodium hydroxide solution
1551is poured into the 3000 ml flask with the reaction mixture. The magnetic
1552stirring bar is put into the flask and magnetic stirring is begun. It is
1553stirred fast enough that a whirlpool develops in the mixture and the~beta
1554keto ester gets into contact with the sodium hydroxide solution. The
1555stirring is continued for 4 hours without heating the solution. The beta
1556keto ester reacts with the sodium hydroxide to produce the compound shown
1557above, plus ethyl alcohol. This is a hydrolysis reaction.
1558    
1559    After 4 hours of stirring, the stirring is stopped and the solution 
1560allowed to sit for a few minutes. A small amount of unreacted material will
1561float up to the top. If there is a large amount of unreacted material, the
1562stirring is begun again and 40 grams of sodium hydroxide and 300 ml of
1563isopropyl rubbing alcohol are added. It is stirred for 4 more hours. But
1564generally this is not necessary.
1565    
1566    The unreacted layer is poured into a 1000 ml sep funnel. A good deal of
1567the sodium hydroxide solution will be poured off with it. The chemist lets
1568it sit for a few minutes, then drains the sodium hydroxide solution back
1569into the 3000 ml flask. The oily unreacted material is poured into a small
1570glass bottle and kept in the freezer. When a good amount of it has
1571accumulated, the chemist tries reacting it again with 5% sodium hydroxide
1572solution. However, this will not yield very much more product, because most
1573of this oily material is the diphenylacetone byproduct.
1574    
1575    The underground chemist is now ready to produce phenylacetone. The
1576compound shown above will react with sulffiuric acid to produce 
1577phenylacetone and carbon dioxide gas. He mixes up 150 ml of 50% sulffiuric
1578acid. To do this, he adds slightly more than 55 ml of sulfuric acid to
1579slightly less than 105 ml of water; if he added more sodium hydroxide and
1580alcohol to his reaction mixture, he mixes up twice as much 50% sulfuric
1581acid.
1582    
1583    The stirrer in the 3000 ml flask containing the sodium hydroxide is 
1584started up again. Then the 50% sulffiuric acid is slowly added to it. It
1585will bubble out carbon dioxide like crazy and crystals of sodium sulfate
1586will be formed. Phenylacetone will also be formed, some of it floating on
1587the surface of the solution, some of it trapped among the crystals formed.
1588When all of the sulffiuric acid has been added, and the bubbling of carbon
1589dioxide has slowed down to just about stopping, the stirring is stopped.
1590    
1591    The glassware is set up as shown in Figure 3. The collecting flask is
15922000 ml. The 3000 ml flask is slowly heated to boiling. The steam carries
1593the phenylacetone along with it to the other flask. This process is called
1594a steam distillation. The distilling is continued until a little more than
15951000 ml is in the collecting flask. By then, almost all the phenylacetone
1596will be carried over into the collecting flask. There will be two layers in
1597the collecting flask, a yellow layer of phenylacetone on top, and a clear
1598water layer. There will be some acid dissolved in the water. Forty grams of
1599sodium hydroxide is dissolved in 150 ml of water, then added to the 2000 ml
1600flask. The flask is stoppered and shaken for one minute to destroy the
1601acid. Then 100 ml of benzene is added to the flask and it is shaken some
1602more. The phenylacetonebenzene layer is poured into a 1000 ml sep ffiunnel
1603and allowed to sit for a couple of minutes. Then the water layer is drained
1604off back into the 2000 ml flask. The phenylacetone layer is poured into a
1605500 ml flask along with a few boiling chips. Then 100 ml of benzene is
1606added to the 2000 ml flask, which is shaken again for about 30 seconds
1607before it is allowed to sit for a few minutes. The benzene layer is poured
1608into the 1000 ml sep funnel and allowed to sit for a couple of minutes. The
1609water layer is drained out, and the benzene layer is poured into the 500 ml
1610flask with the rest of the phenylacetone. The glassware is set up as shown
1611in Figure 5 and the phenylacetone distilled as described in Chapter 3. The
1612yield is about 125 ml of phenylacetone. (For more information on this
1613reaction, see Organic Reactions, Volume 1, published in 1942, page 266.)
1614    
1615    There is another way to make phenylacetone which is better than the
1616method just described. It does not take as long to do, and it is somewhat
1617simpler. As in the first method, the reactants must be measured out
1618carefully. 
1619    
1620    In this case, the main reactant is benzyl cyanide, also called 
1621phenylacetonitrile or alpha-tolunitrile. Benzyl cyanide is now a controlled
1622substance precursor, and so must be made.
1623    
1624    Benzyl cyanide is not outrageously poisonous like sodium cyanide. It is
1625an organic cyanide, called a nitrile. As long as the chemist doesn't drink
1626the stuff, he's OK. It is a somewhat smelly liquid, clear in color.
1627    
1628    This reaction is done similarly to the first method described in this 
1629chapter. First a solution of sodium ethoxide is made, then ethyl acetate is
1630added, mixed in with benzyl cyanide. This produces a solid called 
1631phenylacetacetonitrile. This solid is then added to sulfuric acid, and
1632phenylacetone is produced.
1633    
1634    The same glassware as shown in Figure 12 is used, except that a 3000 ml
1635round bottom flask is used. It is dried out in the oven. Now a sodium
1636ethoxide solution is produced in the same way as described earlier in this
1637chapter. The chemist starts with a chunk of clean sodium metal that weighs
1638128 grams. It is weighed out in a 300 ml beaker half-filled with petroleum
1639distillate or xylene, as described earlier. Then the sodium metal is
1640transferred to another beaker halffilled with anhydrous ether and chopped
1641into small pieces with a clean knife. Then it is scooped out with a spoon
1642and put in the 3000 rnl flask. The glassware is quickly assembled as shown
1643in Figure 12, with the 3000 ml flask sitting in a pan. Water flow through
1644the condenser is begun, and 300 ml of absolute ethyl alcohol is put in the
1645sep funnel. The same precautions as described earlier are used to keep the
1646alcohol free of water. As the alcohol is allowed to flow in onto the
1647sodium, the reaction is kept under control by putting cold water in the pan
1648and wrapping the flask in a wet towel.
1649    
1650    When the reaction is under control, more alcohol is added until a total
1651of 1500 ml has been added. The alcohol is gently boiled until the sodium
1652metal is dissolved.
1653    
1654    Now the chemist mixes 500 grams of benzyl cyanide with 575 grams of
1655ethyl acetate and stops the heating of the ethanol solution. Just as it
1656stops boiling, the mixture of ethyl acetate and benzyl cyanide is added
1657with good magnetic stirring. This addition takes about 15 minutes. The
1658stirring is continued for about 10 minutes after the addition is complete,
1659then the mixture is heated in a steam bath or in a pan of boiling water for
1660about 2 hours. Then it is taken out of the heat and allowed to sit
1661overnight, or at least for a few hours.
1662    
1663    The underground chemist has just made the sodium salt of 
1664phenylacetacetonitrile. To collect it, he cools the flask in a mixture of
1665salt and ice. With a clean wooden stick, he breaks up the chunks of
1666crystals that have formed, as the flask is cooling down. When it reaches
1667-10øC, he keeps it at this temperature for a couple of hours, then filters
1668out the crystals. They are rinsed a couple of times with ether, then, while
1669still wet with ether, added to a large flask or beaker containing 2000 ml
1670of water. They are dissolved by stirring, then the flask or beaker is
1671cooled down to 0øC by packing it in ice mixed with salt. When it reaches
1672this temperature, 200 ml of glacial acetic acid is added to it with
1673vigorous stirring. The chemist must make sure that the temperature does not
1674go up more than a few degrees while he is adding it.
1675    
1676    He has now made phenylacetacetonitrile. He filters the crystals off it
1677and rinses them a few times with water. The crystals must now be kept moist
1678in order for them to be turned into phenylacetone.
1679    
1680    All is now ready for producing phenylacetone from these crystals. In a
16812000 ml flask, he puts 700 ml of concentrated sulfuric acid. It is cooled
1682down to -10ø C by packing the flask in a mixture of salt and ice, then
1683magnetic stirring is begun. The crystals are slowly added to the sulfuric
1684acid. They must be moist, or he will get a mess. It takes about an hour to
1685add the crystals to the sulfuric acid. Once they are added, the flask is
1686heated in a pan of boiling water and swirled around to dissolve the
1687crystals. After they have dissolved, the flask is heated for a couple more
1688minutes, then removed from the pan of boiling water. It is cooled down
1689slowly to 0ø C by first letting it cool down, then packing it in ice.
1690    
1691    The underground chemist puts 1700 ml of water in a 3000 ml flask. Half
1692of the sulfuric acid solution is added to it. It is heated in a pan of
1693boiling water for a couple of hours. It is given a couple of good shakes
1694every 15 minutes. A layer of phenylacetone forms in the mixture.
1695    
1696    After 2 hours of heating, the mixture is poured into a gallon-size 
1697glass jug to cool off. Another 1700 ml of water is put in the flask and the
1698rest of the chilled sulfuric acid solution is poured into it. It is also 
1699heated for 2 hours in a pan of boiling water, then poured into another
1700glass jug.
1701    
1702    The chemist is ready to separate the phenylacetone from the water and
1703distill it. The liquid in the first jug is slowly poured into a 1000 ml sep
1704funnel until the sep funnel is full. Most of the phenylacetone layer will
1705be in the sep funnel, because it is floating on top of the water. The water
1706layer is drained back into the jug, and the phenylacetone layer is poured
1707into a large beaker. He adds 300 ml of benzene to the jug, stoppers it and
1708shakes it for 15 seconds. Then he stops and lets the layer of benzene
1709containing phenylacetone float up to the surface. It is slowly poured into
1710the sep funnel, and the water layer is drained back into the jug. The water
1711is thrown away. This process is repeated with the other jug.
1712    
1713    This phenylacetone has some sulfuric acid in it. The chemist puts 150
1714ml of water in the 1000 ml sep funnel. He also pours half of the 
1715phenylacetone and benzene mixture he got from the two jugs into the sep
1716funnel. He shakes it with the water to remove the sulfuric acid. The water
1717is drained out, and the phenylacetone-benzene layer is poured into a 1000
1718ml round bottom flask. Another 150 ml of water is put into the sep funnel.
1719It is shaken also, then the water layer is drained off. He pours as much of
1720this benzene-phenylacetone mixture into the 1000 ml round bottom flask as
1721he can until it reaches 2/3 full.
1722    
1723    The glassware is set up as shown in Figure 5 in Chapter 3, with a few
1724boiling chips in the 1000 ml flask. The collecting flask is 250 ml. He
1725distills off a couple of hundred ml of benzene to make room for the rest of
1726the product. When there is some room, he turns off the heat and waits for
1727the boiling to stop. Then the rest of the benzenephenylacetone mixture in
1728the sep funnel is added to the 1000 ml flask. The distillation is continued
1729until the benzene stops coming over. About 500 to 600 ml of benzene will be
1730collected.
1731    
1732    When the rate of benzene distillation slows down to just about 
1733stopping, the heat is turned off and it is allowed to cool down. Then the
1734last of the benzene is removed under a vacuum. When the benzene is gone,
1735the collecting flask is changed to a 500 ml flask and the phenylacetone is
1736distilled under a vacuum at the usual temperature range. The yield is about
1737300 ml of phenylacetone. Once the benzene is gone, virtually all of the
1738material left in the flask is phenylacetone. If there is a high boiling
1739residue, it is unchanged phenylacetacetonitrile.
1740    
1741                                 References
1742    
1743   Journal of the American Chemical Society, Volume 60, page 914 (1938).
1744    
1745    
1746--------------------------------------------------------------------------
1747                     PHENYLACETONE VIA THE TUBE FURNACE
1748--------------------------------------------------------------------------
1749    
1750    The best way to produce phenylacetone on a large scale and continuous
1751basis is by a catalyst bed inside a tube furnace. This has several
1752advantages over the other methods described in this book. Cheap and very
1753common acetic acid is used to react with phenylacetic acid instead of the
1754expensive and more exotic acetic anhydride and pyridine. Use of the tube
1755furnace frees up the glassware for use in other operations. The furnace
1756requires very little attention while it is in operation, which allows the
1757underground chemist to spend his time turning the phenylacetone into
1758methamphetamine. There is no reason why this process cannot be used in
1759small-scale production. It is just that its advantages really come out when
1760large amounts of phenylacetone must be produced.
1761    
1762    In this process, a mixture of phenylacetic acid and glacial acetic acid
1763is slowly dripped into a Pyrex combustion tube which is filled with
1764pea-sized pumice stones covered with a coating of either thorium oxide or
1765manganous oxide catalyst. This bed of catalyst is heated to a high
1766temperature with a tube furnace and the vapors of phenylacetic acid and
1767acetic acid react on the surface of the catalyst to produce ketones. Three
1768reactions result.
1769    
1770    The acid mixture is prepared so that there are three molecules of 
1771acetic acid for every molecule of phenylacetic acid. This makes it much
1772more likely that the valuable phenylacetic acid will react with acetic acid
1773to produce phenylacetone rather than with another molecule of phenylacetic
1774to produce the useless dibenzyl ketone.
1775    
1776    The vapors are kept moving in the catalyst tube by a slow stream of
1777nitrogen and eventually the product comes out the far end of the catalyst
1778tube. The vapors are then condensed and collected in a flask.
1779    
1780    The complete apparatus for doing this reaction is shown in Figure 13.
1781The combustion tube is made of Pyrex and is about one meter long. It is
1782about 2 centimeters in internal diameter, with a male 24/40 ground glass
1783joint on one end and a female 24/40 ground glass joint on the other end. If
1784the underground chemist cannot buy the tube with the glass joints already
1785on it, there are many places which will weld these glass joints onto the
1786tube. He can find such a place by asking around and checking the Yellow
1787Pages.
1788    
1789    The tube furnace must be 70 centimeters in length. The only 
1790commercially available tube furnace that I know of is the Hoskins tube
1791furnace. It is a fine furnace, but only 35 cm in length. Two of these would
1792have to be run end-to-end to get the required 70 cm length. The cost,
1793including a transformer for each of the furnaces, would be over $700. It is
1794better and cheaper for the chemist to build his own tube furnace.
1795    
1796    The tube furnace starts with a section of thinwall iron tubing about 75
1797cm long and 3 to 3.2 cm in internal diameter. Thinwall iron tubing has a
1798metal thickness of .024 inch. The outside of the tubing is wrapped with
1799asbestos cloth or asbestos paper to a thickness of about 2 millimeters.
1800Asbestos cloth or paper is available at hardware stores.
1801    
1802    Fifty feet of 28 gauge AWG nichrome wire is wrapped around the central
180370 cm of the tube. The windings are made fairly taut so that the wire sinks
1804slightly into the asbestos paper. Each winding is evenly spaced from the
1805previous one, about 1/2 cm apart. One winding must not be allowed to come
1806into contact with another, or there will be a short circuit.
1807    
1808    The outside of the tubing is insulated with 6 or 7 layers of asbestos
1809paper or cloth. This insulation is held in place by using copper wire
1810ligatures about 6 inches long, wrapped around the outside of the
1811insulation, and tied at the ends to make it tight.
1812    
1813    The two ends of the nichrome wire are attached to insulated connectors
1814(two of them) and then to a transformer. The Variac autotransformer is
1815perfect for this job. It can adjust 115-volt house current anywhere from
1816140 volts down to zero. The transformer can handle 5 amps of current.
1817    
1818    The chemist picks up a couple of pumice foot stones (Dr. Scholl's are
1819suitable) at the pharmacy. With a hammer and screw driver, he breaks them
1820into round pieces somewhat smaller than a pea. Any sharp or protruding
1821edges are knocked off. He makes enough of these pumice pebbles to fill the
1822combustion tube for a length of 70 cm.
1823    
1824    The pumice must now be purified to remove traces of metals and other
1825garbage. This prevents the catalyst from being poisoned. The pumice pebbles
1826are put into a 1000 ml beaker along with a wad of glass wool (Angel Hair)
1827somewhat larger than a fist. The glass wool will be going into the
1828combustion tube, so it must be cleaned off along with the pebbles. The
1829glass wool is packed down. Then nitric acid is added until both the pumice
1830and glass wool are covered. The beaker is put on an electric hot plate and
1831the nitric acid boiled for half an hour. This converts metal impurities
1832into soluble nitrates, and oxidizes other garbage. The nitric acid is all
1833poured off and down the drain. The pumice and glass wool are then covered
1834with distilled water and soaked for 5 minutes. This water is then drained
1835off and replaced with more water. The water is boiled for 10 minutes, then
1836drained off. This boiling water rinse is repeated two more times using
1837distilled water. Finally, the water is drained out and the beaker laid on
1838its side to drip out the last drops of water.
1839    
1840    The pumice pebbles are now ready to be coated with catalyst. About 450
1841ml of distilled water is put into a clean 1000 ml beaker. The chemist
1842dissolves 276 grams of thorium nitrate into this water. In another clean
1843beaker, he dissolves 106 grams of anhydrous sodium carbonate into 400 ml of
1844distilled water. (He uses A.R. grade chemicals.)
1845    
1846    Slowly, and with constant stirring, the sodium carbonate solution is 
1847added to the thorium nitrate solution. Using a mechanical stirrer to stir
1848the thorium nitrate solution is best, but a glass rod also works.
1849    
1850    Thorium nitrate reacts with sodium carbonate to make thorium carbonate
1851and sodium nitrate. Thorium carbonate does not dissolve in water, so it
1852forms a white precipitate. Sodium nitrate stays dissolved in water. The
1853stirring is continued for a couple of minutes after all the sodium
1854carbonate has been added, then it is allowed to settle. The thorium
1855carbonate settles into a gooey gunk at the bottom of the beaker. As much of
1856the water as possible is poured off. Then 600 ml of distilled water is
1857added to the thorium carbonate and stirred around with a clean glass rod.
1858The chemist makes sure that all the thorium carbonate gets into contact
1859with the clean water, and that any lumps are broken up. This dissolves any
1860remaining sodium nitrate.
1861    
1862    The thorium carbonate is allowed to settle again, then as much of the
1863water as possible is poured off. Small amounts of distilled water are added
1864and stirred in until a fairly thick paste is formed. Now the purified
1865pumice pebbles are added and stirred around until they are all evenly
1866coated with thorium carbonate.
1867    
1868    A Pyrex glass cake pan is placed on the electric hot plate. The heat is
1869turned on to 1/4 maximum and about 1/8 of the coated pumice pebbles are
1870added to the glass pan. They are heated there with constant stirring with a
1871thick glass rod, so that the pieces dry out evenly. When the coated pumice
1872pebbles no longer stick together, they are dry enough. They are transferred
1873to a clean sheet and an equal amount of wet pumice pebbles are put in the
1874cake pan. They are dried out like the first group of pebbles. This process
1875is repeated until all the coated pumice pebbles are dry. Any white powder
1876that failed to stick to the pumice is collected and saved in a glass jar.
1877If it is later necessary to change the catalyst bed, this material is
1878wetted and used to coat new pumice pebbles.
1879    
1880    A plug of the purified glass wool about 3 cm long is put into the 
1881combustion tube about 15 cm from the male end. This will hold the catalyst
1882bed in place. The tube is filled up with the coated pumice pebbles for a
1883length of 70 cm or so. A small plug of purified glass wool about 1 cm in
1884length is put every 15 cm. This reduces the danger that tar building up on
1885the pumice pebbles will block the tube.
1886    
1887    The tube is put inside the furnace. If two Hoskins tube furnaces are
1888used end-to-end, the tube is insulated in the space between the two
1889furnaces with several layers of asbestos paper or cloth. In this space, the
1890tube is filled with loose glass wool. This space is not counted as part of
1891the necessary 70 cm of catalyst bed.
1892    
1893    The apparatus is set up as shown in Figure 13. It is tilted at an angle
1894of about 20 degrees, the end with the sep funnel being higher than the end
1895with the collecting flask. The sep funnel has a one-hole stopper with a
1896piece of glass tubing running through it almost all the way to the valve of
1897the sep funnel. This is a constant pressure device that causes the contents
1898of the sep funnel to drip into the tube at a constant rate, no matter what
1899the level of the acids in the sep funnel at a particular instant.
1900    
1901    The sep funnel is connected to the female end of the vacuum adapter.
1902The male end of the vacuum adapter is inserted into the female end of the
1903combustion tube. The male end of the combustion tube is connected to a
1904condenser. The condenser is connected to a vacuum adapter, and the vacuum
1905adapter leads to a 500 ml round bottom flask. The glass joints are lightly
1906greased and wired together where possible. The furnace must be supported to
1907prevent its weight from bending the soon-to-become-soft hot glass tube.
1908Clamps connected to ringstands are used to hold the other pieces in place.
1909    
1910    The vacuum adapter connected to the sep funnel is the nitrogen gas
1911inlet. The underground chemist gets a tank of nitrogen at a welding supply
1912shop. He has to make sure that he knows how to use the regulators. He runs
1913a line of tubing from the tank to the "bubbler." The bubbler is shown in
1914Figure 14. It is a bottle with a 2-hole stopper in the top. One hole has a
1915section of glass tubing reaching nearly to the bottom of the bottle. The
1916bottle has about an inch and a half of concentrated sulfuric acid in it.
1917The purpose of the sulfuric acid is to dry the nitrogen gas and to show how
1918fast it is bubbling into the apparatus. The other hole has a short section
1919of glass tubing. Plastic tubing is attached to this tubing and leads to the
1920vacuum nipple of the vacuum adapter.
1921    
1922    And now the time has come for the underground chemist to fire up the
1923furnace. He places a thermometer capable of reading up to 450øC, or, better
1924yet, a thermocouple, in the furnace against the outside of the glass
1925tubing. (If his thermocouple did not come with wiring instructions, he can
1926find the wiring diagram in the Encyclopedia Britannica and in many
1927college-level physics textbooks.) The thermometer or thermocouple extends
1928into the central regions of the furnace. The space at the end of the
1929furnace between the outside of the glass tubing and the inside of the
1930furnace's iron tubing is plugged up with pieces of asbestos paper or cloth
1931to hold in the heat.
1932    
1933    He turns on the electricity to the furnace, and begins a slow stream of
1934nitrogen (about one bubble per second) through the tube. He keeps a sheet
1935listing the temperatures his furnace gets at various voltage settings on
1936the transformer. Of course, it takes a while for the furnace to heat up to
1937its true temperature at a given setting.
1938    
1939    Now the tube furnace is heated to 425-450øC, while the slow stream of
1940nitrogen continues through the tube. The heat turns the thorium carbonate
1941into thorium oxide. The heating continues for 12 hours, after which the
1942catalyst is ready to produce phenylacetone. 
1943
1944    The chemist mixes 200 grams of phenylacetic acid with 250 ml of glacial
1945acetic acid. He mixes them thoroughly, the phenylacetic acid dissolving
1946easily in the glacial acetic acid. (Glacial acetic acid is the name for
1947pure acetic acid; it is so called because it freezes at a little below room
1948temperature.)
1949    
1950    This acid mixture is poured into the sep funnel and the funnel is 
1951stoppered with the one-hole stopper with the glass tubing constant pressure
1952device. The temperature of the furnace is 425- 450ø C, and a 
1953one-bubble-per-second stream of nitrogen has been flowing through the tube
1954for at least 2 hours. The valve on the sep funnel is opened so that about
195520 drops of the acid mixture drip into the tube from the sep funnel every
195630 seconds.
1957    
1958    A slow flow of water is put through the condenser to condense the
1959ketones as they leave the furnace. The product collects in the 500 ml flask
1960and the nitrogen gas exits through the vacuum nipple of the vacuum adapter
1961connected to the condenser. If there is trouble condensing all the acetone,
1962the 500 ml flask is packed in ice.
1963    
1964    It takes about 5 hours for all the acid to drip into the tube. When all
1965the acid mixture has dripped in, 25 ml of acetic acid is added to the sep
1966funnel and dripped in. This flushes the last of the product out of the
1967catalyst bed.
1968    
1969    The product in the 500 ml flask consists of a lower water layer and a
1970brown-colored organic layer on top. It is poured into a 1000 ml sep funnel;
1971the water layer is then drained off into a clean beaker, and the organic
1972layer is poured into another beaker. The water layer is put back into the
1973sep funnel along with 50 ml of benzene, and the funnel is shaken. It is
1974allowed to sit for a few minutes, then the lower water layer is drained off
1975and thrown away. The benzene layer is poured in with the organic layer in
1976the other beaker.
1977    
1978    The chemist is now ready to clean up the phenylacetone so that it can
1979be distilled. He mixes up a supply of 10% sodium hydroxide solution by
1980adding 10 ounces of lye to 3/4 gallon of water in a glass jug. He pours the
1981organic layer into the sep funnel, adds 400 ml of the sodium hydroxide
1982solution and shakes. The water layer is drained off into a clean beaker and
1983the organic layer is poured into another beaker. The water layer is
1984returned to the sep funnel and 75 ml of benzene added. The funnel is
1985shaken, then the water layer is drained off and thrown away. The benzene
1986layer is poured in with the organic layer. This is repeated three more
1987times, then the phenylacetone is distilled as described in Chapter 3. The
1988yield of phenylacetone is about 100 ml.
1989    
1990    The temperature of the furnace is raised to about 525øC, and a slow
1991stream of air is drawn through the tube for two hours. The air is drawn
1992through by turning off the nitrogen flow, opening up the valve of the sep
1993funnel and attaching a vacuum hose to the vacuum nipple of the vacuum
1994adapter on the 500 ml flask side of the apparatus. This air flow burns off
1995built up crud on the catalyst and charges it up for another run. It is done
1996after the first run, and then after every few batches.
1997    
1998    The furnace temperature is set at 425-450-ø C again and the flow of
1999nitrogen through the tube is resumed. It is flushed out for a couple of
2000hours, then the sep funnel is filled with acid mix for another run. It is
2001dripped in as before to get another batch of phenylacetone. In this way,
2002phenylacetone can be produced on a continuous basis.
2003    
2004    If the homemade furnace has trouble reaching the necessary temperature,
2005the chemist wraps it with more insulation. If that does not do enough, a
2006lower temperature process can be used by replacing the thorium-oxide-coated
2007pumice pebbles with manganous-oxidecoated pumice pebbles. The process goes
2008as follows:
2009    
2010    The pumice pebbles are made and purified with nitric acid as described
2011earlier. In a 1000 ml beaker, 70 grams of manganous chloride (MnCl2) is
2012dissolved in 300 ml of distilled water. In another beaker, 38 grams of
2013anhydrous sodium carbonate is dissolved in 500 rnl of distilled water. The
2014sodium carbonate solution is slowly added to the manganous chloride
2015solution with constant stirring. Manganous chloride reacts to form
2016manganous carbonate, which does not dissolve in water and precipitates out.
2017The manganous carbonate is filtered out in a Buchner funnel as described in
2018Chapter 5. The crystals are rinsed with distilled water.
2019    
2020    The manganous carbonate is returned to a clean beaker and enough
2021distilled water is added to make it into a fairly thick paste. If too much
2022water is added, it does not stick well to the pumice. The pumice pebbles
2023are stirred in until they are evenly coated. The beaker is heated on a hot
2024plate while the pumice stones are vigorously stirred. 
2025    
2026    Local overheating must be avoided or the catalyst will be ruined] When 
2027most of the water is evaporated, the catalyst is transferred to a Pyrex
2028cake pan and gently heated on a hot plate. The pumice chips are stirred
2029constantly to get even drying. When they no longer stick together, they are
2030transferred to a clean sheet of paper.
2031    
2032    The chemist fills the combustion tube with the catalyst as before and
2033sets up the apparatus. He heats the furnace to 360-400øC while passing a
2034stream of nitrogen through the tube. This converts the manganous carbonate
2035to manganous oxide (MnO). This heating is continued for 8 hours. Then the
2036heat is reduced to 350øC, while the stream of nitrogen is continued at a
2037rate of one bubble per second. When 350øC is reached, he drips in the same
2038phenylacetic acid-acetic acid mixture used earlier in this chapter. The
2039correct rate is 20 drops every 30 seconds. When it has all dripped in, he
2040adds 25 ml of acetic acid to the sep funnel and drips it in. He then either
2041adds more acid mix to the sep funnel for another run, or shuts down the
2042furnace. If he shuts down the furnace, he must continue the flow of
2043nitrogen through the tube until it has cooled off. This prevents the MnO
2044catalyst from being oxidized to MnO2, etc. When he turns it back on, he
2045must immediately start the nitrogen flow for the same reason. The product
2046is purified in the same way as described earlier in this chapter.
2047    
2048    Since no air is sucked through the tube at high temperature, gunk 
2049builds up on the catalyst and eventually puts it out of commission. When
2050this happens, the catalyst bed is changed. The yield using the manganous
2051oxide catalyst bed is not as good as that using the thorium oxide catalyst
2052bed. Thorium oxide is used, unless the chemist has no choice.
2053    
2054    A somewhat more complicated way to do this reaction is to use what is
2055called a thorium oxide "aerogel" catalyst. A lower temperature and a higher
2056rate of production are possible. For more information about it, see
2057Industrial and Engineering Chemistry, published in 1934, Volume 20, pages
2058388 and 1014.
2059    
2060                                 References
2061
2062    Journal of the Chemistry Society, page 612 (1948); page 171 (1940).
2063                           
2064--------------------------------------------------------------------------
2065                            MAKING PHENYLACETONE
2066--------------------------------------------------------------------------
2067    
2068    There are many other methods of making phenylacetone described in the
2069scientific literature. Most of them are dogs, not worth the time and
2070effort. But there are some good methods of making phenylacetone that I have
2071not yet described.
2072    
2073    An acceptable method is to oxidize methyl benzyl carbinol  
2074(1-phenyl-2-propanol) to phenylacetone (methyl benzyl ketone) with chrome
2075oxide (CrO3) in pyridine solvent. The problem with this is that methyl
2076benzyl carbinol is not commercially available, and so must be made from
2077benzyl chloride grignard reagent and acetaldehyde. This grignard works
2078well, although there can be a problem getting unreacted benzyl chloride out
2079of the product. Their boiling points are very close, so distillation does
2080not separate them completely. But the real question is: Why make the
2081synthesis of phenylacetone a two-step process when it can be done with one
2082reaction?
2083    
2084    Another two-step method of making phenylacetone is to make benzyl
2085cyanide from benzyl chloride and sodium cyanide, and then make the benzyl
2086cyanide into phenylacetone by the method described in Chapter 7. The way to
2087make benzyl cyanide can be found in Organic Syntheses, Collection Volumes
2088I, II and III. Benzyl cyanide is listed in the table of contents.
2089
2090    A good way to make phenylacetone is to react methyl zinc reagent with
2091phenylacetyl chloride. Methyl zinc reagent is made by reacting methyl
2092iodide with zinc metal, or by adding zinc chloride to methyl grignard
2093reagent. It is not an especially difficult reaction to do, and the yields
2094are very good. The problem is that phenylacetyl chloride is expensive and
2095hard to find, although it can be made from phenylacetic acid and thionyl
2096chloride SOCl2.
2097
2098    In what is actually the best method of making phenylacetone, two  
2099molecules of methyllithium react with phenylacetic acid to produce
2100phenylacetone, or one molecule of methyllithium reacts with one molecule of
2101the lithium salt of phenylacetic acid to produce phenylacetone. This
2102reaction is done in anhydrous ethyl ether under an atmosphere of nitrogen.
2103However, organolithium reagents burst into flame upon contact with air.
2104Although methyllithium is not so bad in this respect as t-butyllithium,
2105organolithium reagents are dangerous to handle. But, apart from the element
2106of danger, this is the best way to make phenylacetone. The high cost of
2107lithium is offset by the high yields of product. This reaction comes in
2108especially handy in building up the substituted phenylacetones used to make
2109the psychedelic amphetamine derivatives, such as STP or
2110trimethoxyamphetamine (TMA).
2111    
2112    Another good way to make phenylacetone is to react phenylacetyl
2113chloride with the ethoxymagnesium derivative of dimethyl malonate.
2114Hydrolysis with acid then produces phenylacetone. This reaction is
2115described in the Journal of the American Chemical Society, Volume 70, page
21164214, (1948). This can be found in any good college library.
2117    
2118    Another good method of making phenylacetone is to use a method called
2119the Knoevenagel reaction. In this method, the starting material is
2120benzaldehyde. The advantages to being able to use a wide variety of
2121starting materials to produce phenylacetone are obvious. A temporary
2122shortage of one chemical is not sufficient to cripple an underground
2123chemist's operation. He can also vary his chemical purchases so that there
2124is not a big run on one particular set of ingredients, which could lead to
2125suspiciousness and snooping.
2126    
2127    This reaction is fairly easy to do, and is pretty hard to mess up, so  
2128long as some basic precautions are taken. The underground chemist does his
2129best to make sure that his glassware is dry, and the alcohol used is
2130absolute (100% with no water). He must also do the processing of this
2131material quickly, because the nitroalkene which is formed in the first
2132phase of this reaction will not keep. The reaction goes like this:
2133    
2134    Benzaldehyde reacts with nitroethane in an alcohol solution with  
2135n-butylamine catalyst to produce a crystalline substance called a
2136nitroalkene. This nitroalkene can then be reduced by means of iron and HCl
2137to produce phenylacetone. The reduction is similar to the use of activated
2138aluminum in the reaction to produce methamphetamine without the bomb, in
2139that the metal, in this case iron, dissolves and produces hydrogen which
2140reduces the nitroalkene. It is not as complicated as it sounds, and is
2141pretty easy to do. The nitroalkene is first reduced to phenylacetone oxime,
2142which is then hydrolyzed to phenylacetone.
2143    
2144    You may wonder, looking at the structure of the nitroalkene molecule,
2145if it is not possible to reduce it directly to the prototype amphetamine,
2146benzedrine. The answer is yes. In fact, one method of making the
2147psychedelic amphetamines such as MDA is to get the properly substituted
2148benzaldehyde (in the case of MDA the proper benzaldehyde is called
2149piperonal) and reduce it using a hydrogenation bomb and Raney nickel, or by
2150use of lithium aluminum hydride. Another good method for reducing the
2151nitroalkene directly to amphetamine is to use zinc amalgam and hydrochloric
2152acid in alcohol solvent. A still better method for direct reduction of the
2153nitroalkene to amphetamine is to use palladium black on charcoal in the
2154champagne bottle hydrogenation bomb seen in Figure 17 in Chapter 11.
2155Directions for making palladium black on charcoal are found in the Meth
2156from Ephedrine chapter. A few grams of catalyst per hundred grams of
2157nitroalkene works nicely. Reaction conditions are room temp at a hydrogen
2158pressure of 30 pounds. Hydrogenation is complete in 5 to 10 hours, and the
2159solvent is 190 proof vodka. Best results are obtained if the nitroalkene is
2160purified by recrystallizing the crude product from alcohol prior to
2161reduction.
2162    
2163    This reaction is done as follows: Into a clean, dry 3000 ml round  
2164bottom flask is placed 400 ml of absolute alcohol, 20 ml of nbutylamine,
2165428 grams of benzaldehyde, and 300 grams of nitroethene. The underground
2166chemist sets up the glassware for refluxing as shown in Figure 2b in
2167Chapter 3. He includes the drying tube with Drierite as shown in Figure 2a.
2168He swirls around the flask to mix the contents, then sets the flask on a
2169hot plate and begins heating it. The water flowing through the condenser
2170should be fairly cool, to be sure of condensing the alcohol vapors. A good,
2171gentle rate of boiling is what he aims for. He continues the boiling for 8
2172hours. The solution will turn yellow.
2173    
2174    He makes sure that his chemicals, especially the nitroethane, are of a
2175good grade. Nitroethane is widely used in the paint and varnish industry as
2176a solvent for cellulose acetate lacquers, vinyl resins, nitrocellulose,
2177waxes and dyes. If he has the industrial grade, he first distills it before
2178use. Benzaldehyde smells like bitter oil of almonds and should be clear.
2179Benzaldehyde is used in flavorings and perfumes.
2180    
2181    When the 8 hours of boiling is done, he turns off the heat and lets the
2182flask cool down. Once crystals begin to appear, he takes off the condenser
2183and begins stirring the solution with a glass rod. He continues the
2184stirring, and transfers the flask to a sink of cool water to help speed the
2185cooling. He continues the stirring until the mass of crystals becomes too
2186thick to stir, or the flask is cooled off. The idea of the stirring is to
2187prevent the batch from setting into one solid mass of crystals. The
2188crystals should be yellow in color.
2189    
2190    He now proceeds to purify this 1-phenyl-2-nitropropene. The simplest
2191way to do this is to add ethyl ether to the crystals until a slurry is
2192formed (about 500 ml) and then break up any lumps of crystals with a glass
2193rod. He then filters the slurry through a large coffee filter and squeezes
2194the mass to force out as much of the ether as possible. Along with the
2195ether, he will be removing most of the unreacted benzaldehyde and
2196nitroethene. The crystals will still be yellow, but they will no longer be
2197sticky and gooey. If he still smells n-butyl amine on them, he may rinse
2198them with ether again.
2199    
2200    A better way to clean up these crystals is to recrystallize them. In  
2201large batches like this one, it is a lot of work and he must make
2202provisions for exhausting the fumes to the outside to prevent the danger of
2203explosion, but he will get a cleaner product.
2204
2205    It is done as follows: To the crystals which have been rinsed off with
2206ether and returned to a cleaned, dry 2000 ml round bottom flask, he adds
2207just enough hot petroleum ether to dissolve the crystals. This takes in the
2208neighborhood of 700 ml of petroleum ether. Any type of petroleum ether will
2209do. If he has access to hexane from some industrial source, that will do
2210fine. Petroleum ether is flammable, so the way he makes the ether hot is to
2211place the flask with the crystals into a pan of hot water, and to begin
2212adding the petroleum ether to it. He swirls it around while adding the
2213petroleum ether and keeps adding ether until the crystals are dissolved.
2214The result will be a clear yellow solution. Now he records how much
2215petroleum ether he added and places the flask on the hot plate and sets up
2216the glassware for simple distillation as shown in Figure 3 in Chapter 3. A
2217500 ml flask is fine for the receiving flask. He turns on the heat to the
2218solution, begins water flow through the condenser and distills off about
22191/3 of the ether he added to the crystals to dissolve them. When 1/3 of the
2220ether is distilled off, he removes the flask from the heat, and cools it
2221off in cool water, followed by ice water. He doesn't want to place the
2222flask immediately into ice water, because it might crack.
2223    
2224    Now, as the petroleum ether cools off, it will no longer be able to  
2225dissolve the crystals, and they will re-form in much cleaner shape because
2226the garbage which is polluting them will stay dissolved in the petroleum
2227ether. Once the petroleum ether is cold, he filters the crystals through a
2228filtering funnel the same way it was described in Chapter 5. He places the
2229crystals out to dry on a glass or china plate, and returns the yellow
2230petroleum ether solution which filtered through to the distilling flask.
2231This solution still contains a good deal of crystals dissolved in it.
2232    
2233    He sets up the glassware as before and distills off another i/3 of the  
2234petroleum ether, then cools off the flask as before. Once again, crystals
2235will form, although they will not be of as high quality as the first crop.
2236He filters them as before, and returns the ether to the distilling flask.
2237Now he distills off about % as much petroleum ether as before, then cools
2238off the flask and waits for the crystals to form. This will be his last
2239crop of crystals. He filters them and sets them out to dry. The total
2240amount of crystals he will get will be about 420 grams.
2241    
2242    The underground chemist must now proceed to reduce these crystals of
22431-phenyl-2-nitropropene to phenylacetone. If he lets them sit around, they
2244will begin to poIymerize into a black, gooey mess (though he can delay them
2245going bad by putting them in the freezer).
2246    
2247    Into a clean 3000 ml flask, he places 164 grams of the nitroalkene  
2248crystals he just made. To that he adds 750 ml of distilled water, 400 grams
2249of cast iron turnings about '/40 inch in size, and four grams of iron
2250chloride (FeCl3). The flask is placed in a glass dish large enough to hold
2251it, and cooking oil is added to the dish so that it reaches about half way
2252up the sides of the flask. He places the flask with the dish of oil onto a
2253hot plate, and heats the oil to about 105ø C. He puts a mechanical stirrer
2254into the flask with a glass rod and Teflon stirring paddle, and begins
2255stirring the mixture in the flask. Once the temperature of the contents of
2256the flask nears 80ø C, he measures out 750 ml concentrated hydrochloric
2257acid. He adds it slowly to the flask over a period of 5 hours. The iron
2258will slowly react with the acid and dissolve, producing hydrogen which will
2259reduce the nitroalkene to phenylacetone oxime. The oxime then reacts with
2260more water and HCl to give phenylacetone.
2261    
2262    When the acid has all been added, he removes the flask from the heat
2263and lets it cool down. Then he mixes up 350 grams of sodium hydroxide or I
2264ye in 1000 ml of water. Once they have both cooled down, he adds the sodium
2265hydroxide solution to the 3000 ml flask and swirls it around.
2266    
2267    He will now distill out the phenylacetone with steam. He adds a few
2268pumice boiling chips to the 3000 ml flask, and places it on the hot plate.
2269He sets up the glassware for simple distillation (not fractional  
2270distillation) as shown in Chapter 3. A 1000 ml flask will do fine for the
2271receiving flask. He heats the 3000 ml flask until it boils. The steam from
2272the water in the flask will carry the phenylacetone along with it and
2273deposit them both in the 1000 ml flask. A reasonable flow of about 1 gallon
2274per minute is enough water flowing through the condenser.
2275    
2276    The liquid collecting in the receiving flask has 2 layers, a lower  
2277layer of water, and floating on top of that a yellowish layer of
2278phenylacetone. He continues boiling the 3000 ml flask until no more
2279phenylacetone is coming over with the steam. The 1000 ml flask will be
2280nearly full of water and phenylacetone when the process is finished. Now he
2281pours both layers into a 1000 ml sep funnel. He drains off the lower layer
2282of water into a beaker. He pours the top layer of phenylacetone into a 500
2283ml flask. Now he takes the water layer and returns it to the sep funnel. He
2284adds 200 ml of benzene and shakes it up. He lets it sit for a while, then
2285drains off the lower layer of water and throws it out. He pours the benzene
2286layer into the 500 ml flask along with the phenylacetone.
2287    
2288    He can now either distill the phenylacetone as described in Chapter 3,
2289or reduce more of the nitroalkene. If he chooses to distill each run
2290separately, he will get about 130 ml of phenylacetone from each run.
2291    
2292    The steam distillation can be omitted if a lower grade of phenylacetone
2293is acceptable. To do this, the chemist simply filters the reaction mixture,
2294after it has been treated with sodium hydroxide, through a one inch thick
2295plug of angel's hair. Then he extracts out the phenylacetone by adding a
2296couple hundred mls of toluene (available at the hardware store in the paint
2297section), and separating off the phenylacetone-toluene layer floating on
2298top with a sep funnel. A more careful fractional distillation of the
2299resulting mixture gives phenylacetone that is almost as pure as with the
2300steam distillation.
2301    
2302    One of the best articles written on the Knoevenagel reaction in the
2303English language is in the Journal of Organic Chemistry, Volume 15, pages 8
2304to 14. Another reference is Organic Reactions, Volume 15.
2305    
2306                                  Method 2
2307    
2308    This variation of the Knoevenagel reaction will give somewhat higher
2309yields of product than the preceding method. The reason for the higher
2310yield is the use in this method of toluene as solvent, and the placement of
2311a Dean Stark trap above the flask to remove water from the mixture as it is
2312formed. Removal of water favors the formation of greater quantities of
2313nitroalkene.
2314    
2315    To do the reaction, a 1000 ml round bottom flask is filled, in this   
2316order, with 200 ml of toluene, 100 ml of benzaldehyde, 90 grams (86 ml) of
2317nitroethane, and 20 ml of butylamine. It is a good idea to swirl the flask
2318after adding each ingredient to prevent layers from forming. Next the flask
2319is placed on a one burner electric buffet range with infinite control, and
2320the glassware is set up as shown in Figure 15.
2321    
2322    The Dean Stark trap is attached to the flask, and a condenser is   
2323attached to the Dean Stark trap. Then the buffet range is turned on at a
2324heat setting high enough to produce a rapid boiling of the toluene, and
2325cold water is flowed through the condenser. As the reaction is progressing,
2326the vapors of toluene carry water along with them, and when they turn back
2327to liquids in the condenser, the water will settle in the trap portion of
2328the Dean Stark trap because water is heavier than toluene. You will also
2329note a milky appearance to the toluene due to suspended water in it. The
2330trap portion of the Dean Stark trap is graduated in milliliters. This
2331allows you to keep track of how much water has been collected. Half of the
2332water is collected in the first hour, and the full amount (18 ml) is
2333collected after five hours of boiling. When this is done, the heat is
2334removed, and the flask allowed to cool. This phase of the reaction has just
2335made the nitroalkene.
2336    
2337    One should wish to collect the nitroalkene for direct reduction to
2338amphetamine, one just needs to remove the Dean Stark trap, rig the flask
2339for simple distillation as shown in Figure 3, and remove the toluene under
2340a vacuum from an aspirator, using gentle heating from a hot water bath. It
2341should be noted that the nitroalkene has a slight tear gassing effect upon
2342the eyes, and also irritates the skin. Do not use the stuff as a body balm.
2343    
2344    If phenylacetone is desired from the nitroalkene, the toluene solution
2345produced in the reaction is used directly in the next step. Once it has
2346cooled down, it is poured into a 2000 ml 3 necked flask. Then into the 3
2347necked flask is added 500 ml of water, 200 grams of iron powder (40 to 100
2348meth), and 4 grams of ferric chloride (FeCl3). Then into the center neck of
2349the flask is put a mechanical stirrer reaching almost to the bottom of the
2350flask. There should be a tight seal so that the ensuing vapors of toluene
2351when the flask is heated do not escape by this route. A good condenser is
2352attached to one of the other necks, and a sep funnel, or dropping funnel
2353with matching ground glass joint is put into the remaining neck. With
2354vigorous stirring, the contents of the flask are heated to about 75øC, and
2355360ml of concentrated hydrochloric acid is added to the flask by means of
2356dripping it into the mix through the sep funnel over a 2 hour period. The
2357reaction mixture will boil vigorously. The heating and stirring are
2358continued for an additional half hour after the last of the hydrochloric
2359acid has been added.
2360    
2361    Next it is time to get the phenylacetone out of the reaction mixture.
2362Once the flask has cooled down, the iron is filtered out by pouring it
2363through the plug of angel hair described earlier in this chapter. It is a
2364good idea to rinse down the trapped iron powder with a dash of toluene to
2365get any clinging phenylacetone off of it. Then the toluene layer is
2366separated using a sep funnel. It is poured into a round bottom flask. The
2367water layer has about 100 ml of toluene added to it, and this is shaken to
2368draw suspended phenylacetone into the toluene. The toluene layer is then
2369separated and added to the aforementioned round bottom flask. It is then
2370rigged for fractional distillation as shown in Figure 5. The toluene
2371distills off first as the toluene-water azeotrope at 85øC, and then as pure
2372toluene at 110øC. Once the toluene is mostly gone, vacuum is applied, and
2373phenylacetone is collected at the usual temperature range. The yield is
2374about 120 ml of phenylacetone.  
2375    
2376    
2377--------------------------------------------------------------------------
2378            A New Breakthrough: Phenylacetone From Allylbenzene
2379--------------------------------------------------------------------------
2380
2381    In 1987, an exciting breakthrough in the field of methamphetamine 
2382manufacture occurred. This new development was so important because it
2383promised to completely turn the tables on the DEA-led chemical blockaders
2384and controllers. The new discovery was a patent issued in that year
2385covering a simple and quick method for converting allylbenzene into
2386phenylacetone. This method is exquisitely suited for clandestine
2387operations, and is easily scaled up to industrial proportions.
2388    
2389    The extreme importance of this discovery can be appreciated by a quick
2390review of the chemical supply situation. Phenylacetic acid is now next to
2391impossible to obtain, with the exception of purchasing it from narco swine
2392front operations. It is reliably made fiom benzyl chloride by the
2393directions given in Organic Syntheses, but this is a hasslesome and very
2394stinky operation. A large scale phenylacetic acid production operation will
2395not go unnoticed by meddlesome neighbors. Furthermore, the cooks will carry
2396the evidence on their bodies and clothing for weeks after they have done
2397their dirty deeds. Turned up noses will follow them wherever they go!
2398    
2399    An alternative and very popular route to methamphetamine featuring the
2400conversion of ephedrine into methamphetamine via chlorephedrine has been
2401similarly, but less successfully, crimped upon. Here the chemical pinch
2402points have been phosphorus and palladium black on charcoal. This method of
2403making methamphetamine was left out of the original edition because of the
2404noxious nature of the impurities caused by this reaction. They can be
2405easily carried into the final product if proper care is not taken in
2406purification. Much of the garbage crank now seen on the streets is made by
2407this method and contains unreacted chlorephedrine along with related filth.
2408    
2409    This chlorinated filth causes a vague "poisoned" feeling as a result of
2410taking it. Dull aches in the liver and kidney areas can be felt. This slop
2411also ruins the more subtle and finer qualities of methamphetamine. This
2412edition will describe how ephedrine is converted into methamphetamine, with
2413special emphasis given to the key steps in removing the noxious byproducts
2414from the final product.
2415    
2416    The new method of producing phenylacetone from allylbenzene completely
2417bypasses the roadblock put up by the narco swine. Allylbenzene is in itself
2418rather overpriced and possibly the subject of central scrutinizer
2419suspicion. However, for the resourceful manufacturer it is easily made
2420either in quantitative (100%) yields and pristine purity by the reaction of
2421arylcopper and allyl bromide, or at bargain basement prices in carload
2422amounts by the direct Freidel-Crafts reaction between benzene and allyl
2423bromide. Add to this the possibility of producing amphetamine directly from
2424allylbenzene by the Ritter reaction, and the position of the chemical
2425controllers becomes hopelessly complicated. The sure result is the prospect
2426of floodgates opened wide to massive amphetamine production.
2427    
2428    This new reaction can be done in any one of several closely related
2429ways, each with excellent results. In each of its variations, the overall
2430path of the reaction is to turn allylbenzene into phenylacetone:
2431    
2432    The reaction appears to work in the following manner: Allylbenzene
2433reacts with two molecules of methyl or ethyl nitrite in alcohol solvent to
2434produce an intermediate product:
2435    
2436    This intermediate product then reacts with water to give phenylacetone.
2437    
2438    A key feature of this reaction is its use of palladium chloride as a 
2439catalyst. Because of the high cost of palladium salts, the inventors of the
2440patent went to great lengths to find ways to make less of it go further.
2441They discovered that by adding some copper chloride or trimethylamine into
2442the reaction mixture, the amount of palladium used could be greatly cut.
2443The drawback to this is that the yield of phenylacetone goes down a little
2444bit. Both variations will be described here.
2445    
2446    A potentially serious problem looms in the path of those who would like
2447to give this reaction a try. The problem is that alkyl nitrites such as
2448methyl or ethyl nitrite are not easily purchased. The reason for this is
2449their use in products which were formerly on sale under such names as
2450"Rush," "Locker Room," or "Jock Aroma." Inhaling this class of substances
2451produces an intense head rush, and disorientation. In many states, these
2452substances are now classified as controlled substances. In all cases, this
2453properly necessitates great care on the part of the chemist in handling
2454this material, lest he be overcome. These nitrites are easily made in large
2455amounts, however, so any serious manufacture operation can quickly
2456stockpile enough in the freezer to supply a massive output. Later in the
2457chapter, I will describe how nitrites are made.
2458    
2459    The alcohols which are best used in this reaction are either methyl
2460alcohol or ethyl alcohol. Methyl alcohol, also known as wood alcohol or
2461methanol, is easily and cheaply purchased in the paint section of the 
2462hardware store. Ethyl alcohol, or ethanol, is best purchased as 190 proof
2463vodka. As such it contains 5% water, but since water is needed for the
2464hydrolysis stage of the reaction, this presents no problem. In all cases,
2465it is best to use the alcohol which has the same number of carbon atoms in
2466it as the nitrite uses. For example, methyl alcohol is used with methyl
2467nitrite, and ethyl alcohol with ethyl nitrite.
2468    
2469    If the number of carbons match between the nitrite and the alcohol,
2470this makes recycling the alcohol and unreacted nitrite at the end of the
2471reaction a much simpler matter. The patent does not specify why this is the
2472case, but I am led to suspect that the possibility of exchange between the
2473alcohol and the nitrite exists. For example, if butyl nitrite is used with
2474ethyl alcohol, one could end up with a mixture containing some butyl
2475alcohol and ethyl nitrite.
2476    
2477    The reason for the use of methyl or ethyl nitrite in this reaction is 
2478two-fold. First of all, the matching alcohols are very easily picked up at
2479the hardware or liquor stores. The second reason is that the methyl and
2480ethyl nitrites give a little higher yields at lower temperatures. For 
2481example, methyl nitrite gives 90% yield of phenylacetone at a reaction
2482temperature of room temperature. Butyl nitrite, on the other hand, gives a
248387% yield at a temperature of 55øC. The possibility of running a batch at
2484room temperature makes bathtub size production easy to envision.
2485    
2486    The drawback to use of methyl or ethyl nitrites comes from their low
2487boiling points. Methyl nitrite is a gas with a boiling point of -12øC. 
2488Ethyl nitrite boils at 16.5øC, which is below usual room temperature. Even
2489cooled well below that point, one could count on it giving off a powerful
2490aroma. The solution to this problem is to dissolve the nitrite into several
2491volumes of its corresponding anhydrous alcohol, and then store the solution
2492in a tightly stoppered bottle in a freezer. This stock alcohol solution is
2493then added to the reaction mixture when its time comes. This still leaves
2494the difficult problem of "catching" these nitrites with a condenser when
2495one makes them in the first place. For these reasons, the most practical
2496nitrite to use in this reaction may well be butyl nitrite. Its boiling
2497point of 78øC makes handling it an easy matter. The lucky experimenter may
2498also be able to purchase it directly off the shelf in the form of "Rush"
2499type inhalers. If the underground chemists forego a simple recycling
2500procedure at the end of the rreaction, then the butyl nitrite can be used
2501with the easily available methyl or ethyl alcohols. All things considered,
2502this may be the best choice for the clandestine operation. Besides, butyl
2503alcohol smells awful, and is expensive.
2504    
2505    The setup needed to run this reaction is simplicity itself. The primary
2506requirement is a glass container to hold the reactants. For the size of
2507batch we will be discussing, a 5000 ml round bottom flask or a one gallon
2508wine jug perform admirably. For scaled up production, a 5 gallon office
2509water cooler carboy fits the bill nicely.
2510    
2511    The second requirement is a stirring device. For the size of batch 
2512discussed here, a magnetic stirrer is perfect. For the larger production
2513levels, at mechanical stirring rig is advisable. The need for good stirring
2514is brought about by the fact that the palladium catalysts are not readily
2515soluble in alcohol. They do dissolve well in water, but since water is a
2516small fraction of the total solution, the underground chemist can't count
2517on it all dissolving as the reaction is run. Good agitation brings any
2518undissolved palladium up into contact with the solution. It does little
2519good sitting on the bottom of the flask.
2520    
2521    To turn out a two mole batch (i.e., a little over 200 ml of 
2522phenylacetone product) by the first, palladium-wasteful method, the
2523following method is used:
2524    
2525    Into the glass reaction vessel is placed three liters of either methyl
2526or ethyl alcohol. To this is added 236 grams (262 ml) of allylbenzene. If
2527methyl alcohol is used, 750 ml of water is then added. If 190 proof spirit
2528is used, then only 630 ml of water is added because it already contains 5%
2529water. Then 28 grams of palladium chloride is added. The adventuresome
2530experimenter may dissolve the palladium chloride into the water added to
2531the reaction instead of putting them in separately. This converts the PdCl2
2532into the hydrate, which is much more soluble in the water portion of the
2533solution.
2534    
2535    Next, the temperature of the mixture is brought up to the correct 
2536level. For butyl nitrite, the temperature of 55øC is reached by using hot
2537water, steam, or heating tape. If a wine jug is the reaction vessel, care
2538is used in rapid and uneven heating, as this could crack the glass. This is
2539the reason why chemical glassware is made of Pyrex. 
2540    
2541    When the correct temperature is reached, 5 moles of nitrite is added
2542with the stirring going full blast. For butyl nitrite, this amounts to 515
2543grams, or 570 ml.
2544    
2545    Almost immediately, the mixture begins bubbling. This buWling is NO gas
2546being given off as a byproduct of the reaction. It combines quickly with
2547air to form NO2, the reddish poisonous gas so familiar to those who have
2548botched batches of explosives. Tubing, or similar gas venting devices, are
2549attached to the flask to carry this gas outside, or down the drain with the
2550vacuum of an aspirator.
2551    
2552    After the bubbling subsides in a couple of hours, the reaction is
2553finished. Underground chemists now turn their efforts to getting the
2554palladium back for reuse, and isolating the phenylacetone product. The
2555first step in this phase is to filter the solution to get back the
2556undissolved palladium chloride for reuse in the next batches.
2557    
2558    The alcohol-water-nitrite components of the reaction mixture are then
2559distilled off under a vacuum. The best way to do this is with a 
2560fractionating set-up similar to the one shown in Figure 5 in Chapter 3.
2561With the large amount of solution to be processed, it is wise to use a 3000
2562or 2000 ml round bottom flask on the distilling side. When about half the
2563original load of mixture has been distilled off, the vacuum is 
2564disconnected, and the distilling flask refilled with more of the reaction
2565mixture. Then the vacuum is reapplied and the distillation continued. This
2566process is repeated until all the original reaction mixture fits into the
2567distilling flask. Distillation is continued until the volume of the 
2568solution is reduced to between 300 and 400 ml.
2569    
2570    Next the solution is filtered again to get the rest of the palladium 
2571chloride back. The palladium is rinsed with a little alcohol, and the
2572rinsing added to the rest of the filtered crude product. The crude product
2573is poured into a 500 ml round bottom flask, and distilled under vacuum as
2574described in Chapta 3. The yield is nearly 250 ml of phenylacetone.
2575    
2576    To use the palladium-conserving method of production, the method 
2577described above is used. The only difference is that the PdC12 is replaced
2578by a mixture of 1.8 grams of PdCl2, and 5 grams of CuCl. Yield in this case
2579is more like 80%, or a little over 200 ml of phenylacetone.
2580    
2581                          Preparation of Nitrites
2582
2583                               Butyl Nitrite
2584    
2585    Since butyl nitrite is the nitrous acid ester of n-butanol, it is not 
2586surprising that it is easily made by bringing nitrous acid into contact
2587with n-butanol in the presence of sulfuric acid catalyst. Nitrous acid is
2588not used directly because it is unstable. Instead it is generated in the
2589reaction flask by allowing excess sulfuric acid to react with sodium
2590nitrite in the mixture. The main precaution taken while running this
2591reaction is to ensure that the temperature of the mixture does not rise
2592above the prescribed limits.
2593    
2594    To make butyl nitrite, a 1000 ml 3 necked flask is equipped with a 
2595mechanical stirrer, a sep funnel with a stem that leads as close to the
2596danger zone caused by the whirling stirrer blades as possible, and a
2597thermometer. (See Figure 16.) The thermometer is also placed close to the
2598stirring blade danger zone so that it measures the temperature of the
2599solution in the critical initial mixing area. The stirring blades are made
2600of Teflon so that they can stand up to the sulfuric acid used here. The
2601metal rod to which it attaches is similarly coated with Teflon. An electric
2602drill rigged up above the flask is OK for spinning the stirring blades.
2603Magnetic stirring is not strong enough here because of the heavy
2604precipitate of sodium sulfate crystals which forms as the result of this
2605reaction.
2606    
2607    The thermometer is secured into place by boring a suitable sized hole
2608into a cork for the thermometer, and stuffing the cork into one of the
2609necks of the flask. This prevents the reactants from splashing out while
2610being stirred.
2611    
2612    To do the reaction, the chemist nestles the reaction flask into a 
2613mixture of ice and salt. About two parts ice to one part salt gives good
2614results. The ice is crushed so that the individual cubes are no larger than
2615a grape. The ice-salt mixture produces a cooling effect well below the 0ø C
2616usually obtained from ice. Then the chemist puts 95 grams of sodium nitrite
2617in the flask along with 375 ml of water. He stirs the mixture while
2618following the temperature on the thermometer. Meanwhile in another beaker,
2619he mixes up 25 ml of water, 34 ml of concentrated sulfuric acid, and 114 ml
2620of n-butanol (butan-1-ol). He puts this mixture into the freezer, and cools
2621it to 0øC. 
2622    
2623    When the temperature reading on the nitrite solution in the reaction
2624vessel falls to 0øC or a little lower, the butanol-sulfuric acid mixture is
2625introduced a little bit at a time through the sep funnel while the chemist
2626maintains good mixing. It is added slowly enough that the temperature
2627reading in the reaction vessel does not stray from the range of -1øC to
2628+1øC. The beaker is stored in the freezer in between fill-ups of the sep
2629funnel, so that this solution does not get warm. The entire addition takes
2630about 45 minutes.
2631    
2632    After the addition has finished, the chemist continues stirring for a 
2633few minutes, then lets the mixture stand for an hour and a half. Next, he
2634filters the solution using the Buchner funnel-vacuum flask set up shown in
2635Figure 11 in Chapter 5. This filters out the sodium sulfate crystals formed
2636in the reaction. He pours the filtrate into a 500 ml sep funnel, and waits
2637for the upper yellow layer of crude butyl nitrite to fully form. This takes
2638a few minutes.
2639    
2640    The lower acid water layer is then drained out of the sep funnel, 
2641leaving only the butyl nitrite layer in the funnel. The chemist mixes up a
2642solution of I gram Arm & Hammer bicarb, and 12.5 grams of table salt in 50
2643ml water. He pours this solution into the sep funnel, and swirls well to
2644get the two layers into contact. A fair amount of fizzing ensues as the
2645bicarb destroys excess acid in the crude product. Then he stoppers the sep
2646funnel with a cork, and shakes it vigorously.
2647    
2648    Periodically, he allows built up gas to escape. After shaking for a 
2649couple of minutes, he allows the sep funnel to sit. The layers form again.
2650He drains off the wata layer, and pours the nitrite into a 250 ml beaker.
2651He adds about 5 grams of anhydrous magnesium sulfate crystals to the beaker
2652and stirs. This soaks up whatever water is dissolved in the nitrite.
2653Anhydrous magnesium sulfate is made by baking epsom salts in a thin laya in
2654a glass baking pan in an electric oven at 4 W F for a couple hours before
2655use. It is used immediately, or allowed to cool down in a dessicator to
2656prevent it from soaking up water from the air.
2657    
2658    The crude butyl nitrite can be used immediately as is. If there is 
2659going to be a delay before usage, it is decanted off the magnesium sulfate
2660and distilled. Using a fractionating column, almost all of the product
2661distills at about 77øC. The yield is about 110 grams (85% yield) of butyl
2662nitrite. This product can be stored in a freeza for a couple of weeks
2663before it goes bad. The colder the temperature, the better. Decomposition
2664products include water, NO2, NO, butanol, and polymerization products of
2665butyl aldehyde. This cheap and easy process is readily scaled up to fit any
2666raw material demand the underground chemist may have.
2667    
2668    This substance is made in the same way as butyl nitrite, with a few
2669variations. The nitrite-water solution in the flask has 76 grams sodium
2670nitrite in 240 ml water. The alcohol-sulfuric acid solution is made by
2671diluting 60 ml of absolute alcohol (65 ml of 190 proof vodka) with an equal
2672volume of water. Then the chemist carefully adds 28 ml of concentrated
2673sulfuric acid to it. He swirls while adding. Then he dilutes this solution
2674to 240 ml total volume by adding water. He cools both solutions to about
267510øC, and adds the alcohol-acid solution to the nitrite solution slowly
2676with constant stirring over a period of about half an hour.
2677    
2678    He pours the reaction mixture into a chilled sep funnel, drains off the
2679lower water-acid layer, and then quickly adds an ice cold mixture of I gram
2680bicarb in 50 ml water to the nitrite layer. He quickly swirls and shakes,
2681and drains off the water layer before the fumes become too intense. He
2682dries the crude ethyl nitrite over about 5 grams of sodium sulfate, then
2683decants it into at least an equal volume of ethyl alcohol. The alcohol is
2684absolute alcohol, and deep freezing is required for storage. It is used as
2685soon as possible. Longer storage is possible if the crude material is
2686distilled (b.p. 17øC). The difficulties attendant to this operation make
2687this inadvisable for the underground lab, however.
2688    
2689    There is a way around the hasslesome purification procedure that will
2690allow the underground chemist to use the ethyl nitrite he has made quickly
2691and easily. The way to do this is to bubble the vapors of the ethyl nitrite
2692into the reaction mixture. This method avoids the unpleasant and possibly
2693dangerous procedure with the sep funnel and subsequent distillation. See
2694Figure 8 back in Chapter 4 on N-methyl formamide. If in that figure, the
2695methylamine containing flask instead contained the ethyl nitrite reaction
2696mixture, and the formic acid containing flask instead had the allylbenzene
2697and palladium chloride in alcohol needed for phenylacetone production, then
2698one could easily picture how to get the ethyl nitrite vapors to directly
2699bubble into the phenylacetone production mix without any need to manipulate
2700the nitrite directly.
2701    
2702    To use this variation, the ethyl nitrite is first prepared as described 
2703above. The cold temperature is important to get best yields of the nitrite.
2704Then the nitrite reaction mixture is poured into a suitable size round
2705bottom flask, the glassware is set up as shown in Figure 8, and heat is
2706applied to the nitrite mixture to bubble its vapors into the phenylacetone
2707production reaction flask. Cold water should not be run through the
2708condenser, as this may hold back the nitrite. Instead, the water should be
2709room temperature. The nitrite solution will have to be heated to almost
2710boiling to get the last of the nitrite to boil out of it. A yield of about
271160 grams of ethyl nitrite can be expected from the directions given above.
2712    
2713    One could also use methyl nitrite in this variation by substituting 
2714methyl alcohol for ethyl alcohol. This would have the advantage of being
2715easier to bubble out of the nitrite reaction mixture because the boiling
2716point of methyl nitrite is -12Q C. This advantage is outweighed by the
2717poisonous nature of methyl alcohol, and also by the difficulty one would
2718have trying to keep it in solution while it is being made. It would be hard
2719to estimate just how much of the methyl nitrite is actually getting into
2720and staying in the phenylacetone reaction mixture.
2721    
2722                                Allylbenzene
2723    
2724    Allylbenzene is best prepared by one of two routes. The method which
2725gives nearly quantitative (100%) yields uses phenyllithium. This expensive
2726and very reactive substance is made by reaction of bromobenzene with
2727lithium metal in ether solution in a manner similar to producing a Grignard
2728reagent. The underground chemist needs to be familiar with the use and
2729production of lithium reagents before attempting this method. The great
2730reactivity of lithium reagents presents many pitfalls.
2731    
2732    This method proceeds as follows: A suspension of 100 grams of cuprous
2733bromide (CuBr) in anhydrous ether is treated with 670 ml of 1 molar
2734phenyllithium. The CuBr becomes yellow and dissolves to give a brownish-red
2735solution which then turns green. Phenylcopper precipitates as a white
2736powder in 90% yield. The phenylcopper is then separated and reacted with a
2737molar equivalent of allylbromide to give allylbenzene in 99% yield after
2738water quenching and usual Grignard workup.
2739    
2740    A cheaper and more direct method uses bromobenzene Grignard reagent.
2741Some precautions are important here. Firstly, bromobenzene is about the
2742most difficult Grignard reagent to get started reacting. It is very
2743sensitive to the presence of traces of water. Great care is taken in drying
2744the glassware and the magnesium turnings. Nitrogen atmosphere is a must.
2745With these precautions, a beautiful red bromobenzene Grignard reagent is
2746prepared.
2747    
2748    Another important point is that bromobenzene finds use in making PCP.
2749For this reason, it is on the watched list. Good directions for making
2750bromobenzene are contained in Vogel 's Textbook of Practical Organic
2751Chemistry. This fine book is must reading for everyone interested in
2752underground chemistry.
2753    
2754    This bromobenzene Grignard reagent is then reacted with a solution of
2755allyl bromide to give 82% yield of allylbenzene after quenching and workup.
2756Complete details can be found in Helv. Chim. Acta, Vol. 17, page 352
2757(1934). The author is Hershberg. 
2758    
2759    
2760--------------------------------------------------------------------------
2761                            The Way Of The Bomb
2762--------------------------------------------------------------------------
2763    
2764                 "Blessed be the bomb... and all its work."
2765              ð the mutants of Beneath the Planet of the Apes
2766    
2767    When underground chemists move up to industrial-scale manufacture of
2768methamphetamine, it soon becomes obvious that the Leuckardt-Wallach
2769reaction is not suitable for making large amounts. There are two reasons
2770for this. N-methylformamide distills slowly, because of its high latent
2771heat of vaporization. This makes the pro auction of large amounts of
2772N-methylformamide a very time-consuming process. Secondly, the
2773Leuckardt-Wallach reaction can take up to 48 hours to complete.
2774    
2775    To increase production, a faster method of turning phenylacetone into
2776methamphetamine is necessary. Reacting phenylacetone with methylamine and
2777hydrogen in an apparatus called a "bomb" is such a method. A bomb is a
2778chemical pressure cooker where hydrogen gas is piped under pressure to
2779react with the phenylacetone and methylamine. It is caed a bomb because
2780sometimes reactions like this are done under thousands of pounds of
2781pressure, and occasionally the bomb will blow up. This reaction is done
2782under a pressure of only 3 atmospheres, 30 pounds per square inch greater
2783than normal air pressure. so there's no danger of the hydrogenation bomb
2784going off. 
2785
2786    This reaction is called reductive amination. It is not especially
2787difficult to do, but it is necessary to have the hardware in proper working
2788condition and to keep out materials that would poison the catalyst.
2789Reductive amination is a quick, very clean and high-yield process.
2790    
2791    Phenylacetone reacts with methylamine to produce a Schiff's base and a
2792molecule of water. This Schiff's base then reacts with hydrogen and Raney
2793nickel catalyst and gets reduced to methamphetamine. To encourage the
2794formation of this Schiff's base, the amount of water in the reaction
2795mixture is held to less than 10%; 5% is even better. If the underground
2796chemist is able to get methylamine gas in a cylinder, it is easy to control
2797the amount of water in the reaction mixture, but 40% methylamine in water
2798can be made to work with a little effort.
2799    
2800    Two main side reactions interfere with the production of  
2801methamphetamine in the hydrogenation bomb. They are both controlled by
2802properly adjusting the conditions inside the bomb. The first side reaction
2803is the reduction of the phenylacetone.
2804    
2805    The phenylacetone can react with hydrogen and Raney nickel instead of
2806with methylamine. This side reaction is held to a minimum by not letting
2807the hydrogen gas pressure get much above 30 psi. It is also controlled by
2808encouraging the phenylacetone to react with methylamine instead. This is
2809done by keeping the amount of water in the reaction mixture small, having
2810enough methylamine around for it to react with, and running the reaction at
2811the right temperature.
2812    
2813    The other side reaction that can be a problem is phenylacetone reacting
2814with methamphetamine to produce a tertiary amine.
2815    
2816    This reaction is held to a minimum by having enough methylamine in the
2817reaction mixture to tie up the phenylacetone, and by keeping the solution
2818fairly diluted, so that they are less likely to bump into one another.
2819    
2820    If the chemist uses ready-made Raney nickel, which is sold as a  
2821suspension in absolute alcohol, then, if any problems arise, he knows that
2822the catalyst is not at fault. But those who are old pros at this reaction
2823can save money by making their own Raney nickel catalyst.
2824    
2825    A special alloy of approximately equal parts of aluminum and nickel is
2826available for making Raney nickel catalyst. Here's how it's done. In a 2000
2827ml beaker, the chemist dissolves 190 grams of sodium hydroxide pellets in
2828750 ml distilled water. The solution is cooled down to 10ø C by packing the
2829beaker in ice. He adds 150 grams of the nickel aluminum alloy to the sodium
2830hydroxide solution. It is added slowly and with vigorous stirring. The
2831temperature of the solution must not get above 25øC. The sodium hydroxide
2832reacts with the aluminum in the alloy and dissolves it, producing aluminum
2833hydroxide and hydrogen gas. The nickel is left as tiny black crystals. The
2834hydrogen which bubbles out of the solution causes foaming, so the alloy is
2835added slowly enough that the foaming doesn't get out of control. If that
2836fails, 1 ml of n-octyl alcohol helps to break up the foam. It takes about 2
2837hours to add all the alloy to the sodium hydroxide. When all of the alloy
2838has been added, the stirring is stopped and the beaker is removed from the
2839ice bath. The bubbling of hydrogen gas from the solution continues as the
2840beaker warms up to room temperature. Hydrogen gas is not poisonous, but it
2841is very flammable. Smoking around it can cause an explosion.
2842
2843    When the bubbling of hydrogen from the solution slows down, the beaker
2844is set in a large pan of hot water. Then the water in the pan is slowly
2845heated to boiling. This will get the hydrogen bubbling again, so it is
2846heated on an electric heater in a well-ventilated area. This heating is
2847continued for 12 hours. Distilled water is added to the beaker to maintain
2848its original volume.
2849    
2850    After the 12 hours are up, the chemist removes the beaker from the
2851boiling water bath and stirs it up. Then he allows the black Raney nickel
2852catalyst to settle to the bottom of the beaker. He pours off as much of the
2853sodium hydroxide solution as possible. The nickel is transferred to a 1000
2854ml graduated cylinder with the help of a little distilled water. If the
2855nickel catalyst is allowed to dry out, it may burst into flames. It must be
2856kept covered with water. Again the chemist pours off as much of the water
2857as possible. Then he adds a solution of 25 grams of sodium hydroxide in 250
2858ml of distilled water to the nickel in the graduated cylinder. The cylinder
2859is stoppered with a cork or glass stopper (not rubber) and shaken for 15
2860seconds. Then it is allowed to settle again and as much of the sodium
2861hydroxide solution as possible is poured off.
2862    
2863    The catalyst is now ready to have the sodium hydroxide removed from it.
2864All traces must be removed, or it will not work. The chemist adds as much
2865distilled water to the cylinder as it will hold, then shakes it to get the
2866nickel in contact with the clean water. He lets it settle, then shakes it
2867again. When the nickel has settled, he pours off the water and replaces it
2868with fresh distilled water. This washing process is repeated 25 times. It
2869takes that much to remove all the sodium hydroxide from the catalyst.
2870    
2871    After the water has been poured off from the last rinse with distilled
2872water, 100 ml of rectified spirit (95% ethyl alcohol) is added to the
2873nickel and shaken. After the nickel has settled, the alcohol is poured off
2874and the washing is repeated two more times with absolute (100%) alcohol.
2875The result is 75 grams of Raney nickel in alcohol. It is transferred to a
2876bottle that it will completely fill up. If necessary, more alcohol (100%)
2877is added to fill up the bottle. Then the bottle is tightly stoppered. When
2878the chemist is ready to use it, he shakes it to suspend the nickel and
2879measures out the catalyst. One ml contains about .6 grams of Raney nickel
2880catalyst.
2881    
2882    It has been claimed that a more active catalyst can be made by adding
2883the sodium hydroxide solution to the nickel-aluminum alloy instead of vice
2884versa But when this is done, care must be taken that the foam doesn't get
2885out of control. Also, the alloy must be stirred into the solution so it can
2886react. Other than that, the catalyst is prepared in exactly the same way.
2887    
2888    There are several ways to do the reductive amination reaction. Each
2889will be described. By far the most convenient and most suited to the needs
2890of the clandestine chemist is a process using platinum black catalyst
2891instead of Raney nickel. Platinum has the advantages of working very well
2892at room temperatures and low pressures of hydrogen. It furthermore does not
2893have the ferromagnetic properties of Raney nickel. This means a magnetic
2894stirrer can be used to agitate the reaction mixture inside a suitable glass
2895container. Besides this, platinum gives nearly quantitative (100%) yields
2896of product using considerably less catalyst than with Raney nickel. Add to
2897this the fact the platinum catalyst is reusable many times over, and can be
2898easily obtained with no suspicion in the form of platinum coins and ingots.
2899All these considerations clearly point to the use of platinum as the method
2900of choice for the underground operation.
2901    
2902    Reductive alkylation with platinum is done in a very easily constructed
2903apparatus. The reaction vessel, or "bomb," is a champagne bottle, 1.5
2904liters or larger. Champagne bottles are built to withstand pressure, and
2905have no problem standing up to the 30 pounds of pressure used in this
2906reaction. In the interest of safety, however, the outside of the bottle is
2907coated with a layer of fiberglass resin about 1/2 inch thick. This guards
2908against accidental overpressurization and fatigue cracking. Fiberglass
2909resin is easily obtained at the local auto supply store.
2910    
2911    To do the reaction, 300 ml of phenylacetone is put into the bottle,  
2912followed by 300 ml of 40% methylamine in water. The two of them react
2913immediately to convert a good portion of the mixture into the intermediate
2914Schiff's base. The mixture gets warm, and some methylamine gas fumes off.
2915It is even better here to use the anhydrous  methylamine gas in a cylinder.
2916This hard to come by item is used by  cooling the cylinder down in a
2917freezer, then tipping the cylinder upside down and cracking open the valve
2918to drain out 150 ml of pure methylamine gas into a chilled beaker.
2919    
2920    To the mixture in the champagne bottle are then added 500 ml of 190
2921proof grain alcohol and 5 grams platinum oxide (Adam's catalyst). A
2922magnetic stirring bar is then slid into the bottle, and it is attached to  
2923an apparatus like the one shown in Figure 17.
2924    
2925    The apparatus shown in Figure 17 can be constructed by anyone with
2926access to machinist's tools. Alternatively, the clandestine operator can
2927have it made for him with little or no chance of anyone suspecting its real
2928purpose. The threads are fine, and coated with Form A Gasket immediately
2929before assembly. The valves are of the swagelock type.
2930    
2931    Before beginning production using this device, the joints are checked
2932for leakage by brushing soapy water on them and looking for the tell-tale
2933bubbles.
2934    
2935    The chief danger in using the hydrogenation apparatus is from fire due
2936to leaking hydrogen coming into contact with spark or flame. The magnetic
2937stirrer is a possible source of static-induced sparks. To eliminate this
2938danger, it is wrapped in a sturdy bread or garbage bag. This prevents
2939hydrogen from coming into contact with it. Good ventilation in the
2940production area likewise prevents hydrogen from building up in the room.
2941    
2942    To begin production using this device, the champagne bottle is attached
2943to the rig immediately after filling with the reactants. The air is sucked
2944out of the bottle by attaching the exit valve, a vacuum line leading to an
2945aspirator. After sucking out the air for 30 seconds, this valve is closed,
2946and hydrogen is fed into the bottle from the cylinder until it has
2947pressurized to a few pounds above normal air pressure (i.e., a few pounds
2948show on the gauge). Then the input valve is closed, and the bottle is
2949vacuumed out once more. Now the bottle is practically free of air. The exit
2950valve is closed once again, and hydrogen is let into the bottle until the
2951gauge shows 30 pounds of pressure. This is 3 atmospheres of pressure,
2952counting the 15 pounds needed to equal air pressure. Magnetic stirring is
2953now started, and set at such a rate that a nice whirlpool forms in the
2954liquid inside the bottle.
2955    
2956    The hydrogen used in this reaction is of the purest grade available.  
2957Cylinders of hydrogen are obtained at welding supply shops, which generally
2958have or can easily get electrolytically produced hydrogen. This is the
2959purest grade. The cylinder must have a regulator on it to control the
2960pressure of hydrogen being delivered to the bomb. The regulator must have
2961two gauges on it, one showing the pressure in the cylinder, the other
2962showing the pressure being fed into the line to the bomb.
2963    
2964    After beginning stirring the contents of the bomb, an induction period
2965of about an hour or so usually follows during which nothing happens. No
2966hydrogen is absorbed by the solution during this period. It is not known
2967just why this is the case, but nothing can be done about it. Use of
2968prereduced platinum catalyst does not eliminate this delay. (Prereducing is
2969a procedure whereby the platinum catalyst is added first, and then
2970contacted with hydrogen to convert the oxide of platinum to the active
2971metal.)
2972    
2973    In an hour or so, hydrogen begins to be absorbed by the solution,  
2974indicating production of methamphetamine. The pressure goes down on the
2975gauge. More hydrogen is let in to maintain the pressure in the 30 pound
2976range. Within 2 to 4 hours after uptake of hydrogen begins, the absorption
2977stops. This indicates the end of the reaction.
2978    
2979    The valve on the cylinder is now closed, and the exit valve slowly  
2980opened to vent the hydrogen gas outside. Now the bottle is removed from the
2981apparatus, and the platinum is recovered for reuse by filtering the
2982solution. The platinum is stored in absolute alcohol until the next batch.
2983Many batches can be run on the same load of platinum catalyst, but it
2984eventually loses its punch. It is then reworked in the manner described
2985later.
2986    
2987    The filtered reaction mixture is then poured into a 2000 ml round  
2988bottom flask, along with 3 or 4 boiling chips. The glassware is set up as
2989shown in Figure 3 in Chapter 3. The chemist heats the oil no hotter than
2990110øC, and distills off the alcohol and water. When the volume] of the
2991mixture gets down to near 500 ml, he turns off the heat and]` transfers the
2992reaction mixture to a 1000 ml round bottom flask with 4 boiling chips. He
2993sets up the glassware for fractional distillation as shown in Figure 5 in
2994Chapter 3, and continues distilling off the alcohol. The temperature shown
2995on the thermometer should be about 80øC. When the volume of the reaction
2996mixture gets down to about 400 ml, he turns off the heat and lets it cool
2997off. He attaches a 250 ml round bottom flask as the collecting flask and
2998begins a vacuum distillation. The last remnants of alcohol are soon gone,
2999and the temperature shown on the thermometer climbs. If he is using an
3000aspirator, when the temperature reaches 80øC, he changes the collecting
3001flask to a 500 ml round bottom flask and distills the methamphetamine under
3002a vacuum. If he is using a vacuum pump, he begins collecting
3003methamphetamine at 70øC. He does not turn the heat setting on the buffet
3004range above l/3 of the maximum. Virtually all of the material distilled is
3005methamphetamine. He will get between 300 and 350 ml of clear to pale yellow
3006methamphetamine, leaving about 20 ml of residue in the flask. A milky color
3007to the distillate is caused by water being mixed with it. This is ignored,
3008or removed by gentle heating under a vacuum.
3009
3010    The distilled methamphetamine is made into crystals of methamphetamine
3011hydrochloride in the same way, as described in Chapter 5. He puts about 75
3012ml of methamphetamine in each Erlenmeyer flask and adds ether or benzene
3013until its volume reaches 300 ml. Then he bubbles dry hydrogen chloride gas
3014through it and filters out the crystals formed. The yield will be close to
3015380 grams of pure methamphetamine.
3016    
3017    It is in the catalyst preparation and recycling that the clear  
3018superiority of the platinum catalyzed reductive alkylation method becomes
3019obvious. In the succeeding methods using Raney nickel, one is dependent
3020upon a supply of aluminum-nickel alloy for making Raney nickel. To make
3021platinum catalyst, one needs only obtain platinum metal and one group of a
3022series of readily available chemicals. The basic metal itself, platinum, is
3023easily obtained from coin or other precious metal dealers. The underground
3024chemist thereby shields himself from suspicion by using the cloud of dust
3025kicked up by avaricious or misguided individuals who purchase platinum
3026metal thinking this will tide them through society collapse.
3027    
3028    The process used to turn platinum metal into active catalyst is  
3029identical to the method used to recycle worn out platinum catalyst into
3030reborn material. The first step is to dissolve the metal in aqua regia.
3031Aqua regia is a mixture of three parts hydrochloric acid, and one part
3032nitric acid. Only laboratory grade acids in in their concentrated forms are
3033used for this process. Lower grades may well introduce catalytic poisons
3034into the precious metal. The nitric acid is the 70% material. The
3035hydrochloric acid is the 37% laboratory material. About a pint of mixed
3036acid serves well to dissolve the few grams of platinum needed to run
3037man-sized batches of methamphetamine. The acids are simply mixed, and then
3038the platinum metal is added. A few fumes of NO2 are given off in the
3039dissolution process. Occasional swirling and some heating speeds the
3040process of dissolving the platinum. The dissolution converts the platinum
3041to chloroplatinic acid H2PtCl6. This substance is the starting point for
3042both of the alternative pathways to active platinum catalyst.
3043    
3044    When all of the platinum metal has disappeared into solution, heat is
3045applied to boil away the acid mixture. Then some concentrated hydrochloric
3046acid is added, and this too is evaporated away to dryness.  
3047
3048    The addition and evaporation of hydrochloric acid is repeated several  
3049times until the residue is free of nitrites.
3050    
3051    With chloroplatinic acid thusly obtained, the manufacturing chemist has
3052two alternative methods with which to convert it into active material ready
3053for use. The first method is the classical route involving a fusion of the
3054chloroplatinic acid, or preferably its ammonium salt, with sodium nitrate
3055at a temperature of about 450ø C. This method entails the obvious
3056difficulty of accurately measuring and controlling such a high temperature.
3057One can read all about this method in Organic Syntheses, Collective Volume
3058I, pages 463 to 470.
3059    
3060    The second method uses sodium borohydride to convert the acid directly
3061into platinum black. This method is simpler and produces a much more active
3062catalyst. The procedure is based on the method given by Brown and Brown in
3063the Journal of the American Chemical Society, Volume 84, pages 1493 to 1495
3064(1962). The yield is about 3 grams of the extra high activity catalyst, and
3065does the job of 5 grams of the catalyst prepared by the classical method.
3066    
3067    To prepare this catalyst, 8 grams of chloroplatinic acid is dissolved  
3068in 80 ml of absolute alcohol. Then, in another beaker, .8 grams of
3069laboratory grade sodium hydroxide is dissolved in 10 ml of distilled water.
3070This is diluted to 200 ml of total volume by adding absolute alcohol, and
3071then 7.71 grams of sodium borohydride is added. The  
3072alcohol-NaOH-water-sodium borohydride solution is stirred until the
3073borohydride is dissolved. The borohydride solution is now added to the
3074chloroplatinic acid solution with vigorous stirring. It is added as quickly
3075as possible without letting the contents foam over. A large amount of
3076hydrogen gas is given off while the borohydride reduces the chloroplatinic
3077acid to platinum black. This process is done in a fume hood or outside to
3078prevent hydrogen explosions.
3079    
3080    About one minute after all the borohydride solution has been added, the
3081excess borohydride is destroyed by adding 160 ml of glacial acetic acid or
3082concentrated hydrochloric acid. The solution is then filtered to collect
3083the platinum black. It is rinsed with a little absolute alcohol, with added
3084filter paper and all (to prevent loss of catalyst sticking to the paper),
3085directly into the champagne bottle for immediate use. If it must be stored
3086before use, it is put in a tightly stoppered bottle filled with absolute
3087alcohol.
3088
3089    The next method uses Raney nickel catalyst instead of platinum. It  
3090works just as well, but requires that the chemist be able to heat the
3091reactants to about 80øC. Also, somewhat higher pressures are used, so a
3092glass reaction bottle is not adequate; it must be made of stainless steel
3093at least 1/8 inch thick, for safety's sake.
3094    
3095    First, the chemist must find out how high the heat must be set to get
3096an 80øC temperature in the contents of the bomb. He fills the bomb
3097half-full of isopropyl rubbing alcohol and turns on the heat. He keeps
3098track of the temperature of the alcohol while stirring it with the  
3099thermometer. He finds the heat setting needed for an 80øC temperature and
3100how long it takes to reach that temperature. Then he removes the isopropyl
3101alcohol from the bomb and rinses it out with ethyl alcohol.
3102    
3103    He is now ready to run the reaction. If he has methylamine gas in a
3104cylinder, he puts 1 liter of 95% ethyl alcohol (190 proof grain alcohol) in
3105the bomb. If he has 40% methylamine in water, he uses 1 liter of absolute
3106ethyl alcohol. Then he adds the same amount of methylamine as used in the
3107first method described in this chapter. If he used methylamine gas from a
3108cylinder, he adds 100 ml each of ether and benzene to the bomb. Then he
3109adds 90 grams of Raney nickel catalyst and 25 grams of sodium acetate.
3110Finally, he adds 300 ml of phenylacetone to the bomb.
3111    
3112    Now the chemist seals up the bomb and pipes in the hydrogen to a  
3113pressure of 300 psi. He turns on the heat and begins shaking the reaction
3114bottle. The reaction begins to kick in at a little over 40øC. He begins
3115timing the reaction when the temperature reaches 50øC. He continues the
3116reaction for 8 hours, making sure that the pressure stays at 300 psi.
3117    
3118    Then he stops the shaking and heating and lets it cool down. After it
3119has cooled, it is filtered to remove the catalyst. The filtered catalyst  
3120cannot be allowed to dry out, or it will burst into flames. He keeps it
3121wet. The bomb is rinsed out with 100 ml of alcohol. The alcohol is
3122filtered, then added to the product. The catalyst is dumped down the drain
3123and flushed away with a lot of water.
3124    
3125    The alcohol, benzene, and ether are distilled off, then the  
3126methamphetamine is distilled under a vacuum, as described earlier in this
3127chapter. The yield is about the same as from the previous method.  
3128    
3129    The next method allows the chemist to use nitromethane, dragster fuel,
3130in place of methylamine. Since everybody, including the narcs, knows that
3131methylamine is required to make methamphetamine, this gives the underground
3132chemist a chance to throw the narcs a curve ball. The way this works is
3133that nitromethane is first put into the bomb along with Raney nickel and
3134reduced to methylamine.
3135    
3136    Phenylacetone is then added, and methamphetamine is produced.
3137    
3138    To do the reaction, the chemist puts one liter of absolute ethyl  
3139alcohol and 450 grams (350 ml) of nitromethane inside the bomb. The
3140nitromethane is either of laboratory grade, or has been fractionally
3141distilled (boiling temperature 101øC) to purify it. He adds 63 grams of
3142Raney nickel to the bomb and seals it up. He pipes in hydrogen to a
3143pressure of 300 psi and begins shaking. He heats the mixture up to about
314485øC, and continues for 3 hours. Then he turns off the heat, and lets it
3145cool off while shaking for about 45 minutes. Then the shaking is stopped,
3146and the hydrogen pressure is released. He adds the following to the bomb:
3147100 ml each of ether and benzene, 25 grams of sodium acetate, 45 more grams
3148of Raney nickel, and 300 ml of phenylacetone. He seals up the bomb, and
3149pipes in hydrogen at a pressure of 300 psi. Shaking is begun and the bomb
3150is heated to 80øC. He keeps this up for 8 hours, being sure to keep the
3151pressure at 300 psi. 
3152    
3153    After 8 hours are up, he turns off the heat and lets it cool off for an
3154hour with shaking. Then he stops the shaking and releases the pressure -
3155slowly. The mixture is then filtered as before, and the bomb is rinsed out.
3156Then the reaction mixture is distilled as described before. The yield is
3157about 300 ml of methamphetamine. It is turned into crystalline
3158methamphetamine hydrochloride as usual.
3159    
3160    The bomb can be used to make smaller batches of methamphetamine. But
3161the bomb and cylinders are not easily packed up and moved, so the bomb is
3162best suited to industrial-scale production.
3163    
3164    The reaction times and pressures I have given are not written in stone.
3165The time required to complete the hydrogenation can be reduced by using
3166more Raney nickel or platinum catalyst, increasing the hydrogen pressure,
3167or using less alcohol.
3168    
3169    If the underground chemist has to make his own one-gallon reaction
3170bottle, he uses stainless steel 1/8 to 3/16 inch thick, such as a section
3171of stainless steel pipe. For a volume of about one gallon, it should be
3172about 16 cm in diameter and 20 cm in height. The bottom is Tig welded on,
3173this process being much easier if it starts out a few millimeters larger in
3174diameter than the pipe section.
3175    
3176    The top of the tank has 2 holes drilled in it. One small one in the  
3177center of the tank is an entrance for the hydrogen gas. This has a section
3178of stainless steel pipe about 5 inches long welded around it. It is usually
3179necessary to melt in some stainless steel welding rod while making this Tig
3180weld, to get it strong enough. This top section is then welded onto the top
3181to create the reaction vessel shown in Figure 18. 
3182    
3183    A steel rocking frame is then welded onto the outside of the reaction
3184vessel as shown in Figures 18 and 19. The area where it is welded should be
3185reinforced. All welds are done with a Tig welder.
3186    
3187    The chemist can now assemble the bomb. He starts out with heavy wooden
3188planks as the base. This will keep vibration to a minimum. He sets up and
3189bolts down the frame. He attaches some clamps to this frame, then puts
3190sheaths and bearings on the arms of the steel rocking frame, and suspends
3191the reaction vessel about 6 inches off the ground. It should swing back and
3192forth easily.
3193
3194    Now he attaches a band around the reaction vessel, just below where the
3195steel rocking frame is attached to the reaction vessel. The band is
3196attached to the rocking arm, which is attached to a spindle on the driving
3197pulley, as shown in Figures 19 and 20. Both these joints should swivel
3198easily. The driving pulley is about 10 cm in radius. The pulley on the
3199motor has a radius of about 2 cm. The spindle, which extends from the
3200driving pulley to the rocking arm, is about 3 cm from the center of the
3201driving Pulley.
3202    
3203    The motor is the usual 1760 rpm type of motor, with a power of at least
32041/30 hp. When the motor is turned on, it spins the driving pulley, which
3205moves the rocking arm back and forth, which in turn shakes the reaction
3206vessel.
3207    
3208    The chemist is now ready to test the system. He opens up the valve and
3209puts 2000 ml of distilled water in the reaction vessel. He closes the valve
3210and turns on the motor to begin shaking. If any water comes out the top of
3211the stainless steel pipe, he secures the wooden base to minimize vibration.
3212He shuts it off and opens the valve, then siphons out all the water.
3213    
3214    He now runs a line of heavy rubber tubing from the hydrogen cylinder to
3215the stainless steel pipe. He crimps in the end of the pipe, then pushes the
3216rubber hose down over the pipe, at least halfway to the tank. He superglues
3217it to help hold it in place. Then he covers the entire length of the hose
3218with a series of pipe clamps so that it does not blow out or slip off the
3219pipe. This hose is slung over a sling in the frame so that it leads
3220straight down to the reaction vessel. There must be enough slack to allow
3221for the rocking motion.  
3222
3223    If any water came out of the pipe in the test run, the hose must have
3224catalytic poisons removed from it by boiling it in 20% sodium hydroxide
3225solution, then rinsing it off in boiling water. 
3226    
3227    
3228    The chemist closes the valve and begins putting pressure in the tank,
3229starting with a pressure value of 50 psi. He brushes soapy water around the
3230joints to look for any leaks. If there aren't any, he works the pressure up
3231to 300 psi. If leaks are found, he tries brazing over the faulty joint. His
3232welds must be nearly perfect. 
3233    
3234    To use the bomb, the reactants are added to the bomb with a funnel
3235through the faucet. If any sodium acetate is left clinging to the valve, it
3236will prevent a good seal. The Raney nickel is added with a pipette. When
3237the reaction is over, the products are siphoned out with a bent section of
3238glass tubing. Vacuum from an aspirator speeds up this process considerably,
3239as does using large-diameter tubing.
3240    
3241    More information on these reactions can be found in Reactions of   
3242Hydrogen by Adkins, published in 1937 by the University of Wisconsin Press.
3243    
3244                                 References
3245    
3246                   Organic Reactions, Volume 4, page 174.
3247      Journal of the American Chemical Society, Volume 61, pages 3499
3248       and 3566 (1939); Volume 66, page 1516 (1944); Volume 70, pages
3249                           1315 and 2811 (1948).
3250            Reductions in Organic Chemistry, by Milos Hudlicky.
3251    
3252    
3253--------------------------------------------------------------------------
3254                   Reductive Alkylation Without The Bomb
3255--------------------------------------------------------------------------
3256    
3257    The process of reductive alkylation using the hydrogenation bomb, as
3258you saw in the previous chapter, is not without difficulties or dangers.
3259Just for starters, consider the danger of hydrogen gas building up in a
3260poorly ventilated workplace. Add to that the danger of the bomb blowing up
3261if the welding of the seams is not done well. Also think about the hassle
3262involved in making enough Raney nickel to produce multi-kilos of
3263methamphetamine. The last problem can be minimized by reusing the Raney
3264nickel used in the previous batch. In this way, the underground chemist can
3265get away with adding only half as much fresh nickel as would otherwise be
3266added, but he must be doing one batch right after another to keep it fresh.
3267    
3268    All of these problems, except for the hydrogen gas danger, can be 
3269eliminated if he is able to get his hands on activated aluminum turnings.
3270In this method, the aluminum turnings take the place of hydrogen gas as the
3271catalyst in the reductive alkylation process. The yields are very good, the
3272process is very simple, and no special equipment is required. The reaction
3273is also quick enough that it can be used in large-scale production.
3274    
3275    Activated aluminum is next to impossible to purchase, but very easy to
3276make. The raw material is aluminum foil. The foil is amalgamated with
3277mercury by using mercury chloride. The result is aluminum amalgam.
3278    
3279    To make activated aluminum, the chemist takes 100 grams of the aluminum
3280foil, and cuts it into strips about 2Yz cm wide, and 15 cm long. He folds
3281them loosely, and puts them into a 3000 ml glass beaker or similar
3282container. He does not stuff them down the neck of the flask or similar
3283container from whence they would be hasslesome to retrieve. He packs them
3284down lightly so that they are evenly arranged, then covers them with a .1%
3285solution (1 gram in one liter of water) by weight solution of sodium
3286hydroxide.
3287    
3288    He warms the mixture by setting it into a hot water bath until a 
3289vigorous bubbling of hydrogen gas has taken place for a few minutes. He is
3290careful here that the mixture does not overflow! Then he pours off all the
3291sodium hydroxide solution as quickly as possible, and rinses the strips
3292with distilled water, and then with 190 proof vodka. This preliminary
3293treatment leaves an exceedingly clean surface on the foil for amalgamating
3294with mercury.
3295    
3296    While the surface of the strips is still moist with vodka, he adds 
3297enough of a 2% by weight solution of mercury QI) chloride (aka mercuric
3298chloride, HgCI2) in distilled water to completely cover the foil. He allows
3299this to react for about 2 minutes, then pours off the mercury solution. He
3300rinses off the strips with distilled water, then with 190 proof vodka, and
3301finally with moist ether. Moist ether is either purchased as is, or made by
3302adding water to anhydrous ether with stirring until a water layer begins to
3303appear at the bottom of the ether. The chemist uses this material
3304immediately after making it.
3305
3306                                  Method 1
3307    
3308    In this method, the activated aluminum turnings react with alcohol to
3309produce hydrogen gas. This hydrogen then reduces the Schiff's base formed
3310from methylamine and phenylacetone to give methamphetamine.
3311    
3312    The chemist needs a magnetic stirrer-ho/plate to do this reaction. On
3313top of the stirrer-hotplate, he places a Pyrex bowl or cake dish large
3314enough to hold a 3000 ml flask. The bowl or dish cannot be made of metal,
3315because the magnetic stirrer will not work through it.
3316
3317    He places the 3000 ml flask in the dish and fills it with cooking oil
3318until the oil reaches about halfway up the sides of the flask. He must be
3319sure to leave enough room for the oil to expand as it heats up. He puts the
3320magnetic stirring bar in the flask along with 1600 ml of absolute alcohol
3321or 190 proof grain alcohol. Then he adds 340 ml of phenylacetone and 450 ml
3322of 40% methylamine in water. Now he turns on the magnetic stirrer and
3323begins heating the oil in the dish. He keeps track of the temperature of
3324the oil with a thermometer, and does not allow it to go above 100øC. While
3325the oil is heating up, he adds 180 grams of activated aluminum turnings to
3326the flask. He makes sure that the stirring is fast enough that the turnings
3327do not settle to the bottom of the flask. The reaction mixture will quickly
3328begin to turn grey and foamy. The aluminum is added at such a rate, the
3329bubbling and foaminess it produces does not overflow the flask. When all of
3330it has been added, a condenser is fitted to the flask, and water flow is
3331begun through it.
3332    
3333    The chemist now lets them react for 8 hours. He keeps the temperature
3334of the oil bath at 100øC, and the stirring strong. The activated aluminum
3335slowly dissolves and produces hydrogen gas. The explosive danger from this
3336gas is eliminated by running a length of tubing from the top of the
3337condenser out the window.
3338    
3339    When the 8 hours are up, he removes the flask from the oil bath and
3340wipes the oil off the outside of the flask. He filters the solution to 
3341remove the aluminum sludge, then rinses the sludge with some more alcohol
3342to remove the last traces of product from it. The rinse alcohol is added to
3343the rest of the filtered product.
3344    
3345    The underground chemist can now distill the product. He pours it in a
33463000 ml round bottom flask that is clean and reasonably dry, and adds a few
3347small pieces of pumice. He places the flask on the electric buffet range,
3348then sets up the glassware for fractional distillation, as shown in Chapter
33493. He begins heating it. The first thing that distills is a mixture of
3350alcohol, water, and methylamine. This occurs when the temperature shown on
3351the thermometer is about 78-80Q C. He collects about 1600 ml of this
3352mixture, then removes the flask from the heat. He lets it cool down, then
3353pours the contents of the 3000 ml flask into a 1000 ml flask, along with a
3354few fresh boiling chips. He puts about 15 ml of alcohol in the 3000 ml
3355flask. swirls it around to dissolve the product left clinging to the
3356insides, then pours it into the 1000 flask.
3357    
3358    The chemist again sets up the glassware for fractional distillation, 
3359with a 250 ml flask as his receiver. He applies a vacuum, preferably from
3360an aspirator, and begins vacuum distillation. When the boiling gets under
3361control, he begins heating the flask. The last remnants of alcohol and
3362water will soon be gone, and the temperature shown on the thermometer will
3363climb. When it reaches about 80øC with an aspirator, or about 70øC with a
3364vacuum pump, he quickly changes the receiving flask to a clean, dry 500 ml
3365flask, and reapplies the vacuum. He will get about 350 ml of clear to pale
3366yellow methamphetamine free base. A few milliliters of tar will be left in
3367the distilling flask. The liquid free base is converted to crystals by
3368dissolving it in ether or benzene and bubbling dry HC1 through it, as
3369described in Chapter 5.
3370    
3371    The underground chemist gets an even purer product by varying this
3372procedure slightly. Once the 1600 ml of alcohol, water, and methylamine is
3373distilled off, he pours a mixture of 650 ml of 28% hardware store variety
3374hydrochloric acid and 650 ml of water into what remains in the 3000 ml
3375flask, after it has cooled down. A lot of heat is produced in the mixing
3376because the methamphetamine free base is reacting to make the
3377hydrochloride. So he adds it slowly, then swirls it. When it has cooled
3378down, he stoppers the 3000 ml flask with a cork or glass stopper and shakes
3379it vigorously for 3 to 5 minutes. It should pretty much all dissolve in the
3380hydrochloric acid solution. Now he adds 200 ml of ether or benzene to the
3381flask and shakes it up well. The ether or benzene dissolves any unreacted
3382phenylacetone and tar. He lets it sit for a few minutes. The ether and
3383benzene layer floats to the top. He pours it slowly into a 1000 ml sep
3384funnel, so that the top layer all gets into the sep funnel. Now he lets it
3385set, then drains the lower acid layer back into the 3000 ml flask.
3386    
3387    The acid must now be neutralized to give back amphetamine free base, so
3388it can be distilled. The chemist mixes up a solution of 350 grams of lye in
3389400 ml of water. When it has cooled down, he pours it slowly into the acid
3390solution in the 3000 ml flask. A lot of heat is generated from the
3391reaction. When it has cooled down, he stoppers the flask and shakes it
3392strongly for about 5 minutes. When standing, the amphetamine forms a layer
3393on top. He slowly pours it into a 1000 ml sep funnel. He drains the water
3394layer back into the 3000 ml flask. The methamphetamine layer in the sep
3395funnel may have some salt crystals floating around in it. He adds 100 ml of
3396benzene to it plus a couple hundred ml of a dilute lye solution. He
3397stoppers and shakes the mixture. The salt will now be dissolved in the
3398water. He drains the water layer into the 3000 ml flask and pours the
3399methamphetamine-benzene solution into a clean 1000 ml flask. There is still
3400some methamphetamine left in the 3000 ml flask, so he adds a couple hundred
3401ml of benzene to it. If there is a lot of undissolved salt in the flask, he
3402adds some more water to it. Now he shakes the flask to dissolve the meth in
3403the benzene, then lets it set. The benzene comes up to the top. He pours it
3404off into the sep funnel, and drains off the water layer. He pours the
3405benzene layer into the 1000 ml flask with the rest of the product.
3406    
3407    He can now begin distilling it. He adds a few boiling chips, sets up 
3408for fractional distillation, and proceeds as described in Chapter 5. The
3409yield once again is about 350 ml of free base, which makes close to 400
3410grams of pure crystal.
3411    
3412                                  Method 2
3413    
3414    This method is not as good as the first one. It takes longer, it uses 
3415up more chemicals to make a given amount of product, and less can be
3416produced at a time.
3417    
3418    The equipment is set up as in Method 1. Into the 3000 ml flask is 
3419placed 1575 ml of 190 proof alcohol and 150 ml of distilled water. Then the
3420chemist adds 150 ml of phenylacetone and 220 ml of 40~o methylamine in
3421water. He begins magnetic stirring and adds 160 grams of activated aluminum
3422turnings. He heats the oil bath to 100ø- C or so and attaches a condenser
3423to the 3000 ml flask. He begins water flow through the condenser and gently
3424boils the contents of the flask for 16 hours. At the end of this time, he
3425removes the flask from the heat and lets the aluminum sludge settle. He
3426filters the alcohol solution, rinses the sludge with alcohol and adds the
3427filtered alcohol to the rest of the product. Then he proceeds as described
3428in Method 1. The yield is about 150 ml of methamphetamine.
3429
3430                                  Method 3
3431    
3432    This method is not as good as Method 1 either. Ether is used as the
3433reaction solvent, which adds danger and expense. The ether is better used
3434to produce the crystals. Another problem with this reaction is that it is
3435done so dilute that large amounts can't be made at one time.
3436    
3437    In the same set-up used in Methods 1 and 2, the underground chemist
3438places 1000 ml of absolute ether in a 3000 ml flask. Then he adds 100 ml of
3439phenylacetone and 160 ml ”f 40% methylamine. He begins stirring and adds 65
3440grams of activated aluminum turnings. He attaches an efficient condenser,
3441runs cold water through it, and heats the oil bath to 45-50øC. He gently
3442boils the solution for 6 hours. The activated aluminum reacts with the
3443water in the methylamine to produce hydrogen.
3444    
3445    When the six hours have passed, he distills off the ether and treats
3446the residue as described in Method 1, i.e., distills it under a vacuum,
3447etc. The yield is about 90 ml of meth.
3448    
3449    For more information on this method, see U.S. Patent Nos. 2,146,474 and
34502,344,356.
3451    
3452                                  Method 4
3453    
3454    This variation on the activated aluminum method of reductive alkylation
3455has the advantage of using methylamine hydrochloride directly in the
3456reaction soup. Since methylamine is now very dangerous or impossible to
3457obtain commercially, and also since the best method for making methylamine
3458yields methylamine hydrochloride, the usefulness of this variation is
3459obvious.
3460    
3461    This method involves the addition of an alcohol solution containing the
3462Schiff's base formed between methylamine and phenylacetone onto the
3463activated aluminum. In the other methods, the opposite order of addition
3464was employed. To maximize yields of product, the competing side reactions
3465are suppressed. In the case of activated aluminum methamphetamine
3466production, the main side reaction is the reduction of phenylacetone into
3467an interesting, but quite useless pinacol. It has the structure shown on
3468the next page:
3469    
3470    This side reaction is minimized by keeping the amount of water in the
3471reaction mixture to a minimum, and also by using a healthy excess of
3472methylamine. This scheme of things encourages the phenylacetone to tie
3473itself up with methylamine to form the Schiff's base, rather than float
3474around freely in solution where it could be reduced by the aluminum.
3475    
3476    To do this reaction, two 2000 ml volumetric flasks are obtained. 
3477Volumetric flasks work well for this reaction because the chemist can swirl
3478around their contents quite forcefully without danger of spillage. They
3479also pour pretty well. One volumetric flask is for preparing the activated
3480aluminum, and is also the ultimate reaction vessel. The other volumetric
3481flask is for the preparation of the Schiff's base. The lab work is
3482organized so that both products are ready to react at about the same time.
3483    
3484    Into the volumetric flask destined to be the ultimate reaction vessel,
3485the chemist places 108 grams of aluminum foil. It is cut into one inch
3486squares. The best brand of aluminum foil for this purpose is Heavy Duty
3487Reynolds Wrap. It is then treated with sodium hydroxide solution as
3488described in Method 1. After a few good rinses to remove the sodium
3489hydroxide, it is ready to become activated aluminum. To do this, the
3490volumetric flask is filled almost to the neck with distilled water,
3491followed by the addition of 4.51 grams of HgCl2. The flask is swirled to
3492dissolve the mercuric chloride, and then every few minutes for the next 30
3493minutes. During this time, the water becomes a cloudy grey color, and the
3494aluminum loses its shine. The water is then decanted off the aluminum, and
3495the flask is filled up with fresh distilled water to carry away unreacted
3496mercury. After a period of swirling, the rinse water is poured off, and the
3497rinse repeated with a fresh portion of distilled water. On the last rinse,
3498the chemist makes sure that the water drains off well. This leaves
3499activated aluminum ready to go.
3500    
3501    In the second volumetric flask, Schiff's base is made. To do this, 
3502163.5 grams of sodium hydroxide is dissolved in one liter of 190 proof
3503vodka. To this is added 270 grams of methylamine hydrochloride. This
3504methylamine is dry so that the chemist is not weighing water contamination.
3505If this is home brew methylamine hydrochloride, the first crop of crystals
3506is acceptable material, but the second and third batches of crystals are
3507recrystallized as described in Organic Syntheses, Collective Volumes I, II
3508or III. Look in the table of contents for methylamine hydrochloride. The
3509mixture is kept cool during the addition to prevent methylamine gas from
3510escaping. Good stirring is also essential. The result of this operation is
3511an alcohol solution of methylamine. Some salt and water are formed.
3512    
3513    To make the Schiff's base, 200 ml of phenylacetone is then added to
3514this solution. The addition produces a fair amount of heat, and some 
3515methylamine fumes are driven off as a result. Active swirling of the flask
3516keeps this to a minimum. The chemist also tips the flask during swirling to
3517dissolve any phenylacetone which may be stuck up in the neck of the flask.
3518This is the Schiff's base solution.
3519    
3520    To do the reaction, the Schiff's base solution is poured onto the 
3521activated aluminum. Once the pouring is complete, they are swirled together
3522energetically for a few seconds, then a thermometer is carefully lowered
3523into the flask. Following this, a section of plastic tubing is stuffed into
3524or over the top of the volumetric flask, and led outside. This is for fume
3525control. The reaction mixture is swirled continuously for the first few
3526minutes. The temperature rises quite rapidly because the reaction is really
3527vigorous. It is necessary to have a bucket of ice water close by to dunk
3528the reaction vessel into to keep it under control. The experimenter strives
3529to keep the reaction mixture in the 50 to 60øC range. After the initial
3530rush, occasional swirling is acceptable, so long as the temperature
3531guidelines are followed. After 90 minutes, the reaction is complete.
3532    
3533    To process the product, the alcohol solution containing the product is
3534poured off into the distilling flask. The mud-like gunk at the bottom of
3535the flask contains a fair amount of trapped product. This gunk is 
3536untreatable as is, but with some lightening up, it can be filtered. A lab
3537product called Celite is added to the gunk until it appears more amenable
3538to filtration. As an altemative, washed white sand, found in the cement
3539section of your friendly neighborhood store, is a good substitute. This is
3540mixed in with the gunk until it lightens up a bit. Then two portions of 200
3541ml of warm vodka (190 proof) are mixed in and the trapped product is
3542filtered out of the gunk. These gunk filtrates are added to the main
3543product, and the whole mother lode readied for processing.
3544    
3545    The first step is to place all the liquid into the distilling flask
3546along with a few boiling chips, and remove the alcohol with a vacuum. A
3547fractional distillation then gives pure methamphetamine free base ready for
3548crystallizing into the hydrochloride.
3549    
3550    The same method can be used to give MDMA just by substituting MDA
3551phenylacetone for regular phenylacetone. 
3552    
3553    
3554--------------------------------------------------------------------------
3555                                Methylamine
3556--------------------------------------------------------------------------
3557    
3558    From time to time, an underground chemist's supply of methylamine may
3559be cut off. If this happens, it is handy to be able to make a supply of his
3560own methylamine until he is able to get his hands on some of the ready-made
3561stuff.
3562    
3563    The reaction to produce methylamine is cheap, but requires a lot of
3564labor. Two molecules of formaldehyde react with ammonium chloride to
3565produce a molecule of methylamine hydrochloride and The glassware is set up
3566as shown in Figure 3 in Chapter 3. The chemist places 1000 grams of
3567ammonium chloride and 2000 ml of 3540% formaldehyde in the 3000 ml flask
3568sitting in the pan of oil. (These chemicals need not be a very high grade;
3569technical grade is good enough.) He puts a thermometer in the oil next to
3570the flask and begins slowly heating it. As it warms up, he swirls the flask
3571to dissolve the ammonium chloride crystals. Over the period of an hour, he
3572raises the temperature of the oil bath to 106øC. He holds the temperature
3573there for five hours.
3574    
3575    Then he turns off the heat and removes the flask from the pan of oil.
3576Some liquid will have collected in the 2000 ml flask; he throws it out and
3577rinses the flask with water. The 3000 ml flask is set in a pan of room
3578temperature water to cool it off. A good amount of ammonium chloride
3579crystals precipitate from the solution. He does not want these chemicals,
3580so he filters them out. He returns the filtered reaction mixture to the
35813000 ml flask and again sets up the glassware as shown in Figure 3. A 250
3582ml flask is used as the collecting flask. The reaction mixture should be
3583clear to pale yellow.
3584    
3585    He turns on the vacuum source and attaches it to the vacuum nipple of
3586the vacuum adapter. He boils off the water and formic acid in the reaction
3587mixture under a vacuum. Heating the flask in the oil pan speeds up the
3588process, but the oil is not heated above 100ø C When the volume of the
3589contents of the flask is reduced to about 1200-1300 ml, he turns off the
3590vacuum and removes the flask from the oil pan. The flask is put in a pan of
3591room temperature water to cool it off. Some more crystals of ammonium
3592chloride come out of solution. He filters out these crystals and pours the
3593filtered reaction mixture into a 2000 ml flask. He sets up the glassware as
3594before, and again boils off the water and formic acid under a vacuum. He
3595does not heat the oil above 100ø C
3596
3597    When the volume of the reaction mixture has been reduced to about 700
3598ml, crystals of methylamine hydrochloride begin to form on the surface of
3599the liquid. It looks a lot like a scummy film. When this happens, the
3600vacuum is disconnected and the flask is removed from the oil bath. The
3601flask is placed in a pan of room temperature water to cool it off. As the
3602flask cools down, a lot of methylamine hydrochloride crystals come out of
3603the solution. When the flask nears room temperature, it is cooled off some
3604more with some cold water. This will cause even more methylamine
3605hydrochloride to come out of the solution.
3606    
3607    The chemist filters out the crystals and puts them in a 1000 ml  
36083-necked flask. The crystals look different from the crystals of ammonium
3609chloride, so he should have no trouble telling the two apart. These
3610crystals soak up water from the air and melt, so he does not waste time
3611getting them in the 3-necked flask after they are filtered.
3612    
3613    He takes the filtered reaction mixture and pours it in a 1000 ml sep
3614funnel. The reaction mixture contains dimethylamine hydrochloride and some
3615other garbage, and he wants to remove some of this unwanted material before
3616he proceeds to get the rest of the methylamine hydrochloride. He adds 200
3617ml of chloroform to the sep funnel, and shakes it with the reaction mixture
3618for 30 seconds. He lets it set for a couple of minutes. The chloroform
3619layer should be on the bottom. It has a lot of dimethylamine hydrochloride
3620and other garbage dissolved in it. He drains out the chloroform layer and
3621throws it out.
3622    
3623    He pours the reaction mixture into a 1000 ml round bottom flask and
3624again sets up the glassware as shown in Figure 3. He reattaches the vacuum
3625and continues boiling off the water and formic acid under a vacuum. When
3626the volume of the mixture reaches 500 ml, he removes the flask from the hot
3627oil and places it in cool water. As it cools off, more crystals of
3628methylamine hydrochloride appear. He filters the cold reaction mixture to
3629obtain these crystals. He transfers them to a beaker and adds 200 ml of
3630cold chloroform to the beaker. He stirs the crystals around in the
3631chloroform for a few minutes, breaking up any chunks. This dissolves any
3632dimethylamine hydrochloride in the product. He filters the crystals in the
3633beaker, then puts them in the 1000 ml, 3-necked flask along with his first
3634crop of methylamine hydrochloride crystals. He throws away the chloroform
3635and retums the reaction mixture to the 1000 ml flask.
3636    
3637    He boils the reaction mixture under a vacuum again. When its volume
3638reaches about 150-170 ml, he turns off the vacuum and removes the flask
3639from the hot oil. He pours the reaction into a beaker and stirs it as it
3640cools down, to prevent it from turning into a solid block. Once it has
3641cooled down, he adds 200 ml of cold chloroform to the slush. He stirs it
3642around with a glass rod for a couple of minutes, being sure to break up any
3643chunks. The mixture is then filtered. The crystals of crude methylamine
3644hydrochloride are kind of gooey, so it may not be possible to filter out
3645all the chloroform. But he does the best he can. He returns the filtered
3646crystals to the beaker and adds 100 ml of cold chloroform to the crystals.
3647He stirs it around again, then filters the crystals. He must do a better
3648job of filtering out the chloro form this time. These crystals also absorb
3649water from the air and melt. As soon as this last crop of crystals is
3650filtered, he adds them to the other crystals in the 3-necked flask. He may
3651have to pack it down to get it all to fit. The yield of methylamine
3652hydrochloride is about 425 grams. He may wish to stopper the flask and dry
3653the crystals under a vacuum, although it is not essential.
3654    
3655    The compound the underground chemist wants is methylamine, not
3656methylamine hydrochloride. Methylamine is a gas which turns into a liquid
3657at -6øC (21øF). He will now neutralize the hydrochloride with sodium
3658hydroxide and liquefy the methylamine gas produced.
3659    
3660    The glassware is set up as shown in Figure 21. The 3-necked flask is
3661sitting on the hotplate. It contains methylamine hydrochloride crystals. He
3662puts the long condenser in the central neck and stoppers the other neck of
3663the flask. He adds 100 grams of sodium hydroxide to the flask. (Lye is an
3664acceptable substitute.) It may begin to react to form methylamine and salt,
3665but it will not get very far without water. He dissolves 220 grams of
3666sodium hydroxide or lye in 350 ml of water and sets it aside for the time
3667being. He puts a sep funnel in the third neck of the 3-necked flask. He
3668connects a stillhead to the top of the condenser and attaches the shorter
3669condenser to it. The water jacket of the condenser is filled with rubbing
3670alcohol. The water entrance and exit are plugged to hold in the alcohol.
3671The outside of this condenser is packed with enough dry ice to keep it good
3672and cold, in the vicinity of 0øF. He insulates this dry ice packing so that
3673it does not evaporate too quickly. He attaches the vacuum adapter to the
3674condenser, then connects a section of plastic tubing to the vacuum nipple
3675to carry fumes of ammonia outside. He attaches a 500 ml round bottom flask
3676to the vacuum adapter. This flask is cooled by placing it in a styro foam
3677container. He pours in alcohol until the rubbing alcohol is halfway up the
3678sides of the flask. He adds dry ice to this alcohol bath until its
3679temperature is about -10øF. (He adds the dry ice slowly at first to keep
3680the alcohol from foaming over.) He keeps it at this temperature until he
3681has collected all the methylamine. Ice water is run through the long
3682condenser, as described in the chapter on N-methylformamide.
3683    
3684    He adds the sodium hydroxide solution to the sep funnel and drips it
3685onto the methylamine hydrochloride and sodium hydroxide in the flask. It
3686reacts rapidly to form methylamine and salt. The heat that the reaction
3687produces causes the methylamine to be driven off and condensed in the
3688collecting flask. He swirls around the flask to get the sodium hydroxide
3689into contact with the methylamine hydrochloride. When all the sodium
3690hydroxide has been added, he closes the valve of the sep funnel and allows
3691it to react for a few minutes. Then he slowly heats the flask to drive off
3692the methylamine. He may have to add some water through the sep funnel to
3693get the methylamine hydrochloride on the bottom of the flask in contact
3694with the sodium hydroxide.
3695    
3696    In the meantime, liquid methylamine has been collecting in the 500 ml
3697flask. It is mixed with some water which made it through the long  
3698condenser, and also some ammonia. He allows the temperature of the alcohol
3699bath surrounding the 500 ml flask to rise to 0øF after all the methylamine
3700has been boiled out of the 3-necked flask. He holds it at that temperature
3701for half an hour. The ammonia will evaporate and exit through the plastic
3702tubing. Since ammonia gas is poisonous, this tubing runs outside.
3703    
3704    Then the chemist adds an equal volume of water to the liquid  
3705methylamine, about 220 ml. He has just made about 450 ml of 40% methylamine
3706in water. The water allows him to keep it at room temperature. He pours it
3707into a champagne bottle and tightly stoppers it. This methylamine can be
3708used to make N-methlyformamide, but cannot be used in the hydrogenation
3709bomb. It may contain traces of chloroform, which would poison the Raney
3710nickel catalyst. Since methylamine is cheap, he will buy it when possible.
3711    
3712    Methylamine can be made by other methods as well. For example, it can
3713be made in 71% yield by reacting methyl iodide with hexamine, also known as
3714hexamethylene tetramine. Good directions for making this substance from
3715ammonia and formaldehyde can be found in Home Workshop Explosives by yours
3716truly. The production details for methylamine are found in the Journal of
3717the American Chemical Society, Volume 61, page 3585, (1939). The authors
3718are Galat and Elion.
3719    
3720    It can also be made by degrading acetamide with Clorox. See Journal of
3721the American Chemical Society, Volume 63, page 1118, (1939). The authors
3722are Whitmore and Thorpe, and the yield is 78%.
3723    
3724    It can also be made via the Curtius reaction in a yield of 60%. See
3725Helv. Chim. Acta, Volume 12, page 227, (1929). The authors are Naegeli,
3726Gruntuch and Lendorff.
3727    
3728                                 References
3729    
3730   Journal of the American Chemical Society, Volume 40, page 1411 (1918).
3731    
3732    
3733--------------------------------------------------------------------------
3734        The Ritter Reaction: Amphetamines Directly From Allylbenzene
3735--------------------------------------------------------------------------
3736    
3737    A most interesting sidelight appears in an article by Ritter and Kalish
3738found in the Journal of the American Chemical Society, Volume 77, pages
37394048 to 4050. This sidelight was a bit of research done by a grad student
3740as part of his master's thesis. The grad student just happened to work out
3741the experimental details for converting allylbenzene directly into
3742amphetamine.
3743    
3744    The main thrust of the article was the good Dr. Ritter telling of his  
3745new method for converting double bonds into amines. The method which he
3746pioneered has since come to be known as the Ritter reaction. This versatile
3747reaction can well serve the underground operator as an alternative pathway
3748to the amphetamines.
3749    
3750    The Ritter reaction in general is a reaction whereby amides are made by
3751adding an alkene to a mixture of a nitrile in sulfuric acid. After the
3752amide is made, it is then boiled in hydrochloric acid solution to give the
3753corresponding amine.
3754    
3755    The particular variation on this theme in which we are interested deals
3756with the case in which the alkene is the now familiar and highly useful
3757allylbenzene. When it is added to a solution of acetonitrile in sulfuric
3758acid, the following reaction takes place:  
3759    
3760[SNiP]
3761    
3762    The acetyl amide thusly produced is not isolated and purified. Rather,
3763it is added in the crude state to hydrochloric acid, and boiled for several
3764hours. A hydrolysis reaction almost identical to the one seen in Chapter 5
3765takes place producing the prototype amphetamine, benzedrine.
3766    
3767    The acetyl amide of amphetamine is very similar to the formyl amide of
3768methamphetamine produced by the Leuckardt-Wallach reaction. Its main
3769difference is that it is more difficult to hydrolyze to the corresponding
3770amphetamine by the action of boiling hydrochloric acid. It must therefore
3771be boiled with the acid for a longer period of time than the formyl amide.
3772The manufacturer may well find it to his advantage to boil the tar left
3773over at the end of the process once more with fresh hydrochloric acid. This
3774will likely yield an additional measure of amphetamine from the stubbornly
3775unreactive amide.
3776    
3777    This small hassle with the hydrolysis process could be avoided if HCN
3778were used as the nitrile in sulfuric acid solution. However, the extreme
3779danger of dealing with hydrogen cyanide more than outweighs the additional
3780work needed when using acetonitrile.
3781
3782    To do the reaction, a solution of 450 grams of concentrated sulfuric
3783acid in 400 grams acetonitrile is made by slowly adding the acid to the
3784acetonitrile. Both ingredients are cold when they are mixed together, and
3785the temperature of the mixture is kept in the 5-10øC range during the
3786mixing by setting the reaction container in ice. An admirable reaction
3787vessel is a glass beer pitcher.
3788    
3789    When the addition of the acid to the nitrile is complete, the pitcher  
3790is taken out of the ice, and 236 grams of allylbenzene is slowly added to
3791it with stirring. The mixture quickly turns an orange color, and begins to
3792warm up.
3793    
3794    Stirring is continued on an occasional basis, and the temperature of
3795the mixture followed. It slowly climbs to 50øC, and then more rapidly to
379680øC, as the color of the mixture darkens.
3797    
3798    When the temperature of the mixture reaches 80øC, the pitcher is cooled
3799down, first by setting the pitcher in cool water, and then into ice. When
3800it has cooled down, the mixture is poured into a gallon of cold water
3801containing 15% by weight of Iye. The Iye solution neutralizes the sulfuric
3802acid, and dissolves most of the acetonitrile. The neutralization of the
3803acid by the Iye solution produces a great deal of heat. The Iye solution is
3804gently stirred during the addition, and then stirred more vigorously during
3805the following minutes. After a few minutes of stirring, the mixture is
3806allowed to sit for a few minutes. A yellow oily layer floats on the top of
3807the solution. This yellow oil is the crude amide. If the oil were to be
3808allowed to sit for a while longer, it would begin to form crystals of crude
3809amide. There is no need for this, however, so the processing continues
3810immediately.
3811    
3812    The top yellow layer is poured off into a sep funnel, and any water
3813carried along is drained off. Then the yellow oil is poured into a 2000 ml
3814round bottom flask. It is now ready for hydrolysis with hydrochloric acid
3815solution to make amphetamine. The approximate volume of the crude amide is
3816determined, and five times that volume of 15% hydrochloric acid solution is
3817added to it. Fifteen (15) percent hydrochloric acid solution is easily made
3818by starting with the 28% hardware store hydrochloric acid, and adding just
3819about an equal volume of water to it. A wise move here is to rinse the
3820inside of the sep funnel with acid. This rinses off the amide clinging to
3821the glass insides of the sep funnel.
3822    
3823    When the acid has been added to the amide, the mixture is swirled. They
3824usually mix together well. If they don't, stronger acid is used. Adding
3825some full strength acid to the mix should do the job. Then a few boiling
3826chips are added to the flask, a condenser attached to the flask, and heat
3827applied to boil the mixture at reflux.
3828    
3829    The reflux boiling is continued for 10 hours. During this time the  
3830mixture will turn black. At the end of the boiling period, the mixture is
3831allowed to cool down. When it is cool, 200 ml of benzene or toluene is
3832added to the flask. The mixture is shaken well for a couple of minutes,
3833then allowed to sit. The benzene floats up to the top, and has dissolved in
3834it most of the unreacted amide, and other unwanted garbage.
3835    
3836    The benzene layer is then poured off into a sep funnel, and any water
3837layer carried along drained back into the flask. The benzene layer is
3838poured off into another container for future processing. It may be
3839difficult to tell exactly where the benzene layer ends and the water starts
3840because of their similar color. A sharp eye and good lighting help to spot
3841the interface of the two fluids.
3842    
3843    The acid solution of the amphetamine is now made alkaline to liberate
3844the free base for distilling. To do this, Iye is added to the acid solution
3845in the 2000 ml flask. Assuming the use of about 1200 ml of 15% hydrochloric
3846acid solution, one 12 oz. can of lye does the job. The mixture is first
3847swirled to release heat, then shaken vigorously for five minutes. I cannot
3848emphasize enough the importance of vigorous and prolonged shaking here
3849because the amphetamine base initially formed tends to dissolve
3850unneutralized amphetamine hydrochloride. The oily droplets protect the
3851hydrochloride from contact with the lye solution unless the shaking is
3852strong and prolonged.
3853    
3854    When the shaking is completed, the mixture is allowed to cool down.
3855Then 300 ml of benzene or toluene is added to the flask, and shaking
3856continued for a minute or two. After sitting for a couple of minutes, a
3857benzene-amphetamine layer floats above the water layer. This is poured off
3858into a sep funnel, and the benzene-amphetamine layer poured into a 1000 ml
3859round bottom flask.
3860    
3861    The amphetamine-benzene mixture is distilled in exactly the same manner
3862as described in Chapter 5. The boiling point of benzedrine is 10ø to 20øC
3863lower than meth. The yield of benzedrine is in the range of 100 to 150 ml.
3864    
3865    The benzedrine produced by this reaction is either used and removed as
3866is, or it is converted to methamphetamine. A very good and simple process
3867for doing this can be found in the Journal of the American Chemical
3868Society, Volume 62, pages 922-4. The author is Woodruff. The yield for this
3869process is over 90%, so a greater volume of methamphetamine comes out of
3870the reaction than the benzedrine input. This is because the gain in
3871molecular weight achieved by adding the methyl group outweighs the small
3872shortfall from 100% yield.
3873    
3874    For those who have difficulty reading the Woodruff article, meth is
3875described as B-phenylisopropylmethylamine. The amine is benzedrine.
3876    
3877    If the benzedrine product is used as is, the producer makes it as the
3878hydrochloride salt. This is made the same way as methamphetamine
3879hydrochloride. An alternative to the hydrochloride salt is the sulfate
3880salt. This more hasslesome procedure calls for the use of cooled solutions
3881of amphetamine base in alcohol and cooled solutions of sulfuric acid in
3882alcohol. Furthermore, a recrystallization from alcohol-ether is required
3883because trapped excess sulfuric acid in the crystals causes them to turn to
3884mush or worse. By using HCl gas, the excess acid floats off as gas.
3885    
3886    An excellent review of this reaction can be found in Organic Reactions,
3887Volume 17. Nearly double these yields can be obtained if the underground
3888chemist is willing to risk using hydrogen cyanide instead of acetonitrile.
3889The hydrogen cyanide is made inside the reaction flask from sodium cyanide
3890and sulfuric acid. For complete directions, see Organic Syntheses,
3891Collective Volume 5, page 471 to 473. The name of the compound is alpha,
3892alpha, Dimethyl beta phenethylamine.
3893    
3894    A good alternative to the Ritter reaction is a two step procedure first
3895reacting safrole with hydrobromic acid to give  3,4-methylenedioxyphenyl-
38962-bromopropane, and then taking this material and reacting it with either
3897ammonia or methylamine to yield MDA or MDMA respectively. This procedure
3898has the advantages of not being at all sensitive to batch size, nor is it
3899likely to "run away" and produce a tarry mess. It shares with the Ritter
3900reaction the advantage of using cheap, simple, and easily available
3901chemicals.
3902    
3903    The sole disadvantage of this method is the need to do the final  
3904reaction with ammonia or methylamine inside a sealed pipe. This is because
3905the reaction must be done in the temperature range of 120-140ø C, and the
3906only way to reach this temperature is to seal the reactants up inside of a
3907bomb. This is not particularly dangerous, and is quite safe if some simple
3908precautions are taken.
3909    
3910    The first stage of the conversion, the reaction with hydrobromic acid,
3911is quite simple, and produces almost a 100% yield of the brominated
3912product. See the Journal of Biological Chemistry, Volume 108 page 619. The
3913author is H.E. Carter. Also see Chemical Abstracts 1961, column 14350. The
3914following reaction takes place:
3915    
3916    To do the reaction, 200 ml of glacial acetic acid is poured into a  
3917champagne bottle nestled in ice. Once the acetic acid has cooled down, 300
3918grams (200 ml) of 48% hydrobromic acid is slowly added with swirling. Once
3919this mixture has cooled down, 100 grams of safrole is slowly added with
3920swirling. Once the safrole is added, the cheap plastic stopper of the
3921champagne bottle is wired back into place, and the mixture is slowly
3922allowed to come to room temperature with occasional shaking. After about 12
3923hours the original two layers will merge into a clear red solution. In 24
3924hours, the reaction is done. The chemist carefully removes the stopper from
3925the bottle, wearing eye protection. Some acid mist may escape from around
3926the stopper.
3927    
3928    The reaction mixture is now poured onto about 500 grams of crushed ice
3929in a 1000 or 2000 ml beaker. Once the ice has melted, the red layer of
3930product is separated, and the water is extracted with about 100 ml of
3931petroleum ether or regular ethyl ether. The ether extract is added to the
3932product, and the combined product is washed first with water, and then with
3933a solution of sodium carbonate in water. The purpose of these washings is
3934to remove HBr from the product. One can be sure that all the acid is
3935removed from the product when some fresh carbonate solution does not fizz
3936in contact with the product.
3937    
3938    Once all the acid in the product is removed, the ether must be removed
3939from it. This is important because if the ether were allowed to remain in
3940it, too much pressure would be generated in the next stage inside of the
3941bomb. Also, it would interfere with the formation of a solution between the
3942product and methylamine or ammonia. It is not necessary to distill the
3943product because with a yield of over 90%, the crude product is pure enough
3944to feed into the next stage. To remove the ether from the product, the
3945crude product is poured into a flask, and a vacuum is applied to it. This
3946causes the ether to boil off. Some gentle heating with hot water is quite
3947helpful to this process. The yield of crude product is in the neighborhood
3948of 200 grams.
3949    
3950    With the bromo compound in hand, it is time to move onto the next step
3951which gives MDA or MDMA. See Chemical Abstracts 1961, column 14350. Also
3952see Journal of the American Chemical Society, Volume 68, page 1805 and
3953Journal of the Chemistry Society, part 2 1938, page 2005. The bromo
3954compound reacts with ammonia or methylamine to give MDA or MDMA:
3955    
3956    To do the reaction, 50 grams of the bromo compound is poured into a
3957beaker, and 200 ml of concentrated ammonium hydroxide (28% NH3) or 40%
3958methylamine is added. Next, isopropyl alcohol is added with stirring until
3959a nice smooth solution is formed. It is not good to add too much alcohol
3960because a more dilute solution reacts slower. Now the mixture is poured
3961into a pipe "bomb." This pipe should be made of stainless steel, and have
3962fine threads on both ends. Stainless steel is preferred because the HBr
3963given off in the reaction will rust regular steel. Both ends of the pipe
3964are securely tightened down. The bottom may even be welded into place. Then
3965the pipe is placed into cooking oil heated to around 130øC. This
3966temperature is maintained for about 3 hours or so, then it is allowed to
3967cool. Once the pipe is merely warm, it is cooled down some more in ice, and
3968the cap unscrewed.
3969    
3970    The reaction mixture is poured into a distilling flask, the glassware  
3971rigged for simple distillation, and the isopropyl alcohol and excess
3972ammonia or methylamine is distilled off. When this is done, the residue
3973inside the flask is made acid with hydrochloric acid. If indicating pH
3974paper is available, a pH of about 3 should be aimed for. This converts the
3975MDA to the hydrochloride which is water soluble. Good strong shaking of the
3976mixture ensures that this conversion is complete. The first stage of the
3977purification is to recover unreacted bromo compound. To do this, 200 to 300
3978ml of ether is added. After some shaking, the ether layer is separated. It
3979contains close to 20 grams of bromo compound which may be used again in
3980later batches.
3981    
3982    Now the acid solution containing the MDA is made strongly basic with
3983lye solution. The mixture is shaken for a few minutes to ensure that the
3984MDA is converted to the free base. Upon sitting for a few minutes, the MDA
3985floats on top of the water as a dark colored oily layer. This layer is
3986separated and placed into a distilling flask. Next, the water layer is
3987extracted with some toluene to get out the remaining MDA free base. The
3988toluene is combined with the free base layer, and the toluene is distilled
3989off. Then a vacuum is applied, and the mixture is fractionally distilled. A
3990good aspirator with cold water will bring the MDA off at a temperature of
3991150g to 160ø C. The free base should be clear to pale yellow, and give a
3992yield of about 20 ml. This free base is made into the crystalline
3993hydrochloride by dissolving it in ether and bubbling dry HCl gas through it
3994as described previously.
3995    
3996    Dr. Shulgin prefers another method of converting the free base to the
3997hydrochloride. Rather than bubbling dry HCl through an ether solution of
3998the free base to get the crystalline hydrochloride, he prefers to dissolve
3999about 25 ml of the free base in about 150 ml of anhydrous isopropyl
4000alcohol, and neutralize this mixture with around 150 drops of concentrated
4001hydrochloric acid. Then the product is precipitated out of solution by
4002adding 300 ml of anhydrous ethyl ether, shaking well and letting the
4003mixture sit for a while before filtering. I do not feel this procedure is
4004as suitable for the production of crystals as the one I have given. There
4005are several reasons for this. First of all, Dr. Shulgin prefers the routes
4006using LAH reductions of the nitrostyrenes. Underground operators must face
4007the facts that LAH and large amounts of anhydrous ethyl ether are not
4008likely to be available. To tout this as the preferred pathway leads to an
4009easy shutdown pinchpoint for the central chemical scrutinizers. There are
4010also methods of using sodium borohydride or sodium cyanoborohydride as the
4011reducing agent for the reductive alkylative (aminative) reaction with
4012phenylacetone to yield amphetamine or methamphetamine. These substances are
4013pretty easily made taboo for the general public; aluminum foil is not. This
4014is the reason for my presentation of the aluminum foil reduction method as
4015the preferred route. It has nothing to do with the narco swine's accusation
4016that I was unfamiliar with this other method. I love to hate these
4017creatures! See the article called "Synthetic Reductions in Clandestine
4018Amphetamine and Methamphetamine Laboratories - A Review," in the
4019pseudoscientific journal, Forensic Science International, Vol. 42 (1989),
4020183-199, by the groveling narco swine, Andrew Allen and Thomas Cantrell. It
4021would be good for these beings to get into private industry where they
4022could be productive.
4023
4024    Back to the reasons why I prefer dry HCl precipitation of the free  
4025base. With a less than 100% pure free base, the resulting crystalline
4026hydrochloride has one hell of a thirst for water. This results in a mush
4027that is better handled by my method. The first few crops of crystals from
4028the HCl bubbling can be kept as same, and the later, more polluted product
4029can be segregated, and this can be given the curative attention it needs
4030through washing with more ether, or recrystallizing from alcohol and then
4031ether. If all I have to face as my nemeses are the likes of Allen and
4032Cantrell, the future is secure for manufacturers everywhere!
4033    
4034--------------------------------------------------------------------------
4035                       Methamphetamine From Ephedrine
4036--------------------------------------------------------------------------
4037    
4038                       Ephedrine and Pseudoephedrine
4039    
4040    Ephedrine and pseudoephedrine are structurally mirror images of each
4041other. This is possible because they have a chiral center, the isopropyl
4042carbon to which the nitrogen atom is attached. If the reduction is done in
4043such a manner that the chiral nature of the substance is not jumbled (i.e.
4044racemization), then ephedrine and pseudoephedrine give rise to "l" and "d"
4045methamphetamine, respectively. The "l" form is several times more potent
4046than the "d" form. Meth produced from phenylacetone is a racemic mixture,
4047meaning that it is a 50-50 mix of the "l" and "d" forms of meth. Obviously,
4048a batch of pure "l" form is most desirable, a racemic mixture is OK, and
4049pure "d" form is bad news.
4050    
4051    Many of the direct and indirect reduction methods retain the chiral  
4052nature of the starting material. A good general rule is if the production
4053method does not use boiling acids, racemization does not occur. One can
4054then conclude that only the direct reduction with palladium black, and the
4055hydroiodic acid and red phosphorus methods lead to racemization of the
4056starting material.  
4057
4058    What then if you are starting with pseudoephedrine, and you want as a
4059result a racemic mixture for a product, but aren't using the palladium
4060black or hydroiodic acid routes? This problem can be sidestepped by
4061dissolving the pseudoephedrine (hydrochloride or sulfate) in some
4062concentrated hydrochloric acid, and boiling it under reflux for a couple
4063hours. The result is a 50-50 mix of ephedrine and pseudoephedrine which
4064upon reduction will give a racemic meth mixture.
4065    
4066        Procedure For Obtaining Pure Ephedrine From Stimulant Pills
4067    
4068    In the present chemical supply environment, the best routes for making
4069meth start with ephedrine as the raw material. To use these routes, a
4070serious hurdle must first be overcome. This hurdle is the fact that the
4071most easily obtained source of ephedrine, the so-called stimulant or
4072bronchodilator pills available cheaply by mail order, are a far cry from
4073the pure starting material a quality minded chemist craves. Luckily, there
4074is a simple and very low profile method for separating the fillers in these
4075pills from the desired active ingredient they contain.
4076    
4077    A superficial paging through many popular magazines reveals them to be
4078brim full of ads from mail order outfits offering for sale "stimulant" or
4079"bronchodilator" pills. These are the raw materials today's clandestine
4080operator requires to manufacture meth without detection. The crank maker
4081can hide amongst the huge herd of people who order these pills for the
4082irritating and nauseating high that can be had by eating them as is. I have
4083heard of a few cases where search warrants were obtained against people who
4084ordered very large numbers of these pills, but I would think that orders of
4085up to a few thousand pills would pass unnoticed. If larger numbers are
4086required, maybe one's friends could join in the effort.
4087    
4088    The first thing one notices when scanning these ads is the large  
4089variety of pills offered for sale. When one's purpose is to convert them
4090into methamphetamine, it is very easy to eliminate most of the pills
4091offered for sale. Colored pills are automatically rejected because one does
4092not want the coloring to be carried into the product. Similarly, capsules
4093are rejected because individually cutting open capsules is just too much
4094work. Bulky pills are to be avoided because they contain too much filler.
4095The correct choice is white cross thins, preferably containing ephedrine
4096HCl instead of sulfate, because the HCl salt can be used in more of the
4097reduction routes than can the sulfate.
4098    
4099    Once the desired supply of pills is in hand, the first thing which  
4100should be done is to weigh them. This will give the manufacturer an idea of
4101how much of the pills is filler, and how much is active ingredient. Since
4102each pill contains 25 milligrams of ephedrine HCl, a 1000 lot bottle
4103contains 25 grams of active ingredient. A good brand of white cross thins
4104will be around 33% to 40% active ingredient. 25 grams of ephedrine HCl may
4105not sound like much, but if it is all recovered from these pills, it is
4106enough to make from 1/2 to  ounce of pure meth. This is worth three or four
4107thousand dollars, not a bad return on the twenty odd dollars a thousand lot
4108of such pills costs.
4109    
4110    To extract the ephedrine from the pills, the first thing which must be
4111done is to grind them into a fine powder. This pulverization must be  
4112thorough in order to ensure complete extraction of the ephedrine from the
4113filler matrix in which it is bound. A blender does a fine job of this  
4114procedure, as will certain brands of home coffee grinders.
4115    
4116    Next, the powder from 1000 pills is put into a glass beaker, or other
4117similar container having a pouring lip, and about 300 ml of  
4118room-temperature distilled water is added. This is stirred at low speed for
411910 minutes. The water is then poured out of the beaker through a filter and
4120set aside. The sludge from the pills is returned to the beaker, and another
4121250 ml of room-temperature distilled water is added. Once again, stir for
412210 minutes, then pour through a filter.
4123    
4124    A little more water can be poured over the sludge to rinse the last of
4125the ephedrine out of it. At this point, the sludge should be nearly  
4126tasteless and gritty in texture. The water filtrate should be clear and
4127very bitter. The filtrate contains all the ephedrine.
4128    
4129    The filtrate is now collected into one beaker and heated over a burner
4130until it reaches a gentle boil. One half of the water is boiled off this
4131way. The liquid is then removed from the heat and poured into a glass
4132baking dish to more slowly evaporate away the remaining liquid. The
4133resulting crystals of ephedrine can then be rinsed with some cold acetone.
4134    
4135    Certain brands of pills are loaded with gummy binders. These brands are
4136recognizable because they are very difficult to crush into a powder, and
4137the hot water extract from them is not easily filtered into a clear
4138solution. When evaporated down to pure extract, they produce a yellow gummy
4139residue at the bottom of the evaporation dish. This gummy mess is not
4140suitable for processing into high grade drugs. The gum is easily removed
4141from the desired product just by adding a few hundred mls of cold acetone
4142to the extract of 1000 stimulant pills, and grinding the gummy mess with a
4143glass rod until the crystals of stimulant are freed from the gum, and a
4144fine dispersion of them floats freely about. The gum colors of acetone
4145yellow, and the floating crystals will be white. Then by filtering this
4146mixture, one obtains the pure crystals of active ingredient free from the
4147polluting binder in the pills.
4148    
4149                             Indirect Reduction
4150    
4151    A popular alternative method for making methamphetamine uses ephedrine
4152as the starting material. This method was not covered in the original
4153edition of this book. It is now presented in all its glory for the  
4154education of the reader.
4155    
4156    The reasons for the popularity of this method are twofold. Firstly,  
4157this method does not require the use of methylamine because the methylamino
4158group is already incorporated in the ephedrine molecule. Secondly,
4159ephedrine is still easily available. It is much more easily obtained than
4160phenylacetic acid. This may change in the future, but at present an
4161underground chemist can buy 1000-lot quantities of stimulant pills
4162(containing 25 milligrams of ephedrine) by mail at very reasonable prices.
4163    
4164    The utility of this method is not limited solely to ephedrine.  
4165Pseudoephedrine and phenylpropanolamine can also be used as starting
4166materials. This means that Sudafed and Dexatrim, and their generic
4167equivalents, can be used as raw materials for clandestine amphetamine
4168manufacture. The active ingredient is easily separated from the diluents in
4169the pills by the method given in this book.
4170    
4171    The bad thing about this method is that foul impurities generated  
4172during the manufacturing process are easily carried into the final product.
4173Due care must be practiced by the chemist during the purifi- cation to
4174exclude this filth. Unscrupulous and/or unskilled manufacturers turn out
4175large volumes of crank containing this abomination. The impurities not only
4176ruin the finer aspects of the meth high, but they also have a pronounced
4177deleterious effect on male sexual function.
4178    
4179    One can quickly see that all a chemist needs to do to turn ephedrine
4180into meth is to replace the alcohol OH grouping with a hydrogen atom. This
4181is not done directly. Instead, a two step process is used whereby the OH is
4182first replaced by a chlorine atom, and then this chlorine is removed by one
4183of several reductive processes, to be replaced with a hydrogen atom. To
4184illustrate:
4185    
4186    [SNiP]
4187    
4188    There are several general methods for converting an alcohol group into
4189a chlorine atom. Substances such as thionyl chloride SOCl2 phosphorus
4190pentachloride (PCl5), phosphorus oxychloride (POCl3), phosphorus bichloride
4191(PCl3), phosphorus pentabromide (PBr5) and phosphorus tribromide (PBr3) can
4192all be used to convert the alcohol group to either a chloride or bromide.
4193Essentially the same reaction conditions are followed when using any of the
4194above listed substances. The only difference is how much ephedrine or PPA
4195(phenylpropanolamine) the substance can chlorinate or brominate. See the
4196table below:
4197    
4198        Substance       Molecular       Reacts with this many
4199                        Weight          moles of ephedrine
4200    
4201        SOCl2           119             1
4202        PCl3            137             2
4203        POCl3           153             2
4204        PBr3            271             2
4205        PCl5            208             3
4206        PBr5            430             3
4207    
4208            molecular weight of ephedrine HCl=202, PPA-HCl = 188
4209    
4210    Using the above table, a person can quickly calculate how much  
4211ephedrine or PPA will react with a given amount of chlorinating agent. Use
4212of excess chlorinating agent will result in a higher percentage yield based
4213on the ephedrine used, but after a point,  this is wasteful. The following
4214example takes this largess to an  extreme, but achieves 100% conversion of
4215ephedrine to  chlorephedrine. This procedure can be followed with all the
4216chlorinating agents. The reaction is fairly easy to do. The main
4217precautions are to make sure that the glassware is free of water, and
4218taking one's time to be sure the mixture stays sufficiently cold. It is
4219also wise to avoid doing this reaction in very humid conditions.
4220    
4221    To convert ephedrine to chlorephedrine, a 2000 ml 3-necked flask is
4222nestled into a bed of ice. A mechanical stirrer is put down the middle neck
4223of the flask as in the preparation of butyl nitrite. One of the outside
4224necks is plugged by sticking a cork into it. The other neck is used as a
4225chemical addition portal. Into this neck, 360 ml of chloroform is added.
4226Then 360 grams of PCl5 is added. When this mixture has cooled down (about
42271/2 hour), 240 grams of ephedrine hydrochloride is added to the brew. It is
4228added by placing a small plastic funnel into the neck of the flask. This
4229ensures that it falls into the mix, rather than being scattered along the
4230walls of the flask. The ephedrine hydrochloride is added in small portions
4231over a 45 minute period. Stirring is fast enough that the PCI5 remains in
4232suspension, and the ephedrine hydrochloride quickly mixes into the brew.
4233Adjusting the angle of the funnel so that it aims the ephedrine HCI toward
4234the center of the whirlpool is a fine point that gives best results.
4235    
4236    The serious experimenter may wish to try replacing the chloroform
4237solvent with l,l,l-trichloroethylene. This very cheap solvent can be found
4238in hardware stores, and has solubility characteristics similar to
4239chloroform. No doubt a greater quantity of trichlorethylene would have to
4240be used, but it would take another item out of the chemical supply loop.
4241    
4242    When all of the ephedrine HCl has been added, an additional 60 ml of
4243chloroform is added. Then the funnel is replaced with another cork, and the
4244stirring is turned up a bit. The stirring is continued for two hours. Then
4245the stirring is turned off, and the flask is allowed to sit for 45 minutes
4246or so. During this period, the unreacted PCl5 settles to the bottom of the
4247flask. At the cold temperature inside the flask, some crystals of ephedrine
4248HCl will appear floating on the surface of the brew.
4249    
4250    When all has settled inside the flask, the mixture IS carefully  
4251decanted off into a one gallon glass jug. Great care is taken during this
4252decanting to make sure that all of the settled PCl5 remains behind. If any
4253of it were mixed in with the product chlorephedrine it would be reduced in
4254the succeeding hydrogenation to phosphine, PH3, an exceedingly deadly gas.
4255If it appears any is being carried along, the mixture is filtered.
4256    
4257    Next, the product is precipitated from the chloroform solution in the
4258gallon jug. This is done by slowly adding ether or, better still, mineral
4259spirits (cheap and easily available in large amounts) to the gallon jug
4260until it is nearly full. The mixture in the gallon jug is continuously
4261stirred during the addition of the ether or mineral spirits for best
4262results. Chlorephedrine does not dissolve in ether or mineral spirits, so
4263as the solution changes from chloroform to predominantly ether, the product
4264is thrown out of solution in the form of crystals. If an oily layer forms
4265at the bottom of the jug, this means a dirty batch. The oil may eventually
4266crystallize, but more likely it must be separated, dissolved in an equal
4267volume of chloroform, and precipitated once again by adding ether or
4268mineral spirits.
4269    
4270    After the addition of the ether or mineral spirits, a large mass of  
4271crystals fills the jug. This is the product. The jug is stoppered, and put
4272into the freezer for an hour to let the crystals fully grow. The crystals
4273are then filtered out and rinsed down with a little bit of cold acetone.
4274Then the crystals are spread out to dry on china plates or glass baking
4275dishes. The yield of chlorephedrine hydrochloride is in the neighborhood of
4276250 grams.
4277
4278                             Production of Meth
4279    
4280    To make meth from chlorephedrine, the chlorine atom is replaced with a
4281hydrogen. This reduction is accomplished by any of several methods. Lithium
4282aluminum hydride does the best job of completely converting the
4283chlorephedrine into meth, but it is very expensive, and a watched chemical.
4284Zinc dust, on the other hand, is cheap and easily available, but it leaves
4285a large proportion of the chlorephedrine unconverted. The most practical
4286and effective way to turn out large volumes of meth is by catalytic
4287hydrogenation. It is possible to use Raney nickel as the catalyst for this
4288hydrogenation, but it has to be used in quite large amounts to do a good
4289job. Potassium Hydroxide (KOH) also has to be added to the bomb in an
4290amount equal to the chlorine given off by the chlorephedrine, i.e., one
4291mole of chlorephedrine would require one mole of KOH added. Platinum can
4292also be used to reduce the chlorephedrine, but it too has to be used in
4293large amounts to get good results. Furthermore, it is rapidly poisoned by
4294the chlorine and becomes useless.
4295    
4296    The best catalyst to use for this reduction is palladium, in the form  
4297of palladium black on charcoal, or palladium on barium sulfate. The
4298palladium stands up well to the chlorine, and can be used to run many
4299batches before it needs to be recycled. Palladium works fine at low
4300pressures of hydrogen, and can be used with the champagne bottle
4301hydrogenation system pictured in Chapter 11.
4302
4303    To do the reaction, a champagne bottle of at least 1.5 liters volume is
4304filled with 50 grams sodium acetate (anhydrous) and 700 ml of distilled
4305water. The pH of this solution is then made neutral (pH 7) by dripping in
4306diluted acetic acid. This forms an acetic buffer which prevents the
4307solution from becoming acidic when chlorephedrine hydrochloride is added to
4308it. It also neutralizes the hydrochloric acid formed when the chlorine atom
4309is removed from the chlorephedrine molecule. Then 40 grams of 5% palladium
4310black on charcoal (palladium content 2 grams) is added, and finally 125
4311grams of chlorephedrine hydrochloride is added.
4312    
4313    Sodium acetate is now on California's list of less restricted  
4314chemicals, so it is wise to avoid using sodium acetate as such. This is not
4315the least bit troublesome, and shows just how stupid the people are who put
4316it on the restricted list. To avoid the need for sodium acetate purchases,
4317acetic buffer is made from vinegar and sodium hydroxide. To do this, 700 ml
4318of vinegar is used instead of distilled water. It should be the cheapest
4319grade of white distilled vinegar, because this is likely to be made just by
4320diluting glacial acetic acid with water down to a 5% strength. Then to this
4321700 ml of vinegar, sodium hydroxide pellets are slowly added until the pH
4322of the solution is around 7. This takes about 23 grams of NaOH.
4323    
4324    The champagne bottle is then attached to the hydrogen line pictured in
4325Figure 17 in Chapter 11, and the air is sucked out and replaced with
4326hydrogen as described in that chapter. Then the pressure of hydrogen is
4327increased to 30 pounds, and magnetic stirring is begun. The solution soaks
4328up hydrogen for several hours, during which time the pressure is maintained
4329around 30 pounds by letting more hydrogen into the bottle.
4330    
4331    When absorption of hydrogen ceases after several hours, the reaction is
4332complete. The hydrogen valve is turned off at the cylinder, and hydrogen
4333inside the bottle released outside through a line of tubing as described in
4334Chapter 11. Stirring is stopped, and the palladium on charcoal catalyst is
4335allowed to settle in the bottle. When it has settled, the solution is
4336carefully poured out of the bottle into a beaker, taking care to try to
4337leave all the catalyst behind in the bottle. The solution is then filtered
4338to remove suspended Pd on charcoal catalyst.  
4339
4340    The catalyst is returned to the bottle, which is then refilled with a   
4341fresh batch, or filled with hydrogen to protect the catalyst.
4342    
4343    Before proceeding further with the processing of the filtered batch, it
4344is wise to look more closely at the nature of the by-products produced by
4345this method of making meth. There are twin villains to be dealt with here:
4346    
4347    These substances, or closely related ones, will always be formed when
4348making meth by this method. The chlorephedrine is the result of incomplete
4349reduction to meth, and the aziridine the result of an intermolecular
4350reaction between the chlorine atom and the nitrogen atom of the
4351chlorephedrine. It is likely that the aziridine by-product is more easily
4352formed when the bromoephedrine variation of this synthetic route is chosen.
4353There are two things which aid in the formation of the aziridine. They are
4354exposure to strong bases such as lye and heat. To minimize formation of the
4355aziridine, one first of all aims for as complete a reduction as possible of
4356the chlorephedrine to meth. Next, during processing, one backs off on the
4357heavy duty use of lye, using bicarb instead to neutralize the last of the
4358acid. Finally, the distillation is done as quickly as feasible under vacuum
4359to get the least heat exposure to the unreduced chlorephedrine. Obviously,
4360the first point is the most important.
4361    
4362    To proceed, the filtered batch is reacted with lye with strong shaking
4363until litmus paper says that the pH is around 7. Then bicarb is added to
4364finally make the solution basic. The fizzing and venting of CO2 gas is a
4365hassle at this point, but it is worth it to avoid the formation of the
4366aziridine. A 2000 ml flask is a good vessel in which to do the
4367neutralization procedure. One must periodically vent off the built up CO2
4368gas after bicarb has been added.
4369    
4370    Upon standing after the shaking, a layer of meth floats on top of the
4371water layer. Then 200 ml of benzene or toluene is added, and the jug is
4372shaken again. After standing for a couple of minutes, the benzene-meth
4373layer floats nicely upon the water. This is carefully poured off into a sep
4374funnel, and the benzene-meth layer is poured into a 500 ml round bottom
4375flask. The water layer is discarded.
4376    
4377    Next, the product is distilled as described in Chapter 5. Here also is
4378a point at which lazy or unskilled operators err and thereby leave their
4379product polluted with chlorephedrine. You see, it is next to impossible to
4380completely convert the chlorephedrine into meth. The conversion can be
4381encouraged by using plenty of catalyst, sufficient pressure, and ample
4382reaction time in the bomb, but there will still be some left unreacted. As
4383the catalyst wears out from doing repeated batches, the proportion of
4384chlorephedrine in the product will increase. Only by doing careful
4385fractional distillation, can the chlorephedrine be removed.
4386Chlorephedrine's solubility characteristics are so similar to meth's that
4387it can't be removed by crystallization or rinsing the crystals. When doing
4388the distillation, the meth distills at the usual temperature range. The
4389next fraction which distills is chlorephedrine. Since this chlorephedrine
4390can then be cycled back into the hydrogenation step, it makes both economic
4391and ethical sense to remove it from the product. By skipping the fractional
4392distillation, lazy operators costs themselves an added measure of meth
4393yield from their raw material inputs.
4394    
4395    The chlorephedrine free base thusly obtained is too unstable to keep as
4396such. Its must immediately be reacted with HCI to form the hydrochloride.
4397    
4398                    Palladium Black on Carbon Catalysts
4399    
4400    Since palladium black on carbon catalyst is on the narco swine's watch
4401list of chemicals, it is wise for the operator to make his own supply.
4402Luckily, this is not too difficult, and gives a catalyst that is fresher
4403and more active than off the shelf catalysts.   
4404
4405    To make the catalyst, the chemist first obtains Norit or Darco brand
4406activated charcoal, and washes it with nitric acid. This is done by
4407measuring out about 100 grams of the charcoal, and then putting it into a
4408beaker along with 10% nitric acid. They are mixed together into a watery
4409slurry, and heated on a steam bath or in a boiling water bath for 2 or 3
4410hours. After the heating, the carbon is filtered and rinsed liberally with
4411distilled water until the last traces of acid are rinsed from it. This
4412requires about a gallon of water.
4413    
4414    The acid washed carbon is then transferred to a 4000 ml beaker. A few
4415grams of the carbon sticks to the filter paper and is otherwise lost, but
4416this is OK since the idea is to get about 93-95 grams of carbon into the
4417beaker. 1200 ml of distilled water is added to the beaker, and it is heated
4418with stirring to 80ø C. When this temperature is reached, a solution of 8.2
4419grams of palladium chloride in 20 ml of concentrated hydrochloric acid and
442050 ml of water is added. This acid solution of palladium chloride is heated
4421for a couple of hours before it is added, because PdCl2 dissolves slowly in
4422the acid solution. It is not added until all the PdCl2 is dissolved. If
4423PdCl2 dihydrate is used, the amount used is increased to 10 grams.
4424    
4425    When the PdCl2 solution has been added and stirred in, 8 ml of 37%
4426formaldehyde solution is added and mixed in. Next, the solution is made
4427slightly alkaline to litmus by adding 30% sodium hydroxide solution to the
4428beaker dropwise with constant stirring. Once the solution has become
4429slightly alkaline to litmus paper, the stirring is continued for another
4430five minutes.
4431    
4432    Next, the solution is filtered to collect the palladium black on  
4433charcoal catalyst. It is rinsed ten times with 250 ml portions of distilled
4434water. Then after removing as much water as possible by filtration, the
4435catalyst is spread out to dry in a glass baking dish. It is not heated  
4436during the drying process since it could burst into flames. When it has
4437dried, it is stored in a tightly stoppered bottle and used as soon as
4438possible. This process gives about 95 grams of 5% palladium black on
4439charcoal catalyst.
4440    
4441                              Direct Reduction
4442    
4443    This section deals with the direct conversion of ephedrine,  
4444pseudoephedrine, or phenylpropanolamine to meth or benzedrine respectively.
4445This conversion can be accomplished by one of four methods. These four
4446methods will be covered and explained in the order of best method to worst
4447method. These conversions are all possible because ephedrine,
4448pseudoephedrine, and phenylpropanolamine are all benzyl alcohols, and
4449benzyl alcohols are the easiest of all alcohols to reduce to the
4450corresponding hydrocarbon.
4451    
4452    These methods all have the advantage of being quick and simple, but
4453they also have their unique disadvantages, along with the general shared
4454disadvantage that the starting material must be gathered bits at a time
4455from bottles of pills.
4456
4457            Method 1: Lithium Metal in Liquid Ammonia Reduction
4458    
4459    This is a new method, and is the best one I've seen come down the pike
4460in ages. This procedure was pioneered by a clandestine operator in
4461California. Unfortunately, he was busted because he bought a jug of
4462ephedrine to use as his starting material. Had he been more cautious, and
4463isolated the ephedrine from legal pills, he may well have gone undetected.
4464This method is ideally suited for the rapid production of truly massive
4465amounts of crank. It suffers from the need to use liquid anhydrous ammonia.
4466This is very smelly stuff, especially in the quantities needed to make
4467large amounts of meth. The smell problem means that this method can only be
4468used in countryside locations, preferably in a large shed with a strong
4469breeze passing through it. In this way, the production masters can position
4470the reaction so that they are upwind from the fumes.
4471    
4472    The countryside location has the further advantage that tanks of  
4473anhydrous ammonia are not at all out of place in such a location. In every
4474agricultural area, tanks of anhydrous ammonia ply the roads all through the
4475growing season. Farmers use it for nitrogen fertilizer on their crops,
4476especially corn. The local co-op hauls out the tank to the farmer, who then
4477applies it to his crops at his leisure. The implication of this is obvious.
4478A well thought out large scale meth production scheme would center upon
4479renting some nondescript piece of land, planting some corn on it, and then
4480getting a tank of "anhydrous" to fertilize the crop. The resulting product
4481will pay much better than corn. A less well thought out plan would involve
4482getting a tank of anhydrous ammonia from a chemical supplier and taking it
4483to a countryside location for further use. In either case, the ammonia is
4484of the same grade.
4485    
4486    This method of making crank is based on the research of Gary Small and
4487Arlene Minnella as published in the Journal of Organic Chemistry, Volume
448840, pages 3151 to 3152 (1975). The article is titled "Lithium-Ammonia
4489Reduction of Benzyl Alcohols to Aromatic Hydrocarbons. An Improved
4490Procedure." It results in the 100% conversion of ephedrine, pseudoephedrine
4491or PPA in a reaction time of 10 minutes or so.
4492    
4493    A disadvantage of this procedure is that it demands the use of the free
4494bases of ephedrine or PPA. Since the material as isolated from the pills
4495will be either the hydrochloride or sulfate salt, a free basing and
4496subsequent distillation is called for to get pure free base, free from salt
4497and traces of water, which would interfere with this reaction.
4498    
4499    A good procedure to follow to get this pure free base is to dissolve
4500the hydrochloride salt in alcohol, and add NaOH or KOH pellets to the
4501solution until the hydrochloride is all neutralized, and then distill off
4502the alcohol, and finally collect the free base by vacuum distillation. The
4503boiling point of ephedrine is around 225øC at normal pressure, and 135øC at
450412 mmHg vacuum. For PPA, the boiling point is a little bit lower. In doing
4505this distillation, the condenser should not have water flowing through it
4506because the free bases melt at 77øC and 101øC respectively. If cold water
4507should flow through the condenser, it would plug up with the solid.
4508Instead, the condenser should be filled with water, and it should be
4509allowed to stay in there until it nears boiling. Then a bit of fresh water
4510can be flowed in. The receiving flask should be packed in ice to assure
4511that all the free base is condensed there.
4512    
4513    This method is superior to dissolving the hydrochloride in water and
4514neutralizing the salt with NaOH in that solvent and then trying to extract
4515out the free base with ether or toluene, and then proceeding with the
4516distillation, because the free bases are soluble in water and form
4517hydrates. They also distill with steam. However, when using the sulfate
4518salt as raw material, one may have no choice but to use the latter method
4519because the sulfate salts do not dissolve well in alcohol.
4520
4521    With a supply of free base in hand, it is now time to consider the  
4522lithium metal in ammonia reduction method. A very good review of this
4523procedure can be found in the book Reduction: Techniques and Applications
4524in Organic Synthesis by Augustine, pages 98 to 105. At the heart of this
4525method is the fact that lithium metal, or sodium metal, or even potassium
4526metal can dissolve in liquid ammonia to form blue colored solutions that
4527have powerful reducing properties. Such solutions are often referred to as
4528"dissolved electrons." These solutions are stable unless water gets in
4529them, or unless they are contaminated with iron from the ammonia tank. When
4530the free bases of ephedrine or PPA are added to these "dissolved
4531electrons," they are quickly and easily reduced to meth or benzedrine
4532respectively. To do the reaction, a 3000 ml round bottom 3 necked flask is
4533set inside a styrofoam tub. The purpose of the tub is to provide
4534insulation, because once liquid ammonia gets out of the cylinder it starts
4535to rapidly boil away until the liquid is lowered to its boiling point of
4536-33øC. This boiling can be kept under control by adding dry ice to the tub.
4537If a cylinder of ammonia is being used, it is a good idea to cool it down
4538before use by putting it in a freezer. With a tank from the co-op, this is
4539not practical. To get the liquid ammonia out of the tank or cylinder,
4540either clear plastic tubing or rubber tubing is placed over the exit valve
4541of the tank or cylinder, and run into the 3 necked flask. Use of metal, and
4542especially copper, is to be avoided. Then the cylinder is tipped upside
4543down, so that the valve is at the bottom of the cylinder. This assures that
4544liquid comes out rather than gas. Next the valve is cautiously cracked
4545open, and liquid ammonia is run into the flask until it is about 1/2 full.
4546It will quickly boil away until the volume of the ammonia is down to about
45471000 ml, and then more slowly because the ammonia has cooled to its boiling
4548point. Then wearing rubber gloves and eye protection to keep the fumes out
4549of the eyes, a magnetic stirring bar is placed in the flask, and the tub is
4550put on a magnetic stirrer, and stirring is begun. Now 14 grams of lithium
4551metal is put into the flask. Lithium usually comes in the form of turnings
4552inside a sealed glass ampule under inert atmosphere. It can be used
4553directly as such. If lithium wire is being used, it should be cut into  
4554short lengths, and rinsed off with petroleum ether prior to use. The
4555lithium metal quickly dissolves, forming a blue solution. Next, 500 ml of
4556tetrahydrofuran is added to this solution. The purpose of the THF is to aid
4557in the dissolution of the ephedrine or PPA which is to be added next. I can
4558see no reason why anhydrous ether can't be used instead of THF, if this is
4559easier to obtain. Next 110 grams of ephedrine (or 100 grams of PPA) is
4560dissolved in 500 ml of THF or ether, and this solution is added to the
4561lithium in ammonia solution over a period of 10 minutes. After allowing the
4562reaction to proceed for an additional 10 minutes, the reaction is quenched
4563by slowly adding water to the ammonia. This is done dropwise at first, and
4564then more rapidly until the blue color disappears from the ammonia
4565solution. The flask is then taken out of the styrofoam tub, and the ammonia
4566is allowed to evaporate overnight. When the ammonia is gone, some more
4567water is added to the remaining ether (or THF) solution to dissolve the
4568salts of lithium in the bottom of the flask. After separating the water
4569layer, the ether layer is dried using anhydrous sodium sulfate, and the
4570meth or benzedrine is obtained as the hydrochloride salt by bubbling HCl
4571gas through the ether solution as described back in Chapter 5. Distillation
4572is unnecessary because of the lack of formation of by products in this
4573reduction. It would just be a colossal waste of ether.
4574    
4575    One may justifiably ask now, "How is this such a great mass production
4576method, when one is only getting 100 grams of product out of each batch?"
4577The answer is that the work can easily be organized so that one batch after
4578another is quickly turned out by this method. Each individual batch only
4579requires a few minutes of attention. After one flask is filled with
4580ammonia, another may be set up and filled, resulting in a virtual assembly
4581line procedure.
4582    
4583    Before moving on here, there is a possible complication which must be
4584addressed. This is the possibility that a tank of ammonia may only be
4585putting out ammonia gas, rather than spewing liquid. This is no great
4586hassle. In that case, the 3000 ml 3 necked flask is well packed in dry ice,
4587and rubbing alcohol poured on the dry ice to create a very cold bath. When
4588the ammonia gas hits the very cold flask, it will be condensed to a liquid.
4589This may actually be a better procedure because it will assure that the
4590ammonia does not have dissolved iron in it from the tank. Iron interferes
4591with some lithium in ammonia reductions. I am not sure whether that is the
4592case with this particular reaction. Input from serious experimenters is
4593welcome.
4594    
4595    It is also possible to use sodium metal or potassium metal in this  
4596reaction. Sodium is much cheaper than lithium, but is on the California
4597list of less restricted chemicals. Use of sodium may also result in partial
4598reduction of the benzene ring. For details on this modified procedure, see
4599the aforementioned Journal of Organic Chemistry article. I suspect that the
4600partial benzene ring reduction could be avoided if sodium metal were used
4601in the procedure given here rather than the modified procedure using sodium
4602given in the JOC article. That procedure uses ethanol instead of THF.
4603Allowance would have to be made in calculating how much sodium metal to use
4604for the greater atomic weight of sodium (23 versus 7).
4605    
4606                     Method 2: Wolff-Kishner Reduction
4607    
4608    This method of directly reducing ephedrine, pseudoephedrine, or  
4609phenylpropanolamine to meth or benzedrine uses hydrazine hydrate as the
4610reducing agent. The Wolff-Kishner reduction is generally used to  
4611deoxygenate ketones to the corresponding hydrocarbon, but in this case, it
4612can be used on these particular substances to reduce them. No doubt, this
4613is because the benzyl alcohol grouping has a ketone nature due to
4614tautomerism.
4615    
4616    The Wolff-Kishner reduction has the advantage of not producing great
4617plumes of stink. It could likely be done in an urban setting without
4618arousing the suspicions of nosey neighbors. Further, the reactants are only
4619moderately expensive, and not tightly controlled at present. Fair amounts
4620of product can be turned out at a rate of one batch per day.
4621    
4622    The disadvantages of this method are twofold. First, hydrazine is a  
4623carcinogen. The chemist must wear gloves while doing the reaction, and do a
4624careful clean-up when finished. If any should be spilled on the skin, a
4625serious, prolonged, and immediate shower is called for. Care must further
4626be taken that the fumes of hydrazine are not breathed in, as this could
4627cause the same problem. Ever try giving your lungs a shower? The other
4628disadvantage to using this method is that the free bases must be used. This
4629necessitates the free basing and distillation procedure described in Method
46301.  
4631    The mechanism by which this procedure works involves first the
4632formation of a hydrazone by reaction between the ephedrine and hydrazine.
4633Then at the high temperatures at which this reaction is done, the hydrazone
4634loses nitrogen (N2) to form meth. This is illustrated:
4635
4636    To do the reaction, a 3000 ml round bottom flask is placed on a buffet
4637range, and then 1500 ml of diethylene glycol and 336 grams of KOH
4638(potassium hydroxide) pellets are put in the flask. Next a condenser is
4639attached to the flask, and water flow is begun through it. Gentle heating
4640of the flask is now begun, with occasional swirling of the flask to try to
4641dissolve the KOH pellets. The operator must be ready here to quickly remove
4642the buffet range, because once the solution warms up, and the KOH pellets
4643start to dissolve, a great amount of heat is released which could cause the
4644solution to boil wildly and squirt out the top of the condenser. Since
4645diethylene glycol has a boiling point of 245øC, this would definitely not
4646be good stuff to be splashed with. Eye protection is, of course, necessary.
4647The heat source is periodically removed, and then reapplied until the
4648dissolution of the KOH pellets is complete.
4649    
4650    Once the KOH pellets have dissolved, the heat is removed, and the
4651temperature of the solution is allowed to fall to about 80øC. Then 300 ml
4652of hydrazine hydrate (85% to 100% pure material is OK) and either 303 grams
4653of PPA free base or 332 grams of ephedrine free base is added to the flask.
4654The condenser is then immediately replaced, and the mixture is heated with
4655great caution until any exothermic (i.e. heat generating) reaction has
4656passed. Then stronger heat is applied to maintain gentle boiling for one
4657hour.
4658    
4659    Now heating is stopped, and as soon as boiling ceases, the condenser is
4660removed, and the flask is rigged for simple distillation as shown in Figure
46613 in Chapter 3. The stillhead should have a thermometer in it reaching down
4662into the middle of the liquid mass in the flask. A cork or rubber holder
4663for this thermometer is unacceptable because hydrazine attacks these
4664materials. The holder must be made of all glass.
4665    
4666    Now the heat is reapplied, and distillation is commenced sufficiently
4667slowly that the froth does not rise out of the flask. Froth can be broken
4668up by occasional application of weak vacuum, as mentioned back in Chapter
46695. When the temperature of the liquid has reached 200øC or so (around 200
4670ml of distillate will have been collected by that point), the heating is
4671stopped. Once boiling ceases, the stillhead is removed, and the condenser
4672is reinserted into the flask. Now heat is reapplied, and the mixture is
4673boiled gently for 3 additional hours.
4674    
4675    The reaction is now complete, and it is time to get the product. The
4676heating is stopped on the flask, and once it has cooled down, the contents
4677of the flask are poured into 2000 ml of water. The 200 ml of distillate
4678obtained earlier is also poured into the water. This mixture is stirred to
4679get the hydrazine out of the meth layer which floats on the top, and into
4680the water. The solution of KOH in water makes the water fairly hot. Once it
4681has cooled down, 500 ml of toluene is added, and the mixture is shaken. A
4682one gallon glass jug is a good vessel to do this in. The top layer of meth
4683dissolved in toluene is then separated, and distilled as described earlier.
4684The yield is 250 to 275 ml of meth. If a careful fractional distillation is
4685not done, the product may be contaminated with a small amount of hydrazine.
4686This is definitely not good, and may be avoided by shaking the separated
4687meth dissolved in toluene layer with a fresh portion of water.
4688
4689           Method 3: Direct Reduction of Ephedrine With Palladium
4690    
4691    This method is very similar to the indirect reduction of ephedrine. The
4692difference in this case is that here the chlorination and reduction are
4693done simultaneously in a "one pot" process. This has the obvious advantages
4694of being quicker and using fewer chemicals. This method has the further
4695advantage of using ephedrine, pseudoephedrine, or PPA in their
4696hydrochloride or sulfate salt forms, so no free basing or distilling of the
4697raw material inputs is needed. Another advantage is that the chlorination
4698is done using dry HCl gas Since this is easily made from dripping sulfuric
4699acid on table salt, the chemist need never worry about having to get
4700suspicion-arousing chemicals to maintain production.
4701    
4702    There are a couple of drawbacks to the use of this method. First and
4703foremost, the contents of the hydrogenation bomb must be heated to about
470480ø-90øC during the reaction. This leads to a possible danger whereby the
4705champagne bottle hydrogenation bomb may crack and burst due to heat stress.
4706This is a possibility even if it is coated on the outside with fiberglass
4707resin. Another drawback is the need to invest in about $1000 worth of
4708palladium chloride to begin production. The catalyst prepared from this
4709palladium chloride can be used over and over again, but it is still a
4710considerable initial cost.
4711    
4712    To do this reaction, the chemist first prepares palladium black  
4713catalyst. This is done as follows: In a 2000 ml beaker, 50 grams of
4714palladium chloride is dissolved in 300 ml of concentrated hydrochloric acid
4715(laboratory grade, 35-37%). Once it has all dissolved, it is diluted with
4716800 ml of distilled water. Next, the beaker is nestled in a bed of ice that
4717has been salted down. This is an ice-salt bath. The contents of the beaker
4718are stirred occasionally, and once it is cold, 300 ml of 40% formaldehyde
4719solution is added with stirring. After a few minutes, a cold solution of
4720350 grams KOH in 350 ml distilled water is added slowly over a period of 30
4721minutes. The palladium solution must be vigorously stirred during the
4722addition. Now the beaker is removed from the ice, and warmed it up to 60ø
4723for 30 minutes with occasional stirring during the heating.
4724    
4725    When the heating is complete, the beaker is set aside to cool, and for
4726the catalyst to settle. Once the catalyst has settled, the chemist pours
4727off as much of the water solution as possible, without losing any catalyst.
4728Then fresh distilled water is added to the beaker, the catalyst is stirred
4729up to wash it off, then the chemist lets it settle again, and pours off the
4730water. This washing is repeated a total of six times. Finally, the catalyst
4731is suspended in a bit of fresh distilled water, and filtered, preferably
4732through sintered glass to be sure of catching all the catalyst. Any
4733catalyst still clinging to the sides of the beaker are rinsed down with
4734water and poured in with the main body of catalyst. It is wise to rinse off
4735the catalyst again with still another large portion of water while it is in
4736the filtering funnel. This process yields 31 grams of palladium black
4737catalyst, once it has dried. It is important that the catalyst be allowed
4738to dry completely, because the presence of water in the reaction mixture is
4739to be avoided.
4740    
4741    With a supply of catalyst on hand, the chemist can move on to  
4742production. To begin, 600 ml of glacial acetic acid is poured into a 1000
4743ml beaker. Now the glassware is set up as shown in Figure 10 back in
4744Chapter 5. The glass tubing is lead into the acetic acid, and bubbling of
4745dry HCl gas into the acetic acid is begun as described in that chapter. It
4746is a good idea here to magnetically stir the acetic acid solution during
4747the bubbling. The whirlpool formed will help the bubbles of HCl gas to
4748dissolve in the acetic acid, rather than escape and waft away on the
4749breezes. This bubbling is continued until the acetic acid solution has
4750gained 30 grams in weight.
4751    
4752    Next, this acetic acid-HCl mix is poured into the 1.5 liter champagne
4753bottle hydrogenation device along with 60 grams of either ephedrine,
4754pseudoephedrine or PPA (sulfate or HCl salt OK for any of these), and 50
4755grams of palladium catalyst. Since the mixture is going to be magnetically
4756stirred, a magnetic stirring bar, of course, is put in the bottle. Now the
4757apparatus is set up as shown in Figure 17 in Chapter 11. The air is sucked
4758out of the bottle as described in that chapter, and replaced with hydrogen.
4759Pressure is avoided for now until the heating of the bottle contents is
4760well underway. To heat the bottle contents, it is best to use a steam
4761cabinet. One can best make such a cabinet from a styrofoam cooler. (See
4762Figure 22).
4763    
4764    The chemist simply leads steam from a pressure cooker into the  
4765styrofoam party cooler via automotive vacuum tubing. The lid is on the
4766cooler, with a small hole in the lid of the cooler for the top of the  
4767bottle to stick out of, or for the hydrogen line to get in through. It is
4768best to poke a small hole in the side of the cooler near the bottom, and
4769stick some plastic tubing into it. This acts as a drain line to carry away
4770condensed water.
4771    
4772    Now the chemist begins stirring, and once the bottle has warmed up a
4773bit, increases pressure to the 15 to 30 pound range. In about an hour, the
4774reaction is finished. The chemist can tell this because it stops absorbing
4775hydrogen. The heating is then stopped, and the stirring is halted. The
4776hydrogen is vented outside as described back in Chapter 11, and the product
4777solution is carefully poured out of the bottle, taking care not to pour out
4778the palladium catalyst. If any comes out, it is filtered, and the palladium
4779returned to the bottle for the next run.
4780    
4781    The product mixture is poured into a 1000 ml round bottom flask along
4782with a few pumice chips, and the glassware is set up as shown in Figure 3.
4783The chemist distills off 500 ml of acetic acid (b.p. 118øC). This acetic
4784acid can probably be used over a few times in the reaction. Eventually,
4785water will build up in it, rendering it useless.
4786    
4787    The residue left in the distilling flask has the product. Once it has  
4788cooled down, lye water is added to it, and shake vigorously. The solution
4789should be strongly basic. Now toluene is added, the top layer separated
4790off, and this top layer is distilled as described so often in this book to
4791yield a little over 50 grams of meth (or benzedrine if PPA was used). This
4792is about 95% yield.
4793    
4794    A variety of other acids besides HC1 can be used to do this reaction.
4795Sulfuric, phosphoric, and perchloric acids will all form esters with the
4796alcohol grouping of ephedrine, pseudoephedrine or PPA, and this ester can
4797be reduced to yield meth or plain amphetamine. See Chem Abstracts, Volume
479834, column 3761, also Volume 38, column 1219 and Volume 34, column 7297.
4799Also see J. Med. Chem., Volume 9, page 996.
4800    
4801        Method 4: Reduction With Hydroiodic Acid and Red Phosphorus
4802    
4803    In this procedure, the alcohol grouping of ephedrine, pseudoephedrine,
4804or PPA is reduced by boiling one of these compounds in a mixture of
4805hydroiodic acid and red phosphorus. Hydroiodic acid works as a reducing
4806agent because it dissociates at higher temperatures to iodine and hydrogen,
4807which does the reducing. This dissociation is reversible. The equilibrium
4808is shifted in favor of dissociation by adding red phosphorus to the
4809mixture. The red phosphorus reacts with the iodine to produce PI3, which
4810then further reacts with water to form phosphorus acid and more hydroiodic
4811acid. Since the hydrogen atom of the HI is being absorbed by the ephedrine,
4812the red phosphorus acts as a recycler.
4813    
4814    In some reductions, the need for HI is dispensed with just by mixing
4815red phosphorus and iodine crystals in a water solution. The red phosphorus
4816then goes on to make HI by the above mentioned process. With a small amount
4817of due care, this is an excellent alternative to either purchasing,
4818stealing, or making your own pure hydroiodic acid.
4819    
4820    This method has the advantage of being simple to do. It was formerly
4821the most popular method of making meth from ephedrine. Now red phosphorus
4822is on the California list of less restricted chemicals, so an increased
4823level of subterfuge is called for to obtain significant amounts. One might
4824think that this is easily gotten around by making your own red phosphorus,
4825but this is a process I would not want to undertake. Ever hear of
4826phosphorus shells? I would much rather face the danger of exploding
4827champagne bottles. Those who insist upon finding out for themselves, will
4828see Journal of the American Chemical Society, volume 68, page 2305. As I
4829recall, The Poor Man's James Bond also has a formula for making red
4830phosphorus. Those with a knack for scrounging from industrial sources will
4831profit from knowing that red phosphorus is used in large quantities in the
4832fireworks and matchmaking industries. The striking pad on books of matches
4833is about 50% red phosphorus. 
4834
4835    The determined experimenter could obtain a pile of red phosphorus by
4836scraping off the striking pad with a sharp knife. A typical composition of
4837the striking pad is about 40% red phosphorus, along with about 30% antimony
4838sulfide, and lesser amounts of glue, iron oxide, MnO2, and glass powder. I
4839don't think these contaminants will seriously interfere with the reaction.
4840Naturally, it is a tedious process to get large amounts of red phosphorus
4841by scraping the striking pad off matchbooks.
4842    
4843    Another problem with this method is that it can produce a pretty crude
4844product if some simple precautions are not followed. From checking out
4845typical samples of street meth, it seems basic precautions are routinely
4846ignored. I believe that the by-products in the garbage meth are
4847iodoephedrine, and the previously mentioned azirine. (See the previous
4848section concerning chloroephedrine.) If a careful fractional distillation
4849is done, these products can be removed. They can be avoided in the first
4850place if, when making hydroiodic acid from iodine and red phosphorus, the
4851acid is prepared first, and allowed to come to complete reaction for 20
4852minutes before adding the ephedrine to it. This will be a hassle for some,
4853because the obvious procedure to follow is to use the water extract of the
4854ephedrine pills to make HI in. The way around the roadblock here is to just
4855boil off some more of the water from the ephedrine pill extract, and make
4856the acid mixture in fresh pure water. Since the production of HI from
4857iodine and red phosphorus gives off a good deal of heat, it is wise to
4858chill the mixture in ice, and slowly add the iodine crystals to the red
4859phosphorus-water mixture.
4860    
4861    To do the reaction, a 1000 ml round bottom flask is filled with 150  
4862grams of ephedrine hydrochloride (or PPA-HCL). The use of the sulfate salt
4863is unacceptable because HI reduces the sulfate ion, so this interferes with
4864the reaction. Also added to the flask are 40 grams of red phosphorus, and
4865340 ml of 47% hydroiodic acid. This same acid and red phosphorus mixture
4866can be prepared from adding 300 grams of iodine crystals to 50 grams of red
4867phosphorus in 300 ml of water. This should produce the strong hydroiodic
4868acid solution needed. Exactly how strong the acid needs to be, I can't say.
4869I can tell you that experiments have shown that one molar HI is ineffective
4870at reducing ephedrine to meth. The 47% acid mentioned above is a little
4871over 7 molar. I would think that so long as one is over 3 molar acid, the
4872reaction will work.
4873    
4874    With the ingredients mixed together in the flask, a condenser is  
4875attached to the flask, and the mixture is boiled for one day. This length
4876of time is needed for best yields and highest octane numbers on the
4877product. While it is cooking, the mixture is quite red and messy looking
4878from the red phosphorus floating around in it.
4879    
4880    When one day of boiling under reflux is up, the flask is allowed to  
4881cool, then it is diluted with an equal volume of water. Next, the red
4882phosphorus is filtered out. A series of doubled-up coffee filters will work
4883to get out all the red phosphorus, but real filter paper is better. The
4884filtered solution should look a golden color. A red color may indicate that
4885all the phosphorus is not out. If so, it is filtered again. The  
4886filtered-out phosphorus can be saved for use in the next batch. If
4887filtering does not remove the red color, there may be iodine floating
4888around the solution. It can be removed by adding a few dashes of sodium
4889bisulfite or sodium thiosulfate.
4890    
4891    The next step in processing the batch is to neutralize the acid. A  
4892strong Iye solution is mixed up and added to the batch with shaking until
4893the batch is strongly basic. This brings the meth out as liquid free base
4894floating on top of the water. The strongly basic solution is shaken  
4895vigorously to ensure that all the meth has been converted to the free base.
4896    
4897    With free base meth now obtained, the next step, as usual, is to form
4898the crystalline hydrochloride salt of meth. To do this, a few hundred mls
4899of toluene is added to the batch, and the meth free base extracted out as
4900usual. If the chemist's cooking has been careful, the color of the toluene
4901extract will be clear to pale yellow. If this is the case, the product is
4902sufficiently pure to make nice white crystals just by bubbling dry HCL gas
4903through the toluene extract as described in Chapter 5. If the toluene
4904extract is darker colored, a distillation is called for to get pure meth
4905free base. The procedure for that is also described in Chapter 5. The yield
4906of pure meth hydrochloride should be from 100 grams to 110 grams.
4907    
4908    If gummy binders from the stimulant pills are carried over into the  
4909reaction mixture, they produce a next-to-impossible-to-break emulsion of
4910meth, gum, toluene and water when the reaction is done and it is time to
4911extract out the meth. If this reaction is chosen as the production method,
4912one must be sure the gum has been thoroughly rinsed away with acetone from
4913the stimulant crystals. They should be long, white, and needle-like. If
4914this emulsion is encountered, the only way to break it is to first let the
4915emulsion sit in a sep funnel for a few hours. Water will slowly work its
4916way out and settle to the bottom where it can be drained away. The stubborn
4917residual emulsion should be transferred to a distilling flask, and the
4918toluene slowly distilled off through a fractionating column. This removes
4919water from the emulsion as the toluene-water azeotrope. It may be necessary
4920to add additionally toluene to the distilling flask to get all the water
4921removed. It sticks to the glass flask, and causes no further problem. Once
4922the emulsion is broken, distilling should be stopped. The toluene-meth
4923solution should be poured from the distilling flask, and the meth
4924precipitated as hydrochloride as per the usual dry HCl bubbling method.
4925    
4926    
4927    
4928    
4929    
4930
4931--------------------------------------------------------------------------
4932                               Methcathinone
4933--------------------------------------------------------------------------
4934    
4935                          Kitchen Improvised Crank
4936    
4937    The latest designer variant upon the amphetamine molecule to gain
4938popularity and publicity is methcathinone, commonly called "cat." This
4939substance is remarkably similar to the active ingredient found in the
4940leaves of the khat tree which the loyal drug warriors on the network news
4941blame for turning peace loving Somalis into murderous psychopaths. The
4942active ingredient in the khat leaves is cathinone, which has the same
4943structural relationship to methcathinone that amphetamine has to
4944methamphetamine. It is made by oxidizing ephedrine, while meth can be made
4945by reducing ephedrine. 
4946    
4947    The high produced by methcathinone is in many ways similar to  
4948methamphetamine. For something so easily made and purified, it is actually
4949quite enjoyable. The main differences between the meth high and the
4950methcathinone high are length of action and body feel. With methcathinone,
4951one can expect to still get to sleep about 8 hours after a large dose. On
4952the down side, it definitely gives me the impression that the substance
4953raises the blood pressure quite markedly. This drug may not be safe for
4954people with weak hearts or blood vessels. Be warned!
4955    
4956    Cat is best made using chrome in the +6 oxidation state as the  
4957oxidizer. I recall seeing an article in the narco swine's Journal of
4958Forensic Science bragging about how they worked out a method for making it
4959using permanganate, but that method gives an impure product in low yields.
4960Any of the common hexavalent chrome salts can be used as the oxidizer in
4961this reaction. This list includes chrome trioxide (CrO3), sodium or
4962potassium chromate (Na2CrO4), and sodium or potassium dichromate
4963(Na2Cr2O3). All of these chemicals are very common. Chrome trioxide is used
4964in great quantities in chrome plating. The chromates are used in tanning
4965and leather making.
4966    
4967    To make methcathinone, the chemist starts with the water extract of
4968ephedrine pills. The concentration of the reactants in this case is not
4969critically important, so it is most convenient to use the water extract of
4970the pills directly after filtering without any boiling away of the water.
4971See the section at the beginning of Chapter 15 on extracting ephedrine from
4972pills. Both ephedrine hydrochloride and sulfate can be used in this
4973reaction.
4974    
4975    The water extract of 1000 ephedrine pills is placed into any convenient
4976glass container. A large measuring cup is probably best since it has a
4977pouring lip. Next, 75 grams of any of the above mentioned +6 chrome
4978compounds are added. They dissolve quite easily to form a reddish or orange
4979colored solution. Finally, concentrated sulfuric acid is added. If CrO3 is
4980being used, 21 ml is enough for the job. If one of the chromates is being
4981used, 42 ml is called for. These ingredients are thoroughly mixed together,
4982and allowed to sit for several hours with occasional stirring.
4983
4984    After several hours have passed, lye solution is added to the batch
4985until it is strongly basic. Very strong stirring accompanies this process
4986to ensure that the cat is converted to the free base. Next, the batch is
4987poured into a sep funnel, and a couple hundred mls of toluene is added.
4988Vigorous shaking, as usual, extracts the cat into the toluene layer. It
4989should be clear to pale yellow in color. The water layer should be orange
4990mixed with green. The green may settle out as a heavy sludge. The water
4991layer is thrown away, and the toluene layer containing the cat is washed
4992once with water, then poured into a beaker. Dry HCl gas is passed through
4993the toluene as described in Chapter 5 to get white crystals of cat. The
4994yield is between 15 and 20 grams. This reaction is scaled up quite easily.
4995    
4996--------------------------------------------------------------------------
4997                MDA, XTC, and Other Psychedelic Amphetamines
4998--------------------------------------------------------------------------
4999
5000    The psychedelic amphetamines are a fascinating and largely ignored
5001group of drugs. They all have the basic amphetamine carbon skeleton
5002structure, but show effects that are more akin to LSD than to the
5003amphetamines. The LSD-like effect is due to the presence of a variety of
5004"add ons" to the benzene ring of the basic amphetamine structure.
5005Generally, these "add ons" are ether groupings on the 3, 4, or 5 positions
5006on the benzene ring. Because of these "add ons" one can consider these
5007compounds more closely related to mescaline than to amphetamine. Consider
5008the mescaline molecule pictured on page 176.
5009    
5010    Mescaline should by all rights be considered an amphetamine derivative.
5011It has the basic phenethylamine structure of the amphetamines with methyl
5012ether groupings on the benzene ring at the 3,4,5 positions. To be a true
5013amphetamine, it would only need its side chain extended by one carbon,
5014putting the nitrogen atom in the central, isopropyl position. Such a
5015compound does in fact exist. It is called trimethoxyamphetamine, or TMA for
5016short. Its effect are very similar to mescaline in much lower dosage levels
5017than the % gram required for pure mescaline. Its chemical cousin, TMA-2
5018(2,4,5 trimethoxyamphetamine) has similar awe inspiring characteristics.
5019
5020    The most popular and, in my opinion, the best of the psychedelic  
5021amphetamines is the MDA family. This family consists of MDA, and its
5022methamphetamine analog, XTC, or Ecstasy, or  
5023MDMA.MDA(3,4-methylenedioxyamphetamine) gives by far the best high of this
5024group. Its effects can best be described as being sort of like LSD without
5025the extreme excited state caused by that substance. It was popularly known
5026as "the love drug" because of the calm state of empathy so characteristic
5027of its effect. It could also be a powerful aphrodisiac under the right
5028circumstances.
5029    
5030    This substance gradually disappeared during the early 80s due to an
5031effective crimping upon the chemicals needed for its easiest manufacture.
5032    
5033    This crimping, and the drug laws in effect at the time, gave rise to a
5034bastard offspring of MDA. This substance was XTC, or MDMA, the so called
5035Ecstasy of the drug trade. This material was a designer variant of MDA, and
5036so was legal. The chemicals needed to make it could be obtained without
5037fear of a bust. It also lacked the best qualities of its parent. While the
5038addition of a methyl group of the nitrogen of the amphetamine molecule
5039accentuates its power and fine effect, the addition of a methyl group to
5040the MDA molecule merely served to make it legal. As fate would have it, the
5041hoopla surrounding the subsequent outlawing of this bastard child served to
5042make it a more desired substance than MDA. This is typical of black-market,
5043prohibition-driven demand.
5044    
5045    To understand the various routes which can be followed to make these
5046substances, note the structures of MDA and MDMA shown below:
5047    
5048    To make these substances, and the rest of the psychedelic amphetamines
5049for that matter, the manufacturer has a choice of two starting materials.
5050He can use the appropriately substituted benzaldehyde, which in the case of
5051MDA or MDMA is piperonal (heliotropin), or he can use the correspondingly
5052substituted allylbenzene, which in this case is safrole.
5053    
5054    Piperonal was the favored starting material for making MDA, as were the
5055other substituted benzaldehydes for making other psychedelic amphetamines.
5056The supply of these raw materials was effectively shut off. Piperonal does
5057find legitimate use in making perfumes, but considerable determination is
5058needed to divert significant amounts of the stuff into clandestine
5059operations.
5060    
5061    Once obtained, these substituted benzaldehydes could be converted into
5062amphetamines by an interesting variant of the Knoevenagel reaction as
5063described in Chapter 9. They could be reacted in a mixture of nitroethane
5064and ammonium acetate to form the appropriately substituted
50651-phenyl-2-nitropropene. This nitropropene could then be reduced to the
5066amphetamine by using lithium aluminum hydride, or palladium black on
5067charcoal in a hydrogenation bomb. This pathway was further crimped upon by
5068the narco swine by watching for purchases of nitroethane and ammonium
5069acetate in combination. For all practical purposes, this pathway can be
5070considered dead.
5071    
5072    This left safrole, and the other substituted allylbenzenes, as starting
5073materials for psychedelic amphetamine manufacture. This route had the
5074advantage of having a raw material source that was nearly impossible to
5075shut down. For instance, sassafras oil consists of 80-90% safrole. One
5076merely has to distill the oil under a vacuum to get very pure safrole.
5077Similarly, other psychedelic amphetamines can be made from the
5078allylbenzenes naturally occurring in various plant oils. For instance,
5079calamus oil contains a large proportion of B-asarone the starting material
5080for TMA-2. Nutmeg contains a mixture of myristicin (potential MMDA) and
5081elemicin (potential TMA). These oils are all available from herbal supply
5082shops and dealers in the occult. Even without this source, the oils can be
5083easily obtained from the plants.
5084    
5085    The reason why the markets have not been flooded with psychedelic
5086amphetamines via the allylbenzene source is because the only method for
5087converting them into amphetamines that was widely known is very cumbersome.
5088For instance, the only method for making MDA from safrole that was listed
5089in Psychedelic Chemistry was the old tedious route. This route called for
5090first converting safrole to isosafrole by the action of alcoholic KOH at
5091243øC for 3 minutes. This isosafrole could then be converted to MDA
5092phenylacetone by a very messy and inefficient method using hydrogen
5093peroxide in a solution of acetone and formic acid. This step is so poor
5094that it rendered the whole route unworkable. Finally, the MDA phenylacetone
5095could be made into MDA by one of several methods. It is interesting that
5096Michael Valentine Smith copied the printing error that appeared in Chem
5097Abstracts concerning this last step into his book.
5098    
5099    Luckily, the relentless advance of chemical science has lifted this  
5100roadblock. The same method which was earlier described for converting
5101allylbenzene into phenylacetone is equally useful for converting
5102substituted allylbenzenes directly into the corresponding substituted
5103phenylacetones. The yield in these reactions is nearly as good as for
5104phenylacetone itself, and the procedure is just as easy.
5105    
5106    The first problem which confronts the chemist in the process of turning
5107sassafras oil into MDA or MDMA is the need to obtain pure safrole from it.
5108In spite of the fact that crude sassafras oil consists of 80-90% safrole,
5109depending on its source, it is a good bet that the impurities will lower
5110the yield of the desired product. The axiom "garbage in, garbage out" was
5111custom made for organic chemistry reactions. It is simplicity itself to
5112turn crude sassafras oil into pure safrole, and well worth the effort of
5113underground chemists bent on MDA production.
5114    
5115    Sassafras oil is an orange colored liquid with a smell just like  
5116licorice. It is a complex mixture of substances which is easily purified by
5117distilling. To obtain pure safrole from sassafras oil, the glassware is set
5118up as shown in Figure 5 in Chapter 3. The distilling flask is filled about
51192/3 full of sassafras oil, along with a few boiling chips, and then vacuum
5120is applied to the system. A little bit of boiling results due to water in
5121the oil, but heat from the buffet range is required to get things moving.
5122Water along with eugenol and related substances distill at the lower
5123temperatures. Then comes the safrole fraction. The safrole fraction is
5124easily spotted because the "oil mixed with water" appearance of the watery
5125forerun is replaced with a clear, homogeneous run of safrole. When the
5126safrole begins distilling, the collecting flask is replaced with a clean
5127new one to receive it. The chemist is mindful that the safrole product is
512880-90% of the total volume of the sassafras oil. Under a vacuum, it boils
5129at temperatures similar to phenylacetone and methamphetamine. When all the
5130safrole has distilled, a small residue of dark orange colored liquid
5131remains in the distilling flask. The distilled safrole is watery in
5132appearance, and smells like licorice.
5133    
5134    With a liberal supply of safrole obtained by distilling sassafras oil,  
5135work can then commence on converting it into 3,4
5136methylenedioxyphenylacetone. This is done in exactly the same manner as
5137described in Chapter 10. As was the case in that chapter, the chemist has
5138the choice of the palladium-wasteful method, and the palladium-conserving
5139method. As was the case in the earlier chapter, the yield of product is
5140about 10% higher using the palladium-wasteful method. The yield is about
514193% for the wasteful method, versus about 83% for the conserving method.
5142The sole difference in the safrole conversion reaction is that in this
5143case, palladium bromide is used instead of the palladium chloride used to
5144convert allylbenzene. Since palladium bromide has a higher molecular weight
5145than palladium chloride, the amount of palladium salt used in this case is
5146increased by a factor of 1.5.
5147    
5148    The methylenedioxyphenylacetone obtained from this reaction can be used
5149in a crude state by boiling off the solvents from it under a vacuum, or it
5150can be distilled under a vacuum to yield pure material. The boiling point
5151of this phenylacetone is around 180øC at a pressure of 15 torn The color of
5152the distilled material is clear to pale yellow.
5153    
5154    With the methylenedioxyphenylacetone obtained in this manner, the
5155chemist proceeds to make it into XTC by one of the methods used to turn
5156phenylacetone into meth. Of all the methods to choose from, the most
5157favored one would have to be reductive alkylation using the bomb and
5158platinum catalyst. The free base is converted into crystalline  
5159hydrochloride salt in exactly the same manner as for making meth crystals.
5160It is interesting to note here that XTC crystals will grow in the form of
5161little strings in the ether solution as the HCl gas is bubbled through it.
5162Once filtered and dried, it bears a remarkable resemblance to meth
5163crystals. It generally has a faint odor which reminds one of licorice.
5164    
5165    To make MDA from the methylenedioxyphenylacetone, one has two good
5166choices. Choice number one is to use the reductive amination method without
5167the bomb using activated aluminum as the reducer. In this case, 28% ammonia
5168solution in water (ammonium hydroxide, NH4OH) is used instead of 40%
5169methylamine in water. The amount of ammonia solution used is doubled over
5170the amount of methylamine solution used. Other than that, the reaction
5171proceeds just as in the case for meth and gives a yield around 40%. The
5172next best method is to use the bomb with Raney nickel catalyst and ammonia.
5173This gives a yield around 80% if plenty of Raney nickel is used. The
5174drawback to this method is the need for a shaker device for the bomb, and
5175also a heater. The use of platinum as the catalyst in the bomb works great
5176when making MDMA, but gives lousy results when making MDA. There may be a
5177way around this, however, for serious experimenters. It has been found in
5178experiments with phenylacetone that a mixture of ammonia and ammonium
5179chloride produces good yields of amphetamine (50%) when used in a bomb with
5180platinum catalyst. Methylenedioxyphenylacetone is quite likely to behave
5181similarly.
5182    
5183    To use this variation, the following materials are placed in the 1.5  
5184liter champagne bottle hydrogenation device: .5 gram platinum in 20 ml
5185distilled water. If this platinum is in the form of PtO2 instead of the
5186reduced platinum metal catalyst obtained with borohydride, the experimenter
5187must now reduce the platinum by pressurizing the bottle with hydrogen and
5188stirring for about an hour. Next 100 ml of methylenedioxyphenylacetone is
5189added along with 40 grams NH4Cl, 500 ml methyl alcohol saturated with
5190ammonia gas, and 50 ml NH4OH. The bottle is then set up as seen in Figure
519117. and the hydrogenation is done as described in that section.
5192    
5193    When the reaction is over, the contents of the flask are filtered to  
5194remove the platinum metal for reuse. Some crystals of NH4Cl are also
5195filtered out; they are rinsed down with some water to remove them.
5196    
5197    Next the filtered batch is poured into a 1000 ml round bottom flask, a
5198few boiling chips are added, and the glassware is set up for refluxing.
5199Plastic tubing is attached to the top of the condenser and led outside. The
5200mixture is boiled under reflux for one hour to force out the excess
5201ammonia.
5202    
5203    Next, the solution is allowed to cool, and made acid to congo red  
5204(about pH 3) with hydrochloric acid. Now the glassware is set up as shown
5205in Figure 3, and the solution is evaporated to about one half its original
5206volume under vacuum. A fair amount of crystalline material forms during the
5207acidification and vacuum evaporation.
5208    
5209    Next, 400 ml of water is added to the solution, and then it is  
5210extracted with about 100 ml of toluene. The toluene layer is thrown away
5211because it contains garbage. The batch is now made strongly basic by adding
5212lye water to it. It should be remembered here that it is very important to
5213shake the batch well once it has been basified to make sure that the MDA
5214hydrochloride gets neutralized. Finally, the MDA is extracted out with a
5215few hundred ml of toluene, and distilled under vacuum. The boiling point is
5216about 170øC under aspirator vacuum. The yield is about 50 ml.
5217    
5218    The other good choice of a method for converting  
5219methylenedioxyphenylacetone into MDA is the Leuckardt reaction. In this
5220case, formamide is used instead of N-methylformamide. The formamide is of
5221the 99% pure grade. 98% formamide is good for nothing except making the
5222dreaded red tar. Good luck in finding 99% formamide these days. This
5223reaction is done in exactly the same manner as the reaction with
5224N-methylformamide, except that the reaction temperature is 160ø to 185øC,
5225raised over the course of 24 hours. The yields are excellent. Processing is
5226done as in the case of meth. The formamide is destroyed by boiling with lye
5227solution. In this case the ammonia gas produced is just led away in tubing.
5228The formyl amide is then separated and hydrolyzed with hydrochloric acid
5229solution.
5230    
5231    Another possible route to MDA and other psychedelic amphetamines is the
5232Ritter reaction. It was encountered earlier in Chapter 14. Since safrole
5233and many other plant oil precursors to the psychedelic amphetamines, such
5234as myristicin, are allylbenzenes, this reaction will work for them as well.
5235with some modifications to the process.
5236    
5237    The first modification is that alcoholic KOH is used to hydrolyze the
5238amide instead of HCl solution. Boiling the amide with about 5 to 10 volumes
5239of 10% KOH solution in 190 proof vodka gives better results than
5240hydrochloric acid. Less tar and other by-products will result. 190 proof
5241vodka and rectified spirit is used, not absolute alcohol. Refluxing for
5242about 5 hours does the job.
5243    
5244    To process the product, the underground chemist first boils away most
5245of the alcohol under a vacuum, then adds water to dissolve the KOH, and
5246extracts out the MDA using benzene or toluene. He distills and crystallizes
5247as usual.
5248    
5249    XTC can be obtained from MDA by using the method cited in the Woodruff
5250article referred to in Chapter 14.
5251    
5252    The yield and purity of the MDA obtained from the Ritter reaction is
5253somewhat less than with the two step method using palladium salts and
5254nitrites. This disadvantage must be weighted against the fact that the
5255Ritter reaction uses very simple, cheap, and easily available chemicals.
5256
5257    Not all psychedelic amphetamines can be produced in this manner. For
5258instance, B-asarone, the precursor of TMA-2, is a 2propenyl-benzene, rather
5259than an allylbenzene. The breakthrough method will fail in this case, and
5260the Ritter reaction will yield an isoquinoline. To convert
52612-propenylbenzenes directly into amphetamines, a very risky reaction using
5262is used.  See Recreational Drugs by Professor Buzz for details.
5263    
5264    For the same reason of relative molecular weight, if safrole is used in
5265either the phenylacetone from allylbenzene method or in the Ritter
5266reaction, the amount of safrole used is greater by a factor of about 1.35
5267as compared to allylbenzene.
5268    
5269    The recommended dosage of MDA or XTC is about a tenth of a gram of Pure
5270material.
5271    
5272                                 References
5273    
5274                Psychedelics Encyclopedia by Peter Stafford.
5275    
5276                          
5277--------------------------------------------------------------------------
5278                                    Ice
5279--------------------------------------------------------------------------
5280    
5281    At the time of the writing of the second edition, the latest drug craze
5282was the smokable form of methamphetamine called "ice." This material
5283consists of large clear crystals of methamphetamine hydrochloride rather
5284than the snowlike microcrystals produced by the methods described in this
5285book.
5286    
5287    I am not going to endorse or encourage the foolhardy practice of  
5288smoking meth. Seeing firsthand what this stuff does to rubber stoppers,
5289razor blades, and corks, I can only imagine what it does to lung tissue.
5290However, since the godless importers of this material have already made a
5291market for it, it is only right that I help American technology catch up.
5292
5293    I have never made nor used "ice" as such, but I know quite well how to
5294obtain large clear rocklike crystals of meth. There are two routes which
5295can be followed. The first is to simply melt the pure meth crystals and
5296then allow them to slowly cool into a solid mass. This is a piss poor
5297choice because the heat is likely to discolor even very pure meth melted
5298under a nitrogen atmosphere blanket. The accompanying "off" smell and god
5299knows what breakdown products make this a method that only hacks would use.
5300    
5301    A much better method is to take the pure meth crystals, and add just
5302enough absolute alcohol to them to dissolve them. Gentle heating, swirling,
5303and the use of warm alcohol keeps the volume of alcohol used to a minimum.
5304The beaker holding the dissolved meth is then put into a dessicator to
5305prevent the alcohol from soaking up water from the air. If the desiccator
5306has a portal for the attachment of vacuum, this is ideal. Then a vacuum
5307amounting to 1/2 normal pressure is applied, and the solution slowly cools
5308and evaporates its alcohol solvent. The result is a large rocklike mass of
5309meth which can then be chipped off of the beaker.
5310
5311--------------------------------------------------------------------------
5312                           Calibrating The Vacuum
5313--------------------------------------------------------------------------
5314    
5315    Before he starts doing the vacuum distillations described in this book,
5316the underground chemist wants to know what kind of vacuum he is able to
5317produce inside his glassware. This is important because the temperature at
5318which a substance distills under vacuum depends directly on how strong the
5319vacuum is. The distillation temperatures given in this book assume a vacuum
5320of about 20 torr for an aspirator and about 5 torr for a vacuum pump. This
5321chapter describes an easy method by which the chemist finds out just how
5322strong his vacuum is. Once he knows how good his vacuum is, he adjusts the
5323temperatures of his distillations accordingly. The better the vacuum, the
5324lower the temperature at which the substance will distill. He keeps in mind
5325that an aspirator will get a better vacuum in winter because the water
5326flowing through it is colder in that season. The vacuum obtained with a
5327vacuum pump may get poorer over time because solvents from the chemicals he
5328is distilling, such as benzene, may dissolve in the pump's oil. If this
5329happens, he changes the oil.
5330    
5331    To begin, the chemist sets up the glassware for fractional distillation
5332as shown in Figure 5 in Chapter 3. He uses a 500 ml round bottom flask for
5333the distilling flask, and a 250 ml flask as the collecting flask. He uses
5334the shorter condenser, and puts 3 boiling chips in the distilling flask
5335along with 200 ml of lukewarm water. He lightly greases all the ground
5336glass joints. (This is always done when distilling, because the silicone
5337grease keeps the pieces from getting stuck together, and seals the joint so
5338that it doesn't leak under the vacuum).
5339    
5340    He turns on the vacuum full force and attaches the vacuum hose to the
5341vacuum nipple of the vacuum adapter. The water in the distilling flask
5342should begin boiling immediately. As the water boils away, the temperature
5343shown on the thermometer steadily drops. Finally, the water gets cold
5344enough that it no longer boils. He notes the temperature reading when this
5345happens, or, better yet, disconnects the vacuum and takes apart the
5346glassware and takes the temperature of the water in the distilling flask.
5347Using a graph such as the one above, he reads off the vacuum that goes with
5348the boiling temperature.
5349    
5350    If his vacuum is bad, the water will not boil. In that case, he checks
5351to make sure that all the joints are tight, and that the stopper in the
5352claisen adapter fractionating column is not leaking. He also makes sure
5353that his vacuum hose is not collapsed. If, after this, the water still  
5354doesn't boil, he has to heat the water. He turns on the buffet range at low
5355heat while continuing the vacuum. In a while the water begins boiling. He
5356checks the temperature reading on the thermometer while it is boiling, and
5357notes the temperature. From the graph he reads off the vacuum that goes
5358with that boiling point.
5359    
5360    His vacuum should be 50 torr or lower to be able to make  
5361methamphetamine. If his vacuum reading is more than 50 torr, he gets a new
5362aspirator or changes the oil in the vacuum pump.
5363
5364    The chemist can use this information to adjust the temperature at which
5365he collects his distilled product. The boiling temperature of phenylacetone
5366is about 105øC at 13 torr, and about 115øC at 20 torn The boiling
5367temperature of N-methylformamide is about 107øC at 20 torn The boiling
5368temperature of methamphetamine is about the same as phenylacetone.
5369Phenylacetone and methamphetamine should be collected over a 20-degree
5370range centered on their true boiling points. This makes sure that the
5371chemist gets all of it. The purification scheme he goes through before
5372distilling removes all the impurities with boiling points close to that of
5373his product.  
5374
5375--------------------------------------------------------------------------
5376Transcriber's Notes:
5377
5378I have omitted many of the pictures in the book, I want you to see this as
5379a reason to buy the real book instead of this ASCII version. This is a part
5380of my shareware book concept; If you want to have the whole book, then go
5381buy it. You can order it directly from Loompanics Unlimited, PO Box 1197,
5382Port Townsend, WA 98368, USA. A fourth edition is on its way, Fester says.
5383
5384-------------------------------------------------------------------------