23JW9y9L

1HAPPY HALLOWEEN !!!   DIY JACK O LANTERN TEETH :4
2-------------------------------------------
3
4              Secrets of Methamphetamine Manufacture (3rd ed.)
5                              by Uncle Fester
6              
7
8                                INTRODUCTION
9    
10    This book is the result of six years experience in the field of 
11manufacturing methamphetamine. It contains virtually everything I know
12about the subject. There are a lot of secrets in this area, hence the title
13Secrets of Methamphetamine Manufacture.
14    
15    A thorough review of the scientific literature on this subject will 
16show that the descriptions of this process are, at best, vague and
17imprecise, at worst, downright wrong. The Russian journals are especially
18unreliable.
19    
20    There are two reasons for this. First of all, the companies holding 
21patents on the processes want to keep their trade secrets secure, so they
22disclose no more than is absolutely necessary to obtain their patents.
23Secondly, the articles written by university scientists cover the making of
24large numbers of compounds and so do not delve deeply into the details of
25making any particular one.
26    
27    This book fills the glaring gap in published scientific literature. The 
28reader receives the benefit of my lengthy scientific education at expensive
29and prestigious universities and detailed knowledge of these processes that
30would otherwise be available only through tedious and expensive
31experiments. There is no magic involved, only good chemistry, and I show
32how underground chemists manufacture illegal drugs and get away with it.
33    
34    Skilled and successful underground chemists have usually taken a 
35college level Organic Chemistry course, with lab, for at least one
36semester. In this lab, they get practice in distillation, extraction, and
37other skills involved in making methamphetamine. At the very least, they
38will go to a college bookstore and purchase the lab manual for the Organic
39Chemistry class. That book goes into some detail on how to distill, reflux,
40etc.
41    
42    While this book is not meant to encourage anyone to break the law, it
43does point out the ultimate futility of government prohibition of 
44"controlled substances" by showing just how easily these substances can be
45manufactured.
46    
47    Underground drug manufacturers sometimes enjoy chipping into their own
48product. If there is one product which underground chemists can make, and
49also enjoy themselves, it is methamphetamine, the fuel that powered the
50Third Reich. They need have no fear of messing up their batches while under
51the influence of methamphetamine, unlike chemical garbage such as PCP.
52    
53    Legal methamphetamine is sold under such trade names as Desoxyn,
54Methedrine, etc. It is closely related both in structure and effects to
55regular amphetamine, called benzedrine and dexedrine.
56    
57    The difference between methedrine and benzedrine is that meth is more
58potent and its effect lasts a longer time. Meth is a potent stimulant
59similar in effect to cocaine, but much longer lasting. Where I come from,
60if people have a choice between coke and meth, they will choose meth,
61unless it's 2 AM. This is because meth is a much better bargain and can
62keep a man rolling through a hard day's work or a long night of play, or
63both. It sharpens the mind, allowing great amounts of mental work to be
64done quickly and error-free. It also sharpens one's reflexes to previously
65unknown levels, perfect for football. If you are planning to get into a
66fight, there is nothing better. It's not banned from boxing for nothing.
67    
68    The effects of meth on sexual function is a crap shoot. One day you
69will be a sexual athlete, the likes of which has never been seen this side
70of the porno flicks, the next you will be a complete failure. The odds in
71favor of athleticism are about 3 to 1, but can be improved by moderate
72alcohol consumption, and worsened by heavy drinking or immoderate use of
73meth. Poorly purified meth also has this drawback. The product should be
74distilled carefully.
75    
76    On the street, methamphetamine is known by such names as meth, crystal
77meth, crystal, speed, crank or wire. Most of the stuff on the street shows
78the telltale signs of sloppy lab work: yellow crystals, sticky crystals, or
79a tendency to soak up water from the air and melt.
80    
81    Back in the 60s, meth got a bad name because fools were shooting the
82stuff up constantly, starving themselves to death or getting hepatitis.
83This is how the slogan "speed kills" got started. If you do not have
84suicidal tendencies, accept the fact that your sinus cavities are close
85enough to your brain. You must also control your intake of meth. I would
86recommend no more than 50 milligrams (1/20 gram), no more than three times a
87week. Any more than this, and bad effects begin to appear, such as
88difficulty in thinking clearly, paranoid behavior and excessive weight loss
89leading finally to amphetamine psychosis, which quickly fades upon stopping
90consumption of amphetamine. Meth is not physically addicting, but since
91good effective stimulation is so enjoyable, it is habit-forming. People
92have been known to take extremely large doses, over a gram, and survive
93with no after effects, so overdoses are not a problem unless you have some
94underlying problem like a bad heart or hard arteries.
95    
96    I have some recommendations for underground chemists who consume their
97own product. First of all, they must eat well whether they feel like eating
98or not. Most people can stand to lose 10 pounds or so, but beyond that,
99forget it. It has been my experience that a few beers is usually all it
100takes to get a speed demon in the mood to eat. They'll probably need a few
101beers to get to sleep anyway, so they might as well take care of both
102things at once. I also recommend a 1/2 gram of phenylalanine per day. This
103is because meth works by releasing stores of norepinephrine from the brain,
104charging it up to new levels of activity. The amino acid phenylalanine is
105the starting material for making more norepinephrine, and a good supply of
106it will help refill spent stocks. They should also take a good
107mega-multi-vitamin with the minerals, selenium and zinc. They must not take
108methamphetamine closer than 6-8 hours before bedtime, or they will have to
109drink the bar dry to get to sleep.
110
111--------------------------------------------------------------------------
112                          CHEMICALS AND EQUIPMENT
113--------------------------------------------------------------------------
114    
115    The heart of the chemical laboratory is the set of glassware 
116collectively called "the kit." It consists of several round bottom flasks,
117a claisen adapter, a still head with thermometer holder, a thermometer, a
118condenser, a vacuum adapter and a separatory funnel (sep funnel, for
119short). These pieces each have ground glass joints of the same size, so
120that the set can be put together in a variety of ways, depending on the
121process being done. For the production of quarter to third of a pound
122batches, 24/40 size ground glass joints are used. Also necessary are one
123each of the following sizes of round bottom flasks: 3000 ml, 2000 ml and
124500 ml; and two each of 1000 ml and 250 ml. Two condensers are also
125required, both of the straight central tube variety, one about 35 cm in
126length, the other about 50 cm in length.
127    
128    Other glassware used are several 500 ml Erlenmeyer flasks, about 5
129pieces of plain (not Pyrex) glass tubing about three feet long, and a
130Buchner filtering funnel with the filtering flask it fits into.
131    
132    All this glassware costs in the range of $600-$700, and is available at
133many scientific supply houses on a cash-and-carry basis. The best equipment
134supply house in the Midwest is Sargent-Welch in Skokie. Illinois.
135    
136    Another necessary piece of equipment is a source of vacuum for vacuum
137distillation and filtering the crystal product. Here there are two choices.
138each with its advantages and disadvantages.
139    
140    One choice is the aspirator, also called a water pump. It works by 
141running tap water through it under good pressure, producing a vacuum in the
142side arm theoretically equal to the vapor pressure of the water being run
143through it (see Figure 1). For this reason, the best vacuum is obtained
144with cold water, since it has a lower vapor pressure. The vacuum is brought
145from the side arm to the glassware by an automotive type vacuum hose such
146as can be purchased at an auto parts store. The vacuum adapter and
147filtering flask each have nipples to which the other end of the hose is
148attached, making it possible to produce a vacuum inside the glassware. The
149top end of the aspirator is threaded so it can be threaded into the water
150source. Alternatively, the threaded head can be pushed inside a section of
151garden house and secured by a pipe clamp. The hose can then be attached to
152a cold water faucet. The bottom end of the aspirator, where the water comes
153out, is rippled and can also be pushed and clamped inside a section of
154garden hose leading to the drain. The aspirator is kept in an upright
155position and at a lower level than the glassware it serves. This is because
156water has a habit of finding its wav into the vacuum hose and running into
157the batch. Keeping the aspirator lower forces the water to run uphill to
158get into the glassware. The aspirator has the disadvantage that it requires
159constant water pressure flowing through it, or the vacuum inside the
160glassware draws water from it inside to make a mess of the batch. For this
161reason, only city water is used. And, unless the vacuum line is
162disconnected from the glassware before the water flow through the aspirator
163is turned off, the same thing will happen. The aspirator has these
164advantages: it flushes fumes from the chemicals down with the water flow,
165costs only about $10, and produces no sparks. A well-working aspirator
166produces a vacuum of 10 to 20 torr (2 to 3% of normal air pressure)(The
167unit "torr" means one milliliter of Mercury pressure. Normal air pressure
168is 760 torr.).
169    
170    The other choice for a source of vacuum is an electric vacuum pump,
171which costs about $200, not including the electric motor, purchased
172separately. To avoid the danger of sparks, the motor must be properly
173grounded. The pump has the advantage that it can be used in the country,
174where steady water pressure is not available. It also produces a better
175vacuum than the aspirator, about 5 torr, for faster and lower temperature
176distillation. It has the disadvantage of exhausting the chemical fumes it
177pumps into the room air, unless provision is made to pump them outside. The
178oil inside the pump also tends to absorb the vapors of ether or benzene it
179is pumping, thereby ruining the vacuum it can produce and making it
180necessary to change the oil.
181    
182    Another necessary piece of equipment is a single-burner-element buffet
183range with infinite temperature control. It is perfect for every heating
184operation and only costs about $20 at a department store. Finally, a couple
185of ringstands with a few Fisher clamps are used to hold the glassware in
186position.
187    
188    A number of troublesome yet futile laws have been enacted since the
189publication of the first edition of this book. On the federal level, 
190phenylacetic acid and phenylacetronitrile are now restricted chemicals. See
191Federal Register, Section 1310.02 Section A, "listed precursor chemicals."
192This means that clandestine operators wishing to use these materials will
193either have to smuggle them in from abroad, or make them from simpler,
194noncontrolled materials. For this last option, see Organic Syntheses,
195Collective Volumes I, II, and III. Check the table of contents to find
196directions for making the desired substance.
197    
198    An even more noxious, yet similarly futile law has been enacted in 
199California. Since this is bound to be the model for similar laws enacted
200throughout the country, let's examine it more closely.
201    
202    The most easily defeated part of the law concems the sale of chem lab
203equipment and chemicals. The law states that purchasers of equipment and/or
204chemicals in excess of $100 must present proper ID, and that the seller
205must save the bill of sale for inspection by officers of the law. Since
206most individual pieces of chem lab equipment go for less than $100, this
207law is gotten around by keeping one's equipment purchases under $100, and
208splitting up one's business between various suppliers. The five finger
209discount method while attending college chem lab courses is another option.
210Similarly, transfers between friends, and the old fashioned heist from
211well-stocked labs are other ways around this law.
212    
213    The most stringent section of the law is aimed primarily at production
214of meth, LSD, MDA and MDMA, PCP, and the barbiturates. Of those chemicals
215relevant to this book, it lists: phenylacetone, methylamine, phenylacetic
216acid, ephedrine, pseudoephedrine, norpseudoephedrine, phenylpropanolamine,
217isosafrole, safrole, piperonal, benzyl cyanide, chlorephedrine, thionyl
218chloride, and N-methyl derivatives of ephedrine.
219    
220    This section of the law states that anyone wishing to purchase these
221chemicals must obtain a permit. Anyone wishing to obtain such a permit must
222submit two sets of his ten fingerprints to the authorities. It is
223interesting to note here that the over-the-counter stimulants which contain
224ephedrine sulfate or phenylpropanolamine hydrochloride are exempt from
225these restrictions. Dexatrim, and those mail order white crosses, have not
226been made illegal. The determined experimenter can easily extract the
227needed starting material out of the legal "stimulant" pills.
228    
229    A third, and less restricted, class of chemicals deals mainly with 
230meth, and PCP. The chemicals of interest here are: sodium and potassium
231cyanide, bromobenzene, magnesium turnings (the last two also have PCP
232implications), mercuric chloride, sodium metal, palladium black, and acetic
233anhydride. For this class of chemicals, the law requires presentation of
234proper ID (i.e., state-issued photo ID) and calls for the seller to record
235said ID. The obvious ways around this section of the law are to do business
236in less nosy states, or to obtain false identification.
237    
238    Clandestine operators also need to know that the law allows the central
239scrutinizers to add chemicals to the lists without waming or approval. So
240the new precursors mentioned in this book could go on the lists of
241restricted chemicals at any time.
242    
243--------------------------------------------------------------------------
244                THE LEUCKARDT-WALLACH REACTION: AN OVERVIEW
245--------------------------------------------------------------------------
246    
247    The best way to produce batches of up to one-half pound in size is by
248the Leuckardt-Wallach reaction. It is one of the touchiest reactions there
249is, right up there with the Grignard reaction.
250    
251    The Leuckardt-Wallach reaction involves reacting a ketone with two
252molecules of a formamide to produce the formyl derivative of an amine,
253which is then hydrolyzed with hydrochloric acid to produce the desired
254amine. In this case, the reaction is shown on page 14.
255    
256    There are several reviews of this reaction in the scientific 
257literature, the best of them Crossley and More in the Journal of Chemistry
258(1949).
259    
260    The conditions which favor the production of high yields of fine 
261quality products are as follows. There should be a small amount of formic
262acid in the reaction mixture, because it acts as a catalyst. It should be
263buffered by the presence of some free methylamine, to prevent the pH of the
264reaction mixture from falling too low (becoming too acidic). The presence
265of water in the reaction mixture is to be avoided at all costs, because
266this really messes up the reaction. It prevents the phenylacetone from
267dissolving in the N-methylformamide, leading to low yields of
268purple-colored crystal. The directions I give in a later chapter for making
269N-methylformamide give a product which is perfect for this reaction.
270    
271    It is also important that the reaction be done at the lowest 
272temperature at which it will proceed smoothly, and that the heating be
273continued for as long as the reaction is still going. In this way nearly
274all the phenylacetone is converted to methamphetamine.
275
276    There is one stumbling block in the path of underground chemists: in
2771979, the DEA made phenylacetone illegal to purchase or possess. 
278N-methylformamide is also risky to obtain, although it is not illegal and
279is used in industry as a solvent.
280    
281    However, they are both easy to make. And, because of these 
282restrictions, the price of methamphetamine has gone above $100 per gram,
283while it costs only $1 or $2 per gram to make. 
284    
285--------------------------------------------------------------------------
286                        PREPARATION OF PHENYLACETONE
287--------------------------------------------------------------------------
288    
289    Phenylacetone, also known as methyl benzyl ketone, or 
2901-phenyl2-propanone, is easy but tedious to make. In this reaction,
291phenylacetic acid reacts with acetic anhydride with pyridine catalysts to
292produce phenylacetone plus carbon dioxide and water. In chemical writing:
293    
294[Deleted]
295    
296    A Russian journal tells of using sodium acetate instead of pyridine, 
297which would be great if it worked, because sodium acetate is much cheaper
298than pyridine. However, I have tried it and the results are unsatisfactory.
299Typical of those lying Commies.
300    
301    The reaction is done as follows: Into a clean, dry 3000 ml round bottom
302flask is placed 200 grams of phenylacetic acid, 740 ml of acetic anhydride
303and 740 nil of pyridine. This is done on a table covered with a sheet of
304newspaper, because phenylacetic acid, once it is exposed to the air, smells
305like cat urine, and the smell is next to impossible to get rid of. Pyridine
306also smells awful. The pyridine and acetic anhydride are measured out in a
307large glass measuring cup.
308    
309    The flask is then gently swirled until the phenylacetic acid is 
310dissolved. The flask is then assembled with the 50 cm condensa and the
311vacuum adapter, as shown in Figure 2a. Before assembly, the joints are
312lightly greased with silicone based stop cock grease. This prevents the
313pieces from getting stuck together. All pieces should be clean and dry. The
314vacuum nipple of the vacuum adapter is plugged with a piece of tape. In the
315rounded section of the vacuum adapter is a plug of cotton, then about two
316teaspoons of Drierite (anhydrous calcium sulfate), then another plug of
317cotton. This makes a bed of Drierite which is prevented from falling into
318the flask by a ball of cotton. The purpose of this is to keep moisture from
319the air away from the reaction.
320    
321    Now the underground chemist is ready to begin heating the flask. Notice
322that in Figure 2b, the flask is in a large pan which sits on the buffet
323range. The pan is filled about half-full of cooking oil (Wesson works
324fine). This is so that the flask is heated evenly. The heat is turned about
325half-way to maximum, and the flow of cold water through the condenser is
326begun. A length of plastic or rubber tubing runs from the cold water faucet
327to the lower water inlet of the condenser. The cold water runs through the
328condenser and out of the top water exit, through another length of tubing
329to the drain. In this way, the rising vapors from the boiling pyridine are
330condensed and returned to the flask. A rate of water flow of about one
331gallon per minute is good.
332    
333    Within a half hour, the flask is hot enough to begin boiling. The heat
334is then turned down to stabilize the flask at a gentle rate of boiling.
335This is called a reflux. The boiling is allowed to continue for 7 hours.
336During this time, the reaction mixture turns from clear to brownish-red in
337color. Periodically, the rate of water flow coming out of the condenser is
338checked, because faucet washers tend to swell after a while and slow down
339the rate of water flow.
340    
341    After 7 hours, the heat is turned off. Twenty minutes after the boiling
342stops, the glassware is set up as shown in Figure 3. The cotton and
343Drierite are removed from the vacuum adapter. Then 4 pea-sized pieces are
344broken off a pumice foot stone (purchased at the local pharmacy). These are
345called boiling chips, because they cause liquids to boil faster and more
346evenly. They are added to the flask with the reaction mixture in it. But
347they are not added until 20 minutes after the boiling stops; otherwise they
348could produce a geyser of hot chemicals.
349    
350    Now the heat is turned back on, a little hotter than when refluxing the
351reaction mixture. Water flow to the condenser is resumed. The mixture soon
352begins boiling again and the vapors condense in the condenser and flow to
353the collecting round bottom flask. What is being boiled off is a mixture of
354pyridine and acetic anhydride. The phenylacetone remains behind in the
355distilling round bottom flask, because its boiling point is about 100
356degrees Celsius higher than the pyridine and acetic anhydride. This process
357is called simple distillation. Distillation continues until 1300 ml has
358been collected in the collecting round bottom flask, then the heat is
359turned off. The 1300 ml is poured into a clean dry glass jug about one
360gallon in size which is then stoppered with a cork. At the end of this
361chapter, I will describe a process by which this pyridine is recycled for
362future use. Since pyridine is so expensive, this cuts production costs
363considerably.
364    
365    What is left in the distilling round bottom flask is a mixture of 
366phenylacetone, some acetic anhydride and pyridine, and a
367high-molecular-weight, tarry polymer which is reddish-brown in color. The
368next step is to isolate and purify the phenylacetone.
369    
370    The flask is taken out of the hot oil and allowed to cool down. 
371Three-quarters of a gallon of 10% sodium hydroxide solution (NaOH) is
372needed. So a gallon-size glass jug is filled three-quarters full of cold 
373water and about 10 ounces of sodium hydroxide pellets are added to it. A
374good quality lye, such as Red Devil or Hi-Test, is a substitute that saves
375a good deal of money and works fine. Eye protection is always worn when
376mixing this up. It is mixed thoroughly by swirling, or by stirring with a
377clean, wooden stick. The dissolution of NaOH in water produces a great deal
378of heat. It is allowed to cool off before the chemist proceeds.
379    
380    About 500 ml of the 10% NaOH is put in a 1000 ml sep funnel, then the
381crude phenylacetone mixture from the round bottom flask is poured in the
382sep funnel also. The top of the sep funnel is stoppered and mixed by
383swirling. When the funnel gets hot, it is allowed to set for a while. Then
384the mixing is continued, with the underground chemist working his way up to
385shaking the sep funnel, with his finger holding in the stopper. What he is
386doing is removing and destroying the acetic anhydride. Acetic anhydride
387reacts with the sodium hydroxide solution to prodbce sodium acetate, which
388stays dissolved in the water, never to be seen again. Some of the pyridine
389and red-colored tar also go into the water. The destruction of the acetic
390anhydride is what produces the heat.
391    
392    After it has cooled down, about 100 ml of benzene is added to the sep
393funnel and shaken vigorously for about 15 seconds. The sep funnel is
394unstoppered and allowed to sit in an upright position for about one minute.
395The liquid in the funnel will now have separated into two layers. On top is
396a mixture of benzene, phenylacetone, and red tar. On the bottom is the
397water layer, which has some phenylacetone in it. Pyridine is in both
398layers.
399    
400    Two 500 ml Erlenmeyer flasks are placed on the table, one marked "A,"
401the other marked "B." The stop cock on the sep funnel is opened, and the
402water layer is drained into B. The top layer is poured into A. B is poured
403back into the sep funnel, and 50 ml of benzene is added. The funnel is
404shaken for lS seconds, then the water layer is drained back into B. The top
405layer is poured into A. The purpose of this is to get the phenylacetone out
406of the water. Once again the water in B is put in the sep funnel. 50 ml of
407benzene is added, and shaken. The water is drained into B and the benzene
408layer poured into A. The water in B is poured down the drain and the
409contents of A put into the sep funnel along with 400 ml of 10% NaOH
410solution from the jug. After shaking, the water layer is drained into B and
411the benzene layer poured into A. The contents of B are put back in the sep
412funnel and 50 ml of benzene added. After shaking, the chemist drains the
413water layer into B and pours it down the drain. The contents of A are added
414to the funnel again, along with 400 ml of 10% NaOH solution; the funnel is
415shaken again. The water layer is drained into B and the benzene layer
416poured into A. The contents of B are returned to the sep funnel, along with
41750 ml benzene, and shaken again. The water layer is poured into B and
418poured down the drain. The benzene layer is poured into A. The sep funnel
419is washed out with hot water.
420    
421    Now the last traces of pyridine are removed from the phenylacetone. For
422this purpose, some hydrochloric acid is needed. Hardware stores usually
423have the 28% strength sometimes called muriatic acid. A bottle in which the
424acid seems clear-colored is used; the ones with a green tint have been
425sifflng around too long.
426    
427    The contents of A are returned to the clean sep funnel. Then 10 ml of
428hydrochloric acid, mixed with 10 ml of water, is added to the sep funnel
429and shaken for 30 seconds. The stopper is pulled out to check whether or
430not the odor of pyridine has disappeared. If not, another 20 ml of the
431acid-water mix is added and shaken. The odor should now be gone, but if it
432is not, some more of the mix is added and shaken. Now 200 rnl of water is
433added and shaken. Flask A is rinsed out with hot water; the water layer is
434drained into B and poured down the drain. The benzene layer is poured into
435A. What has just been done is to convert the pyridine into pyridine
436hydrochloride, which dissolves in water, but not in benzene. It is now down
437the drain.
438    
439    Finally, for one last time, the contents of A are returned to the sep 
440funnel, along with 200 ml of the 10% NaOH solution. This is shaken and the
441water layer drained into B. The benzene layer is allowed to stay in the sep
442funnel for the time being; more water will slowly fall out to the area of
443the stop cock, where it can be drained out. It is now ready to be
444distilled, and stray water must be removed beforehand.
445    
446    The glassware is set up as shown in Figure 4. Figure 4 shows a 
447glass-packed fractionating column which an underground chemist can make
448himself. The claisen adapter is checked to make sure it is clean and dry. A
449clear glass beer bottle is washed out with hot water, then smashed on the
450cement floor. A few pieces are picked out that are small enough to fit in
451the lower opening of the claisen, yet big enough that they will not fall
452out of the bottom opening of the claisen adapter. Pieces of the broken
453bottle are dropped in the lower opening until that section of the claisen
454adapter is filled to about the level shown in the drawing. The chemist
455tries to get it to land in a jumbled pattern, as shown in the drawing. Then
456more similarly-sized pieces of glass are dropped in the upper opening of
457the claisen adapter until it is filled to the level shown. Again a jumbled
458pattern is striven for. The lower opening is then stoppered with the proper
459size of glass or rubber stopper. Finally, the outside is wrapped with a
460layer or two of aluminum foil, except for the ground glass joint.
461    
462    The underground chemist is now ready to distill the phenylacetone.
463First, here is some information on the process to be performed. The crude
464phenylacetone the underground chemist has is a mixture of benzene,
465phenylacetone, red tarry polymer, some water and maybe some dibenzyl
466ketone. These substances all have very different boiling temperatures. By
467distilling this mixture through a fractionating column, the chemist can
468separate them very effectively and get a highpurity product. The way it
469works is easy to understand. The vapors from the boiling mixture in the
470distilling flask rise up into the fractionating column and come into
471contact with the pieces of glass inside. Here the vapors are separated
472according to boiling point. The substance in the mixture with the lowest
473boiling point is able to pass on through, while the other substances are
474condensed and flow back into the distilling flask. This is why the pieces
475of glass in the column can't be tightly packed, as that would interfere
476with the return flow, leading to a condition called flooding. Once all of
477the lowest-boiling substance has been distilled, the substance with the
478next higher boiling point can come through the fractionating column. In the
479distillation process to be described, the order is as follows: benzenewater
480azeotrope, 68øC; benzene, 80-ø C; phenylacetone, 120-130-ø C (under a
481vacuum of about 20 torr).
482    
483    Why must the phenylacetone be distilled under a vacuum? Because its
484boiling point at normal pressure is 216ø C, which is much too hot.
485Distilling it at that temperature would ruin the product. By distilling it
486under a vacuum, it boils at a much lower temperature. The exact temperature
487depends on how strong the vacuum is; the stronger the vacuum, the lower the
488temperature. For example, at a vacuum of 13 torr, the boiling point goes
489down to about 105ø C.
490    
491    The glassware is set up as shown in Figure 5. The distilling flask is
492no more than 2/3 full. If the underground chemist has more crude 
493phenylacetone than that, he has to wait until some of the benzene has
494distilled off, then turns off the heat, waits until the boiling stops and
495adds the rest of it to the distilling flask.
496    
497    The glassware should be clean and dry. A faster way of drying glassware
498after washing is to put it in the oven at 400øF for 20 minutes. Rubber
499stoppers do not go in the oven. Water tends to stay inside round bottom
500flasks dried in this way. SO, while they are still hot, the chemist takes a
501piece of glass tubing and puts it inside the flask. He sucks the moist air
502out of the flask with the glass tubing before it has a chance to cool down
503and condense. For the distillation, two 250 ml round bottom flasks are
504needed, one to collect the benzene in, the other to collect the
505phenylacetone in. Five boiling chips are put in the distilling flask.
506    
507    The heat source is turned on, to the low range, about 1/4 maximum.
508Water must be flowing through the shorter condenser at about one gallon per
509minute. When the mixture has begun boiling, the heat is adjusted so that
510about one or two drops per second drip into the collecting flask. The
511temperature on the thermometer should say about 68øC. For accurate
512temperature readings, the tip of the thermometer extends into the stillhead
513to the depth shown in Figure 6. 
514    
515    The material distilling at 68øC is the benzene-water azeotrope. It is 
516about 95% benzene and 5% water. It is milky white from suspended droplets
517of water. Once the water is all gone, pure benzene is distilled at about
51880øC. It is clear in color. If the liquid in the collecting flask is not
519clear or white in color, then undistilled material is being carried over
520from the distilling flask. This is caused either by having the distilling
521flask too full or by having the heat turned too high. In either case, the
522chemist must correct accordingly and redistill it. Once the temperature
523reaches 85øC on the thermometer, or the rate of benzene appearing in the
524collecting flask slows to a crawl, the heat is turned off because the
525chemist is ready to vacuum distill the phenylacetone.
526    
527    There is a problem that is sometimes encountered while distilling off
528the benzene. Sometimes the benzene in the distilling flask will foam up in
529the distilling flask instead of boiling nicely. These bubbles refuse to
530break and they carry undistilled material along with them to the collecting
531flask, leaving a red liquid over there. This cannot be allowed to happen.
532One effective method of dealing with this is to turn on the water supply to
533the aspirator at a slow rate so that a weak vacuum is produced. Then the
534vacuum hose is attached to the vacuum adapter and a weak vacuum produced
535inside the glassware. This causes the bubbles to break. Every few seconds,
536the vacuum hose is removed, then reattached. In a while, the benzene begins
537to boil normally and the vacuum can be left off.
538    
539    After it has cooled off, the collected distilled benzene is poured into
540a labeled glass bottle. It can be used again in later batches of 
541phenylacetone. The same 250 ml round bottom flask is reattached to the
542collecting side, and the vacuum hose attached to the vacuum adapter. The
543vacuum source is turned on. If an aspirator is being used, the water is
544turned all the way on. All the pieces of glassware must be fitted snugly
545together. A strong vacuum quickly develops inside the glassware. The heat
546is turned on to about i/3 maximum. The boiling begins again. At first, what
547distills over are the last remnants of benzene and water left in the
548distilling flask. Then the temperature shown on the thermometer begins to
549climb. The phenylacetone begins to distill. When the thermometer reaches
5501009 C, the vacuum hose is removed and the collecting 250 ml flask is
551replaced with the clean, dry 250 ml flask, then the vacuum hose is
552reattached. If a good vacuum pump is being used, the flasks are changed at
553about 809 C. This flask changing is done as fast as possible to prevent the
554material in the distilling flask from getting too hot during the change
555over. If it gets too hot, it distills too rapidly when the vacuum is
556reapplied, resulting in some red tar being carried over along with it.
557    
558    So the vacuum is reapplied, and the phenylacetone is collected. With a
559properly working aspirator, the phenylacetone will all be collected once
560the temperature on the thermometer reaches 140-1SOQ C. With a good vacuum
561pump, it will all come over by the time the temperature reaches 110-llSQ C.
562Once it is all collected, the heat is turned off, the vacuum hose is
563removed from the vacuum adapter and the vacuum source is turned off.
564    
565    The yield is about 100 ml of phenylacetone. It should be clear to pale
566yellow in color. It has a unique but not unpleasant smell. The flask
567holding this product is stoppered and stored upright in a safe place.
568Although phenylacetone can be stored in a freezer, to keep it fresh, the
569chemist now proceeds to making N-methylformamide.
570    
571    Once the distilling flask has cooled down, the glassware is taken apart
572and cleaned. The red tar left in the distilling flask and the fractionating
573column is rinsed out with rubbing alcohol. Then hot soapy water is used on
574all pieces. A long, narrow brush comes in handy for this.
575    
576    One last word about vacuum distillation. To keep the vacuum strong, the
577vacuum hose is no more than three feet long. This forces the chemist to do
578the distilling close to the source of the vacuum.
579    
580    Now for that pyridine recycling process I mentioned earlier in this 
581chapter. After the underground chemist has made a few batches of
582phenylacetone, he will have accumulated a fair amount of pyridineacetic
583anhydride mixture in the gallon-sized glass jug. He will now fractionally
584distill it to recover the pyridine from it. The clean dry glassware is set
585up as shown in Figure 7. It has a long-column fractionating column instead
586of the short type just used. This is because pyridine and acetic anhydride
587are harder to separate, so a longer column is needed to do the job.
588    
589    The distilling flask is a 3000 ml round bottom flask with 5 boiling 
590chips in it. The chemist pours 2000 ml of the acetic anhydride-pyridine
591mixture into it. The heat is turned on to about 1/3 maximum and the cold
592water is started flowing slowly through the condenser. Within a half hour,
593the mixture will begin to boil. A couple of minutes later, the vapors will
594have worked their way through the fractionating column and hegin appearing
595in the 2000 ml collecting flask. The heat source is adjusted so that it is
596collecting at the rate of one or two drops per second. Distilling is
597continued until 1000 ml have accumulated in the collecting flask. If the
598temperature reading on the thermometer goes above 135øC, the heat is turned
599down a little to slow the rate of distillation.
600    
601    Once 1000 ml has been collected, the heat is turned off and it is 
602allowed to cool down. After it is cool, the distilling flask is removed and
603its contents (mainly acetic anhydride) poured down the drain. The contents
604of the collecting flask (mainly pyridine) are poured into a clean, dry 2000
605ml round bottom flask with 5 boiling chips, or 5 boiling chips are simply
606added to the 2000 ml round bottom flask that the pyridine collected in and
607that flask is put on the distilling side in place of the 3000 ml flask. A
608clean, dry 1000 ml round bottom flask is put on the collecting side. The
609heat is turned back on and in a while the distilling begins again. As
610before, the rate of distillation is adjusted to one or two drops per
611second. The distillation is continued until 750 ml of pyridine has been
612collected. Sometimes it does not keep well, but so long as it is used to
613make another batch of phenylacetone within a few hours after it is made,
614this pyridine works just as well as new pyridine. 
615    
616--------------------------------------------------------------------------
617                      PREPARATION OF N-METHYLFORMAMIDE
618--------------------------------------------------------------------------
619    
620    N-methylformamide is best made by the reaction of methylamine with
621formic acid. The reaction proceeds like this:
622    
623    [SNiP]
624
625    The methylamine (a base) reacts with formic acid to form the 
626methylamine salt of formic acid. The heat that this reaction builds up then
627causes this intermediate salt to lose a molecule of water and form
628N-methylformamide. Since water is a product of this reaction, the
629underground chemist warts to keep water out of his starting materials as
630far as is possible. That is because having less water in them will shift
631the equilibrium of the reaction in favor of producing more 
632N-methylformamide.
633    
634    Both of the starting materials have water in them. The usual grade of
635formic acid is 88% pure and 12% water. It cannot be made any purer by
636distilling. The chemist can put up with the 12% water, but if a higher
637purity formic acid is available, it is worth the extra cost. The usual
638grade of methylamine is 40% by weight in water. The majority of this water
639can be removed by using the apparatus shown in Figure 8. Methylamine may
640also be obtained as a gas in a cylinder. In that case, the methylamine can
641be piped directly into the formic acid.
642    
643    The glassware is set up as shown in Figure 8. The 40% methylamine is in
644a 1000 ml round bottom flask attached to a long condenser. In the top of
645this condenser is a one-hole stopper. A bent piece of glass tubing is
646pushed all the way through this stopper so that the end of the piece of
647tubing extends about one or two millimeters below the bottom of the
648stopper. This bent piece of tubing then extends down through the center of
649the other condenser into the flask containing the formic acid. It should
650extend below the surface of the formic acid and end about one centimeter
651above the bottom of the flask containing the formic acid. The idea here is
652simple. The 40% methylamine is heated, causing methylamine gas to be boiled
653out along with some water vapor. These gases then travel up the condenser,
654where the water is condensed out, allowing nearly pure methylamine gas to
655be forced by pressure through the glass tubing into the formic acid.
656    
657    The bent tubing has to be bent by the chemist himself from a 
6583-foot-long piece of glass tubing. Its outer diameter should be about 1/4
659inch. The glassware is set up as shown in Figure 8 and he decides about
660where the tubing should be bent. If necessary, he will consult the chapter
661on bending glass in an Organic Chemistry lab manual. With a little
662practice, it is easy. A good source of flame to soften up the glass is a
663propane torch with the flame spreader attachment. After it is bent, he will
664blow through the tubing to make sure he did not melt it shut.
665    
666    He is now ready to proceed. All pieces of glassware are clean and dry.
667Into the round bottom 1000 ml flask sitting on the heat source is placed
668500 grams (about 500 ml) of 40% methylamine in water, along with 3 or 4
669boiling chips. Into the other 1000 ml round bottom flask is placed 250 ml
670of 88% formic acid. Water flow is begun through the longer condenser. It is
671advantageous to use ice cold water in this condenser, because it will then
672do a better job of removing water vapor from the methylamine. A good way to
673get ice cold water for the condenser is to get a couple of 5-gallon pails.
674One of them is filled with ice cubes no bigger than a fist and topped off
675with water. Then the section of plastic tubing that runs to the lower water
676inlet of the condenser is placed in the pail. Its end is weighted to keep
677it on the bottom of the pail. This pail is placed on the table along with
678the glassware. The other pail is placed on the floor and the plastic tubing
679from the upper water exit of the condenser is run to this pail. By sucking
680on the end of the water exit tubing, the ice cold water can be siphoned
681from the pail on the table, through the condenser, to the pail on the
682floor. The rate of water flow can be regulated to about one gallon per
683minute by putting a clamp on the tubing to slow its flow. When the pail on
684the table is about empty, the water that has flowed to the pail on the
685floor is returned to the table.
686    
687    The heat on the methylamine is turned on to about i/4 maximum. Soon the
688methylamine begins boiling out and moving through the tubing into the
689formic acid. The underground chemist checks for gas leaks in the system by
690sniffing for the smell of escaping methylamine. If such a leak is detected,
691the joint it is escaping from is tightened up.
692    
693    The methylamine bubbling into the formic acid produces a cloud of white
694gas inside the flask containing the formic acid. It makes its way up to the
695condenser, then returns to the flask as a liquid. For this condenser, tap
696water flow is fine. The rate of methylamine boiling is adjusted so that the
697white gas does not escape out the top of the condenser. As more methylamine
698is boiled out, a higher heat setting is required to maintain the same rate
699of methylamine flow.
700    
701    In this process, the formic acid gets very hot. It must get hot to 
702produce good yields of N-methylformamide. It sometimes gets hot enough to
703boil a little bit (105øC), but this is no problem. As the chemist continues
704bubbling methylamine into the formic acid, its volume increases until it is
705double its starting volume, about 500 ml. At about this time, the cloud of
706white gas thins and then disappears. This white gas is formed by the fumes
707of formic acid reacting with methylamine above the surface of the liquid
708formic acid. It disappears because there is no longer much formic acid
709left. The chemist now begins checking to see if the reaction is complete.
710He pulls out one of the stoppers from the 3-necked flask that contains the
711N-methylformamide and sniffs the escaping fumes for the odor of
712methylamine. He does this periodically until he smells methylamine. Once he
713smells it, he turns off the heat on the methylamine. When the methylamine
714stops bubbling into the N-methylformamide, he immediately lowers the level
715of the 3-necked flask so that the bent glass tubing is above the surface of
716the N-methylformamide. This is done because, as the methylamine cools, it
717will contract and create a vacuum which would suck the N-methylformamide
718over into the other flask in a flash, ruining his work.
719    
720    Both flasks are allowed to cool down. The methylamine is almost gone,
721so it can be poured down the drain. The next step is to fractionally
722distill the N-methylformamide. The glass-packed claisen adapter is used as
723the fractionating column. The glassware is set up as shown in Figure 5,
724back in Chapter 3. The distilling flask is a 1000 ml round bottom flask
725with 5 boiling chips in it. The collecting flask is a 250 ml round bottom
726flask. Unlike the distillation of phenylacetone, in this case the
727distillation is done under a vacuum from the beginning. The ice water
728siphoning system is used for the condenser, because N-methylformamide has a
729very high latent heat of vaporization, and, without this precaution, it may
730collect very hot in the collecting flask.
731    
732    The underground chemist is now ready to distill the N-methylformamide.
733All of the crude product is put in the 1000 ml round bottom flask. It will
734fill it about half full. The vacuum is applied at full strength, and the
735heat source is turned on to 1/3 to 1/2 maximum. The water in the mixture
736begins distilling. The temperature shown on the thermometer will show a
737steady climb during the process.
738    
739    In a while, the temperature rises high enough that the chemist can 
740begin collecting the distilled liquid as suspected N-methylformamide. If he
741is using an aspirator, he begins collecting in a clean, dry 250 ml round
742bottom flask when the temperature reaches 95-100øC. If he is using a good
743vacuum pump, he begins saving the distilled material at about gSQ C As the
744N-methylformamide distills, the temperature rises a little bit above the
745temperature at which he first began collecting the N-methylformamide, then
746holds steady. This temperature is noted. Distilling is continued until he
747has collected 100 ml. Then the heat is turned off. When the boiling stops,
748the vacuum hose is disconnected from the glassware.
749    
750    During the distillation process, a fair amount of methylamine was lost,
751leaving the N-methylformamide with too much formic acid. The next step is
752to correct this problem.
753    
754    The 100 ml of N-methylformamide that has been distilled is poured back
755in the distilling flask with the undistilled material. The distilled
756material is clear, while the undistilled material has turned yellow from
757the heat of distilling. The glassware is set up again as shown in Figure 8.
758This time, the round bottom flask holding the methylamine is a 500 ml
759flask. It has 100 ml of fresh 40% methylamine in water in it. The bent
760glass tubing leads into the flask containing the N-methylformamide. This
761flask does not need to have a condenser on it.
762    
763    The heat is turned on the methylamine and the flow of ice water through
764its condenser is begun. Soon the methylamine gas is bubbling into the
765N-methylformamide, reacting with the excess formic acid in it. Within about
76610 seconds, the odor of methylamine can be detected above the
767N-methylformamide. The heat is turned off, and when the bubbling stops, the
768level of the N-methylformamide is lowered so that it is not sucked into the
769other flask. Once the methylamine has cooled off, it can be poured back in
770with the good me~ylamine, because it is not exhausted. Once a bottle of
771methylamine has been opened, it should be reclosed tightly and the cap
772sealed with vinyl electrical tape in order to hold in the methylamine gas.
773    
774    Now the N-methylformamide is to be distilled again. The glassware is
775set up again for fractional distillation as shown in Figure 5. The
776distilling flask is a 500 ml round bottom flask, while the collecting flask
777is 250 ml. All pieces are clean and dry.
778    
779    The N-methylformamide is placed inside the distilling flask with 5 
780boiling chips. (Fresh chips are used every time.) The vacuum is reapplied
781and the heat is turned on again to 1/3 to 1/2 maximum. A little bit of
782water is again distilled. The temperature shown on the thermometer climbs
783as before. When it reaches a temperature 7øC below the temperature at which
784it leveled off the first time around, the chemist begins collecting in a
785clean dry 250 ml flask. The distilling continues until it has almost all
786distilled over. About 10 or 1S ml is left in the distilling flask. If he is
787using an aspirator, the chemist makes sure that no water is backing into
788the product from the vacuum line. The yield is about 250 ml
789N-methylformamide. If he gets a little more, it won't all fit in the 250 ml
790collecting flask. If that happens, he pours what has collected into a clean
791dry Erlenmeyer flask and continues distilling. N-methylformamide is a clear
792liquid with no odor.
793    
794    The N-methylformamide the underground chemist has just made is perfect
795for the Leuckardt-Wallach reaction. Because he began collecting it 7
796degrees below the leveling off temperature, it contains a mixture of
797N-methylformamide, formic acid and methylamine. To get good results, he
798uses it within a few hours after distilling it.
799    
800                                 References
801    
802Journal of the American Chemical Society, Volume 53, page 1879 (1931).
803    
804    
805--------------------------------------------------------------------------
806                           MAKING METHAMPHETAMINE
807--------------------------------------------------------------------------
808    
809    I explained the general theory behind this reaction in Chapter 2. Now,
810after doing the reactions described in the previous two chapters, the
811underground chemist has phenylacetone and N-methylformamide suitable for
812making methamphetamine. He will want to get going before the chemicals get
813stale.
814    
815    The first thing he does is test the chemicals. He puts 5 ml of 
816phenylacetone and 10 ml of N-methylformamide in a clean dry test tube or
817similar small glass container. Within a few seconds they should mix
818together entirely. At this point, he may offer a prayer to the chemical
819god, praising his limitless chemical power and asking that some of this
820power be allowed to flow through him, the god's High Priest. He may also
821ask to be delivered from the red tar that can be the result of this
822reaction. If they do not mix, there is water in the Nmethylformamide. In
823this case, he must distill it again, being more careful this time.
824    
825    Having tested the chemicals, he is ready to proceed with the batch.
826(However, if the underground chemist was reckless enough to obtain
827N-methylformamide ready made, he will have to distill it under a vacuum
828before it can be used in this reaction.) The phenylacetone he made (about
829100 ml) is mixed with the N-methylformamide. The best amount of
830N-methylformamide to use is about 250 ml, but any amount from 200 to 300 ml
831will work fine. With 200 ml of N-methylformamide, there are about four
832molecules of N-methylformamide to one of phenylacetone. This is the bare
833minimum. With 300 ml, the ratio is nearly six to one. Any more than this is
834a waste of N-methylformamide. The best flask for mixing them is a 500 ml
835round bottom flask. After they are mixed, this flask is set up as shown in
836Figure 9. The flask is sitting in an oil bath, to supply even heating to
837the flask. The oil (once again, Wesson is a good choice) should extend
838about 2/3 of the way up the side of the flask. A metal bowl makes a good
839container for this oil bath. This is better than a pan, because it will be
840important to see into the flask. The fact that the oil will expand when
841heated is kept in mind when filling the bowl with oil. A thermometer is
842also needed in the oil bath to follow its temperature.
843    
844    The test material is added to the flask. The heat source to the flask
845is turned on. A low heat setting is used so that the rise in temperature
846can be closely controlled. The thermometer used in the distillations is
847placed (clean and dry) inside the flask.
848    
849    The rise in temperature of both the oil bath and the flask is 
850monitored. The contents of the flask are stirred regularly with the
851thermometer. The temperature of the oil bath is brought to lOOQ C over the
852course of about 45 minutes. Once it reaches this level, the heat is turned
853back down a little bit to stabilize it in this area. The chemist must
854closely control every degree of temperature increase from here on. The
855temperature of the contents of the flask is worked up to 105g C. The
856contents of the flask are stirred every 15 minutes. At about lOSQ C, the
857reaction kicks in, although sometimes the heat must go as high as 110g C
858before it starts. When the reaction starts, the contents of the flask begin
859to bubble, sort of like beer, except that a head does not develop. A trick
860to get this reaction going at a nice low temperature is to gently scrape
861the thermometer along the bottom of the flask. Although I have never had
862the sophisticated equipment to prove it, it is a pet theory of mine that
863this is because ultrasonic waves are generated, producing a condition of
864resonance with the reactants that causes the reaction to start.
865    
866    The chemist wants to keep the temperature down at the same level at
867which the reaction first kicked in for as long as the reaction will
868continue at that level. Generally, it can go for a couple of hours at this
869level before the reaction dies down and an increase in temperature is
870necessary. The reaction mixture has the same color as beer and gently
871bubbles. The bubbles rise up from the bottom of the flask, come to the
872surface, and then head for where the thermometer breaks the surface. Here
873they collect to form bubbles about 1 centimeter in size before they break.
874This may look like boiling, but it is not. Everything inside the flask has
875a much higher boiling point than the temperatures being used. These are
876actually bubbles of carbon dioxide gas being formed as by-products of the
877reaction. The chemist can tell how well the reaction is going by the amount
878of bubbling going on.
879    
880    When the rate of bubbling slows down to almost stopping, it is time to
881raise the temperature. It should only be raised about 3g C. This requires
882turning up the heat only slightly. The highest yield of product is obtained
883when the lowest possible temperature is used. For the duration of the
884reaction, the contents of the flask are stirred with the thermometer every
885half hour. 
886    
887    And so the reaction is continued. As the reaction dies down at one
888temperature setting, the temperature is raised a few degrees to get it
889going again. It will be able to stay in the 1209 to 130Q C range for a long
890time. The reaction has a lot of staying power in this range. Finally, after
89124 to 36 hours, 140Q or 145Q C is reached. The reaction stops. The chemist
892takes his time working up to this temperature because the amount and
893quality of the product depends on it.
894    
895    Once 140ø to 145ø C is reached and the reaction stops, the heat is
896turned off and the contents allowed to cool down. It should still look like
897beer. A reddish tint means that his prayer failed and he was not delivered
898from the tar. Even so, there's still lots of good product in it.
899    
900    While it is cooling down, the underground chemist gets ready for the
901next step in the process. He is going to recover the unused methylamine for
902use in the next batch. This cuts his consumption of methylamine to about
903half of what it would be without this technique. What he is going to do is
904react the unused N-methylformamide with a strong solution of sodium
905hydroxide. The N-methylformamide is hydrolyzed to form methylamine gas and
906the sodium salt of formic acid (sodium formate). In chemical writing, this
907reaction is as follows:
908    
909    [SNiP]
910    
911    The methylamine gas produced is piped into formic acid to make 
912N-methylformamide for use in the next batch.
913    
914    First, 6 ounces (about 180 grams) of sodium hydroxide pellets are added
915to 450 ml of water. A good quality lye is an acceptable substitute. Eye
916protection is worn. Once the solution has cooled down, it is poured in a
9172000 ml round bottom flask with 5 boiling chips. Then all of the
918methamphetamine reaction mixture is poured into the flask along with it. It
919is swirled around a little bit to try to get some of the N-methylformamide
920dissolved into the water. This does not accomplish much, however, as the
921reaction mixture floats on the sodium hydroxide solution. The glassware is
922set up as shown in Figure 8 in Chapter 4. The 2000 ml flask containing the
923NaOH solution and the methamphetamine reaction mixture sits on the heat
924source. The bent piece of glass tubing once again leads to a 1000 ml round
925bottom flask equipped with a condenser. The 1000 ml flask once again
926contains 250 ml of 88% formic acid.
927    
928    The heat source is turned on to about 1/3 maximum. The flow of ice
929water through the long condenser is begun. In a while, the boiling chips
930float up to the interface of the sodium hydroxide solution and the reaction
931mixture, and some bubbling and frothing of the reaction mixture begins. The
932heat is turned down some, since the temperature of the mixture should rise
933slowly from now on. That is because the hydrolysis reaction forming
934methylamine tends to kick in all at once, if this precaution is not taken,
935leaving the chemist in a dangerous situation with a runaway reaction.
936    
937    After the first rush of the reaction has subsided and the bubbling of
938the methylamine into the formic acid has slowed down, the heat applied to
939the 2000 ml flask is increased to maintain a good rate of methylamine flow
940to the formic acid. Eventually, all the methylamine will be boiled out.
941This will be when methylamine no longer flows evenly into the formic acid.
942The flask must not be heated so strongly that water is forced through the
943bent glass tubing.
944    
945    The heat is turned off and the level of the flask containing formic 
946acid is lowered so that the acid is not sucked back into the other flask.
947This formic acid is about half reacted with methylamine. When it has cooled
948down, it is poured in a tall glass bottle and kept in the freezer until the
949next batch is made, when it is used for the production of Nmethylformamide.
950Since it is already half reacted, the amount of methylamine used is reduced
951accordingly.
952    
953    Meanwhile, back in the 2000 ml flask, the methamphetamine reaction
954mixture is about 100 ml in volume and has a red color. It floats above the
955sodium hydroxide solution. Once it has cooled down, the contents of this
956flask are poured into a 1000 ml sep funnel. The sodium hydroxide solution
957is drained out and thrown away. The red methamphetamine formyl amide is
958poured into a 500 ml round bottom flask with 3 boiling chips. 200 ml of
959hydrochloric acid is measured out. (The 28% hardware store variety is fine
960for this purpose.) It is poured into the sep funnel and swirled around to
961dissolve any product left behind in the sep funnel. Then it is poured into
962the 500 ml flask with the product. When swirled around, they mix easily.
963    
964    The glassware is set up as shown in Figure 2b in Chapter 3. Tap water
965flow is proper for use in the condenser. The heat is turned on to the 500
966ml flask, and a gentle rate of boiling is maintained for 2 hours. The
967mixture quickly turns black. The reaction going on here is metharnphetamine
968formyl amide reacting w~th hydrochloric acid to produce methamphetamine
969hydrochloride and formic acid. This is a hydrolysis reaction.
970    
971    After the two hours have passed, the heat to the flask is turned off.
972While the flask is cooling down, 80 grams of sodium hydroxide and 250 ml of
973water are mixed in a 1000 ml round bottom flask. Once again, a good quality
974lye is acceptable. If the 35% laboratory grade of hydrochloric acid was
975used in the last step, then 100 grams of sodium hydroxide is mixed with 300
976ml of water.
977    
978    When both flasks have cooled down, the black reaction mixture is 
979cautiously added to the sodium hydroxide solution. It is added in small
980portions, then swirled around to mix it. They react together quite
981violently. The reaction here is sodium hydroxide reacting with hydrochloric
982acid to produce table salt, with formic acid to produce sodium formate, and
983with methamphetamine hydrochloride to produce methamphetamine free base.
984When the sodium hydroxide solution gets very hot, the chemist stops adding
985the reaction mixture to it until it cools down again.
986    
987    After all the black reaction mixture has been added to the sodium 
988hydroxide solution, there is a brown liquid layer floating above the sodium
989hydroxide solution. This brown layer is methamphetamine free base. It also
990has a good deal of unreacted methamphetamine hydrochloride dissolved in it.
991This latter has to be neutralized because it will not distill in its
992present form. The 1000 ml flask is stoppered and shaken vigorously for 5
993minutes. This gets the methamphetamine hydrochloride into contact with the
994sodium hydroxide so it can react.
995    
996    The bottom of the flask is full of salt crystals that cannot dissolve 
997in the water because the water is already holding all the salt it can.
998
999    The chemist adds 100 ml of water to the flask and swirls it around for 
1000a few minutes. If that does not dissolve it all, he adds another 100 ml of
1001water.
1002    
1003    After the flask has cooled down, it is poured into a 1000 ml sep 
1004funnel, and 100 ml of benzene is added. The sep funnel is stoppered and
1005shaken for 15 seconds. It is allowed to stand for a couple of minutes, then
1006the lower water layer is drained into a glass container. The brown
1007methamphetamine-benzene layer is poured into a clean, dry 500 ml round
1008bottom flask. The water layer is extracted once more with 100 ml benzene,
1009then thrown away. The benzene layer is poured into the 500 ml flask along
1010with the rest of the methamphetamine.
1011    
1012    The chemist is now ready to distill the methamphetamine. He adds three
1013boiling chips to the 500 ml round bottom flask and sets up the glassware
1014for fractional distillation as shown in Figure 5. The 500 ml flask sits
1015directly on the heat source. The glass-packed claisen adapter is the proper
1016fractionating column. The collecting flask is a 250 ml round bottom flask.
1017Tap water is used in the condenser.
1018    
1019    The heat source is turned on to 1/4 to 1/3 maximum. Soon the mixture
1020begins boiling. The first thing that distills is benzene water azeotrope at
102168ø C. Then pure benzene comes over at 80øC. Once again, as in the
1022distillation of phenylacetone, foaming can sometimes be a problem. In that
1023case, it is dealt with in the same way as described in Chapter 3.
1024    
1025    When the temperature reaches 85øC, or the rate of benzene collecting
1026slows to a crawl, the heat is turned off and the flask allowed to cool
1027down. The collected benzene is poured into a bottle. It can be used again
1028the next time this process is done. The same 250 ml flask is put on the
1029collecting side.
1030    
1031    The distilling flask is now cool, so vacuum is applied to the glassware
1032at full strength. The last remnants of benzene begin to boil, and the heat
1033is turned back on to 1/3 maximum. The temperature begins to climb. If an
1034aspirator is being used, when the temperature reaches 80-ø C, the chemist
1035quickly removes the vacuum hose and replaces the 250 ml flask with a clean
1036dry one. If he is using a good vacuum pump, he makes this change at about
103770øC. The flask change is done quickly to avoid overheating in the
1038distilling flask. 
1039    
1040    The methamphetamine distills over. With an aspirator, the chemist 
1041collects from 80øC to about 140ø or 150ø C, depending on how strong the
1042vacuum is. With a vacuum pump, he collects to about 120ø or 130øC. Once it
1043has distilled, the heat is turned off and the vacuum hose disconnected.
1044    
1045    The product is about 90 ml of clear to pale yellow methamphetamine. If
1046the chemist is feeling tired now, he may take out a drop on a glass rod and
1047lick it off. It tastes truly awful and has a distinctive odor, somewhat
1048biting to the nostrils.
1049    
1050    He is now ready to make his liquid methamphetamine free base into
1051crystalline methamphetamine hydrochloride. Half of the product is put into
1052each of two clean dry 500 ml Erlenmeyer flasks.
1053    
1054    The chemist now has a choice to make. He can use either benzene or
1055ethyl ether as the solvent to make the crystals in. Benzene is cheaper, and
1056less of it is needed because it evaporates more slowly during the filtering
1057process. Ether is more expensive, and flammable. But since it evaporates
1058more quickly, the crystals are easier to dry off. If ether is used, it is
1059anhydrous (contains no water).
1060    
1061    A third choice is also possible for use as a crystallization solvent. 
1062This is mineral spirits available from hardware stores in the paint
1063department. Mineral spirits are roughly equivalent to the petroleum ether
1064or ligroin commonly seen in chem labs. Those brands which boast of low odor
1065are the best choice. Before using this material it is best to fractionally
1066distill it, and collect the lowest boiling point half of the product. This
1067speeds crystal drying. Since the choice of mineral spirits eliminates ether
1068from the supply loop, the clandestine operator may well go this route.
1069Toluene is also an acceptable solvent.
1070    
1071    With the solvent of his choice, the chemist rinses the insides of the 
1072condenser, vacuum adapter and 250 ml flask to get out the methamphetamine
1073clinging to the glass. This rinse is poured in with the product. Solvent is
1074added to each of the Erlenmeyer flasks until the volume of liquid is 300
1075ml. They are mixed by swirling.
1076    
1077    A source of anhydrous hydrogen chloride gas is now needed. The chemist
1078will generate his own. The glassware is set up as in Figure 10. He will
1079have to bend another piece of glass tubing to the shape shown. It should
1080start out about 18 inches long. One end of it should be pushed through a
1081one-hole stopper. A 125 ml sep funnel is the best size. The stoppers and
1082joints must be tight, since pressure must develop inside this flask to
1083force the hydrogen chloride gas out through the tubing as it is generated.
1084    
1085    Into the 1000 ml, three-necked flask is placed 200 grams of table salt.
1086Then 35% concentrated hydrochloric acid is added to this flask until it
1087reaches the level shown in the figure. The hydrochloric acid must be of
1088laboratory grade.
1089    
1090    Some concentrated sulfuric acid (99-98%) is put into the sep funnel and
1091the spigot turned so that 1 ml of concentrated sulfuric acid flows into the
1092flask. It dehydrates the hydrochloric acid and produces hydrogen chloride
1093gas. This gas is then forced by pressure through the glass tubing.
1094    
1095    One of the Erlenmeyer flasks containing methamphetamine in solvent is
1096placed so that the glass tubing extends into the methamphetamine, almost
1097reaching the bottom of the flask. Dripping in more sulfuric acid as needed
1098keeps the flow of gas going to the methamphetamine. If the flow of gas is
1099not maintained, the methamphetamine may solidify inside the glass tubing,
1100plugging it up.
1101    
1102    Within a minute of bubbling, white crystals begin to appear in the 
1103solution. More and more of them appear as the process continues. It is an
1104awe-inspiring sight. In a few minutes, the solution becomes as thick as
1105watery oatmeal.
1106    
1107    It is now time to filter out the crystals, which is a two-man job. The
1108flask with the crystals in it is removed from the HC1 source and 
1109temporarily set aside. The three-necked flask is swirled a little to spread
1110around the sulfuric acid and then the other Erlenmeyer flask is subjected
1111to a bubbling with HC1. While this flask is being buWled, the crystals
1112already in the other flask are filtered out.
1113    
1114    The filtering flask and Buchner funnel are set up as shown in Figure
111511. The drain stem of the Buchner funnel extends all the way through the
1116rubber stopper, because methamphetamine has a nasty tendency to dissolve
1117rubber stoppers. This would color the product black. A piece of filter
1118paper covers the flat bottom of the Buchner funnel. The vacuum is turned on
1119and the hose attached to the vacuum nipple. Then the crystals are poured
1120into the Buchner funnel. The solvent and the uncrystallized methamphetamine
1121pass through the filter paper and the crystals stay in the Buchner funnel
1122as a solid cake. About 15 ml of solvent is poured into the Erlenmeyer
1123flask. The top of the flask is covered with a palm and it is shaken to
1124suspend the crystals left clinging to the sides. This is also poured into
1125the Buchner funnel. Finally, another 15 ml of solvent is poured over the
1126top of the filter cake.
1127    
1128    Now the vacuum hose is disconnected and the Buchner funnel, stopper and
1129all, is pulled from the filtering flask. All of the filtered solvent is
1130poured back into the Erlenmeyer flask it came from. It is returned to the
1131HC1 source for more bubbling. The Buchner funnel is put back into the top
1132of the filtering flask. It still contains the filter cake of
1133methamphetamine crystals. It will now be dried out a little bit. The vacuum
1134is turned back on, the vacuum hose is attached to the filtering flask, and
1135the top of the Buchner funnel is covered with the palm or a section of
1136latex rubber glove. The vacuum builds and removes most of the solvent from
1137the filter cake. This takes about 60 seconds. The filter cake can now be
1138dumped out onto a glass or China plate (not plastic) by tipping the Buchner
1139funnel upside-down and tapping it gently on the plate.
1140    
1141    And so, the filtering process continues, one flask being filtered while
1142the other one is being bubbled with HC1. Solvent is added to the Erlenmeyer
1143flask to keep their volumes at 300 ml. Eventually, after each flask has
1144been bubbled for about seven times, no more crystal will come out and the
1145underground chemist is finished.
1146    
1147    If ether was used as the solvent, the filter cakes on the plates will 
1148be nearly dry now. With a knife from the silverware drawer, the cakes are
1149cut into eighths. They are allowed to dry out some more then chopped up
1150into powder. If benzene was used, this process takes longer. Heat lamps may
1151be used to speed up this drying, but no stronger heat source.
1152    
1153    The yield of product is about 100 grams of nearly pure product. It 
1154should be white and should not get wet, except in the most humid weather.
1155It is suitable for any purpose. It can be cut in half and the underground
1156chemists will still have a better product than their competition. But they
1157will not cut it until a few days have passed, so that their options are not
1158limited should one of the problems described in the next few paragraphs
1159arise.
1160    
1161    Here are some of the common problems that arise with the crystals, and
1162how they are dealt with. To spot these possible problems, the crystals are
1163first left on the plate to dry out, and then transferred to glass jars or
1164plastic baggies.
1165    
1166    Yellow Crystals. This is caused by not properly rinsing off the 
1167crystals while in the Buchner funnel, or not using enough solvent to
1168dissolve the methamphetamine in the Erlenmeyer flasks. To whiten them up,
1169they are allowed to soak in some ether in a glass jar, then filtered again.
1170    
1171    Yellow Stinky Crystals. The smell takes a few days to develop fully.
1172They are left alone for 5 days, then soaked in ether and filtered again.
1173The smell should not return. (The problem is caused by heating the reaction
1174mixture above the 145øC upper limit.)
1175
1176    Crystals Refuse To Dry. This can especially be a problem using benzene
1177as a solvent. It can also be a problem on very humid days. The crystals are
1178placed in the clean, dry filtering flask, the top is stoppered and vacuum
1179applied at full strength for 15 minutes. Warming the outside of the
1180filtering flask with hot water while it is under vacuum speeds the process.
1181    
1182    Crystals Melt. Here the crystals soak up water from the air and melt.
1183This is usually caused by raising the temperature of the reaction too
1184rapidly, or by collecting too much high boiling material during the 
1185distillation. First, they are put into the filtering flask and a vacuum
1186applied to dry them out. They are soaked in ether and filtered. If this
1187doesn't cure the problem, cutting the material to 50% purity should take
1188care of it.
1189
1190    Crystals Are Sticky. Here the crystals seem covered by a thin layer of
1191oily material, causing them to stick to razor blades, etc. The problem is
1192dealt with in the same way as melting crystals.
1193    
1194    Crystals Fail to Form. This problem occurs during the process of 
1195bubbling HCl into the methamphetamine. Instead of forming crystals, an oil
1196settles to the bottom of the flask. This is generally caused by incomplete
1197hydrolysis of the formyl amide. Perhaps it didn't mix with the hydrochloric
1198acid. It is put in a flask and the solvent boiled off under a vacuum. Then
1199200 ml of hydrochloric acid is added and the process is repeated, starting
1200from the hydrolysis of the formyl amide of methamphetamine. The 35%
1201laboratory grade of hydrochloric acid is used.
1202    
1203    In the event of melting or sticky crystals, cutting is first tried on a 
1204small sample of the crystals to see if that will solve the problem. If it
1205does not, then a recrystallization must be resorted to. This is done by
1206dissolving the crystals in the smallest amount of warm alcohol that will
1207dissolve them. 190-proof grain alcohol, 95% denatured alcohol, or absolute
1208alcohol may be used. Then 20 times that volume of ether is added. After
1209vigorous shaking for three minutes, the crystals reappear. If not, more
1210ether is added, followed by more shaking. After being filtered, the
1211crystals should be in good shape.
1212    
1213    A technique which may be used in especially stubborn cases is to 
1214dissolve the crystals in dilute hydrochloric acid solution, extract out the
1215oily impurities with benzene, and then isolate the methamphetamine. This is
1216done as follows:
1217    
1218    For every 100 grams of crystal, 200 ml of 10% hydrochloric acid is
1219prepared by mixing 60 ml of 35% hydrochloric acid with 140 ml of water. The
1220crystals are dissolved in the acid solution by stirring or shaking in the
1221sep funnel. 100 ml of benzene is added to the solution in the sep funnel,
1222which is then shaken vigorously for about 2 minutes. The lower layer is
1223drained out into a clean beaker. It contains the methamphetamine. The
1224benzene layer is thrown out. It contains the oil grunge which was polluting
1225the crystals.
1226    
1227    The acid solution is returned to the sep funnel and the acid 
1228neutralized by pouring in a solution of 70 grams of sodium hydroxide in 250
1229ml of water. After it has cooled down, the mixture is shaken for 3 minutes
1230to make sure that all the methamphetamine hydrochloride has been converted
1231to free base. Then 100 ml of benzene is added and the mixture shaken again.
1232The lower water layer is drained out and thrown away. The
1233benzene-methamphetamine solution is distilled as described earlier in this
1234chapter. Then, as described earlier in this chapter, dry hydrogen chloride
1235gas is bubbled through it to obtain clean crystals. (Hydrogen chloride gas
1236must be made in a well-ventilated area; otherwise, it will get into the
1237chemist's lungs and do real damage.)
1238    
1239    There is an alternative method for converting amphetamine free base
1240into the crystalline hydrochloride. It is based on the method that South
1241American cocaine manufacturers use to turn coca paste into cocaine
1242hydrochloride. This method does not give the really high quality crystals
1243that the bubble through method gives, but its use is justified when really
1244big batches are being handled.
1245    
1246    In this alternative procedure, the free base is dissolved in two or 
1247three volumes of acetone. Concentrated hydrochloric acid (37%) is then
1248added to the acetone while stirring until the mixture becomes acid to
1249litmus paper. Indicating pH paper should show a pH of 4 or lower. The
1250hydrochloride is then precipitated from solution by slowly adding ether
1251with stirring. It will take the addition of 10 to 20 volumes of ether to
1252fully precipitate the hydrochloride. Toluene or mineral spirits may be
1253substituted for the ether. Then the crystals are filtered out using a
1254Buchner funnel as described before, and set aside to dry. The filtrate
1255should be tested for completeness of precipitation by adding some more
1256ether to it.
1257    
1258                                 References
1259    
1260    Journal of Organic Chemistry, Volume 14, page 559 (1949).  
1261    Journal of the American Chemical Society, Volume 58, page 1808  
1262    (1936); Volume 61, page 520 (1939); Volume 63, page 3132 (1941).  
1263    Organic Syntheses, Collective Volume II, page 503. 
1264    
1265--------------------------------------------------------------------------
1266                        INDUSTRIAL-SCALE PRODUCTION
1267--------------------------------------------------------------------------
1268    
1269    In the previous five chapters, I described a process by which 
1270underground chemists make smaller amounts of methamphetamine, up to about
1271one-half pound of pure methamphetamine. The process takes about three days
1272with two people working in shifts around the clock. Thus, the maximum
1273production level is stuck at one pound per week.
1274    
1275    There is a way to break through this production limit, which is to 
1276produce phenylacetone and turn it into methamphetamine by different
1277methods. These methods produce more in less time, and they are cheaper. Two
1278of them, the tube fumace and the hydrogenation bomb, are major engineering
1279projects. But they are no problem for those with a Mr. Handyman streak.
1280    
1281    However, underground chemists will not move up to industrialscale
1282production until they are sure that they are going to be able to sell it
1283without having to deal with strangersðunless, of course, they want to get
1284busted.
1285    
1286    One major difference in the logistics of a large-scale operation versus
1287a smaller one is that a different source of chemicals is required. An
1288outlet that specializes in pints and quarts of chemicals is not going to be
1289much help when multi-gallons are needed. Here a factor comes into play
1290which cannot be taken advantage of at lower levels of production. Most
1291chemical suppliers will not deal with individuals, only with corporations
1292and companies.
1293    
1294    Now the underground chemist can turn this situation to his advantage by
1295means of subterfuge. First he develops a false identity. He gets some of
1296the books on false ID andðAbracadabra!ðhe's Joe Schmoe. He uses this
1297identity to form several companies. If he wants to be official, he consults
1298the book, How to Forrn Your Own Corporation For Under 50 Dollars, available
1299in most libraries. Otherwise, he just has some invoice-order forms printed
1300up for his company. He may also open a checking account for his company to
1301pay for chemicals. He uses checks with high numbers on them so that they
1302don't think that he just appeared out of thin air. As an alternative, he
1303may pay with certified checks from the bank.
1304    
1305    The next step is to rent some space as his company headquarters and
1306chemical depot. Indeed, he'll probably rent a couple such depots to house
1307hisvarious companies. Now he starts contacting chemical dealers, ordering
1308enough of one or two chemicals to last for a couple of years. Then he
1309contacts another dealer and orders a similar quantity of one or two other
1310chemicals under a different company name. He continues this process until
1311he has everything he needs. He offers to pick them up so that they do not
1312see the dump he's rented as his headquarters. As a precaution, he equips
1313these dumps with a phone and answering machine so that they can call him
1314back. If he doesn't live in a large city, he does business out of town.
1315That way they won't be surprised that they never heard of him. But he does
1316not do business too far away from home base, so they won't wonder why he
1317came so far.
1318    
1319    There is a better strategy to follow in getting the equipment and 
1320chemicals needed for clandestine meth production. The best method to use is
1321to first order the equipment and a couple of the most suspicion arousing
1322chemicals. Then the underground operator lays low for a while. The narco
1323swine have a habit of going off half-cocked on their search warrants. If
1324the initial purchases caught their eyes, they will likely swoop right in,
1325planning on finding an operating lab, or at least enough to make a
1326conspiracy charge stick. If they move now, the meth meister will not be
1327prosecutable, so long as he does not admit guilt. An alternative narco
1328swine strategy would be for them to initiate intense surveillance upon Joe
1329Schmoe. So long as Joe is not brain dead, this will be pretty obvious after
1330awhile. If surveillance is noticed, it is time to put the plan into a deep
1331freeze, and consider the initial purchases a long term investment rather
1332than a quick payoff. If Joe is able to get the most sensitive materials
1333unnoticed, it is then time to quickly get the more mundane items needed and
1334immediately turn to the production end of the operation.
1335    
1336    When it is time for the underground chemist to pick up the chemicals,
1337he uses a pick-up or van registered in Joe Schmoe's name. As a precaution,
1338he equips his vehicle with a radio scanner. He buys the book, U.S.
1339Government Radio Frequencies, and tunes the scanner to pick up the FBI, the
1340DEA, the state and local police. He picks up the chemicals and returns with
1341them to his headquarters and depot. He takes a roundabout route to make
1342sure he isn't being followed. Two tricks he may use to detect a tail are to
1343turn into a dead-end street and to drive either too fast or too slow. He
1344leaves Joe's vehicle at the depot and takes a roundabout route home. He
1345stops at a few bars and leaves by the back exit.
1346    
1347    A very common, and quite stale trick is for the narco swine to place a
1348radio tracing device in the packing materials surrounding jugs of chemicals
1349purchased by suspected drug manufacturers. All items purchased should be
1350carefully inspected during the drive away from the point of purchase. If
1351such a device is found, it is cause for clear thinking action, rather than
1352panic. While using such a device, the heat will usually lay quite far back
1353on their pursuit to avoid being noticed. They will rely on the transmitter
1354to tell them where you are going. It is best not to smash such a
1355transmitter, but rather keep it in hand, and toss it into the back of
1356another pickup truck at a stoplight. This is then followed by putting the
1357plan into a deep freeze until the heat grows bored with you.
1358    
1359    The next thing the underground chemist needs is a laboratory location.
1360A country location makes any surveillance very obvious and keeps chemical
1361smells out of the way of nosy neighbors. Electricity and running water are
1362absolutely necessary. Now he loads the chemicals onto Joe's wheels and
1363heads for the laboratory in a very roundabout manner, keeping an eye open
1364for any tail and paying close attention to the scanner. He leaves the
1365scanner at the lab for entertainment in the long hours ahead.
1366    
1367    A nice addition to any underground laboratory is a self-destruct 
1368device. This consists of a few sticks of dynamite armed with a blasting
1369cap, held inside an easily opened metal can. The purpose of the metal can
1370is to prevent small accidental fires from initiating the self-destruct 
1371sequence. If Johnny Law pays an uninvited visit to his lab, the underground
1372chemist lights the fuse and dives out the window. The resulting blast will
1373shatter all the glass chemical containers and set the chemicals on fire.
1374This fire will destroy all the evidence. He keeps his mouth shut and lets
1375his lying lawyer explain why the blast happened to come at the same time as
1376the raid. He has no reason to fear the state crime lab putting the pieces
1377of his lab back together. These guys learned their chemistry in school and
1378are truly ignorant when it comes to the particulars of a well-designed lab.
1379    
1380    The feds, on the other hand, have a higher grade of chemist working for
1381them, but they are tiny individuals who are haunted by nagging self doubt,
1382wondering why after obtaining a Ph.D., they are just faceless cogs in a
1383machine. To compensate for this, they will claim to make great discoveries
1384of the obvious. Case in point is an article published in the Journal of
1385Forensic Sciences. This is a petty journal published by Johnny Law where
1386the aforementioned tiny individuals can stroke their egos by getting
1387published. In an article covering the lithium in ammonia reduction of
1388ephedrine to meth production method featured in this third edition of my
1389book, the unnamed tiny, frustrated chemists trumpeted "we found that a
1390nitrogen atmosphere to protect the reaction was unnecessary, contrary to
1391the claims of the authors who said it was essential."
1392    
1393    The authors to which they refer here are Gary Small and Arlene 
1394Minnella, legitimate scientists who were published in a legitimate
1395scientific journal, the Journal of Organic Chemistry. In their article
1396covering the lithium in ammonia reduction of benzyl alcohols, they used
1397really tiny batches that might actually need a nitrogen atmosphere to
1398protect them, and in no place claimed that it was essential. See the
1399Journal of Organic Chemistry article cited in Chapter 15 of this book. It
1400was obvious that the steady boiling away of liquid am monia would form its
1401own protective gas blanket when done on a scale corresponding to real meth
1402production.
1403    
1404    They further went on to nitpick the purification procedure used by the
1405real scientists, claiming it was unnecessary. Everyone who reads the
1406journals knows that it is unnecessary. This is just the protocol that has
1407been followed by research scientists for the past god-knows-howmany ages.
1408They just do this so that if they get unexpected results in their research,
1409they will know that it is not due to impurities in the reaction mix. To
1410make a great discovery out of finding that these rigorous purification
1411schemes are not needed for practical production methods just shows how
1412shallow these people are.
1413    
1414    
1415--------------------------------------------------------------------------
1416                      PHENYLACETONE FROM B-KETO ESTERS
1417--------------------------------------------------------------------------
1418    
1419    In this chapter, I will cover two separate but similar methods of 
1420making phenylacetone. Neither of them is actually suitable for
1421industrial-scale production, but they have the advantage of not using
1422phenylacetic acid. This allows an underground chemist to diversify the
1423chemicals used, and enables him to defeat a blockade on his phenylacetic
1424acid supply. Neither of these reactions is foolproof; both require a
1425certain amount of laboratory skill. The chemicals must be weighed and
1426measured fairly exactly. This is unlike the method described in Chapter 3,
1427where anything within a ballpark range will work. These methods require a
1428reliable scale.
1429    
1430    Both of these reactions use sodium metal, which is some nasty stuff. It
1431reacts violently with water to produce sodium hydroxide and hydrogen. It
1432will also react with air. The chemist never touches it intentionally; if he
1433does touch it, he washes it off with warm water. Sodium metal comes in a
1434can, covered with a bath of petroleum distillate. This is to protect it
1435from water and air. As long as it stays covered, it causes the chemist no
1436problems.
1437    
1438    In this reaction, sodium metal is reacted with absolute alcohol to make
1439sodium ethoxide (NaOCH2CH3). Ethyl acetoacetate and bromobenzene are then
1440added to this to produce a beta keto ester. Reaction with acid then
1441produces phenylacetone. 
1442    
1443    A side reaction which sometimes becomes a problem is bromobenzene
1444reacting with beta keto ester to produce di-phenylacetone. This can be
1445controlled by not using too much bromobenzene, adding it slowly and
1446stirring it well.
1447    
1448    Figure 12 shows the glassware used. The glassware must be very dry, so
1449it is dried out in the oven for an hour or so. If the sep funnel has a
1450plastic valve, the valve is taken out before the sep funnel is put in the
1451oven. The magnetic stirring bar does not go in the oven either. It is
1452coated with Teflon, so it does not have any water on it. A magnetic stirrer
1453is necessary to do this reaction, because good stirring is very important.
1454An extra claisen adapter is needed for this reaction; one is filled with
1455broken pieces of glass for use as a fractionating column, the other is kept
1456as is for use in the Figure 12 apparatus.
1457    
1458    To begin, the underground chemist puts a bed of Drierite in the vacuum
1459adapter as shown in Figure 2a, being sure to plug up the vacuum nipple. The
1460water lines are attached to the condenser and cold water started flowing
1461through it. But if it is humid, the water flow is not started until the
1462glassware is assembled.
1463    
1464    The can of sodium is opened. A chunk about the size of a medium egg is
1465needed. The chemist selects a convenient corner of the block of sodium to
1466work on. With a clean, sharp knife, he scrapes off any discolored skin
1467there might be in the area he plans to use. Good clean sodium has a bright
1468metallic look. He keeps the block under the petroleum as he scrapes the
1469discolored skin.
1470    
1471    Now he must weigh the sodium. A 100 ml beaker is filled halffull of the
1472petroleum distillate from the can of sodium, or with xylene. He puts it on
1473the scale and weighs it. He needs 34.5 grams of sodium metal, so with a
1474clean sharp knife. he cuts off a chunk of sodium, transfers it to the
1475beaker and weighs it. If it is not quite 34.5 grams, he cuts a little more
1476sodium and adds it to the beaker. This is done quickly, so that evaporation
1477of the petroleum does not throw the measurement off. Then another 100 ml
1478beaker is filled half-full of anhydrous ethyl ether. The sodium metal is
1479transferred to it with a spoon. The petroleum is poured back in with the
1480block of sodium and the can sealed up so that it does not evaporate. With a
1481clean sharp knife, the sodium is cut up into little pieces about 1/2 the
1482size of a pea.
1483
1484    The sodium is kept under the ether while this is being done. Eye 
1485protection is always worn when working with sodium.
1486    
1487    After the sodium is cut up, the magnetic stirring bar is put in the 
14882000 ml flask. Then the sodium metal pieces are scooped out with a spoon
1489and put in the 2000 ml flask. The glassware is immediately assembled as
1490shown in Figure 12. One liter (1000 ml) of absolute ethyl alcohol is
1491measured out. Absolute alcohol absorbs water out of air, so this is done
1492rapidly. Here's how. The chemist gets a quart beer bottle, marks on the
1493outside how full one liter is, and bakes the bottle in the oven to dry it
1494out. When he takes it out of the oven, he sucks the hot, moist air out of
1495it with a section of glass tubing. Once it has cooled down, he fills it
1496with one liter of absolute alcohol and stoppers it to keep it dry. He wants
1497to get the alcohol in with the sodium before the ether on it evaporates,
1498and this saves him the time of measuring it out.
1499    
1500    About 200 ml of the absolute alcohol is put in the sep funnel and the
1501valve opened to allow the alcohol to flow down onto the sodium metal. Cold
1502water should be flowing through the condenser. Magnetic stirring is not
1503necessary at this time, but the 2000 ml flask is sitting in a large pan. A
1504pail of cold water and a towel are kept handy. Sodium and alcohol react
1505together vigorously, and the alcohol boils like crazy. The condenser is
1506checked to see how far up the alcohol vapors are reaching. The chemist does
1507not want the alcohol vapors to escape out the top of the condenser. If the
1508vapors are making it more than halfway up the condenser, cold water is
1509poured from the pail into the pan the flask is sitting in. That cools it
1510off and slows down the boiling. But if that does not do enough, the wet
1511towel is put on top of the flask. When the boiling slows down, the towel
1512and the pan of water are removed, then more alcohol is added to the sep
1513funnel. A fresh ball of cotton is put in the top of the sep funnel to
1514protect the alcohol from water in the air. The alcohol is added to the
1515flask at such a Mte that the boiling of the alcohol continues at a nice
1516Mte. When all of the original one liter of absolute alcohol has been added
1517to the flask, the flask is gently heated on the hot plate to keep the
1518alcohol boiling until the little pieces of sodium are dissolved. If the
1519chemist has done a very good job, the result is a clear solution. If not,
1520it will be milkycolored.
1521    
1522    The magnetic stirring is now begun, and 195 grams (190 ml) of 
1523ethylacetoacetate is put in the sep funnel over the next 15 minutes. The
1524solution is heated to a gentle boiling. As it is boiling and stirring, 236
1525grams of bromobenzene is put in the sep funnel and dripped into it over a
1526period of an hour. The boiling and stirring is continued for 8 hours.
1527    
1528    Then the stirring is stopped and the solution allowed to cool down. A
1529good amount of sodium bromide crystals settle to the bottom of the flask.
1530When they have settled to the bottom, the glassware is taken apart and as
1531much of the alcohol solution as possible is poured into a 3000 ml flask.
1532The last of the product is rinsed off the sodium bromide crystals by adding
1533about 50 ml of absolute alcohol to them, swirling around the mixture, then
1534filtering it. This alcohol is added to the alcohol in the 3000 ml flask.
1535    
1536    The glassware is set up as shown in Figure 3 in Chapter 3. A 1000 ml
1537flask is used as the collecting flask. The alcohol in the 3000 ml flask is
1538heated. The oil in the pan is not heated above 115ø C. The distillation is
1539continued until the chemist has collected over 900 ml of alcohol in the
1540collecting flask.
1541    
1542    When the alcohol has been boiled out, the heat is turned off and the
1543flask removed from the pan of oil. As it is cooling off, 1500 ml of 5%
1544sodium hydroxide solution is mixed. To do this, 75 grams of sodium
1545hydroxide is put in a flask and 1400 ml of water added. (Lye may be used as
1546a sodium hydroxide substitute.) When both the sodium hydroxide solution and
1547the reaction mixture near room temperature, the sodium hydroxide solution
1548is poured into the 3000 ml flask with the reaction mixture. The magnetic
1549stirring bar is put into the flask and magnetic stirring is begun. It is
1550stirred fast enough that a whirlpool develops in the mixture and the~beta
1551keto ester gets into contact with the sodium hydroxide solution. The
1552stirring is continued for 4 hours without heating the solution. The beta
1553keto ester reacts with the sodium hydroxide to produce the compound shown
1554above, plus ethyl alcohol. This is a hydrolysis reaction.
1555    
1556    After 4 hours of stirring, the stirring is stopped and the solution 
1557allowed to sit for a few minutes. A small amount of unreacted material will
1558float up to the top. If there is a large amount of unreacted material, the
1559stirring is begun again and 40 grams of sodium hydroxide and 300 ml of
1560isopropyl rubbing alcohol are added. It is stirred for 4 more hours. But
1561generally this is not necessary.
1562    
1563    The unreacted layer is poured into a 1000 ml sep funnel. A good deal of
1564the sodium hydroxide solution will be poured off with it. The chemist lets
1565it sit for a few minutes, then drains the sodium hydroxide solution back
1566into the 3000 ml flask. The oily unreacted material is poured into a small
1567glass bottle and kept in the freezer. When a good amount of it has
1568accumulated, the chemist tries reacting it again with 5% sodium hydroxide
1569solution. However, this will not yield very much more product, because most
1570of this oily material is the diphenylacetone byproduct.
1571    
1572    The underground chemist is now ready to produce phenylacetone. The
1573compound shown above will react with sulffiuric acid to produce 
1574phenylacetone and carbon dioxide gas. He mixes up 150 ml of 50% sulffiuric
1575acid. To do this, he adds slightly more than 55 ml of sulfuric acid to
1576slightly less than 105 ml of water; if he added more sodium hydroxide and
1577alcohol to his reaction mixture, he mixes up twice as much 50% sulfuric
1578acid.
1579    
1580    The stirrer in the 3000 ml flask containing the sodium hydroxide is 
1581started up again. Then the 50% sulffiuric acid is slowly added to it. It
1582will bubble out carbon dioxide like crazy and crystals of sodium sulfate
1583will be formed. Phenylacetone will also be formed, some of it floating on
1584the surface of the solution, some of it trapped among the crystals formed.
1585When all of the sulffiuric acid has been added, and the bubbling of carbon
1586dioxide has slowed down to just about stopping, the stirring is stopped.
1587    
1588    The glassware is set up as shown in Figure 3. The collecting flask is
15892000 ml. The 3000 ml flask is slowly heated to boiling. The steam carries
1590the phenylacetone along with it to the other flask. This process is called
1591a steam distillation. The distilling is continued until a little more than
15921000 ml is in the collecting flask. By then, almost all the phenylacetone
1593will be carried over into the collecting flask. There will be two layers in
1594the collecting flask, a yellow layer of phenylacetone on top, and a clear
1595water layer. There will be some acid dissolved in the water. Forty grams of
1596sodium hydroxide is dissolved in 150 ml of water, then added to the 2000 ml
1597flask. The flask is stoppered and shaken for one minute to destroy the
1598acid. Then 100 ml of benzene is added to the flask and it is shaken some
1599more. The phenylacetonebenzene layer is poured into a 1000 ml sep ffiunnel
1600and allowed to sit for a couple of minutes. Then the water layer is drained
1601off back into the 2000 ml flask. The phenylacetone layer is poured into a
1602500 ml flask along with a few boiling chips. Then 100 ml of benzene is
1603added to the 2000 ml flask, which is shaken again for about 30 seconds
1604before it is allowed to sit for a few minutes. The benzene layer is poured
1605into the 1000 ml sep funnel and allowed to sit for a couple of minutes. The
1606water layer is drained out, and the benzene layer is poured into the 500 ml
1607flask with the rest of the phenylacetone. The glassware is set up as shown
1608in Figure 5 and the phenylacetone distilled as described in Chapter 3. The
1609yield is about 125 ml of phenylacetone. (For more information on this
1610reaction, see Organic Reactions, Volume 1, published in 1942, page 266.)
1611    
1612    There is another way to make phenylacetone which is better than the
1613method just described. It does not take as long to do, and it is somewhat
1614simpler. As in the first method, the reactants must be measured out
1615carefully. 
1616    
1617    In this case, the main reactant is benzyl cyanide, also called 
1618phenylacetonitrile or alpha-tolunitrile. Benzyl cyanide is now a controlled
1619substance precursor, and so must be made.
1620    
1621    Benzyl cyanide is not outrageously poisonous like sodium cyanide. It is
1622an organic cyanide, called a nitrile. As long as the chemist doesn't drink
1623the stuff, he's OK. It is a somewhat smelly liquid, clear in color.
1624    
1625    This reaction is done similarly to the first method described in this 
1626chapter. First a solution of sodium ethoxide is made, then ethyl acetate is
1627added, mixed in with benzyl cyanide. This produces a solid called 
1628phenylacetacetonitrile. This solid is then added to sulfuric acid, and
1629phenylacetone is produced.
1630    
1631    The same glassware as shown in Figure 12 is used, except that a 3000 ml
1632round bottom flask is used. It is dried out in the oven. Now a sodium
1633ethoxide solution is produced in the same way as described earlier in this
1634chapter. The chemist starts with a chunk of clean sodium metal that weighs
1635128 grams. It is weighed out in a 300 ml beaker half-filled with petroleum
1636distillate or xylene, as described earlier. Then the sodium metal is
1637transferred to another beaker halffilled with anhydrous ether and chopped
1638into small pieces with a clean knife. Then it is scooped out with a spoon
1639and put in the 3000 rnl flask. The glassware is quickly assembled as shown
1640in Figure 12, with the 3000 ml flask sitting in a pan. Water flow through
1641the condenser is begun, and 300 ml of absolute ethyl alcohol is put in the
1642sep funnel. The same precautions as described earlier are used to keep the
1643alcohol free of water. As the alcohol is allowed to flow in onto the
1644sodium, the reaction is kept under control by putting cold water in the pan
1645and wrapping the flask in a wet towel.
1646    
1647    When the reaction is under control, more alcohol is added until a total
1648of 1500 ml has been added. The alcohol is gently boiled until the sodium
1649metal is dissolved.
1650    
1651    Now the chemist mixes 500 grams of benzyl cyanide with 575 grams of
1652ethyl acetate and stops the heating of the ethanol solution. Just as it
1653stops boiling, the mixture of ethyl acetate and benzyl cyanide is added
1654with good magnetic stirring. This addition takes about 15 minutes. The
1655stirring is continued for about 10 minutes after the addition is complete,
1656then the mixture is heated in a steam bath or in a pan of boiling water for
1657about 2 hours. Then it is taken out of the heat and allowed to sit
1658overnight, or at least for a few hours.
1659    
1660    The underground chemist has just made the sodium salt of 
1661phenylacetacetonitrile. To collect it, he cools the flask in a mixture of
1662salt and ice. With a clean wooden stick, he breaks up the chunks of
1663crystals that have formed, as the flask is cooling down. When it reaches
1664-10øC, he keeps it at this temperature for a couple of hours, then filters
1665out the crystals. They are rinsed a couple of times with ether, then, while
1666still wet with ether, added to a large flask or beaker containing 2000 ml
1667of water. They are dissolved by stirring, then the flask or beaker is
1668cooled down to 0øC by packing it in ice mixed with salt. When it reaches
1669this temperature, 200 ml of glacial acetic acid is added to it with
1670vigorous stirring. The chemist must make sure that the temperature does not
1671go up more than a few degrees while he is adding it.
1672    
1673    He has now made phenylacetacetonitrile. He filters the crystals off it
1674and rinses them a few times with water. The crystals must now be kept moist
1675in order for them to be turned into phenylacetone.
1676    
1677    All is now ready for producing phenylacetone from these crystals. In a
16782000 ml flask, he puts 700 ml of concentrated sulfuric acid. It is cooled
1679down to -10ø C by packing the flask in a mixture of salt and ice, then
1680magnetic stirring is begun. The crystals are slowly added to the sulfuric
1681acid. They must be moist, or he will get a mess. It takes about an hour to
1682add the crystals to the sulfuric acid. Once they are added, the flask is
1683heated in a pan of boiling water and swirled around to dissolve the
1684crystals. After they have dissolved, the flask is heated for a couple more
1685minutes, then removed from the pan of boiling water. It is cooled down
1686slowly to 0ø C by first letting it cool down, then packing it in ice.
1687    
1688    The underground chemist puts 1700 ml of water in a 3000 ml flask. Half
1689of the sulfuric acid solution is added to it. It is heated in a pan of
1690boiling water for a couple of hours. It is given a couple of good shakes
1691every 15 minutes. A layer of phenylacetone forms in the mixture.
1692    
1693    After 2 hours of heating, the mixture is poured into a gallon-size 
1694glass jug to cool off. Another 1700 ml of water is put in the flask and the
1695rest of the chilled sulfuric acid solution is poured into it. It is also 
1696heated for 2 hours in a pan of boiling water, then poured into another
1697glass jug.
1698    
1699    The chemist is ready to separate the phenylacetone from the water and
1700distill it. The liquid in the first jug is slowly poured into a 1000 ml sep
1701funnel until the sep funnel is full. Most of the phenylacetone layer will
1702be in the sep funnel, because it is floating on top of the water. The water
1703layer is drained back into the jug, and the phenylacetone layer is poured
1704into a large beaker. He adds 300 ml of benzene to the jug, stoppers it and
1705shakes it for 15 seconds. Then he stops and lets the layer of benzene
1706containing phenylacetone float up to the surface. It is slowly poured into
1707the sep funnel, and the water layer is drained back into the jug. The water
1708is thrown away. This process is repeated with the other jug.
1709    
1710    This phenylacetone has some sulfuric acid in it. The chemist puts 150
1711ml of water in the 1000 ml sep funnel. He also pours half of the 
1712phenylacetone and benzene mixture he got from the two jugs into the sep
1713funnel. He shakes it with the water to remove the sulfuric acid. The water
1714is drained out, and the phenylacetone-benzene layer is poured into a 1000
1715ml round bottom flask. Another 150 ml of water is put into the sep funnel.
1716It is shaken also, then the water layer is drained off. He pours as much of
1717this benzene-phenylacetone mixture into the 1000 ml round bottom flask as
1718he can until it reaches 2/3 full.
1719    
1720    The glassware is set up as shown in Figure 5 in Chapter 3, with a few
1721boiling chips in the 1000 ml flask. The collecting flask is 250 ml. He
1722distills off a couple of hundred ml of benzene to make room for the rest of
1723the product. When there is some room, he turns off the heat and waits for
1724the boiling to stop. Then the rest of the benzenephenylacetone mixture in
1725the sep funnel is added to the 1000 ml flask. The distillation is continued
1726until the benzene stops coming over. About 500 to 600 ml of benzene will be
1727collected.
1728    
1729    When the rate of benzene distillation slows down to just about 
1730stopping, the heat is turned off and it is allowed to cool down. Then the
1731last of the benzene is removed under a vacuum. When the benzene is gone,
1732the collecting flask is changed to a 500 ml flask and the phenylacetone is
1733distilled under a vacuum at the usual temperature range. The yield is about
1734300 ml of phenylacetone. Once the benzene is gone, virtually all of the
1735material left in the flask is phenylacetone. If there is a high boiling
1736residue, it is unchanged phenylacetacetonitrile.
1737    
1738                                 References
1739    
1740   Journal of the American Chemical Society, Volume 60, page 914 (1938).
1741    
1742    
1743--------------------------------------------------------------------------
1744                     PHENYLACETONE VIA THE TUBE FURNACE
1745--------------------------------------------------------------------------
1746    
1747    The best way to produce phenylacetone on a large scale and continuous
1748basis is by a catalyst bed inside a tube furnace. This has several
1749advantages over the other methods described in this book. Cheap and very
1750common acetic acid is used to react with phenylacetic acid instead of the
1751expensive and more exotic acetic anhydride and pyridine. Use of the tube
1752furnace frees up the glassware for use in other operations. The furnace
1753requires very little attention while it is in operation, which allows the
1754underground chemist to spend his time turning the phenylacetone into
1755methamphetamine. There is no reason why this process cannot be used in
1756small-scale production. It is just that its advantages really come out when
1757large amounts of phenylacetone must be produced.
1758    
1759    In this process, a mixture of phenylacetic acid and glacial acetic acid
1760is slowly dripped into a Pyrex combustion tube which is filled with
1761pea-sized pumice stones covered with a coating of either thorium oxide or
1762manganous oxide catalyst. This bed of catalyst is heated to a high
1763temperature with a tube furnace and the vapors of phenylacetic acid and
1764acetic acid react on the surface of the catalyst to produce ketones. Three
1765reactions result.
1766    
1767    The acid mixture is prepared so that there are three molecules of 
1768acetic acid for every molecule of phenylacetic acid. This makes it much
1769more likely that the valuable phenylacetic acid will react with acetic acid
1770to produce phenylacetone rather than with another molecule of phenylacetic
1771to produce the useless dibenzyl ketone.
1772    
1773    The vapors are kept moving in the catalyst tube by a slow stream of
1774nitrogen and eventually the product comes out the far end of the catalyst
1775tube. The vapors are then condensed and collected in a flask.
1776    
1777    The complete apparatus for doing this reaction is shown in Figure 13.
1778The combustion tube is made of Pyrex and is about one meter long. It is
1779about 2 centimeters in internal diameter, with a male 24/40 ground glass
1780joint on one end and a female 24/40 ground glass joint on the other end. If
1781the underground chemist cannot buy the tube with the glass joints already
1782on it, there are many places which will weld these glass joints onto the
1783tube. He can find such a place by asking around and checking the Yellow
1784Pages.
1785    
1786    The tube furnace must be 70 centimeters in length. The only 
1787commercially available tube furnace that I know of is the Hoskins tube
1788furnace. It is a fine furnace, but only 35 cm in length. Two of these would
1789have to be run end-to-end to get the required 70 cm length. The cost,
1790including a transformer for each of the furnaces, would be over $700. It is
1791better and cheaper for the chemist to build his own tube furnace.
1792    
1793    The tube furnace starts with a section of thinwall iron tubing about 75
1794cm long and 3 to 3.2 cm in internal diameter. Thinwall iron tubing has a
1795metal thickness of .024 inch. The outside of the tubing is wrapped with
1796asbestos cloth or asbestos paper to a thickness of about 2 millimeters.
1797Asbestos cloth or paper is available at hardware stores.
1798    
1799    Fifty feet of 28 gauge AWG nichrome wire is wrapped around the central
180070 cm of the tube. The windings are made fairly taut so that the wire sinks
1801slightly into the asbestos paper. Each winding is evenly spaced from the
1802previous one, about 1/2 cm apart. One winding must not be allowed to come
1803into contact with another, or there will be a short circuit.
1804    
1805    The outside of the tubing is insulated with 6 or 7 layers of asbestos
1806paper or cloth. This insulation is held in place by using copper wire
1807ligatures about 6 inches long, wrapped around the outside of the
1808insulation, and tied at the ends to make it tight.
1809    
1810    The two ends of the nichrome wire are attached to insulated connectors
1811(two of them) and then to a transformer. The Variac autotransformer is
1812perfect for this job. It can adjust 115-volt house current anywhere from
1813140 volts down to zero. The transformer can handle 5 amps of current.
1814    
1815    The chemist picks up a couple of pumice foot stones (Dr. Scholl's are
1816suitable) at the pharmacy. With a hammer and screw driver, he breaks them
1817into round pieces somewhat smaller than a pea. Any sharp or protruding
1818edges are knocked off. He makes enough of these pumice pebbles to fill the
1819combustion tube for a length of 70 cm.
1820    
1821    The pumice must now be purified to remove traces of metals and other
1822garbage. This prevents the catalyst from being poisoned. The pumice pebbles
1823are put into a 1000 ml beaker along with a wad of glass wool (Angel Hair)
1824somewhat larger than a fist. The glass wool will be going into the
1825combustion tube, so it must be cleaned off along with the pebbles. The
1826glass wool is packed down. Then nitric acid is added until both the pumice
1827and glass wool are covered. The beaker is put on an electric hot plate and
1828the nitric acid boiled for half an hour. This converts metal impurities
1829into soluble nitrates, and oxidizes other garbage. The nitric acid is all
1830poured off and down the drain. The pumice and glass wool are then covered
1831with distilled water and soaked for 5 minutes. This water is then drained
1832off and replaced with more water. The water is boiled for 10 minutes, then
1833drained off. This boiling water rinse is repeated two more times using
1834distilled water. Finally, the water is drained out and the beaker laid on
1835its side to drip out the last drops of water.
1836    
1837    The pumice pebbles are now ready to be coated with catalyst. About 450
1838ml of distilled water is put into a clean 1000 ml beaker. The chemist
1839dissolves 276 grams of thorium nitrate into this water. In another clean
1840beaker, he dissolves 106 grams of anhydrous sodium carbonate into 400 ml of
1841distilled water. (He uses A.R. grade chemicals.)
1842    
1843    Slowly, and with constant stirring, the sodium carbonate solution is 
1844added to the thorium nitrate solution. Using a mechanical stirrer to stir
1845the thorium nitrate solution is best, but a glass rod also works.
1846    
1847    Thorium nitrate reacts with sodium carbonate to make thorium carbonate
1848and sodium nitrate. Thorium carbonate does not dissolve in water, so it
1849forms a white precipitate. Sodium nitrate stays dissolved in water. The
1850stirring is continued for a couple of minutes after all the sodium
1851carbonate has been added, then it is allowed to settle. The thorium
1852carbonate settles into a gooey gunk at the bottom of the beaker. As much of
1853the water as possible is poured off. Then 600 ml of distilled water is
1854added to the thorium carbonate and stirred around with a clean glass rod.
1855The chemist makes sure that all the thorium carbonate gets into contact
1856with the clean water, and that any lumps are broken up. This dissolves any
1857remaining sodium nitrate.
1858    
1859    The thorium carbonate is allowed to settle again, then as much of the
1860water as possible is poured off. Small amounts of distilled water are added
1861and stirred in until a fairly thick paste is formed. Now the purified
1862pumice pebbles are added and stirred around until they are all evenly
1863coated with thorium carbonate.
1864    
1865    A Pyrex glass cake pan is placed on the electric hot plate. The heat is
1866turned on to 1/4 maximum and about 1/8 of the coated pumice pebbles are
1867added to the glass pan. They are heated there with constant stirring with a
1868thick glass rod, so that the pieces dry out evenly. When the coated pumice
1869pebbles no longer stick together, they are dry enough. They are transferred
1870to a clean sheet and an equal amount of wet pumice pebbles are put in the
1871cake pan. They are dried out like the first group of pebbles. This process
1872is repeated until all the coated pumice pebbles are dry. Any white powder
1873that failed to stick to the pumice is collected and saved in a glass jar.
1874If it is later necessary to change the catalyst bed, this material is
1875wetted and used to coat new pumice pebbles.
1876    
1877    A plug of the purified glass wool about 3 cm long is put into the 
1878combustion tube about 15 cm from the male end. This will hold the catalyst
1879bed in place. The tube is filled up with the coated pumice pebbles for a
1880length of 70 cm or so. A small plug of purified glass wool about 1 cm in
1881length is put every 15 cm. This reduces the danger that tar building up on
1882the pumice pebbles will block the tube.
1883    
1884    The tube is put inside the furnace. If two Hoskins tube furnaces are
1885used end-to-end, the tube is insulated in the space between the two
1886furnaces with several layers of asbestos paper or cloth. In this space, the
1887tube is filled with loose glass wool. This space is not counted as part of
1888the necessary 70 cm of catalyst bed.
1889    
1890    The apparatus is set up as shown in Figure 13. It is tilted at an angle
1891of about 20 degrees, the end with the sep funnel being higher than the end
1892with the collecting flask. The sep funnel has a one-hole stopper with a
1893piece of glass tubing running through it almost all the way to the valve of
1894the sep funnel. This is a constant pressure device that causes the contents
1895of the sep funnel to drip into the tube at a constant rate, no matter what
1896the level of the acids in the sep funnel at a particular instant.
1897    
1898    The sep funnel is connected to the female end of the vacuum adapter.
1899The male end of the vacuum adapter is inserted into the female end of the
1900combustion tube. The male end of the combustion tube is connected to a
1901condenser. The condenser is connected to a vacuum adapter, and the vacuum
1902adapter leads to a 500 ml round bottom flask. The glass joints are lightly
1903greased and wired together where possible. The furnace must be supported to
1904prevent its weight from bending the soon-to-become-soft hot glass tube.
1905Clamps connected to ringstands are used to hold the other pieces in place.
1906    
1907    The vacuum adapter connected to the sep funnel is the nitrogen gas
1908inlet. The underground chemist gets a tank of nitrogen at a welding supply
1909shop. He has to make sure that he knows how to use the regulators. He runs
1910a line of tubing from the tank to the "bubbler." The bubbler is shown in
1911Figure 14. It is a bottle with a 2-hole stopper in the top. One hole has a
1912section of glass tubing reaching nearly to the bottom of the bottle. The
1913bottle has about an inch and a half of concentrated sulfuric acid in it.
1914The purpose of the sulfuric acid is to dry the nitrogen gas and to show how
1915fast it is bubbling into the apparatus. The other hole has a short section
1916of glass tubing. Plastic tubing is attached to this tubing and leads to the
1917vacuum nipple of the vacuum adapter.
1918    
1919    And now the time has come for the underground chemist to fire up the
1920furnace. He places a thermometer capable of reading up to 450øC, or, better
1921yet, a thermocouple, in the furnace against the outside of the glass
1922tubing. (If his thermocouple did not come with wiring instructions, he can
1923find the wiring diagram in the Encyclopedia Britannica and in many
1924college-level physics textbooks.) The thermometer or thermocouple extends
1925into the central regions of the furnace. The space at the end of the
1926furnace between the outside of the glass tubing and the inside of the
1927furnace's iron tubing is plugged up with pieces of asbestos paper or cloth
1928to hold in the heat.
1929    
1930    He turns on the electricity to the furnace, and begins a slow stream of
1931nitrogen (about one bubble per second) through the tube. He keeps a sheet
1932listing the temperatures his furnace gets at various voltage settings on
1933the transformer. Of course, it takes a while for the furnace to heat up to
1934its true temperature at a given setting.
1935    
1936    Now the tube furnace is heated to 425-450øC, while the slow stream of
1937nitrogen continues through the tube. The heat turns the thorium carbonate
1938into thorium oxide. The heating continues for 12 hours, after which the
1939catalyst is ready to produce phenylacetone. 
1940
1941    The chemist mixes 200 grams of phenylacetic acid with 250 ml of glacial
1942acetic acid. He mixes them thoroughly, the phenylacetic acid dissolving
1943easily in the glacial acetic acid. (Glacial acetic acid is the name for
1944pure acetic acid; it is so called because it freezes at a little below room
1945temperature.)
1946    
1947    This acid mixture is poured into the sep funnel and the funnel is 
1948stoppered with the one-hole stopper with the glass tubing constant pressure
1949device. The temperature of the furnace is 425- 450ø C, and a 
1950one-bubble-per-second stream of nitrogen has been flowing through the tube
1951for at least 2 hours. The valve on the sep funnel is opened so that about
195220 drops of the acid mixture drip into the tube from the sep funnel every
195330 seconds.
1954    
1955    A slow flow of water is put through the condenser to condense the
1956ketones as they leave the furnace. The product collects in the 500 ml flask
1957and the nitrogen gas exits through the vacuum nipple of the vacuum adapter
1958connected to the condenser. If there is trouble condensing all the acetone,
1959the 500 ml flask is packed in ice.
1960    
1961    It takes about 5 hours for all the acid to drip into the tube. When all
1962the acid mixture has dripped in, 25 ml of acetic acid is added to the sep
1963funnel and dripped in. This flushes the last of the product out of the
1964catalyst bed.
1965    
1966    The product in the 500 ml flask consists of a lower water layer and a
1967brown-colored organic layer on top. It is poured into a 1000 ml sep funnel;
1968the water layer is then drained off into a clean beaker, and the organic
1969layer is poured into another beaker. The water layer is put back into the
1970sep funnel along with 50 ml of benzene, and the funnel is shaken. It is
1971allowed to sit for a few minutes, then the lower water layer is drained off
1972and thrown away. The benzene layer is poured in with the organic layer in
1973the other beaker.
1974    
1975    The chemist is now ready to clean up the phenylacetone so that it can
1976be distilled. He mixes up a supply of 10% sodium hydroxide solution by
1977adding 10 ounces of lye to 3/4 gallon of water in a glass jug. He pours the
1978organic layer into the sep funnel, adds 400 ml of the sodium hydroxide
1979solution and shakes. The water layer is drained off into a clean beaker and
1980the organic layer is poured into another beaker. The water layer is
1981returned to the sep funnel and 75 ml of benzene added. The funnel is
1982shaken, then the water layer is drained off and thrown away. The benzene
1983layer is poured in with the organic layer. This is repeated three more
1984times, then the phenylacetone is distilled as described in Chapter 3. The
1985yield of phenylacetone is about 100 ml.
1986    
1987    The temperature of the furnace is raised to about 525øC, and a slow
1988stream of air is drawn through the tube for two hours. The air is drawn
1989through by turning off the nitrogen flow, opening up the valve of the sep
1990funnel and attaching a vacuum hose to the vacuum nipple of the vacuum
1991adapter on the 500 ml flask side of the apparatus. This air flow burns off
1992built up crud on the catalyst and charges it up for another run. It is done
1993after the first run, and then after every few batches.
1994    
1995    The furnace temperature is set at 425-450-ø C again and the flow of
1996nitrogen through the tube is resumed. It is flushed out for a couple of
1997hours, then the sep funnel is filled with acid mix for another run. It is
1998dripped in as before to get another batch of phenylacetone. In this way,
1999phenylacetone can be produced on a continuous basis.
2000    
2001    If the homemade furnace has trouble reaching the necessary temperature,
2002the chemist wraps it with more insulation. If that does not do enough, a
2003lower temperature process can be used by replacing the thorium-oxide-coated
2004pumice pebbles with manganous-oxidecoated pumice pebbles. The process goes
2005as follows:
2006    
2007    The pumice pebbles are made and purified with nitric acid as described
2008earlier. In a 1000 ml beaker, 70 grams of manganous chloride (MnCl2) is
2009dissolved in 300 ml of distilled water. In another beaker, 38 grams of
2010anhydrous sodium carbonate is dissolved in 500 rnl of distilled water. The
2011sodium carbonate solution is slowly added to the manganous chloride
2012solution with constant stirring. Manganous chloride reacts to form
2013manganous carbonate, which does not dissolve in water and precipitates out.
2014The manganous carbonate is filtered out in a Buchner funnel as described in
2015Chapter 5. The crystals are rinsed with distilled water.
2016    
2017    The manganous carbonate is returned to a clean beaker and enough
2018distilled water is added to make it into a fairly thick paste. If too much
2019water is added, it does not stick well to the pumice. The pumice pebbles
2020are stirred in until they are evenly coated. The beaker is heated on a hot
2021plate while the pumice stones are vigorously stirred. 
2022    
2023    Local overheating must be avoided or the catalyst will be ruined] When 
2024most of the water is evaporated, the catalyst is transferred to a Pyrex
2025cake pan and gently heated on a hot plate. The pumice chips are stirred
2026constantly to get even drying. When they no longer stick together, they are
2027transferred to a clean sheet of paper.
2028    
2029    The chemist fills the combustion tube with the catalyst as before and
2030sets up the apparatus. He heats the furnace to 360-400øC while passing a
2031stream of nitrogen through the tube. This converts the manganous carbonate
2032to manganous oxide (MnO). This heating is continued for 8 hours. Then the
2033heat is reduced to 350øC, while the stream of nitrogen is continued at a
2034rate of one bubble per second. When 350øC is reached, he drips in the same
2035phenylacetic acid-acetic acid mixture used earlier in this chapter. The
2036correct rate is 20 drops every 30 seconds. When it has all dripped in, he
2037adds 25 ml of acetic acid to the sep funnel and drips it in. He then either
2038adds more acid mix to the sep funnel for another run, or shuts down the
2039furnace. If he shuts down the furnace, he must continue the flow of
2040nitrogen through the tube until it has cooled off. This prevents the MnO
2041catalyst from being oxidized to MnO2, etc. When he turns it back on, he
2042must immediately start the nitrogen flow for the same reason. The product
2043is purified in the same way as described earlier in this chapter.
2044    
2045    Since no air is sucked through the tube at high temperature, gunk 
2046builds up on the catalyst and eventually puts it out of commission. When
2047this happens, the catalyst bed is changed. The yield using the manganous
2048oxide catalyst bed is not as good as that using the thorium oxide catalyst
2049bed. Thorium oxide is used, unless the chemist has no choice.
2050    
2051    A somewhat more complicated way to do this reaction is to use what is
2052called a thorium oxide "aerogel" catalyst. A lower temperature and a higher
2053rate of production are possible. For more information about it, see
2054Industrial and Engineering Chemistry, published in 1934, Volume 20, pages
2055388 and 1014.
2056    
2057                                 References
2058
2059    Journal of the Chemistry Society, page 612 (1948); page 171 (1940).
2060                           
2061--------------------------------------------------------------------------
2062                            MAKING PHENYLACETONE
2063--------------------------------------------------------------------------
2064    
2065    There are many other methods of making phenylacetone described in the
2066scientific literature. Most of them are dogs, not worth the time and
2067effort. But there are some good methods of making phenylacetone that I have
2068not yet described.
2069    
2070    An acceptable method is to oxidize methyl benzyl carbinol  
2071(1-phenyl-2-propanol) to phenylacetone (methyl benzyl ketone) with chrome
2072oxide (CrO3) in pyridine solvent. The problem with this is that methyl
2073benzyl carbinol is not commercially available, and so must be made from
2074benzyl chloride grignard reagent and acetaldehyde. This grignard works
2075well, although there can be a problem getting unreacted benzyl chloride out
2076of the product. Their boiling points are very close, so distillation does
2077not separate them completely. But the real question is: Why make the
2078synthesis of phenylacetone a two-step process when it can be done with one
2079reaction?
2080    
2081    Another two-step method of making phenylacetone is to make benzyl
2082cyanide from benzyl chloride and sodium cyanide, and then make the benzyl
2083cyanide into phenylacetone by the method described in Chapter 7. The way to
2084make benzyl cyanide can be found in Organic Syntheses, Collection Volumes
2085I, II and III. Benzyl cyanide is listed in the table of contents.
2086
2087    A good way to make phenylacetone is to react methyl zinc reagent with
2088phenylacetyl chloride. Methyl zinc reagent is made by reacting methyl
2089iodide with zinc metal, or by adding zinc chloride to methyl grignard
2090reagent. It is not an especially difficult reaction to do, and the yields
2091are very good. The problem is that phenylacetyl chloride is expensive and
2092hard to find, although it can be made from phenylacetic acid and thionyl
2093chloride SOCl2.
2094
2095    In what is actually the best method of making phenylacetone, two  
2096molecules of methyllithium react with phenylacetic acid to produce
2097phenylacetone, or one molecule of methyllithium reacts with one molecule of
2098the lithium salt of phenylacetic acid to produce phenylacetone. This
2099reaction is done in anhydrous ethyl ether under an atmosphere of nitrogen.
2100However, organolithium reagents burst into flame upon contact with air.
2101Although methyllithium is not so bad in this respect as t-butyllithium,
2102organolithium reagents are dangerous to handle. But, apart from the element
2103of danger, this is the best way to make phenylacetone. The high cost of
2104lithium is offset by the high yields of product. This reaction comes in
2105especially handy in building up the substituted phenylacetones used to make
2106the psychedelic amphetamine derivatives, such as STP or
2107trimethoxyamphetamine (TMA).
2108    
2109    Another good way to make phenylacetone is to react phenylacetyl
2110chloride with the ethoxymagnesium derivative of dimethyl malonate.
2111Hydrolysis with acid then produces phenylacetone. This reaction is
2112described in the Journal of the American Chemical Society, Volume 70, page
21134214, (1948). This can be found in any good college library.
2114    
2115    Another good method of making phenylacetone is to use a method called
2116the Knoevenagel reaction. In this method, the starting material is
2117benzaldehyde. The advantages to being able to use a wide variety of
2118starting materials to produce phenylacetone are obvious. A temporary
2119shortage of one chemical is not sufficient to cripple an underground
2120chemist's operation. He can also vary his chemical purchases so that there
2121is not a big run on one particular set of ingredients, which could lead to
2122suspiciousness and snooping.
2123    
2124    This reaction is fairly easy to do, and is pretty hard to mess up, so  
2125long as some basic precautions are taken. The underground chemist does his
2126best to make sure that his glassware is dry, and the alcohol used is
2127absolute (100% with no water). He must also do the processing of this
2128material quickly, because the nitroalkene which is formed in the first
2129phase of this reaction will not keep. The reaction goes like this:
2130    
2131    Benzaldehyde reacts with nitroethane in an alcohol solution with  
2132n-butylamine catalyst to produce a crystalline substance called a
2133nitroalkene. This nitroalkene can then be reduced by means of iron and HCl
2134to produce phenylacetone. The reduction is similar to the use of activated
2135aluminum in the reaction to produce methamphetamine without the bomb, in
2136that the metal, in this case iron, dissolves and produces hydrogen which
2137reduces the nitroalkene. It is not as complicated as it sounds, and is
2138pretty easy to do. The nitroalkene is first reduced to phenylacetone oxime,
2139which is then hydrolyzed to phenylacetone.
2140    
2141    You may wonder, looking at the structure of the nitroalkene molecule,
2142if it is not possible to reduce it directly to the prototype amphetamine,
2143benzedrine. The answer is yes. In fact, one method of making the
2144psychedelic amphetamines such as MDA is to get the properly substituted
2145benzaldehyde (in the case of MDA the proper benzaldehyde is called
2146piperonal) and reduce it using a hydrogenation bomb and Raney nickel, or by
2147use of lithium aluminum hydride. Another good method for reducing the
2148nitroalkene directly to amphetamine is to use zinc amalgam and hydrochloric
2149acid in alcohol solvent. A still better method for direct reduction of the
2150nitroalkene to amphetamine is to use palladium black on charcoal in the
2151champagne bottle hydrogenation bomb seen in Figure 17 in Chapter 11.
2152Directions for making palladium black on charcoal are found in the Meth
2153from Ephedrine chapter. A few grams of catalyst per hundred grams of
2154nitroalkene works nicely. Reaction conditions are room temp at a hydrogen
2155pressure of 30 pounds. Hydrogenation is complete in 5 to 10 hours, and the
2156solvent is 190 proof vodka. Best results are obtained if the nitroalkene is
2157purified by recrystallizing the crude product from alcohol prior to
2158reduction.
2159    
2160    This reaction is done as follows: Into a clean, dry 3000 ml round  
2161bottom flask is placed 400 ml of absolute alcohol, 20 ml of nbutylamine,
2162428 grams of benzaldehyde, and 300 grams of nitroethene. The underground
2163chemist sets up the glassware for refluxing as shown in Figure 2b in
2164Chapter 3. He includes the drying tube with Drierite as shown in Figure 2a.
2165He swirls around the flask to mix the contents, then sets the flask on a
2166hot plate and begins heating it. The water flowing through the condenser
2167should be fairly cool, to be sure of condensing the alcohol vapors. A good,
2168gentle rate of boiling is what he aims for. He continues the boiling for 8
2169hours. The solution will turn yellow.
2170    
2171    He makes sure that his chemicals, especially the nitroethane, are of a
2172good grade. Nitroethane is widely used in the paint and varnish industry as
2173a solvent for cellulose acetate lacquers, vinyl resins, nitrocellulose,
2174waxes and dyes. If he has the industrial grade, he first distills it before
2175use. Benzaldehyde smells like bitter oil of almonds and should be clear.
2176Benzaldehyde is used in flavorings and perfumes.
2177    
2178    When the 8 hours of boiling is done, he turns off the heat and lets the
2179flask cool down. Once crystals begin to appear, he takes off the condenser
2180and begins stirring the solution with a glass rod. He continues the
2181stirring, and transfers the flask to a sink of cool water to help speed the
2182cooling. He continues the stirring until the mass of crystals becomes too
2183thick to stir, or the flask is cooled off. The idea of the stirring is to
2184prevent the batch from setting into one solid mass of crystals. The
2185crystals should be yellow in color.
2186    
2187    He now proceeds to purify this 1-phenyl-2-nitropropene. The simplest
2188way to do this is to add ethyl ether to the crystals until a slurry is
2189formed (about 500 ml) and then break up any lumps of crystals with a glass
2190rod. He then filters the slurry through a large coffee filter and squeezes
2191the mass to force out as much of the ether as possible. Along with the
2192ether, he will be removing most of the unreacted benzaldehyde and
2193nitroethene. The crystals will still be yellow, but they will no longer be
2194sticky and gooey. If he still smells n-butyl amine on them, he may rinse
2195them with ether again.
2196    
2197    A better way to clean up these crystals is to recrystallize them. In  
2198large batches like this one, it is a lot of work and he must make
2199provisions for exhausting the fumes to the outside to prevent the danger of
2200explosion, but he will get a cleaner product.
2201
2202    It is done as follows: To the crystals which have been rinsed off with
2203ether and returned to a cleaned, dry 2000 ml round bottom flask, he adds
2204just enough hot petroleum ether to dissolve the crystals. This takes in the
2205neighborhood of 700 ml of petroleum ether. Any type of petroleum ether will
2206do. If he has access to hexane from some industrial source, that will do
2207fine. Petroleum ether is flammable, so the way he makes the ether hot is to
2208place the flask with the crystals into a pan of hot water, and to begin
2209adding the petroleum ether to it. He swirls it around while adding the
2210petroleum ether and keeps adding ether until the crystals are dissolved.
2211The result will be a clear yellow solution. Now he records how much
2212petroleum ether he added and places the flask on the hot plate and sets up
2213the glassware for simple distillation as shown in Figure 3 in Chapter 3. A
2214500 ml flask is fine for the receiving flask. He turns on the heat to the
2215solution, begins water flow through the condenser and distills off about
22161/3 of the ether he added to the crystals to dissolve them. When 1/3 of the
2217ether is distilled off, he removes the flask from the heat, and cools it
2218off in cool water, followed by ice water. He doesn't want to place the
2219flask immediately into ice water, because it might crack.
2220    
2221    Now, as the petroleum ether cools off, it will no longer be able to  
2222dissolve the crystals, and they will re-form in much cleaner shape because
2223the garbage which is polluting them will stay dissolved in the petroleum
2224ether. Once the petroleum ether is cold, he filters the crystals through a
2225filtering funnel the same way it was described in Chapter 5. He places the
2226crystals out to dry on a glass or china plate, and returns the yellow
2227petroleum ether solution which filtered through to the distilling flask.
2228This solution still contains a good deal of crystals dissolved in it.
2229    
2230    He sets up the glassware as before and distills off another i/3 of the  
2231petroleum ether, then cools off the flask as before. Once again, crystals
2232will form, although they will not be of as high quality as the first crop.
2233He filters them as before, and returns the ether to the distilling flask.
2234Now he distills off about % as much petroleum ether as before, then cools
2235off the flask and waits for the crystals to form. This will be his last
2236crop of crystals. He filters them and sets them out to dry. The total
2237amount of crystals he will get will be about 420 grams.
2238    
2239    The underground chemist must now proceed to reduce these crystals of
22401-phenyl-2-nitropropene to phenylacetone. If he lets them sit around, they
2241will begin to poIymerize into a black, gooey mess (though he can delay them
2242going bad by putting them in the freezer).
2243    
2244    Into a clean 3000 ml flask, he places 164 grams of the nitroalkene  
2245crystals he just made. To that he adds 750 ml of distilled water, 400 grams
2246of cast iron turnings about '/40 inch in size, and four grams of iron
2247chloride (FeCl3). The flask is placed in a glass dish large enough to hold
2248it, and cooking oil is added to the dish so that it reaches about half way
2249up the sides of the flask. He places the flask with the dish of oil onto a
2250hot plate, and heats the oil to about 105ø C. He puts a mechanical stirrer
2251into the flask with a glass rod and Teflon stirring paddle, and begins
2252stirring the mixture in the flask. Once the temperature of the contents of
2253the flask nears 80ø C, he measures out 750 ml concentrated hydrochloric
2254acid. He adds it slowly to the flask over a period of 5 hours. The iron
2255will slowly react with the acid and dissolve, producing hydrogen which will
2256reduce the nitroalkene to phenylacetone oxime. The oxime then reacts with
2257more water and HCl to give phenylacetone.
2258    
2259    When the acid has all been added, he removes the flask from the heat
2260and lets it cool down. Then he mixes up 350 grams of sodium hydroxide or I
2261ye in 1000 ml of water. Once they have both cooled down, he adds the sodium
2262hydroxide solution to the 3000 ml flask and swirls it around.
2263    
2264    He will now distill out the phenylacetone with steam. He adds a few
2265pumice boiling chips to the 3000 ml flask, and places it on the hot plate.
2266He sets up the glassware for simple distillation (not fractional  
2267distillation) as shown in Chapter 3. A 1000 ml flask will do fine for the
2268receiving flask. He heats the 3000 ml flask until it boils. The steam from
2269the water in the flask will carry the phenylacetone along with it and
2270deposit them both in the 1000 ml flask. A reasonable flow of about 1 gallon
2271per minute is enough water flowing through the condenser.
2272    
2273    The liquid collecting in the receiving flask has 2 layers, a lower  
2274layer of water, and floating on top of that a yellowish layer of
2275phenylacetone. He continues boiling the 3000 ml flask until no more
2276phenylacetone is coming over with the steam. The 1000 ml flask will be
2277nearly full of water and phenylacetone when the process is finished. Now he
2278pours both layers into a 1000 ml sep funnel. He drains off the lower layer
2279of water into a beaker. He pours the top layer of phenylacetone into a 500
2280ml flask. Now he takes the water layer and returns it to the sep funnel. He
2281adds 200 ml of benzene and shakes it up. He lets it sit for a while, then
2282drains off the lower layer of water and throws it out. He pours the benzene
2283layer into the 500 ml flask along with the phenylacetone.
2284    
2285    He can now either distill the phenylacetone as described in Chapter 3,
2286or reduce more of the nitroalkene. If he chooses to distill each run
2287separately, he will get about 130 ml of phenylacetone from each run.
2288    
2289    The steam distillation can be omitted if a lower grade of phenylacetone
2290is acceptable. To do this, the chemist simply filters the reaction mixture,
2291after it has been treated with sodium hydroxide, through a one inch thick
2292plug of angel's hair. Then he extracts out the phenylacetone by adding a
2293couple hundred mls of toluene (available at the hardware store in the paint
2294section), and separating off the phenylacetone-toluene layer floating on
2295top with a sep funnel. A more careful fractional distillation of the
2296resulting mixture gives phenylacetone that is almost as pure as with the
2297steam distillation.
2298    
2299    One of the best articles written on the Knoevenagel reaction in the
2300English language is in the Journal of Organic Chemistry, Volume 15, pages 8
2301to 14. Another reference is Organic Reactions, Volume 15.
2302    
2303                                  Method 2
2304    
2305    This variation of the Knoevenagel reaction will give somewhat higher
2306yields of product than the preceding method. The reason for the higher
2307yield is the use in this method of toluene as solvent, and the placement of
2308a Dean Stark trap above the flask to remove water from the mixture as it is
2309formed. Removal of water favors the formation of greater quantities of
2310nitroalkene.
2311    
2312    To do the reaction, a 1000 ml round bottom flask is filled, in this   
2313order, with 200 ml of toluene, 100 ml of benzaldehyde, 90 grams (86 ml) of
2314nitroethane, and 20 ml of butylamine. It is a good idea to swirl the flask
2315after adding each ingredient to prevent layers from forming. Next the flask
2316is placed on a one burner electric buffet range with infinite control, and
2317the glassware is set up as shown in Figure 15.
2318    
2319    The Dean Stark trap is attached to the flask, and a condenser is   
2320attached to the Dean Stark trap. Then the buffet range is turned on at a
2321heat setting high enough to produce a rapid boiling of the toluene, and
2322cold water is flowed through the condenser. As the reaction is progressing,
2323the vapors of toluene carry water along with them, and when they turn back
2324to liquids in the condenser, the water will settle in the trap portion of
2325the Dean Stark trap because water is heavier than toluene. You will also
2326note a milky appearance to the toluene due to suspended water in it. The
2327trap portion of the Dean Stark trap is graduated in milliliters. This
2328allows you to keep track of how much water has been collected. Half of the
2329water is collected in the first hour, and the full amount (18 ml) is
2330collected after five hours of boiling. When this is done, the heat is
2331removed, and the flask allowed to cool. This phase of the reaction has just
2332made the nitroalkene.
2333    
2334    One should wish to collect the nitroalkene for direct reduction to
2335amphetamine, one just needs to remove the Dean Stark trap, rig the flask
2336for simple distillation as shown in Figure 3, and remove the toluene under
2337a vacuum from an aspirator, using gentle heating from a hot water bath. It
2338should be noted that the nitroalkene has a slight tear gassing effect upon
2339the eyes, and also irritates the skin. Do not use the stuff as a body balm.
2340    
2341    If phenylacetone is desired from the nitroalkene, the toluene solution
2342produced in the reaction is used directly in the next step. Once it has
2343cooled down, it is poured into a 2000 ml 3 necked flask. Then into the 3
2344necked flask is added 500 ml of water, 200 grams of iron powder (40 to 100
2345meth), and 4 grams of ferric chloride (FeCl3). Then into the center neck of
2346the flask is put a mechanical stirrer reaching almost to the bottom of the
2347flask. There should be a tight seal so that the ensuing vapors of toluene
2348when the flask is heated do not escape by this route. A good condenser is
2349attached to one of the other necks, and a sep funnel, or dropping funnel
2350with matching ground glass joint is put into the remaining neck. With
2351vigorous stirring, the contents of the flask are heated to about 75øC, and
2352360ml of concentrated hydrochloric acid is added to the flask by means of
2353dripping it into the mix through the sep funnel over a 2 hour period. The
2354reaction mixture will boil vigorously. The heating and stirring are
2355continued for an additional half hour after the last of the hydrochloric
2356acid has been added.
2357    
2358    Next it is time to get the phenylacetone out of the reaction mixture.
2359Once the flask has cooled down, the iron is filtered out by pouring it
2360through the plug of angel hair described earlier in this chapter. It is a
2361good idea to rinse down the trapped iron powder with a dash of toluene to
2362get any clinging phenylacetone off of it. Then the toluene layer is
2363separated using a sep funnel. It is poured into a round bottom flask. The
2364water layer has about 100 ml of toluene added to it, and this is shaken to
2365draw suspended phenylacetone into the toluene. The toluene layer is then
2366separated and added to the aforementioned round bottom flask. It is then
2367rigged for fractional distillation as shown in Figure 5. The toluene
2368distills off first as the toluene-water azeotrope at 85øC, and then as pure
2369toluene at 110øC. Once the toluene is mostly gone, vacuum is applied, and
2370phenylacetone is collected at the usual temperature range. The yield is
2371about 120 ml of phenylacetone.  
2372    
2373    
2374--------------------------------------------------------------------------
2375            A New Breakthrough: Phenylacetone From Allylbenzene
2376--------------------------------------------------------------------------
2377
2378    In 1987, an exciting breakthrough in the field of methamphetamine 
2379manufacture occurred. This new development was so important because it
2380promised to completely turn the tables on the DEA-led chemical blockaders
2381and controllers. The new discovery was a patent issued in that year
2382covering a simple and quick method for converting allylbenzene into
2383phenylacetone. This method is exquisitely suited for clandestine
2384operations, and is easily scaled up to industrial proportions.
2385    
2386    The extreme importance of this discovery can be appreciated by a quick
2387review of the chemical supply situation. Phenylacetic acid is now next to
2388impossible to obtain, with the exception of purchasing it from narco swine
2389front operations. It is reliably made fiom benzyl chloride by the
2390directions given in Organic Syntheses, but this is a hasslesome and very
2391stinky operation. A large scale phenylacetic acid production operation will
2392not go unnoticed by meddlesome neighbors. Furthermore, the cooks will carry
2393the evidence on their bodies and clothing for weeks after they have done
2394their dirty deeds. Turned up noses will follow them wherever they go!
2395    
2396    An alternative and very popular route to methamphetamine featuring the
2397conversion of ephedrine into methamphetamine via chlorephedrine has been
2398similarly, but less successfully, crimped upon. Here the chemical pinch
2399points have been phosphorus and palladium black on charcoal. This method of
2400making methamphetamine was left out of the original edition because of the
2401noxious nature of the impurities caused by this reaction. They can be
2402easily carried into the final product if proper care is not taken in
2403purification. Much of the garbage crank now seen on the streets is made by
2404this method and contains unreacted chlorephedrine along with related filth.
2405    
2406    This chlorinated filth causes a vague "poisoned" feeling as a result of
2407taking it. Dull aches in the liver and kidney areas can be felt. This slop
2408also ruins the more subtle and finer qualities of methamphetamine. This
2409edition will describe how ephedrine is converted into methamphetamine, with
2410special emphasis given to the key steps in removing the noxious byproducts
2411from the final product.
2412    
2413    The new method of producing phenylacetone from allylbenzene completely
2414bypasses the roadblock put up by the narco swine. Allylbenzene is in itself
2415rather overpriced and possibly the subject of central scrutinizer
2416suspicion. However, for the resourceful manufacturer it is easily made
2417either in quantitative (100%) yields and pristine purity by the reaction of
2418arylcopper and allyl bromide, or at bargain basement prices in carload
2419amounts by the direct Freidel-Crafts reaction between benzene and allyl
2420bromide. Add to this the possibility of producing amphetamine directly from
2421allylbenzene by the Ritter reaction, and the position of the chemical
2422controllers becomes hopelessly complicated. The sure result is the prospect
2423of floodgates opened wide to massive amphetamine production.
2424    
2425    This new reaction can be done in any one of several closely related
2426ways, each with excellent results. In each of its variations, the overall
2427path of the reaction is to turn allylbenzene into phenylacetone:
2428    
2429    The reaction appears to work in the following manner: Allylbenzene
2430reacts with two molecules of methyl or ethyl nitrite in alcohol solvent to
2431produce an intermediate product:
2432    
2433    This intermediate product then reacts with water to give phenylacetone.
2434    
2435    A key feature of this reaction is its use of palladium chloride as a 
2436catalyst. Because of the high cost of palladium salts, the inventors of the
2437patent went to great lengths to find ways to make less of it go further.
2438They discovered that by adding some copper chloride or trimethylamine into
2439the reaction mixture, the amount of palladium used could be greatly cut.
2440The drawback to this is that the yield of phenylacetone goes down a little
2441bit. Both variations will be described here.
2442    
2443    A potentially serious problem looms in the path of those who would like
2444to give this reaction a try. The problem is that alkyl nitrites such as
2445methyl or ethyl nitrite are not easily purchased. The reason for this is
2446their use in products which were formerly on sale under such names as
2447"Rush," "Locker Room," or "Jock Aroma." Inhaling this class of substances
2448produces an intense head rush, and disorientation. In many states, these
2449substances are now classified as controlled substances. In all cases, this
2450properly necessitates great care on the part of the chemist in handling
2451this material, lest he be overcome. These nitrites are easily made in large
2452amounts, however, so any serious manufacture operation can quickly
2453stockpile enough in the freezer to supply a massive output. Later in the
2454chapter, I will describe how nitrites are made.
2455    
2456    The alcohols which are best used in this reaction are either methyl
2457alcohol or ethyl alcohol. Methyl alcohol, also known as wood alcohol or
2458methanol, is easily and cheaply purchased in the paint section of the 
2459hardware store. Ethyl alcohol, or ethanol, is best purchased as 190 proof
2460vodka. As such it contains 5% water, but since water is needed for the
2461hydrolysis stage of the reaction, this presents no problem. In all cases,
2462it is best to use the alcohol which has the same number of carbon atoms in
2463it as the nitrite uses. For example, methyl alcohol is used with methyl
2464nitrite, and ethyl alcohol with ethyl nitrite.
2465    
2466    If the number of carbons match between the nitrite and the alcohol,
2467this makes recycling the alcohol and unreacted nitrite at the end of the
2468reaction a much simpler matter. The patent does not specify why this is the
2469case, but I am led to suspect that the possibility of exchange between the
2470alcohol and the nitrite exists. For example, if butyl nitrite is used with
2471ethyl alcohol, one could end up with a mixture containing some butyl
2472alcohol and ethyl nitrite.
2473    
2474    The reason for the use of methyl or ethyl nitrite in this reaction is 
2475two-fold. First of all, the matching alcohols are very easily picked up at
2476the hardware or liquor stores. The second reason is that the methyl and
2477ethyl nitrites give a little higher yields at lower temperatures. For 
2478example, methyl nitrite gives 90% yield of phenylacetone at a reaction
2479temperature of room temperature. Butyl nitrite, on the other hand, gives a
248087% yield at a temperature of 55øC. The possibility of running a batch at
2481room temperature makes bathtub size production easy to envision.
2482    
2483    The drawback to use of methyl or ethyl nitrites comes from their low
2484boiling points. Methyl nitrite is a gas with a boiling point of -12øC. 
2485Ethyl nitrite boils at 16.5øC, which is below usual room temperature. Even
2486cooled well below that point, one could count on it giving off a powerful
2487aroma. The solution to this problem is to dissolve the nitrite into several
2488volumes of its corresponding anhydrous alcohol, and then store the solution
2489in a tightly stoppered bottle in a freezer. This stock alcohol solution is
2490then added to the reaction mixture when its time comes. This still leaves
2491the difficult problem of "catching" these nitrites with a condenser when
2492one makes them in the first place. For these reasons, the most practical
2493nitrite to use in this reaction may well be butyl nitrite. Its boiling
2494point of 78øC makes handling it an easy matter. The lucky experimenter may
2495also be able to purchase it directly off the shelf in the form of "Rush"
2496type inhalers. If the underground chemists forego a simple recycling
2497procedure at the end of the rreaction, then the butyl nitrite can be used
2498with the easily available methyl or ethyl alcohols. All things considered,
2499this may be the best choice for the clandestine operation. Besides, butyl
2500alcohol smells awful, and is expensive.
2501    
2502    The setup needed to run this reaction is simplicity itself. The primary
2503requirement is a glass container to hold the reactants. For the size of
2504batch we will be discussing, a 5000 ml round bottom flask or a one gallon
2505wine jug perform admirably. For scaled up production, a 5 gallon office
2506water cooler carboy fits the bill nicely.
2507    
2508    The second requirement is a stirring device. For the size of batch 
2509discussed here, a magnetic stirrer is perfect. For the larger production
2510levels, at mechanical stirring rig is advisable. The need for good stirring
2511is brought about by the fact that the palladium catalysts are not readily
2512soluble in alcohol. They do dissolve well in water, but since water is a
2513small fraction of the total solution, the underground chemist can't count
2514on it all dissolving as the reaction is run. Good agitation brings any
2515undissolved palladium up into contact with the solution. It does little
2516good sitting on the bottom of the flask.
2517    
2518    To turn out a two mole batch (i.e., a little over 200 ml of 
2519phenylacetone product) by the first, palladium-wasteful method, the
2520following method is used:
2521    
2522    Into the glass reaction vessel is placed three liters of either methyl
2523or ethyl alcohol. To this is added 236 grams (262 ml) of allylbenzene. If
2524methyl alcohol is used, 750 ml of water is then added. If 190 proof spirit
2525is used, then only 630 ml of water is added because it already contains 5%
2526water. Then 28 grams of palladium chloride is added. The adventuresome
2527experimenter may dissolve the palladium chloride into the water added to
2528the reaction instead of putting them in separately. This converts the PdCl2
2529into the hydrate, which is much more soluble in the water portion of the
2530solution.
2531    
2532    Next, the temperature of the mixture is brought up to the correct 
2533level. For butyl nitrite, the temperature of 55øC is reached by using hot
2534water, steam, or heating tape. If a wine jug is the reaction vessel, care
2535is used in rapid and uneven heating, as this could crack the glass. This is
2536the reason why chemical glassware is made of Pyrex. 
2537    
2538    When the correct temperature is reached, 5 moles of nitrite is added
2539with the stirring going full blast. For butyl nitrite, this amounts to 515
2540grams, or 570 ml.
2541    
2542    Almost immediately, the mixture begins bubbling. This buWling is NO gas
2543being given off as a byproduct of the reaction. It combines quickly with
2544air to form NO2, the reddish poisonous gas so familiar to those who have
2545botched batches of explosives. Tubing, or similar gas venting devices, are
2546attached to the flask to carry this gas outside, or down the drain with the
2547vacuum of an aspirator.
2548    
2549    After the bubbling subsides in a couple of hours, the reaction is
2550finished. Underground chemists now turn their efforts to getting the
2551palladium back for reuse, and isolating the phenylacetone product. The
2552first step in this phase is to filter the solution to get back the
2553undissolved palladium chloride for reuse in the next batches.
2554    
2555    The alcohol-water-nitrite components of the reaction mixture are then
2556distilled off under a vacuum. The best way to do this is with a 
2557fractionating set-up similar to the one shown in Figure 5 in Chapter 3.
2558With the large amount of solution to be processed, it is wise to use a 3000
2559or 2000 ml round bottom flask on the distilling side. When about half the
2560original load of mixture has been distilled off, the vacuum is 
2561disconnected, and the distilling flask refilled with more of the reaction
2562mixture. Then the vacuum is reapplied and the distillation continued. This
2563process is repeated until all the original reaction mixture fits into the
2564distilling flask. Distillation is continued until the volume of the 
2565solution is reduced to between 300 and 400 ml.
2566    
2567    Next the solution is filtered again to get the rest of the palladium 
2568chloride back. The palladium is rinsed with a little alcohol, and the
2569rinsing added to the rest of the filtered crude product. The crude product
2570is poured into a 500 ml round bottom flask, and distilled under vacuum as
2571described in Chapta 3. The yield is nearly 250 ml of phenylacetone.
2572    
2573    To use the palladium-conserving method of production, the method 
2574described above is used. The only difference is that the PdC12 is replaced
2575by a mixture of 1.8 grams of PdCl2, and 5 grams of CuCl. Yield in this case
2576is more like 80%, or a little over 200 ml of phenylacetone.
2577    
2578                          Preparation of Nitrites
2579
2580                               Butyl Nitrite
2581    
2582    Since butyl nitrite is the nitrous acid ester of n-butanol, it is not 
2583surprising that it is easily made by bringing nitrous acid into contact
2584with n-butanol in the presence of sulfuric acid catalyst. Nitrous acid is
2585not used directly because it is unstable. Instead it is generated in the
2586reaction flask by allowing excess sulfuric acid to react with sodium
2587nitrite in the mixture. The main precaution taken while running this
2588reaction is to ensure that the temperature of the mixture does not rise
2589above the prescribed limits.
2590    
2591    To make butyl nitrite, a 1000 ml 3 necked flask is equipped with a 
2592mechanical stirrer, a sep funnel with a stem that leads as close to the
2593danger zone caused by the whirling stirrer blades as possible, and a
2594thermometer. (See Figure 16.) The thermometer is also placed close to the
2595stirring blade danger zone so that it measures the temperature of the
2596solution in the critical initial mixing area. The stirring blades are made
2597of Teflon so that they can stand up to the sulfuric acid used here. The
2598metal rod to which it attaches is similarly coated with Teflon. An electric
2599drill rigged up above the flask is OK for spinning the stirring blades.
2600Magnetic stirring is not strong enough here because of the heavy
2601precipitate of sodium sulfate crystals which forms as the result of this
2602reaction.
2603    
2604    The thermometer is secured into place by boring a suitable sized hole
2605into a cork for the thermometer, and stuffing the cork into one of the
2606necks of the flask. This prevents the reactants from splashing out while
2607being stirred.
2608    
2609    To do the reaction, the chemist nestles the reaction flask into a 
2610mixture of ice and salt. About two parts ice to one part salt gives good
2611results. The ice is crushed so that the individual cubes are no larger than
2612a grape. The ice-salt mixture produces a cooling effect well below the 0ø C
2613usually obtained from ice. Then the chemist puts 95 grams of sodium nitrite
2614in the flask along with 375 ml of water. He stirs the mixture while
2615following the temperature on the thermometer. Meanwhile in another beaker,
2616he mixes up 25 ml of water, 34 ml of concentrated sulfuric acid, and 114 ml
2617of n-butanol (butan-1-ol). He puts this mixture into the freezer, and cools
2618it to 0øC. 
2619    
2620    When the temperature reading on the nitrite solution in the reaction
2621vessel falls to 0øC or a little lower, the butanol-sulfuric acid mixture is
2622introduced a little bit at a time through the sep funnel while the chemist
2623maintains good mixing. It is added slowly enough that the temperature
2624reading in the reaction vessel does not stray from the range of -1øC to
2625+1øC. The beaker is stored in the freezer in between fill-ups of the sep
2626funnel, so that this solution does not get warm. The entire addition takes
2627about 45 minutes.
2628    
2629    After the addition has finished, the chemist continues stirring for a 
2630few minutes, then lets the mixture stand for an hour and a half. Next, he
2631filters the solution using the Buchner funnel-vacuum flask set up shown in
2632Figure 11 in Chapter 5. This filters out the sodium sulfate crystals formed
2633in the reaction. He pours the filtrate into a 500 ml sep funnel, and waits
2634for the upper yellow layer of crude butyl nitrite to fully form. This takes
2635a few minutes.
2636    
2637    The lower acid water layer is then drained out of the sep funnel, 
2638leaving only the butyl nitrite layer in the funnel. The chemist mixes up a
2639solution of I gram Arm & Hammer bicarb, and 12.5 grams of table salt in 50
2640ml water. He pours this solution into the sep funnel, and swirls well to
2641get the two layers into contact. A fair amount of fizzing ensues as the
2642bicarb destroys excess acid in the crude product. Then he stoppers the sep
2643funnel with a cork, and shakes it vigorously.
2644    
2645    Periodically, he allows built up gas to escape. After shaking for a 
2646couple of minutes, he allows the sep funnel to sit. The layers form again.
2647He drains off the wata layer, and pours the nitrite into a 250 ml beaker.
2648He adds about 5 grams of anhydrous magnesium sulfate crystals to the beaker
2649and stirs. This soaks up whatever water is dissolved in the nitrite.
2650Anhydrous magnesium sulfate is made by baking epsom salts in a thin laya in
2651a glass baking pan in an electric oven at 4 W F for a couple hours before
2652use. It is used immediately, or allowed to cool down in a dessicator to
2653prevent it from soaking up water from the air.
2654    
2655    The crude butyl nitrite can be used immediately as is. If there is 
2656going to be a delay before usage, it is decanted off the magnesium sulfate
2657and distilled. Using a fractionating column, almost all of the product
2658distills at about 77øC. The yield is about 110 grams (85% yield) of butyl
2659nitrite. This product can be stored in a freeza for a couple of weeks
2660before it goes bad. The colder the temperature, the better. Decomposition
2661products include water, NO2, NO, butanol, and polymerization products of
2662butyl aldehyde. This cheap and easy process is readily scaled up to fit any
2663raw material demand the underground chemist may have.
2664    
2665    This substance is made in the same way as butyl nitrite, with a few
2666variations. The nitrite-water solution in the flask has 76 grams sodium
2667nitrite in 240 ml water. The alcohol-sulfuric acid solution is made by
2668diluting 60 ml of absolute alcohol (65 ml of 190 proof vodka) with an equal
2669volume of water. Then the chemist carefully adds 28 ml of concentrated
2670sulfuric acid to it. He swirls while adding. Then he dilutes this solution
2671to 240 ml total volume by adding water. He cools both solutions to about
267210øC, and adds the alcohol-acid solution to the nitrite solution slowly
2673with constant stirring over a period of about half an hour.
2674    
2675    He pours the reaction mixture into a chilled sep funnel, drains off the
2676lower water-acid layer, and then quickly adds an ice cold mixture of I gram
2677bicarb in 50 ml water to the nitrite layer. He quickly swirls and shakes,
2678and drains off the water layer before the fumes become too intense. He
2679dries the crude ethyl nitrite over about 5 grams of sodium sulfate, then
2680decants it into at least an equal volume of ethyl alcohol. The alcohol is
2681absolute alcohol, and deep freezing is required for storage. It is used as
2682soon as possible. Longer storage is possible if the crude material is
2683distilled (b.p. 17øC). The difficulties attendant to this operation make
2684this inadvisable for the underground lab, however.
2685    
2686    There is a way around the hasslesome purification procedure that will
2687allow the underground chemist to use the ethyl nitrite he has made quickly
2688and easily. The way to do this is to bubble the vapors of the ethyl nitrite
2689into the reaction mixture. This method avoids the unpleasant and possibly
2690dangerous procedure with the sep funnel and subsequent distillation. See
2691Figure 8 back in Chapter 4 on N-methyl formamide. If in that figure, the
2692methylamine containing flask instead contained the ethyl nitrite reaction
2693mixture, and the formic acid containing flask instead had the allylbenzene
2694and palladium chloride in alcohol needed for phenylacetone production, then
2695one could easily picture how to get the ethyl nitrite vapors to directly
2696bubble into the phenylacetone production mix without any need to manipulate
2697the nitrite directly.
2698    
2699    To use this variation, the ethyl nitrite is first prepared as described 
2700above. The cold temperature is important to get best yields of the nitrite.
2701Then the nitrite reaction mixture is poured into a suitable size round
2702bottom flask, the glassware is set up as shown in Figure 8, and heat is
2703applied to the nitrite mixture to bubble its vapors into the phenylacetone
2704production reaction flask. Cold water should not be run through the
2705condenser, as this may hold back the nitrite. Instead, the water should be
2706room temperature. The nitrite solution will have to be heated to almost
2707boiling to get the last of the nitrite to boil out of it. A yield of about
270860 grams of ethyl nitrite can be expected from the directions given above.
2709    
2710    One could also use methyl nitrite in this variation by substituting 
2711methyl alcohol for ethyl alcohol. This would have the advantage of being
2712easier to bubble out of the nitrite reaction mixture because the boiling
2713point of methyl nitrite is -12Q C. This advantage is outweighed by the
2714poisonous nature of methyl alcohol, and also by the difficulty one would
2715have trying to keep it in solution while it is being made. It would be hard
2716to estimate just how much of the methyl nitrite is actually getting into
2717and staying in the phenylacetone reaction mixture.
2718    
2719                                Allylbenzene
2720    
2721    Allylbenzene is best prepared by one of two routes. The method which
2722gives nearly quantitative (100%) yields uses phenyllithium. This expensive
2723and very reactive substance is made by reaction of bromobenzene with
2724lithium metal in ether solution in a manner similar to producing a Grignard
2725reagent. The underground chemist needs to be familiar with the use and
2726production of lithium reagents before attempting this method. The great
2727reactivity of lithium reagents presents many pitfalls.
2728    
2729    This method proceeds as follows: A suspension of 100 grams of cuprous
2730bromide (CuBr) in anhydrous ether is treated with 670 ml of 1 molar
2731phenyllithium. The CuBr becomes yellow and dissolves to give a brownish-red
2732solution which then turns green. Phenylcopper precipitates as a white
2733powder in 90% yield. The phenylcopper is then separated and reacted with a
2734molar equivalent of allylbromide to give allylbenzene in 99% yield after
2735water quenching and usual Grignard workup.
2736    
2737    A cheaper and more direct method uses bromobenzene Grignard reagent.
2738Some precautions are important here. Firstly, bromobenzene is about the
2739most difficult Grignard reagent to get started reacting. It is very
2740sensitive to the presence of traces of water. Great care is taken in drying
2741the glassware and the magnesium turnings. Nitrogen atmosphere is a must.
2742With these precautions, a beautiful red bromobenzene Grignard reagent is
2743prepared.
2744    
2745    Another important point is that bromobenzene finds use in making PCP.
2746For this reason, it is on the watched list. Good directions for making
2747bromobenzene are contained in Vogel 's Textbook of Practical Organic
2748Chemistry. This fine book is must reading for everyone interested in
2749underground chemistry.
2750    
2751    This bromobenzene Grignard reagent is then reacted with a solution of
2752allyl bromide to give 82% yield of allylbenzene after quenching and workup.
2753Complete details can be found in Helv. Chim. Acta, Vol. 17, page 352
2754(1934). The author is Hershberg. 
2755    
2756    
2757--------------------------------------------------------------------------
2758                            The Way Of The Bomb
2759--------------------------------------------------------------------------
2760    
2761                 "Blessed be the bomb... and all its work."
2762              ð the mutants of Beneath the Planet of the Apes
2763    
2764    When underground chemists move up to industrial-scale manufacture of
2765methamphetamine, it soon becomes obvious that the Leuckardt-Wallach
2766reaction is not suitable for making large amounts. There are two reasons
2767for this. N-methylformamide distills slowly, because of its high latent
2768heat of vaporization. This makes the pro auction of large amounts of
2769N-methylformamide a very time-consuming process. Secondly, the
2770Leuckardt-Wallach reaction can take up to 48 hours to complete.
2771    
2772    To increase production, a faster method of turning phenylacetone into
2773methamphetamine is necessary. Reacting phenylacetone with methylamine and
2774hydrogen in an apparatus called a "bomb" is such a method. A bomb is a
2775chemical pressure cooker where hydrogen gas is piped under pressure to
2776react with the phenylacetone and methylamine. It is caed a bomb because
2777sometimes reactions like this are done under thousands of pounds of
2778pressure, and occasionally the bomb will blow up. This reaction is done
2779under a pressure of only 3 atmospheres, 30 pounds per square inch greater
2780than normal air pressure. so there's no danger of the hydrogenation bomb
2781going off. 
2782
2783    This reaction is called reductive amination. It is not especially
2784difficult to do, but it is necessary to have the hardware in proper working
2785condition and to keep out materials that would poison the catalyst.
2786Reductive amination is a quick, very clean and high-yield process.
2787    
2788    Phenylacetone reacts with methylamine to produce a Schiff's base and a
2789molecule of water. This Schiff's base then reacts with hydrogen and Raney
2790nickel catalyst and gets reduced to methamphetamine. To encourage the
2791formation of this Schiff's base, the amount of water in the reaction
2792mixture is held to less than 10%; 5% is even better. If the underground
2793chemist is able to get methylamine gas in a cylinder, it is easy to control
2794the amount of water in the reaction mixture, but 40% methylamine in water
2795can be made to work with a little effort.
2796    
2797    Two main side reactions interfere with the production of  
2798methamphetamine in the hydrogenation bomb. They are both controlled by
2799properly adjusting the conditions inside the bomb. The first side reaction
2800is the reduction of the phenylacetone.
2801    
2802    The phenylacetone can react with hydrogen and Raney nickel instead of
2803with methylamine. This side reaction is held to a minimum by not letting
2804the hydrogen gas pressure get much above 30 psi. It is also controlled by
2805encouraging the phenylacetone to react with methylamine instead. This is
2806done by keeping the amount of water in the reaction mixture small, having
2807enough methylamine around for it to react with, and running the reaction at
2808the right temperature.
2809    
2810    The other side reaction that can be a problem is phenylacetone reacting
2811with methamphetamine to produce a tertiary amine.
2812    
2813    This reaction is held to a minimum by having enough methylamine in the
2814reaction mixture to tie up the phenylacetone, and by keeping the solution
2815fairly diluted, so that they are less likely to bump into one another.
2816    
2817    If the chemist uses ready-made Raney nickel, which is sold as a  
2818suspension in absolute alcohol, then, if any problems arise, he knows that
2819the catalyst is not at fault. But those who are old pros at this reaction
2820can save money by making their own Raney nickel catalyst.
2821    
2822    A special alloy of approximately equal parts of aluminum and nickel is
2823available for making Raney nickel catalyst. Here's how it's done. In a 2000
2824ml beaker, the chemist dissolves 190 grams of sodium hydroxide pellets in
2825750 ml distilled water. The solution is cooled down to 10ø C by packing the
2826beaker in ice. He adds 150 grams of the nickel aluminum alloy to the sodium
2827hydroxide solution. It is added slowly and with vigorous stirring. The
2828temperature of the solution must not get above 25øC. The sodium hydroxide
2829reacts with the aluminum in the alloy and dissolves it, producing aluminum
2830hydroxide and hydrogen gas. The nickel is left as tiny black crystals. The
2831hydrogen which bubbles out of the solution causes foaming, so the alloy is
2832added slowly enough that the foaming doesn't get out of control. If that
2833fails, 1 ml of n-octyl alcohol helps to break up the foam. It takes about 2
2834hours to add all the alloy to the sodium hydroxide. When all of the alloy
2835has been added, the stirring is stopped and the beaker is removed from the
2836ice bath. The bubbling of hydrogen gas from the solution continues as the
2837beaker warms up to room temperature. Hydrogen gas is not poisonous, but it
2838is very flammable. Smoking around it can cause an explosion.
2839
2840    When the bubbling of hydrogen from the solution slows down, the beaker
2841is set in a large pan of hot water. Then the water in the pan is slowly
2842heated to boiling. This will get the hydrogen bubbling again, so it is
2843heated on an electric heater in a well-ventilated area. This heating is
2844continued for 12 hours. Distilled water is added to the beaker to maintain
2845its original volume.
2846    
2847    After the 12 hours are up, the chemist removes the beaker from the
2848boiling water bath and stirs it up. Then he allows the black Raney nickel
2849catalyst to settle to the bottom of the beaker. He pours off as much of the
2850sodium hydroxide solution as possible. The nickel is transferred to a 1000
2851ml graduated cylinder with the help of a little distilled water. If the
2852nickel catalyst is allowed to dry out, it may burst into flames. It must be
2853kept covered with water. Again the chemist pours off as much of the water
2854as possible. Then he adds a solution of 25 grams of sodium hydroxide in 250
2855ml of distilled water to the nickel in the graduated cylinder. The cylinder
2856is stoppered with a cork or glass stopper (not rubber) and shaken for 15
2857seconds. Then it is allowed to settle again and as much of the sodium
2858hydroxide solution as possible is poured off.
2859    
2860    The catalyst is now ready to have the sodium hydroxide removed from it.
2861All traces must be removed, or it will not work. The chemist adds as much
2862distilled water to the cylinder as it will hold, then shakes it to get the
2863nickel in contact with the clean water. He lets it settle, then shakes it
2864again. When the nickel has settled, he pours off the water and replaces it
2865with fresh distilled water. This washing process is repeated 25 times. It
2866takes that much to remove all the sodium hydroxide from the catalyst.
2867    
2868    After the water has been poured off from the last rinse with distilled
2869water, 100 ml of rectified spirit (95% ethyl alcohol) is added to the
2870nickel and shaken. After the nickel has settled, the alcohol is poured off
2871and the washing is repeated two more times with absolute (100%) alcohol.
2872The result is 75 grams of Raney nickel in alcohol. It is transferred to a
2873bottle that it will completely fill up. If necessary, more alcohol (100%)
2874is added to fill up the bottle. Then the bottle is tightly stoppered. When
2875the chemist is ready to use it, he shakes it to suspend the nickel and
2876measures out the catalyst. One ml contains about .6 grams of Raney nickel
2877catalyst.
2878    
2879    It has been claimed that a more active catalyst can be made by adding
2880the sodium hydroxide solution to the nickel-aluminum alloy instead of vice
2881versa But when this is done, care must be taken that the foam doesn't get
2882out of control. Also, the alloy must be stirred into the solution so it can
2883react. Other than that, the catalyst is prepared in exactly the same way.
2884    
2885    There are several ways to do the reductive amination reaction. Each
2886will be described. By far the most convenient and most suited to the needs
2887of the clandestine chemist is a process using platinum black catalyst
2888instead of Raney nickel. Platinum has the advantages of working very well
2889at room temperatures and low pressures of hydrogen. It furthermore does not
2890have the ferromagnetic properties of Raney nickel. This means a magnetic
2891stirrer can be used to agitate the reaction mixture inside a suitable glass
2892container. Besides this, platinum gives nearly quantitative (100%) yields
2893of product using considerably less catalyst than with Raney nickel. Add to
2894this the fact the platinum catalyst is reusable many times over, and can be
2895easily obtained with no suspicion in the form of platinum coins and ingots.
2896All these considerations clearly point to the use of platinum as the method
2897of choice for the underground operation.
2898    
2899    Reductive alkylation with platinum is done in a very easily constructed
2900apparatus. The reaction vessel, or "bomb," is a champagne bottle, 1.5
2901liters or larger. Champagne bottles are built to withstand pressure, and
2902have no problem standing up to the 30 pounds of pressure used in this
2903reaction. In the interest of safety, however, the outside of the bottle is
2904coated with a layer of fiberglass resin about 1/2 inch thick. This guards
2905against accidental overpressurization and fatigue cracking. Fiberglass
2906resin is easily obtained at the local auto supply store.
2907    
2908    To do the reaction, 300 ml of phenylacetone is put into the bottle,  
2909followed by 300 ml of 40% methylamine in water. The two of them react
2910immediately to convert a good portion of the mixture into the intermediate
2911Schiff's base. The mixture gets warm, and some methylamine gas fumes off.
2912It is even better here to use the anhydrous  methylamine gas in a cylinder.
2913This hard to come by item is used by  cooling the cylinder down in a
2914freezer, then tipping the cylinder upside down and cracking open the valve
2915to drain out 150 ml of pure methylamine gas into a chilled beaker.
2916    
2917    To the mixture in the champagne bottle are then added 500 ml of 190
2918proof grain alcohol and 5 grams platinum oxide (Adam's catalyst). A
2919magnetic stirring bar is then slid into the bottle, and it is attached to  
2920an apparatus like the one shown in Figure 17.
2921    
2922    The apparatus shown in Figure 17 can be constructed by anyone with
2923access to machinist's tools. Alternatively, the clandestine operator can
2924have it made for him with little or no chance of anyone suspecting its real
2925purpose. The threads are fine, and coated with Form A Gasket immediately
2926before assembly. The valves are of the swagelock type.
2927    
2928    Before beginning production using this device, the joints are checked
2929for leakage by brushing soapy water on them and looking for the tell-tale
2930bubbles.
2931    
2932    The chief danger in using the hydrogenation apparatus is from fire due
2933to leaking hydrogen coming into contact with spark or flame. The magnetic
2934stirrer is a possible source of static-induced sparks. To eliminate this
2935danger, it is wrapped in a sturdy bread or garbage bag. This prevents
2936hydrogen from coming into contact with it. Good ventilation in the
2937production area likewise prevents hydrogen from building up in the room.
2938    
2939    To begin production using this device, the champagne bottle is attached
2940to the rig immediately after filling with the reactants. The air is sucked
2941out of the bottle by attaching the exit valve, a vacuum line leading to an
2942aspirator. After sucking out the air for 30 seconds, this valve is closed,
2943and hydrogen is fed into the bottle from the cylinder until it has
2944pressurized to a few pounds above normal air pressure (i.e., a few pounds
2945show on the gauge). Then the input valve is closed, and the bottle is
2946vacuumed out once more. Now the bottle is practically free of air. The exit
2947valve is closed once again, and hydrogen is let into the bottle until the
2948gauge shows 30 pounds of pressure. This is 3 atmospheres of pressure,
2949counting the 15 pounds needed to equal air pressure. Magnetic stirring is
2950now started, and set at such a rate that a nice whirlpool forms in the
2951liquid inside the bottle.
2952    
2953    The hydrogen used in this reaction is of the purest grade available.  
2954Cylinders of hydrogen are obtained at welding supply shops, which generally
2955have or can easily get electrolytically produced hydrogen. This is the
2956purest grade. The cylinder must have a regulator on it to control the
2957pressure of hydrogen being delivered to the bomb. The regulator must have
2958two gauges on it, one showing the pressure in the cylinder, the other
2959showing the pressure being fed into the line to the bomb.
2960    
2961    After beginning stirring the contents of the bomb, an induction period
2962of about an hour or so usually follows during which nothing happens. No
2963hydrogen is absorbed by the solution during this period. It is not known
2964just why this is the case, but nothing can be done about it. Use of
2965prereduced platinum catalyst does not eliminate this delay. (Prereducing is
2966a procedure whereby the platinum catalyst is added first, and then
2967contacted with hydrogen to convert the oxide of platinum to the active
2968metal.)
2969    
2970    In an hour or so, hydrogen begins to be absorbed by the solution,  
2971indicating production of methamphetamine. The pressure goes down on the
2972gauge. More hydrogen is let in to maintain the pressure in the 30 pound
2973range. Within 2 to 4 hours after uptake of hydrogen begins, the absorption
2974stops. This indicates the end of the reaction.
2975    
2976    The valve on the cylinder is now closed, and the exit valve slowly  
2977opened to vent the hydrogen gas outside. Now the bottle is removed from the
2978apparatus, and the platinum is recovered for reuse by filtering the
2979solution. The platinum is stored in absolute alcohol until the next batch.
2980Many batches can be run on the same load of platinum catalyst, but it
2981eventually loses its punch. It is then reworked in the manner described
2982later.
2983    
2984    The filtered reaction mixture is then poured into a 2000 ml round  
2985bottom flask, along with 3 or 4 boiling chips. The glassware is set up as
2986shown in Figure 3 in Chapter 3. The chemist heats the oil no hotter than
2987110øC, and distills off the alcohol and water. When the volume] of the
2988mixture gets down to near 500 ml, he turns off the heat and]` transfers the
2989reaction mixture to a 1000 ml round bottom flask with 4 boiling chips. He
2990sets up the glassware for fractional distillation as shown in Figure 5 in
2991Chapter 3, and continues distilling off the alcohol. The temperature shown
2992on the thermometer should be about 80øC. When the volume of the reaction
2993mixture gets down to about 400 ml, he turns off the heat and lets it cool
2994off. He attaches a 250 ml round bottom flask as the collecting flask and
2995begins a vacuum distillation. The last remnants of alcohol are soon gone,
2996and the temperature shown on the thermometer climbs. If he is using an
2997aspirator, when the temperature reaches 80øC, he changes the collecting
2998flask to a 500 ml round bottom flask and distills the methamphetamine under
2999a vacuum. If he is using a vacuum pump, he begins collecting
3000methamphetamine at 70øC. He does not turn the heat setting on the buffet
3001range above l/3 of the maximum. Virtually all of the material distilled is
3002methamphetamine. He will get between 300 and 350 ml of clear to pale yellow
3003methamphetamine, leaving about 20 ml of residue in the flask. A milky color
3004to the distillate is caused by water being mixed with it. This is ignored,
3005or removed by gentle heating under a vacuum.
3006
3007    The distilled methamphetamine is made into crystals of methamphetamine
3008hydrochloride in the same way, as described in Chapter 5. He puts about 75
3009ml of methamphetamine in each Erlenmeyer flask and adds ether or benzene
3010until its volume reaches 300 ml. Then he bubbles dry hydrogen chloride gas
3011through it and filters out the crystals formed. The yield will be close to
3012380 grams of pure methamphetamine.
3013    
3014    It is in the catalyst preparation and recycling that the clear  
3015superiority of the platinum catalyzed reductive alkylation method becomes
3016obvious. In the succeeding methods using Raney nickel, one is dependent
3017upon a supply of aluminum-nickel alloy for making Raney nickel. To make
3018platinum catalyst, one needs only obtain platinum metal and one group of a
3019series of readily available chemicals. The basic metal itself, platinum, is
3020easily obtained from coin or other precious metal dealers. The underground
3021chemist thereby shields himself from suspicion by using the cloud of dust
3022kicked up by avaricious or misguided individuals who purchase platinum
3023metal thinking this will tide them through society collapse.
3024    
3025    The process used to turn platinum metal into active catalyst is  
3026identical to the method used to recycle worn out platinum catalyst into
3027reborn material. The first step is to dissolve the metal in aqua regia.
3028Aqua regia is a mixture of three parts hydrochloric acid, and one part
3029nitric acid. Only laboratory grade acids in in their concentrated forms are
3030used for this process. Lower grades may well introduce catalytic poisons
3031into the precious metal. The nitric acid is the 70% material. The
3032hydrochloric acid is the 37% laboratory material. About a pint of mixed
3033acid serves well to dissolve the few grams of platinum needed to run
3034man-sized batches of methamphetamine. The acids are simply mixed, and then
3035the platinum metal is added. A few fumes of NO2 are given off in the
3036dissolution process. Occasional swirling and some heating speeds the
3037process of dissolving the platinum. The dissolution converts the platinum
3038to chloroplatinic acid H2PtCl6. This substance is the starting point for
3039both of the alternative pathways to active platinum catalyst.
3040    
3041    When all of the platinum metal has disappeared into solution, heat is
3042applied to boil away the acid mixture. Then some concentrated hydrochloric
3043acid is added, and this too is evaporated away to dryness.  
3044
3045    The addition and evaporation of hydrochloric acid is repeated several  
3046times until the residue is free of nitrites.
3047    
3048    With chloroplatinic acid thusly obtained, the manufacturing chemist has
3049two alternative methods with which to convert it into active material ready
3050for use. The first method is the classical route involving a fusion of the
3051chloroplatinic acid, or preferably its ammonium salt, with sodium nitrate
3052at a temperature of about 450ø C. This method entails the obvious
3053difficulty of accurately measuring and controlling such a high temperature.
3054One can read all about this method in Organic Syntheses, Collective Volume
3055I, pages 463 to 470.
3056    
3057    The second method uses sodium borohydride to convert the acid directly
3058into platinum black. This method is simpler and produces a much more active
3059catalyst. The procedure is based on the method given by Brown and Brown in
3060the Journal of the American Chemical Society, Volume 84, pages 1493 to 1495
3061(1962). The yield is about 3 grams of the extra high activity catalyst, and
3062does the job of 5 grams of the catalyst prepared by the classical method.
3063    
3064    To prepare this catalyst, 8 grams of chloroplatinic acid is dissolved  
3065in 80 ml of absolute alcohol. Then, in another beaker, .8 grams of
3066laboratory grade sodium hydroxide is dissolved in 10 ml of distilled water.
3067This is diluted to 200 ml of total volume by adding absolute alcohol, and
3068then 7.71 grams of sodium borohydride is added. The  
3069alcohol-NaOH-water-sodium borohydride solution is stirred until the
3070borohydride is dissolved. The borohydride solution is now added to the
3071chloroplatinic acid solution with vigorous stirring. It is added as quickly
3072as possible without letting the contents foam over. A large amount of
3073hydrogen gas is given off while the borohydride reduces the chloroplatinic
3074acid to platinum black. This process is done in a fume hood or outside to
3075prevent hydrogen explosions.
3076    
3077    About one minute after all the borohydride solution has been added, the
3078excess borohydride is destroyed by adding 160 ml of glacial acetic acid or
3079concentrated hydrochloric acid. The solution is then filtered to collect
3080the platinum black. It is rinsed with a little absolute alcohol, with added
3081filter paper and all (to prevent loss of catalyst sticking to the paper),
3082directly into the champagne bottle for immediate use. If it must be stored
3083before use, it is put in a tightly stoppered bottle filled with absolute
3084alcohol.
3085
3086    The next method uses Raney nickel catalyst instead of platinum. It  
3087works just as well, but requires that the chemist be able to heat the
3088reactants to about 80øC. Also, somewhat higher pressures are used, so a
3089glass reaction bottle is not adequate; it must be made of stainless steel
3090at least 1/8 inch thick, for safety's sake.
3091    
3092    First, the chemist must find out how high the heat must be set to get
3093an 80øC temperature in the contents of the bomb. He fills the bomb
3094half-full of isopropyl rubbing alcohol and turns on the heat. He keeps
3095track of the temperature of the alcohol while stirring it with the  
3096thermometer. He finds the heat setting needed for an 80øC temperature and
3097how long it takes to reach that temperature. Then he removes the isopropyl
3098alcohol from the bomb and rinses it out with ethyl alcohol.
3099    
3100    He is now ready to run the reaction. If he has methylamine gas in a
3101cylinder, he puts 1 liter of 95% ethyl alcohol (190 proof grain alcohol) in
3102the bomb. If he has 40% methylamine in water, he uses 1 liter of absolute
3103ethyl alcohol. Then he adds the same amount of methylamine as used in the
3104first method described in this chapter. If he used methylamine gas from a
3105cylinder, he adds 100 ml each of ether and benzene to the bomb. Then he
3106adds 90 grams of Raney nickel catalyst and 25 grams of sodium acetate.
3107Finally, he adds 300 ml of phenylacetone to the bomb.
3108    
3109    Now the chemist seals up the bomb and pipes in the hydrogen to a  
3110pressure of 300 psi. He turns on the heat and begins shaking the reaction
3111bottle. The reaction begins to kick in at a little over 40øC. He begins
3112timing the reaction when the temperature reaches 50øC. He continues the
3113reaction for 8 hours, making sure that the pressure stays at 300 psi.
3114    
3115    Then he stops the shaking and heating and lets it cool down. After it
3116has cooled, it is filtered to remove the catalyst. The filtered catalyst  
3117cannot be allowed to dry out, or it will burst into flames. He keeps it
3118wet. The bomb is rinsed out with 100 ml of alcohol. The alcohol is
3119filtered, then added to the product. The catalyst is dumped down the drain
3120and flushed away with a lot of water.
3121    
3122    The alcohol, benzene, and ether are distilled off, then the  
3123methamphetamine is distilled under a vacuum, as described earlier in this
3124chapter. The yield is about the same as from the previous method.  
3125    
3126    The next method allows the chemist to use nitromethane, dragster fuel,
3127in place of methylamine. Since everybody, including the narcs, knows that
3128methylamine is required to make methamphetamine, this gives the underground
3129chemist a chance to throw the narcs a curve ball. The way this works is
3130that nitromethane is first put into the bomb along with Raney nickel and
3131reduced to methylamine.
3132    
3133    Phenylacetone is then added, and methamphetamine is produced.
3134    
3135    To do the reaction, the chemist puts one liter of absolute ethyl  
3136alcohol and 450 grams (350 ml) of nitromethane inside the bomb. The
3137nitromethane is either of laboratory grade, or has been fractionally
3138distilled (boiling temperature 101øC) to purify it. He adds 63 grams of
3139Raney nickel to the bomb and seals it up. He pipes in hydrogen to a
3140pressure of 300 psi and begins shaking. He heats the mixture up to about
314185øC, and continues for 3 hours. Then he turns off the heat, and lets it
3142cool off while shaking for about 45 minutes. Then the shaking is stopped,
3143and the hydrogen pressure is released. He adds the following to the bomb:
3144100 ml each of ether and benzene, 25 grams of sodium acetate, 45 more grams
3145of Raney nickel, and 300 ml of phenylacetone. He seals up the bomb, and
3146pipes in hydrogen at a pressure of 300 psi. Shaking is begun and the bomb
3147is heated to 80øC. He keeps this up for 8 hours, being sure to keep the
3148pressure at 300 psi. 
3149    
3150    After 8 hours are up, he turns off the heat and lets it cool off for an
3151hour with shaking. Then he stops the shaking and releases the pressure -
3152slowly. The mixture is then filtered as before, and the bomb is rinsed out.
3153Then the reaction mixture is distilled as described before. The yield is
3154about 300 ml of methamphetamine. It is turned into crystalline
3155methamphetamine hydrochloride as usual.
3156    
3157    The bomb can be used to make smaller batches of methamphetamine. But
3158the bomb and cylinders are not easily packed up and moved, so the bomb is
3159best suited to industrial-scale production.
3160    
3161    The reaction times and pressures I have given are not written in stone.
3162The time required to complete the hydrogenation can be reduced by using
3163more Raney nickel or platinum catalyst, increasing the hydrogen pressure,
3164or using less alcohol.
3165    
3166    If the underground chemist has to make his own one-gallon reaction
3167bottle, he uses stainless steel 1/8 to 3/16 inch thick, such as a section
3168of stainless steel pipe. For a volume of about one gallon, it should be
3169about 16 cm in diameter and 20 cm in height. The bottom is Tig welded on,
3170this process being much easier if it starts out a few millimeters larger in
3171diameter than the pipe section.
3172    
3173    The top of the tank has 2 holes drilled in it. One small one in the  
3174center of the tank is an entrance for the hydrogen gas. This has a section
3175of stainless steel pipe about 5 inches long welded around it. It is usually
3176necessary to melt in some stainless steel welding rod while making this Tig
3177weld, to get it strong enough. This top section is then welded onto the top
3178to create the reaction vessel shown in Figure 18. 
3179    
3180    A steel rocking frame is then welded onto the outside of the reaction
3181vessel as shown in Figures 18 and 19. The area where it is welded should be
3182reinforced. All welds are done with a Tig welder.
3183    
3184    The chemist can now assemble the bomb. He starts out with heavy wooden
3185planks as the base. This will keep vibration to a minimum. He sets up and
3186bolts down the frame. He attaches some clamps to this frame, then puts
3187sheaths and bearings on the arms of the steel rocking frame, and suspends
3188the reaction vessel about 6 inches off the ground. It should swing back and
3189forth easily.
3190
3191    Now he attaches a band around the reaction vessel, just below where the
3192steel rocking frame is attached to the reaction vessel. The band is
3193attached to the rocking arm, which is attached to a spindle on the driving
3194pulley, as shown in Figures 19 and 20. Both these joints should swivel
3195easily. The driving pulley is about 10 cm in radius. The pulley on the
3196motor has a radius of about 2 cm. The spindle, which extends from the
3197driving pulley to the rocking arm, is about 3 cm from the center of the
3198driving Pulley.
3199    
3200    The motor is the usual 1760 rpm type of motor, with a power of at least
32011/30 hp. When the motor is turned on, it spins the driving pulley, which
3202moves the rocking arm back and forth, which in turn shakes the reaction
3203vessel.
3204    
3205    The chemist is now ready to test the system. He opens up the valve and
3206puts 2000 ml of distilled water in the reaction vessel. He closes the valve
3207and turns on the motor to begin shaking. If any water comes out the top of
3208the stainless steel pipe, he secures the wooden base to minimize vibration.
3209He shuts it off and opens the valve, then siphons out all the water.
3210    
3211    He now runs a line of heavy rubber tubing from the hydrogen cylinder to
3212the stainless steel pipe. He crimps in the end of the pipe, then pushes the
3213rubber hose down over the pipe, at least halfway to the tank. He superglues
3214it to help hold it in place. Then he covers the entire length of the hose
3215with a series of pipe clamps so that it does not blow out or slip off the
3216pipe. This hose is slung over a sling in the frame so that it leads
3217straight down to the reaction vessel. There must be enough slack to allow
3218for the rocking motion.  
3219
3220    If any water came out of the pipe in the test run, the hose must have
3221catalytic poisons removed from it by boiling it in 20% sodium hydroxide
3222solution, then rinsing it off in boiling water. 
3223    
3224    
3225    The chemist closes the valve and begins putting pressure in the tank,
3226starting with a pressure value of 50 psi. He brushes soapy water around the
3227joints to look for any leaks. If there aren't any, he works the pressure up
3228to 300 psi. If leaks are found, he tries brazing over the faulty joint. His
3229welds must be nearly perfect. 
3230    
3231    To use the bomb, the reactants are added to the bomb with a funnel
3232through the faucet. If any sodium acetate is left clinging to the valve, it
3233will prevent a good seal. The Raney nickel is added with a pipette. When
3234the reaction is over, the products are siphoned out with a bent section of
3235glass tubing. Vacuum from an aspirator speeds up this process considerably,
3236as does using large-diameter tubing.
3237    
3238    More information on these reactions can be found in Reactions of   
3239Hydrogen by Adkins, published in 1937 by the University of Wisconsin Press.
3240    
3241                                 References
3242    
3243                   Organic Reactions, Volume 4, page 174.
3244      Journal of the American Chemical Society, Volume 61, pages 3499
3245       and 3566 (1939); Volume 66, page 1516 (1944); Volume 70, pages
3246                           1315 and 2811 (1948).
3247            Reductions in Organic Chemistry, by Milos Hudlicky.
3248    
3249    
3250--------------------------------------------------------------------------
3251                   Reductive Alkylation Without The Bomb
3252--------------------------------------------------------------------------
3253    
3254    The process of reductive alkylation using the hydrogenation bomb, as
3255you saw in the previous chapter, is not without difficulties or dangers.
3256Just for starters, consider the danger of hydrogen gas building up in a
3257poorly ventilated workplace. Add to that the danger of the bomb blowing up
3258if the welding of the seams is not done well. Also think about the hassle
3259involved in making enough Raney nickel to produce multi-kilos of
3260methamphetamine. The last problem can be minimized by reusing the Raney
3261nickel used in the previous batch. In this way, the underground chemist can
3262get away with adding only half as much fresh nickel as would otherwise be
3263added, but he must be doing one batch right after another to keep it fresh.
3264    
3265    All of these problems, except for the hydrogen gas danger, can be 
3266eliminated if he is able to get his hands on activated aluminum turnings.
3267In this method, the aluminum turnings take the place of hydrogen gas as the
3268catalyst in the reductive alkylation process. The yields are very good, the
3269process is very simple, and no special equipment is required. The reaction
3270is also quick enough that it can be used in large-scale production.
3271    
3272    Activated aluminum is next to impossible to purchase, but very easy to
3273make. The raw material is aluminum foil. The foil is amalgamated with
3274mercury by using mercury chloride. The result is aluminum amalgam.
3275    
3276    To make activated aluminum, the chemist takes 100 grams of the aluminum
3277foil, and cuts it into strips about 2Yz cm wide, and 15 cm long. He folds
3278them loosely, and puts them into a 3000 ml glass beaker or similar
3279container. He does not stuff them down the neck of the flask or similar
3280container from whence they would be hasslesome to retrieve. He packs them
3281down lightly so that they are evenly arranged, then covers them with a .1%
3282solution (1 gram in one liter of water) by weight solution of sodium
3283hydroxide.
3284    
3285    He warms the mixture by setting it into a hot water bath until a 
3286vigorous bubbling of hydrogen gas has taken place for a few minutes. He is
3287careful here that the mixture does not overflow! Then he pours off all the
3288sodium hydroxide solution as quickly as possible, and rinses the strips
3289with distilled water, and then with 190 proof vodka. This preliminary
3290treatment leaves an exceedingly clean surface on the foil for amalgamating
3291with mercury.
3292    
3293    While the surface of the strips is still moist with vodka, he adds 
3294enough of a 2% by weight solution of mercury QI) chloride (aka mercuric
3295chloride, HgCI2) in distilled water to completely cover the foil. He allows
3296this to react for about 2 minutes, then pours off the mercury solution. He
3297rinses off the strips with distilled water, then with 190 proof vodka, and
3298finally with moist ether. Moist ether is either purchased as is, or made by
3299adding water to anhydrous ether with stirring until a water layer begins to
3300appear at the bottom of the ether. The chemist uses this material
3301immediately after making it.
3302
3303                                  Method 1
3304    
3305    In this method, the activated aluminum turnings react with alcohol to
3306produce hydrogen gas. This hydrogen then reduces the Schiff's base formed
3307from methylamine and phenylacetone to give methamphetamine.
3308    
3309    The chemist needs a magnetic stirrer-ho/plate to do this reaction. On
3310top of the stirrer-hotplate, he places a Pyrex bowl or cake dish large
3311enough to hold a 3000 ml flask. The bowl or dish cannot be made of metal,
3312because the magnetic stirrer will not work through it.
3313
3314    He places the 3000 ml flask in the dish and fills it with cooking oil
3315until the oil reaches about halfway up the sides of the flask. He must be
3316sure to leave enough room for the oil to expand as it heats up. He puts the
3317magnetic stirring bar in the flask along with 1600 ml of absolute alcohol
3318or 190 proof grain alcohol. Then he adds 340 ml of phenylacetone and 450 ml
3319of 40% methylamine in water. Now he turns on the magnetic stirrer and
3320begins heating the oil in the dish. He keeps track of the temperature of
3321the oil with a thermometer, and does not allow it to go above 100øC. While
3322the oil is heating up, he adds 180 grams of activated aluminum turnings to
3323the flask. He makes sure that the stirring is fast enough that the turnings
3324do not settle to the bottom of the flask. The reaction mixture will quickly
3325begin to turn grey and foamy. The aluminum is added at such a rate, the
3326bubbling and foaminess it produces does not overflow the flask. When all of
3327it has been added, a condenser is fitted to the flask, and water flow is
3328begun through it.
3329    
3330    The chemist now lets them react for 8 hours. He keeps the temperature
3331of the oil bath at 100øC, and the stirring strong. The activated aluminum
3332slowly dissolves and produces hydrogen gas. The explosive danger from this
3333gas is eliminated by running a length of tubing from the top of the
3334condenser out the window.
3335    
3336    When the 8 hours are up, he removes the flask from the oil bath and
3337wipes the oil off the outside of the flask. He filters the solution to 
3338remove the aluminum sludge, then rinses the sludge with some more alcohol
3339to remove the last traces of product from it. The rinse alcohol is added to
3340the rest of the filtered product.
3341    
3342    The underground chemist can now distill the product. He pours it in a
33433000 ml round bottom flask that is clean and reasonably dry, and adds a few
3344small pieces of pumice. He places the flask on the electric buffet range,
3345then sets up the glassware for fractional distillation, as shown in Chapter
33463. He begins heating it. The first thing that distills is a mixture of
3347alcohol, water, and methylamine. This occurs when the temperature shown on
3348the thermometer is about 78-80Q C. He collects about 1600 ml of this
3349mixture, then removes the flask from the heat. He lets it cool down, then
3350pours the contents of the 3000 ml flask into a 1000 ml flask, along with a
3351few fresh boiling chips. He puts about 15 ml of alcohol in the 3000 ml
3352flask. swirls it around to dissolve the product left clinging to the
3353insides, then pours it into the 1000 flask.
3354    
3355    The chemist again sets up the glassware for fractional distillation, 
3356with a 250 ml flask as his receiver. He applies a vacuum, preferably from
3357an aspirator, and begins vacuum distillation. When the boiling gets under
3358control, he begins heating the flask. The last remnants of alcohol and
3359water will soon be gone, and the temperature shown on the thermometer will
3360climb. When it reaches about 80øC with an aspirator, or about 70øC with a
3361vacuum pump, he quickly changes the receiving flask to a clean, dry 500 ml
3362flask, and reapplies the vacuum. He will get about 350 ml of clear to pale
3363yellow methamphetamine free base. A few milliliters of tar will be left in
3364the distilling flask. The liquid free base is converted to crystals by
3365dissolving it in ether or benzene and bubbling dry HC1 through it, as
3366described in Chapter 5.
3367    
3368    The underground chemist gets an even purer product by varying this
3369procedure slightly. Once the 1600 ml of alcohol, water, and methylamine is
3370distilled off, he pours a mixture of 650 ml of 28% hardware store variety
3371hydrochloric acid and 650 ml of water into what remains in the 3000 ml
3372flask, after it has cooled down. A lot of heat is produced in the mixing
3373because the methamphetamine free base is reacting to make the
3374hydrochloride. So he adds it slowly, then swirls it. When it has cooled
3375down, he stoppers the 3000 ml flask with a cork or glass stopper and shakes
3376it vigorously for 3 to 5 minutes. It should pretty much all dissolve in the
3377hydrochloric acid solution. Now he adds 200 ml of ether or benzene to the
3378flask and shakes it up well. The ether or benzene dissolves any unreacted
3379phenylacetone and tar. He lets it sit for a few minutes. The ether and
3380benzene layer floats to the top. He pours it slowly into a 1000 ml sep
3381funnel, so that the top layer all gets into the sep funnel. Now he lets it
3382set, then drains the lower acid layer back into the 3000 ml flask.
3383    
3384    The acid must now be neutralized to give back amphetamine free base, so
3385it can be distilled. The chemist mixes up a solution of 350 grams of lye in
3386400 ml of water. When it has cooled down, he pours it slowly into the acid
3387solution in the 3000 ml flask. A lot of heat is generated from the
3388reaction. When it has cooled down, he stoppers the flask and shakes it
3389strongly for about 5 minutes. When standing, the amphetamine forms a layer
3390on top. He slowly pours it into a 1000 ml sep funnel. He drains the water
3391layer back into the 3000 ml flask. The methamphetamine layer in the sep
3392funnel may have some salt crystals floating around in it. He adds 100 ml of
3393benzene to it plus a couple hundred ml of a dilute lye solution. He
3394stoppers and shakes the mixture. The salt will now be dissolved in the
3395water. He drains the water layer into the 3000 ml flask and pours the
3396methamphetamine-benzene solution into a clean 1000 ml flask. There is still
3397some methamphetamine left in the 3000 ml flask, so he adds a couple hundred
3398ml of benzene to it. If there is a lot of undissolved salt in the flask, he
3399adds some more water to it. Now he shakes the flask to dissolve the meth in
3400the benzene, then lets it set. The benzene comes up to the top. He pours it
3401off into the sep funnel, and drains off the water layer. He pours the
3402benzene layer into the 1000 ml flask with the rest of the product.
3403    
3404    He can now begin distilling it. He adds a few boiling chips, sets up 
3405for fractional distillation, and proceeds as described in Chapter 5. The
3406yield once again is about 350 ml of free base, which makes close to 400
3407grams of pure crystal.
3408    
3409                                  Method 2
3410    
3411    This method is not as good as the first one. It takes longer, it uses 
3412up more chemicals to make a given amount of product, and less can be
3413produced at a time.
3414    
3415    The equipment is set up as in Method 1. Into the 3000 ml flask is 
3416placed 1575 ml of 190 proof alcohol and 150 ml of distilled water. Then the
3417chemist adds 150 ml of phenylacetone and 220 ml of 40~o methylamine in
3418water. He begins magnetic stirring and adds 160 grams of activated aluminum
3419turnings. He heats the oil bath to 100ø- C or so and attaches a condenser
3420to the 3000 ml flask. He begins water flow through the condenser and gently
3421boils the contents of the flask for 16 hours. At the end of this time, he
3422removes the flask from the heat and lets the aluminum sludge settle. He
3423filters the alcohol solution, rinses the sludge with alcohol and adds the
3424filtered alcohol to the rest of the product. Then he proceeds as described
3425in Method 1. The yield is about 150 ml of methamphetamine.
3426
3427                                  Method 3
3428    
3429    This method is not as good as Method 1 either. Ether is used as the
3430reaction solvent, which adds danger and expense. The ether is better used
3431to produce the crystals. Another problem with this reaction is that it is
3432done so dilute that large amounts can't be made at one time.
3433    
3434    In the same set-up used in Methods 1 and 2, the underground chemist
3435places 1000 ml of absolute ether in a 3000 ml flask. Then he adds 100 ml of
3436phenylacetone and 160 ml ”f 40% methylamine. He begins stirring and adds 65
3437grams of activated aluminum turnings. He attaches an efficient condenser,
3438runs cold water through it, and heats the oil bath to 45-50øC. He gently
3439boils the solution for 6 hours. The activated aluminum reacts with the
3440water in the methylamine to produce hydrogen.
3441    
3442    When the six hours have passed, he distills off the ether and treats
3443the residue as described in Method 1, i.e., distills it under a vacuum,
3444etc. The yield is about 90 ml of meth.
3445    
3446    For more information on this method, see U.S. Patent Nos. 2,146,474 and
34472,344,356.
3448    
3449                                  Method 4
3450    
3451    This variation on the activated aluminum method of reductive alkylation
3452has the advantage of using methylamine hydrochloride directly in the
3453reaction soup. Since methylamine is now very dangerous or impossible to
3454obtain commercially, and also since the best method for making methylamine
3455yields methylamine hydrochloride, the usefulness of this variation is
3456obvious.
3457    
3458    This method involves the addition of an alcohol solution containing the
3459Schiff's base formed between methylamine and phenylacetone onto the
3460activated aluminum. In the other methods, the opposite order of addition
3461was employed. To maximize yields of product, the competing side reactions
3462are suppressed. In the case of activated aluminum methamphetamine
3463production, the main side reaction is the reduction of phenylacetone into
3464an interesting, but quite useless pinacol. It has the structure shown on
3465the next page:
3466    
3467    This side reaction is minimized by keeping the amount of water in the
3468reaction mixture to a minimum, and also by using a healthy excess of
3469methylamine. This scheme of things encourages the phenylacetone to tie
3470itself up with methylamine to form the Schiff's base, rather than float
3471around freely in solution where it could be reduced by the aluminum.
3472    
3473    To do this reaction, two 2000 ml volumetric flasks are obtained. 
3474Volumetric flasks work well for this reaction because the chemist can swirl
3475around their contents quite forcefully without danger of spillage. They
3476also pour pretty well. One volumetric flask is for preparing the activated
3477aluminum, and is also the ultimate reaction vessel. The other volumetric
3478flask is for the preparation of the Schiff's base. The lab work is
3479organized so that both products are ready to react at about the same time.
3480    
3481    Into the volumetric flask destined to be the ultimate reaction vessel,
3482the chemist places 108 grams of aluminum foil. It is cut into one inch
3483squares. The best brand of aluminum foil for this purpose is Heavy Duty
3484Reynolds Wrap. It is then treated with sodium hydroxide solution as
3485described in Method 1. After a few good rinses to remove the sodium
3486hydroxide, it is ready to become activated aluminum. To do this, the
3487volumetric flask is filled almost to the neck with distilled water,
3488followed by the addition of 4.51 grams of HgCl2. The flask is swirled to
3489dissolve the mercuric chloride, and then every few minutes for the next 30
3490minutes. During this time, the water becomes a cloudy grey color, and the
3491aluminum loses its shine. The water is then decanted off the aluminum, and
3492the flask is filled up with fresh distilled water to carry away unreacted
3493mercury. After a period of swirling, the rinse water is poured off, and the
3494rinse repeated with a fresh portion of distilled water. On the last rinse,
3495the chemist makes sure that the water drains off well. This leaves
3496activated aluminum ready to go.
3497    
3498    In the second volumetric flask, Schiff's base is made. To do this, 
3499163.5 grams of sodium hydroxide is dissolved in one liter of 190 proof
3500vodka. To this is added 270 grams of methylamine hydrochloride. This
3501methylamine is dry so that the chemist is not weighing water contamination.
3502If this is home brew methylamine hydrochloride, the first crop of crystals
3503is acceptable material, but the second and third batches of crystals are
3504recrystallized as described in Organic Syntheses, Collective Volumes I, II
3505or III. Look in the table of contents for methylamine hydrochloride. The
3506mixture is kept cool during the addition to prevent methylamine gas from
3507escaping. Good stirring is also essential. The result of this operation is
3508an alcohol solution of methylamine. Some salt and water are formed.
3509    
3510    To make the Schiff's base, 200 ml of phenylacetone is then added to
3511this solution. The addition produces a fair amount of heat, and some 
3512methylamine fumes are driven off as a result. Active swirling of the flask
3513keeps this to a minimum. The chemist also tips the flask during swirling to
3514dissolve any phenylacetone which may be stuck up in the neck of the flask.
3515This is the Schiff's base solution.
3516    
3517    To do the reaction, the Schiff's base solution is poured onto the 
3518activated aluminum. Once the pouring is complete, they are swirled together
3519energetically for a few seconds, then a thermometer is carefully lowered
3520into the flask. Following this, a section of plastic tubing is stuffed into
3521or over the top of the volumetric flask, and led outside. This is for fume
3522control. The reaction mixture is swirled continuously for the first few
3523minutes. The temperature rises quite rapidly because the reaction is really
3524vigorous. It is necessary to have a bucket of ice water close by to dunk
3525the reaction vessel into to keep it under control. The experimenter strives
3526to keep the reaction mixture in the 50 to 60øC range. After the initial
3527rush, occasional swirling is acceptable, so long as the temperature
3528guidelines are followed. After 90 minutes, the reaction is complete.
3529    
3530    To process the product, the alcohol solution containing the product is
3531poured off into the distilling flask. The mud-like gunk at the bottom of
3532the flask contains a fair amount of trapped product. This gunk is 
3533untreatable as is, but with some lightening up, it can be filtered. A lab
3534product called Celite is added to the gunk until it appears more amenable
3535to filtration. As an altemative, washed white sand, found in the cement
3536section of your friendly neighborhood store, is a good substitute. This is
3537mixed in with the gunk until it lightens up a bit. Then two portions of 200
3538ml of warm vodka (190 proof) are mixed in and the trapped product is
3539filtered out of the gunk. These gunk filtrates are added to the main
3540product, and the whole mother lode readied for processing.
3541    
3542    The first step is to place all the liquid into the distilling flask
3543along with a few boiling chips, and remove the alcohol with a vacuum. A
3544fractional distillation then gives pure methamphetamine free base ready for
3545crystallizing into the hydrochloride.
3546    
3547    The same method can be used to give MDMA just by substituting MDA
3548phenylacetone for regular phenylacetone. 
3549    
3550    
3551--------------------------------------------------------------------------
3552                                Methylamine
3553--------------------------------------------------------------------------
3554    
3555    From time to time, an underground chemist's supply of methylamine may
3556be cut off. If this happens, it is handy to be able to make a supply of his
3557own methylamine until he is able to get his hands on some of the ready-made
3558stuff.
3559    
3560    The reaction to produce methylamine is cheap, but requires a lot of
3561labor. Two molecules of formaldehyde react with ammonium chloride to
3562produce a molecule of methylamine hydrochloride and The glassware is set up
3563as shown in Figure 3 in Chapter 3. The chemist places 1000 grams of
3564ammonium chloride and 2000 ml of 3540% formaldehyde in the 3000 ml flask
3565sitting in the pan of oil. (These chemicals need not be a very high grade;
3566technical grade is good enough.) He puts a thermometer in the oil next to
3567the flask and begins slowly heating it. As it warms up, he swirls the flask
3568to dissolve the ammonium chloride crystals. Over the period of an hour, he
3569raises the temperature of the oil bath to 106øC. He holds the temperature
3570there for five hours.
3571    
3572    Then he turns off the heat and removes the flask from the pan of oil.
3573Some liquid will have collected in the 2000 ml flask; he throws it out and
3574rinses the flask with water. The 3000 ml flask is set in a pan of room
3575temperature water to cool it off. A good amount of ammonium chloride
3576crystals precipitate from the solution. He does not want these chemicals,
3577so he filters them out. He returns the filtered reaction mixture to the
35783000 ml flask and again sets up the glassware as shown in Figure 3. A 250
3579ml flask is used as the collecting flask. The reaction mixture should be
3580clear to pale yellow.
3581    
3582    He turns on the vacuum source and attaches it to the vacuum nipple of
3583the vacuum adapter. He boils off the water and formic acid in the reaction
3584mixture under a vacuum. Heating the flask in the oil pan speeds up the
3585process, but the oil is not heated above 100ø C When the volume of the
3586contents of the flask is reduced to about 1200-1300 ml, he turns off the
3587vacuum and removes the flask from the oil pan. The flask is put in a pan of
3588room temperature water to cool it off. Some more crystals of ammonium
3589chloride come out of solution. He filters out these crystals and pours the
3590filtered reaction mixture into a 2000 ml flask. He sets up the glassware as
3591before, and again boils off the water and formic acid under a vacuum. He
3592does not heat the oil above 100ø C
3593
3594    When the volume of the reaction mixture has been reduced to about 700
3595ml, crystals of methylamine hydrochloride begin to form on the surface of
3596the liquid. It looks a lot like a scummy film. When this happens, the
3597vacuum is disconnected and the flask is removed from the oil bath. The
3598flask is placed in a pan of room temperature water to cool it off. As the
3599flask cools down, a lot of methylamine hydrochloride crystals come out of
3600the solution. When the flask nears room temperature, it is cooled off some
3601more with some cold water. This will cause even more methylamine
3602hydrochloride to come out of the solution.
3603    
3604    The chemist filters out the crystals and puts them in a 1000 ml  
36053-necked flask. The crystals look different from the crystals of ammonium
3606chloride, so he should have no trouble telling the two apart. These
3607crystals soak up water from the air and melt, so he does not waste time
3608getting them in the 3-necked flask after they are filtered.
3609    
3610    He takes the filtered reaction mixture and pours it in a 1000 ml sep
3611funnel. The reaction mixture contains dimethylamine hydrochloride and some
3612other garbage, and he wants to remove some of this unwanted material before
3613he proceeds to get the rest of the methylamine hydrochloride. He adds 200
3614ml of chloroform to the sep funnel, and shakes it with the reaction mixture
3615for 30 seconds. He lets it set for a couple of minutes. The chloroform
3616layer should be on the bottom. It has a lot of dimethylamine hydrochloride
3617and other garbage dissolved in it. He drains out the chloroform layer and
3618throws it out.
3619    
3620    He pours the reaction mixture into a 1000 ml round bottom flask and
3621again sets up the glassware as shown in Figure 3. He reattaches the vacuum
3622and continues boiling off the water and formic acid under a vacuum. When
3623the volume of the mixture reaches 500 ml, he removes the flask from the hot
3624oil and places it in cool water. As it cools off, more crystals of
3625methylamine hydrochloride appear. He filters the cold reaction mixture to
3626obtain these crystals. He transfers them to a beaker and adds 200 ml of
3627cold chloroform to the beaker. He stirs the crystals around in the
3628chloroform for a few minutes, breaking up any chunks. This dissolves any
3629dimethylamine hydrochloride in the product. He filters the crystals in the
3630beaker, then puts them in the 1000 ml, 3-necked flask along with his first
3631crop of methylamine hydrochloride crystals. He throws away the chloroform
3632and retums the reaction mixture to the 1000 ml flask.
3633    
3634    He boils the reaction mixture under a vacuum again. When its volume
3635reaches about 150-170 ml, he turns off the vacuum and removes the flask
3636from the hot oil. He pours the reaction into a beaker and stirs it as it
3637cools down, to prevent it from turning into a solid block. Once it has
3638cooled down, he adds 200 ml of cold chloroform to the slush. He stirs it
3639around with a glass rod for a couple of minutes, being sure to break up any
3640chunks. The mixture is then filtered. The crystals of crude methylamine
3641hydrochloride are kind of gooey, so it may not be possible to filter out
3642all the chloroform. But he does the best he can. He returns the filtered
3643crystals to the beaker and adds 100 ml of cold chloroform to the crystals.
3644He stirs it around again, then filters the crystals. He must do a better
3645job of filtering out the chloro form this time. These crystals also absorb
3646water from the air and melt. As soon as this last crop of crystals is
3647filtered, he adds them to the other crystals in the 3-necked flask. He may
3648have to pack it down to get it all to fit. The yield of methylamine
3649hydrochloride is about 425 grams. He may wish to stopper the flask and dry
3650the crystals under a vacuum, although it is not essential.
3651    
3652    The compound the underground chemist wants is methylamine, not
3653methylamine hydrochloride. Methylamine is a gas which turns into a liquid
3654at -6øC (21øF). He will now neutralize the hydrochloride with sodium
3655hydroxide and liquefy the methylamine gas produced.
3656    
3657    The glassware is set up as shown in Figure 21. The 3-necked flask is
3658sitting on the hotplate. It contains methylamine hydrochloride crystals. He
3659puts the long condenser in the central neck and stoppers the other neck of
3660the flask. He adds 100 grams of sodium hydroxide to the flask. (Lye is an
3661acceptable substitute.) It may begin to react to form methylamine and salt,
3662but it will not get very far without water. He dissolves 220 grams of
3663sodium hydroxide or lye in 350 ml of water and sets it aside for the time
3664being. He puts a sep funnel in the third neck of the 3-necked flask. He
3665connects a stillhead to the top of the condenser and attaches the shorter
3666condenser to it. The water jacket of the condenser is filled with rubbing
3667alcohol. The water entrance and exit are plugged to hold in the alcohol.
3668The outside of this condenser is packed with enough dry ice to keep it good
3669and cold, in the vicinity of 0øF. He insulates this dry ice packing so that
3670it does not evaporate too quickly. He attaches the vacuum adapter to the
3671condenser, then connects a section of plastic tubing to the vacuum nipple
3672to carry fumes of ammonia outside. He attaches a 500 ml round bottom flask
3673to the vacuum adapter. This flask is cooled by placing it in a styro foam
3674container. He pours in alcohol until the rubbing alcohol is halfway up the
3675sides of the flask. He adds dry ice to this alcohol bath until its
3676temperature is about -10øF. (He adds the dry ice slowly at first to keep
3677the alcohol from foaming over.) He keeps it at this temperature until he
3678has collected all the methylamine. Ice water is run through the long
3679condenser, as described in the chapter on N-methylformamide.
3680    
3681    He adds the sodium hydroxide solution to the sep funnel and drips it
3682onto the methylamine hydrochloride and sodium hydroxide in the flask. It
3683reacts rapidly to form methylamine and salt. The heat that the reaction
3684produces causes the methylamine to be driven off and condensed in the
3685collecting flask. He swirls around the flask to get the sodium hydroxide
3686into contact with the methylamine hydrochloride. When all the sodium
3687hydroxide has been added, he closes the valve of the sep funnel and allows
3688it to react for a few minutes. Then he slowly heats the flask to drive off
3689the methylamine. He may have to add some water through the sep funnel to
3690get the methylamine hydrochloride on the bottom of the flask in contact
3691with the sodium hydroxide.
3692    
3693    In the meantime, liquid methylamine has been collecting in the 500 ml
3694flask. It is mixed with some water which made it through the long  
3695condenser, and also some ammonia. He allows the temperature of the alcohol
3696bath surrounding the 500 ml flask to rise to 0øF after all the methylamine
3697has been boiled out of the 3-necked flask. He holds it at that temperature
3698for half an hour. The ammonia will evaporate and exit through the plastic
3699tubing. Since ammonia gas is poisonous, this tubing runs outside.
3700    
3701    Then the chemist adds an equal volume of water to the liquid  
3702methylamine, about 220 ml. He has just made about 450 ml of 40% methylamine
3703in water. The water allows him to keep it at room temperature. He pours it
3704into a champagne bottle and tightly stoppers it. This methylamine can be
3705used to make N-methlyformamide, but cannot be used in the hydrogenation
3706bomb. It may contain traces of chloroform, which would poison the Raney
3707nickel catalyst. Since methylamine is cheap, he will buy it when possible.
3708    
3709    Methylamine can be made by other methods as well. For example, it can
3710be made in 71% yield by reacting methyl iodide with hexamine, also known as
3711hexamethylene tetramine. Good directions for making this substance from
3712ammonia and formaldehyde can be found in Home Workshop Explosives by yours
3713truly. The production details for methylamine are found in the Journal of
3714the American Chemical Society, Volume 61, page 3585, (1939). The authors
3715are Galat and Elion.
3716    
3717    It can also be made by degrading acetamide with Clorox. See Journal of
3718the American Chemical Society, Volume 63, page 1118, (1939). The authors
3719are Whitmore and Thorpe, and the yield is 78%.
3720    
3721    It can also be made via the Curtius reaction in a yield of 60%. See
3722Helv. Chim. Acta, Volume 12, page 227, (1929). The authors are Naegeli,
3723Gruntuch and Lendorff.
3724    
3725                                 References
3726    
3727   Journal of the American Chemical Society, Volume 40, page 1411 (1918).
3728    
3729    
3730--------------------------------------------------------------------------
3731        The Ritter Reaction: Amphetamines Directly From Allylbenzene
3732--------------------------------------------------------------------------
3733    
3734    A most interesting sidelight appears in an article by Ritter and Kalish
3735found in the Journal of the American Chemical Society, Volume 77, pages
37364048 to 4050. This sidelight was a bit of research done by a grad student
3737as part of his master's thesis. The grad student just happened to work out
3738the experimental details for converting allylbenzene directly into
3739amphetamine.
3740    
3741    The main thrust of the article was the good Dr. Ritter telling of his  
3742new method for converting double bonds into amines. The method which he
3743pioneered has since come to be known as the Ritter reaction. This versatile
3744reaction can well serve the underground operator as an alternative pathway
3745to the amphetamines.
3746    
3747    The Ritter reaction in general is a reaction whereby amides are made by
3748adding an alkene to a mixture of a nitrile in sulfuric acid. After the
3749amide is made, it is then boiled in hydrochloric acid solution to give the
3750corresponding amine.
3751    
3752    The particular variation on this theme in which we are interested deals
3753with the case in which the alkene is the now familiar and highly useful
3754allylbenzene. When it is added to a solution of acetonitrile in sulfuric
3755acid, the following reaction takes place:  
3756    
3757[SNiP]
3758    
3759    The acetyl amide thusly produced is not isolated and purified. Rather,
3760it is added in the crude state to hydrochloric acid, and boiled for several
3761hours. A hydrolysis reaction almost identical to the one seen in Chapter 5
3762takes place producing the prototype amphetamine, benzedrine.
3763    
3764    The acetyl amide of amphetamine is very similar to the formyl amide of
3765methamphetamine produced by the Leuckardt-Wallach reaction. Its main
3766difference is that it is more difficult to hydrolyze to the corresponding
3767amphetamine by the action of boiling hydrochloric acid. It must therefore
3768be boiled with the acid for a longer period of time than the formyl amide.
3769The manufacturer may well find it to his advantage to boil the tar left
3770over at the end of the process once more with fresh hydrochloric acid. This
3771will likely yield an additional measure of amphetamine from the stubbornly
3772unreactive amide.
3773    
3774    This small hassle with the hydrolysis process could be avoided if HCN
3775were used as the nitrile in sulfuric acid solution. However, the extreme
3776danger of dealing with hydrogen cyanide more than outweighs the additional
3777work needed when using acetonitrile.
3778
3779    To do the reaction, a solution of 450 grams of concentrated sulfuric
3780acid in 400 grams acetonitrile is made by slowly adding the acid to the
3781acetonitrile. Both ingredients are cold when they are mixed together, and
3782the temperature of the mixture is kept in the 5-10øC range during the
3783mixing by setting the reaction container in ice. An admirable reaction
3784vessel is a glass beer pitcher.
3785    
3786    When the addition of the acid to the nitrile is complete, the pitcher  
3787is taken out of the ice, and 236 grams of allylbenzene is slowly added to
3788it with stirring. The mixture quickly turns an orange color, and begins to
3789warm up.
3790    
3791    Stirring is continued on an occasional basis, and the temperature of
3792the mixture followed. It slowly climbs to 50øC, and then more rapidly to
379380øC, as the color of the mixture darkens.
3794    
3795    When the temperature of the mixture reaches 80øC, the pitcher is cooled
3796down, first by setting the pitcher in cool water, and then into ice. When
3797it has cooled down, the mixture is poured into a gallon of cold water
3798containing 15% by weight of Iye. The Iye solution neutralizes the sulfuric
3799acid, and dissolves most of the acetonitrile. The neutralization of the
3800acid by the Iye solution produces a great deal of heat. The Iye solution is
3801gently stirred during the addition, and then stirred more vigorously during
3802the following minutes. After a few minutes of stirring, the mixture is
3803allowed to sit for a few minutes. A yellow oily layer floats on the top of
3804the solution. This yellow oil is the crude amide. If the oil were to be
3805allowed to sit for a while longer, it would begin to form crystals of crude
3806amide. There is no need for this, however, so the processing continues
3807immediately.
3808    
3809    The top yellow layer is poured off into a sep funnel, and any water
3810carried along is drained off. Then the yellow oil is poured into a 2000 ml
3811round bottom flask. It is now ready for hydrolysis with hydrochloric acid
3812solution to make amphetamine. The approximate volume of the crude amide is
3813determined, and five times that volume of 15% hydrochloric acid solution is
3814added to it. Fifteen (15) percent hydrochloric acid solution is easily made
3815by starting with the 28% hardware store hydrochloric acid, and adding just
3816about an equal volume of water to it. A wise move here is to rinse the
3817inside of the sep funnel with acid. This rinses off the amide clinging to
3818the glass insides of the sep funnel.
3819    
3820    When the acid has been added to the amide, the mixture is swirled. They
3821usually mix together well. If they don't, stronger acid is used. Adding
3822some full strength acid to the mix should do the job. Then a few boiling
3823chips are added to the flask, a condenser attached to the flask, and heat
3824applied to boil the mixture at reflux.
3825    
3826    The reflux boiling is continued for 10 hours. During this time the  
3827mixture will turn black. At the end of the boiling period, the mixture is
3828allowed to cool down. When it is cool, 200 ml of benzene or toluene is
3829added to the flask. The mixture is shaken well for a couple of minutes,
3830then allowed to sit. The benzene floats up to the top, and has dissolved in
3831it most of the unreacted amide, and other unwanted garbage.
3832    
3833    The benzene layer is then poured off into a sep funnel, and any water
3834layer carried along drained back into the flask. The benzene layer is
3835poured off into another container for future processing. It may be
3836difficult to tell exactly where the benzene layer ends and the water starts
3837because of their similar color. A sharp eye and good lighting help to spot
3838the interface of the two fluids.
3839    
3840    The acid solution of the amphetamine is now made alkaline to liberate
3841the free base for distilling. To do this, Iye is added to the acid solution
3842in the 2000 ml flask. Assuming the use of about 1200 ml of 15% hydrochloric
3843acid solution, one 12 oz. can of lye does the job. The mixture is first
3844swirled to release heat, then shaken vigorously for five minutes. I cannot
3845emphasize enough the importance of vigorous and prolonged shaking here
3846because the amphetamine base initially formed tends to dissolve
3847unneutralized amphetamine hydrochloride. The oily droplets protect the
3848hydrochloride from contact with the lye solution unless the shaking is
3849strong and prolonged.
3850    
3851    When the shaking is completed, the mixture is allowed to cool down.
3852Then 300 ml of benzene or toluene is added to the flask, and shaking
3853continued for a minute or two. After sitting for a couple of minutes, a
3854benzene-amphetamine layer floats above the water layer. This is poured off
3855into a sep funnel, and the benzene-amphetamine layer poured into a 1000 ml
3856round bottom flask.
3857    
3858    The amphetamine-benzene mixture is distilled in exactly the same manner
3859as described in Chapter 5. The boiling point of benzedrine is 10ø to 20øC
3860lower than meth. The yield of benzedrine is in the range of 100 to 150 ml.
3861    
3862    The benzedrine produced by this reaction is either used and removed as
3863is, or it is converted to methamphetamine. A very good and simple process
3864for doing this can be found in the Journal of the American Chemical
3865Society, Volume 62, pages 922-4. The author is Woodruff. The yield for this
3866process is over 90%, so a greater volume of methamphetamine comes out of
3867the reaction than the benzedrine input. This is because the gain in
3868molecular weight achieved by adding the methyl group outweighs the small
3869shortfall from 100% yield.
3870    
3871    For those who have difficulty reading the Woodruff article, meth is
3872described as B-phenylisopropylmethylamine. The amine is benzedrine.
3873    
3874    If the benzedrine product is used as is, the producer makes it as the
3875hydrochloride salt. This is made the same way as methamphetamine
3876hydrochloride. An alternative to the hydrochloride salt is the sulfate
3877salt. This more hasslesome procedure calls for the use of cooled solutions
3878of amphetamine base in alcohol and cooled solutions of sulfuric acid in
3879alcohol. Furthermore, a recrystallization from alcohol-ether is required
3880because trapped excess sulfuric acid in the crystals causes them to turn to
3881mush or worse. By using HCl gas, the excess acid floats off as gas.
3882    
3883    An excellent review of this reaction can be found in Organic Reactions,
3884Volume 17. Nearly double these yields can be obtained if the underground
3885chemist is willing to risk using hydrogen cyanide instead of acetonitrile.
3886The hydrogen cyanide is made inside the reaction flask from sodium cyanide
3887and sulfuric acid. For complete directions, see Organic Syntheses,
3888Collective Volume 5, page 471 to 473. The name of the compound is alpha,
3889alpha, Dimethyl beta phenethylamine.
3890    
3891    A good alternative to the Ritter reaction is a two step procedure first
3892reacting safrole with hydrobromic acid to give  3,4-methylenedioxyphenyl-
38932-bromopropane, and then taking this material and reacting it with either
3894ammonia or methylamine to yield MDA or MDMA respectively. This procedure
3895has the advantages of not being at all sensitive to batch size, nor is it
3896likely to "run away" and produce a tarry mess. It shares with the Ritter
3897reaction the advantage of using cheap, simple, and easily available
3898chemicals.
3899    
3900    The sole disadvantage of this method is the need to do the final  
3901reaction with ammonia or methylamine inside a sealed pipe. This is because
3902the reaction must be done in the temperature range of 120-140ø C, and the
3903only way to reach this temperature is to seal the reactants up inside of a
3904bomb. This is not particularly dangerous, and is quite safe if some simple
3905precautions are taken.
3906    
3907    The first stage of the conversion, the reaction with hydrobromic acid,
3908is quite simple, and produces almost a 100% yield of the brominated
3909product. See the Journal of Biological Chemistry, Volume 108 page 619. The
3910author is H.E. Carter. Also see Chemical Abstracts 1961, column 14350. The
3911following reaction takes place:
3912    
3913    To do the reaction, 200 ml of glacial acetic acid is poured into a  
3914champagne bottle nestled in ice. Once the acetic acid has cooled down, 300
3915grams (200 ml) of 48% hydrobromic acid is slowly added with swirling. Once
3916this mixture has cooled down, 100 grams of safrole is slowly added with
3917swirling. Once the safrole is added, the cheap plastic stopper of the
3918champagne bottle is wired back into place, and the mixture is slowly
3919allowed to come to room temperature with occasional shaking. After about 12
3920hours the original two layers will merge into a clear red solution. In 24
3921hours, the reaction is done. The chemist carefully removes the stopper from
3922the bottle, wearing eye protection. Some acid mist may escape from around
3923the stopper.
3924    
3925    The reaction mixture is now poured onto about 500 grams of crushed ice
3926in a 1000 or 2000 ml beaker. Once the ice has melted, the red layer of
3927product is separated, and the water is extracted with about 100 ml of
3928petroleum ether or regular ethyl ether. The ether extract is added to the
3929product, and the combined product is washed first with water, and then with
3930a solution of sodium carbonate in water. The purpose of these washings is
3931to remove HBr from the product. One can be sure that all the acid is
3932removed from the product when some fresh carbonate solution does not fizz
3933in contact with the product.
3934    
3935    Once all the acid in the product is removed, the ether must be removed
3936from it. This is important because if the ether were allowed to remain in
3937it, too much pressure would be generated in the next stage inside of the
3938bomb. Also, it would interfere with the formation of a solution between the
3939product and methylamine or ammonia. It is not necessary to distill the
3940product because with a yield of over 90%, the crude product is pure enough
3941to feed into the next stage. To remove the ether from the product, the
3942crude product is poured into a flask, and a vacuum is applied to it. This
3943causes the ether to boil off. Some gentle heating with hot water is quite
3944helpful to this process. The yield of crude product is in the neighborhood
3945of 200 grams.
3946    
3947    With the bromo compound in hand, it is time to move onto the next step
3948which gives MDA or MDMA. See Chemical Abstracts 1961, column 14350. Also
3949see Journal of the American Chemical Society, Volume 68, page 1805 and
3950Journal of the Chemistry Society, part 2 1938, page 2005. The bromo
3951compound reacts with ammonia or methylamine to give MDA or MDMA:
3952    
3953    To do the reaction, 50 grams of the bromo compound is poured into a
3954beaker, and 200 ml of concentrated ammonium hydroxide (28% NH3) or 40%
3955methylamine is added. Next, isopropyl alcohol is added with stirring until
3956a nice smooth solution is formed. It is not good to add too much alcohol
3957because a more dilute solution reacts slower. Now the mixture is poured
3958into a pipe "bomb." This pipe should be made of stainless steel, and have
3959fine threads on both ends. Stainless steel is preferred because the HBr
3960given off in the reaction will rust regular steel. Both ends of the pipe
3961are securely tightened down. The bottom may even be welded into place. Then
3962the pipe is placed into cooking oil heated to around 130øC. This
3963temperature is maintained for about 3 hours or so, then it is allowed to
3964cool. Once the pipe is merely warm, it is cooled down some more in ice, and
3965the cap unscrewed.
3966    
3967    The reaction mixture is poured into a distilling flask, the glassware  
3968rigged for simple distillation, and the isopropyl alcohol and excess
3969ammonia or methylamine is distilled off. When this is done, the residue
3970inside the flask is made acid with hydrochloric acid. If indicating pH
3971paper is available, a pH of about 3 should be aimed for. This converts the
3972MDA to the hydrochloride which is water soluble. Good strong shaking of the
3973mixture ensures that this conversion is complete. The first stage of the
3974purification is to recover unreacted bromo compound. To do this, 200 to 300
3975ml of ether is added. After some shaking, the ether layer is separated. It
3976contains close to 20 grams of bromo compound which may be used again in
3977later batches.
3978    
3979    Now the acid solution containing the MDA is made strongly basic with
3980lye solution. The mixture is shaken for a few minutes to ensure that the
3981MDA is converted to the free base. Upon sitting for a few minutes, the MDA
3982floats on top of the water as a dark colored oily layer. This layer is
3983separated and placed into a distilling flask. Next, the water layer is
3984extracted with some toluene to get out the remaining MDA free base. The
3985toluene is combined with the free base layer, and the toluene is distilled
3986off. Then a vacuum is applied, and the mixture is fractionally distilled. A
3987good aspirator with cold water will bring the MDA off at a temperature of
3988150g to 160ø C. The free base should be clear to pale yellow, and give a
3989yield of about 20 ml. This free base is made into the crystalline
3990hydrochloride by dissolving it in ether and bubbling dry HCl gas through it
3991as described previously.
3992    
3993    Dr. Shulgin prefers another method of converting the free base to the
3994hydrochloride. Rather than bubbling dry HCl through an ether solution of
3995the free base to get the crystalline hydrochloride, he prefers to dissolve
3996about 25 ml of the free base in about 150 ml of anhydrous isopropyl
3997alcohol, and neutralize this mixture with around 150 drops of concentrated
3998hydrochloric acid. Then the product is precipitated out of solution by
3999adding 300 ml of anhydrous ethyl ether, shaking well and letting the
4000mixture sit for a while before filtering. I do not feel this procedure is
4001as suitable for the production of crystals as the one I have given. There
4002are several reasons for this. First of all, Dr. Shulgin prefers the routes
4003using LAH reductions of the nitrostyrenes. Underground operators must face
4004the facts that LAH and large amounts of anhydrous ethyl ether are not
4005likely to be available. To tout this as the preferred pathway leads to an
4006easy shutdown pinchpoint for the central chemical scrutinizers. There are
4007also methods of using sodium borohydride or sodium cyanoborohydride as the
4008reducing agent for the reductive alkylative (aminative) reaction with
4009phenylacetone to yield amphetamine or methamphetamine. These substances are
4010pretty easily made taboo for the general public; aluminum foil is not. This
4011is the reason for my presentation of the aluminum foil reduction method as
4012the preferred route. It has nothing to do with the narco swine's accusation
4013that I was unfamiliar with this other method. I love to hate these
4014creatures! See the article called "Synthetic Reductions in Clandestine
4015Amphetamine and Methamphetamine Laboratories - A Review," in the
4016pseudoscientific journal, Forensic Science International, Vol. 42 (1989),
4017183-199, by the groveling narco swine, Andrew Allen and Thomas Cantrell. It
4018would be good for these beings to get into private industry where they
4019could be productive.
4020
4021    Back to the reasons why I prefer dry HCl precipitation of the free  
4022base. With a less than 100% pure free base, the resulting crystalline
4023hydrochloride has one hell of a thirst for water. This results in a mush
4024that is better handled by my method. The first few crops of crystals from
4025the HCl bubbling can be kept as same, and the later, more polluted product
4026can be segregated, and this can be given the curative attention it needs
4027through washing with more ether, or recrystallizing from alcohol and then
4028ether. If all I have to face as my nemeses are the likes of Allen and
4029Cantrell, the future is secure for manufacturers everywhere!
4030    
4031--------------------------------------------------------------------------
4032                       Methamphetamine From Ephedrine
4033--------------------------------------------------------------------------
4034    
4035                       Ephedrine and Pseudoephedrine
4036    
4037    Ephedrine and pseudoephedrine are structurally mirror images of each
4038other. This is possible because they have a chiral center, the isopropyl
4039carbon to which the nitrogen atom is attached. If the reduction is done in
4040such a manner that the chiral nature of the substance is not jumbled (i.e.
4041racemization), then ephedrine and pseudoephedrine give rise to "l" and "d"
4042methamphetamine, respectively. The "l" form is several times more potent
4043than the "d" form. Meth produced from phenylacetone is a racemic mixture,
4044meaning that it is a 50-50 mix of the "l" and "d" forms of meth. Obviously,
4045a batch of pure "l" form is most desirable, a racemic mixture is OK, and
4046pure "d" form is bad news.
4047    
4048    Many of the direct and indirect reduction methods retain the chiral  
4049nature of the starting material. A good general rule is if the production
4050method does not use boiling acids, racemization does not occur. One can
4051then conclude that only the direct reduction with palladium black, and the
4052hydroiodic acid and red phosphorus methods lead to racemization of the
4053starting material.  
4054
4055    What then if you are starting with pseudoephedrine, and you want as a
4056result a racemic mixture for a product, but aren't using the palladium
4057black or hydroiodic acid routes? This problem can be sidestepped by
4058dissolving the pseudoephedrine (hydrochloride or sulfate) in some
4059concentrated hydrochloric acid, and boiling it under reflux for a couple
4060hours. The result is a 50-50 mix of ephedrine and pseudoephedrine which
4061upon reduction will give a racemic meth mixture.
4062    
4063        Procedure For Obtaining Pure Ephedrine From Stimulant Pills
4064    
4065    In the present chemical supply environment, the best routes for making
4066meth start with ephedrine as the raw material. To use these routes, a
4067serious hurdle must first be overcome. This hurdle is the fact that the
4068most easily obtained source of ephedrine, the so-called stimulant or
4069bronchodilator pills available cheaply by mail order, are a far cry from
4070the pure starting material a quality minded chemist craves. Luckily, there
4071is a simple and very low profile method for separating the fillers in these
4072pills from the desired active ingredient they contain.
4073    
4074    A superficial paging through many popular magazines reveals them to be
4075brim full of ads from mail order outfits offering for sale "stimulant" or
4076"bronchodilator" pills. These are the raw materials today's clandestine
4077operator requires to manufacture meth without detection. The crank maker
4078can hide amongst the huge herd of people who order these pills for the
4079irritating and nauseating high that can be had by eating them as is. I have
4080heard of a few cases where search warrants were obtained against people who
4081ordered very large numbers of these pills, but I would think that orders of
4082up to a few thousand pills would pass unnoticed. If larger numbers are
4083required, maybe one's friends could join in the effort.
4084    
4085    The first thing one notices when scanning these ads is the large  
4086variety of pills offered for sale. When one's purpose is to convert them
4087into methamphetamine, it is very easy to eliminate most of the pills
4088offered for sale. Colored pills are automatically rejected because one does
4089not want the coloring to be carried into the product. Similarly, capsules
4090are rejected because individually cutting open capsules is just too much
4091work. Bulky pills are to be avoided because they contain too much filler.
4092The correct choice is white cross thins, preferably containing ephedrine
4093HCl instead of sulfate, because the HCl salt can be used in more of the
4094reduction routes than can the sulfate.
4095    
4096    Once the desired supply of pills is in hand, the first thing which  
4097should be done is to weigh them. This will give the manufacturer an idea of
4098how much of the pills is filler, and how much is active ingredient. Since
4099each pill contains 25 milligrams of ephedrine HCl, a 1000 lot bottle
4100contains 25 grams of active ingredient. A good brand of white cross thins
4101will be around 33% to 40% active ingredient. 25 grams of ephedrine HCl may
4102not sound like much, but if it is all recovered from these pills, it is
4103enough to make from 1/2 to  ounce of pure meth. This is worth three or four
4104thousand dollars, not a bad return on the twenty odd dollars a thousand lot
4105of such pills costs.
4106    
4107    To extract the ephedrine from the pills, the first thing which must be
4108done is to grind them into a fine powder. This pulverization must be  
4109thorough in order to ensure complete extraction of the ephedrine from the
4110filler matrix in which it is bound. A blender does a fine job of this  
4111procedure, as will certain brands of home coffee grinders.
4112    
4113    Next, the powder from 1000 pills is put into a glass beaker, or other
4114similar container having a pouring lip, and about 300 ml of  
4115room-temperature distilled water is added. This is stirred at low speed for
411610 minutes. The water is then poured out of the beaker through a filter and
4117set aside. The sludge from the pills is returned to the beaker, and another
4118250 ml of room-temperature distilled water is added. Once again, stir for
411910 minutes, then pour through a filter.
4120    
4121    A little more water can be poured over the sludge to rinse the last of
4122the ephedrine out of it. At this point, the sludge should be nearly  
4123tasteless and gritty in texture. The water filtrate should be clear and
4124very bitter. The filtrate contains all the ephedrine.
4125    
4126    The filtrate is now collected into one beaker and heated over a burner
4127until it reaches a gentle boil. One half of the water is boiled off this
4128way. The liquid is then removed from the heat and poured into a glass
4129baking dish to more slowly evaporate away the remaining liquid. The
4130resulting crystals of ephedrine can then be rinsed with some cold acetone.
4131    
4132    Certain brands of pills are loaded with gummy binders. These brands are
4133recognizable because they are very difficult to crush into a powder, and
4134the hot water extract from them is not easily filtered into a clear
4135solution. When evaporated down to pure extract, they produce a yellow gummy
4136residue at the bottom of the evaporation dish. This gummy mess is not
4137suitable for processing into high grade drugs. The gum is easily removed
4138from the desired product just by adding a few hundred mls of cold acetone
4139to the extract of 1000 stimulant pills, and grinding the gummy mess with a
4140glass rod until the crystals of stimulant are freed from the gum, and a
4141fine dispersion of them floats freely about. The gum colors of acetone
4142yellow, and the floating crystals will be white. Then by filtering this
4143mixture, one obtains the pure crystals of active ingredient free from the
4144polluting binder in the pills.
4145    
4146                             Indirect Reduction
4147    
4148    A popular alternative method for making methamphetamine uses ephedrine
4149as the starting material. This method was not covered in the original
4150edition of this book. It is now presented in all its glory for the  
4151education of the reader.
4152    
4153    The reasons for the popularity of this method are twofold. Firstly,  
4154this method does not require the use of methylamine because the methylamino
4155group is already incorporated in the ephedrine molecule. Secondly,
4156ephedrine is still easily available. It is much more easily obtained than
4157phenylacetic acid. This may change in the future, but at present an
4158underground chemist can buy 1000-lot quantities of stimulant pills
4159(containing 25 milligrams of ephedrine) by mail at very reasonable prices.
4160    
4161    The utility of this method is not limited solely to ephedrine.  
4162Pseudoephedrine and phenylpropanolamine can also be used as starting
4163materials. This means that Sudafed and Dexatrim, and their generic
4164equivalents, can be used as raw materials for clandestine amphetamine
4165manufacture. The active ingredient is easily separated from the diluents in
4166the pills by the method given in this book.
4167    
4168    The bad thing about this method is that foul impurities generated  
4169during the manufacturing process are easily carried into the final product.
4170Due care must be practiced by the chemist during the purifi- cation to
4171exclude this filth. Unscrupulous and/or unskilled manufacturers turn out
4172large volumes of crank containing this abomination. The impurities not only
4173ruin the finer aspects of the meth high, but they also have a pronounced
4174deleterious effect on male sexual function.
4175    
4176    One can quickly see that all a chemist needs to do to turn ephedrine
4177into meth is to replace the alcohol OH grouping with a hydrogen atom. This
4178is not done directly. Instead, a two step process is used whereby the OH is
4179first replaced by a chlorine atom, and then this chlorine is removed by one
4180of several reductive processes, to be replaced with a hydrogen atom. To
4181illustrate:
4182    
4183    [SNiP]
4184    
4185    There are several general methods for converting an alcohol group into
4186a chlorine atom. Substances such as thionyl chloride SOCl2 phosphorus
4187pentachloride (PCl5), phosphorus oxychloride (POCl3), phosphorus bichloride
4188(PCl3), phosphorus pentabromide (PBr5) and phosphorus tribromide (PBr3) can
4189all be used to convert the alcohol group to either a chloride or bromide.
4190Essentially the same reaction conditions are followed when using any of the
4191above listed substances. The only difference is how much ephedrine or PPA
4192(phenylpropanolamine) the substance can chlorinate or brominate. See the
4193table below:
4194    
4195        Substance       Molecular       Reacts with this many
4196                        Weight          moles of ephedrine
4197    
4198        SOCl2           119             1
4199        PCl3            137             2
4200        POCl3           153             2
4201        PBr3            271             2
4202        PCl5            208             3
4203        PBr5            430             3
4204    
4205            molecular weight of ephedrine HCl=202, PPA-HCl = 188
4206    
4207    Using the above table, a person can quickly calculate how much  
4208ephedrine or PPA will react with a given amount of chlorinating agent. Use
4209of excess chlorinating agent will result in a higher percentage yield based
4210on the ephedrine used, but after a point,  this is wasteful. The following
4211example takes this largess to an  extreme, but achieves 100% conversion of
4212ephedrine to  chlorephedrine. This procedure can be followed with all the
4213chlorinating agents. The reaction is fairly easy to do. The main
4214precautions are to make sure that the glassware is free of water, and
4215taking one's time to be sure the mixture stays sufficiently cold. It is
4216also wise to avoid doing this reaction in very humid conditions.
4217    
4218    To convert ephedrine to chlorephedrine, a 2000 ml 3-necked flask is
4219nestled into a bed of ice. A mechanical stirrer is put down the middle neck
4220of the flask as in the preparation of butyl nitrite. One of the outside
4221necks is plugged by sticking a cork into it. The other neck is used as a
4222chemical addition portal. Into this neck, 360 ml of chloroform is added.
4223Then 360 grams of PCl5 is added. When this mixture has cooled down (about
42241/2 hour), 240 grams of ephedrine hydrochloride is added to the brew. It is
4225added by placing a small plastic funnel into the neck of the flask. This
4226ensures that it falls into the mix, rather than being scattered along the
4227walls of the flask. The ephedrine hydrochloride is added in small portions
4228over a 45 minute period. Stirring is fast enough that the PCI5 remains in
4229suspension, and the ephedrine hydrochloride quickly mixes into the brew.
4230Adjusting the angle of the funnel so that it aims the ephedrine HCI toward
4231the center of the whirlpool is a fine point that gives best results.
4232    
4233    The serious experimenter may wish to try replacing the chloroform
4234solvent with l,l,l-trichloroethylene. This very cheap solvent can be found
4235in hardware stores, and has solubility characteristics similar to
4236chloroform. No doubt a greater quantity of trichlorethylene would have to
4237be used, but it would take another item out of the chemical supply loop.
4238    
4239    When all of the ephedrine HCl has been added, an additional 60 ml of
4240chloroform is added. Then the funnel is replaced with another cork, and the
4241stirring is turned up a bit. The stirring is continued for two hours. Then
4242the stirring is turned off, and the flask is allowed to sit for 45 minutes
4243or so. During this period, the unreacted PCl5 settles to the bottom of the
4244flask. At the cold temperature inside the flask, some crystals of ephedrine
4245HCl will appear floating on the surface of the brew.
4246    
4247    When all has settled inside the flask, the mixture IS carefully  
4248decanted off into a one gallon glass jug. Great care is taken during this
4249decanting to make sure that all of the settled PCl5 remains behind. If any
4250of it were mixed in with the product chlorephedrine it would be reduced in
4251the succeeding hydrogenation to phosphine, PH3, an exceedingly deadly gas.
4252If it appears any is being carried along, the mixture is filtered.
4253    
4254    Next, the product is precipitated from the chloroform solution in the
4255gallon jug. This is done by slowly adding ether or, better still, mineral
4256spirits (cheap and easily available in large amounts) to the gallon jug
4257until it is nearly full. The mixture in the gallon jug is continuously
4258stirred during the addition of the ether or mineral spirits for best
4259results. Chlorephedrine does not dissolve in ether or mineral spirits, so
4260as the solution changes from chloroform to predominantly ether, the product
4261is thrown out of solution in the form of crystals. If an oily layer forms
4262at the bottom of the jug, this means a dirty batch. The oil may eventually
4263crystallize, but more likely it must be separated, dissolved in an equal
4264volume of chloroform, and precipitated once again by adding ether or
4265mineral spirits.
4266    
4267    After the addition of the ether or mineral spirits, a large mass of  
4268crystals fills the jug. This is the product. The jug is stoppered, and put
4269into the freezer for an hour to let the crystals fully grow. The crystals
4270are then filtered out and rinsed down with a little bit of cold acetone.
4271Then the crystals are spread out to dry on china plates or glass baking
4272dishes. The yield of chlorephedrine hydrochloride is in the neighborhood of
4273250 grams.
4274
4275                             Production of Meth
4276    
4277    To make meth from chlorephedrine, the chlorine atom is replaced with a
4278hydrogen. This reduction is accomplished by any of several methods. Lithium
4279aluminum hydride does the best job of completely converting the
4280chlorephedrine into meth, but it is very expensive, and a watched chemical.
4281Zinc dust, on the other hand, is cheap and easily available, but it leaves
4282a large proportion of the chlorephedrine unconverted. The most practical
4283and effective way to turn out large volumes of meth is by catalytic
4284hydrogenation. It is possible to use Raney nickel as the catalyst for this
4285hydrogenation, but it has to be used in quite large amounts to do a good
4286job. Potassium Hydroxide (KOH) also has to be added to the bomb in an
4287amount equal to the chlorine given off by the chlorephedrine, i.e., one
4288mole of chlorephedrine would require one mole of KOH added. Platinum can
4289also be used to reduce the chlorephedrine, but it too has to be used in
4290large amounts to get good results. Furthermore, it is rapidly poisoned by
4291the chlorine and becomes useless.
4292    
4293    The best catalyst to use for this reduction is palladium, in the form  
4294of palladium black on charcoal, or palladium on barium sulfate. The
4295palladium stands up well to the chlorine, and can be used to run many
4296batches before it needs to be recycled. Palladium works fine at low
4297pressures of hydrogen, and can be used with the champagne bottle
4298hydrogenation system pictured in Chapter 11.
4299
4300    To do the reaction, a champagne bottle of at least 1.5 liters volume is
4301filled with 50 grams sodium acetate (anhydrous) and 700 ml of distilled
4302water. The pH of this solution is then made neutral (pH 7) by dripping in
4303diluted acetic acid. This forms an acetic buffer which prevents the
4304solution from becoming acidic when chlorephedrine hydrochloride is added to
4305it. It also neutralizes the hydrochloric acid formed when the chlorine atom
4306is removed from the chlorephedrine molecule. Then 40 grams of 5% palladium
4307black on charcoal (palladium content 2 grams) is added, and finally 125
4308grams of chlorephedrine hydrochloride is added.
4309    
4310    Sodium acetate is now on California's list of less restricted  
4311chemicals, so it is wise to avoid using sodium acetate as such. This is not
4312the least bit troublesome, and shows just how stupid the people are who put
4313it on the restricted list. To avoid the need for sodium acetate purchases,
4314acetic buffer is made from vinegar and sodium hydroxide. To do this, 700 ml
4315of vinegar is used instead of distilled water. It should be the cheapest
4316grade of white distilled vinegar, because this is likely to be made just by
4317diluting glacial acetic acid with water down to a 5% strength. Then to this
4318700 ml of vinegar, sodium hydroxide pellets are slowly added until the pH
4319of the solution is around 7. This takes about 23 grams of NaOH.
4320    
4321    The champagne bottle is then attached to the hydrogen line pictured in
4322Figure 17 in Chapter 11, and the air is sucked out and replaced with
4323hydrogen as described in that chapter. Then the pressure of hydrogen is
4324increased to 30 pounds, and magnetic stirring is begun. The solution soaks
4325up hydrogen for several hours, during which time the pressure is maintained
4326around 30 pounds by letting more hydrogen into the bottle.
4327    
4328    When absorption of hydrogen ceases after several hours, the reaction is
4329complete. The hydrogen valve is turned off at the cylinder, and hydrogen
4330inside the bottle released outside through a line of tubing as described in
4331Chapter 11. Stirring is stopped, and the palladium on charcoal catalyst is
4332allowed to settle in the bottle. When it has settled, the solution is
4333carefully poured out of the bottle into a beaker, taking care to try to
4334leave all the catalyst behind in the bottle. The solution is then filtered
4335to remove suspended Pd on charcoal catalyst.  
4336
4337    The catalyst is returned to the bottle, which is then refilled with a   
4338fresh batch, or filled with hydrogen to protect the catalyst.
4339    
4340    Before proceeding further with the processing of the filtered batch, it
4341is wise to look more closely at the nature of the by-products produced by
4342this method of making meth. There are twin villains to be dealt with here:
4343    
4344    These substances, or closely related ones, will always be formed when
4345making meth by this method. The chlorephedrine is the result of incomplete
4346reduction to meth, and the aziridine the result of an intermolecular
4347reaction between the chlorine atom and the nitrogen atom of the
4348chlorephedrine. It is likely that the aziridine by-product is more easily
4349formed when the bromoephedrine variation of this synthetic route is chosen.
4350There are two things which aid in the formation of the aziridine. They are
4351exposure to strong bases such as lye and heat. To minimize formation of the
4352aziridine, one first of all aims for as complete a reduction as possible of
4353the chlorephedrine to meth. Next, during processing, one backs off on the
4354heavy duty use of lye, using bicarb instead to neutralize the last of the
4355acid. Finally, the distillation is done as quickly as feasible under vacuum
4356to get the least heat exposure to the unreduced chlorephedrine. Obviously,
4357the first point is the most important.
4358    
4359    To proceed, the filtered batch is reacted with lye with strong shaking
4360until litmus paper says that the pH is around 7. Then bicarb is added to
4361finally make the solution basic. The fizzing and venting of CO2 gas is a
4362hassle at this point, but it is worth it to avoid the formation of the
4363aziridine. A 2000 ml flask is a good vessel in which to do the
4364neutralization procedure. One must periodically vent off the built up CO2
4365gas after bicarb has been added.
4366    
4367    Upon standing after the shaking, a layer of meth floats on top of the
4368water layer. Then 200 ml of benzene or toluene is added, and the jug is
4369shaken again. After standing for a couple of minutes, the benzene-meth
4370layer floats nicely upon the water. This is carefully poured off into a sep
4371funnel, and the benzene-meth layer is poured into a 500 ml round bottom
4372flask. The water layer is discarded.
4373    
4374    Next, the product is distilled as described in Chapter 5. Here also is
4375a point at which lazy or unskilled operators err and thereby leave their
4376product polluted with chlorephedrine. You see, it is next to impossible to
4377completely convert the chlorephedrine into meth. The conversion can be
4378encouraged by using plenty of catalyst, sufficient pressure, and ample
4379reaction time in the bomb, but there will still be some left unreacted. As
4380the catalyst wears out from doing repeated batches, the proportion of
4381chlorephedrine in the product will increase. Only by doing careful
4382fractional distillation, can the chlorephedrine be removed.
4383Chlorephedrine's solubility characteristics are so similar to meth's that
4384it can't be removed by crystallization or rinsing the crystals. When doing
4385the distillation, the meth distills at the usual temperature range. The
4386next fraction which distills is chlorephedrine. Since this chlorephedrine
4387can then be cycled back into the hydrogenation step, it makes both economic
4388and ethical sense to remove it from the product. By skipping the fractional
4389distillation, lazy operators costs themselves an added measure of meth
4390yield from their raw material inputs.
4391    
4392    The chlorephedrine free base thusly obtained is too unstable to keep as
4393such. Its must immediately be reacted with HCI to form the hydrochloride.
4394    
4395                    Palladium Black on Carbon Catalysts
4396    
4397    Since palladium black on carbon catalyst is on the narco swine's watch
4398list of chemicals, it is wise for the operator to make his own supply.
4399Luckily, this is not too difficult, and gives a catalyst that is fresher
4400and more active than off the shelf catalysts.   
4401
4402    To make the catalyst, the chemist first obtains Norit or Darco brand
4403activated charcoal, and washes it with nitric acid. This is done by
4404measuring out about 100 grams of the charcoal, and then putting it into a
4405beaker along with 10% nitric acid. They are mixed together into a watery
4406slurry, and heated on a steam bath or in a boiling water bath for 2 or 3
4407hours. After the heating, the carbon is filtered and rinsed liberally with
4408distilled water until the last traces of acid are rinsed from it. This
4409requires about a gallon of water.
4410    
4411    The acid washed carbon is then transferred to a 4000 ml beaker. A few
4412grams of the carbon sticks to the filter paper and is otherwise lost, but
4413this is OK since the idea is to get about 93-95 grams of carbon into the
4414beaker. 1200 ml of distilled water is added to the beaker, and it is heated
4415with stirring to 80ø C. When this temperature is reached, a solution of 8.2
4416grams of palladium chloride in 20 ml of concentrated hydrochloric acid and
441750 ml of water is added. This acid solution of palladium chloride is heated
4418for a couple of hours before it is added, because PdCl2 dissolves slowly in
4419the acid solution. It is not added until all the PdCl2 is dissolved. If
4420PdCl2 dihydrate is used, the amount used is increased to 10 grams.
4421    
4422    When the PdCl2 solution has been added and stirred in, 8 ml of 37%
4423formaldehyde solution is added and mixed in. Next, the solution is made
4424slightly alkaline to litmus by adding 30% sodium hydroxide solution to the
4425beaker dropwise with constant stirring. Once the solution has become
4426slightly alkaline to litmus paper, the stirring is continued for another
4427five minutes.
4428    
4429    Next, the solution is filtered to collect the palladium black on  
4430charcoal catalyst. It is rinsed ten times with 250 ml portions of distilled
4431water. Then after removing as much water as possible by filtration, the
4432catalyst is spread out to dry in a glass baking dish. It is not heated  
4433during the drying process since it could burst into flames. When it has
4434dried, it is stored in a tightly stoppered bottle and used as soon as
4435possible. This process gives about 95 grams of 5% palladium black on
4436charcoal catalyst.
4437    
4438                              Direct Reduction
4439    
4440    This section deals with the direct conversion of ephedrine,  
4441pseudoephedrine, or phenylpropanolamine to meth or benzedrine respectively.
4442This conversion can be accomplished by one of four methods. These four
4443methods will be covered and explained in the order of best method to worst
4444method. These conversions are all possible because ephedrine,
4445pseudoephedrine, and phenylpropanolamine are all benzyl alcohols, and
4446benzyl alcohols are the easiest of all alcohols to reduce to the
4447corresponding hydrocarbon.
4448    
4449    These methods all have the advantage of being quick and simple, but
4450they also have their unique disadvantages, along with the general shared
4451disadvantage that the starting material must be gathered bits at a time
4452from bottles of pills.
4453
4454            Method 1: Lithium Metal in Liquid Ammonia Reduction
4455    
4456    This is a new method, and is the best one I've seen come down the pike
4457in ages. This procedure was pioneered by a clandestine operator in
4458California. Unfortunately, he was busted because he bought a jug of
4459ephedrine to use as his starting material. Had he been more cautious, and
4460isolated the ephedrine from legal pills, he may well have gone undetected.
4461This method is ideally suited for the rapid production of truly massive
4462amounts of crank. It suffers from the need to use liquid anhydrous ammonia.
4463This is very smelly stuff, especially in the quantities needed to make
4464large amounts of meth. The smell problem means that this method can only be
4465used in countryside locations, preferably in a large shed with a strong
4466breeze passing through it. In this way, the production masters can position
4467the reaction so that they are upwind from the fumes.
4468    
4469    The countryside location has the further advantage that tanks of  
4470anhydrous ammonia are not at all out of place in such a location. In every
4471agricultural area, tanks of anhydrous ammonia ply the roads all through the
4472growing season. Farmers use it for nitrogen fertilizer on their crops,
4473especially corn. The local co-op hauls out the tank to the farmer, who then
4474applies it to his crops at his leisure. The implication of this is obvious.
4475A well thought out large scale meth production scheme would center upon
4476renting some nondescript piece of land, planting some corn on it, and then
4477getting a tank of "anhydrous" to fertilize the crop. The resulting product
4478will pay much better than corn. A less well thought out plan would involve
4479getting a tank of anhydrous ammonia from a chemical supplier and taking it
4480to a countryside location for further use. In either case, the ammonia is
4481of the same grade.
4482    
4483    This method of making crank is based on the research of Gary Small and
4484Arlene Minnella as published in the Journal of Organic Chemistry, Volume
448540, pages 3151 to 3152 (1975). The article is titled "Lithium-Ammonia
4486Reduction of Benzyl Alcohols to Aromatic Hydrocarbons. An Improved
4487Procedure." It results in the 100% conversion of ephedrine, pseudoephedrine
4488or PPA in a reaction time of 10 minutes or so.
4489    
4490    A disadvantage of this procedure is that it demands the use of the free
4491bases of ephedrine or PPA. Since the material as isolated from the pills
4492will be either the hydrochloride or sulfate salt, a free basing and
4493subsequent distillation is called for to get pure free base, free from salt
4494and traces of water, which would interfere with this reaction.
4495    
4496    A good procedure to follow to get this pure free base is to dissolve
4497the hydrochloride salt in alcohol, and add NaOH or KOH pellets to the
4498solution until the hydrochloride is all neutralized, and then distill off
4499the alcohol, and finally collect the free base by vacuum distillation. The
4500boiling point of ephedrine is around 225øC at normal pressure, and 135øC at
450112 mmHg vacuum. For PPA, the boiling point is a little bit lower. In doing
4502this distillation, the condenser should not have water flowing through it
4503because the free bases melt at 77øC and 101øC respectively. If cold water
4504should flow through the condenser, it would plug up with the solid.
4505Instead, the condenser should be filled with water, and it should be
4506allowed to stay in there until it nears boiling. Then a bit of fresh water
4507can be flowed in. The receiving flask should be packed in ice to assure
4508that all the free base is condensed there.
4509    
4510    This method is superior to dissolving the hydrochloride in water and
4511neutralizing the salt with NaOH in that solvent and then trying to extract
4512out the free base with ether or toluene, and then proceeding with the
4513distillation, because the free bases are soluble in water and form
4514hydrates. They also distill with steam. However, when using the sulfate
4515salt as raw material, one may have no choice but to use the latter method
4516because the sulfate salts do not dissolve well in alcohol.
4517
4518    With a supply of free base in hand, it is now time to consider the  
4519lithium metal in ammonia reduction method. A very good review of this
4520procedure can be found in the book Reduction: Techniques and Applications
4521in Organic Synthesis by Augustine, pages 98 to 105. At the heart of this
4522method is the fact that lithium metal, or sodium metal, or even potassium
4523metal can dissolve in liquid ammonia to form blue colored solutions that
4524have powerful reducing properties. Such solutions are often referred to as
4525"dissolved electrons." These solutions are stable unless water gets in
4526them, or unless they are contaminated with iron from the ammonia tank. When
4527the free bases of ephedrine or PPA are added to these "dissolved
4528electrons," they are quickly and easily reduced to meth or benzedrine
4529respectively. To do the reaction, a 3000 ml round bottom 3 necked flask is
4530set inside a styrofoam tub. The purpose of the tub is to provide
4531insulation, because once liquid ammonia gets out of the cylinder it starts
4532to rapidly boil away until the liquid is lowered to its boiling point of
4533-33øC. This boiling can be kept under control by adding dry ice to the tub.
4534If a cylinder of ammonia is being used, it is a good idea to cool it down
4535before use by putting it in a freezer. With a tank from the co-op, this is
4536not practical. To get the liquid ammonia out of the tank or cylinder,
4537either clear plastic tubing or rubber tubing is placed over the exit valve
4538of the tank or cylinder, and run into the 3 necked flask. Use of metal, and
4539especially copper, is to be avoided. Then the cylinder is tipped upside
4540down, so that the valve is at the bottom of the cylinder. This assures that
4541liquid comes out rather than gas. Next the valve is cautiously cracked
4542open, and liquid ammonia is run into the flask until it is about 1/2 full.
4543It will quickly boil away until the volume of the ammonia is down to about
45441000 ml, and then more slowly because the ammonia has cooled to its boiling
4545point. Then wearing rubber gloves and eye protection to keep the fumes out
4546of the eyes, a magnetic stirring bar is placed in the flask, and the tub is
4547put on a magnetic stirrer, and stirring is begun. Now 14 grams of lithium
4548metal is put into the flask. Lithium usually comes in the form of turnings
4549inside a sealed glass ampule under inert atmosphere. It can be used
4550directly as such. If lithium wire is being used, it should be cut into  
4551short lengths, and rinsed off with petroleum ether prior to use. The
4552lithium metal quickly dissolves, forming a blue solution. Next, 500 ml of
4553tetrahydrofuran is added to this solution. The purpose of the THF is to aid
4554in the dissolution of the ephedrine or PPA which is to be added next. I can
4555see no reason why anhydrous ether can't be used instead of THF, if this is
4556easier to obtain. Next 110 grams of ephedrine (or 100 grams of PPA) is
4557dissolved in 500 ml of THF or ether, and this solution is added to the
4558lithium in ammonia solution over a period of 10 minutes. After allowing the
4559reaction to proceed for an additional 10 minutes, the reaction is quenched
4560by slowly adding water to the ammonia. This is done dropwise at first, and
4561then more rapidly until the blue color disappears from the ammonia
4562solution. The flask is then taken out of the styrofoam tub, and the ammonia
4563is allowed to evaporate overnight. When the ammonia is gone, some more
4564water is added to the remaining ether (or THF) solution to dissolve the
4565salts of lithium in the bottom of the flask. After separating the water
4566layer, the ether layer is dried using anhydrous sodium sulfate, and the
4567meth or benzedrine is obtained as the hydrochloride salt by bubbling HCl
4568gas through the ether solution as described back in Chapter 5. Distillation
4569is unnecessary because of the lack of formation of by products in this
4570reduction. It would just be a colossal waste of ether.
4571    
4572    One may justifiably ask now, "How is this such a great mass production
4573method, when one is only getting 100 grams of product out of each batch?"
4574The answer is that the work can easily be organized so that one batch after
4575another is quickly turned out by this method. Each individual batch only
4576requires a few minutes of attention. After one flask is filled with
4577ammonia, another may be set up and filled, resulting in a virtual assembly
4578line procedure.
4579    
4580    Before moving on here, there is a possible complication which must be
4581addressed. This is the possibility that a tank of ammonia may only be
4582putting out ammonia gas, rather than spewing liquid. This is no great
4583hassle. In that case, the 3000 ml 3 necked flask is well packed in dry ice,
4584and rubbing alcohol poured on the dry ice to create a very cold bath. When
4585the ammonia gas hits the very cold flask, it will be condensed to a liquid.
4586This may actually be a better procedure because it will assure that the
4587ammonia does not have dissolved iron in it from the tank. Iron interferes
4588with some lithium in ammonia reductions. I am not sure whether that is the
4589case with this particular reaction. Input from serious experimenters is
4590welcome.
4591    
4592    It is also possible to use sodium metal or potassium metal in this  
4593reaction. Sodium is much cheaper than lithium, but is on the California
4594list of less restricted chemicals. Use of sodium may also result in partial
4595reduction of the benzene ring. For details on this modified procedure, see
4596the aforementioned Journal of Organic Chemistry article. I suspect that the
4597partial benzene ring reduction could be avoided if sodium metal were used
4598in the procedure given here rather than the modified procedure using sodium
4599given in the JOC article. That procedure uses ethanol instead of THF.
4600Allowance would have to be made in calculating how much sodium metal to use
4601for the greater atomic weight of sodium (23 versus 7).
4602    
4603                     Method 2: Wolff-Kishner Reduction
4604    
4605    This method of directly reducing ephedrine, pseudoephedrine, or  
4606phenylpropanolamine to meth or benzedrine uses hydrazine hydrate as the
4607reducing agent. The Wolff-Kishner reduction is generally used to  
4608deoxygenate ketones to the corresponding hydrocarbon, but in this case, it
4609can be used on these particular substances to reduce them. No doubt, this
4610is because the benzyl alcohol grouping has a ketone nature due to
4611tautomerism.
4612    
4613    The Wolff-Kishner reduction has the advantage of not producing great
4614plumes of stink. It could likely be done in an urban setting without
4615arousing the suspicions of nosey neighbors. Further, the reactants are only
4616moderately expensive, and not tightly controlled at present. Fair amounts
4617of product can be turned out at a rate of one batch per day.
4618    
4619    The disadvantages of this method are twofold. First, hydrazine is a  
4620carcinogen. The chemist must wear gloves while doing the reaction, and do a
4621careful clean-up when finished. If any should be spilled on the skin, a
4622serious, prolonged, and immediate shower is called for. Care must further
4623be taken that the fumes of hydrazine are not breathed in, as this could
4624cause the same problem. Ever try giving your lungs a shower? The other
4625disadvantage to using this method is that the free bases must be used. This
4626necessitates the free basing and distillation procedure described in Method
46271.  
4628    The mechanism by which this procedure works involves first the
4629formation of a hydrazone by reaction between the ephedrine and hydrazine.
4630Then at the high temperatures at which this reaction is done, the hydrazone
4631loses nitrogen (N2) to form meth. This is illustrated:
4632
4633    To do the reaction, a 3000 ml round bottom flask is placed on a buffet
4634range, and then 1500 ml of diethylene glycol and 336 grams of KOH
4635(potassium hydroxide) pellets are put in the flask. Next a condenser is
4636attached to the flask, and water flow is begun through it. Gentle heating
4637of the flask is now begun, with occasional swirling of the flask to try to
4638dissolve the KOH pellets. The operator must be ready here to quickly remove
4639the buffet range, because once the solution warms up, and the KOH pellets
4640start to dissolve, a great amount of heat is released which could cause the
4641solution to boil wildly and squirt out the top of the condenser. Since
4642diethylene glycol has a boiling point of 245øC, this would definitely not
4643be good stuff to be splashed with. Eye protection is, of course, necessary.
4644The heat source is periodically removed, and then reapplied until the
4645dissolution of the KOH pellets is complete.
4646    
4647    Once the KOH pellets have dissolved, the heat is removed, and the
4648temperature of the solution is allowed to fall to about 80øC. Then 300 ml
4649of hydrazine hydrate (85% to 100% pure material is OK) and either 303 grams
4650of PPA free base or 332 grams of ephedrine free base is added to the flask.
4651The condenser is then immediately replaced, and the mixture is heated with
4652great caution until any exothermic (i.e. heat generating) reaction has
4653passed. Then stronger heat is applied to maintain gentle boiling for one
4654hour.
4655    
4656    Now heating is stopped, and as soon as boiling ceases, the condenser is
4657removed, and the flask is rigged for simple distillation as shown in Figure
46583 in Chapter 3. The stillhead should have a thermometer in it reaching down
4659into the middle of the liquid mass in the flask. A cork or rubber holder
4660for this thermometer is unacceptable because hydrazine attacks these
4661materials. The holder must be made of all glass.
4662    
4663    Now the heat is reapplied, and distillation is commenced sufficiently
4664slowly that the froth does not rise out of the flask. Froth can be broken
4665up by occasional application of weak vacuum, as mentioned back in Chapter
46665. When the temperature of the liquid has reached 200øC or so (around 200
4667ml of distillate will have been collected by that point), the heating is
4668stopped. Once boiling ceases, the stillhead is removed, and the condenser
4669is reinserted into the flask. Now heat is reapplied, and the mixture is
4670boiled gently for 3 additional hours.
4671    
4672    The reaction is now complete, and it is time to get the product. The
4673heating is stopped on the flask, and once it has cooled down, the contents
4674of the flask are poured into 2000 ml of water. The 200 ml of distillate
4675obtained earlier is also poured into the water. This mixture is stirred to
4676get the hydrazine out of the meth layer which floats on the top, and into
4677the water. The solution of KOH in water makes the water fairly hot. Once it
4678has cooled down, 500 ml of toluene is added, and the mixture is shaken. A
4679one gallon glass jug is a good vessel to do this in. The top layer of meth
4680dissolved in toluene is then separated, and distilled as described earlier.
4681The yield is 250 to 275 ml of meth. If a careful fractional distillation is
4682not done, the product may be contaminated with a small amount of hydrazine.
4683This is definitely not good, and may be avoided by shaking the separated
4684meth dissolved in toluene layer with a fresh portion of water.
4685
4686           Method 3: Direct Reduction of Ephedrine With Palladium
4687    
4688    This method is very similar to the indirect reduction of ephedrine. The
4689difference in this case is that here the chlorination and reduction are
4690done simultaneously in a "one pot" process. This has the obvious advantages
4691of being quicker and using fewer chemicals. This method has the further
4692advantage of using ephedrine, pseudoephedrine, or PPA in their
4693hydrochloride or sulfate salt forms, so no free basing or distilling of the
4694raw material inputs is needed. Another advantage is that the chlorination
4695is done using dry HCl gas Since this is easily made from dripping sulfuric
4696acid on table salt, the chemist need never worry about having to get
4697suspicion-arousing chemicals to maintain production.
4698    
4699    There are a couple of drawbacks to the use of this method. First and
4700foremost, the contents of the hydrogenation bomb must be heated to about
470180ø-90øC during the reaction. This leads to a possible danger whereby the
4702champagne bottle hydrogenation bomb may crack and burst due to heat stress.
4703This is a possibility even if it is coated on the outside with fiberglass
4704resin. Another drawback is the need to invest in about $1000 worth of
4705palladium chloride to begin production. The catalyst prepared from this
4706palladium chloride can be used over and over again, but it is still a
4707considerable initial cost.
4708    
4709    To do this reaction, the chemist first prepares palladium black  
4710catalyst. This is done as follows: In a 2000 ml beaker, 50 grams of
4711palladium chloride is dissolved in 300 ml of concentrated hydrochloric acid
4712(laboratory grade, 35-37%). Once it has all dissolved, it is diluted with
4713800 ml of distilled water. Next, the beaker is nestled in a bed of ice that
4714has been salted down. This is an ice-salt bath. The contents of the beaker
4715are stirred occasionally, and once it is cold, 300 ml of 40% formaldehyde
4716solution is added with stirring. After a few minutes, a cold solution of
4717350 grams KOH in 350 ml distilled water is added slowly over a period of 30
4718minutes. The palladium solution must be vigorously stirred during the
4719addition. Now the beaker is removed from the ice, and warmed it up to 60ø
4720for 30 minutes with occasional stirring during the heating.
4721    
4722    When the heating is complete, the beaker is set aside to cool, and for
4723the catalyst to settle. Once the catalyst has settled, the chemist pours
4724off as much of the water solution as possible, without losing any catalyst.
4725Then fresh distilled water is added to the beaker, the catalyst is stirred
4726up to wash it off, then the chemist lets it settle again, and pours off the
4727water. This washing is repeated a total of six times. Finally, the catalyst
4728is suspended in a bit of fresh distilled water, and filtered, preferably
4729through sintered glass to be sure of catching all the catalyst. Any
4730catalyst still clinging to the sides of the beaker are rinsed down with
4731water and poured in with the main body of catalyst. It is wise to rinse off
4732the catalyst again with still another large portion of water while it is in
4733the filtering funnel. This process yields 31 grams of palladium black
4734catalyst, once it has dried. It is important that the catalyst be allowed
4735to dry completely, because the presence of water in the reaction mixture is
4736to be avoided.
4737    
4738    With a supply of catalyst on hand, the chemist can move on to  
4739production. To begin, 600 ml of glacial acetic acid is poured into a 1000
4740ml beaker. Now the glassware is set up as shown in Figure 10 back in
4741Chapter 5. The glass tubing is lead into the acetic acid, and bubbling of
4742dry HCl gas into the acetic acid is begun as described in that chapter. It
4743is a good idea here to magnetically stir the acetic acid solution during
4744the bubbling. The whirlpool formed will help the bubbles of HCl gas to
4745dissolve in the acetic acid, rather than escape and waft away on the
4746breezes. This bubbling is continued until the acetic acid solution has
4747gained 30 grams in weight.
4748    
4749    Next, this acetic acid-HCl mix is poured into the 1.5 liter champagne
4750bottle hydrogenation device along with 60 grams of either ephedrine,
4751pseudoephedrine or PPA (sulfate or HCl salt OK for any of these), and 50
4752grams of palladium catalyst. Since the mixture is going to be magnetically
4753stirred, a magnetic stirring bar, of course, is put in the bottle. Now the
4754apparatus is set up as shown in Figure 17 in Chapter 11. The air is sucked
4755out of the bottle as described in that chapter, and replaced with hydrogen.
4756Pressure is avoided for now until the heating of the bottle contents is
4757well underway. To heat the bottle contents, it is best to use a steam
4758cabinet. One can best make such a cabinet from a styrofoam cooler. (See
4759Figure 22).
4760    
4761    The chemist simply leads steam from a pressure cooker into the  
4762styrofoam party cooler via automotive vacuum tubing. The lid is on the
4763cooler, with a small hole in the lid of the cooler for the top of the  
4764bottle to stick out of, or for the hydrogen line to get in through. It is
4765best to poke a small hole in the side of the cooler near the bottom, and
4766stick some plastic tubing into it. This acts as a drain line to carry away
4767condensed water.
4768    
4769    Now the chemist begins stirring, and once the bottle has warmed up a
4770bit, increases pressure to the 15 to 30 pound range. In about an hour, the
4771reaction is finished. The chemist can tell this because it stops absorbing
4772hydrogen. The heating is then stopped, and the stirring is halted. The
4773hydrogen is vented outside as described back in Chapter 11, and the product
4774solution is carefully poured out of the bottle, taking care not to pour out
4775the palladium catalyst. If any comes out, it is filtered, and the palladium
4776returned to the bottle for the next run.
4777    
4778    The product mixture is poured into a 1000 ml round bottom flask along
4779with a few pumice chips, and the glassware is set up as shown in Figure 3.
4780The chemist distills off 500 ml of acetic acid (b.p. 118øC). This acetic
4781acid can probably be used over a few times in the reaction. Eventually,
4782water will build up in it, rendering it useless.
4783    
4784    The residue left in the distilling flask has the product. Once it has  
4785cooled down, lye water is added to it, and shake vigorously. The solution
4786should be strongly basic. Now toluene is added, the top layer separated
4787off, and this top layer is distilled as described so often in this book to
4788yield a little over 50 grams of meth (or benzedrine if PPA was used). This
4789is about 95% yield.
4790    
4791    A variety of other acids besides HC1 can be used to do this reaction.
4792Sulfuric, phosphoric, and perchloric acids will all form esters with the
4793alcohol grouping of ephedrine, pseudoephedrine or PPA, and this ester can
4794be reduced to yield meth or plain amphetamine. See Chem Abstracts, Volume
479534, column 3761, also Volume 38, column 1219 and Volume 34, column 7297.
4796Also see J. Med. Chem., Volume 9, page 996.
4797    
4798        Method 4: Reduction With Hydroiodic Acid and Red Phosphorus
4799    
4800    In this procedure, the alcohol grouping of ephedrine, pseudoephedrine,
4801or PPA is reduced by boiling one of these compounds in a mixture of
4802hydroiodic acid and red phosphorus. Hydroiodic acid works as a reducing
4803agent because it dissociates at higher temperatures to iodine and hydrogen,
4804which does the reducing. This dissociation is reversible. The equilibrium
4805is shifted in favor of dissociation by adding red phosphorus to the
4806mixture. The red phosphorus reacts with the iodine to produce PI3, which
4807then further reacts with water to form phosphorus acid and more hydroiodic
4808acid. Since the hydrogen atom of the HI is being absorbed by the ephedrine,
4809the red phosphorus acts as a recycler.
4810    
4811    In some reductions, the need for HI is dispensed with just by mixing
4812red phosphorus and iodine crystals in a water solution. The red phosphorus
4813then goes on to make HI by the above mentioned process. With a small amount
4814of due care, this is an excellent alternative to either purchasing,
4815stealing, or making your own pure hydroiodic acid.
4816    
4817    This method has the advantage of being simple to do. It was formerly
4818the most popular method of making meth from ephedrine. Now red phosphorus
4819is on the California list of less restricted chemicals, so an increased
4820level of subterfuge is called for to obtain significant amounts. One might
4821think that this is easily gotten around by making your own red phosphorus,
4822but this is a process I would not want to undertake. Ever hear of
4823phosphorus shells? I would much rather face the danger of exploding
4824champagne bottles. Those who insist upon finding out for themselves, will
4825see Journal of the American Chemical Society, volume 68, page 2305. As I
4826recall, The Poor Man's James Bond also has a formula for making red
4827phosphorus. Those with a knack for scrounging from industrial sources will
4828profit from knowing that red phosphorus is used in large quantities in the
4829fireworks and matchmaking industries. The striking pad on books of matches
4830is about 50% red phosphorus. 
4831
4832    The determined experimenter could obtain a pile of red phosphorus by
4833scraping off the striking pad with a sharp knife. A typical composition of
4834the striking pad is about 40% red phosphorus, along with about 30% antimony
4835sulfide, and lesser amounts of glue, iron oxide, MnO2, and glass powder. I
4836don't think these contaminants will seriously interfere with the reaction.
4837Naturally, it is a tedious process to get large amounts of red phosphorus
4838by scraping the striking pad off matchbooks.
4839    
4840    Another problem with this method is that it can produce a pretty crude
4841product if some simple precautions are not followed. From checking out
4842typical samples of street meth, it seems basic precautions are routinely
4843ignored. I believe that the by-products in the garbage meth are
4844iodoephedrine, and the previously mentioned azirine. (See the previous
4845section concerning chloroephedrine.) If a careful fractional distillation
4846is done, these products can be removed. They can be avoided in the first
4847place if, when making hydroiodic acid from iodine and red phosphorus, the
4848acid is prepared first, and allowed to come to complete reaction for 20
4849minutes before adding the ephedrine to it. This will be a hassle for some,
4850because the obvious procedure to follow is to use the water extract of the
4851ephedrine pills to make HI in. The way around the roadblock here is to just
4852boil off some more of the water from the ephedrine pill extract, and make
4853the acid mixture in fresh pure water. Since the production of HI from
4854iodine and red phosphorus gives off a good deal of heat, it is wise to
4855chill the mixture in ice, and slowly add the iodine crystals to the red
4856phosphorus-water mixture.
4857    
4858    To do the reaction, a 1000 ml round bottom flask is filled with 150  
4859grams of ephedrine hydrochloride (or PPA-HCL). The use of the sulfate salt
4860is unacceptable because HI reduces the sulfate ion, so this interferes with
4861the reaction. Also added to the flask are 40 grams of red phosphorus, and
4862340 ml of 47% hydroiodic acid. This same acid and red phosphorus mixture
4863can be prepared from adding 300 grams of iodine crystals to 50 grams of red
4864phosphorus in 300 ml of water. This should produce the strong hydroiodic
4865acid solution needed. Exactly how strong the acid needs to be, I can't say.
4866I can tell you that experiments have shown that one molar HI is ineffective
4867at reducing ephedrine to meth. The 47% acid mentioned above is a little
4868over 7 molar. I would think that so long as one is over 3 molar acid, the
4869reaction will work.
4870    
4871    With the ingredients mixed together in the flask, a condenser is  
4872attached to the flask, and the mixture is boiled for one day. This length
4873of time is needed for best yields and highest octane numbers on the
4874product. While it is cooking, the mixture is quite red and messy looking
4875from the red phosphorus floating around in it.
4876    
4877    When one day of boiling under reflux is up, the flask is allowed to  
4878cool, then it is diluted with an equal volume of water. Next, the red
4879phosphorus is filtered out. A series of doubled-up coffee filters will work
4880to get out all the red phosphorus, but real filter paper is better. The
4881filtered solution should look a golden color. A red color may indicate that
4882all the phosphorus is not out. If so, it is filtered again. The  
4883filtered-out phosphorus can be saved for use in the next batch. If
4884filtering does not remove the red color, there may be iodine floating
4885around the solution. It can be removed by adding a few dashes of sodium
4886bisulfite or sodium thiosulfate.
4887    
4888    The next step in processing the batch is to neutralize the acid. A  
4889strong Iye solution is mixed up and added to the batch with shaking until
4890the batch is strongly basic. This brings the meth out as liquid free base
4891floating on top of the water. The strongly basic solution is shaken  
4892vigorously to ensure that all the meth has been converted to the free base.
4893    
4894    With free base meth now obtained, the next step, as usual, is to form
4895the crystalline hydrochloride salt of meth. To do this, a few hundred mls
4896of toluene is added to the batch, and the meth free base extracted out as
4897usual. If the chemist's cooking has been careful, the color of the toluene
4898extract will be clear to pale yellow. If this is the case, the product is
4899sufficiently pure to make nice white crystals just by bubbling dry HCL gas
4900through the toluene extract as described in Chapter 5. If the toluene
4901extract is darker colored, a distillation is called for to get pure meth
4902free base. The procedure for that is also described in Chapter 5. The yield
4903of pure meth hydrochloride should be from 100 grams to 110 grams.
4904    
4905    If gummy binders from the stimulant pills are carried over into the  
4906reaction mixture, they produce a next-to-impossible-to-break emulsion of
4907meth, gum, toluene and water when the reaction is done and it is time to
4908extract out the meth. If this reaction is chosen as the production method,
4909one must be sure the gum has been thoroughly rinsed away with acetone from
4910the stimulant crystals. They should be long, white, and needle-like. If
4911this emulsion is encountered, the only way to break it is to first let the
4912emulsion sit in a sep funnel for a few hours. Water will slowly work its
4913way out and settle to the bottom where it can be drained away. The stubborn
4914residual emulsion should be transferred to a distilling flask, and the
4915toluene slowly distilled off through a fractionating column. This removes
4916water from the emulsion as the toluene-water azeotrope. It may be necessary
4917to add additionally toluene to the distilling flask to get all the water
4918removed. It sticks to the glass flask, and causes no further problem. Once
4919the emulsion is broken, distilling should be stopped. The toluene-meth
4920solution should be poured from the distilling flask, and the meth
4921precipitated as hydrochloride as per the usual dry HCl bubbling method.
4922    
4923    
4924    
4925    
4926    
4927
4928--------------------------------------------------------------------------
4929                               Methcathinone
4930--------------------------------------------------------------------------
4931    
4932                          Kitchen Improvised Crank
4933    
4934    The latest designer variant upon the amphetamine molecule to gain
4935popularity and publicity is methcathinone, commonly called "cat." This
4936substance is remarkably similar to the active ingredient found in the
4937leaves of the khat tree which the loyal drug warriors on the network news
4938blame for turning peace loving Somalis into murderous psychopaths. The
4939active ingredient in the khat leaves is cathinone, which has the same
4940structural relationship to methcathinone that amphetamine has to
4941methamphetamine. It is made by oxidizing ephedrine, while meth can be made
4942by reducing ephedrine. 
4943    
4944    The high produced by methcathinone is in many ways similar to  
4945methamphetamine. For something so easily made and purified, it is actually
4946quite enjoyable. The main differences between the meth high and the
4947methcathinone high are length of action and body feel. With methcathinone,
4948one can expect to still get to sleep about 8 hours after a large dose. On
4949the down side, it definitely gives me the impression that the substance
4950raises the blood pressure quite markedly. This drug may not be safe for
4951people with weak hearts or blood vessels. Be warned!
4952    
4953    Cat is best made using chrome in the +6 oxidation state as the  
4954oxidizer. I recall seeing an article in the narco swine's Journal of
4955Forensic Science bragging about how they worked out a method for making it
4956using permanganate, but that method gives an impure product in low yields.
4957Any of the common hexavalent chrome salts can be used as the oxidizer in
4958this reaction. This list includes chrome trioxide (CrO3), sodium or
4959potassium chromate (Na2CrO4), and sodium or potassium dichromate
4960(Na2Cr2O3). All of these chemicals are very common. Chrome trioxide is used
4961in great quantities in chrome plating. The chromates are used in tanning
4962and leather making.
4963    
4964    To make methcathinone, the chemist starts with the water extract of
4965ephedrine pills. The concentration of the reactants in this case is not
4966critically important, so it is most convenient to use the water extract of
4967the pills directly after filtering without any boiling away of the water.
4968See the section at the beginning of Chapter 15 on extracting ephedrine from
4969pills. Both ephedrine hydrochloride and sulfate can be used in this
4970reaction.
4971    
4972    The water extract of 1000 ephedrine pills is placed into any convenient
4973glass container. A large measuring cup is probably best since it has a
4974pouring lip. Next, 75 grams of any of the above mentioned +6 chrome
4975compounds are added. They dissolve quite easily to form a reddish or orange
4976colored solution. Finally, concentrated sulfuric acid is added. If CrO3 is
4977being used, 21 ml is enough for the job. If one of the chromates is being
4978used, 42 ml is called for. These ingredients are thoroughly mixed together,
4979and allowed to sit for several hours with occasional stirring.
4980
4981    After several hours have passed, lye solution is added to the batch
4982until it is strongly basic. Very strong stirring accompanies this process
4983to ensure that the cat is converted to the free base. Next, the batch is
4984poured into a sep funnel, and a couple hundred mls of toluene is added.
4985Vigorous shaking, as usual, extracts the cat into the toluene layer. It
4986should be clear to pale yellow in color. The water layer should be orange
4987mixed with green. The green may settle out as a heavy sludge. The water
4988layer is thrown away, and the toluene layer containing the cat is washed
4989once with water, then poured into a beaker. Dry HCl gas is passed through
4990the toluene as described in Chapter 5 to get white crystals of cat. The
4991yield is between 15 and 20 grams. This reaction is scaled up quite easily.
4992    
4993--------------------------------------------------------------------------
4994                MDA, XTC, and Other Psychedelic Amphetamines
4995--------------------------------------------------------------------------
4996
4997    The psychedelic amphetamines are a fascinating and largely ignored
4998group of drugs. They all have the basic amphetamine carbon skeleton
4999structure, but show effects that are more akin to LSD than to the
5000amphetamines. The LSD-like effect is due to the presence of a variety of
5001"add ons" to the benzene ring of the basic amphetamine structure.
5002Generally, these "add ons" are ether groupings on the 3, 4, or 5 positions
5003on the benzene ring. Because of these "add ons" one can consider these
5004compounds more closely related to mescaline than to amphetamine. Consider
5005the mescaline molecule pictured on page 176.
5006    
5007    Mescaline should by all rights be considered an amphetamine derivative.
5008It has the basic phenethylamine structure of the amphetamines with methyl
5009ether groupings on the benzene ring at the 3,4,5 positions. To be a true
5010amphetamine, it would only need its side chain extended by one carbon,
5011putting the nitrogen atom in the central, isopropyl position. Such a
5012compound does in fact exist. It is called trimethoxyamphetamine, or TMA for
5013short. Its effect are very similar to mescaline in much lower dosage levels
5014than the % gram required for pure mescaline. Its chemical cousin, TMA-2
5015(2,4,5 trimethoxyamphetamine) has similar awe inspiring characteristics.
5016
5017    The most popular and, in my opinion, the best of the psychedelic  
5018amphetamines is the MDA family. This family consists of MDA, and its
5019methamphetamine analog, XTC, or Ecstasy, or  
5020MDMA.MDA(3,4-methylenedioxyamphetamine) gives by far the best high of this
5021group. Its effects can best be described as being sort of like LSD without
5022the extreme excited state caused by that substance. It was popularly known
5023as "the love drug" because of the calm state of empathy so characteristic
5024of its effect. It could also be a powerful aphrodisiac under the right
5025circumstances.
5026    
5027    This substance gradually disappeared during the early 80s due to an
5028effective crimping upon the chemicals needed for its easiest manufacture.
5029    
5030    This crimping, and the drug laws in effect at the time, gave rise to a
5031bastard offspring of MDA. This substance was XTC, or MDMA, the so called
5032Ecstasy of the drug trade. This material was a designer variant of MDA, and
5033so was legal. The chemicals needed to make it could be obtained without
5034fear of a bust. It also lacked the best qualities of its parent. While the
5035addition of a methyl group of the nitrogen of the amphetamine molecule
5036accentuates its power and fine effect, the addition of a methyl group to
5037the MDA molecule merely served to make it legal. As fate would have it, the
5038hoopla surrounding the subsequent outlawing of this bastard child served to
5039make it a more desired substance than MDA. This is typical of black-market,
5040prohibition-driven demand.
5041    
5042    To understand the various routes which can be followed to make these
5043substances, note the structures of MDA and MDMA shown below:
5044    
5045    To make these substances, and the rest of the psychedelic amphetamines
5046for that matter, the manufacturer has a choice of two starting materials.
5047He can use the appropriately substituted benzaldehyde, which in the case of
5048MDA or MDMA is piperonal (heliotropin), or he can use the correspondingly
5049substituted allylbenzene, which in this case is safrole.
5050    
5051    Piperonal was the favored starting material for making MDA, as were the
5052other substituted benzaldehydes for making other psychedelic amphetamines.
5053The supply of these raw materials was effectively shut off. Piperonal does
5054find legitimate use in making perfumes, but considerable determination is
5055needed to divert significant amounts of the stuff into clandestine
5056operations.
5057    
5058    Once obtained, these substituted benzaldehydes could be converted into
5059amphetamines by an interesting variant of the Knoevenagel reaction as
5060described in Chapter 9. They could be reacted in a mixture of nitroethane
5061and ammonium acetate to form the appropriately substituted
50621-phenyl-2-nitropropene. This nitropropene could then be reduced to the
5063amphetamine by using lithium aluminum hydride, or palladium black on
5064charcoal in a hydrogenation bomb. This pathway was further crimped upon by
5065the narco swine by watching for purchases of nitroethane and ammonium
5066acetate in combination. For all practical purposes, this pathway can be
5067considered dead.
5068    
5069    This left safrole, and the other substituted allylbenzenes, as starting
5070materials for psychedelic amphetamine manufacture. This route had the
5071advantage of having a raw material source that was nearly impossible to
5072shut down. For instance, sassafras oil consists of 80-90% safrole. One
5073merely has to distill the oil under a vacuum to get very pure safrole.
5074Similarly, other psychedelic amphetamines can be made from the
5075allylbenzenes naturally occurring in various plant oils. For instance,
5076calamus oil contains a large proportion of B-asarone the starting material
5077for TMA-2. Nutmeg contains a mixture of myristicin (potential MMDA) and
5078elemicin (potential TMA). These oils are all available from herbal supply
5079shops and dealers in the occult. Even without this source, the oils can be
5080easily obtained from the plants.
5081    
5082    The reason why the markets have not been flooded with psychedelic
5083amphetamines via the allylbenzene source is because the only method for
5084converting them into amphetamines that was widely known is very cumbersome.
5085For instance, the only method for making MDA from safrole that was listed
5086in Psychedelic Chemistry was the old tedious route. This route called for
5087first converting safrole to isosafrole by the action of alcoholic KOH at
5088243øC for 3 minutes. This isosafrole could then be converted to MDA
5089phenylacetone by a very messy and inefficient method using hydrogen
5090peroxide in a solution of acetone and formic acid. This step is so poor
5091that it rendered the whole route unworkable. Finally, the MDA phenylacetone
5092could be made into MDA by one of several methods. It is interesting that
5093Michael Valentine Smith copied the printing error that appeared in Chem
5094Abstracts concerning this last step into his book.
5095    
5096    Luckily, the relentless advance of chemical science has lifted this  
5097roadblock. The same method which was earlier described for converting
5098allylbenzene into phenylacetone is equally useful for converting
5099substituted allylbenzenes directly into the corresponding substituted
5100phenylacetones. The yield in these reactions is nearly as good as for
5101phenylacetone itself, and the procedure is just as easy.
5102    
5103    The first problem which confronts the chemist in the process of turning
5104sassafras oil into MDA or MDMA is the need to obtain pure safrole from it.
5105In spite of the fact that crude sassafras oil consists of 80-90% safrole,
5106depending on its source, it is a good bet that the impurities will lower
5107the yield of the desired product. The axiom "garbage in, garbage out" was
5108custom made for organic chemistry reactions. It is simplicity itself to
5109turn crude sassafras oil into pure safrole, and well worth the effort of
5110underground chemists bent on MDA production.
5111    
5112    Sassafras oil is an orange colored liquid with a smell just like  
5113licorice. It is a complex mixture of substances which is easily purified by
5114distilling. To obtain pure safrole from sassafras oil, the glassware is set
5115up as shown in Figure 5 in Chapter 3. The distilling flask is filled about
51162/3 full of sassafras oil, along with a few boiling chips, and then vacuum
5117is applied to the system. A little bit of boiling results due to water in
5118the oil, but heat from the buffet range is required to get things moving.
5119Water along with eugenol and related substances distill at the lower
5120temperatures. Then comes the safrole fraction. The safrole fraction is
5121easily spotted because the "oil mixed with water" appearance of the watery
5122forerun is replaced with a clear, homogeneous run of safrole. When the
5123safrole begins distilling, the collecting flask is replaced with a clean
5124new one to receive it. The chemist is mindful that the safrole product is
512580-90% of the total volume of the sassafras oil. Under a vacuum, it boils
5126at temperatures similar to phenylacetone and methamphetamine. When all the
5127safrole has distilled, a small residue of dark orange colored liquid
5128remains in the distilling flask. The distilled safrole is watery in
5129appearance, and smells like licorice.
5130    
5131    With a liberal supply of safrole obtained by distilling sassafras oil,  
5132work can then commence on converting it into 3,4
5133methylenedioxyphenylacetone. This is done in exactly the same manner as
5134described in Chapter 10. As was the case in that chapter, the chemist has
5135the choice of the palladium-wasteful method, and the palladium-conserving
5136method. As was the case in the earlier chapter, the yield of product is
5137about 10% higher using the palladium-wasteful method. The yield is about
513893% for the wasteful method, versus about 83% for the conserving method.
5139The sole difference in the safrole conversion reaction is that in this
5140case, palladium bromide is used instead of the palladium chloride used to
5141convert allylbenzene. Since palladium bromide has a higher molecular weight
5142than palladium chloride, the amount of palladium salt used in this case is
5143increased by a factor of 1.5.
5144    
5145    The methylenedioxyphenylacetone obtained from this reaction can be used
5146in a crude state by boiling off the solvents from it under a vacuum, or it
5147can be distilled under a vacuum to yield pure material. The boiling point
5148of this phenylacetone is around 180øC at a pressure of 15 torn The color of
5149the distilled material is clear to pale yellow.
5150    
5151    With the methylenedioxyphenylacetone obtained in this manner, the
5152chemist proceeds to make it into XTC by one of the methods used to turn
5153phenylacetone into meth. Of all the methods to choose from, the most
5154favored one would have to be reductive alkylation using the bomb and
5155platinum catalyst. The free base is converted into crystalline  
5156hydrochloride salt in exactly the same manner as for making meth crystals.
5157It is interesting to note here that XTC crystals will grow in the form of
5158little strings in the ether solution as the HCl gas is bubbled through it.
5159Once filtered and dried, it bears a remarkable resemblance to meth
5160crystals. It generally has a faint odor which reminds one of licorice.
5161    
5162    To make MDA from the methylenedioxyphenylacetone, one has two good
5163choices. Choice number one is to use the reductive amination method without
5164the bomb using activated aluminum as the reducer. In this case, 28% ammonia
5165solution in water (ammonium hydroxide, NH4OH) is used instead of 40%
5166methylamine in water. The amount of ammonia solution used is doubled over
5167the amount of methylamine solution used. Other than that, the reaction
5168proceeds just as in the case for meth and gives a yield around 40%. The
5169next best method is to use the bomb with Raney nickel catalyst and ammonia.
5170This gives a yield around 80% if plenty of Raney nickel is used. The
5171drawback to this method is the need for a shaker device for the bomb, and
5172also a heater. The use of platinum as the catalyst in the bomb works great
5173when making MDMA, but gives lousy results when making MDA. There may be a
5174way around this, however, for serious experimenters. It has been found in
5175experiments with phenylacetone that a mixture of ammonia and ammonium
5176chloride produces good yields of amphetamine (50%) when used in a bomb with
5177platinum catalyst. Methylenedioxyphenylacetone is quite likely to behave
5178similarly.
5179    
5180    To use this variation, the following materials are placed in the 1.5  
5181liter champagne bottle hydrogenation device: .5 gram platinum in 20 ml
5182distilled water. If this platinum is in the form of PtO2 instead of the
5183reduced platinum metal catalyst obtained with borohydride, the experimenter
5184must now reduce the platinum by pressurizing the bottle with hydrogen and
5185stirring for about an hour. Next 100 ml of methylenedioxyphenylacetone is
5186added along with 40 grams NH4Cl, 500 ml methyl alcohol saturated with
5187ammonia gas, and 50 ml NH4OH. The bottle is then set up as seen in Figure
518817. and the hydrogenation is done as described in that section.
5189    
5190    When the reaction is over, the contents of the flask are filtered to  
5191remove the platinum metal for reuse. Some crystals of NH4Cl are also
5192filtered out; they are rinsed down with some water to remove them.
5193    
5194    Next the filtered batch is poured into a 1000 ml round bottom flask, a
5195few boiling chips are added, and the glassware is set up for refluxing.
5196Plastic tubing is attached to the top of the condenser and led outside. The
5197mixture is boiled under reflux for one hour to force out the excess
5198ammonia.
5199    
5200    Next, the solution is allowed to cool, and made acid to congo red  
5201(about pH 3) with hydrochloric acid. Now the glassware is set up as shown
5202in Figure 3, and the solution is evaporated to about one half its original
5203volume under vacuum. A fair amount of crystalline material forms during the
5204acidification and vacuum evaporation.
5205    
5206    Next, 400 ml of water is added to the solution, and then it is  
5207extracted with about 100 ml of toluene. The toluene layer is thrown away
5208because it contains garbage. The batch is now made strongly basic by adding
5209lye water to it. It should be remembered here that it is very important to
5210shake the batch well once it has been basified to make sure that the MDA
5211hydrochloride gets neutralized. Finally, the MDA is extracted out with a
5212few hundred ml of toluene, and distilled under vacuum. The boiling point is
5213about 170øC under aspirator vacuum. The yield is about 50 ml.
5214    
5215    The other good choice of a method for converting  
5216methylenedioxyphenylacetone into MDA is the Leuckardt reaction. In this
5217case, formamide is used instead of N-methylformamide. The formamide is of
5218the 99% pure grade. 98% formamide is good for nothing except making the
5219dreaded red tar. Good luck in finding 99% formamide these days. This
5220reaction is done in exactly the same manner as the reaction with
5221N-methylformamide, except that the reaction temperature is 160ø to 185øC,
5222raised over the course of 24 hours. The yields are excellent. Processing is
5223done as in the case of meth. The formamide is destroyed by boiling with lye
5224solution. In this case the ammonia gas produced is just led away in tubing.
5225The formyl amide is then separated and hydrolyzed with hydrochloric acid
5226solution.
5227    
5228    Another possible route to MDA and other psychedelic amphetamines is the
5229Ritter reaction. It was encountered earlier in Chapter 14. Since safrole
5230and many other plant oil precursors to the psychedelic amphetamines, such
5231as myristicin, are allylbenzenes, this reaction will work for them as well.
5232with some modifications to the process.
5233    
5234    The first modification is that alcoholic KOH is used to hydrolyze the
5235amide instead of HCl solution. Boiling the amide with about 5 to 10 volumes
5236of 10% KOH solution in 190 proof vodka gives better results than
5237hydrochloric acid. Less tar and other by-products will result. 190 proof
5238vodka and rectified spirit is used, not absolute alcohol. Refluxing for
5239about 5 hours does the job.
5240    
5241    To process the product, the underground chemist first boils away most
5242of the alcohol under a vacuum, then adds water to dissolve the KOH, and
5243extracts out the MDA using benzene or toluene. He distills and crystallizes
5244as usual.
5245    
5246    XTC can be obtained from MDA by using the method cited in the Woodruff
5247article referred to in Chapter 14.
5248    
5249    The yield and purity of the MDA obtained from the Ritter reaction is
5250somewhat less than with the two step method using palladium salts and
5251nitrites. This disadvantage must be weighted against the fact that the
5252Ritter reaction uses very simple, cheap, and easily available chemicals.
5253
5254    Not all psychedelic amphetamines can be produced in this manner. For
5255instance, B-asarone, the precursor of TMA-2, is a 2propenyl-benzene, rather
5256than an allylbenzene. The breakthrough method will fail in this case, and
5257the Ritter reaction will yield an isoquinoline. To convert
52582-propenylbenzenes directly into amphetamines, a very risky reaction using
5259is used.  See Recreational Drugs by Professor Buzz for details.
5260    
5261    For the same reason of relative molecular weight, if safrole is used in
5262either the phenylacetone from allylbenzene method or in the Ritter
5263reaction, the amount of safrole used is greater by a factor of about 1.35
5264as compared to allylbenzene.
5265    
5266    The recommended dosage of MDA or XTC is about a tenth of a gram of Pure
5267material.
5268    
5269                                 References
5270    
5271                Psychedelics Encyclopedia by Peter Stafford.
5272    
5273                          
5274--------------------------------------------------------------------------
5275                                    Ice
5276--------------------------------------------------------------------------
5277    
5278    At the time of the writing of the second edition, the latest drug craze
5279was the smokable form of methamphetamine called "ice." This material
5280consists of large clear crystals of methamphetamine hydrochloride rather
5281than the snowlike microcrystals produced by the methods described in this
5282book.
5283    
5284    I am not going to endorse or encourage the foolhardy practice of  
5285smoking meth. Seeing firsthand what this stuff does to rubber stoppers,
5286razor blades, and corks, I can only imagine what it does to lung tissue.
5287However, since the godless importers of this material have already made a
5288market for it, it is only right that I help American technology catch up.
5289
5290    I have never made nor used "ice" as such, but I know quite well how to
5291obtain large clear rocklike crystals of meth. There are two routes which
5292can be followed. The first is to simply melt the pure meth crystals and
5293then allow them to slowly cool into a solid mass. This is a piss poor
5294choice because the heat is likely to discolor even very pure meth melted
5295under a nitrogen atmosphere blanket. The accompanying "off" smell and god
5296knows what breakdown products make this a method that only hacks would use.
5297    
5298    A much better method is to take the pure meth crystals, and add just
5299enough absolute alcohol to them to dissolve them. Gentle heating, swirling,
5300and the use of warm alcohol keeps the volume of alcohol used to a minimum.
5301The beaker holding the dissolved meth is then put into a dessicator to
5302prevent the alcohol from soaking up water from the air. If the desiccator
5303has a portal for the attachment of vacuum, this is ideal. Then a vacuum
5304amounting to 1/2 normal pressure is applied, and the solution slowly cools
5305and evaporates its alcohol solvent. The result is a large rocklike mass of
5306meth which can then be chipped off of the beaker.
5307
5308--------------------------------------------------------------------------
5309                           Calibrating The Vacuum
5310--------------------------------------------------------------------------
5311    
5312    Before he starts doing the vacuum distillations described in this book,
5313the underground chemist wants to know what kind of vacuum he is able to
5314produce inside his glassware. This is important because the temperature at
5315which a substance distills under vacuum depends directly on how strong the
5316vacuum is. The distillation temperatures given in this book assume a vacuum
5317of about 20 torr for an aspirator and about 5 torr for a vacuum pump. This
5318chapter describes an easy method by which the chemist finds out just how
5319strong his vacuum is. Once he knows how good his vacuum is, he adjusts the
5320temperatures of his distillations accordingly. The better the vacuum, the
5321lower the temperature at which the substance will distill. He keeps in mind
5322that an aspirator will get a better vacuum in winter because the water
5323flowing through it is colder in that season. The vacuum obtained with a
5324vacuum pump may get poorer over time because solvents from the chemicals he
5325is distilling, such as benzene, may dissolve in the pump's oil. If this
5326happens, he changes the oil.
5327    
5328    To begin, the chemist sets up the glassware for fractional distillation
5329as shown in Figure 5 in Chapter 3. He uses a 500 ml round bottom flask for
5330the distilling flask, and a 250 ml flask as the collecting flask. He uses
5331the shorter condenser, and puts 3 boiling chips in the distilling flask
5332along with 200 ml of lukewarm water. He lightly greases all the ground
5333glass joints. (This is always done when distilling, because the silicone
5334grease keeps the pieces from getting stuck together, and seals the joint so
5335that it doesn't leak under the vacuum).
5336    
5337    He turns on the vacuum full force and attaches the vacuum hose to the
5338vacuum nipple of the vacuum adapter. The water in the distilling flask
5339should begin boiling immediately. As the water boils away, the temperature
5340shown on the thermometer steadily drops. Finally, the water gets cold
5341enough that it no longer boils. He notes the temperature reading when this
5342happens, or, better yet, disconnects the vacuum and takes apart the
5343glassware and takes the temperature of the water in the distilling flask.
5344Using a graph such as the one above, he reads off the vacuum that goes with
5345the boiling temperature.
5346    
5347    If his vacuum is bad, the water will not boil. In that case, he checks
5348to make sure that all the joints are tight, and that the stopper in the
5349claisen adapter fractionating column is not leaking. He also makes sure
5350that his vacuum hose is not collapsed. If, after this, the water still  
5351doesn't boil, he has to heat the water. He turns on the buffet range at low
5352heat while continuing the vacuum. In a while the water begins boiling. He
5353checks the temperature reading on the thermometer while it is boiling, and
5354notes the temperature. From the graph he reads off the vacuum that goes
5355with that boiling point.
5356    
5357    His vacuum should be 50 torr or lower to be able to make  
5358methamphetamine. If his vacuum reading is more than 50 torr, he gets a new
5359aspirator or changes the oil in the vacuum pump.
5360
5361    The chemist can use this information to adjust the temperature at which
5362he collects his distilled product. The boiling temperature of phenylacetone
5363is about 105øC at 13 torr, and about 115øC at 20 torn The boiling
5364temperature of N-methylformamide is about 107øC at 20 torn The boiling
5365temperature of methamphetamine is about the same as phenylacetone.
5366Phenylacetone and methamphetamine should be collected over a 20-degree
5367range centered on their true boiling points. This makes sure that the
5368chemist gets all of it. The purification scheme he goes through before
5369distilling removes all the impurities with boiling points close to that of
5370his product.  
5371
5372--------------------------------------------------------------------------
5373Transcriber's Notes:
5374
5375I have omitted many of the pictures in the book, I want you to see this as
5376a reason to buy the real book instead of this ASCII version. This is a part
5377of my shareware book concept; If you want to have the whole book, then go
5378buy it. You can order it directly from Loompanics Unlimited, PO Box 1197,
5379Port Townsend, WA 98368, USA. A fourth edition is on its way, Fester says.
5380
5381-------------------------------------------------------------------------