· 6 years ago · May 26, 2019, 08:10 AM
1
2
3 Jacked (Ancient Alchemist Delux)
407-27-01 05:48
5No 199197
6 Biosynth: Homebrewing Ephedrine
7
8This is a work in progress. It’s by Mobius Bandsaw
9At present I have a fairly good grasp of the means and the end.
10You are invited and encouraged to contribute information you may have relating to this subject, we can work together to advance the cause of knowledge.
11
12Shall we begin?
13
14Forward:
15
16When I was given this forum I was also given something of a research assignment.
17It seems there is a great deal of interest in the production of ephedrine and pseudoephedrine. (The forum was called “Homebrewingâ€)
18Both of these products may be obtained in quantity using methods which are in normal practice in industry.
19Industrial production of L-PACs uses methodologies which are not altogether removed from the art of distillers of spirits.
20While still speaking about theoretical methods of production of alcohols, and products of alcohols, it is hoped that a practical method of production of ephedrine and pseudoephedrine will be achieved which could be employed by the individual
21should circumstance find him in need of such capability.
22It should be noted from the outset that these methods, recipies, informations, and observations, are not intended to be used by any person.
23Further, all persons are hereby advised that use of this information to produce any substance for any illegal purpose is forbidden, and that the author expressly withdraws any permission to read, store, record, or in any way archive this work,
24from any person, persons, entity, or organisation, intending to use this information for any illegal purpose.
25Any methods discussed here are purely speculative, and for informative and entertainment purposes only, and have not been attempted.
26Untrained persons working with devices and substances mentioned here risk serious injury or death.
27Production by unlicensed individuals of any substance mentioned or described here could lead to criminal prosecution.
28
29~~~~~~~~~~~~~~~~~~~ 1.~~~~~~~~~~~~~~~~~~~~~
30FUN WITH L-PAC production!
31
32Biotransformation processes involving both yeast (Candida utilis) and pyruvate decarboxylase (PDC) for the production of L-phenylacetylcarbinol (L-PAC) from substrates benzaldehyde and pyruvate are an interesting field of study!
33L-PAC is an intermediate in the production of ephedrine and pseudoephedrine.
34Models for the process with a substrate feeding profile for benzaldehyde will be proposed.
35Chiral vicinal aminoalcohols are key building blocks for the production of a number of pharmaceutical products.
36Important compounds which may be produced from chiral vicinal aminoalcohol precursors span a range of therapeutic categories and include pseudoephedrine.
37Patent US5834261 describes a process that may be employed to produce a broad range of chiral vicinal aminoalcohols, both cyclic and acyclic.
38A particularly notable feature of this method is the ability to control the absolute configuration at chiral centers bearing both the amino and alcohol functionality to produce any of the four possible stereoisomers in high stereochemical purity.
39Patent US5942644 (issued in August 1999), is related to the process patent described above.
40
41This second patent covers the key intermediates that are involved in the production of chiral vicinal aminoalcohols. These compounds include the hydrazides and hydroxamic acids that are the immediate precursors of chiral vicinal aminoalcohols.
42The process for producing chiral vicinal aminoalcohols relies on readily available þ-ketoesters as starting materials.
43
44Examples of þ-ketoesters useful for the production of chiral vicinal aminoalcohols include the inexpensive compounds acetoacetic ester and þ-keto-phenylpropionic acid esters.
45
46Central to this method for the production of these chiral vicinal aminoalcohols is the combination of two key steps, each of which proceeds with a well-defined and controllable stereochemical outcome.
47
48The first step is the stereoselective reduction of the keto group of a þ-ketoester to produce the corresponding þ-hydroxyester.
49
50This reaction is catalyzed by an alcohol dehydrogenase in the presence of a nicotinamide cofactor.
51
52Because of the facile equilibrium between the two enantiomers of a 2-substituted-þ-ketoester in aqueous solution, the interconversion of these two stereoisomers occurs rapidly.
53
54The reduction of the ketone by an alcohol dehydrogenase occurs with a high degree of stereoselectivity, reducing only one of the two ketone enantiomers.
55The reduction of the ketone is highly stereoselective for the production of a single alcohol stereoisomer.
56
57so, two chiral centers are generated simultaneously by this enzymatic reaction, and this reaction provides for control of stereochemistry at both the C-2 and C-3 positions of the 2-substituted-þ-ketoester.
58
59NEXT: How earth people do it.
60
61~~~~~~~~~~HOW EARTH PEOPLE DO IT~~~~~~~~~~~~
62
63 If your nitemares never include metalic voices coming over loudspeakers
64demanding that you throw out your five gallon plastic buckets and come out with
65your hands up, congratulations...you may be on Earth.
66Earth people find many wonderful uses for the humble five gallon plastic bucket, as we shall soon see.
67 Any earth native who wishes to produce L-PAC at home may discover these utilitarian devices to be worth well more than their wieght in gold.
68To produce L-PAC using biosynth methods, one must first decide what will be fermented in the buckets.
69In the course of my research I have discovered that the liquid obtained by the crushing, grinding, pressing, and filtering of the common sugar beet is in fact the best possible substance to use for this method due to natural enzyme feeding, but it
70is by no means the only one, according to everyones favorite Uncle, even water may be used as a starting point!
71After obtaining the liquid to be used, one may wish to fortify it with a bit of brewers sugar.
72Into the 4.5 gallons of liquified beet extract one may add about 5 lbs of brewers sugar until the sugar no longer wishes to disolve, the reason for this being the already high sugar content of the extract.
73The next requirement is to add yeast. Not just any yeast will do.
74For our purposes the strain named Candida Utilis is understood to be best, however, experimentation is encouraged.
75Candida Utilis enjoys wide popularity, and may easily be obtained.
76The proper addition of yeast is a point of contention.
77Many "experts" say that one adds only a small amount, such as say a couple of packets of brewers yeast.
78Others state that it is necessary to put in an amount of wieght equal to the added sugar. It would seem to me that a benefit of doing this would be that the process will progress much quicker (three or four days, as opposed to three or four weeks) if
79one were to add the larger amount of yeast.
80Yeast is expensive if you buy it one package at a time.
81Most brewers know how to increase yeast.
82Those who do not are again encouraged to purchase a brewers manual detailing the method.
83
84Another required substance is Benzaldehyde.
85
86The production of L-PAC will be directly proportional to the amount of Benzaldehyde used. Returns are expected to be in the range of 60 to 80% the wieght of the added Benzaldehyde.
87
88Once the needed items have been procured one may begin the progress of biosynthesis.
89
90Step one involves mixing the nutrient, which is the liquid, and sugar. Next one adds the yeast to the mixture.
91
92Be careful to avoid contamination of your mixture!
93
94After combining the ingredients, place the top loosely on the five gallon bucket. With the passage of an hour or so one may begin to see the process of fermentation begining, it is felt that the passage of at least 10 hours is needed to allow the fermentation process to fully become active.
95
96After ten hours one must add the benzaldehyde. For this feeding profile the proper amount is calculated to be 60ML.
97
98After adding the Benzaldehyde the fermentation should be left to progress in a cool place away from sunlight. While underway this process also needs to be free of physical shock, such as thumps, and quaking, since this retards the process. If you have a Rock and Roll band and practice in the garage, don't do your biosynth there.
99
100NEXT: IT WORKED! NOW WHAT?
101
102~~~~~~~~~IT WORKED! NOW WHAT?~~~~~~~~~~~~~
103
104Now that your fermentation has completed you have your precurson to ephedrine just floating around in your five gallon bucket.
105It's not doing you much good in there is it?
106The next thing you want to do is to recover your phenylpropanol which is what the yeast turned the sugars into with the help of the benzaldehyde.
107The most direct method of recovery is to use a centrifuge, but few of us have one on hand. A more practical method for the small scale producer is filtration.
108Now that you have your filtered liquid it is time to begin extracting the phenylpropanol.
109To extract the phenylpropanol, you will need to use a non polar solvent, here you may choose between Acetone, Tolulene, or Xylene (personal preference here is toward acetone).
110The about 200ml of NP should be added to the mixture, swirled, then allowed to seperate, then decanted, save it, your goodies are there. Repeat this proceedure three times.
111At the end of the third wash you should have your phenylpropanol in solvent.
112Next you will need to distill the solvent/phenylpropanol in order to remove the solvent.
113Once your solvent is largely gone you will again need to distill, but this time you will need to use vacuum in your distillation process. You will need to pull between 14 and 18 torr and your product will come over as phenylacetylcarbinol at between 105c and 155c.
114All that remains to be done is a fairly standard reductive amination, whereupon you will find yourself in possession of pure gak free ephedrine.
115
116~~~~~~~~~~~~~~~~~~~NOTE~~~~~~~~~~~~~~~~~~~
117Comments, suggestions, and refinements are all solicited.
118
119
120~~~~~~~~~~~~~~~REFERENCES~~~~~~~~~~~~~~~~~~
121
122Uncle Fester, SOMM
123Shin, H.S. and Rogers, Production of L-PAC from benzaldehyde using partially purified pyruvate decarboxylase.
124Rogers, P.L., Shin, H.S. and Wang, Biotransformation for L-ephredrine production.
125
126
127Benzaldehyde: Artificial essential oil of almond; artificial almond flavor is water,
128benzaldehyde and alcohol.
129Occurs in kernels of bitter almonds; made synthetically from benzal chloride (C6H5CHCl2)
130and lime, or by oxidation of toluene.
131Hydrolysing benzal chloride is no challenge, boiling in alkaline water. It's making it, by
132chlorinating toluene, and keeping it separated from benzyl chloride, the monochloro
133derivative, that's the challenge.
134In toluene oxidation, the challenge is to prevent overoxidation to benzoic acid. My ballot
135is marked for acidic manganese dioxide, but I have seen chromyl chloride mentioned.
136A convenient natural source of benzaldehyde is by hydrolysis of amygdalin. That spelling
137challenge is a double glucoside of mandelonitrile, benzaldehyde's cyanide derivative.
138Mostly in apricot pits and bitter almonds, also the seeds of peaches and cherries.
139In these natural sources is some free benzaldehyde, but most of it is locked in the
140amygdalin. But there is an enzyme in the natural seeds, which will hydrolyse the
141amygdalin for you, when you let the ground seed material stand in water; glucose,
142benzaldehyde, and hydrogen cyanide result.
143
144Posted by--anomolon
145
146This is a link you might want to look at: http://www.geocities.com/dritte123/ephyeast.html
147
148Be sure to look up these two patents, Patent US1956950 & Patent US1962476.
149
150My intent on posting this information is for others to join in on the positive and see if we as a whole could bring this to a standard in our quest to rid our self’s of the dependance of a pill to produce a product. It should be looked at and responded to in that light... one bee of the Hive, Jacked
151
152
153
154 Jacked
155(Ancient Alchemist Delux)
15607-27-01 16:38
157No 199320
158 Re: Biosynth (homebrewing E)
159
160Could this thread be moved to the serious chemistry forum. It was a mistake placing it
161here I believe.
162Paid in Full
163
164
165
166 slowhand
167(Stranger)
16807-29-01 04:53
169No 199661
170 Re: Biosynth (homebrewing E)
171
172Swish is very happy that someone was able to rescue this post from the Zonez. Swish has full intention of giving this some serious experimentation when everything is gathered.
173
174
175
176 Ololuiqui
177(Newbee)
17808-20-01 23:22
179No 206068
180 Re: Biosynth (homebrewing E)
181
182This is veerrrrrrry interesting! laugh I have just a couple of Qs...
183
1841) You suggest using acetone as the non-polar solvent... wouldnt acetone bee miscible with the sugar beet juice?
185
1862) You use 200mL solvent for each extraction - isnt this far too little for 4.5gallons of solution?
187
1883) Would this work for substituted benzaldehydes? laugh
189
1904) Is it really necessary to vac-distil the L-PAC before doing a reductive amination?
191
192Many thanks,
193Ololiuqui
194
195
196
197 Rhodium
198(Chief Bee)
19908-21-01 00:59
200No 206116
201 Re: Biosynth (homebrewing E)
202
203I have heard that the yields are very low with substituted benzaldehydes.
204
205
206
207 jim
208(Hive Bee)
20908-22-01 02:36
210No 206424
211 Re: Biosynth (homebrewing E)
212
213I refer you to this tid bit of info.
214__________________________________
215 !!!! I FORGOT TO QUOTE THAT THIS REACTION IS STRONGLY pH DEPENDENT AND
216 BEST PROCEEDS AT A pH OF 8-9. !!!!!
217
218 From Agric. Biol. Chem., Volume 50, yr 1986, page 1261
219
220 "Reductive C3-Homologation of Substituted Benzaldehydes by
221 Fermenting Bakers' Yeast
222
223 ...
224
225 ... A unique reaction catalyzed by Bakers' Yeast is the reductive C-C bond formation in
226 benzaldehyde that results in the formation of 1-phenylpropane-1,2-diol [ref 3]. This reaction is
227 supposed to involve the attack of pyruvic acid, which is formed from sugars through a well known
228 pathway, by benzaldhyde to give phenyl-1-hydroxy-2-propanone [ref 4]. This ketol is considered to
229 be reduced by alcohol dehydrogenase of the yeast to give the
230 diol. ...
231
232 ...
233
234 Reduction of aldehydes by fermenting yeast. General procedure. To 50 mL of tap water, 12.5 g
235 of dry yeast and 10 g glucose were added, followed by stirring
236 at room temperature for 10 minutes. Then a solution of aldehyde 1 (about 600 mg) in 1 mL of
237 ethanol was added to the suspension of fermenting yeast with stirring. After 1 hour yeast (6.2 g)
238 and glucose (5 g) were added to the reaction mixture, followed by stirring for an additional 3.5
239 hours. The reaction mixture was then poured into a beaker containing 35 grams of celite and
240 extracted with 100 mL of ethyl acetate three times. The combined organic layer was dried over
241 anhydrous Na2SO4. The solvent removed under reduced pressure to give an oil consisting of
242 benzylic alcohol 3, 1-arylpropane-1,2 diol 3, and in
243 some cases, 1-aryl-1-hydroxy-2-propanone 4. ...
244
245 Table II. Yields and Steroselectivities of propanediols (a)
246
247 _____________________________________________________________
248 Substrate______Yield %____...
249
250 ______________________________________________________________
251 H______________30
252 p-OMe__________22
253 p-Me____________28
254 p-Cl____________27
255 p-F_____________26
256 p-NO2__________14
257 o-Me____________7
258 o-Cl_____________32
259 o-F_____________30
260 m-F____________31
261 CF3(e)__________0
262 _________________________
263 (a) Reactions were carried out in tap water at room
264 temperature ... (e) All of the o-, m-
265 p-substituted isomers gave no diols."
266_________________
267If i remember correctly, the diol can be rearranged to form P2P with H2SO4
268
269
270
271 Jacked
272(Ancient Alchemist Delux)
27308-22-01 11:45
274No 206519
275 Re: Biosynth (homebrewing E)
276
277You suggest using acetone as the non-polar solvent... wouldnt acetone bee
278 miscible with the sugar beet juice?
279
280At the point in the procedure that the acetone is used, the sugar beet
281juice has been fermented.
282The solvent will collect what it is after, and seperate (layer).
283
284You use 200mL solvent for each extraction - isnt this far too little for 4.5gallons of solution?
285
286Most of the 4.5 gallons is junk that you are not interested in. The 200Ml
287per extraction is conservative, you may use more if you wish, the only
288complication is the added seperation/evaporation time.
289
290Would this work for substituted benzaldehydes?
291
292It would depend on the substitution
293
294Is it really necessary to vac-distil the L-PAC before doing a reductive
295amination?
296
297 Yes. Without the vacuum distillation you will not be aminating only the
298desired substance. I am unsure what contaminates may reside in the
299undistilled form. For safety's sake, I would not skip this step.
300
301Answers were given to these questions by the writer of the original post.
302http://crystalninjas.net/jacked/disclaimer.htm
303
304
305
306 Whizard
307(Stranger)
30808-22-01 19:07
309No 206566
310 Re: Biosynth (homebrewing E)
311
312In your quotation from the journal you say:
313The solvent removed under reduced pressure to give an oil consisting of
314 benzylic alcohol 3, 1-arylpropane-1,2 diol 3, and in
315 some cases, 1-aryl-1-hydroxy-2-propanone 4. ...
316
317 What is the 4. part of the last word? I do not want to assume anything!!!
318It also appears that the large excess of yeast is used to allow immediate gratification to the above mentioned experimentalists!
319I dunno, but I been told ... You never slow down, you never grow old!
320
321
322
323 jim
324(Hive Bee)
32508-23-01 04:03
326No 206663
327 Re: Biosynth (homebrewing E)
328
329To clarify:
330
331"... benzylic alcohol 3, 1-arylpropane-1,2 diol 3, and in
332 some cases, 1-aryl-1-hydroxy-2-propanone 4. ..."
333
334the 3, and 4 refer drawings of the compounds on diagram not included.
335
336
337
338 Antoncho
339(Official Hive Translator)
34009-19-01 19:14
341No 215161
342 Re: Biosynth (homebrewing E)
343
344....having read the proc. about getting -propanediol from benzaldehyde, i couldn't help wondering about 2 things:
345
3461) The procedure doesn't mention any sort of pH adjustment - how is pH supposed to get to 9? It also just looks strange - what is the origin of that 1st phrase, the one in CAPS? Jim, you still around? Please, explain!
347
3482) Apart from the pH thing, the whole procedure seems completely identical to l-PAC production!! What is you think that makes the difference?
349
350Antoncho will bee VERY appreciative of any help on this issue, cause SW He Doesn't Even Know just happens to have a kilo of benzaldehyde lying around with no use for it :):):)
351
352Thank you all in advance,
353
354impatiently awaiting
355Antoncho
356
357P.S. Dear Moderators, do you really think this thread belongs here? - if mr. Jacked doesn't mind...
358
359
360
361 foxy2
362(Distinctive Doe)
36309-20-01 05:05
364No 215347
365 Re: Biosynth (homebrewing E)
366
367*****ADVANCES IN BIOCHEMICAL ENGINEERING/BIOTECHNOLOGY*****
368Rogers PL Shin HS Wang B
369Biotransformation for L-ephedrine production.
370In: Adv Biochem Eng Biotechnol (1997) 56:33-59
371ISSN: 0724-6145
372
373L-ephedrine is widely used in pharmaceutical preparations as a decongestant and
374anti-asthmatic compound. One of the key intermediates in its production is
375L-phenylacetylcarbinol (L-PAC) which can be obtained either from plants (Ephedra
376sp.), chemical synthesis involving resolution of a racemic mixture, or by
377biotransformation of benzaldehyde using various yeasts. In the present review,
378recent significant improvements in the microbial biotransformation are assessed
379for both fed-batch and continuous processes using free and immobilised yeasts.
380From previous fed-batch culture data, maximal levels of L-PAC of 10-12 gl-1 were
381reported with yields of 55-60% theoretical based on benzaldehyde. However,
382recently concentrations of more than 22 gl-1 have been obtained using a
383wild-type strain of Candida utilis. This has been achieved through optimal
384control of yeast metabolism (via microprocessor control of the respiratory
385quotient, RQ) in order to enhance substrate pyruvate production and induce
386pyruvate decarboxylase (PDC) activity. Processes involving purified PDC have
387also been evaluated and it has been demonstrated that L-PAC levels up to 28 gl-1
388can be obtained with yields of 90-95% theoretical based on the benzaldehyde
389added. In the review the advantages and disadvantages of the various strategies
390for the microbial and enzymatic production of L-PAC are compared. In view of the
391increasing interest in microbial biotransformations, L- PAC production provides
392an interesting example of enhancement through on-line control of a process
393involving both toxic substrate (benzaldehyde) and end-product (L-PAC, benzyl
394alcohol) inhibition.
395
396
397
398Shin, H.S. and Rogers, P.L. (1996) Production of L-PAC from benzaldehyde using partially purified pyruvate decarboxylase (PDC). Biotechnol. Bioeng. 49, 52-62.
399
400Shin, H.S. and Rogers, P.L. (1996) Kinetic evaluation of biotransformation of benzaldehyde to L-PAC by immobilized pyruvate decarboxylase. Biotechnol. Bioeng. 49, 429-436.
401
402This one looks really good, a review article!
403Oliver, A. L., Anderson, B. N. and Roddick, F. A. (1999) Factors affecting the production of L-phenylacetylcarbinol by yeast - a case study, Advances in Microbial Physiology, vol 41, pp1-41.
404
405V.B. Shukla and P.R. Kulkarni, (2000) L-Phenylacetylcarbinol (LPAC) : biosynthesis and industrial applications,World J. Microb. Biotech. 16, 499-506 (UK).
406
407
408
409Do Your Part To Win The War
410
411
412
413 Prdy2GO
414(Newbee)
41509-24-01 18:27
416No 216691
417 Re: Biosynth (homebrewing E)
418
419SWIM translation:
420
421OK all motovation inside starting with 4lbs white sugar and 2-3gallons h2o boiled and allowed to cool then added 1oz of active dry yeaqst (red and yellow jar)
422Question is this canditas utilits ? what would work better? Is that super yeast for beer the right stuff?
423About ten hours and then 60 ml distalled benzaldehyde was added.
4244 days have elapsed and now I am thinking about what to do next?
425Thanks
426
427Hum did you get that?
428
429
430
431 foxy2
432(Distinctive Doe)
43309-25-01 02:02
434No 216825
435 Re: Biosynth (homebrewing E)
436
437Process parameters and reusability of the free cell mass of Torulaspora delbrueckii for the production of L-phenylacetylcarbinol (L-PAC).
438AU: Shukla-V-B; Kulkarni-P-R {a}
439SO: World-Journal-of-Microbiology-and-Biotechnology.
440April, 2001; 17 (3): 301-306..
441PY: 2001
442
443
444The effect of process parameters on the biotransformation of benzaldehyde to L-phenylacetylcarbinol (L-PAC) using a yeast isolate identified as Torulaspora delbrueckii was studied. The maximum yield of L-PAC obtained was (331 mg) per 100 ml biotransformation medium (glucose 3%, peptone 0.6% and at pH 4.5) from 600 mg of benzaldehyde with 8 h of reaction at 30+-2degreeC. Growing the organism in presence of 3% glucose reduced the biotransformation time to 120 min. Addition of 0.6% acetaldehyde (30-35%) lead to an increase in L-PAC yield to 450 mg%. Semi-continuous feeding of benzaldehyde (200 mg) and acetaldehyde (200 mul) four times at 30 min intervals could produce 683 mg of L-PAC/100 ml biotransformation medium. Chiral HPLC analysis of purified L-PAC and PAC-diol showed 99% enantiomeric purity. The cell mass was found to be reusable for biotransformation up to nine times when benzaldehyde and acetaldehyde levels were maintained at (350 mg and 350 mul)-(400 mg and 400 mul). At concentrations from 450 mg and 450 mul to 600 mg and 600 mul, however the cell mass could give efficient biotransformation only during one use.
445
446
447Based on this you could get up to 100+ grams of L-PAC in a one day 5-gallon fermentation!!
448Do Your Part To Win The War
449
450
451
452 foxy2
453(Distinctive Doe)
45409-26-01 07:11
455No 217273
456 Re: Biosynth (homebrewing E)
457
458I wonder what would happen if you put indolecarboxaldehyde in this fermentation??? Easy AMT?
459
460Would a RP/I reaction reduce indole?
461Do Your Part To Win The War
462
463
464
465 thissuks
466(Hive Addict)
46710-12-01 01:07
468No 223365
469 Re: Biosynth (homebrewing E)
470
471 both yeast (Candida utilis) and pyruvate
472 decarboxylase (PDC)
473
474
475
476What type of home brewing are these used for?
477BISD: Built-in shit detector
478
479
480
481
482 encopo
483(Hive Bee)
48410-13-01 01:48
485No 223832
486 Re: Biosynth (homebrewing E)
487
488pardon my stupidity, but:
489this biosynth states that it creates l-ephedrine (after
490reductive amination of l-pac).
491However, upon reduction, won't this yield l-methamphetamine?
492Forgive me if I am incorrect, but isn't the l-isomer of
493methamphetamine much less effective, and is used in vicks'
494inhalers?
495Flames welcome.
496Don't mind me. I'm mentally ill.
497
498
499
500 Rhodium
501(Synaptic Cleft Mountaineer)
50210-13-01 10:00
503No 223952
504 Re: Biosynth (homebrewing E)
505
506l-ephedrine gives d-methamphetamine, and d-pseudoephedrine gives d-methamphetamine. Seems a little illogical at the first glance, but that is indeed the case.
507
508
509
510 encopo
511(Hive Bee)
51210-13-01 17:05
513No 224026
514 Re: Biosynth (homebrewing E)
515
516yes, thanks rhodium, I realised that after I left and
517was reading a doc on catalytic hydrogenation, and it
518said (-)-ephedrine and (+)-psuedoephedrine yield
519(+)-methamphetamine. I knew d-psuedoephedrine gave us
520the right isomer, I assumed it was the same for ephedrine.
521
522I've been looking around for a nice way to get some
523benzaldehyde to use in this. looking at the
524"phenylacetones.htm" file I found a patent reference
525for the production of benzyl chloride by the chlorination
526of toluene (it's the same thing as toluene with 1 xtra
527Cl on the carbon outcrop).
528The process bubbled Cl2 through Toluene, but it also said
529that using "bleaching powder" at high temperature with
530an acid provides nascent chlorine.
531However, the guy who wrote this has a bitch about side
532products. Now here is the NICE bit:
533
534"I have discovered, however....,
535by heating to a high temperature
536an anhydrous mixture of toluene
537and bleachin powder, with thorough
538commingling, and without the use of
539any acid, the chlorination of the
540toluene is effected without any of
541the disadvantages incident to the
542processes above referred to. In
543the absence of any added water the
544chlorin from the bleaching powder
545seems to go directly to produce
546benzyl chlorid in the side chain
547without attacking the nucleus, even
548though the process is carried on in
549the presence of iron, as in an
550iron vessel"
551
552Hmm. That looks nice. The reaction is pretty much:
553Heat toluene to 90'C. Slowly add equal amount (weight)
554of Ca(OCl)2 (pool shock), and raise temperature to
555100'-105'C, leaving it there 1 hour or until reaction
556complete. Settle. Decant of oil.
557
558This oil contains 30-35% benzyl chloride and 65-70%
559toluene.
560However, We don't want benzyl chloride, do we? We want
561BENZAL chloride. The patent goes on to describe that if
562sufficient amount of Ca(OCl)2 is added, the toluene is
563completely converted to Benzal Chloride and
564Benzo Trichloride. Upon boiling in alkaline water, we
565get Benzaldehyde and Benzoic acid. Voila.
566
567Hope this will be a good addition to the home-brew-E
568method, as many bees don't have that much benzaldehyde
569lying around.
570
571Check out the patent:
572
573
574
575Don't mind me. I'm mentally ill.
576
577
578
579 encopo
580(Hive Bee)
58110-13-01 22:58
582No 224105
583 Re: Biosynth (homebrewing E)
584
585Sorry you can't see the above. The patent is:
586U.S. Pat.#1,280,612
587
588Also, if the concentration of benzaldehyde in synthetic
589almond essence is high enough, then the alcohol could
590just be boiled off, and the rest plopped into the bucket.
591
592Also, is it possible to get out the L-PAC in a fashion that
593does not require vacumn distillation?
594
595Ooooh! Here we go, info on the almond essence:
596
597Bitter Almond oil is a light colourless liquid with a characteristic 'marzipan' scent. It main constituents are benzaldehyde (95%) and prussic acid (3%)."
598
599bitchin! That's an extremely high amount. However, I'm not
600convinced that this will be the concentration in OTC almond
601essence. Perhaps if "imitation" essence is used, there will
602be no prussic acid, as the essence will be made from
603benzaldehyde, rather than via almonds. Maybe? Maybe not.
604
605I'll be watching & working with you on this one.
606
607
608Don't mind me. I'm mentally ill.
609
610
611
612 encopo
613(Hive Bee)
61410-13-01 23:06
615No 224112
616 Re: Biosynth (homebrewing E)
617
618pardon my ever growing list of posts but...
619It seems that the strain Candida Utilis is often
620one of the organisms responsible for...
621VAGINAL YEAST INFECTIONS!
622This is really, really, really gross.
623Okay, so who's going to be the first person to make
624ephedrine from almond essence, vaginal yeast & sugar beets
625and then meth from phosphorous from a human skull, and
626iodine from stinky ol' kelp & dead fish.
627
628Mmmmm. yummy. You can't get much more ORGANIC with this
629organic chemistry.
630
631This is bad. This is very very bad. Vaginal yeast. <Shudder>
632Don't mind me. I'm mentally ill.
633
634
635 encopo
636(Hive Bee)
63710-14-01 00:41
638No 224148
639 Re: Biosynth (homebrewing E)
640
641So ya's all want some Candida Utilis, ey?
642There's pretty much three ways of getting it:
6431. By accident.
6442. From a culture collection - fork out $100
645 and get the third degree - "now ma'am, why did
646 you want to buy this sealed culture container?"
647 You should see the license agreement you have to
648 sign.
6493. Go to a health store / pet store / big supermarket and
650ask for Torula Yeast. After much searching around for this
651damned strain of yeast, I found it.
652
653Candida utilis (formerly Torulopsis utilis) is the yeast known as Torula Yeast. This yeast is also important in industry because it can utilize the pentose sugars from processed wood pulp used in making paper.
654
655Gee, ya don't say?
656
657Don't mind me. I'm mentally ill.
658
659
660
661 PolytheneSam
662(Master Searcher)
66310-14-01 01:29
664No 224184
665 Re: Biosynth (homebrewing E)
666
667See US patent 2061136 for some other ways (other than MeNH2 and Al/Hg) of aminating L-PAC and 3,4- substituted L-PACs.
668http://www.geocities.com/dritte123/PSPF.html
669
670
671
672 encopo
673(Hive Bee)
67410-15-01 02:43
675No 224546
676 Re: Biosynth (homebrewing E)
677
678SWIM's choice of action would be to aminate with
679methylamine, then reduce with either palladium or
680Urushibara Nickel (NiCl2 and Al).
681
682A thought on the reductive amination of L-PAC:
683the product of this is l-ephedrine, correct? If this
684is so, and catalytic hydrogenation is applied (in leiu
685of NaBH4 or LiAlH4), then shouldn't this l-ephedrine
686be further reduced to d-methamphetamine at the same
687time? (naturally, extra time/hydrogen would be given
688to ensure complete reduction.
689
690I assume that since methamphetamine has no more oxygen to
691reduce, that there is no risk of over-reducing with this
692method?
693
694I am particularly interested in the above procedure, and
695would love to hear some more from the author.
696
697In wishing to simplify this procedure a bit more, mainly
698for the sake of those who do not have vacumn distillation
699apparatus, but also to reduce time and effort in create
700large quantities, I am currently looking into different
701ways of extracting the L-PAC from the fermentation mixture
702that does not require the above-mentioned apparatus.
703Perhaps a clever adaptation of selective solubility may
704be in order? I'll check the library later, but if anybody
705has solubility data regarding L-PAC, It would be very
706welcome.
707But then again, a fermentation is rather organic (gee ya
708don't say), and much speculation could be made as to what
709this mixture actually contains (anyone care for trying to
710read a GC/MS?).
711
712I'm sure people don't want to be snorting Torula yeast up
713their nose - but then again, it is a diet suppliment, is
714it no?
715
716
717Tired but still working as always,
718
719Encopo.
720Don't mind me. I'm mentally ill.
721
722
723
724 dickdastardly
725(Stranger)
72610-18-01 21:09
727No 226338
728 Re: Biosynth (homebrewing E)
729
730Kudos to you for putting this info out there jacked. But I only have one last question left how do you perform a simple reductive amination. You see I'm a newbee and would like to get a simpler version of what I've seen posted thanks
731_________________________________________________________
732
733Knowlege is power
734
735
736
737 encopo
738(Hive Bee)
73910-19-01 02:36
740No 226514
741 Re: Biosynth (homebrewing E)
742
743Okie dokie, here's how it is.
744Reductive Amination:
745Well the "reductive" bit refers to reducing. Reducing is
746synonymous with "hydrogenation". Let's say you have a
747compound like the following:
748# double bond
749/ - \ single bond
750O oxygen atom
751C carbon atom
752H hydrogen atom
753
754 O
755 #
756 H C H
757 \ / \ /
758 H-C C-H
759 | |
760 H-C C-H
761 / \ / \
762 H C H
763 / \
764 H H
765
766Pardon the ascii art. This is cyclohexanone (keto form).
767If we REDUCE this (HYDROGENATION) using catalytic
768hydrogenation (that just means reducing with hydrogen and
769a catalyst - something that speeds up the reaction, but
770doesn't become part of the reaction products), we
771will get:
772
773 OH
774 |
775 H C H
776 \ / \ /
777 H-C C-H
778 | |
779 H-C C-H
780 / \ / \
781 H C H
782 / \
783 H H
784
785cyclohexanol.
786Can you see how the hydrogen has "attached" itself to the
787oxygen atom, by breaking one of the bonds that it had with
788the carbon atom? If we continue to reduce we get:
789
790 H H
791 \ /
792 H C H
793 \ / \ / H
794 H-C C-H /
795 | | + O
796 H-C C-H \
797 / \ / \ H
798 H C H
799 / \
800 H H
801
802cyclohexane
803Can you see how further reducing(hydrogenation) has fully
804removed the Oxygen atom from the compound? Now it has
805bonded with another hydrogen atom, and no-longer has a
806bond to the carbon atom, so it drops off as water (H2O).
807Now the carbon is 2 bonds too short, and bonds with 2 more
808hydrogens to "fill itself up".
809
810This is how reducing works. If you look at ephedrine, you'll
811see that it has an alpha-hydroxy group (another name for
812an OH). If you reduce ephedrine, this O bonds with another
813H atom and drops off as H2O. Then more H's come along to
814"fill up the space", and we get methamphetamine (a powerful
815and dangerous stimulant, a controlled substance in many
816countries).
817
818So now you know what REDUCING is. But you want to know what
819reductive amination means?
820Well, to AMINATE something refers to reacting a compound
821with ammonia (NH3), or an ammonia-containing compound, such
822as methylamine (NH2CH3) to produce an imine (never mind
823what that means). Reductive amination is the action of:
8241. reacting a compound with an ammonia-containing compound.
8252. reducing the formed imine
826
827Thus, when we reductively aminate safrole, we add NH2CH3,
828and then we hydrogenate it (reduce it), to give us
8293,4-methylenedioxymethamphetamine (pay honey).
830
831If we're making honey from bromosafrole, we don't need to
832reduce it, we just aminate it with ammonia (NH3). This is
833why the bromosafrole method is popular with some people, as
834it can be sealed up inside a container and sat for several
835days (until it finished aminating), or put into a pipe-bomb
836and heated to 130'C in hot oil for 2 hours (this aminates
837faster).
838
839In turning L-PAC into l-ephedrine, one could aminate with
840methylamine in the pipe-bomb, and then reduce it with
841sodium borohydride (NaBH4), or aluminum amalgam (Al/Hg),
842catalytic hydrogenation with raney nickel, or possibly
843even with an urushibara catalyst such as created from
844nickel chloride (NiCl2) and aluminum. Many other ways
845exist to reduce this formed imine. If one had the glassware,
846the pipe-bomb would be replaced with a reflux condenser
847and a round-bottomed flask, and the mixture of methylamine
848in methanol and the L-PAC would be refluxed for the
849necessary amount of time.
850Many reductive aminations reduce and aminate at the same
851time, such as the popular Al/Hg method (not actually the
852Al/Hg method, but an extension a bee has made to it that
853aminates and reduces at the same time).
854
855So I hope that explains reductive amination. For more info,
856visit Rhodium's site at ../rhodium/chemistry
857and look at some of the info on different methods (of
858interest to you might be the bromosafrole/halosafrole route
859that uses the pipe-bomb for aminating. However, this
860reaction aminates with ammonia, not methylamine as is
861required for reductively aminating L-PAC).
862
863Hope I could sort some things out for you.
864And now I need a big dump (darned coffee).
865
866Sphincterally yours,
867 Encopo.
868
869Don't mind me. I'm mentally ill.
870
871
872
873 dickdastardly
874(Stranger)
87510-19-01 17:08
876No 226773
877 Re: Biosynth (homebrewing E)
878
879aha that was just the info that is going to be saving me some money dag nabbit. You my freind encopo are a lifesaver. I just read a post on microwave hydrogenation. Would you reccomend this method. No more stupid pills for me.------------------------------------------------------------->Knowlege is power
880
881
882
883 malvaxman
884(Newbee)
88510-19-01 17:39
886No 226786
887 Re: Biosynth (homebrewing E)
888
889What about reducing the imine with elektricity, is´nt that a way to go?
890I still dont understand how one could sepate out l-pac out of the soup with acetone.
891Is normal yeast for baking bread possible to use?tongue
892
893
894
895 dickdastardly
896(Stranger)
89710-19-01 17:50
898No 226789
899 Re: Biosynth (homebrewing E)
900
901IN the halosafrole amination should I put the 1 mole of the L-PAC instead of the methylamine in the reaction to produce ephedrine
902
903
904
905 encopo
906(Hive Bee)
90710-19-01 21:45
908No 226850
909 Re: Biosynth (homebrewing E)
910
911oooh, nononononono. That would have dire consqeuences.
912Well, not dire, but not what you want. And wasteful
913(two nice precursors down the drain).
914I'm not sure what you want to do, but:
915* If you want to use the halosafrole method to make
916a halosafrole (such as bromosafrole), and then reductively
917aminate it, then you should aminate it with AMMONIA, as
918outlined nicely in the halosafrole/bromosafrole docs.
919* If you want to make the L-PAC into ephedrine, then
920you want to reductively aminate with methylamine, and
921your choice of reducing procedure. A procedure that used
922the pipe bomb FROM the halosafrole procedure to be able
923to aminate the L-PAC with methylamine (NOT ammonia) in the
924proper methanol solution, would aminate nicely, and then
925you could procede to reduce.
926
927As for extracting L-PAC with acetone, I'll be looking up
928on the solubility of L-PAC in various solvents. Then I
929will let you all in on the info. If someone can suggest
930a better method than selective solubility, I'd be glad to
931hear it (no, not distilling - many bees don't have/can't
932afford the glassware).
933
934And yes, I believe that a catalytic hydrogenation of some
935description would be best for reducing the formed imine
936(using electrolytically produced hydrogen, or if using
937Urushibara, perhaps the nascent hydrogen generation from
938aluminum would be sufficient (although I doubt it).).
939
940Don't mind me. I'm mentally ill.
941
942
943
944 dickdastardly
945(Stranger)
94610-20-01 06:24
947No 227038
948 Re: Biosynth (homebrewing E)
949
950I was just reminiscing on my days of youth in my physical science class and remembered a procedure in which a large flashlight battery was used to seperate hydrogen and oxygen and as I remember it it produced hydrogen quite well. Hell the teacher even lit the test tube full of hydrogen when he was done. Nuff to convince me man.
951
952
953
954 encopo
955(Hive Bee)
95610-20-01 15:26
957No 227143
958 Re: Biosynth (homebrewing E)
959
960In response to the use of normal baker's yeast in creating
961L-PAC, I wouldn't suggest it. In just the same way that
962cows are different animals to lions, you can't expect Simba
963to be able to provide the solvent for your breakfast cereal,
964no? Sure, SOMETHING will be created, and maybe even SOME
965L-PAC will be created, but the conditions under which
966baker's yeast proliferates would be different, and the end
967products would not really be the ones we're after here.
968
969On microwave hydrogenation:
970Microwave hydrogenation seems to reduce reaction times when
971compared to a reaction that provides hydrogen by a
972dissolving metal such as aluminum, but not when compared to
973using raney nickel in a parr-shaker hydrogenation setup.
974Since Urushibara catalysts are far more OTC than raney
975nickel, and don't have the pyrophoric properties, they would
976be an easier choice for the chemical/apparatus deprived.
977
978The use of one of the electrolytic hydrogenation device
979mentioned throughout the hive (the ultrasonic refreshing
980one looks VERY nice), would be good in this respect, if
981a high-enough quality urushibara catalyst was prepared.
982The hydrogen in this method is provided by the electrolysis
983of water with an electrolyte (such as NaOH) dissolved in
984it to provide H2 gas (and O2 gas), and this cuts down
985on reaction time.
986The use of ultrasonic refreshing acts to create the
987environment at an atomic level of high-pressure and temp,
988whilst being performed in an apparatus at room temp & press.
989As someone said "the ultrasonic transducers literally
990slam the hydrogen and ephedrine together". Of course, that
991was in reference to reducing ephedrine to methamphetamine,
992but a simliar principle would apply.
993
994A note of warning though:
995A method that myself and many other bees would find easy
996may be more daunting and/or dangerous to an unexperienced
997newbee.
998The creation of Urushibara catalysts requires the
999use of a carcinogenic and toxic compound - NiCl2 (nickel
1000chloride).
1001
1002However, a chip a stray cat recently coughed up (this time
1003in my lounge) describes a person who has done some
1004experiments in creating the NiCl2 in situ. from nickel
1005oxide, and then directly proceeding with the creation of
1006an Urushibara catalyst.
1007
1008I will post these findings later this week, after I have
1009deciphered the strange dialect that it is written in.
1010
1011If this works, many newbees would be able to explore the
1012use of this exciting reducing agent, requiring only OTC
1013products, some time, and some caution.
1014By creating the NiCl2 in situ, one avoids cancerous tumours
1015forming in embarrasing places.
1016
1017lymphatically bloatedly yours,
1018 Encopo.
1019
1020Don't mind me. I'm mentally ill.
1021
1022
1023
1024 thissuks
1025(Hive Addict)
102611-05-01 02:22
1027No 233119
1028 Re: Biosynth (homebrewing E)
1029
1030€€€€€€€€€€€€€€€€€€€€€€€€€€€€€€€€€€€€€€€€€€€€€€€€€€€€€€
1031
1032*****AMERICAN JOURNAL OF GASTROENTEROLOGY*****
1033Nadir A Agrawal S King PD Marshall JB
1034Acute hepatitis associated with the use of a Chinese herbal product, ma-huang
1035[see comments]
1036In: Am J Gastroenterol (1996 Jul) 91(7):1436-8
1037ISSN: 0002-9270
1038
1039Herbal medicines are widely perceived by the public as being healthful and
1040innocuous. A number of herbal medicines have now been linked with
1041hepatotoxicity. We report a case of acute hepatitis associated with the use of
1042ma-huang, a herbal product derived from plants of the Ephedra species, which is
1043advertised as being useful for causing weight loss and enhancing energy levels.
1044Given the lack of reports in the literature of hepatotoxicity with ma-huang and
1045ephedrine, we speculate that the ma-huang product our patient took contained
1046some other ingredient or contaminant or was misidentified. Our report and others
1047in the literature, which we review, indicate that the clinician should consider
1048herbal medicines as a possible cause of unexplained liver injury.
1049
1050Registry Numbers:
1051299-42-3 (Ephedrine)
1052
1053€€€€€€€€€€€€€€€€€€€€€€€€€€€€€€€€€€€€€€€€€€€€€€€€€€€€€€
1054
1055*****EMBO JOURNAL*****
1056Malek O Lattig K Hiesel R Brennicke A Knoop V
1057RNA editing in bryophytes and a molecular phylogeny of land plants.
1058In: EMBO J (1996 Mar 15) 15(6):1403-11
1059ISSN: 0261-4189
1060
1061RNA editing has been observed to date in all groups of vascular plants, but not
1062in bryophytes. Its occurrence was therefore assumed to correlate with the
1063evolution of tracheophytes. To gain more insight into both the phylogeny of
1064early land plants and the evolution of mitochondrial RNA editing we have
1065investigated a number of vascular and non-vascular plant species. Contrary to
1066the belief that editing is absent from bryophytes, here we report mitochondrial
1067RNA editing in cox3 mRNA of the liverwort Pellia epiphylla, the mosses Tetraphis
1068pellucida and Ceratodon purpureus and the hornwort Anthroceros crispulus. RNA
1069editing in plants consequently predates the evolution of tracheophytes. Editing
1070is also found in the eusporangiate ferns Ophioglossum petiolatum and Angiopteris
1071palmiformis, the whisk fern Tmesipteris elongata and the gnetopsid Ephedra
1072gerardiana, but was not detected in Gnetum gnemon.cox3 mRNA of the lycopsid
1073Isoetes lacustris shows the highest frequency of RNA editing ever observed in a
1074plant, with 39% of all cytidine residues converted to uridines. The frequency of
1075RNA editing correlates with the genomic GC content rather than with the
1076phylogenetic position of a species. Phylogenetic trees derived from the slowly
1077evolving mitochondrial sequences find external support from the assessments of
1078classical systematics.
1079
1080Registry Numbers:
1081EC 1.9.3.1 (Cytochrome-c Oxidase)
1082
1083€€€€€€€€€€€€€€€€€€€€€€€€€€€€€€€€€€€€€€€€€€€€€€€€€€€€€€
1084
1085*****ADVANCES IN BIOCHEMICAL ENGINEERING/BIOTECHNOLOGY*****
1086Rogers PL Shin HS Wang B
1087Biotransformation for L-ephedrine production.
1088In: Adv Biochem Eng Biotechnol (1997) 56:33-59
1089ISSN: 0724-6145
1090
1091L-ephedrine is widely used in pharmaceutical preparations as a decongestant and
1092anti-asthmatic compound. One of the key intermediates in its production is
1093L-phenylacetylcarbinol (L-PAC) which can be obtained either from plants (Ephedra
1094sp.), chemical synthesis involving resolution of a racemic mixture, or by
1095biotransformation of benzaldehyde using various yeasts. In the present review,
1096recent significant improvements in the microbial biotransformation are assessed
1097for both fed-batch and continuous processes using free and immobilised yeasts.
1098From previous fed-batch culture data, maximal levels of L-PAC of 10-12 gl-1 were
1099reported with yields of 55-60% theoretical based on benzaldehyde. However,
1100recently concentrations of more than 22 gl-1 have been obtained using a
1101wild-type strain of Candida utilis. This has been achieved through optimal
1102control of yeast metabolism (via microprocessor control of the respiratory
1103quotient, RQ) in order to enhance substrate pyruvate production and induce
1104pyruvate decarboxylase (PDC) activity. Processes involving purified PDC have
1105also been evaluated and it has been demonstrated that L-PAC levels up to 28 gl-1
1106can be obtained with yields of 90-95% theoretical based on the benzaldehyde
1107added. In the review the advantages and disadvantages of the various strategies
1108for the microbial and enzymatic production of L-PAC are compared. In view of the
1109increasing interest in microbial biotransformations, L- PAC production provides
1110an interesting example of enhancement through on-line control of a process
1111involving both toxic substrate (benzaldehyde) and end-product (L-PAC, benzyl
1112alcohol) inhibition.
1113
1114Registry Numbers:
1115EC 4.1.1.1 (Pyruvate Decarboxylase)
1116100-52-7 (benzaldehyde)
1117299-42-3 (Ephedrine)
111867-64-1 (Acetone)
111990-63-1 (1-hydroxy-1-phenyl-2-propanone)
1120
1121
1122palladium foil
1123
1124
1125
1126 foxy2
1127(Distinctive Doe)
112811-06-01 03:23
1129No 233432
1130 Re: Biosynth (homebrewing E)
1131
1132Manufacture of L-phenylacetylcarbinol with Saccharomyces and preparation of L-ephedrine therefrom.
1133Horitsu, Hiroaki; Otsubo, Tetsuya. (Alps Yakuhin Kogyo K. K., Japan; Horitsu, Hiroaki).
1134Jpn. Kokai Tokkyo Koho (1997), 4 pp. CODEN: JKXXAF
1135JP 09234090 A2 19970909 Heisei.
1136Patent written in Japanese.
1137
1138Abstract
1139L-Phenylacetylcarbinol (I) is manufd. from pyruvic acid (II) and PhCHO in a medium contg. C source with Saccharomyces yeast. L-Ephedrine (III) is prepd. from I manufd. by the above method. Bakers' yeast was precultured in a medium contg. molasses, salts, II, and vitamin B1 at 30° for 1 h. Subsequently PhCHO was added to the culture over 1 h and the incubation was continued for 5 h to give I. A mixt. of I, AcOBu, MeOH soln. of MeNH2, Adams Pt oxide, and MeOH was autoclaved at 3 atm H ro give III.
1140
1141
1142Method for isolation of L-ephedrine hydrochloride and sulfate salts.
1143Vondracek, Miloslav; Svoboda, Ivan. (Vyzkumny Ustav Antibiotik A Biotransformaci S.P., Czech Rep.). Czech Rep. (1996), 4 pp. CODEN: CZXXED
1144CZ 281218 B6 19960717 Patent written in Czech.
1145
1146Abstract
1147L-Ephedrine hydrochloride and sulfate salts can be isolated from a reaction mixt. by reductive amination of D-(-)-1-phenyl-1-hydroxy-2-propanone at pH 10-13 and removing the catalyst with an org. phase, then bringing the pH to 1-6 with concd. HCl or H2SO4, with azeotropic distn. to remove 70-100% of the vol. of the water present and to release the desired salt.
1148
1149L-Ephedrine from phenylacetyl carbinol.
1150Nebesky, Ferdinand; Souhrada, Josef; Jakl, Vladimir. (Czech.). Czech. (1978), 3 pp. CODEN: CZXXA9
1151CS 186027 19781130 Patent written in Czech.
1152
1153Abstract
1154Phenylacetylcarbinol was hydrogenated at 50-5° and H pressure 202.6 kPa over a Pt catalyst in AcOBu contg. HCl with portionwise addn. of an aq. 35-40% MeNH2 soln. To give a mixt. of the L-(I) and DL-ephedrine, which was sepd. by crystn. to yield 88% I.HCl.
1155
1156Do Your Part To Win The War
1157
1158
1159
1160 foxy2
1161(Distinctive Doe)
116211-06-01 03:29
1163No 233436
1164 Re: Biosynth (homebrewing E)
1165
1166This is cool, If you are up to the plant cell culture, which is much more difficult than growing yeast.
1167
1168Method for producing ephedrine from large-scale Ephedra cell culture.
1169Cha, Lihang; Jiao, Yuxia; Liu, Dalu; Zhu, Weixing; Zhang, Guozheng; Tang, Lianghong. (Institute of Chemical Metallurgy, Chinese Academy of Sciences, Peop. Rep. China; Xinjiang Tuofeng Pharmaceutic Industry Co., Ltd.). Faming Zhuanli Shenqing Gongkai Shuomingshu (2000), 13 pp. CODEN: CNXXEV
1170CN 1256316 A 20000614 Patent written in Chinese.
1171
1172Abstract
1173Ephedrine is produced by inoculating Ephedra cell ZHJ-25CGMCCNo.0359 in a culture, culturing at 25° for 20-50 d by solid culturing, suspension culturing, or bioreactor culturing, and drying at 60°. The culture is prepd. by adding 0.7% agar to a soln. contg. KNO3 2.0-10.0, CuSO4 0.0001-0.001, NaH2PO4 0.3- 5.0, ZnSO4 0.001-0.01, MgSO4 0.5-3.5, (EDTA)Fe 0.1-2, Na3BO3 0.001-0.007, kinetin 0.001-0.01, (NH4)2SO4 0.5- 2.0, indoleacetic acid 0.001-0.01, CaCl2 0.5-5.0 mM, and sugar 1.0-10.0%, boiling, and sterilizing at 121° for 15 min. The culture may also contain phenylalanine 0.1-20 mM, fungus fermn. liquor 10-50%, vitamin B 0.4-0.5 mM, and nicotinic acid 0.078 mM.
1174Do Your Part To Win The War
1175
1176
1177
1178 foxy2
1179(Distinctive Doe)
118011-06-01 03:33
1181No 233440
1182 An Article in English!!!!
1183
1184Ephedra species: in vitro culture, micropropagation, and the production of ephedrine and other alkaloids.
1185O'dowd, N. A.; Mccauley, P. G.; Wilson, G.; Parnell, J. A. N.; Kavanagh, T. A. K.; Mcconnell, D. J. School of Botany, Trinity College, University of Dublin, Dublin, Ire.
1186Biotechnol. Agric. For. (1998), 41(Medicinal and Aromatic Plants X), 154-193.
1187CODEN: BAFOEG ISSN: 0934-943X. Journal; General Review written in English. CAN 128:101114
1188
1189Abstract
1190A review with 102 refs.
1191
1192This could bee very interesting.
1193Do Your Part To Win The War
1194
1195
1196
1197 foxy2
1198(Distinctive Doe)
119911-06-01 03:51
1200No 233448
1201 Re: Biosynth (homebrewing E)
1202
12031-Ephedrine.
1204Groeger, Detlef; Schmauder, Hans P.; Froemmel, Helmut. Ger. (East) (1966), 3 pp. CODEN: GEXXA8
1205DD 51651 19661125 Patent written in German.
1206
1207Abstract
1208The title compd. (I) is prepd. by aerobic fermentation of a soln. of 18-25% beet molasses, 0.03-0.07% MgSO4.7H2O, 0.1-0.15% KH2PO4, 0.3-0.6% (NH4)2SO4 at pH 4.7-5.2, contg. small amts. of coenzymes, vitamin B, or whey and Saccharomyces cerevisiae, during 9 hrs. Within 4 hrs., 4 addns. of 0.2% C6H5CHO and AcH are added. A yield of 55-76% L-phenylacetylcarbinol is obtained which is treated by known methods to give I.
1209
1210
1211This one here looks like GOLD!!!
1212
1213Factors affecting the production of L-phenylacetylcarbinol by yeast: a case study.
1214Oliver A L; Anderson B N; Roddick F A
1215ADVANCES IN MICROBIAL PHYSIOLOGY (1999), 41 1-45.
1216Ref: 112. Journal code: 2NT. ISSN:0065-2911.
1217
1218Abstract
1219L-Phenylacetylcarbinol (L-PAC) is the precursor for L-ephedrine and D-pseudoephedrine, alkaloids possessing alpha- and beta-adrenergic activity. The most commonly used method for production of L-PAC is a biological method whereby the enzyme pyruvate decarboxylase (PDC) decarboxylates pyruvate and then condenses the product with added benzaldehyde. The process may be undertaken by either whole cells or purified PDC. If whole cells are used, the biomass may be grown and allowed to synthesize endogenous pyruvate, or the cells may be used as a catalyst only, with both pyruvate and benzaldehyde being added. Several yeast species have been investigated with regard to L-PAC-producing potential; the most commonly used organisms are strains of Saccharomyces cerevisiae and Candida utilis. It was found that initial high production rates did not necessarily result in the highest final yields. Researchers then examined ways of improving the productivity of the process. The substrate, benzaldehyde, and the product, L-PAC, as well as the by-products, were found to be toxic to the biomass. Methods examined to reduce toxicity include modification of benzaldehyde dosing regimes, immobilization of biomass or purified enzymes, modification of benzaldehyde solubility and the use of two-phase reaction systems. Various means of modifying metabolism to enhance enzyme activity, relevant metabolic pathways and yield have been examined. Methods investigated include the use of respiratory quotient to influence pyruvate production and induce fermentative activity, reduced aeration to increase PDC activity, and carbohydrate feeding to modify glycolytic enzyme activity. The effect of temperature on L-PAC yield has been examined to identify conditions which provide the optimal balance between L-PAC and benzyl alcohol production, and L-PAC inactivation. However, relatively little work has been undertaken on the effect of medium composition on L-PAC yield.
1220Do Your Part To Win The War
1221
1222
1223
1224 thissuks
1225(Hive Addict)
122611-06-01 06:05
1227No 233543
1228 Re: Biosynth (homebrewing E)
1229
1230where did you find all that? I might be wrong but dont we want D-ephedrine
1231palladium foil
1232
1233
1234
1235 TrickEMethod
1236(Newbee)
123711-06-01 07:08
1238No 233585
1239 Re: Biosynth (homebrewing E)
1240
1241Here's two more possibilities for Benz from Toluene that I have found.
1242
1243 1) Photooxidation of Toluene in Cation-Exchange Zeolites
1244
1245 2) Oxygenation of Hydrocarbons using Nanostructured TiO2 as a Photocatalyst
1246
1247Now number one is interesting, here is the puchline...
1248
1249Toluene photooxidation was investigated in BaX and BaY (zeolites - BIG MAGIC). Toluene was introduced into the infrared cell at a pressure of approximately 10 torr and alllowed to equilibrate for one hour. Gas-phase toluene was subsiquently pumped out leaving strongly absorbed toluene. Quantitative measures of the toluene absorption indicated that the loading was approximately 2 toluene molecules per supercage. Molecular oxygen was then added to the infrared cell... sample was irradiated with broadband for 1hr... The end result is that BaY zeolite produced a 87% yeald then was nearly fully recycled.
1250
1251Now BaY Zeolite can only be gotten from the petuitary of the invitro fetus of an extinct species of tree lizards, but otherwise the method is perfect.
1252
1253The second synth is more viable however, needing only Tol, O2 (atm probably would work with patience) and TiO2 which is Titanium white used as a paint thickener and coloring...
1254
1255Details were irritatingly thin, but Tol was oxidized in the presence of a TiO2 catalyst produced via flame deposition on a unnamed substrate. Two hours with bubbled O2 (rate not provided) under UV radiation from a Hg lamp with nearly theoretic conversion and selectivity.
1256
1257Too tired to retype the reference tonight, but if people are interested I might tomorrow.
1258
1259
1260Let me know what you think, butI intend to try a TiO2 held in suspension by bubbling O2 thru Toluene. I figure recycle the O2 with a pump to really churn things up and hit it hard with UV from all sides via a reflector. Of course I just realized that: Toluene + O2 + Heat might lead to an exothermic side reactions involving the local authorities via kitchen rearangement which would reduce the selectivity of the outcome. Maybe I'll wait to hear from wiser bee's, and maybe some sleep, before I dream such things...
1261
1262TrickE
1263And on the eight day, God created Meth...
1264... and hasn't done much of anything usefull since!
1265
1266
1267
1268 foxy2
1269(Distinctive Doe)
127011-06-01 18:18
1271No 233782
1272 Re: Biosynth (homebrewing E)
1273
1274suk
1275No you want L-ephedrine.
1276
1277I have a good book here
1278"Principles of Brewing Science" by George Fix
1279It has some pretty good basic info on all the chemical transformations in yeast. Mine is the old edition, I heard the new one was easier to understand, that could mean that he left out many good details but maybee he didn't.
1280
1281Ok now to the goods.
1282Mr Fix says that Mg++ is a cofactor for the pyruvic acid decarboxylase enzyme. So I would say that you definately want/need some Magnesium in your media. Use epsom salt (MgSO4) in the amount recommended in one of the above media compositions.
1283Do Your Part To Win The War
1284
1285
1286
1287 dickdastardly
1288(Stranger)
128911-10-01 07:49
1290No 235102
1291 Re: Biosynth (homebrewing E)
1292
1293Well I went to the grocery store to find me some Torula Yeast. No luck so's I decided to look for it on the net and guess what I found Ya'll
1294http://www.ohly.de/hutch.htm [url]http://
1295
1296
1297 Shooting_Star
1298(Newbee)
129902-17-02 20:05
1300No 270916
1301 Re: Biosynth (homebrewing E)
1302
1303Since this same subject came up in the Crystal Meth forum, ressurecing this seems worthwhile.
1304
1305My questions on the matter are:
1306Since both the precursor and the product (along with the side reaction products) are toxic to the biomass, is there perhaps some way to periodically rinse the yeast so as to refresh them and keep them viable?
1307
1308Perhaps some sort of filtering to remove the nascent liquor for processing out the ephedrine, then returning the yeast to the fermenttion vessle to continue eating, reproducing and makeing more gold?
1309
1310This one really seems like a good way to keep a low profile whilst continuing to cook.
1311
1312(BTW, while vaginal yeas may be a strain of Candida, it is C albicans, not C. utilis)
1313
1314burn-out only occurs if you go too fast in the wrong direction
1315
1316
1317
1318 Organikum
1319(Newbee)
132003-10-02 13:27
1321No 280073
1322 Re: Biosynth (homebrewing E)
1323
1324Yeast & L-PAC
1325
1326Look up:
1327WO 90/04631
1328US 6,271,008
1329WO 01/44486
1330US 5,173,413
1331DE 518029 (german)
1332GB 365535
1333
1334all at:
1335http://ch.espacenet.com/espacenet/ch/en/e_net.htm
1336
1337more to follow, if someone cares
1338
1339ORGY
1340(who seeks for a bee experienced in catalytic hydrogenation/red. alkylation for putting together parts fitting so easily. Has done research on yeast not only in theory and now... PM!)
1341"I hope I'm becoming more eccentric. More room, you know.
1342 More room in the brain."
1343
1344
1345
1346
1347 Organikum
1348(Newbee)
134903-11-02 18:49
1350No 280685
1351 Re: Biosynth (homebrewing E)
1352
1353Sorry in thy above post was a typo:
1354Thy german patent is:
1355DE1518029
1356it is identical with
1357GB1118293
1358
1359whoooo not one noticed it.
1360seems me and my ketoalcohol will stay thy lonesome riders...
1361...no! Not all alone.
1362
1363Shop closed.
1364ORGY
1365
1366"I hope I'm becoming more eccentric. More room, you know.
1367 More room in the brain."
1368
1369
1370
1371
1372 Organikum
1373(Newbee)
137403-15-02 14:28
1375No 282983
1376 Re: Biosynth (homebrewing E)
1377
1378Yes we proudly present, thy neverbefore shown image of thy mysterious
1379
1380EPHEDRINE BIOSYNTH
1381
1382
1383
1384
1385A Pic, a pic, a pic!
1386As nobody wants to read patents nowadays (P-SAM ya thy guilty one ya did it intentional confess! wink)
1387
1388Hey look, thats what it looks like, hold it before it undergoes racemisation! Oh, too late, its only PAC, no L-PAC anymore.
1389
1390For those searching for valid information before starting thy part of free phantasting this may be helpful.
1391
1392WO 90/04631
1393
1394enough is enough
1395ya´ll get no colored one.
1396
1397ORGY
1398
1399
1400
1401"I hope I'm becoming more eccentric. More room, you know.
1402 More room in the brain."
1403
1404
1405
1406
1407 java
1408(Stranger)
140903-21-02 16:52
1410No 285901
1411 biotransformation .....to ephedrine
1412
1413I read the posting and I have also tried to understand the reading on Biotransformation for L-ephedrine Production. by P.L. Rogers,H.S. Shin and B. Wang found in the pub lished by Springer on volume 56 Advances in Biochemical Engineering Biotechnology
1414
1415First in the use of Candida Utilis, the max growth occured at PH 7 while the RQ( respiratory quotient ) value = 4 this value being the O2 AND CO2 concentration and the relative stirring of the metabolic step of the production.
1416
1417While the article is good the data ca be confusing , also they use equipment out of reach for many of us.
1418However I would like to post the whole article for the interpretation of the reader , since many may not have access to the original work.
1419
1420I would like to know if this would be cool or does it go against some type of policy of the forum ? The Journal that contains the article is pricy $150 dol. but its info is worth it.
1421
1422
1423
1424 ballzofsteel
1425(Hive Bee)
142603-21-02 22:06
1427No 286014
1428 e
1429
1430Dont know if its cool or not,but I shure would like to catch a glimpse of that.Ive searched briefly on the net for it but only keep coming up with the same few paragraphs,telling me that it can be done and the basic procedure,not going into any specific detail.
1431Any info or links would be much appreciated by me.
1432
1433Im pretty sure it would be cool to post some of it at least.
1434
1435Its not on rhodiums page yet is it?
1436
1437I realy think,seeing as the C.M board seems to have dried up when it comes to novel or new ideas and how the OTC sources of feedstock are becoming more of a bitch every day,that this subject should be the focus of all the meth bees.
1438Im sure within a couple of months we could get it cracked and form a relatively OCT method for biosynthimg e.
1439Then all we would have to worry about is when big brother makes yeast available by presription and starts regulating sugar purchases.
1440
1441Whadda ya say bees?This would be one huge battle won in this war of ours.wink
1442
1443BIOBALLZ
1444
1445Then we just gotta get flinger to let us in on how to grow his meth plants and were laughing.smile
1446
1447
1448
1449 java
1450(Stranger)
145103-23-02 02:28
1452No 286649
1453 refrences to the Biotransformation for L- Ephedrin
1454
1455I wasn't able to post the whole refrence to the P.L.Rogers- H.S. Shin, B. Wang......BIOTRANSFORMATION FOR L- EPHEDRINE
1456so I sent it to the forum moderator see where he puts it, I also sent it to Rhodium maybe they will post it in its
1457entirety..................Question , is it possible to use fructose sugar as the source ? or just raw sugar cane sugar?blush
1458
1459Here is recent finding , I thought it was interesting:
1460
1461
14621: Biotechnol Bioeng 2001 Aug 20;74(4):317-25
1463
1464Continuous production of (R)-phenylacetylcarbinol in an enzyme-membrane reactor
1465using a potent mutant of pyruvate decarboxylase from Zymomonas mobilis.
1466
1467Goetz G, Iwan P, Hauer B, Breuer M, Pohl M.
1468
1469Institut fur Enzymtechnologie der Universitat Dusseldorf im Forschungszentrum
1470Julich, D-52426 Julich, Germany.
1471
1472The optimization of a continuous enzymatic reaction yielding
1473(R)-phenylacetylcarbinol (PAC), an intermediate of the L-ephedrine synthesis, is
1474presented. We compare the suitability of three pyruvate decarboxylases (PDC),
1475PDC from Saccharomyces cerevisiae, PDC from Zymomonas mobilis, and a potent
1476mutant of the latter, PDCW392M, with respect to their application in the
1477biotransformation using acetaldehyde and benzaldehyde as substrates. Among
1478these, the mutant enzyme was the most active and most stable one. The reaction
1479conditions of the carboligation reaction were investigated by determining
1480initial rate velocities with varying substrate concentrations of both aldehydes.
1481From the resulting data a kinetic model was inferred which fits the experimental
1482data with sufficient reliability to deduce the optimal concentrations of both
1483substrates for the enzymatic process. The results demonstrate that the
1484carboligation is most efficiently performed using a continuous reaction system
1485and feeding both aldehydes in equimolar concentration. Initial studies using a
1486continuously operated enzyme-membrane reactor gave (R)-PAC with a space-time
1487yield of 81 g L(-1). d(-1) using a substrate concentration of 50 mM of both
1488aldehydes. The yield was easily increased by cascadation of enzyme-membrane
1489reactors. The new strategy allows the synthesis of (R)-PAC from cheap substrates
1490in an aqueous reaction system. It thereby overcomes the limitation of by-product
1491formation that severely limits the current fermentative process.
1492
1493PMID: 11410856 [PubMed - indexed for MEDLINE]
1494
1495most recent article found and lots of research stuff on biotransformation at:
1496http://www3.ncbi.nlm.nih.gov/htbin-post/Entrez/query?db=0&form=1&term=biotransformation+for+L-ephedrine
1497......good reading
1498
1499
1500
1501
1502 Rhodium
1503(Chief Bee)
150403-23-02 03:02
1505No 286662
1506 Ref?
1507
1508Sent it to me? Resend it please - rhodium@ziplip.com
1509
1510
1511
1512 Organikum
1513(Hive Bee)
151403-23-02 05:32
1515No 286705
1516 feed thy yeast
1517
1518what thy heck frucose?
1519I cannot say it will not work, but never heard about.
1520
1521what thy yeast needs: vitamines, minerals its a lifeform.
1522
1523happa, happa for yeast:
1524starting fermentation broth: molasses + yeast extract(does RECYCLING say anything to ya?) + glucose aka dextrose aka fucking plain sugar.
1525+ ceremony of sacrifice at choice.
1526
1527it´s all in thy patents
1528
1529hungry yeast is bad yeastmad
1530ORGY
1531
1532"I hope I'm becoming more eccentric. More room, you know.
1533 More room in the brain."
1534
1535
1536
1537
1538 Rhodium
1539(Chief Bee)
154003-23-02 10:57
1541No 286795
1542 biotransformation.ephedrine.pdf
1543
1544Here is the document I got from Java: ../rhodium/archive/biotransformation.ephedrine.pdf
1545
1546
1547
1548 MMM
1549(Newbee)
155004-27-02 07:02
1551No 301971
1552 Fructose nope.
1553
1554It is unlikely you could use Fructose. It may depend on the strain of yeast being used, but in brewing of drinkable stuff Fructose is added to sweeten the drink as it is unfermentable by the std yeasts used. Tastes twice as sweet as sugar, and one hell of a lot better than the artificial gunk.
1555When sugar is added, the yeast produces an enzyme which breaks sugar (sucrose) into Fructose and Glucose. The Glucose is then fermented to alcohol.
1556
1557HTH, MMM
1558When the day is bad,and life's a curse
1559CHEER UP!!! Tomorrow may be Worse!!
1560('HAGAR' Comic)
1561
1562
1563
1564 Organikum
1565(Hive Bee)
156604-29-02 15:24
1567No 302974
1568 Sugar is not Dextrose
1569
1570
1571MMM you are absolutely right.
1572Glucose = Dextrose but not Sucrose.
1573My thought was, that plain sugar can be supplied to feed the yeast, but as Dextrose is cheap and available this may be taken.
1574If betacyclodextrin is added it is possible to apply more benzaldehyde and better yields are reached. The adding of about 10% ethylalcohol may be substituted for betacyclodextrin.
1575
1576
1577
1578thanks MMM
1579ORGY
1580
1581
1582
1583 Jetson
1584(Hive Bee / Eraser)
158507-29-02 20:11
1586No 338609
1587 any breaks?
1588
1589any new updates or breaks on this subject? jetson thought this had died long ago but to his surprise the last reply was just last april. cool jetson's going to do some independant studying and will post anything new he finds but most likely it'll be more catching up than anything.
1590the devil is so lonelymad
1591
1592
1593
1594 Organikum
1595(Hive Bee)
159609-21-02 03:14
1597No 358648
1598 Biotech still in progress...
1599
1600
1601have a look at this quite new abstract and hope this sophisticated techniques will soon serve the clandestine chemist in his daily fight.
1602
1603
1604
1605
1606
1607 © Springer-Verlag 2002
1608
1609 Original Paper
1610
1611 Enzymatic (R)-phenylacetylcarbinol production in benzaldehyde emulsions
1612
1613 B. Rosche1, , N. Leksawasdi1, V. Sandford1, M. Breuer2, B. Hauer2 and P. Rogers1
1614
1615 (1)
1616 School of Biotechnology and Biomolecular Sciences, University of New South Wales, Sydney NSW 2052, Australia
1617
1618 (2)
1619 BASF-AG, Hauptlaboratorium, 67056 Ludwigshafen, Germany
1620
1621 Abstract. (R)-Phenylacetylcarbinol [(R)-PAC)] is the chiral precursor for the production of the pharmaceuticals ephedrine and pseudoephedrine. Reaction conditions were improved to achieve increased (R)-PAC levels in a simple batch biotransformation of benzaldehyde emulsions and pyruvate, using partially purified pyruvate decarboxylase (PDC) from the filamentous fungus Rhizopus javanicus NRRL 13161 as the catalyst. Lowering the temperature from 23°C to 6°C decreased initial rates but increased final (R)-PAC concentrations. Addition of ethanol, which increases benzaldehyde solubility, was not beneficial for (R)-PAC production. It was established that proton uptake during biotransformation increases the pH above 7 thereby limiting (R)-PAC production. For small-scale studies, biotransformations were buffered with 2-2.5 M MOPS (initial pH 6.5). High concentrations of MOPS as well as some alcohols and KCl stabilised PDC. A balance between PDC and substrate concentrations was determined with regards to (R)-PAC production and yields on enzyme and substrates. R. javanicus PDC (7.4 U/ml) produced 50.6 g/l (337 mM) (R)-PAC in 29 h at 6°C with initial 400 mM benzaldehyde and 600 mM pyruvate. Molar yields on consumed benzaldehyde and pyruvate were 97% and 59%, respectively, with 17% pyruvate degraded and 24% converted into acetaldehyde and acetoin; 43% PDC activity remained, indicating reasonable enzyme stability at high substrate and product concentrations.
1622
1623
1624
1625 E-mail: B.Rosche@unsw.edu.au
1626 Phone: +61-2-93853895
1627 Fax: +61-2-93136710
1628
1629
1630
1631
1632some perhaps valuable information on L-PAC:
1633
1634L-PAC, aka laevo-phenylacetylcarbinol, is also named:
1635
16361-hydroxy-1-phenyl-2-propanone
16371-hydroxy-1-phenylpropanone
1638l-1-phenylpropan-1-ol-2-on (phenylpropanolon) -> old german
1639laevo-phenylpropanolone
16401-phenyl-2-ketoalcohol-(1)
16411-phenyl-propanol-1-one-2
1642R-PAC
1643
1644I am sure the babylonians have still more names for this simple compound. If somebody finds another one - PM me.
1645
1646Also is this molecule well known since 1921, and heavily used in pharmaceutic industry, but there is no entry at chemfinder or another public database I have access.
1647
1648Please, somebody who has access to better resources could look up the properties (boiling point, soluble in...)? Post them here or/and PM me?
1649THANKS!
1650Racemisation in basic solution is very fast, thats what I could dig up.
1651
1652IMHO biotransformations are a sharp sword in the hand of clandestine chemistry. And I don´t speak of genetically engineered or otherwise dangerous organisms. All day everywhere yeasts are keeping a widely undeveloped (or not published) power of transformation. Enzyme extraction isn´t rocket science also.
1653
1654I will be happy if I would get the L-PAC properties
1655ORGY
1656~ Love is the law, love under will. ~
1657
1658
1659
1660
1661 Organikum
1662(Hive Bee)
166309-29-02 04:17
1664No 361794
1665 some more L-PAC data
1666
1667
1668
1669I found some more data for L-PAC:
1670
1671Formula C9H10O2
1672Composition C, 71.98; H, 6.71; O, 21.31
1673Mol. Weight 150.1745
1674Exact Mass 150.06808
1675
1676and the CAS NR is: 90-63-1
1677
1678
1679if now somebody with STN or BEILSTEIN access, AFAIK anyone living in GB and most people on universities have this for example, could be so kind and look this up and post the properties of L-PAC?
1680
1681thanks
1682ORGY
1683
1684<begin rant>
1685app. 30 seconds after a synth is posted they will come and show you all the goodies with the wise smile and this "we knew all this for long, boy" expression. Lot of Yogis here. Teacherism.
1686<end rant>
1687~ Love is the law, love under will. ~
1688
1689
1690
1691
1692 lugh
1693(Moderator)
169409-29-02 23:31
1695No 362049
1696 Carbinol Data & References
1697
16981-hydroxy-1-phenylacetone, aka Acetylphenylcarbinol, boils at 205-7° C at atmospheric pressure, 135-7° C at 24 mm Hg, 140-5° C at 11 mm Hg and 66° C at .2 mm Hg smile It's miscible with most organic solvents, and more information can be found in JCS 1232 (1930), Ann 484 1 (1930), Compt Rend 198 1998 (1934), Biochem Z 245 238 (1932) & 230 320 (1931) and Bull Soc Chim 43 573 (1928) smilesmile
1699
1700Phenylacetylcarbinol, aka 1-hydroxy-3-phenylacetone has a melting point of 48° C and boils at 144-5° C at 12-13 mm Hg, and more information can be found in Compt Rend 197 1328 & 1649 (1933) laughlaughlaugh
1701
1702
1703
1704 java
1705(Hive Bee)
170612-18-02 17:47
1707No 390532
1708 RE: biotransformation the thread continues
1709
1710Organikum Post No 388164 and there after.......that should have been here , and so it is now!.
1711
1712
1713
1714 roger2003
1715(Stranger)
171601-11-03 15:23
1717No 397227
1718 Industrial Biotransformation: ...
1719
1720Industrial Biotransformation:
1721
1722http://www.ct.utwente.nl/ipp/docs/Papersparasu/2001_SPKP.pdf
1723
1724http://imb.usal.es/castellano/personales/rss/SchmidetalEnzymes2002.pdf
1725roger2003
1726
1727
1728
1729 placebo
1730(not quite as irritable lately)
173101-23-03 23:23
1732No 400937
1733 I apoligise if any of this has already been...
1734
1735I apologise if any of this has already been posted....
1736
1737Here is the relevant bits from the SchmidetalEnzymes2002.pdf in the above post...
1738
1739The flavoenzyme tryptophan 7-halogenase has been evaluated for selective chlorination of tryptophan and indole derivatives. The reaction is thought to proceed via the formation of an epoxide and ring-opening to a chlorohydrin followed by dehydration. Glaxo Wellcome Research and Development reported on the use of nucleoside oxidase. The enzyme was found to have a very broad substrate spectrum towards unnatural nucleosides.
1740
1741Immobilization of the oxidase directly from crude extracts onto Eupergit-C resulted in stabilization of its activity, which also allowed reuse of the enzyme and an easy scale-up of the reaction. An interesting carbon–carbon bond formation reaction was reported for the preparation of (R)-phenylacetylcarbinol by carboligation of pyruvate and benzaldehyde using various pyruvate decarboxylases. Continuous production of (R)-phenylacetylcarbinol from acetaldehyde and benzaldehyde could be achieved using a mutant of pyruvate decarboxylase from Zymomonas mobilis in an enzyme membrane reactor (EMR) with space-time yields of 81g L–1 d–1.
1742
1743Widespread application of enzymes in the chemical industry will depend on the ability to couple enzymatic and chemical steps. Chemoenzymatic reaction sequences profit from the high technical development level of both chemical and enzymatic reactions. DSM uses well-established amidase catalysis to produce enantiopure Cá-tetrasubstituted á-amino acids containing terminal double bonds that react to cyclic oligopeptides by Grubbs olefin metathesis. Lonza uses a sequence of nitrile hydratase catalysis, chemical hydrogenation, and amidase-catalyzed reactions to obtain enantiopure pipecolic and piperazine carboxylic acids from aromatic nitrile precursors. Making biocatalysis compatible with chemical multistep synthesis is one of the important future challenges for this new technology.
1744
1745Conclusions
1746Today, applications of enzymes in the chemical industry are already well established and, given the current developments, the number of biocatalytic processes will continue to increase rapidly. The first hurdle, confidence in the new technology, has been taken and as more and more processes, technology and infrastructure are implemented, efforts in biocatalytic research and development will also increase. This will allow the discovery and application of new enzymes and biological counterparts for traditional chemical reactions and will facilitate the integration of enzymatic steps in chemical multistep syntheses.
1747
1748Biotransformation processes for L-PAC production
1749Prof Peter Rogers
1750
1751Biotransformation processes involving both yeast (Candida utilis) and pyruvate decarboxylase (PDC) are being evaluated for the production of L-phenylacetylcarbinol (L-PAC) from substrates benzaldehyde and pyruvate. L-PAC is an intermediate in the production of the decongestant and antiasthmatic pharmaceuticals, ephedrine and pseudoephedrine. Kinetic models for the process are under development together with a computer-based optimal substrate feeding profile for benzaldehyde.
1752
1753Funding sources: Commercial (ICI 1994-6; other 1997-9)
1754Student involvement: One Postdoctoral Research Fellow and two PhD students, MAppSc and Honours students
1755
1756Recent publications:
1757Shin, H.S. and Rogers, P.L. (1996) Production of L-PAC from benzaldehyde using partially purified pyruvate decarboxylase (PDC). Biotechnol. Bioeng. 49, 52-62.
1758
1759Shin, H.S. and Rogers, P.L. (1996) Kinetic evaluation of biotransformation of benzaldehyde to L-PAC by immobilized pyruvate decarboxylase. Biotechnol. Bioeng. 49, 429-436.
1760
1761Rogers, P.L., Shin, H.S. and Wang, B. (1997) Biotransformation for L-ephredrine production. Adv. Biochem. Eng. 56, 33-60.
1762
1763Liew, M.K.H., Fane, A.G. and Rogers, P.L. (1997) Fouling effects of yeast culture with antifoam agents on microfilters. Biotechnol. Bioeng. 53, 10-16.
1764
1765Liew, M.K.H., Fane, A.G. and Rogers, P.L. (1997) Fouling of microfiltration membranes by broth-free antifoam agents. Biotechnol. Bioeng. 56, 89-98.
1766
1767
1768http://www.biotech.unsw.edu.au/research2.htm
1769
1770
1771http://www.iupac.org/publications/ci/1997/november/review.pdf
1772Here is the details from this one...
1773
1774Environmental biotechnology
1775
1776The November issue also contains selected proceedings of an International Conference on Environmental Biotechnology ‘96 held in Palmerston North, New Zealand, 1–4 September 1996. The published conference papers offer a wide-ranging analysis of the potential of biotechnology to waste treatment, specific perspectives on environmental damage and remediation, industrial research on pollutant mitigation, research into the area of upflow anaerobic sludge blanket reactors, the biological treatment of food industry wastes and two examples of cleaner technology for developments from the pharmaceutical and paper industries. The cleaner technology examples included production of phenylacetylcarbinol (PAC) and production of phenylacetylcarbinol by yeast through productivity improvements and waste minimisation. LPhenylacetylcarbinol is a precursor for the synthesis of L-ephedrine and D-pseudoephedrine, two pharmaceuticals with nasal decongestant properties. LPhenylacetylcarbinol is generated biologically through the pyruvate decarboxylase-mediated condensation of added benzaldehyde with acetaldehyde generated metabolically from feed stock sugars via pyruvate. Some of the added benzaldehyde is converted through the action of alcohol dehydrogenase(s) to benzyl alcohol, an undesired by-product.
1777
1778L-Phenylacetylcarbinol extracted from the fermentation broth is converted chemically by hydroamination in the presence of methylamine and hydrogen to L-ephedrine, and then by isomerization to D-pseudoephedrine. Bruce Anderson and colleagues at the Royal Melbourne Institute of Technology present a dual approach strategy to enhance the ratio of product to by-product generated and to minimize the waste treatment burden of the spent fermentation broth. He explains that benzaldehyde delivery to the fermentation has been modified to ensure that sufficient raw material is available, together with pyruvate, during peak periods of pyruvate decarboxylase activity, and that benzaldehyde is less available during periods of high alcohol dehydrogenase activity. The inorganic content of the spent fermentation broth has been reduced substantially by the partial substitution of raw sugar for molasses in the medium, with a reduction of molasses content by 60% resulting in an increase of phenylacetylcarbinol production.
1779
1780Further work on the optimization of the concentration of carbohydrate, nitrogen and phosphate in the fermentation has been conducted and has led, he claims, to further productivity increases, together with reduced waste generation, resulting in an L-phenylacetylcarbinol process which is considerably ‘cleaner’ than the parent process.
1781
1782Taken from some guy's resume I found in a search engine...
1783
1784Head, Food & Fermentation Technology Division.
1785
1786The project dealt with the biotransformation of benzaldehyde to L- phenyl acetyl carbinol (synthon for various drugs) using yeast isolate. Various aspects like standardization of the method of analysis, purification and identification of product & byproducts of the biotransformation using various techniques were standardised. Using yeast isolate, various process parameters for increasing yield of the product and reusability of the biocatalyst were studied. A novel immobilization method for the aforesaid biotransformation was standardised and the process parameters using immobilized cell system studied. The mass transfer coefficient, power consumption and hold up in a stirred tank reactor with a dual impeller system were studied for the growth and biotransformation medium and were compared with those for air-water system.
1787
1788After establishing the correlation between these operating parameters, a scaling up of this biotransformation to 5 L was achieved in a systematic manner. Work was also carried out on the synthesis of various chiral compounds using a combination of chemical synthesis and biotransformation using Rhizopus arrhizus.
1789
1790to be continued.
1791Intelligence is not the recall of knowledge, but the ability to use it. (Rainman was a retard)
1792
1793
1794
1795 placebo
1796(not quite as irritable lately)
179701-23-03 23:40
1798No 400943
1799 From http://www.swsbm.com/Abstracts/Ephedra-AB....
1800
1801From
1802http://www.swsbm.com/Abstracts/Ephedra-AB.txt
1803
1804*****ADVANCES IN BIOCHEMICAL ENGINEERING/BIOTECHNOLOGY*****
1805Rogers PL Shin HS Wang B
1806Biotransformation for L-ephedrine production.
1807In: Adv Biochem Eng Biotechnol (1997) 56:33-59
1808ISSN: 0724-6145
1809
1810L-ephedrine is widely used in pharmaceutical preparations as a decongestant and anti-asthmatic compound. One of the key intermediates in its production is L-phenylacetylcarbinol (L-PAC) which can be obtained either from plants (Ephedra sp.), chemical synthesis involving resolution of a racemic mixture, or by biotransformation of benzaldehyde using various yeasts. In the present review, recent significant improvements in the microbial biotransformation are assessed for both fed-batch and continuous processes using free and immobilised yeasts. From previous fed-batch culture data, maximal levels of L-PAC of 10-12 gl-1 were reported with yields of 55-60% theoretical based on benzaldehyde. However, recently concentrations of more than 22 gl-1 have been obtained using a wild-type strain of Candida utilis. This has been achieved through optimal control of yeast metabolism (via microprocessor control of the respiratory quotient, RQ) in order to enhance substrate pyruvate production and induce pyruvate decarboxylase (PDC) activity.
1811
1812Processes involving purified PDC have also been evaluated and it has been demonstrated that L-PAC levels up to 28 gl-1 can be obtained with yields of 90-95% theoretical based on the benzaldehyde added. In the review the advantages and disadvantages of the various strategies for the microbial and enzymatic production of L-PAC are compared. In view of the increasing interest in microbial biotransformations, L- PAC production provides an interesting example of enhancement through on-line control of a process involving both toxic substrate (benzaldehyde) and end-product (L-PAC, benzyl alcohol) inhibition.
1813
1814Registry Numbers:
1815EC 4.1.1.1 (Pyruvate Decarboxylase)
1816100-52-7 (benzaldehyde)
1817299-42-3 (Ephedrine)
181867-64-1 (Acetone)
181990-63-1 (1-hydroxy-1-phenyl-2-propanone)
1820
1821Taken from http://www.ephedra.nu/engels/
1822Also found same info mirrored here...
1823http://www.r00t-access.org/texts/ephedrine.html
1824First site is interesting site devoted completely to ephedrine.
1825
1826Synthesis of ephedrine
1827======================
1828
1829Actively fermenting yeast transforms benzaldehyde into L-phenylacetylcarbinol (L-PAC), which can be reductively aminated to afford ephedrine or phenypropa-nolamine (depending on the amine used)
1830---------------------------------------------------------------------------
1831
1832Title: ISOLATION, ANALYSIS, AND SYNTHESIS OF EPHEDRINE AND ITS DERIVATIVES
1833
1834Abstract: A review is given of methods for the isolation, quantitative determination, and modification of the ephedrine alkaloids, and advances in this field of natural compound chemistry.
1835
1836Author: Gazaliev, A. N.; Zhurinov, M. Zh.; Fazylov, S. D.; Balitskii, S. N.
1837Reference: Chem.Nat.Compd.(Engl.Transl.), 25, 3, 1989, 261-271
1838--------------------------------------------------------------------------
1839
1840Title: The biosynthesis of ephedrine
1841
1842Abstract: It is shown by 13C nuclear magnetic resonance spectroscopy that the labelled C2 fragment of <2,3-13C2>pyruvic acid is transferred intact into the C-methyl group and the adjacent carbon atom of the Ephedra alkaloids, norephedrine, ephedrine, norpseudoephedrine, and pseudoephedrine, in growing plants of Ephedra gerardiana.This finding serves to identify pyruvate as the elusive precursor of the aliphatic C2 terminus of the skeleton of the alkaloids.In earlier experiments with 14C-labelled substrates, label from <3-14C>pyruvic acid was incorporated mainly, but not exclusively, into the C-methyl group of ephedrine, and label from <2-14C>pyruvate was incorporated similarly into the carbon atom adjacent to the C-methyl group.A C6-C1 unit related to benzaldehyde or benzoic acid has long been known to generate the benzylic fragment of the carbon skeleton of the Ephedra alkaloids.It is likely that the carbon skeleton of ephedrine is generated from pyruvate and either benzaldehyde or benzoic acid, by a reaction analogous to the formation of acetoin or diacetyl from pyruvate and acetaldehyde or acetic acid, respectively.Key words: biosynthesis of ephedrine, Ephedra alkaloids, 13C NMR spectra, ephedrine, biosynthesis of pyruvic acid, incorporation into ephedrine 13C NMR spectra.
1843
1844Grue-Sorensen et al, Can.J.Chem., EN, 67, 1989, 998-1009
1845--------------------------------------------------------------------------------
1846
1847Stereoselectrive Syntheses of Ephedrine and Related 2-Aminoalcohols of High Optical Purity from Protected Cyanohydrins
1848
1849Abstract: Ephedrine and related optically active b-aminoalcohols can be prepared by zinc borohydride reduction of aryl O-protected magnesium imines and aryl a-hydroxyimimes which in turn are readily available from optically active cyanohydrins.
1850
1851Jackson et al, Tetrahedron Lett., 31, 10, 1990, 1447-1450
1852-------------------------------------------------------------------------
1853
1854Title: SYNTHESIS OF EPHEDRINE (DIALKYL PHOSPHOROTHIOATE)S. CRYSTALLOGRAPHIC STRUCTURE OF EPHEDRINE (DIETHYL PHOSPHOROTHIOATE)
1855
1856Abstract: The synthesis of ephedrine (dialkyl phosphorothioate)s has been effected.The method of their preparation and their properties are described.The IR and PMR spectra of ephedrine (dialkyl phosphorothioate)s and some results of an x-ray structural investigation of the spatial structure of ephedrine (diethylphosphorothioate) are given.
1857-----------------------------------------------------------------------
1858
1859Methods for Biocatalyst Screening
1860[url]http://www.google.com/search?q=cache:mMkB389mue4C:link.springer-ny.com/link/service/series/0010/papers/2074/20740001.pdf+1-hydroxy-1-phenyl-2-propanone&hl=en&ie=UTF-8[/url]
1861
1862Again, sorry if some is redundant, I tried to check everything back thru this thread, but it's a bit of a mission. It seems as though the limited amount of info on the net regarding this matter is mostly the same stuff.
1863
1864Intelligence is not the recall of knowledge, but the ability to use it. (Rainman was a retard)
1865
1866
1867 Organikum
1868(Hive Addict)
186901-24-03 09:44
1870No 401069
1871 The most effective way to L-PAC
1872
1873
1874The most effective way to do this biotransformation is:
1875benzaldehyde + acetaldehyde + molasses + brewers wort + some salts
1876whereby:
1877benzaldehyde from toluene and/or benzylalcohol
1878acetaldehyde from ethylalcohol
1879Yields up to 70% on benzaldehyde. But who minds if less, as the benzaldehyde not converted to L-PAC gets converted to benzylalcohol which can be oxidized to benzaldehyde again quite easily. Without acetaldehyde yields are cut by half.
1880Java has linked to the post with the writeup, if some is interested in the details. To the writeup is to add that it is not necessary to distill the L-PAC as written, but the extract from the fermentation broth can be reductive animated as is. No strong vacuum pump necessary! Tested with Al/Hg reductive alkylation.
1881
1882The method is unbeaten by now (except by pure separated enzymes, >90% but extreme expensive).
1883
1884Great work Placebo! Quite comprehensive, real good work.
1885ORG
1886
1887
1888
1889Post 399486 (not existing)
1890
1891
1892
1893
1894 placebo
1895(not quite as irritable lately)
189601-24-03 12:26
1897No 401090
1898 Re: I will be happy if I would get the L-PAC...
1899
1900 I will be happy if I would get the L-PAC properties
1901
1902
1903Tell me about it, I looked for about 12 hours today!
1904
1905Org, check if there is anything useful on that last link and save it, otherwise it will disappear from the cache and the .pdf has to be paid for.
1906Intelligence is not the recall of knowledge, but the ability to use it. (Rainman was a retard)
1907
1908
1909
1910 Organikum
1911(Hive Addict)
191201-24-03 15:24
1913No 401113
1914 What Rhodium sent me
1915(Rated as: excellent)
1916
1917 (R)-(+)-Mandelic acid + MeLi -> (+)-acetylphenylmethanol (45%)
1918 Tetrahedron Lett.; EN; 28; 50; 1987; 6313-6316.
1919
1920 (R)-(-)-1-hydroxy-1-phenyl-2-propanone, bp 72-74°C/0.2mmHg
1921 Collect.Czech.Chem.Commun.; EN; 55; 8; 1990; 2046-2051.
1922 Collect.Czech.Chem.Commun.; EN; 55; 11; 1990; 2685-2691.
1923
1924 1-phenyl-propane-1,2-dione -H2/Pt/Al2O3-> (S)-(+)-1-hydroxy-1-phenyl-2-propanone
1925 J.Catal.; EN; 204; 2; 2001; 281 - 291.
1926
1927 Constitution
1928 Justus Liebigs Ann. Chem.; 526; 1936; 143, 170.
1929 Biochem.Z.; 127; 1922; 338.
1930 Chem.Zentralbl.; GE; 111; II; 1940; 1860.
1931
1932 (RS)-1-Hydroxy-1-phenyl-aceton (racemic), mp 9.5-11°C (ether, pentane)
1933 Can.J.Chem.; EN; 68; 11; 1990; 2060-2069.
1934
1935 (RS)-1-Hydroxy-1-phenyl-aceton:
1936 Boiling Point mmHg Reference
1937 66°C 0.2 1
1938 236-238°C 760 2
1939 143-145°C 31 3
1940 130-132°C 20 4
1941 124°C 14 2
1942 129-131°C 14 5
1943 129-130°C 13 6
1944 106-108°C 7 7-8
1945 104-106°C 6 9
1946
1947 Ref. 1 J.Amer.Chem.Soc.; 73; 1951; 4284.
1948 Ref. 2 Justus Liebigs Ann. Chem.; 526; 1936; 143, 170.
1949 Ref. 3 Biochem.Z.; 127; 1922; 338.
1950 Ref. 4 Bull.Soc.Chim.Fr.; <4> 33; 1923; 770, 771;
1951 C.R.Hebd.Seances Acad.Sci.; 176; 1923; 313.
1952 Ref. 5 Zh.Obshch.Khim.; 27; 1957; 1622,1625;engl.Ausg.S.1694,1697.
1953 Ref. 6 Mem.Inst.Sci.Ind.Res.Osaka Univ.; 6; 1948; 96, 98.
1954 Ref. 7 Yakugaku Zasshi; 77; 1957; 851,853; Chem.Abstr.; 1958; 1949.
1955 Ref. 8 Yakugaku Zasshi; 76; 1956; 1250, 1253; Chem.Abstr.; 1957; 4309.
1956 Ref. 9 Zh.Obshch.Khim.; 21; 1951; 183,185;engl.Ausg.S.199,201.
1957
1958 (R)-1-Hydroxy-1-phenyl-aceton
1959 Boiling Point mmHg Ref:
1960 65-67°C 0.4 1
1961 100-102°C 0.01 2
1962 123-124°C 12 3
1963 124-125°C 12 4
1964 118-119°C 8 5-6
1965
1966 Ref. 1 J.Med.Chem.; EN; 7; 1964; 427-433.
1967 Ref. 2 Collect.Czech.Chem.Commun.; EN; 37; 1972; 3897-3901.
1968 Ref. 3 Chem.Zvesti; 12; 1958; 687; Chem.Abstr.; 1959; 11289.
1969 Ref. 4 Biochem.Z.; 127; 1922; 133.
1970 Ref. 5 Chemia anal.; 3; 1958; 573; Chem.Abstr.; 1959; 13841.
1971 Ref. 6 Chem.Zvesti; 12; 1958; 17,19; Chem.Abstr.; 1958; 10768.
1972
1973
1974
1975Thats on the properties. Plus what lugh posted.
1976some tidbits out of patents and articles:
1977- L-PAC racemizes fast under basic conditions and higher temperatures. So keeping fermentation temperatures low and ph as acidic as possible (4,3 - 4,7, whereby 4,3 is only possible with yeast harvested in acidic enviroment). On the other side this offers a perfect way to tune your gear after your personal preferences. smile
1978- Useful for extraction of L-PAC from the fermentation broth are most nonpolar solvents as: (diethyl-)ether, petrolether, DCM and ethyl acetate. A continous extraction is favorable at low temperatures one can also boil away some of the water as long not dealing with serious amounts to synthesize. Salting out helps a lot.
1979- The yeast may be washed and reused after the fermentation one or two times, then undergo autolysis to gain yeast extract useful as feed in following fermentations. The extract reduces the needed amounts of salts and brewers wort.
1980- The yeast to use is not critical. Bakers yeast from the supermarket. Harvesting this yeast under acidic conditions aka adding up to 3% sulfuric acid hardens the yeast and makes a ph as low as 4,3. possible (if not hardened ph 4,7 to 5,2).
1981
1982what brings up this sudden interest again I wonder?
1983perhaps the wintertime
1984ORG
1985
1986Placebo: 12 hours? I tried it 2 weeks and didn´t get anything some time ago...
1987Post 399486 (not existing)
1988
1989
1990
1991
1992 java
1993(Hive Bee)
199402-03-03 23:13
1995No 404101
1996 Re: biosynth-transformation
1997
1998I thought I bring in this piece of the puzzle to this thread since it seems to fit in in the quest to a source of starting material......the elusive Ephedrine Hcl,
1999
2000Organikum fills in some more pieces to the puzzle, here...java
2001
2002Post 400469 (Organikum: "L-PAC reductive alkylation", Novel Discourse)
2003
2004
2005
2006 roger2003
2007(Newbee)
200802-19-03 18:18
2009No 409782
2010 Toluenes to aldehydes by peroxidase
2011
2012Benzylic biooxidation of various toluenes to aldehydes by peroxidase
2013
2014Russ, Rainer; Zelinski, Thomas; Anke, Timm
2015Tetrahedron Lett. 2002, 43: 5 791 – 794
2016
2017A catalytic method is described for the oxidation of toluene and substituted derivatives to the corresponding benzaldehydes by hydrogen peroxide, using peroxidase. In most cases the respective benzoic acid was produced as a byproduct. The reaction proceeds under mild conditions in an aqueous medium.
2018
2019
2020
2021
2022 StraightEdge
2023(Hive Addict)
202404-20-03 01:34
2025No 428138
2026 Benzylic biooxidation of various toluenes to aldeh
2027
2028Substituted benzaldehydes are often used as feedstock in industrial chemistry. The selective oxidation of aromatic methyl groups to the respective aldehyde is, however, difficult.[1] The chemical oxidation of the methyl group commonly proceeds directly to the carboxylic acid. We therefore chose to investigate enzymatic methods, because enzymes can be chemoselective. We started with the laccase/2,2-azino-bis(3-ethylbenzthiazoline-6-sulfonic acid) (ABTS) system of Potthast et al. [2] However, with toluene and laccase from different fungi, such as Bjerkandera adusta, Coriolus sp., Phellinus sp., and Pleurotus ostreatus, we found no transformation at all, which is in accordance with the findings of Fritz-Langhals and Kunath.[3] Subsequently, we tried several peroxidases with hydrogen peroxide as the oxidant. Using lignin peroxidase from Phanerochaete chrysosporium[4] or Coprinus cinereus,[5] we found no transformation of toluene. Chloroperoxidase from Caldariomyces fumago gave a slight transformation to benzyl alcohol and benzaldehyde, as reported earlier.[6 and 7] Finally, peroxidases isolated from a Coprinus species of our strain collection were able to catalyze the transformation of toluene to benzaldehyde and, only to a minor extent, benzoic acid (Table 1).
2029
2030The transformation of 21 different substituted methyl aromatics by hydrogen peroxide and Coprinus peroxidase was tested. Only three of the compounds tested, p-cymene (4-isopropyl-toluene), m-cresol, and p-cresol, were not at all transformed into the corresponding benzaldehydes. All other 18 compounds were transformed into the respective benzaldehydes whereby the efficiency of the reaction varied (Table 1). Suitable substituents comprised methyl, halogen, methoxy, and nitro groups. It seems that the position of the substituent was more important than its composition. Ortho or para positions of the substituent to the methyl group were preferred against meta, except for the nitrotoluenes. o-Nitrobenzaldehyde was obtained in a low yield, whereas m-nitrobenzaldehyde was formed with yields comparable to the p-isomer. In the case of o-nitrotoluene, an interaction of the intermediate methyl cation radical with the nitro group perhaps prevented the formation of the aldehyde. o-Nitrotoluene was the only substrate that produced the alcohol derivative. The cresols were found not suitable for catalytic conversion by Coprinus peroxidase and hydrogen peroxide, probably due to polymerization reactions as described for lignin peroxidase.[4] The preparation with o-cresol immediately turned yellow after addition of the enzyme. A weaker discoloration to yellow was observed for m- and p-cresol, as well as toluene, 3-chloro-, 4-methoxy-, and 4-fluorotoluene. p-Cymene was transformed into two compounds that were not identified. A molecular mass of 132 and 136 inferred that none of the compounds was either an aldehyde- or carboxyl-derivative of p-cymene.
2031
2032In summary, the method presented here used Coprinus peroxidase and hydrogen peroxide to oxidize a variety of toluene derivatives to their corresponding aldehydes. Further studies are underway to characterize the enzyme responsible, as well as improving the reaction conditions to provide better yields.
2033
2034References
20351. W.J. Mijs and C.R.H.I. de Jonge. Organic syntheses by oxidation with metal compounds, Plenum, London (1986).
2036
20372. A. Potthast, T. Rosenau, C.-L. Chen and J.S. Gratzl. J. Org. Chem. 60 (1995), pp. 4320–4621.
2038
20393. E. Fritz-Langhals and B. Kunath. Tetrahedron Lett. 39 (1998), pp. 5955–5956. Abstract | PDF (107 K)
2040
20414. M. Tien and T.K. Kirk. Proc. Natl. Acad. Sci. USA 81 (1984), pp. 2280–2284.
2042
20435. F. van Rantwijk and R.A. Sheldon. Curr. Opin. Biotechnol. 11 (2000), pp. 554–564. SummaryPlus | Full Text + Links | PDF (234 K)
2044
20456. V.P. Miller, A. Tschirret-Guth and P.R. Ortiz de Montellano. Arch. Biochem. Biophys. 319 (1995), pp. 333–340. Abstract | PDF (735 K)
2046
20477. J. Geigert, D.J. Dalietos, S.L. Neidlman, T.D. Lee and J. Wadsworth. Biochem. Biophys. Res. Comm. 114 (1983), pp. 1104–1108. Abstract-MEDLINE
2048
2049There is a graphical abstract and a table that I can put up if anyone is interested.
2050
2051
2052
2053 roger2003
2054(Hive Bee)
205507-10-03 12:27
2056No 446145
2057 Phenylacetylcarbinol
2058
2059Benzaldehyde (0,010 g, 0,1 mmol), sodiumpyruvate (0,205g), baker`s yeast (0,415 g) and citrate buffer (0,415 ml, pH 6) was placed into a 15 ml stainless steel vessel. The vessel was pressurised to 2000 psi by pumping dried liquid carbon dioxide into the vessel and stirred for 24 h at 33° C.
2060
2061The vessel was than cooled to RT an slowly degassed.
2062
206382% yield of Phenylacetylcarbinol
2064
2065US Pat 2003/0077769 Apr. 24, 2003
2066
2067Patent WO0144486
2068
2069
2070
2071 Osmium
2072(Stoni's sexual toy)
207307-10-03 18:00
2074No 446214
2075 I love 10mg synths. Let's scale this one up by
2076
2077I love 10mg synths.
2078
2079Let's scale this one up by a factor of 1000:
2080
2081Benzaldehyde (10g), sodiumpyruvate (205g), baker`s yeast (415 g) and citrate buffer (415 ml, pH 6) was placed into a 15 l stainless steel vessel. The vessel was pressurised to 2000 psi (150 bar) by pumping dried liquid carbon dioxide into the vessel and stirred for 24 h at 33° C.
2082The vessel was than cooled to RT an slowly degassed.
2083(Note: not one word about workup of the glob of slime, how to keep it from foaming all over the place etc...)
208482% yield of Phenylacetylcarbinol.
2085I'm not fat just horizontally disproportionate.
2086http://www.whatreallyhappened.com
2087
2088
2089
2090 roger2003
2091(Hive Bee)
209207-10-03 18:32
2093No 446222
2094 Workup and Vessel
2095
2096The workup in the patent (example 1) was carried out by radial chromatography, but in the above theads are a lot of methods for the workup.
2097
2098You think, you need a vessel about 15 l for a 10 g (benzaldehyde) synthesis ?
2099
2100I think it is only a question of the pressue (CO2) and you can take a 3-4 l vessel for a 30 g (benzaldehyde) synthesis.
2101roger2003
2102
2103
2104
2105 Osmium
2106(Stoni's sexual toy)
210707-10-03 19:44
2108No 446239
2109 Probably so. The CO2 should be supercritical...
2110
2111Probably so. The CO2 should be supercritical at that pressure (I think), so it will also act as a solvent. It's not the pressure that counts, some volume is definitely needed.
2112I'm not fat just horizontally disproportionate.
2113http://www.whatreallyhappened.com
2114
2115
2116
2117 maple_honey
2118(Stranger)
211910-09-03 08:10
2120No 463523
2121 Reductive amination
2122
2123So, has anyone tried using the Sodium Borohydride reduction with methylamine? Works with amazing yield for MDMA so is this a viable reduction method for L-PAC? I always thought this to be the best high yield, large scale amination I had seen. And let's face it, if one is going to go through all these hassles to produce a relatively valueless product such as ephedrine, when it can be acquired easier than one might think, it should be done on a large scale to justify the procedure. To me it does not seem much easier than the conversion of safrole to MDMA using a good wacker oxidation method yet it is worth far less.
2124Go Hard Or Go Home
2125
2126
2127
2128 BOS
2129(Stranger)
213010-09-03 10:06
2131No 463553
2132 I thought Id throw this patent up while we`re...
2133
2134I thought Id throw this patent up while we`re at it.
2135It might be of interest of those out there who are lazy like me.Sorry If it has been posted previously.
2136
2137It describes a simular process as above,only it claims it can be worked in in non fermenting conditions,using common solvents at lower temps. Patent US6271008
2138
2139Recycling may raise yield,but still, it looks a lot more like tweeer chemistry than ever before.
2140Sorrywink
2141
2142
2143
2144 roger2003
2145(Hive Bee)
214610-09-03 12:19
2147No 463560
2148 Pyruvic Acid
2149
2150Pyruvic acid [127-17-3] , 2-oxopropanoic acid, pyroracemic acid, a-ketopropionic acid, H3C–CO–COOH, Mr 88.06, is the most important a-oxocarboxylic acid. It plays a central role in energy metabolism in living organisms [8]. During exertion, pyruvic acid is formed from glycogen in the muscle and reduced to lactic acid [79-33-4]. In the liver, pyruvic acid can be converted into alanine [56-41-7] by reductive amination. Pyruvic acid was discovered and first described in 1835 by BERZELIUS [9].
2151Pyruvic acid is totally miscible with water, ethanol, and ether. Pyruvic acid exists in the keto form; the enol form cannot be detected [10].
2152
2153Chemical Properties Pyruvic acid reacts as both an acid and a ketone. It forms, for example, oximes, hydrazones, and salts. 4,5-Dioxo-2-methyltetrahydrofuran-2-carboxylic acid [24891-71-2] is formed from pyruvic acid either slowly on standing or more quickly under acid catalysis [11].
2154
2155On standing in aqueous solution, pyruvic acid polymerizes to higher molecular mass products via the dimeric ketoglutaric acid [19071-44-4] and the trimeric aldol product [12] , [13].
2156Like all 2-oxo acids, pyruvic acid eliminates carbon monoxide on treatment with concentrated sulfuric acid [14].
2157Oxidation of pyruvic acid gives acetic or oxalic acid [144-62-7] and carbon dioxide, depending on the conditions [15]. Lactic acid is obtained by reaction with reducing agents [1].
2158Reaction of a-amino acids with pyruvic acid gives, besides carbon dioxide, alanine [56-41-7] (transamination reaction) and the corresponding aldehyde with one carbon atom less [16]. Alanine is also obtained by reductive amination of pyruvic acid [1]. Phenylethylamines react with pyruvic acid to form the corresponding tetrahydroisoquinolines via the Bischler – Napieralski reaction [17]. Reaction with o-phenylenediamines gives quinoxalinols [18]. In a similar reaction the corresponding hydroxypteridines are obtained from 4,5-diaminopyrimidines and pyruvic acid [19]. Pyruvic acid reacts with aldehydes to form the corresponding a-keto-g-hydroxy acids, which then cyclize to butyrolactone derivatives [1] . Friedel – Crafts type reactions of aromatic compounds with pyruvic acid yield diarylpropionic acids. These compounds have achieved a certain degree of importance because they provide a good route to 1,1-diarylethylenes by dehydration and decarbonylation [15] , [20].
2159
2160
2161Production On an industrial scale, pyruvic acid is produced by dehydration and decarboxylation of tartaric acid [87-69-4] [21]. In this process, pyruvic acid is distilled from a mixture of tartaric acid and potassium and sodium hydrogen sulfates at 220 °C. The crude acid obtained (ca. 60 %) is then distilled in vacuum. The reaction temperature can be lowered to 160 °C by adding ethylene glycol [107-21-1] [22]. Pyruvic acid can also be obtained by the gas-phase oxidation of lactic acid [23] , but this process has not been successful industrially. In contrast, microbial oxidation of D-lactic acid by a new process results in high yields [24]. Microbial oxidation of 1,2-propanediol [57-55-6] to pyruvic acid has also been described [25]. Another process describes the hydrolysis of 2,2-dihalopropionic acids to pyruvic acid [26]. A process for the oxidation of methylglyoxal [78-98-8] with halogens has recently been published [27].
2162
2163Uses Pyruvic acid is used mainly as an intermediate in the synthesis of pharmaceuticals. It is also employed in the production of crop protection agents, polymers, cosmetics, and foods.
2164
2165Storage and Quality Specifications Pyruvic acid is stored and transported in tightly closed polyethylene containers. It can be kept for only a limited period and must therefore be stored in refrigerated areas at a maximum of 10 °C. At higher temperature, explosion can occur through spontaneous self-condensation [28]. The concentration of the commercial product is determined acidimetrically and decreases by ca. 1 % per month during storage.
2166
2167Toxicology Pyruvic acid has a corrosive effect and irritates the eyes, skin, and respiratory passages.
2168
2169
2170[1] A. J. L. Cooper, J. Z. Ginos, A. Meister, Chem. Rev. 83 (1983) 321.
2171[8] K. Schreiber: Die Brenztraubensäure und ihr Stoffwechsel, Editio Cantor, Aulendorf 1956.
2172[9] J. J. Berzelius, Ann. Phys. 36 (1835) 1.
2173[10] A. Schellenberger, K. Winter, Chem. Ber. 92 (1959) 793.
2174[11] L. Wolff, Justus Liebigs Ann. Chem. 317 (1901) 1.
2175[12] H. Goldfine, Biochim. Biophys. Acta 40 (1960) 557.
2176[13] A. Schellenberger, E. Podany, Chem. Ber. 91 (1958) 1781.
2177[14] A. Bistrzycki, B. v. Siemiradzki, Ber. Dtsch. Chem. Ges. 39 (1906) 58.
2178[15] S. Patai, S. Dayagi, J. Chem. Soc. 1958, 3058.
2179[16] R. M. Herbst, L. L. Engel, J. Biol. Chem. 107 (1934) 505.
2180[17] G. Hahn, A. Hansel, Ber. Dtsch. Chem. Ges. 71 (1938) 2163.
2181[18] O. Hinsberg, Justus Liebigs Ann. Chem. 237 (1887) 327.
2182[19] G. B. Elion, G. H. Hitchings, P. B. Russel, J. Am. Chem. Soc. 72 (1950) 78.
2183[20] Bayer, Patent DE2830953 , 1978 (W. Meyer, H. Rudolf, E. Cleur, E. Schoenhals). = Patent US4369206
2184[21] J. W. Howard, W. A. Fraser, Org. Synth. Coll. Vol. 1 , 475. http://www.orgsyn.org/orgsyn/prep.asp?prep=cv1p0475
2185[22] J. D. Riedel, Patent DE281902 , 1913.
2186[23] C. H. Boehringer Sohn, Patent DE523190 1931 (F. Zumstein).
2187[24] BASF, Patent EP313850 1988 (B. Cooper).
2188[25] Y. Izumi, Y. Matsumura, Y. Tani, H. Yamada, Agric. Biol. Chem. 46 (1982) 2673.
2189[26] Dow Chemical, Patent US3524880 1966 (L. H. Lee, D. E. Ranck).
2190[27] BASF, Patent DE3219355 1982 (U. R. Samel, L. Hupfer).
2191[28] Sichere Chemiearbeit 29 (1977) 87.
2192
2193
2194
2195 lugh
2196(Moderator)
219711-01-03 22:45
2198No 468182
2199 Single Cell Proteins
2200
2201While there are some changes necessary in the inputs and outputs for producing L-PAC, as opposed to simply growing yeast for protein; this article by Litchfield about culturing single cell proteins should bee very helpful in gaining understanding of what's required wink
2202
2203
2204Bacteria are also capable of growing on a variety of raw materials, ranging from carbohydrates such as starch, and sugars, to gaseous and liquid hydrocarbons such as methane and petroleum fractions, to petrochemicals such as methanol and ethanol. Suitable nitrogen sources for bacterial growth include ammonia, ammonium salts, urea, nitrates, and the organic nitrogen in wastes. A mineral nutrient supplement must be added to the bacterial culture medium to furnish nutrients that may not be present in natural waters in concentrations sufficient to support growth.
2205The bacterial species most likely to be used for singly-cell protein production grow best in slightly acid to neutral pH in the range 5 to 7. The bacteria should also be able to tolerate temperatures in the 35 to 45 C range, because heat is released during the bacterial growth. The use of temperature-tolerant strains will minimize the need for refrigerating the water that cools the fermentation vessel. Bacterial species cannot be used for single-cell protein production if they are pathogenic for plants, animals or humans.
2206Bacterial single-cell protein may be produced in conventional hatch systems in which all of the nutrients are supplied to the fermentor initially; the cells are harvested when they have conÂsumed the nutrients and stopped growing. However, in the more advanced production methods the nutrients are supplied continuously in the concentrations needed to support bacterial growth and the cells are harvested continuously once the popuÂlation reaches the desired concentration.
2207The concentration of the carbon and energy source usually ranges from 2 to 10 per cent in batch processes. In the continuÂous process the supply of the carbon source is regulated so that the concentration in the growth medium does not exceed that required by the growing bacterial cells. This concentration will generally be lower than those used in batch processes.
2208Maintaining sterile conditions during single-cell protein proÂduction is very important because contaminating microorganisms grow very well in the culture medium. The incoming air, the nutrient medium and the fermentation equipment must be sterilized in all bacterial single-cell protein processes, and sterile conditions; must be maintained throughout the producÂtion cycle.
2209In continuous processes the nutrients are replenished as they are consumed to maintain the concentrations needed by the bacteria. The solution containing the bacteria is drawn off, treated to cause the bacteria to agglomerate or flocculate, and centrifuged. The liquid may then be recycled in the fermentor while the bacteria are spray-dried and ground to yield the final product.
2210After the nutrients are sterilized and intoduced into a fermentation vessel and inoculated with the bacteria to be grown. The vessel, which is known as a 'bioreactor', must be supplied with sterile air and with cooling water to prevent the heat released during fermentation from building up and killing the cells. The cooling water is circulated in either the outer jacket of the fermentor or through internal cooling coils.
2211The vessels are also fitted with instruments that measure and control the pH and temperature of the contents and the concentÂration of dissolved oxygen. The exhaust air from the bioreactor contains carbon dioxide that may be separated and compressed for sale to industrial users of carbon dioxide.
2212After the bacteria are removed from the fermentation tank, they must he separated from the culture broth, which is usually done by adding chemicals that will cause the cells to clump and then centrifuging them. The separated cells are dried to yield a product that will be stable during shipment and storage. Finally, there must be equipment for grinding and packaging the cells and a system for treating and recycling the spent culture fluid.
2213Oxygen transfer to the cells in the fermentor is a critical factor in obtaining growth rates and yields that are economically satisfactory. A variety of fermentor designs can provide suitable aeration. The most commonly used are the baffled stirred-tank reactor and the air-lift fermentor.
2214Although considerable research was conducted on the production of bacterial single-cell protein during the 1960s and early 1970s, Imperial Chemical Industries (ICI) in the United Kingdom developed the only process to reach a commerÂcial scale of operation. In the ICI process the bacterium Methylophilas methvlotrophus, which has a generation time of about 2 hours, is grown continuously with methanol as the substrate and additional nutrients including ammonia and the minerals phosphorus, calcium and potassium. The company developed for the process a unique air-lift fermentor with a capacity of 1500 cubic metres. The fermentor design minimizes the requirements for cooling the vessel and the problem of oxygen limitation.
2215Schematic diagram of a baffled stirred tank fermentor. The air introduced into the fermentor is dispersed by the propellor-like agitator. The baffles projecting from the side of the tank shown in cross-sectional view help to ensure that the contents of the tank are thoroughly mixed and oxygenated.
2216
2217
2218
2219In 1980 ICI commissioned a plant, with the capacity of proÂdicing 50 000 metric tons of single-cell protein every year, at Billingham, England. The plant has since been operated interÂmittently, with a production of 6000 metric tons per month. The bacteria grow on methanol as their energy source. Two metric tons of methanol yield about 1 metric ton of dry 'Pruteen' single-cell protein. The dried product, which contains about 72 per cent protein and 8 per cent moisture, has been sold as an animal feed supplement in Western European markets.
2220With soybean meal now costing just $190 per metric ton, however, 'Pruteen' is no longer competitive as an animal feedstuff and the plant is not being operated on a commercial scale at present. Nevertheless the development of the ICI process for making the bacterial single-cell protein exemplifies the application of modern chemical engineering to the field of biotechnology.
2221During the development of 'Pruteen' ICI scientists investigated the possibility of improving the conversion of methanol it single-cell protein by genetically modifying the ability of M. methvlotrophus to use ammonia. They introduced into the bacÂteria a gene for an ammonia-assimilating enzyme that is more efficient than the endogenous bacterial enzyme. Although the new gene was stable in the bacteria and was expressed there, only a 3 to 5 per cent increase in single-cell protein yield was, obtained with the genetically modified strain of bacteria.
2222Yeasts
2223Modern technology for producing yeast single-cell protein has largely developed since World War II. Today, yeast products for human or animal consumption are produced on a commerÂcial scale in many countries. In addition, baker's yeast, which is grown on molasses, is sold as a food flavouring and nutritive ingredient in addition to being used as a leavening agent.
2224Yeast can be grown on a number of substrates. These include carbohydrates, both of the complex type, such as starch, and of the simple type, such as the sugars glucose, sucrose and lactose. Alternatively, sugar-containing raw materials such as corn syrup, molasses and cheese whey can be used. Some yeasts are able to grow on straight-chain hydrocarbons, which are obtained from petroleum, or on ethanol or methanol.
2225In addition to a carbon source, a nitrogen source is required. The nitrogen can be provided by addition of ammonia or ammonium salts to the culture medium. A supplement of minÂeral nutrients is also required.
2226The requirements for production of yeast single-cell protein are similar to those previously described for production by bacteria. The yeast should have a generation time of about 2 to 3 hours. It should he pH- and temperature-tolerant and genetically stable, giving satisfactory yields from the substrate used, and not cause disease in plants, animals or humans.
2227The, technology for producing yeast single-cell protein is also similar to that for making the bacterial products. The baffled, stirred-tank fermentor is the most common type of vessel for yeast single-cell protein production, but air-lift fermentors are also used. As in the bacterial cultures, heat is released during yeast growth and the fermentor must be proÂvided with a cooling system.
2228The yeast fermentations may be operated either in the batch or continuous mode, or by a third mode called 'fed-batch'. In fed-batch processes the substrate and other nutrients are added in an incremental manner to meet the growth requirements of the yeast while maintaining very low nutrient concentrations in the growth medium at any time. This method yields 3.5 to 4.5 per cent dry weight of product compared with the 1.0 to 1.5 dry weight of product yielded by batch cultivation. Cells grown by fed-batch processes are harvested as they are in the batch: mode of production.
2229
2230Although batch and fed-batch culture systems have been used in baker's yeast production for many years, only recently has the technology been available for monitoring and adjusting the pH and substrate concentrations to permit the continuous type of operation. Yeast cell concentrations of up to 16 per cent (dry weight) can be obtained in the continuous culture operaÂtions.
2231Yeasts have certain advantages over bacteria for production of single-cell protein. For one, the yeasts tolerate a more acid environment, in the range of 3.5 to 4.5 instead of the near Âneutral pHs preferred by bacteria. Consequently, yeast procesÂses can be operated in a clean but non-sterile mode at a pH of 4.0 to 4,5 because most bacterial contaminants will not grow well in this degree of acidity. For another, yeast cell diameters are about 0.0005 centimetres as compared with 0.0001 cenÂtimetres for bacteria. Because of their larger size yeasts may be separated from the growth medium by centrifugation, withÂout the need for a flocculation step.
2232Yeast single-cell protein production depends upon meeting the oxygen demand of the growing cultures. Yeasts grown on carbohydrates generally require about 1 kilogram of oxygen per kilogram dry weight of cells and when grown on hydrocarbons they need about twice that much. Air, which is sterilized by filtration, is supplied to the fermentor through a perforated screen or perforated pipes in the bottom of the vessel, or by a rotating aeration wheel or air-lift device similar to those used for culturing bacterial cells.
2233Yeast single-cell protein may be produced either under sterile, or clean but non-sterile, conditions. In a typical batch or fed-batch non-sterile operation in which carbohydrate is used as the carbon and energy source the medium is sterilized by passing it through a heat-exchanger and then charged into clean fennentors. Contamination control is based on having a pH of 4.0 to 5.0, supplying sterile air, and maintaining large populations of yeast cells in the fermentor to overwhelm any small numbers of contaminating microorganisms. In some continuous yeast fermentations that use hydrocarbons or ethanol as the substrate, completely sterile conditions may he needed to achieve the desired yields and product quality.
2234Candsda units, which is known as torula yeast and used both as an animal feed supplement and for human consumption, is manufactured from a wide range of raw materials, among which are ethanol, the sulphite waste liquor from paper mills, normal paraffin hydrocarbons and cheese whey.
2235
2236smilewinklaugh
2237Chemistry is our Covalent Bond
2238
2239
2240
2241 Organikum
2242(Horrible Personality)
224311-25-03 22:12
2244No 473151
2245 thanks lugh
2246
2247thats a good piece of information again, love it.
2248
2249But the problem is actually that ppl are talking here about biosynthesis who are obviously not even able to make some acetal or benzaldehyde from OTC chems. Thats the only problem - the easy biosynth is posted already. Not more difficult as brewing beer - what is not so easy as some may think btw..
2250
2251One last piece of information:
2252How to determine the biosynthesis process is actually over?
2253- it doesnt smell like oil of bitter almonds anymore.
2254thats it, the technique is called "nosing", ask DWARFER.....
2255
2256
2257I am outa this.
2258done
2259ORG
2260
2261
2262
2263 halfkast
2264(Hive Addict)
226511-28-03 00:53
2266No 473520
2267 Re: thats a good piece of information again,...
2268
2269 thats a good piece of information again, love it.
2270
2271 But the problem is actually that ppl are talking here about biosynthesis who are obviously not even able to make some acetal or benzaldehyde from OTC chems. Thats the only problem - the easy biosynth is posted already. Not more difficult as brewing beer - what is not so easy as some may think btw..
2272
2273
2274
2275
2276No, that's not true sorry. Senior chemistry bees have continually given the misleading impression that there was vital or atleast important information mission necessary to success.
2277
2278What do you mean beer-making is hard?!?!?!?!!?!??! That's an infuriating implication to make at this late stage.
2279
2280Oh so it is a walk in the park then, I thought so, thats what the first references I've read translated to a long time ago..... seemed straightforward and complete enough, it seems it always was.
2281
2282I think Ill trust the references on the yeast species, candida utilis.
2283
2284The benzaldehyde and acetaldehyde was always something to work at, it's just that uncertainties were portrayed.
2285
2286Ohh you meant difficult as in you'd have to follow instructions and a few parametres.
2287You don't need 2 Bee High to follow the goings-on @The-Hive--Just Addikted!
2288
2289
2290
2291 Organikum
2292(Horrible Personality)
229311-28-03 14:00
2294No 473625
2295 making good beer is an art
2296
2297I didnt write it is difficult - but it is more than throwing some yeast in a bucket with sugar.
2298
2299
2300
2301I see Java has provided the post number but no direct link. Here it is:
2302Post 388164 (Organikum: "substituted hydroxyphenylacetone", Novel Discourse) and followups
2303and
2304Post 400469 (Organikum: "L-PAC reductive alkylation", Novel Discourse)
2305The procedure as described is straight after an east german patent and works fine. Tried and true. And probably the way most ephedrine on the world is manufactured in China and India. Low tech process.
2306
2307yeast:
2308actively fermenting saccaromyces cerevesiae aka bakers yeast is to use - actively fermenting says aerated and feeded with dextrose. ph-control is important. Brewers wort and acetaldehyde are important but can be substituted by diminished yields.
2309If your batch after 10 hours of active fermentation still smells like christmaspunch use another sort (strain) of bakers yeast.
2310Brewers wort here is wort before the hops are added - the temperature of the wort must never have exceeded 78°C or the essential enzymes are destroyed and its near to worthless.
2311
2312and now I am realy out here.
2313ORG
2314
2315
2316
2317 Rhodium
2318(Chief Bee)
231912-04-03 02:16
2320No 474575
2321 some L-PAC info
2322
2323Review: Application of beta-keto acid decarboxylases in biotransformations
2324H. Iding, P. Siegert, K. Mesch and M. Pohl
2325Biochimica et Biophysica Acta (BBA) - Protein Structure and Molecular Enzymology, 1385(2), 307-322 (1998) (../rhodium/pdf /l-pac.biotransformation.pdf)
2326DOI:10.1016/S0167-4838(98)00076-4
2327
2328Abstract
2329The advantages of using enzymes in the synthesis of organic compounds relate to their versatility, high reaction rates, and regio- and stereospecificity and the relatively mild reaction conditions involved. Stereospecificity is especially important in the synthesis of bioactive molecules, as only one of the enantiomeric forms usually manifests bioactivity, whereas the other is often toxic. Although enzymes which catalyze asymmetric carbon-carbon bond formation are of great importance in bioorganic chemistry, only a few examples are known for thiamin diphosphate (ThDP)-dependent enzymes, whereas transformations using e.g. aldolases, lipases and lyases are well documented already. The present review surveys recent work on the application of pyruvate decarboxylase and benzoylformate decarboxylase in organic synthesis. These enzymes catalyze the synthesis of chiral beta-hydroxy ketones which are versatile building blocks for organic and pharmaceutical chemistry. Besides the substrate spectra of both enzymes amino acid residues relevant for substrate specificity and enantioselectivity of pyruvate decarboxylase have been investigated by site-directed mutagenesis.
2330
2331
2332
2333 Organikum
2334(Horrible Personality)
233501-24-04 17:40
2336No 484386
2337 immobilized yeast
2338
2339Production of yeast-alginate pearls:
2340(hope alginat is alginate in english LOL)
2341
23422,5g yeast is mixed with 3ml waterby shaking.
23430,25g sodiumalginate is shaken with 7ml of water.
2344Then the yeast suspension is given to the dissolved alginate.
2345
23460,3g CaCl2 is dissolved in 15ml water and stirred like hell (vortex stirring). Whilst stirring the yeast/alginate mixture is added to the CaCl2/water dropwise using a syringe. The syringe should be hold vertically when doing this.
2347
23483mm diameter pearls of yeast enclosed in alginate will drop out and can be removed by using an ultrahightech teasieve device.
2349
2350voila - immobilized yeast.
2351
2352
2353I know I said I am out here, but thats to good to disclose it I believe. And it might come VERY handy not only in the L-PAC process which btw is called "acloin condensation" in newer publications. Ah these chemists - always a new name for an old reaction.....
2354
2355
2356ORG
2357Shareholder of Paranoid Fucks inc.
2358
2359
2360
2361
2362 spectralshift
2363(Hive Bee)
236401-29-04 01:35
2365No 485174
2366 PDC questions
2367
2368sorry about that outburst up there, it looks disgraceful and immature now. what a **cken baby.
2369=============================
2370
2371It seems like the biotranformation is highly dependent on Can high PDC activity the type of PDC and yeast one can get a hold of, including mutated forms.
2372
2373Organikum, I'm not clear-minded regarding whether acetaldehyde addition is beneficial in a batch process...
2374
2375Is alcohol dehydrogenase activity decreased with higher concentrations of acetaldehyde already present, necessarily?
2376
2377Is it possible to produce acetaldehyde in situ before addition of benzaldehyde in a second phase of the fermentation process? Perhaps after the addition of more yeast, and developing this second culture.
2378
2379(see: 'LPhenylacetylcarbinol is generated biologically through the pyruvate decarboxylase-mediated condensation of added benzaldehyde with acetaldehyde generated metabolically from feed stock sugars via pyruvate...')
2380
2381Do we know the response time of increased PDC activity as a result of reduced aeration? (For the purpose of having high PDC activity at the moment of substrate addition(s))
2382
2383Do we know the amount of yeast that is required for developing enough of it in a specific time for a given quantity of benzaldehyde feedstock? An estimate?
2384
2385
2386Tell me if I'm unclear, it's happened before.
2387
2388
2389 Organikum
2390(Horrible Personality)
239101-29-04 17:16
2392No 485311
2393 answers
2394
2395- Acetaldehyde works as a hydrogen acceptor - it is essential for good yields.
2396- Too much acetaldehyde as benzaldehyde kills the yeast.
2397- The yeast "cycles" through phases of high PDC activity and lower activity. The monitoring of these cycles is high tech and warrants not the efforts IMHO.
2398- Ethylalcohol may be added to suppress the benzaldehyde -> benzylalcohol transformation, about 10% to 15% is ok, more may disable or even kill the yeast.
2399- The benzaldehyde -> L-PAC transformation is depenedent on MANY factors not only PDC activity - yeasts with lots of PDC in a highly active state dont give the best results.
2400
2401 Do we know the amount of yeast that is required for developing enough of it in a specific time for a given quantity of benzaldehyde feedstock? An estimate?
2402
2403
2404Thats covered in my posts I linked to before.
2405
2406The acetaldehyde added is NOT converted to L-PAC, only the acetaldehyde which is made in situ from the pyruvate is converted to L-PAC. This is not acetaldehyde in a pure form but a kind of nascent acetaldehyde compound.
2407It works without the addition of acetaldhyde with lowered yields.
2408
2409The process which is used in the production of heaps of ephedrine to lowest prices in China and India is described in my former posts. No need to make it overly complicated.
2410
2411Get yourself a nice b-dehyde synth and an acetaldehyde synth - thats the problem to solve. The biosynth is easy.
2412Shareholder of Paranoid Fucks inc.
2413
2414
2415
2416
2417 nightshade
2418(Newbee)
241902-07-04 18:28
2420No 487103
2421 Phenylacetic acid
2422
2423Does anyone have information concerning US patent #5,420,022
2424phenylacetic acid from yeast and phenylalanine. How much phenylalanine is added to the brew, and how does one extract the phenylacetic acid from the brew? Can nutrasweet be used as more of it can be dissolved in water,so it is easier to mix?
2425
2426
2427
2428 Methodman
242902-14-04 04:44
2430 I think,not positive,but I think you need to...
2431(Rated as: insignificant)
2432
2433
2434
2435 Nicodem
2436(Hive Bee)
243703-06-04 16:32
2438No 493430
2439 Anybody cares for R-PAC...
2440
2441...well, that -OH is obsolete anyway.
2442
2443Patent CA2414742: Microbial Production Of R-Phenylacetylcarbinol By Biotransformation Of Benzaldehyde By Filamentous Fungi
2444Abstract: Process for the production of R-phenylacetylcarbinol by biotransformation of benzaldehyde by filamentous fungi.
2445
2446Just some investigations of R-PAC production by filamentous fungi selected from the group of Rhizopus, Neurospora, Polyporus, Fusarium, Monilia, Paecilomyces, Mucor.
2447“The real drug-problem is that we need more and better drugs.†– J. Ott
2448
2449
2450
2451 Organikum
2452(Wonderful Personality)
245303-08-04 13:18
2454No 493730
2455 Its the same. l -(laevo)- phenylacetylcarbinol
2456
2457Its the same.
2458
2459l -(laevo)- phenylacetylcarbinol is identical with R-Phenylacetylcarbinol.
2460
2461So many compounds but much more names - oh Babylon, oh Babylon laugh.
2462
2463S we have the funny fact arising that:
2464l-PAC = L-PAC (whats wrong but often used anyways) = R-PAC
2465This doesnt matter anyways as "phneylacetylcarbinol is the wrong name also - a mistake made by the discoverers Neuberg and Hirsch.
2466Look above there are all names (known to me) listed.
2467Shareholder of Paranoid Fucks inc.
2468
2469
2470
2471
2472 Nicodem
2473(Hive Bee)
247403-08-04 14:03
2475No 493737
2476 L-PAC to CATs in one step?
2477
2478Thanks for the correction Organikum. I already figured that out, but it was too late to edit the post. Yes, it is just a different nomenclature, but I always mix up those R,S/D,L nomenclatures if I don’t think enough about stereochemistry and I almost never thinktongue.
2479
2480Well, sometimes I do think but the results of such an irresponsible activity might be wrongcool. Did anybody ever considered the following transformation:
2481
2482Similar mechanisms are already known for alpha-hydroxy-ketones, especially in the heterocyclic chemistry. Here we have one more driving force to push the equilibrium on the right: the conjugation of the enamine and latter of the carbonyl double bond with the benzene ring. One additional push would be to eliminate the water that forms during the enamine formation. Azeotropic distillation with a Dean-Stark trap would be a little hard to acomplish due to the volatility of dimethylamine, diethylamine, methylethylamine etc. N,N-dimethylcathinone is a relatively good stimulant, isn't it? And it is much more straightforward for the kitchen chemist than reduction to ephedrine and so on.
2483“The real drug-problem is that we need more and better drugs.†– J. Ott
2484
2485
2486
2487 Organikum
2488(Wonderful Personality)
248903-08-04 15:52
2490No 493748
2491 You want it easy AND good?
2492
2493You want it easy AND good?
2494
2495
2496Go:
2497benzaldehyde + bakers yeast = l-PAC
2498l-PAC (crude extract from the biosynth is ok) + NH3 = imine *
2499imine + Al/Hg = l-norephedrine
2500l-norephedrine + KOCN = carbamyl
2501carbamyl + HCl = "XYZ" surprise, surprise what can this bee....? laugh
2502
2503* hydroxyphenylacetones form stable imines, so the formation of the same in advance before reduction is possible and advantegous regarding yields which are bad if the reductive amination is done one-step as usual.
2504Shareholder of Paranoid Fucks inc.
2505
2506
2507
2508
2509 roger2003
2510(Hive Bee)
251103-08-04 17:07
2512No 493762
2513 Industrial Biotransformation
2514
2515Very interesting book (5 MB)
2516
2517Industrial Biotransformations:
2518A Collection of Processes by Andreas Liese (Author), Karsten Seelbach (Author), Christian Wandrey (Author)
2519
2520
2521http://www.amazon.com/exec/obidos/tg/detail/-/3527300945/qid=1078761717/sr=1-1/ref=sr_1_1/102-0732881-5495322?v=glance&s=books
2522roger2003
2523
2524
2525
2526 Organikum
2527(Wonderful Personality)
252803-09-04 01:07
2529No 493820
2530 ?????????
2531
2532You wanted to say 150$$ I guess.
2533
2534Thats a joke, there are hundreds of interesting books at amazon, you know?
2535Thousands probably.
2536
2537weird.
2538Shareholder of Paranoid Fucks inc.
2539
2540
2541
2542
2543 roger2003
254403-09-04 10:16
2545 Books
2546(Rated as: insignificant)
2547
2548
2549
2550 elfspice
2551(Hive Bee)
255204-09-04 05:37
2553No 499839
2554 pyruvic acid
2555
2556I did a little research on pyruvic acid and discovered that it's right under our noses - well, when we're making our dinner it can make the eyes water... yes ONIONS! sorry if that was known to the reader... Pyruvic acid is produced during the decomposition of sugars (glucose i think) and it can reduce quite readily to lactic acid.
2557
2558so all you need is a source of pyruvate decarboxylase, and with a few experiments one should find that a particular set of conditions is conducive to the PDC reacting with the pyruvic acid in such a way as to increase the chances of this decarboxylation occurring in proximity to the benzaldehyde so that one gets maximum transformation.
2559
2560Or better still, is there a way to make benzaldehyde and pyruvic acid join together the right way without using an enzyme?
2561
2562Pyruvic acid could probably be easily sublimation purified out of extract from onion - subzero alcohol extraction would extract solid pyruvic acid into the alcohol and then the material boiled off and the fraction boiling at 165 degrees distilled, and then sublimed onto a dry ice cooled dewar type condenser as it solidifies at 11.8°C.
2563
2564This might be useful information for the biosynthesis process, as pyruvic acid probably doesn't have a very long lifespan in actively brewing warm vat... maybe it could be added with a dripping funnel thingy? I'm sure it wouldn't cost much to get a few litres of pyruvic acid from the supermarket... wink
2565
2566
2567
2568 Nicodem
2569(Hive Bee)
257004-09-04 10:12
2571No 499867
2572 Pyruvic acid could probably be easily ...
2573
2574Pyruvic acid could probably be easily sublimation purified out of extract from onion
2575
2576Are you serious?
2577You can make pyruvic acid with the dry distillation of tartaric acid which is OTC and cheap (at least where I live). I don't remember the exact procedure but I'm sure it is as easy as it can get (maybe some sulphuric acid has to be added or something like that).
2578“The real drug-problem is that we need more and better drugs.†– J. Ott
2579
2580
2581
2582 elfspice
2583(Hive Bee)
258404-09-04 12:31
2585No 499877
2586 pyruvic acid (again)
2587
2588the question is, would it help to add it? It is naturally formed as a part of the yeast's metabolism, (and virtually any organism that uses sugars to provide energy) but is the rate of production equal the rate of PDC production? If PDC was being produced in excess to the proportion of pyruvic acid, we could probably squeeze more out of it (?) If not, the whole line of thought is worthless... unless we can get PDC out of yeast somehow perhaps, or if it is commercially available. or... maybe there's some way to make pyruvic acid useful here somehow (chlorinate it and react with benzyl chloride perhaps?)
2589
2590(just looking at molecules) oh i see decarboxylate tartaric acid one time and remove one hydrogen (or add an oxygen) and you get *tada* pyruvic acid.
2591
2592
2593I've been trying to nut out how exactly the PDC goes about joining these things together and what i've figured out is this: The pyruvic acid decarboxylates, and the free carbon bond remaining of what used to be pyruvic acid reacts with the aldehyde, which bonds by saturating the carbon with the acetaldehyde which is lacking a hydrogen (which is floating around from the decarboxylation), and the hydrogen goes onto the now single-bonded oxygen at the first carbon on the now phenylacetylcarbinol.
2594
2595If one created reaction conditions of pyruvate decarboxylating in the presence of benzaldehyde, it doesn't make any difference how it is done so long as the process allows the freshly decarboxylated pyruvic acid take up the carbon bond. or am i missing some vital point here? The stereoselectivity is inherent in this reaction because of the way it reacts via the production of an aldehyde with an extra proton on the carbon with the aldehyde on it, because the keto group has some kind of interaction with the oxygen with a free electron. I think in this case we always want the OH and keto group to end up opposite each other, and i suspect that is exactly what they do. One could imagine that there would be some kind of interaction leading to a fairly predictable bonding formation.
2596
2597Tricky thing is, how do we get the pyruvic acid to decarboxylate with benzaldehyde around? perhaps a high boiling ketone? pressure (*ducks flamethrower blasts*) ? *wince* ... ooh, maybe something simple like a natural organic ketone, eg carvone or something similar... That would dissolve the benzaldehyde well enough but the determining factor for the best ketone solvent/matrix/decarboxylation catalyst would be good solubility of pyruvic acid.
2598
2599
2600
2601 Organikum
2602(Wonderful Personality)
260304-09-04 13:14
2604No 499880
2605 No. Pyruvic acid or molasses or even plain...
2606
2607No. Pyruvic acid or molasses or even plain sugar makes no real difference. Molasses is even better for the nutrients it contains.
2608
2609But pyruvic acid may be useful in another way.
2610- pyruvic acid and diluted H2SO4 gives acetaldehyde.
2611
2612The biosynthesis is absolutely no problem. Acetaldehyde and benzaldehyde are the limiting factors here.
2613
2614For the biosynth:
2615- permanent ph control and adjustment is essential.
2616Shareholder of Paranoid Fucks inc.
2617
2618
2619
2620
2621 roger2003
2622(Hive Bee)
262304-09-04 15:59
2624No 499900
2625 Acetaldehyde
2626
2627- pyruvic acid and diluted H2SO4 gives acetaldehyde.
2628
2629Any references ?
2630roger2003
2631
2632
2633
2634 nightshade
2635(Newbee)
263604-09-04 18:29
2637No 499907
2638 bio brew tryptophan->tryptophol.
2639
2640bio brew tryptophan->tryptophol.
2641bio brew phenylalanine ->phenyl acetic acid.
2642now to do this can one use the same set up as is used for L-pac,I read that patent for phenyl acetic acid production but was wondering if it could be brewed more like beer as with the L-pac?
2643
2644
2645
2646 BOS
2647(Newbee)
264804-09-04 22:09
2649No 499937
2650 Here is a good Pyruvic acid patent.
2651
2652Here is a good Pyruvic acid patent.
2653Claimed 90% yield from cream of tartar and h2so4Patent US4136111
2654
2655
2656
2657 elfspice
2658(Hive Bee)
265904-10-04 06:23
2660No 499995
2661 correction
2662
2663if only it made phenylacetic acid... no sorry, biobrew is gonna turn the material into phenylethanol or maybe phenylacetaldehyde (i'm fairly sure it's the alcohol)
2664
2665phenylethanol is not going to be an easy way to start if one wants to end up with an amphetamine, since the amine has to go on there but it needs another methyl group after it as well...
2666
2667
2668
2669 nightshade
2670(Newbee)
267104-10-04 18:29
2672No 500077
2673 phenylethanol can changed to phenyl acetic...
2674
2675phenylethanol can changed to phenyl acetic acid then ran through a tube furnace to get p2p right? what is needed to change phenylethanol to phenyl acetic acid? in patent 5420022 it seems they were producing phenyl acetic acid,the beer brewing set up would be somewhat different than their set up so maybe the the main product would be phenyl ethanol.so can I get more feed back on this, thank you.
2676
2677
2678
2679 elfspice
2680(Hive Bee)
268104-10-04 23:53
2682No 500117
2683 oxidation of course
2684
2685phenylethanol probably oxidises to it's carboxylic acid equivalent via some means, ordinary ethanol certainly seems to. This requires some kind of bio-catalysing normally, i think, you can't just let ever clear sit open and expect it to oxidise, a lot of water is needed. Probably you just brew it up, then don't stop until the thing gets really acidic and full of acetic acid. I would think the same oxidation would occur, but then i can't be sure cos phenylethyl alcohol is a lot bigger.
2686
2687If there's a way to make phenylacetic acid, then couldn't tryptophol also be turned into indoleacetic acid?
2688
2689
2690 mellow
2691(Hive Bee)
269204-18-04 09:56
2693No 501439
2694 RE: Biosynth (homebrewing E)
2695
2696How about modifying this: Method for producing L-3,4-dihydroxyphenylalanine - European Patent (EP 0636695-A1) (http://l2.espacenet.com/espacenet/viewer?PN=EP0636695&CY=ep&LG=en&DB=EPD). There's lots of stuff similar to that.
2697
26981: Instead of aiming for DOPA one could aim for alpha-methyl-DOPA by using catechol with alpha-methyl-serine. Possibly may not work but surely worth investigating.
2699
2700People have discussed the conversion of alpha-methyl-DOPA to MDA via decarboxylation followed by methylenation but Rhodium told me that it wouldn't work. I can't see why not. But I suppose it's academic without any alpha-methyl-DOPA.
2701
27022nd point. Why not try the above Euro patent with hydroquinone and serine rather than catechol and serine? - to, possibly, get 2,5-dihydroxy-phenyl-alanine - which is just a decarboxylation and a methylation (I daren't go further) away from something interesting.
2703
2704Apologies is this post interrupts the thread and is thought to be off-topic.
2705
2706
2707
2708 Organikum
2709(Wonderful Personality)
271004-24-04 21:45
2711No 502714
2712 acetaldehyde
2713
2714As acetaldehyde is very useful in the biosynthesis of l-PAC I want to point interested bees here:
2715
2716Post 502712 (Organikum: "Rhodium wrote: Re: If you do not remove the...", Stimulants)
2717
2718ferrous/ferric sulfate + hydrogen peroxide + ethylalcohol
2719=
2720acetaldehyde + acetic acid
2721
2722ORG
2723Shareholder of Paranoid Fucks inc.
2724
2725
2726
2727
2728 7is
2729(Newbee)
273004-24-04 23:01
2731No 502720
2732 Free for this week, Encyclopedia of Bioprocess
2733
2734Free for this week, Encyclopedia of Bioprocess Technology - Fermentation, Biocatalysis, and Bioseparation, Volumes 1-5: http://www.knovel.com/knovel2/Toc.jsp?BookID=678
2735
2736
2737
2738 foxy2
2739(Fragile ego)
274005-04-04 21:21
2741No 504822
2742 You can make pyruvic acid with the dry ...
2743
2744You can make pyruvic acid with the dry distillation of tartaric acid which is OTC and cheap
2745
2746Or you can search froogle for "calcium pyruvate"
2747http://www.democracynow.org/ - The Exception to the Rulers
2748
2749
2750
2751 borolithium
2752(Stranger)
275305-06-04 05:05
2754No 505189
2755 Acetaldehyde Generator
2756
2757[blue]But pyruvic acid may be useful in another way.
2758- pyruvic acid and diluted H2SO4 gives acetaldehyde.
2759
2760[black]Well, if this is true, since the patent I was just reading claims that potassium bitartrate and H2SO4 mixed in equimolar ratios, yields 90% pyruvic acid when heated at 170C to 270C for one hour, can't one just use an excess of H2SO4, thereby turning this reaction into an acetaldehyde generator?
2761
2762This sounds too easy and too OTC to be true?
2763Anyone going to try this before I get a chance?
2764Uncle Fester's Recipes suck
2765
2766
2767
2768 Organikum
2769(Wonderful Personality)
277005-06-04 11:08
2771No 505253
2772 I cannot answer your question on the tartrate...
2773
2774I cannot answer your question on the tartrate to acetaldehyde borolithium, sorry, but I must tell that FeSO4 + H2O2 + EtOH = acetaldehyde maybe theoretically nice but is practically a pain in the ass as the reaction tends to runaways.
2775
2776Except one wants to go for real large amounts of product - kilos - I would suggest to skip the acetaldehyde, to concentrate on the production of benzaldehyde instead and to get a bigger bucket for the fermentation smile
2777Also I suggest to use diethylether for the extraction of the fermentation broth as the reductive amination/alkylation can be done directly onto the raw extract in ether - say: extract with ether, reduce the volume and do the Al/Hg in ether instead of alcohol.
2778Shareholder of Paranoid Fucks inc.
2779
2780
2781
2782
2783 borolithium
2784(Stranger)
278505-07-04 06:00
2786No 505504
2787 Why make benzaldehyde?
2788
2789It is not that hard to get you know. Where I am from, the grocery store will suffice. Granted, they are tiny bottles, but can't one just send a bunch of people out for the day?
2790
2791IMITATION ALMOND EXTRACT
2792
2793Also, bitter almond oil is not hard to get abroad. There are a thousand ways to smuggle it in, as I doubt there are any dogs that are trained to smell it. Shampoo Bottle?
2794
2795That being said, it is my understanding that the presence of acetaldehyde is critical to the yield of L-PAC. Valuable benzaldehyde will be converted to benzyl alcohol in the absense of the acetaldehyde, and since acetaldehyde cannot be readily purchased, a simple and cost effective system of generating it is needed.
2796
2797There are several patents detailing the use of acetylene, passed through a mercury or heavy metal catalyst at moderate temperatures.
2798
2799Acetylene is available to all of us without raising any suspicion, but the mercury salts may be an issue.
2800
2801Tartrates are OTC and would provide simple means of generating acetyldahyde without working with hard to obtain and dangerous ingredients, such as mercury salts.
2802Uncle Fester's Recipes suck
2803
2804
2805
2806 Vitus_Verdegast
2807(Hive Addict)
280805-07-04 11:48
2809No 505564
2810 this has been discussed a zillion times before
2811
2812There are lots of ways to oxidise ethanol, for example pass ethanol/air over hot copper in a tube. Simple and cost-effective.
2813http://www.geocities.com/eric_vornoff/government_is_your_friend.jpg
2814
2815
2816
2817 borolithium
2818(Newbee)
281905-09-04 07:22
2820No 505929
2821 Pyruvic Acid Reference
2822
2823http://86.1911encyclopedia.org/P/PY/PYRUVIC_ACID.htm
2824
2825 When heated with hydrochloric acid to 10o C. it yields carbon dioxide and pyrotartaric acid C5H804, and when warmed with dilute sulphuric acid to 150 C it gives carbon dioxide and acetaldehyde.
2826
2827This sounds waaaaaaaaaaaaaaaaaaayyyyyyyyyyyy easier than bulding some high temp, silver coated mesh catalyst burning tube, injecting ethanol and air streams in perfect proportions, and hopefully not having a big ass blow back or explosion. State of the art 19th century technology.
2828
2829So, to simplify things:
2830
2831Potassium Bitartrate + conc. H2SO4 in equimolar amounts, heated to 170C to 270C for 1 hour = 90% pyruvic acid
2832
2833AND
2834
2835Pyruvic Acid + dilute H2S04 heated to 150C = CO2 + acetaldehyde = essential ingredient for high yielding L-PAC
2836
2837I would run the evolving gas through a cooling tube at 40C to condense any moisture, while allowing the acetaldehyde to mostly pass through. The gas can be bubbled into an aqueous solution, with conc. estimated by weight or volume. This solution can be later introduced into the bioreactor with the benzaldehyde to maximize the L-PAC yield.
2838
2839Any objections?
2840Do Your Part To Help Stop Bovine Scatology
2841
2842
2843
2844 Organikum
2845(Wonderful Personality)
284605-09-04 10:13
2847No 505962
2848 Re: Any objections? No.
2849
2850 Any objections?
2851
2852No. laugh
2853
2854Of course you will need some routine to get the very good yields told in literature (as always smile), but it will work exactly like this. A powerful condensor for the acetaldehyde or bubbling it into ice-cold water is recommended.
2855
2856ORG
2857Schnabufugl!
2858
2859
2860
2861
2862 borolithium
2863(Newbee)
286405-20-04 03:42
2865No 508310
2866 Bioreactor
2867
2868A bioreactor seems to be the best way to maximize yields in a minimal amount of space. Constant aeration, agitation, and the slow introduction of the benzaldehyde and acetaldehyde are reported to provide the highest yield in the smallest amount of space.
2869
2870Now if one was trying to purchase a bioreactor, there is only a handful of companies manufacturing these units, and they would likely ask what it was being used for, as these units are often customized. Can anyone think of a good, plausible industrial reason for wanting a bioreactor?
2871Do Your Part To Help Stop Bovine Scatology
2872
2873
2874
2875 foxy2
2876(Fragile ego)
287705-23-04 01:57
2878No 508869
2879 You want to do some carefully controlled beer...
2880
2881You want to do some carefully controlled beer brewing experiments.
2882http://www.democracynow.org/ - The Exception to the Rulers
2883
2884
2885
2886 borolithium
2887(Newbee)
288805-23-04 03:20
2889No 508895
2890 Hmmmmm............
2891
2892Thanks Foxy. I suppose that's too obvious. Mind you, I can't imagine any company getting too suspicious about a bioreactor.
2893
2894Now here is a question for you foxy. as I remember a post you had put up eons ago regarding the strain candidus utilis. The majority of research papers I have come across using bioreactors use a strain of Sacharamyces Cerevesiae (I'm spelling this from memory so forgive me), a common yeast for white wine, for the conversion of benzaldehyde to L-PAC.
2895
2896Is the candidus utilis (tarula yeast) superior in it's L-PAC/Benzyl Alcohol production ratio, and would it function much the same in a bioreactor as a substituted yeast strain?
2897Do Your Part To Help Stop Bovine Scatology
2898
2899
2900
2901 foxy2
2902(Fragile ego)
290305-23-04 05:08
2904No 508917
2905 An interesting Brewing Chemistry article for...
2906
2907An interesting Brewing Chemistry article for you L-PACer's.
2908
2909http://www.brewingtechniques.com/library/backissues/issue1.2/fix.html
2910
2911You can buy different yeast strains from a brewing yeast company that has high and low diacetyl strains. A high diacetyl strain might bump up yeilds nicely?
2912http://www.democracynow.org/ - The Exception to the Rulers
2913
2914
2915
2916 Aurelius
2917(Active Asperger Archivist)
291805-23-04 18:15
2919No 509027
2920 References
2921
2922pyruvic acid synthesis from K bitartrate and Sulfuric acid
2923
2924Post 384565 (cthulhujr: "Pyruvic Acid Synthesis and 24%", Stimulants)
2925Act quickly or not at all.
2926
2927
2928
2929 Shane_Warne
2930(Stranger)
293105-28-04 22:42
2932No 510097
2933 yields and long term planning? (personal use)
2934
2935The pyruvic acid route to acetaldehyde sounds much more practical than from EtOH at high temperatures.
2936
2937It's preparing an effective yeast that I have my doubts about.
2938The yeasts in industry are specially selected from colonies prepared. They are more resilient to B-aldehyde induced death. The hard-working ones are then extracted for the next experiment.
2939
2940
2941What about isolating yeast that survive certain treatments, and very small test-runs, then culturing those?
2942
2943
2944There's a method at Rhodium's using yeast from moldy apricots, and the yield from 264gm of B-Aldehyde was 24gm of L-PAC.
2945
2946Not encouraging considering the level of skill in the art, that the experimenter probably has, and the equipment available.
2947Although no acetaldehyde was incorporated, or EtOH.
2948
2949Here's that write-up: http://rhodium.ws/chemistry/ppa.l-pac.raney-ni.html
2950
2951How many liters of B-aldehyde is your average joe-bee going to go through before being comfortable with his procedure? For personal use I mean. (toluene will disappear.)
2952
2953What B-aldehyde contaminents and by-products from it's preparation absolute no-no's for yeast, and which, if any, are acceptable?
2954
2955How should air bee sterilized before introduction in to the bioreactor?
2956
2957
2958
2959 methyl_ethyl
2960(Guardian)
296105-28-04 23:41
2962No 510103
2963 Bioreactor Air Purification
2964
2965How should air bee sterilized before introduction in to the bioreactor?
2966
2967Depending on the sensitivity of the reaction, usually using two in-line .2micron air sterilizing filters would work on the intake line. Or even placing an activated charcoal in- line filter upstream from the air sterilizing filters. If humidity would have to be introduced it can be done downstream from the .2 micron filters using water for injection as a source of humidity introduction. You can pick up the .2 micron air sterilizing filters for ~1.00 a piece USD for a pack of 100.
2968
2969m_e
2970 Unipolar Mania, It's good for life... laugh
2971
2972
2973
2974 roger2003
2975(Hive Bee)
297605-30-04 16:55
2977No 510309
2978 Adv Microb Physiol. 1999;41:1-45.
2979
2980Adv Microb Physiol. 1999;41:1-45.
2981
2982
2983Factors affecting the production of L-phenylacetylcarbinol by yeast: a case study.
2984
2985Oliver AL, Anderson BN, Roddick FA.
2986
2987Department of Chemical and Metallurgical Engineering, RMIT University, Melbourne, Victoria, Australia.
2988
2989L-Phenylacetylcarbinol (L-PAC) is the precursor for L-ephedrine and D-pseudoephedrine, alkaloids possessing alpha- and beta-adrenergic activity. The most commonly used method for production of L-PAC is a biological method whereby the enzyme pyruvate decarboxylase (PDC) decarboxylates pyruvate and then condenses the product with added benzaldehyde. The process may be undertaken by either whole cells or purified PDC. If whole cells are used, the biomass may be grown and allowed to synthesize endogenous pyruvate, or the cells may be used as a catalyst only, with both pyruvate and benzaldehyde being added. Several yeast species have been investigated with regard to L-PAC-producing potential; the most commonly used organisms are strains of Saccharomyces cerevisiae and Candida utilis. It was found that initial high production rates did not necessarily result in the highest final yields. Researchers then examined ways of improving the productivity of the process. The substrate, benzaldehyde, and the product, L-PAC, as well as the by-products, were found to be toxic to the biomass. Methods examined to reduce toxicity include modification of benzaldehyde dosing regimes, immobilization of biomass or purified enzymes, modification of benzaldehyde solubility and the use of two-phase reaction systems. Various means of modifying metabolism to enhance enzyme activity, relevant metabolic pathways and yield have been examined. Methods investigated include the use of respiratory quotient to influence pyruvate production and induce fermentative activity, reduced aeration to increase PDC activity, and carbohydrate feeding to modify glycolytic enzyme activity. The effect of temperature on L-PAC yield has been examined to identify conditions which provide the optimal balance between L-PAC and benzyl alcohol production, and L-PAC inactivation. However, relatively little work has been undertaken on the effect of medium composition on L-PAC yield.
2990
2991Publication Types:
2992Review
2993Review, Academic
2994
2995PMID: 10500843 [PubMed - indexed for MEDLINE]
2996.
2997
2998
2999
3000 jsorex
300105-31-04 03:41
3002 Can anybody access this?
3003(Rated as: UTFSE!)
3004
3005
3006
3007 Rhodium
3008(Chief Bee)
300905-31-04 05:48
3010No 510457
3011 Already posted
3012
3013Yes, everyone who UTFSE for it will be able to access it here: Post 505265 (Organikum: "Benzaldehyde -> L-PAC -> Ephedrine", Stimulants)
3014
3015This article is also excellent: Post 507915 (Rhodium: "Benzaldehyde -> L-PAC -> PPA", Stimulants)
3016The Hive - Clandestine Chemists Without Borders
3017
3018
3019 borolithium
3020(Newbee)
302105-31-04 09:17
3022No 510497
3023 Air sterilization
3024
3025A charcoal filter alone will not sterilize the air in itself, as bacteria will breed quite easily on the charcoal surface. This is often a desired effect, such as in aquaculture, as the aerobic bacteria that colonizes on the charcoal will break down ammonia produced by fish waste into nitrite and ultimately into nitrate. The charcoal will only serve to absorb contaminates out of the air and will allow fungal spores or bacteria to pass easily through.
3026
3027A HEPA filter or micron filter will catch most spores but not necessarily all of them, and not bacteria.
3028
3029A UVC Sterilizer Lamp is a common option, available from hydroponic shops and water purification places. These bulbs sterilize the air or water that pass by them and will easily kill any bacteria or fungal spore. They do however, have the unfortunate effect of producing ozone, which may find it's way into the reactor and kill the substrate. If a charcoal filter is used after the UVC lamp, the ozone will be absorbed by the charcoal and %100 sterile air will pass through.
3030
3031Another simpler option that I read from a brewing manual was having an air lock filled with bleach or alcohol. When suction is applied, air will be drawn through the liquid from one side of the air lock to the other, which will result in "sterile" air.
3032
3033Just remember that there is a very distinct difference between contaminated air and sterile air, as contaminated air is often sterile and relatively clean air can still have microbes present. Charcoal only serves to decontaminate air and only certain contaminates at that.
3034Do Your Part To Help Stop Bovine Scatology
3035
3036
3037
3038 jsorex
3039(Hive Addict)
304006-02-04 20:21
3041No 510994
3042 Air
3043
3044Well, the air temperature could be increased to the point that all or most bacteria would die. Then let cool for the reaction.
3045
3046what about these ultrafilters (0.1µ) used for filtering pyrogenes and viruses?
3047
3048What about buying a sterilizing filtering device/machine, used in industrial production, into which you install a membrane filter (cellulose nitrate).
3049
3050These should not be expensive either.
3051
3052
3053
3054
3055 Mikael_Bakunin
3056(Stranger)
305706-04-04 20:51
3058No 511482
3059 air sterilisation
3060
3061 How should air bee sterilized before introduction in to the bioreactor?
3062
3063Use HEPA filters or bubble the air through EtOH. NOT denaturated alcohol of course.
3064eat the rich
3065
3066
3067
3068
3069 Organikum
3070(Wonderful Personality)
307107-11-04 17:13
3072No 518701
3073 hydrogen acceptor
3074
3075It seems like acetaldehyde can be substituted by acetone in the biotransformation of benzaldehyde to phenylacetylcarbinol mediated by bakers yeast. This refers to the method using molasses, nutrient salts and thiamine (or whey, or brewers wort) and plain BAKERs YEAST (saccharomyces cerevesiae).
3076
3077Acetaldehyde was applied as a hydrogen-acceptor in this reaction, its role was to scavenge hydrogen and to get converted to ethylalcohol. Every acetaldehyde converted to the alcohol says one benzaldehyde saved from being converted to benzylalcohol. (the main side product in this reaction).
3078It is long known that acetone is converted to isopropylalcohol by fermenting yeast (even mono and di-chloroacetone btw. - at least partially). The question if it will substitute acetaldehyde was not answered. Probably because it was never asked. laugh
3079
3080Now it was asked and answered all in one.
3081
3082ORG smile
3083thats it.
3084
3085
3086
3087
3088 Osmium
3089(Stoni's sexual toy)
309007-11-04 17:23
3091No 518703
3092 If acetone won't work (and your theory is...
3093
3094If acetone won't work (and your theory is correct), then maybe other, easier to handle aldehydes could be added?
3095BUSH/CHENEY 2004! After all, it ain't my country!
3096www.american-buddha.com/addict.war.1.htm
3097
3098
3099
3100 Organikum
3101(Wonderful Personality)
310207-12-04 18:53
3103No 518922
3104 It´s not my theory
3105
3106Acetaldehyde serving as hydrogen-acceptor is told in several articles and for example in the Patent DD51651 (some of the examples in the patent are proven to be working well btw.).
3107Acetone works, as with acetaldehyde the amount which can be added is limited due to its toxity to the yeast (benzaldehyde the same). Formaldehyde cannot be used for this reason - its plain too toxic. Acetone has the advantage not to kill the yeast (except in VERY high concentrations but only to suppress fermentation. After some time the yeast will recover as the processes which transform the acetone to the alcohol (which is also toxic but much less) and the benzaldehyde to the l-PAC are independent from fermentation. The fermentation replentishes enzymes which are used up though.
3108
3109A lower toxity substitute would be preferred of course. Any suggestions?
3110grey world
3111
3112
3113
3114
3115 Nicodem
3116(Hive Bee)
311707-12-04 23:20
3118No 518974
3119 Pyruvic acid maybe?
3120
3121Pyruvic acid maybe?
3122I'm not in the mood to go trough the whole thread, but aren't pyruvates used in some patents? Pyruvic acid is surely less toxic than acetone and acetaldehyde, besides being quite OTC and yielding only the edible lactic acid as a side product. Another less toxic ketone should be 2-butanone, but it is less soluble in water.
3123“The real drug-problem is that we need more and better drugs.†– J. Ott
3124
3125
3126
3127 aia2
3128(Newbee)
312907-12-04 23:37
3130No 518980
3131 pyruvic acid
3132
3133Yes, one of the patents I liked used pyruvic acid and the yeast saccharomycae cervisiae (sp?). Pyruvate is very OTC, too.
3134--aia
3135
3136
3137
3138 Organikum
3139(Wonderful Personality)
314007-13-04 03:47
3141No 519028
3142 No, Nicodem...
3143
3144Look:
3145
3146
3147
3148As you can see, the pyruvic acid is the reactand which produces l-PAC with benzaldehyde. If the pyruvic acid is added directly or if it is produced by the yeast from molasses or glucose doesnt make so much difference. If pyruvic acid or a salt of it is added directly non-fermenting conditions are used, if molasses or another source of fermentable sugars is used activly fermenting conditions have to be used. But this nothing to do at all with the question for a hydrogen acceptor, which plays solely the role to act as additional prey for the also yeast mediated aldehyde to alcohol reaction.
3149This for acetaldehyde is usually added which ends up as ethylalcohol.
3150Also ethylalcohol can be added to the biosynthesis to suppress ALL alcohol producing processes mediated by the yeast as far as possible. Yeast reduces them when a certain level of alcohol is reached in an attempt not to commit suicide.
3151
3152I hope I could clear this up.
3153ORG
3154Schnabufugl!