04-04-04 05:49
No 498951
It's been a while since I've been here, but I remember after reading UF's book on LSD, that there were several Bees who had said that there were some mistakes in his book. I'm not sure if it was only the SOMM or if it was for the LSD book as well. I have checked TFSE and can't find any specifics, so is his book pretty accurate or are there some detrimental mistakes that need to be corrected? Thanks!
(Hive Bee)
04-06-04 13:01
No 499327
I'll check my personal files to see if I can find out what precisely was said and post it later. But 'Practical LSD Manufacture' is a work of fiction. It's clear as daylight that Fester wouldn't be able to make acid even if he tried.
Acid is made by getting ET on the grey market and then following Shulgin's instructions in Tihkal. It's only ever been made by a few hundred people worldwide. A competent chemist dedicated to suceeding would be able to do it but you won't be able to if you want to work entirely alone.
(Hive Bee)
04-06-04 14:00
No 499330
Reposted from the old Hive:
Note: I think the critique below about growing a rye field is a bit harsh as this is actually an effective if laborious way to get LSA.
> oh ok..thanks for your reply...but if you've never actually performed
> an lsd synthesis how do you really know?
If you only want answers from people who've done acid synths you should expect to wait here for eternity. As likely as not, no one who reads this news group has synthed acid.
> are you experienced in chemistry lab techniques.
He obviously knows what he's talking about.
> apparently you are not the only one who thinks festers book is useless
> with regard to lsd synthesis. just wondeing cause i have the book.
> i really don't know enough to have an opinion, but aparrently you do.
> please inform. thankjs again.
> peace..delysid
Fester's book is appalling - not bad. It contains several fundamental errors that anyone who knows anything about acid synths would detect. There is a good LSD synthesis in Tihkal that dates from the mid 1970's. Fester has only the archaic synths from the 1950's and '60's! Some of the advice - to grow a field of rye and infect it with ergot - to harvest 'ears' of ergot - is just plain 'fantasy'. For an experienced chemist - who can detect the errors - the book wouldn't be too bad because it has some useful references. For a novice it would be madness to take this book as a bible of acid manufacture. Synths that use toxic materials such as SO3, hydrazine and phosgene are dangerous to pros and especially to amateurs. The speculation about 'Method X' is nonsense.
Fester has written up reports of chemistry he thinks works - often by rewriting scientific papers to make them read better. These reports are mixed-in (in SoMM) with reports of actual procedures he HAS done. One of the consequences of this is that SoMM contains some procedures that will not work (some of the MDMA synths). How do we know this? - you ask - simple: people who've tried to reproduce some of the MDMA synths from SoMM have not been able to because they won't work with MDMA!
Fester's book has some useful references - you could read some of them before you continue. There is another book, on acid chemistry, which Bob has at www.promind.com - but I haven't read that so I can't comment but Rhodium said that it wasn't any good either.
psyloxy (Hive Bee) 05-31-00 11:13
Re: New tryptamine literature
What about the book 'LSD 25 and Tryptamine Syntheses' by O. Snow ? I didn't like his book on amphetamines much but the reference section was good.
--psyloxy--
Rhodium, (Chief Bee) 05-31-00 17:18
Re: New tryptamine literature
I think it sucks.
From Tihkal, by A Shulgin.
#26. LSD-25
ACID
LYSERGIDE
D-LYSERGIC ACID DIETHYLAMIDE
METH-LAD
D-LYSERGAMIDE, N,N-DIETHYL
N,N-DIETHYL-D-LYSERGAMIDE
9,10-DIDEHYDRO-N,N-DIETHYL-6-METHYLERGOL
SYNTHESIS: A solution of 6.7 g KOH in 100 mL H2O, under an inert atmosphere and magnetically stirred, was brought to 75 °C, and 10 g ergotamine tartrate (ET) added. The reaction mixture turned yellow as the ergotamine went into solution over the course of 1 h. The stirring was continued for an additional 3 h. The reaction mixture was cooled to about 10 °C with an external ice bath, and acidified to a pH of about 3.0 by the dropwise addition of 2.5 N H2SO4. White solids started to appear early in the neutralization; approximately 60 mL of sulfuric acid was required. The reaction mixture was cooled overnight, the solids removed by filtration, and the filter cake washed with 10 mL Et2O. The dry solids were transferred to a beaker, suspended in 50 mL 15 % ammonia in anhydrous ethanol, stirred for 1 h, and separated by decantation. This extraction was repeated, and the original decantation and the second extract combined and filtered to remove a few hundred milligrams of unwanted solids. The clear filtrate was stripped of solvent under vacuum, the residual solids dissolved in 50 mL of 1% aqueous ammonia, and this solution was acidified as before with 2.5 N H2SO4. The precipitated solids were removed by filtration and washed with Et2O until free of color. After drying under vacuum to a constant weight, there was obtained 3.5 g of d-lysergic acid hydrate, which should be stored in a dark, sealed container.
A suspension of 3.15 g d-lysergic acid hydrate and 7.1 g of diethylamine in 150 mL CHCl3 was brought to reflux with stirring. With the external heating removed, there was added 3.4 g POCl3 over the course of 2 min, at a rate sufficient to maintain refluxing conditions. The mixture was held at reflux for an additional 5 min, at which point everything had gone into solution. After returning to room temperature, the solution was added to 200 mL of 1 N NH4OH. The phases were separated, the organic phase dried over anhydrous MgSO4, filtered, and the solvent removed under vacuum. The residue was chromatographed over alumina with elution employing a 3:1 C6H6/CHCl3 mixture, and the collected fraction stripped of solvent under hard vacuum to a constant weight. This free-base solid can be recrystallized from benzene to give white crystals with a melting point of 87-92 °C. IR (in cm-1): 750, 776, 850, 937 and 996, with the carbonyl at 1631. The mass spectrum of the free base has a strong parent peak at mass 323, with sizable fragments at masses of 181, 196, 207 and 221.
This base was dissolved in warm, dry MeOH, using 4 mL per g of product. There was then added dry d-tartaric acid (0.232 g per g of LSD base), and the clear warm solution treated with Et2O dropwise until the cloudiness did not dispel on continued stirring. This opaqueness set to a fine crystalline suspension (this is achieved more quickly with seeding) and the solution allowed to crystallize overnight in the refrigerator. Ambient light should be severely restricted during these procedures. The product was removed by filtration, washed sparingly with cold methanol, with a cold 1:1 MeOH/Et2O mixture, and then dried to constant weight. The white crystalline product was lysergic acid diethylamide tartrate with two molecules of methanol of crystallization, with a mp of about 200 °C with decomposition, and weighed 3.11 g (66%). Repeated recrystallizations from methanol produced a product that became progressively less soluble, and eventually virtually insoluble, as the purity increased. A totally pure salt, when dry and when shaken in the dark, will emit small flashes of white light.
There are other possible (modern) synths apart from this one but unless one of them pops up in the scientific literature we're not likely to see it. Real acid chemists have no desire to notify the DEA about exactly what precursors they use!
Here's another review of Fester's book - interspersed with some interesting references to acid chemistry and ergot:
Forest Gump (Dec. 24, 1997 at 19:15):
The book that you refer to "Practical LSD Manufacture" by Uncle Fester, now in its 2nd Ed. isn't completely about LSD, although from the title one could get that impression. The first edition contianed 115 pages, of which only about 70 pages actually had anything to do with LSD synthesis, the rest mostly about Fester's pet project: TMA-2 synthesis. The second edition contains 142 pages, almost all the extra pages going to his pet project -- which now consumes about halve the book -- while the LSD portion remains virtually unchanged (all the errors and mistakes of the first edition were remarkably well preserved into the second). A naive person could be forgiven for mistakenly thinking the book of being just a vehicle for his pet project -- but of course we know better.
Before I list just some of those errors let me preface it with this: it is obvious that not only does Fester not have any practical experience with Lysergic chemistry, but that he is also confused by it.
1.) Isomer Confusion. In chapter 4 Fester makes repeated mistakes as to chirality. On page 24, in reference to the anhydrous hydrazine degradation method, he tells us that this procedure produces very little iso- compound, when in fact it produces predominately iso- material. On page 25 he informs us of the importance of maintaining anhydrous conditions to avoid getting racemic product -- on further reading it is obvious that by "racemic" he means iso/normal mixtures, as nowhere is there to be found any reference to the l (levo) compound.
The older hydrazine hydrate method produced a 1/1 mixture of d and l compounds; the l compounds are inactive and represent a total loss, as there is no convenient method to convert them into the desired d compound. The anhydrous hydrazine method is a newer improvement upon this which avoids the l compound, but it still gives about 2/3 of the iso- compound which is also inactive; 2/3 inactive product sounds real bad, but it's not nearly as bad as the older method because the iso- compound is easily isomerized into the active compound in about 2/3 yield. When Hofmann refers to this new method as not producing any "racemic" material what he means is that it doesn't produce any of the useless l compound, not that it doesn't produce iso- compound.
Also, the amidation procedure he gives in the same chapter produces some iso- compound, although nowhere does he mention that. Indeed, from reading the purifacation procedure, he seems to think that this amidation method also preserves chirality.
2.) Continuum Error. The first paragraph on page 27 (i.e., "Both of these choices are really very poor, ...") picks up from nowhere, and we're left to wonder what he's refering to. Chalk this one upto bad proofreading (this is Loompanics we're talking about after all).
3.) Outdated Methods. The four amidation methods in the book have long since been superseded by the phosphorus oxychloride in chloroform method, which is not in the book.
4.) Method X. In the book a big deal is made about his erroneous discovery of a "superior" LSD method which he calls "method x". I'll spare you all the convoluted details and inane logic of how he came about this "discovery" except for this one statement of his: "Note that propionic anhydride is a listed chemical under the Chemical Diversion Act, with a reporting threshold of 1 gram. There is only one substance in the field of clandestine drug manufacture where 1 gram is a significant amount -- LSD"
I'm sure not a few DEA chemists must have laughed there ass off after having read that. Propionic anhydride is used to make fentanyl and its analogues. Some fentanyl analogues are 10 times more potent than LSD!!!!
And that is just some of the errors contained within that book. And with that I'll leave you, hopefully a little bit more knowlegable.
-- Forest Gump
(Hive Bee)
04-06-04 14:02
No 499331
Reposted in 2 parts due to hive restrictions on article size:
Thanks for the info.
FX (Dec. 25, 1997 at 09:51):
Hey, thanks a lot. You seem to know quite a bit about LSD chemistry. I'm sure that Fester's book has some errors, but I am not aware of any other book in existence on practical LSD manufacture. Are you? It is amazing how few people know anything about LSD synth, apparently it is the hardest recreational drug to manufacture of them all, much much harder than ectacy or meth. Why is this? How should someone go about learning about LSD manufacture assuming that they don't have PhDs in chemistry? According to DEA, almost all of the LSD made in the United States is made but just a handful of chemists in california! Can you believe that? A half a dozen people make amost 100 million hits per year, and they have been doing it since the 1960s! This almost blows the mind!
Forest Gump (Dec. 25, 1997 at 15:42):
Below are all the books that are in print that I know of which contain LSD synthesis procedures:
The Anarchist Cookbook, William Powell (1971);
The Book of Acid, Adam Gottlieb (1975);
Psychedelic Chemistry, Michael V. Smith (2nd Ed., 1981);
Recreational Drugs, Prof. Buzz (1989);
Practical LSD Manufacture, Uncle Fester (2nd Ed., 1997);
TIHKAL: The Continuation, Alexander Shulgin (1997).
So, which ones do I recomend for someone serious about LSD chemistry? Well, all of them! But not for the reasons you might think at first.
Most of these books contain serious errors. The Anarchist Cookbook for example has a method of "Making LSD in the kitchen" which is incorrect of course, although it does give an accurate procedure which is merely a reprint of the first part of Pioch's patent method. The Book of Acid calls to use sodium nitrate in one method, when in fact it is sodium nitrite which is used in that procedure. Recreational Drugs doesn't really contain anything that wasn't already in Psychedelic Chemistry, although it does give an incorrect LSD structure. All these books can go a long way in developing one's critical faculties though -- which is an important attribute for an LSD researcher to have, considering the B.S. factor that surrounds LSD.
So, which of these books do I think are the most important to have? All the books listed below, in order of importance:
1.) Psychedelic Chemistry; 2.) Practical LSD Manufacture; 3.) TIHKAL.
Again, not for all the obvious reasons. Number 1 and 2 contain many journal references, and so can be a good step-off point to the real gold mine: the chemical journals at your nearest university science library. TIHKAL and #1 both have the most up-to-date method, although that's the only method TIHKAL has.
Believe it or not, you can probably start learning about LSD chemistry right now if you have a chemistry text-book or are near any library. Just look-up the following (numbered in order of importance):
1.) carboxyl group;
2.) carboxylic acids;
3.) amides;
4.) amines;
also, look-up:
acid halides;
anhydrides;
mixed anhydrides;
hydrazides;
azides;
azoles;
esters;
and of course, alkaloids.
You see, LSD is an amide. LSD is usually made from lysergic acid which is a carboxylic acid and diethylamine which is an amine. Lysergic acid is in turn usually made by degradation of an amide, such as ergotamine.
All of these procedures involve the changing of one functional group: the caboxyl group. A good LSD chemistry researcher will devote much (MUCH) study to this group.
I hope that this has been helpful.
-- Forest Gump
Re: Thanks for the info
=================
Posted by Forest Gump on December 30, 1997 at 23:08:13:
In Reply to: Thanks for the info - posted by Cherry baby on December 30, 1997 at 19:30:43:
CB: (2) Another dodgy thing about Fester's "Practical LSD Manufacture" is his recommendation to make LSAs by growing ergot on rye and to plant your own rye field in order to do this! Is the man mad? Fester appears to be ignorant of the existence of C. paspali.
FG: Yes, Fester is a bit loopy to think that prospective LSD chemists are going to become Farmer for a Year. Although the method certaintly works, the labor and amount of solvents required make it impractical for one or two people.
some more references:
CB: (4) In D. M. Perrine's book "The chemistry of mind-altering drugs" pages 274-278 outline syntheses of LSD. He includes both modern total synthetic methods and clandestine methods [he figures that lysergic acid is made from either growing C. paspali to produce paspalic acid OR by diverting LSA from medicines]
Some of Perrine's references are:
Kornfeld et al; JACS 1956, 78, 3087-114 [early obsolete method]
Horwell; Tetrahedron 1980, 36, 3123-49 [review of early synth]
Oppolzer et al; Helv. Chim. Acta 1981, 64, 478-81 [modern total synth]
Oppolzer et al; Tetrahedron 1983, 39, 3695 [modern total synth]
Rebek & Tai; TL 24, 859-60 (1983), (and refs. therein.) "A New Synthesis of Lysergic Acid", [total synth from tryptophan]
Rebek, Tai & Shue; JACS 106, 1813-19 (1984) "Synthesis of Ergot Alkaloids from Tryptophan"
Kobel et al; Helv. Chim. Acta 1964, 47, 1052 [paspalic acid form C. paspali]
Troxler; Helv. Chim. Acta 1968, 51, 1372 [Isomerisation of paspalic acid to lysergic acid]
CB: (5) In M. V. Smith's "Psychedelic Chemistry" growth of C purpurea on synthetic media is described. Just about everyone claims that C purpurea will only grow on grain in a field. What's Up Doc?
FG: Getting species of Claviceps to grow in culture is easy. Getting species of Claviceps to grow in culture and produce lysergamides' is what's hard. I'm sure M. V. Smith's method in said book will work just fine for _growing_ Claviceps species, but it will all be for nought, as no lysergamides' will be produced by it.
Successful culture methods have been developed which use specific strains of both C. paspali and purpurea to produce as much as 2 to 5 g of lyseramides' per L of culture!!!!
I direct you to "Biosynthesis of Ergot Alkaloids and Related Compounds", Tetrahedron, Vol. 32, pp. 873-912 (1976). On page 883 under the heading "Industrial production of ergolines" it gives a brief overview of what I just mentioned, and gives references to those procedures.
I hope that this has been helpful for you.
Subject: References as promised...
From: aankrom@blackfoot.ucs.indiana.edu (aankrom)
Date: Thu, 7 Apr 1994 14:41:27 GMT
FN Johnson et al, JMC 16, 532 (1973) "Emetic Activity of Reduced Lysergamides", (LSAs using s-amine and POCl3)
JACS 76. 5256: TL 1969, 1569.
Detlef Groger - Chapter 12 - Ergot, p 321
----------------
References:
Boisynthesis of ergot in submerged culture: Arcamone et al, 1961, Proc. Roy. Soc. B155, 26.
Stoll & Hofmann - In "The Alkaloids" - ed Manske & Holmes, vol 8, 725-83, Acad. Press NY.
Fetoclavine & fumigaclavine in Aspergillus fumigatus Fres, Spilsbury & Wilkinson 1961,
fumigaclavine in Rhizopus nigricans - Yamano et al, 1962,
KrZ - posted 06-21-98 06:57 PM CT (US)
http://www.alltheway.com/html/ergot.html
CA: 71:P69351y : describes mutants of strain NRRL 3027 producing 2270mg/l of ergoline compounds of which 85% were amides of lysergic and isolysergic acids. (Swiss patent application)
CA: 77:P156333n : describes a method used to get 9.75g pure lysergamides from a 10 litre fermentation originally containing an estimated 15g.
CA: 94:13992r : reference Indian Drugs; 1980; 17(8) 228-31 Eng.
CA: 90:118108c : reference Indian Drugs; 1979; 16(4) 88-93 Eng.
Very interesting>:-||
CA: 102:219574y : Serbo-Croat areticle describing 2.2g/l prod. by C. paspali Stevens and Hall (1984).
Life History and Poisonous Properties of Claviceps paspali; H. B. Brown (Mississippi Agricultural Experiment Station); Journal of Agricultural Research ,vol. 7(9), pgs 401-405. describes on brief glance through it --- germination of the yellowish-grey sclerotia found on Paspalum dilatatum Poir. observed in the region of the Mississippi Agricultural College.
Also contains reference to Stevens and Halls' original article (1910).
* Biotechnological Exploitation of the Ergot Fungus (Claviceps Purpurea); Karl Esser and Andrea Duvell; Process Biochemistry, August 1984 pgs 142-149.
Synopsis: "The alkaloids of the ergot fungus C. purpurea and related species already known as drugs in the middle ages are still finding many uses in medical therapy (he he). Since the supply of natural grown ergots is not sufficient, the biotechnological production of ergot alkaloids has gained in importance. This requires not only an undestanding of physiological and environmental conditions, but also concerted breeding in order to increase and stabilize the production level."
* Biology of Claviceps; Willard A. Taber; Chapter 15 (sorry - i don't remember which book this came from, but it should be indexed under Taber in Biological Abstracts) pgs 449-486.
"If one desires isolates of C. paspali (which are high producers of simple amides), one must go to paspalum grass. ... C. paspali differs from all other species in possesing a yellowish tan cauliflower- shaped sclerotium rather than the purplish banana-shaped sclerotium, and it has been suggested that this species be trasnsferred to the genus Mothesia. "
*The Ergot Alkaloids; A. Stoll and A. Hofmann (THE); Chapter 21, The Alkaloids, Manske (ed. ?) vol. VIII, pgs 725-779+.
Describes lots and lots and lots of chemical detail regarding everything from biogenesis to complete chemical synthesis as a means of confirming structure. Also has a section completely devoted to "Derivatives of Ergot Alkaloids" in which the following processes for synthesizing amides are discussed:
=> The azide process.
=> DMF-SO3 mixed anhydride method.
=> mixed Lysergic acid trifluoroacetic anhydride.
=> Lysergic acid chloride hydrochloride method.
=> N,N'- carbonyldiimidazole as condensing agent (Best IMHO).
Kobel, Schreier, Rutschmann. Helv. Chim. Acta 1964, 47, 1052
(Hive Bee)
04-08-04 04:37
No 499626
I have some questions on Shulgins synthesis. First. Do you not need to reflux ergotamine in a N-methyl alkoholic potassium hydroxide solution, to obtain Lysergic acid?
Secondly should you not use the free base ergotamine instead of the tartrate salt? A method of obtaining the base can be found in the Journal of Organic Chemistry vol 1,245-53(1936), by Walter A. Jacobs and Lyman C. Craig. They treat ergotamine tartrate with an excess of sodium carbonate solution, and extract with warm chloroform. After drying of the extract, the chloroform was removed in vacuo. etc,etc. JUST WONDERING ANY ANSWERS
(Chief Bee)
04-08-04 05:10
No 499633
I have archived the above discussion as well as many more LSD references at ../rhodium /lsd.syn
bbell: In Shulgin's procedure, the first step is to heat the ergotamine tartrate in an aqueous potassium hydroxide solution, which will instantly form potassium tartrate and freebase ergotamine, and during the prescribed 4 hour reflux the ergotamine will hydrolyze to lysergic acid.
The reason Shulgin uses the salt instead of the freebase is probably simply because the salt is the form his ergotamine tartrate was stored in, and his use of water instead of methanol as solvent is probably just a matter of preference. Methanol is possibly slightly higher-yielding, but the workup of the reaction mixture is easier if you use water, as you only need to acidify and extract, rather than first having to evaporate the methanol before performing the acid/base workup.
The Jacobs & Craig article you reference has been posted in Post 437085 (Rhodium: "Okay then, here you go. Collect the whole series!", Tryptamine Chemistry)
Edit: I just noticed that I have already told you this last year in Post 435281 (Rhodium: "I don't think that shulgin is wrong here...", Tryptamine Chemistry)
The Hive - Clandestine Chemists Without Borders
(Hive Bee)
04-08-04 06:03
No 499643
I am reading Patent US2090429 this article gives several preferences for this method one being "whereby for the preparation of the hydrazide the pure alkaloids like ergotamine, ergotoxine, ergotaminine, ergotinine, ergobasine etc. and also raw alkaloids or raw mixtures thereof can be used." Next. "The degradation of alkaloids of ergot with hydrazine to lysergic acid hydrazide is, especially with respect to the obtained yield, much superior and rational as compared with the known degradation with aqueous or alkoholic alkalis. The fact that by the present process not the L.A., but it's hydrazide will be obtained, is a further advantage, because this new derivative of L.A. can by one simple recrystallization be obtained in quite pure state and is more stable than the free L.A. Furthermore the hydrazide is a more suitable starting product for synthetical work than the free acid." I have noticed a lot of people don't care for this method. Any comment?
(Hive Bee)
04-08-04 11:36
No 499696
I think people don’t like the hydrazine method simply because other methods are superior in the sense that in many others you don’t get complete racemisation. The other problem is that in these preparations it is the anhydrous hydrazine that is used. Besides being toxic and dangerous it is also some hard work too prepare.
I did heard some people implying that the procedure works with hydrazine hydrate too, but I still have to see it written somewhere in a believable way. Anybee has any such references?
“The real drug-problem is that we need more and better drugs.” – J. Ott