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9,10-dihydro derivative of lysergic acid where the double bond two
spaces upstream from the carboxyl group has been reduced.
The Operation Julie cooker had made the obvious analogy that if
the procedure works for these substances closely related to LSD, it
should also work for LSD. This type of underground research and
discovery is not at all unusual. If you look through the Chem. Abstracts
for references to the use of hydriodic acid and red phosphorus in the
reduction of ephedrine to meth, you will find nothing. This procedure is
a general method of reducing alcohols to alkanes, and was applied by
clandestine chemists to ephedrine with excellent results. Ditto for the
lithium-metal-in-liquid-ammonia reduction of ephedrine to meth.
To get the full details of the following procedure, your command of
Russian or Hungarian had better be firmer than mine. All this research
came out of Eastern Europe. For example, see Chem. Abstracts,
Volume 93, column 186636. This will then direct you to: Otkrytiya,
hobret., Prom. Obraztsy, Tovarnye Znaki 1980, (19), 303. Also Italian
patent application 76/50,746 dating to Dec. 6, 1976.
For this method to be superior to the procedures given in the
earlier chapters of this book, the need for a close stoichiometric
quantity of anhydride added would have to be done away with. It must be
possible to add a healthy excess of the propionic anhydride to get
100% conversion of the lysergic acid to the mixed anhydride. It would
Method X 67
further be nice if the procedure works with the hydrous form of
lysergic acid, doing away with the need to bake it under high vacuum.
Further advances in LSD manufacture taken from analogy to
closely related compounds can also be found in the hydrazide "one-pot
shot" route to LSD. It would appear that lysergic acid hydrazide can
be reacted with the very common chemical sodium nitrite, and then
diethylamine to give LSD. This eliminates the need to synthesize or
otherwise obtain 2,4-pentanedione. (For synthesis of 2,4-
pentanedione, see U.S. Patent 2,737,528 and 2,834,811.) See Chem.
Abstracts Volume 94, column 209051 (1981) and German Patent
2,924,102. Another analogy can be found in Chem. Abstracts Volume
99, column 71069 which then refers you to German Patent DE
3,239,788. It would appear that phosgene, as used in Chapter 8, can be
replaced with oxalyl chloride. This substance is much less
dangerous than phosgene, and more easily measured out.
Preparation of Propionic Anhydride
Propionic anhydride is obviously going to be impossible to
purchase without getting busted. It is, however, not too difficult to
make in good yield and high purity. The simplest method of
preparation is via the general method found on page 28 of Organic
Synthesis Collective Volume 3. In this method propionic acid reacts
with propionyl chloride in the presence of pyridine to yield propionic
anhydride. Propionyl chloride is at present an easily obtained
substance, but in the future, this may change. When that time comes,
propionyl chloride can be easily made from propionic acid by the
directions found in The Journal of the American Chemical Society
Volume 60, page 1325 (1938). Propionic acid will never be a
restricted chemical because it has such wide use as a means to kill
fungus and mold growing on stored grain.
To do the reaction, a 250 ml flask and a dropping funnel are first
thoroughly dried, then a magnetic stirring bar is placed in the flask,
followed by 16 ml of pyridine and 25 ml of benzene. If there is a
question as to whether the pyridine or benzene are completely free of
Practical LSD Manufacture
68
water, the pryridine should be dried by adding some KOH pellets to
the jug of pyridine, and the benzene dried azeotropically by distilling
off 10% of it, and using the residue.
Now to the stirred solution, rapidly add 9.25 grams (8.75 ml) of
propionyl chloride. This causes a small rise in temperature, and
pyridium complex conies out of solution. Then, with continued
stirring, add 7.4 grams (7.4 ml) of propionic acid over a period of 5
minutes from a dropping funnel. This causes the solution to get hot,
and pyridine hydrochloride comes out of solution.
The stirring is continued for an additional 10 minutes, then the
pyridine hydrochloride is filtered out in a Buchner funnel. This should be
done rapidly, and on a dry day, because the pyridine hydrochloride is
very hygroscopic, and will melt. The filter cake of pyridine
hydrochloride should then be quickly rinsed with dry benzene, and the
combined filtrate should be concentrated under a vacuum, using
steam or hot water to heat the flask. When the benzene and pyridine
have distilled off, they will be followed by the product, propionic
anhydride, boiling at about 70� C under a typical aspirator vacuum of 20
torr. This product may be contaminated with some propionic acid, and
it can be removed by redistilling the product through a
fractionating column, either at normal pressure or under a vacuum.
Propionic acid boils at 141� C, while the anhydride boils at 168� C at
normal pressure.
10 Solvent
Management
69
10 Solvent Management
A cursory reading of this text will make it plain to everyone that
the production of LSD involves heavy usage of solvents. From the
defatting and extraction of the crops to the crystallization of pure
LSD, a variety of solvents must be used in large amounts relative to
the product to get a fairly pure product.
"Fairly pure product"... how we starved masses long for such a
thing. Back in the 70s when I dropped my first doses of acid, the
stories were already impossibly ingrained in the consuming public's
mind that the acid was cut with speed or strychnine. All of the stories
are easily disproved, yet they persist to this day. If the entire weight of a
blotter paper was made of pure meth or strychnine, its effect would be
less than pronounced. The truth of the matter is that lysergic-
similar compounds contaminating the LSD are responsible for these
undesirable effects. From clavine alkaloids to unhydrolysed ergot
alkaloids, to unreacted lysergic acid, or lysergic acid hydrazides to iso-
LSD and God knows what substances created by the mishandling of
the raw materials and product, a contaminated product is much easier to
make than a pure one.
The use of large volumes of solvents poses twin problems: [ Pobierz całość w formacie PDF ]