SUBSTITUTED TRYPTAMINES
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DMT Synthesis (Dimethyltryptamine)
STEP I
Using an area of good ventilation or a fume hood, place a 1000ml roundbottom
flask in an ice bath using the set-up in Figure I. Add 400ml cold anhydrous
ether to this flask, in which 60g indole is then dissolved using the stirrer.
To 100ml anhydrous ether in a separatory funnel add 50g of oxalyl chloride.
Slowly drip this solution into the vigorously stirred indole solution over a
period of 10 to 15 minutes. Continue stirring 10 minutes longer. Allow the
precipitate to settle a few minures and decant the liquid. Add anhydrous
ether and mix well. Allow this to settle and decant the liquid again. When
satisfied as to the purity of the precipitate, leave the golden precipitate
in the flask for the next step which must follow immediately. Yield is
approximately 100g.
STEP II
Dimethylamine reacts readily with indole oxalyl chloride. Use about 400ml
ice-cold anhydrous ether in the same 2-neck 1000ml RB flask used in Step I,
with the precipitate in it from Step I. Cool the ice bath further by using
salt and ice. Estimate the weight of the precipitate and use 100g indole
oxalyl chloride. For this weight of IOC use two entire 50g containers of
dimethylamine since it will not keep if the container seal is broken. Cool
the amine in container much below 0-degrees Centigrade and dissolve 1 part
amine in 3 parts anhydrous cold ether. Amine may be stored in this solution.
For use, warm stock solution to room temperature and use the appropriate
aliqout. Set up the entire apparatus the same as when adding the oxalyl
chloride. Add the amine solution slowly to the IOC with vigourous stirring.
Stir for 1/2 hour after the addition is complete, allowing the temperature to
rise to ambient. Vacuum filter the precipitate using ether as a wash,
followed by an ether-water wash. It is better to slurry the ether-water with
the precipitate before filtering. Recrystallize from hot ethanol or from a
50-50 methanol-benzene mixture.
STEP III
Prepare the apparatus as in Figure II. Prepare the indol glycoxalamide by
melting and casting it into sticks if ether is to be used as a solvent.
Aluminum foil makes a good mold, casting pieces which will fit through the
condenser. Also a Soxhlet extractor may be used to add the crystals by slow
solution into the ether. Tetrahydrofuran, if available, dissolves IGA and the
compound is added slowly in the solution form.
To a stirred mixture of 15g LiAlH4 in 300ml anhydrous ether (or THF) slowly
add the sticks (or solution) of IGA until 20g in all have been added. Keep
the rate of reaction at a reasonable level or boil-over may occur. Stir and
reflux for 90 minutes after the addition is complete. Cool in an ice-bath and
begin to cautiously hydrolyse the complex with chips of ice or a cold
solution of methanol, added through the condenser. When there is no further
reaction, add a few ml extra water and allow to sit for a few hours, sloshing
the contents occasionally. Allow to settle finally and decant the clear
liquid into an evaporating vessel. Filter the residue and wash several times
with ether-methanol or THF-methanol. Evaporate the combined extracts and if
necessary, seed the heavy syrup with crystals of DMT. With no seed crystals
the product may take days or even weeks to crystallize. This crude product is
adequate for smoking. In order to purify DMT, begin after the LiAlH4 has been
hydrolysed with methanol. Add 500ml saturated Na2SO4 solution, mix and
filter. Wash with ether or THF and neutralize the filtrate with 0.1 N HCl.
Extract with ether in a separatory funnel and neutralize the lower layer with
0.1 N NaOH, extracting this solution in turn with chloroform. The chloroform
layer is dried over anhydrous Na2SO4, concentrated, and from it DMT
crystalizes on addition of petroleum ether. The mother liquor can be
chromatographed on an alumina column using benzene-methanol in a 99.8 to 0.2
ratio.
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DET Synthesis (Diethyltryptamine)
STEP I
Same as for DMT
STEP II
Use 200g diethylamine per 100g IOC. Diethylamine is less volatile and
poisonous than dimethylamine, so cooling is not necessary, but the fumes are
poisonous. Use the same procedure otherwise. Diethyl derivative is easier to
work with.
STEP III
Use same procedure and equipment. Use 22g indoleglycoxal diethylamide. The
final product is also easier to purify.
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NOTES
STEP I
Absolutely anhydrous ether is essential. A container that has been opened
previously is no longer anhydrous. Where cooled reactions are necessary,
remember that moisture is drawn to cold objects, and cold reagents, when left
open or poured, become quite wet. This applies to the initial reaction on all
three steps. A magnetic stirrer will not work for steps I and II. The
vigorous wobble-stirrer has been found adequate do deliver the violent
stirring needed, especially when several stirring balls are used in
conjunction with the paddle-bar. Sparkless motors must be used around ether.
Oxalyl chloride is very toxic and ventilation or a fume hood must be used.
Water vapor hydrolyses product I, producing a gummy dark-red mass. Proceed
to Step II as soon as possible.
STEP II
Refer to notes on anhydrous ether, stirrer, sparkless equipment, and
ventilation in the notes for Step I.
The color of the precipitate lightens somewhat as the amine is added to the
compound I.
The water in the ether is used to dissolve all low-molecular-weight amines.
STEP III
The crystalline amide is difficult to add to the LiAlH4 mixture. A Soxhlet
extractor may be used to add the amide by placing it in-between the flask and
condenser. Casting it into rods or bars is one of the simplest methods.
Tetrahydrofuran, if available, enables the indole glycoxal amide to be
dissolved and added as a solution; a procedure which is best and fastest of
all. LiAlH4 is a very dangerous inflammable compound, especially so when in
ether solution. The ether must be absolutely anhydrous or a violent
effervescence occurs, destroying the LiAlH4 and creating a fire hazard.
Contact of LiAlH4-ether solution with any water, damp materials, or even
chemically bound water such as cellulose causes spontaneous combustion. A
safety shield made from auto windshield material is a must when working with
LiAlH4 in any form. Handling LiAlH4 is done wearing rubber gloves in a dry or
inert atmosphere with a minimum of friction involved. Hydrolysis of the
complex is dangerous and should be done slowly and cautiously, using an
ice-bath to cool the mixture.
Difficulty in producing crystals the first time should cause no concern
since many organics need seed crystals to crystallize. The syrup may be used
for some purposes but be sure to save some seed crystals if you should happen
to get some.
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BIBLIOGRAPHY
Journal of Organic Chemistry Vol.23, p.1977
Journal of American Chemical Society Vol.76 p.6208
Journal of American Chemical Society Vol.82 p.2184
Chemical Abstracts Vol.53, p.11324
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See the accompanying .GIF files for Figures illustrating the apparatus
and structural chemical reactions.