dmt via methiodide/ethanolamine

[urushibara]

SWIM is seriously considering doing the tryptamine-MeI/EtOHAM synthesis, this is how he sees it going (basically)


dissolve 10g of trytpamine in 100ml of IPA

add 30g methiodide stir for 12 hours at RT

filter NNNtrimethyltryptammoniumiodide (dmt iodomethylate) wash with IPA, dry

then take 10g of dmt iodomethylate mixed with 40g of ethanolamine, reflux for 20 minutes

then acid/base the dmt out


can anyone advise SWIM on the fiddly bits of this reaction, he knows it yields fairly low, but it's a two pot reaction and nothing required is terribly difficult to get (SWIM's already eyeing off some appropriate lab ware for this). What things can be done to increase yield, and what is the procedure for recovering unreacted tryptamine?

sorry to ask, I have u('d)tfse, and only person here who's saying anything about the MeI/ethanolamine route is that rdxhmx (sp?). what he says makes sense, but I am looking for any further depth of understanding of this synthesis that there might be around the place. so I can make sure that SWIM has a minimum of speedbumps along the road.

[freakyDMT]

the forming of the quartenairy ammoniumsalt can also be done by the method of wieland in justus liebigs annalen der chemie 1934 page 1-25
he uses ethanol abs. tryptamine MeI and NaCO3 anhydrous
boils it for 5 hrs.
1.5 gram tryptamine in 1.8 gram amm.salt out

I will write the complete text from german as soon as possible for you down,O.K?

[urushibara]

I have an austrian friend who is interested in this subject too, and he could probably read the text as well - is it online or will you type it in? but anyways, a translation is good. chemistry info regarding experiments is almost readable from german by english speaking chemists. so many things are the same, the grammar is very similar.


thanks

oh, other than that, what is your personal reccommended most simple and effective method of producing this material? is it this synth or something else?

[freakyDMT]

You could use this route or the one with sodiumcyanoboronhydride/sodiummethoxide in methanol
but about this one here's the first:
1.6 grams of tryptamine (0.01 moles) is mixed in 36 ml of anhydrous alcohol.
6 grams of methyliodide containing 5.4 grams of anhydrous sodiumcarbonate are added to the solution and refluxed on a hot waterbath for 5 hrs.
the hot solution is then rapidly suction filtered.
alcohol is added to the residue and heated to boiling and rapidly suction filtered.
the filtrate is concentrated under reduced pressure.
large colorless needles of trimethyl-beta-3-indolyl-ethyl-
ammoniumiodide precipitate and are suction filtered.
the solution is reduced further to crystallize more of the iodide.
ref. otto snow/lsd-25 & tryptamine syntheses
psychoactive synthesis series volume 2

second one (in german,can you translate and put in onthe hive,i'm very,very bussy at the moment?!)
0.25 g des primären amins wurden in 20 ccm abs. alkohols gelöst und mit 5 g methyliodid verzetzt.
Man machte mit thalliumäthylat schwach alkalich und erhitzte das gemisch 4-5 stunden auf dem wasserbad,wobei man die reaktion dauernd alkalisch hielt.
Schliesslich fügte man noch 1 g methyliodid hinzu und kochte weiter bis zum verschwinden der alkalischen reaktion.
Die vom thalliumiodid abgesaugte lösung hinterliess nach dem eindampfen einen farblosen,krystallisierten rückstand,aus dem beim digerieren mit abs. alkohol ein nicht weiter untersuchtes jodid vom schmeltzp. 260-270°C hinterblieb.
Die alkoholische lösung schied nach dem einengen farblose kristallkrusten aus,die durch mehrmaliges umkristallisieren aus abs. alkohol in derbe,prismatische krystalle vom schmelzp. 182-183°C übergeführt wurden.
C14H21ON2I
pikrat. orangegelbe feine nadeln vom schmeltzp. 84-85°C
flavianat. Rötliche nadeln vom schmelzp. 233°C.
ref. justus liebigs annalen der chemie vol.513/page 21-22 (1934)

O,rhodium i have your polish translation but i have to do some corrections to it before i can send it to you,because it would'nt make sense if you read it.
its translated by a non-chemists so i have to correct to the proper terms.
about the other translations and the copies i will do my best,O.K?
and about the use of ethanolamine the amount you nead is 1 mole quaternairy salt and 10-15 moles of ethanolamine and boil for 10-15 minutes.
there is also an other way of doing this,thy use something called "DOBRO" instaid of ethanolamine,does anybody know what this could be thy tell me that this gives a higher yield!

[Vitus_Verdegast]

Man machte mit thalliumäthylat schwach alkalich

     Why TF do they use thallium ethylate? I hope it was just because they had some handy. Thallium and its salts are real heavy poisons, a thallium poisoning is known to make your hair fall out.

Crazy ole chemists of yesterday's yore, loveable aren't they?  

[freakyDMT]

yes i know thallium is extremely poisonious but if you reed the article you see thy form thalliumiodide with
crystalizes out of the solution as a solid.
but i would'nt use this route as a first choice!
i think the one from otto snow with methyliodide/sodiumcarbonate is a good one with a yield of 50-60%
English translation of the german article:
0.25 gram of the primary amine (tryptamine or 5-methoxytryptamine) is dissolved in 20 ml ethanol abs. and to this 5 gram of methyliodide is added.
Then the solution is made lightly basic with thalliumethylate and refluxed for 4-5 hours on a waterbath
whereby the solution is kept slightly basic.
Supplementary 1 gram methyliodide is added and refluxed further untill the basidity is faded away.
The formed thalliumiodide is filtered off and the solution is boiled down whereby colorless crystals form.
These are (digerieren?) with ethanol abs. and are iodide of unknown origin with a mp. of 260-270°C.
The alcaholic solution is boiled down further and forms a colorless crystalcrust.
These are recrystallized from ethanol,prismatic crystals mp 182-183°C.
C13H19N2I (C14H21ON2I is incorrect!)
picrate orangeyellow fine needles mp. 84-85°C
flavianate reddish needles mp. 233°C
ref. justus liebigs annalen der chemie vol.513/page 21-22(1934)

[Rhodium]

If you just want something to precipitate I^- with, then I'd suggest to go with Pb²⁺ or Ag⁺ first. Even if they too are heavy metals, they don't get my "antisocial chemical" stamp...

[freakyDMT]

Other references on this method are:
Hoshino T.,Shimodaira K.,
Uber die synthese des bufotenin-methyl-athers (5-methoxy-N-dimethyl-Tryptamin) und bufotenins
(about the synthese of bufotenine-methylethers (5-methoxy-N-dimethyltryptamine) and bufotenines)
Synthesen in der indolgruppe 15
Bulletin of the chemical society of Japan 11/221-224 (1936)
see also:
Manske R.H.F
Calycanthine 2
The degradation of calycanthine to N-methyltryptamine
Canadian journal of chemistry 275-282 (1927).
and Chemical Abstracts 52/14083