02-16-01 09:16
No 173728
This should be possible (it's from the textbooks):
indole-CH2-CH2-NH2 + HNO2 ---->
indole-CH2-CH2-OH + N2 + H2O
That gives tryptophol. Well ok, i don't have any indole-AcOH nor Na metal lying around, but as someone else here has said before: tryptophan is easily obtainable by the kilo, even the pharmaceutical grade is cheap (at least where i live).
Another idea for the decarboxylation of tryp: I don't remember exactly where i read it but, heating it with barium oxide, than separating T from the latter by addition of dil H2SO4, and filtering off the barium sulfate.
Then , refluxing tryptophol with dialkylamine (base) in alcohol and skeletal nickel, but i would try CHEMGUY's beloved Urushibara Ni-catalyst, whose effectiveness has recently been proven in reduction of certain NO2-compounds.
I believe this procedure is on Rhodium's .
Well, whadda ya think ?
e109
(Hive Bee)
02-16-01 17:36
No 173824
You might form a nitrosamine with the indole nitrogen atom. Secondary amines form nitrosamines in the presence of nitrous acid. Maybe there's a way to convert the nitrosamine back to =NH, ie. hydrogenation.
(Hive Bee / Eraser)
02-17-01 03:30
No 173932
Yeah, I know i was maybe a little too optimistic, as indolic NH attack is prolly going to happen, but i thought the NH2 at the 3-position was a more favorable place for nitrite attack, or is it not at all specific?
Damn, been too quick again
, if only there was a better way to tryptophol than reduction of indole-AcOH,although i suppose Al-isopropoxide would work well.
Are there no ways from tryptophan/tryptamine to the AcOH ?
e109
(Hive Addict)
02-17-01 05:21
No 173940
tryptophane -1-> indole-3-acetaldehyde -2-> tryptophol
Step 1 is deteiled at rhodium.lycaeuem.org and for 2 someone has to find a
good reaction, maybe Al(OiPr)3/IPA is enough.
--psyloxy--
(Stranger)
02-18-01 19:51
No 174213
psyloxy,
you translated this, but did you ever try it?
Post 9775 (in_outsider: "Tryptophol from Tryptophan via yeast", Tryptamine Chemistry)
Snap, Crackle, Pop
(Hive Addict)
02-19-01 04:13
No 174280
nope. even if I had the proper equipment to do that I would have avoided it
because it really looks messy, the extraction part reads like a pain in the
ass, that's why I stopped translating it at this point.
It is intresting but, if you ask me, of no big value for clandestine chemists.
--psyloxy--
(Stranger)
02-19-01 08:59
No 174314
I totally agree,
I can't imagine trying to scale it up to a couple hundred grams.
The only thing I wondered about is if there is a way to improve the yields or the amount of tryptophan processed by the yeast. I'm not particularly interested in this dream right now, but at a later date I thought it might warrant a day or two in the library just to see if you could find some way to tweak this. Might also be a strain of yeast out there particularly suited for this task. But thats not a problem for today.Snap, Crackle, Pop
(Hive Addict)
02-20-01 04:24
No 174451
Uhm, what about reducing indole-3-CH2-COH to tryptophol with Urushibara Ni ?
--psyloxy--
(Hive Bee)
02-20-01 18:24
No 174565
While enjoying a leisurely stroll through the chemistry library today on my way to J. Org. Chem I spotted a book on heterocycles and remembered this thread. I found a sentence on page 82 in 'The Chemistry of Carbon Compounds' by E H Rodd:
Nitrosation of 3-substituted indoles having a free imino group gives yellow I-nitroso compounds which revert to the original indole on reduction.
It didn't give details on how the nitrosation worked. I also looked up an article in J. Org. Chem. 33 (1968) 2586 which US patent 4014893 references which I found by putting the keyword pseudonitrosite in a patent database. The article includes the preparation of norbornene pseudonitrosite from norbornene in pentane-ether using nitric oxide.
(Hive Bee / Eraser)
02-25-01 08:58
No 175418
Polythene Sam:
Are you saying that this could be possible:
tryptamine + HNO2 --> 1-nitroso-indole-3-ethanol
then the latter compound's reduced with Ni (in presence of the dialkylamine base) to give the corresponding N,N-dialkyltryptamine; only adjusting the amount of Ni required?
(2 reductions in one pot)
Psyloxy:
The way to synth I-3-AcO on Rhodium's is rather crappy if you look at the amount of benzene used, and the large amount of diluted NaOCl, i find it impractical.
What is the correct equation for this anyway, it's an oxidation, isn't it, so...
Couldn't one , instead of diluting it so much, adjust the pH to 8 or 9?
e109
(Hive Bee)
02-25-01 09:39
No 175427
It seems to suggest that this would work:
tryptamine + HNO2 --> 1-nitroso-indole-3-ethanol
But the reaction
ROH + R'R"NH --> RR'R"N + H2O
seems to be a substitution reaction and isn't reduction. It looks like the 1-nitroso-indole-3-ethanol could be reduced to tryptophol according to that reference I found, though.
(Hive Bee / Eraser)
02-26-01 04:00
No 175551
I see, the Ni is catalyst in a substitution rxn, so the 1-nitroso-DMT has to be reduced afterwards, or does someone feel anything for carcinogenic hallucinogens?
Hmm... maybe better to first reduce to tryptophol...
e109