Idea for dialkylating T (longer way)

[element109]

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

[PolytheneSam]

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.

[element109]

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

[psyloxy]

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--

[firecracker]

psyloxy,

you translated this, but did you ever try it?

Post 9775

(in_outsider: "Tryptophol from Tryptophan via yeast", Tryptamine Chemistry)



Snap, Crackle, Pop

[psyloxy]

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--

[firecracker]

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

[psyloxy]

Uhm, what about reducing indole-3-CH2-COH to tryptophol with Urushibara Ni ?

--psyloxy--

[PolytheneSam]

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.

[element109]

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

[PolytheneSam]

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.

[element109]

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