Tryptamines in the wild

[pHarmacist]

Indole Alkaloids of Acer saccharinum (the Silver Maple), Dictyoloma incanescens, Piptadenia colubrina, and Mimosa hostilis
Irwin J. Pachter, David E. Zacharias, Oscar Ribeiro
J. Org. Chem. 24, 1285-1287 (1959)

Abstract
Gramine was isolated from the leaves of Acer saccharinum L., N,N-dimethyl-5-methoxytryptamine from the bark of
Dictyobma incanescens D.C., bufotenine from the seeds of Piptadenia colubrina Benth., and N,N-dimethyltryptamine from the roots of Mimosa hostilis Benth.


Old and New Alkaloids from Zanthoxylum arborescens
Jonas A. Grina, Matthew R. Ratcliff, Frank R. Stermitz;
J. Org. Chem. 47, 2648-2651 (1982)

Abstract
The new alkaloids (2S,5S)-2,5-dibenzyl-1,4-dimethylpiperazine, 8-hydroxy-4,7-dimethoxyfuranoquinoline, and 8-isopentenyloxy-4,7-dimethoxyfuranoquinoline were isolated from Zanthoxylum arborescens (Rutaceae). The 6-D-glucopyranoside of hordenine (previously known only as a synthetic) was also found. The known alkaloids skimmianine, tembetarine, hordenine, N,”-dimethyltryptamine, N-methyltryptamine, l-methyl-3-(2’-phenylethyl)-1H,3H-quinazoline-2,4-dione and 1-methyl-3-[ 2’-(4’’-methoxyphenyl)ethyl]-1H,3H-quinazoline-2,4-dione also were isolated. Structure proof of the two new furanoquinoline alkaloids necessitated a revision in the previously suggested structure for perfamine, a cyclohexadienone alkaloid from Haplophyllum perforatum.

[Blind_Angel]

In the text they said that Silver Maple contain 0.05% of DMT and Gramine, in the method in the lower part, they only explain the Gramine extraction, is it because the twa are alkaloid so they are extracted the same way or because Silver Maple only contain gramine?
If Silver Maple contain DMT this would be a very good news for Canadian Bees

[ClearLight]

needs another carbon on the side chain...

[Nick_J]

This was something that I was thinking about, since gramine is relatively easy to make.
IIRC, reacting gramine with CH3NO2 produces Indole-CH2-CH2-NO2 and (CH3)2NH, which can then be seperated, reacted with CH2O, then with indole to form more gramine (Mannich rxn). Indole-CH2-CH2-NO2 can therefore be made by the following reaction: Indole + CH2O + CH3NO2 --(R2NH)--> Indole-CH2-CH2-NO2 + H2O.
If that nitro group could be reduced, then you would have tryptamine which could be alkylated. The trouble is, the C=C bond in the heterocyclic ring of indole is apparently quite easy to reduce to CH-CH (eg sodium cyanoborohydride will do it in yields over 90% at rt on unsubstituted indole), and might therefore be affected by the conditions necessary to reduce the nitro group. I was wondering about adding HBr accross the double bond, then performing an elimination reaction after the reduction to get tryptamine, but I have no idea if it would work, and even if it did the extra steps (= extra time and effort and lower yield) would mean that it would probably be better to use a totally different method.

[Chimimanie]

Swap the gramine with a cyanide ion, get the indoleacetonitrile.

And then

Post 354293

(Rhodium: "This together with what's been posted in Post ...", Tryptamine Chemistry) and

Post 351772

(Barium: "Nitriles to tertiary amines", Tryptamine Chemistry)

You will have DMT

[Rhodium]

Gramine can be used as a starting material for AMT and AET too, see

https://www.thevespiary.org/rhodium/Rhodium/chemistry/it-290.html

[Lilienthal]

Nick-J: AFAIK it is not possible to reduce an indole to an indoline with the common hydrides as long as you don't work under stronger acidic conditions like neat acetic acid.

[Nick_J]

A bit more reading told me that NaBH3CN in AcOH was used...
So perhaps the nitro group could be removed with a polysulphide. I'll have to try this some time.
First step for me is indole from albumin, I have not had any luck with this so far. It's a pitty the tryptophan can not be isolated from the protein directly   .