M.V. Smith ; psychedelic chemistry

Tryptamine from tryptophan JCS 3993 (1965)


tryptophan, if oxidized by H202, and cyclized by HCL gives a psychedelic compound

Tryptamine from Tryptophan JCS 3993(1965)

10 g tryptophan in 500 ml diphenyl ether; reflux one hour under N2; cool and extract with 3x40 ml 2N HCl. Wash extract with ether, basify with 6N NaOH and extract with 5X50 ml ether. Wash extract with water, NaCl; dry and evaporate in vacuum and recrystallize-benzene to get tryptamine which can be alkylated to dialkyltryptamine as described previously.(Tryptophan, if oxidized by H2O2 and cyclised with HCl, gives a psychedelic compound.) Much interest has been generated by the mention of tryptophan oxidation to a psychedelic compound, but the original reference gives no details of the method.

https://www.erowid.org/a...cchemistry/chapter3.html

The oxidation rate of Trp and the formation of 16 possible degradation compounds were examined using RP-HPLC and UV, fluorescence, and photodiode array detection. The rate of Trp degradation increased from lysozyme to short-chain peptides to unbound Trp
http://www.ncbi.nlm.nih.gov/pubmed/10554268

Oxindolylalanine (Oia), 3a-hydroxy-1,2,3,3a,8,8a-hexahydropyrrolo[2,3-b]indole-2-carboxylic acid (PIC), N-formylkynurenine (NFK), dioxindolylalanine (DiOia), kynurenine (Kyn), and 5-hydroxytryptophan (5-OH-Trp) were identified in this order of quantity as degradation compounds, showing the Trp pyrrole moiety to be most susceptible to oxidation

Abstract
The oxidation of free tryptophan (Trp) and Trp residues in peptides and proteins by hydrogen peroxide as oxidative agent has been used to evaluate Trp losses and the pattern of degradation products formed. Besides free Trp, four Trp-containing peptides and lysozyme were used as substrates in the aqueous model system. The oxidation rate of Trp and the formation of 16 possible degradation compounds were examined using RP-HPLC and UV, fluorescence, and photodiode array detection. The rate of Trp degradation increased from lysozyme to short-chain peptides to unbound Trp. Only approximately 20% of the total Trp loss could be elucidated by the determined Trp degradation compounds. Oxindolylalanine (Oia), 3a-hydroxy-1,2,3,3a,8,8a-hexahydropyrrolo[2,3-b]indole-2-carboxylic acid (PIC), N-formylkynurenine (NFK), dioxindolylalanine (DiOia), kynurenine (Kyn), and 5-hydroxytryptophan (5-OH-Trp) were identified in this order of quantity as degradation compounds, showing the Trp pyrrole moiety to be most susceptible to oxidation. As short peptides such as H-Ala-Trp-Ala-OH were completely hydrolyzed with immobilized Pronase E, Oia and NFK could be identified as main degradation compounds, as could minor amounts of Kyn, DiOia, PIC, and 5-OH-Trp. Acid (6 M HCl), alkaline (4.2 M NaOH), and enzymatic hydrolyses were compared for the determination of Trp degradation compounds in lysozyme. Kyn, Oia, and DiOia could be detected in the hydrogen peroxide treated protein.

New oxidation products and free radicals derived from tryptophan (Trp) oxidation under Fenton reaction conditions were identified using mass spectrometry. After the oxidation of tryptophan using hydrogen peroxide and iron (II) system (Fenton reaction), mono- and dihydoxy tryptophans and N-formylkynurenine were identified using electrospray mass spectrometry (ES-MS) and ES-MS/MS. Besides these products, new products resulting from the reaction of tryptophan and oxidized tryptophan and 3-methyl indole derivatives were also identified. The 3-methyl indole derivatives resulted, most probably, from the oxidation process and not from in-source processes. A dimer formed by cross-linking between two Trp radicals (Trp-Trp), similar to the previously described tyrosine dimer was observed, as well as the corresponding monohydroxy-dimer (Trp-Trp-OH). Tandem mass spectrometry was used to identify the structures of these new oxidation products. Free radicals derived from tryptophan oxidation under Fenton reaction were detected using as spin trap the DMPO. The free radical species originated during the oxidation reaction formed stable adducts with the spin trap, and these adducts were identified by ES-MS. New adducts of oxidized tryptophan radicals, namely monohydroxy-tryptophan and dihydroxy-Trp dimer radicals, with one and two DMPO spin trap molecules where identified. Tandem mass spectrometry was used to confirm the proposed structure of the observed adducts
http://www.sciencedirect...le/pii/S1044030503001272

A fascinating cyclization product of this "nor-compound" [5-meo-NMT] is a cyclic dehydrogenation product where there is a direct coupling of the tryptamine nitrogen to the 4 position of the indole ring. This tricyclic material, O-methyl-nor-dehydrobufotenine proved to be of comparable activity to DMT in rat studies, but has not apparently been studied in man