Hi!
After reading and drooling over Post 475109 (https://www.thevespiary.org/talk/index.php?topic=11892.msg47510900#msg47510900)
(Lego: "Amphetamines/PEAs w/o benzaldehyde or nitroethane", Novel Discourse). Swim decided to test the procedure. The only currently available substrate was indole, but swim decided that it probably would work with this as it is activated at the correct sites and also reacts with the Villsmeyer complex in the same manner as the other substrates(dimethoxytoluene etc).
Thus the procedure w/o HBr was tried out. Because the substrate was indole(which is a solid) and not benzene(liquid) 5X the amount of GAA was used in order to dissolve most of the sludge. Everything turned very purple immediately and the reaction was allowed to commence as described in the procedure.
Was it correct to assume that indole would react in the same manner as benzene? I'd say that it would be even more reactive than benzene because of the more activated site. If it works, it sure is an slick'n'easy route to AMT...
Feedback appreciated!
Regards
Bandil
...and also referenced in Post 304144 (https://www.thevespiary.org/talk/index.php?topic=9369.msg30414400#msg30414400)
(Aengus: "Alkylation of nitroalkanes", Methods Discourse):
The Chemistry of Nitroacetic Acid and its esters. I. The alkylation of Alkylnitroacetates with Gramine.
Lyttle and Weisblat.
J. Amer. Chem. Soc. 69 (1947), 2118-2119.
(https://www.thevespiary.org/rhodium/Rhodium/hive/hiveboard/picproxie_imgs/pdf.gif)
Abstract: A new synthesis of dl-tryptophan which consists of the alkylation of ethyl nitroacetate by gramme, reduction of the resulting ethyl a-nitro-beta-(3-indole)-propionate, and hydrolysis of ethyl dl-tryptophan is presented. An investigation of the chemistry of nitro acetic acid and its esters is being undertaken.
The Chemistry of Nitroacetic Acid and its esters. II. The Synthesis of Ethyl-alpha-Nitro-betta-(3-indole)-propionate from Gramine and Ethyl Nitromalonate.
Lyttle and Weisblat.
J. Amer. Chem. Soc. 71 (1949), 3079-3081.
(https://www.thevespiary.org/rhodium/Rhodium/hive/hiveboard/picproxie_imgs/pdf.gif)
Abstract:
1. A new synthesis of dl-tryptophan employing ethyl nitromalonate and gramine is reported.
2. An improved method for preparing and stabilizing esters of nitromalonic acid is described.