SYNTHESIS OF ACYLAMIDO KETENE DITHIOACETALS AND 5-OXO-4,5-DIHYDROBENZO[F]-1,4-THIAZEPINE-DERIVATIVES BY DITHIOCARBOXYLATION OF α-AZA-C-NUCLEOPHILES

Abstract

N-acceptor methyl substituted 2,2,N-trimethyl-propionamides (1 acc-group = p-MeOC₆H₄CO-, 2 acc-group = COOMe) afford in the procedure of dithiocarboxylation 3,3-[bis(alkylthio)]-prop-2-ene-1-ones 4a-c and methyl 3,3-[bis(alkylthio)]-acrylates 5a-c, respectively. 2-Chloro- or 2,4-dichloro-N-cyanomethyl-N-methyl-benzamide 3a,b form in the reaction with carbon disulfide at lower temperature 3,3-bis(methylthio)-acrylonitriles 7a,b whereas 2-alkylthio-4-methyl-5-oxo-4,5-dihydrobento[f]-1,4-thiazepine-3-carbonitriles 8a-c are obtained at higher temperatures.

Key Words:

• Carbon disulfide
• 2,2,N-trimethyl-propionamides
• 2-chloro-N-cyanomethyl-N-methyl-benzamide
• 2-alkylthio-4-methyl-5-oxo-4,5-dihydrobenzo[f]-1,4-thiozepine-3-carbonitriles
• methyl 3,3-[bis(methylthio)]-acrylates
• 3,3-[bis(methylthio)]-prop-2-ene-1-ones