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Reaction of a brominated benzolactone/lactam with 4-methoxythiobenzamide and thiourea: an Eschenmoser coupling reaction, ring transformation, or dimerization?

Author:
Kammel, Richard, Tarabová, Denisa, Růžičková, Zdeňka, Hanusek, Jiří
Source:
Tetrahedron letters 2015 v.56 no.20 pp. 2548-2550
ISSN:
0040-4039
Subject:
bromination, chemical structure, dimerization, lactams, reaction mechanisms, salts, thiourea
Abstract:
The reactions of 3-bromo-1-benzofuran-2(3H)-one (1a) and 3-bromo-1,3-dihydro-2H-indol-2-one (1b) with 4-methoxythiobenzamide and thiourea under mildly basic conditions are reported. While brominated lactone 1a gave the expected 5-(2-hydroxyphenyl)-2-(4-methoxyphenyl)-1,3-thiazol-4-ol (2) or 2-amino-5-(2-hydroxyphenyl)-1,3-thiazol-4(5H)-one (5) products, the analogous brominated lactam 1b reacted with the thioamide via an unexpected Eschenmoser coupling reaction to give (3Z)-3-[amino(4-methoxyphenyl)-methylidene]-1,3-dihydro-2H-indol-2-one (3). When lactam 1b was treated with thiourea, isoindigo (4) was the only isolated product. The reaction mechanisms, involving formation of α-thioiminium or isothiouronium salts and their base-catalyzed decomposition are also proposed.
Agid:
6025291