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Reactions of trichloroacetyl isothiocyanate with organic azides
Author(s) -
L'Abbé Gerrit,
Bosnian Joris,
Toppet Suzanne
Publication year - 1992
Publication title -
journal of heterocyclic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.321
H-Index - 59
eISSN - 1943-5193
pISSN - 0022-152X
DOI - 10.1002/jhet.5570290104
Subject(s) - chemistry , azide , carbodiimide , isothiocyanate , chloroform , acetone , isopropyl , carbon 13 nmr , hydrazide , organic chemistry , medicinal chemistry
Benzyl azide reacts with trichloroacetyl isothiocyanate to give 7a in chloroform solution, and 11 in acetone solution. These 1,2,4‐oxathiazolidines were characterized by 13 C nmr spectroscopy (Scheme 2), but could not be isolated since they deteriorated via the carbodiimide 8a into the 1,2,4‐thiadiazolidine 9a . The oxathiazoline 6a is assumed as an intermediate and was trapped by isocyanates and dicyclohexylcarbodiimide to give the 1,2,4‐thiadiazolidines 10a,b and 12 respectively. Isopropyl azide also reacts with trichloroacetyl isothiocyanate to give the labile oxathiazolidine 7b , which decomposes to the carbodiimide 8b and the 1,2,4‐thiadiazolidine 9b . In the case of diphenylmethyl azide, however, no evidence was obtained for the presence of the oxathiazolidine 7c in the 1 H nmr spectra; only the carbodiimide 8c was observed. A mechanistic rationalization is presented in Scheme 1.