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Réactions du diazométhane. I. Transformation de la fonction N‐phénylthio‐carbonyle (C 6 H 5 SCO‐NH‐R) avec production d'isocyanate (OCNR) par élimination bimoléculaire
Author(s) -
Baudet P.,
Calin M.,
Cherbuliez E.
Publication year - 1965
Publication title -
helvetica chimica acta
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.74
H-Index - 82
eISSN - 1522-2675
pISSN - 0018-019X
DOI - 10.1002/hlca.19650480822
Subject(s) - chemistry , nitromethane , diazomethane , isocyanate , medicinal chemistry , amine gas treating , anisole , organic chemistry , catalysis , polyurethane
Diazomethane transforms N‐(phenylthio‐carbonyl)‐amino acid esters or amides into the corresponding N‐carbonyl derivatives, similarly it converts N‐(phenylthio‐carbonyl)‐butyl‐1‐amine into butyl‐isocyanate. Solvents with a high dielectric constant ( e. g. nitromethane, ethanol) favour this transformation. The analogous but N‐substituted N‐(phenyloxy‐carbonyl)‐amino acid esters are not modified by diazomethane. This new reaction appears to proceed by a bimolecular elimination ( E 2), where the transition state leads very rapidly to the formation of an isocyanate on the one hand and thio‐anisole on the other.

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