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O‐Phenylisourea Synthesis and Deprotonation: Carbodiimide Elimination Precludes the Reported Chapman Rearrangement
Author(s) -
Tate Joseph A.,
Hodges George,
LloydJones Guy C.
Publication year - 2016
Publication title -
european journal of organic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.825
H-Index - 155
eISSN - 1099-0690
pISSN - 1434-193X
DOI - 10.1002/ejoc.201600386
Subject(s) - deprotonation , chemistry , carbodiimide , solvolysis , phenol , hydroxide , medicinal chemistry , kinetics , organic chemistry , hydrolysis , ion , physics , quantum mechanics
The kinetics of the addition of phenol to diisopropylcarbodiimide, and reaction of the resulting N , N′ ‐diisopropyl‐ O ‐phenylisourea with hydroxide, are reported. The isourea is generated by a slow overall termolecular equilibrium process, inhibited by isourea–phenol salt generation. In contrast to an earlier report, reaction of the isourea with hydroxide does not induce a synthetically useful 1,3‐O–N (Chapman) rearrangement. Instead, deprotonation results in solvolysis by carbodiimide elimination.