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Effect of substitution of oxygen by sulfur in the nonleaving group of a carbonate: kinetics of the phenolysis and benzenethiolysis of S ‐methyl aryl thiocarbonates
Author(s) -
Castro Enrique A.,
Aliaga Margarita,
Santos José G.
Publication year - 2007
Publication title -
journal of physical organic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.325
H-Index - 66
eISSN - 1099-1395
pISSN - 0894-3230
DOI - 10.1002/poc.1192
Subject(s) - chemistry , sulfur , medicinal chemistry , aryl , nucleophilic substitution , nucleophile , kinetics , oxygen , carbonate , reaction mechanism , substitution reaction , catalysis , organic chemistry , alkyl , physics , quantum mechanics
The phenolysis and benzenethiolysis of S ‐methyl 4‐nitrophenyl thiocarbonate ( 1 ) and S ‐methyl 2,4‐dinitrophenyl thiocarbonate ( 2 ) in water are studied kinetically. The Brønsted plots (log k N versus nucleophile basicity) are linear for all reactions. The Brønsted slopes for 1 and 2 are, 0.51 and 0.66 (phenolysis) and 0.55 and 0.70 (benzenethiolysis), respectively. These values suggest a concerted mechanism for these reactions, as found in the corresponding carbonates. Namely, substitution of O Me by S Me in the nonleaving group does not change the mechanism. Copyright © 2007 John Wiley & Sons, Ltd.