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 | Zendy

Castro Enrique A. | Zendy; Aliaga Margarita | Zendy; Santos José G. | Zendy

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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.

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