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Kinetic and equilibrium studies of σ‐adduct formation and substitution in the reactions of sulphite ions with some alkyl and aryl ethers and thioethers
Author(s) -
Crampton Michael R.,
Holmes Anthony J.
Publication year - 1998
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/(sici)1099-1395(1998110)11:11<787::aid-poc38>3.0.co;2-0
Subject(s) - chemistry , adduct , alkyl , nucleophilic substitution , aryl , medicinal chemistry , yield (engineering) , substitution reaction , nucleophile , leaving group , organic chemistry , catalysis , thermodynamics , physics
Kinetic and equilibrium results are reported for the reactions of sulphite with the ethyl and phenyl ethers of 2,4,6‐trinitrophenol and 2,4,6‐trinitrothiophenol in 80/20 (v/v) water/DMSO. In each case 1:1 and 1:2 adducts are observed by reaction of sulphite at one or two unsubstituted ring positions respectively. In the case of the ethyl derivatives these adducts are long‐lived however, the phenyl derivatives rapidly yield 2,4,6‐trinitrobenzenesulphonate, the substitution product. This difference is attributed to a change in the nature of the rate‐determining step, from nucleophilic attack with the phenyl derivatives to leaving group departure with the alkyl derivatives. © 1998 John Wiley & Sons, Ltd.