ISSN:
0894-3230
Keywords:
Organic Chemistry
;
Physical Chemistry
Source:
Wiley InterScience Backfile Collection 1832-2000
Topics:
Chemistry and Pharmacology
,
Physics
Notes:
Kinetic studies on the reactions of methyl (MBS) and ethyl benzenesulphonates (EBS) with N,N-dimethylanilines (DMA) in methanol and acetonitrile are reported. The cross interaction constants ρXZ and βXZ, between the substituents in the nucleophile (X) and the leaving group (Z) indicated that the transition states (TS) are looser than those for the reactions with anilines, but the relative tightness between the two substrates was the same; the TS was tighter for EBS despite the increase in steric effect leading to looser TSs for MBS and EBS alike. The TS variation between two different reaction series expected from the simple Hammett and Brønsted coefficients, ρX, ρZ, βX and βZ, was incompatible with that predicted by the cross interaction constants, demonstrating again the unreliability of the simple parameters.
Additional Material:
2 Ill.
Type of Medium:
Electronic Resource
URL:
http://dx.doi.org/10.1002/poc.610031109
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