ISSN:
0894-3230
Keywords:
Chemistry
;
Theoretical, Physical and Computational Chemistry
Source:
Wiley InterScience Backfile Collection 1832-2000
Topics:
Chemistry and Pharmacology
,
Physics
Notes:
The reactions of O-(2,4-dinitrophenyl)-substituted p,p′-dimethoxybenzophenone oxime, p,p′-fluorobenzophenone oxime and p,p′-dichlorobenzophenone oxime with pyrrolidine and piperidine in benzene were found to be third order in amine, with no uncatalytic route. The overall rate is a combined effect of rates of two routes, one of which increases and the other decreases with rise in temperature. The relative contribution of the two routes to overall rate varies with temperature, nucleofugicity of the substrate, nucleophilicity and concentration of amine. As a result, the effect of temperature on the overall rate for some reactions is positive and for others negative. This unusual temperature effect on the overall rate supports Hirst's mechanism.
Additional Material:
5 Ill.
Type of Medium:
Electronic Resource
