Bulletin of the Korean Chemical Society

  • 제24권7호
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  • Pages.993-998
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  • 2003
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  • 0253-2964(pISSN)
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  • 1229-5949(eISSN)
대한화학회 (Korean Chemical Society)
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Kinetics and Mechanism of the Aminolysis of Phenacyl Bromides in Acetonitrile. A Stepwise Mechanism with Bridged Transition State

  • 발행 : 2003.07.20
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초록

In the aminolysis of phenacyl bromides ($YC_6H_4COCH_2Br$) with benzylamines ($XC_6H_4CH_2NH_2$) in acetonitrile, the Bronsted βx (βnuc) values observed are rather low ( βX = 0.69-0.73). These values are similar to those (βx $^~_=$ 0.7) for other aminolysis reactions of phenacyl compounds with anilines and pyridines, but are much smaller than those ( βx = 1.1-2.5) for the aminolysis of esters with benzylamines which are believed to proceed stepwise with rate-limiting expulsion of the leaving group. The relative constancy of the βx values (βx $^~_=$ 0.7) irrespective of the amine, leaving group and solvent can be accounted for by a bridged type transition state in the rate-limiting expulsion of the leaving group. Thus the aminolysis of phenacyl derivatives are proposed to proceed stepwise through a zwitterionic tetrahedral intermediate ($T^{\pm}$), with rate-limiting expulsion of the leaving group from $T^{\pm}$. In the transition state, the amine is bridged between the carbonyl and α-carbons, which leads to negligible effect of amine on the leaving group expulsion rate.

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