EFFECT OF CYCLODEXTRINS ON THE HYDROLYSIS OF AMIDES

被引:17
作者
GRANADOS, A [1 ]
DEROSSI, RH [1 ]
机构
[1] NATL UNIV CORDOBA,FAC CIENCIAS QUIM,DEPT QUIM ORGAN,INST INVEST & FIS QUIM CORDOBA,SUC 16,CC 61,RA-5016 CORDOBA,ARGENTINA
关键词
D O I
10.1021/jo00059a030
中图分类号
O62 [有机化学];
学科分类号
070303 ; 081704 ;
摘要
The hydrolysis of p-nitrotrifluoroacetanilide (1), trifluoroacetanilide (2), m-nitrotrifluoroacetanilide (3), and p-nitroacetanilide (4) was studied in the presence of cyclodextrins. The reactions of 1 are catalyzed by alpha-cyclodextrin (alpha-CD) and beta-cyclodextrin (beta-CD) and also by (hydroxypropyl)cyclodextrin (HPCD). The hydrolysis of 4 is catalyzed by beta-CD. The reaction of 2 is inhibited by beta-CD and so is the reaction of 3 by HPCD. Compounds 1 and 4 form two types of inclusion complexes with beta-CD, a 1:1 and a 1:2 substrate:cyclodextrin complex. Both types of complexes react faster than the free substrate, and for 1 at pH = 7 all the catalysis is due to the reaction of the 1:2 complex since the 1:1 complex reacts at about the same rate as the free substrate. The results are explained in terms of two mechanisms: one which involves the acylation of CD by the amides and another which predominates at neutral pH where the two cyclodextrins complexing the substrate stabilize the transition state for water addition.
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页码:1771 / 1777
页数:7
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