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Title:Kinetics and Mechanism of Syn, Alpha' Lithiation of Tertiary Benzamides
Author(s):Hay, David Raymond
Department / Program:Chemistry
Degree Granting Institution:University of Illinois at Urbana-Champaign
Subject(s):Chemistry, Organic
Abstract:The reaction of N,N-dialkyl-2,4,6-triisopropylbenzamides with sec-butyllithium in cyclohexane yields a product in which metalation has occurred exclusively at the carbon adjacent to nitrogen and syn to the carbonyl group. Evidence obtained by nuclear magnetic reso- nance, freezing point depression and stopped-flow infrared spectros- copy indicates the reaction proceeds with rapid initial formation of tetrameric complexes followed by rate determining deprotonation. Model studies using N,N,N',N'-tetramethylethylenediamine (TMEDA)
confirmed the tetrameric nature of the complexes. Computer modelling of the kinetic data gave the following mechanism. (UNFORMATTED TABLE FOLLOWS)
K(,1) k(,4)
(sec-BuLi)(,4) + Amide (DBLHARR) (sec-BuLi)(,4)*Amide (--->) Product
K(,2) k(,5)
(sec-BuLi)(,4)*Amide + Amide (DBLHARR) (sec-BuLi)(,4)*Amide(,2) (--->) Product
K(,3) k(,6)
(sec-BuLi)(,4)*Amide(,2) + Amide (DBLHARR) (sec-BuLi)(,4)*Amide(,3) (--->) Product (TABLE ENDS)
Issue Date:1986
Description:185 p.
Thesis (Ph.D.)--University of Illinois at Urbana-Champaign, 1986.
Other Identifier(s):(UMI)AAI8701508
Date Available in IDEALS:2014-12-15
Date Deposited:1986

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