University of Illinois Urbana-Champaign

Kinetics and Mechanism of Syn, Alpha' Lithiation of Tertiary Benzamides

Hay, David Raymond

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Description

Title
Kinetics and Mechanism of Syn, Alpha' Lithiation of Tertiary Benzamides
Author(s)
Hay, David Raymond
Issue Date
1986
Department of Study
Chemistry
Discipline
Chemistry
Degree Granting Institution
University of Illinois at Urbana-Champaign
Degree Name
Ph.D.
Degree Level
Dissertation
Keyword(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)
Graduation Semester
1986
Type of Resource
text
Permalink
http://hdl.handle.net/2142/70346

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