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

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)

Name thesis:degree_name

Ph.D.

Level thesis:degree_level

Dissertation

Discipline thesis:degree_discipline

Chemistry

Grantor

University of Illinois at Urbana-Champaign

Year dc:date

2014

Author dc:creator

• Hay, David Raymond

• Chemistry, Organic

Identifier

(UMI)AAI8701508

OAI identifier oai:identifier

oai:www.ideals.illinois.edu:2142/70346