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Hay, David Raymond 2014-12-15T23:18:50Z 2014-12-15T23:18:50Z 10000-01-01 1986 1986 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) Made available in DSpace on 2014-12-15T23:18:50Z (GMT). No. of bitstreams: 1 8701508.pdf: 4053452 bytes, checksum: 35fb9b09f95cd7bcd25b2a42ef9b3d96 (MD5) Previous issue date: 1986 Embargo set by: Seth Robbins for item 70512 Lift date: Forever Reason: Restricted to the U of I community idenfinitely during batch ingest of legacy ETDs Restricted to the U of I community idenfinitely during batch ingest of legacy ETDs U of I Only 185 p. Thesis (Ph.D.)--University of Illinois at Urbana-Champaign, 1986. http://hdl.handle.net/2142/70346 (UMI)AAI8701508 Chemistry, Organic Kinetics and Mechanism of Syn, Alpha' Lithiation of Tertiary Benzamides text Chemistry Chemistry University of Illinois at Urbana-Champaign Dissertation Ph.D.