Synthesis of O-alkyl oximes

ORGN 57

Debra D. Dolliver1, David B. Delatte1, Joshua Austin1, James E. Johnson2, Jeffrey E. Rowe3, Simon G. Bott4, and Diana C. Canseco2. (1) Department of Chemistry & Physics, Southeastern Louisiana University, SLU 10878, Hammond, LA 70402, (2) Department of Chemistry and Physics, Texas Woman's University, P.O.Box 425859, Denton, TX 76204, (3) Department of Chemistry, La Trobe University, Bundoora, Victoria, Australia, (4) Department of Chemistry, University of Houston, Houston, TX 77204
Nucleophilic substitution on O-alkyl-4-chlorobenzohydroximoyl fluorides (ClC6H4C(F)=NOCH3 (1) and ClC6H4C(F)=NOCH(CH3)2 (2)] by enolate anions and Grignard reagents have given the following O-alkyl oximes (3-8): [ClC6H4CCH(CN)2=NOCH3 (3), ClC6H4CCH(CN)(CO2Et)=NOCH3 (4), ClC6H4CCH(CO2Et)2=NOCH3 (5), ClC6H4C(CH3)=NOCH(CH3)2 (6), ClC6H4C(C6H5)=NOCH(CH3)2(7), and ClC6H4C(C6H5CC)=NOCH(CH3)2 (8)]. An X-ray crystallographic analysis of 4 has shown that the compound exits in the enamine tautomer in the solid state. The 13C-NMR spectrum of 4 indicates that it is a mixture of the enamine and imine tautomers in CDCl3.