Synthesis and Characterization of α,β-Unsaturated Hydroximoyl Chlorides and Hydroximates

Abstract

New α,β-unsaturated hydroximoyl chlorides (PhC(Cl)=CHC(Cl)=NOCH3) and hydroximates (PhC(OCH3)=CHC(OCH3)=NOCH3) were prepared. The ZZ-isomer of PhC(Cl)=CHC(Cl)=NOCH3 was prepared in four steps from ethyl benzoylacetate. Ultraviolet irradiation of the ZZ-isomer gives a mixture of all four possible isomers. Sodium methoxide was reacted with these isomers to determine the configuration about the carbon–carbon double bond for each. The Z-isomers reacted with sodium methoxide to give the corresponding alkyne by elimination whereas the E-isomers gave the substitution product. The configuration about the carbon–nitrogen double bond was determined from the 1H NMR chemical shift of the NOCH3 group.

Palladium-Catalyzed Cross Coupling Reaction of N-Alkoxyimidoyl Bromides and Its Application to One-Pot Synthesis of N-Arylamines

“…1,2) In particular, N-alkyl or N-arylimidoyl halides are utilized in transition metal-catalyzed cross-coupling reactions. [3][4][5][6][7][8] In contrast, although the substitution reactions of N-alkoxyimidoyl halides with nucleophiles such as carbanion, 9) alkoxide, 10,11) amine, 12,13) azide 14) and halogen 15,16) have been developed, the catalytic cross-coupling reaction is less studied, despite the fact that the oxime ethers produced are useful intermediates for the syntheses of amines and heterocycles. [17][18][19][20] Kim and Chang's group reported that N-alkoxyimidoyl halides are efficient coupling partners in the Stille reaction.…”