Disulfide Reduction Enone ¦Á-functionalization Reaction And Synthetic Applications

As versatile intermediates in synthesis, a -oxo ketene dithioacetals have been studied extensively and especially as 1,3-electrophiles to form aroy and heterocyclic compounds. Researches on the a -carbon atom of these intermediates are limited. Junjappa and co-workers had done some researches in this field, but the usage is limited for the flexibility about the functional groups on the a -carbon atom.In this paper, the reactions on the a -carbon atom of ketene dithioacetals were exploited, the a -position of ketene dithioacetals were functionlized by diazonium and halogens. The main results are listed as follow:(l).Eight of l-[l,3]-Dithiolan/Dithian/Dithiepan-2-ylidene-l-(4-chloro / nitro-phenylazo)-propan- 2-one, four of [l,3]-Dimiolan/Dithian/Dithiepan-2-(4-chloro/nitro -phenylazo)-acetic acid, one of [l,3]-dithiolan-2-ylidene- (4-nitro-benylazo) -acetic acid ethyl ester and four of 1-[1,3]- Dithiolan /Dithoan-2-ylidene-1 -(4-chloro/nitro-phenylazo)-4-aryl-but-3-en-2-one comp -lexes were synthesized by the azo-coupling decarboxylation reaction of a -carbonyl ketene dithioacetals and diazonium chloride.(2). Eight of [l,3]-Dithiolan/Dithian/Dithiepan -2-ylidene-halomethyl- (4-chloro/nitro-phenyl) -diazene complexes were synthesized by the halodecarboxylation reaction.(3).Eight of l-Imidazolidin-2-ylidene-l-(4-nitro-phenylazo)-4-aryl-but-3-en-2-one complexes were synthesized.(4).The acid catylized rearrangement of (2,2-bis-memylsulfanyl-vinyl) -(4-nitro-phenyl)-diazene was discovered, and [(4-Nitro-phenyl)-hydrazono] -thioactic acid S-methyl ester five complexes were synthesized.(5).Four Schiff base Ni(II) complexes were synthesized and assigned by IRand 'H NMR methods. 3-{l-[2-(3-hydroxy-l-methyI-but-2-ebylideneamino)-pheno \ ylimino]-ethyl}-4-methylthio-penta-2,4-dien-2-ol Ni( II) 2 was characterized by X-ray diffraction analysis. The crystal of complex 2 belongs to monoclinic space group: P2l/C, with a- 1.1476(2) nm, b = 1.1782(2) nm. c = 1.4810(3) nm, p = 111.73(2)? V =1.8602(7) nm3, Z = 4, Rf = 0.0535.In this paper, forty-five new products were synthesized and characterized via IR and 1H NMR,and one Schiff base Ni(II) coordination complex was characterized by X-ray diffraction analysis.