The reactions of silyl phosphites, i.e., tris (trimethylsilyl) phosphite (1), diethyl trimethylsilyl phosphite (11), and bis(trimethylsilyl) ethyl phosphite (12), with a variety of -halo carbonyl compounds gave the 1:1 carbonyl addition products (6,13, and 14), enol phosphates (5 and 26), and/or 2-oxophosphonates (4 and 25). Substituents on the phosphites and the -halo carbonyl compounds have influenced the product ratios. The results of these reactions strongly suggest that the Perkow reaction proceeds via an initial attack of phosphite on the carbonyl carbon of the -halo carbonyl compound. Treatment of bis(trimethylsilyl) 1-[ (trimethylsilyl)oxy] -2-halo phosphonates (6) with sodium methoxide in methanol followed by retrimethylsilylation gave bis(trimethylsilyl) 1,2-epoxy phosphonates (17), bis(trimethylsilyl) 2-oxo phosphonates (4), and bis(trimethylsilyl) methyl phosphate (21). On the other hand, diethyl l-hydroxy-2-halo phosphonates (22) were converted by treatment with different bases to 1,2-epoxy phosphonates (23) predominantly in good yields. When some of tri-n-butyltin alkoxides were used as bases, enol phosphates (26) were obtained selectively. Several bis(trimethylsilyl) esters obtained in the above reactions were successfully converted to the corresponding monoanilinium salts in high yields by treatment with aniline-containing alcohols.
Acetatotrichloro(triphenylphosphine oxide)tin(IV) was synthesized by the reaction of stannic chloride, acetic acid and triphenylphosphine oxide or by the reaction of dichlorotin(IV) diacetate with tetrachlorobis(triphenylphosphine oxide)tin(IV). The structure of the complex was determined by the X-ray method. The molecule is monomeric and tin atom is six-coordinated.
Three types of zinc complexes, chlorotris[2(1H)-pyridinethionato]dizinc (3), dichlorotetrakis[2(1H)-pyridinethionato]trizinc (4), and chloro[2(1H)-pyridinethionato]zinc (5) were produced by the reactions of bis[2(1H)-pyridinethionato]zinc (2) and zinc chloride. The product in the reactions varies depending on the solvent. The mutual transformation reactions among 3, 4, 5, 2, and oxohexakis[2(1H)-pyridinethionato]tetrazinc were described. The formations of 5, 4, and 3 were explained by stepwise additions of 2 to zinc chloride based upon a view that these complexes are the adducts of 2 with zinc chloride in molar ratios of 1 : 1,2 : 1, and 3 : 1. Analogously, the correlation of the known polynuclear zinc complexes was systematically rationalized by stepwise additions of L2Zn (L=ligand) to ZnX2 (X=Cl or OH) or ZnO.
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