Sulphur-substituted organometallic compounds. Part II. Reaction of vinyltin compounds with arenesulphenyl halides and thiocyanates and some properties and reactions of the (2-arylthio-1-halogenoethyl)-triphenyltin addition products
作者:James L. Wardell
DOI:10.1039/dt9750001786
日期:——
Vinyltin compounds, [R3Sn(CHCH2)](R = Me and Ph), react with sulphenyl chlorides and thiocyanates, R′SX, in aprotic solvents to give products of addition (Markownikoff) to the vinyl bond and cleavage of the vinyl–tin bond [equation (i)]. Cleavage products are exclusively obtained from the most reactive sulphenyl chloride [R3Sn(CHCH2)]+ R′SX →[R3Sn(CHXCH2SR′)]+ CH2CHSR′+[R3SnX](i) used, p-MeC6H4SCI
乙烯基锡化合物[R 3 Sn(CH CH 2)](R = Me和Ph)在非质子传递溶剂中与亚硫酰氯和硫氰酸酯R'SX反应,生成乙烯基键加成产物(Markownikoff)并裂解乙烯基-锡键[等式(i)]。裂解产物仅从反应性最强的亚磺酰氯[R 3 Sn(CH CH 2)] + R'SX → [R 3 Sn(CHXCH 2 SR')] + CH 2 CHSR'+ [R 3 SnX](i )p -MeC 6 H 4 SCI,而裂解和加成发生在低亲电性物质2-O 2上N-4-YC 6 H 3 SX(Y = H,Me或NO 2; X = Cl或SCN)。亚磺酸酯不反应。加合物[Ph 3 Sn-(CHXCH 2 SR')]在极性溶剂(例如CHCl 3)中是热不稳定的,得到CH 2 = CHSR'。它们与亚硫酰卤R“ SX'反应,生成不对称的二硫化物R'SSR”,CH 2 CHX。和[Ph 3 SnX']。这种类型的反应与Br