描述了一种基于二芳炔硫醚(Ar—C—C—S—C;C—Ar)底物合成2,6-二芳基-1,4-二噻烯的方法.将二芳炔硫醚和Na2S·9H2O在C2HsOH/C2H5ONa体系中回流反应,以80%~96%的产率合成了一系列2,6-二芳基-1,4-二噻烯化合物.该方法反应条件温和、产率高并且表现出很好的选择性.反应机理涉及硫负离子对底物分子的两个C=C键的选择性亲核加成,即硫负离子(包括S2和中间体B硫负离子)总是选择性地加到芳基一侧的炔碳上形成1,4-二噻烯.对化合物1a进行了X线晶体结构解析.分子中的六元杂环呈“船式”构型.C(1)-C(2)和C(1A)-C(2A)具有典型的双键性质,S(1)-C(2)和S(2)-C(1)的键长数则比一般C—S单键稍短,显示硫原子上的孤对电子与C(1)=C(2)双键上的π电子存在一定程度的共轭作用.1a的晶体学参数:属正交晶系,Pnma空间群,0=10.1330(11)A°,b=27.318(3)A,c=5.5402(6)A°,a=90.00°,β=90.00°,γ=90.00°,V=1533.6(3)A°,Z=4,ρcalcd=1.422g/cm^3.最终偏离因子R=0.038,RW=0.102。
An effective preparation for 2,6-diaryl-l,4-dithiins (1) was accomplished by the reaction ofbis(arylethynyl) sulfide (Ar-C≡C-S-C≡C-Ar) with Na2So9H20. The mild and simple method showed a good selectivity, and allowed the formation of 2,6-diaryl-l,4-dithiins (1) in up to 96% yields. A plausible mechanism for the reaction was also proposed. Thus, bis(arylethynyl) sulfide reacts with S2-, leading first to intermediate B, followed by addition of S anion in B to another C≡C bond to afford 1. The structure of la was unambiguously determined by X-ray analysis, la exhibited a six-membered hetero ring with boat conformation. The bond lengths of C(1)--C(2) and C(1A)--C(2A) are the typical characteristic of C = C double bond. S(1)-C(2) and S(2)-C(1) are slightly shorter than general C-S single bonds, indicating a certain degree of conjuga- tion between the lone pair on the sulfur atom and n electrons of the C=C bond. Crystal data for la: orthorhombic, Pnma space group, a=10.1330(11) A°,b=27.318(3)A,c=5.5402(6)A°,a=90.00°,β=90.00°,γ=90.00°,V=1533.6(3)A°,Z=4,ρcalcd=1.422g/cm^3.. The final deviation factor R =0.038, Rw= 0.102.