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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C2H5OH/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,a=10.1330(11),b=27.318(3),c=5.5402(6),α=90.00°,β=90.00°,γ=90.00°,V=1533.6(3)3,Z=4,ρcalcd=1.422 g/cm3.最终偏离因子R=0.038,Rw=0.102。
A method for the synthesis of 2,6-diaryl-1,4-dithiines based on a diarylacetylene sulfide (Ar-C≡C-S-C≡C-Ar) substrate is described The diarylacetylene Thioether and Na2S · 9H2O were refluxed in C2H5OH / C2H5ONa system to synthesize a series of 2,6-diaryl-1,4-dithienyl compounds in the yield of 80% ~ 96% .The reaction conditions were mild , High yield and showed good selectivity.The reaction mechanism involves the selective nucleophilic addition of sulfur anions to the two C≡C bonds of the substrate molecule, namely sulfur anions (including S2- and intermediate B sulfur anions ) Was always selectively added to the aryl side of the alkyne carbon to form 1,4-dithiane. The X-ray crystal structure of compound 1a was analyzed. The six-membered heterocyclic ring in the molecule was " C (1) -C (2) and C (1A) -C (2A) have the typical double bond properties. The bond between S (1) -C The longer number is slightly shorter than the normal C-S single bond, indicating that there is some degree of conjugation between the lone pair of electrons on the sulfur atom and the π electron on the C (1) = C (2) double bond. The crystallographic parameters : Is an orthorhombic, Pnma space group, a = 10.1330 (11) , b = 27.318 (3) , c = 5.5402 6, α = 90.00 °, β = 90.00 °, γ = 90.00 °, V = 1533.6 (3) 3, Z = 4, calcd = 1.422 g / cm3. departing final factor R = 0.038, Rw = 0.102.