Irgashev Roman A, Demina Nadezhda S, Rusinov Gennady L
Postovsky Institute of Organic Synthesis, Ural Division, Russian Academy of Sciences, S. Kovalevskoy Str., 22, Ekaterinburg, 620990, Russia.
Org Biomol Chem. 2020 Apr 29;18(16):3164-3168. doi: 10.1039/d0ob00300j.
A series of 3-(hetero)aryl-substituted benzo[b]thieno[2,3-d]thiophenes, bearing various electron withdrawing groups at C-2 position of their scaffolds, were obtained using a convenient approach based on the Fiesselmann thiophene synthesis. To realize this strategy, the Friedel-Crafts acylation of (hetero)arenes with easily accessible 3-chlorobenzo[b]thiophene-2-carbonyl chlorides was initially performed to afford 3-chloro-2-(hetero)aroylbenzo[b]thiophenes. The latter ketones were treated either with methyl thioglycolate in the presence of DBU and calcium oxide powder or successively with sodium sulfide, an alkylating agent, containing methylene active component, and also DBU and calcium oxide, to form the desired benzo[b]thieno[2,3-d]thiophene derivatives. In addition, similar benzo[4,5]selenopheno[3,2-b]thiophene derivatives were prepared in the same manner using 3-bromobenzo[b]selenophen-2-yl substrates. The obtained functional derivatives of both benzo[b]thieno[2,3-d]thiophene and benzo[4,5]selenopheno[3,2-b]thiophene are of interest for further elaboration of organic semiconductor materials.
通过基于菲塞尔曼噻吩合成的简便方法，获得了一系列在其骨架的C-2位带有各种吸电子基团的3-（杂）芳基取代的苯并[b]噻吩并[2,3-d]噻吩。为实现该策略，首先进行（杂）芳烃与易于获得的3-氯苯并[b]噻吩-2-羰基氯的傅克酰基化反应，以得到3-氯-2-（杂）芳酰基苯并[b]噻吩。将后者的酮用巯基乙酸甲酯在DBU和氧化钙粉末存在下处理，或依次用硫化钠、含有亚甲基活性成分的烷基化剂以及DBU和氧化钙处理，以形成所需的苯并[b]噻吩并[2,3-d]噻吩衍生物。此外，使用3-溴苯并[b]硒吩-2-基底物以相同方式制备了类似的苯并[4,5]硒吩并[3,2-b]噻吩衍生物。所获得的苯并[b]噻吩并[2,3-d]噻吩和苯并[4,5]硒吩并[3,2-b]噻吩的功能衍生物对于进一步开发有机半导体材料具有重要意义。
