Synthesis and Reactivity of New 1,4-Bis(alkylthio)-3,6-diarylthieno[3,4-c]thiophene Derivatives.
Synthesis and Reactivity of New 1,4-Bis(alkylthio)-3,6-diarylthieno[3,4-c]thiophene Derivatives.
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新型1,4-双(烷硫基)-3,6-二芳基噻吩并[3,4-c]噻吩衍生物的合成和反应性。
DOI：
10.1002/chin.199823110
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发表时间：
1998
期刊：
影响因子：
--
通讯作者：
F. Iwasaki
中科院分区：
文献类型：
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作者：
N. Matsumura;Hirokazu Tanaka;Y. Yagyu;K. Mizuno;H. Inoue;Kiwamu Takada;M. Yasui;F. Iwasaki
由2-(叔丁硫基)-3-苯基-和3-(2-噻吩基)环丙烯硫酮(1a,b)和三苯基膦在干燥苯中合成1,4-双(叔丁硫基)-3,6-二苯基-和3,6-二(2-噻吩基)噻吩并[3,4-c]噻吩(2a,b) 尽管对 2,4,6-三异丙基苯基、N,N-二乙氨基、吡咯烷和二苯基取代的环丙烯硫酮 (1c-h) 进行类似处理，但并未产生相应的噻吩并[3,4-c]噻吩衍生物。描述了形成 2a、b 的可能反应途径。用三氟乙酸（TFA）将2a质子化，得到4-（叔丁硫基）-3,6-二苯基噻吩并[3,4-c]噻吩-1(3H)-硫酮（13a），用氢化钠处理，然后用异丙碘处理，得到 通过噻吩并[3,4-c]噻吩环系的再生得到4-(叔丁硫基)-3,6-二苯基-1-(异丙硫基)噻吩并[3,4-c]噻吩(16)，这使得合成其他烷硫基取代的噻吩并[3,4-c]噻吩衍生物成为可能。 2a,b与N-苯基马来酰亚胺(NPM)的反应主要在1-位和3-位生成内环加合物(17a,b)，2a与乙炔二甲酸二甲酯(DMAD)的反应通过脱硫生成苯并[c]噻吩衍生物(19)。
1,4-Bis(tert-butylthio)-3,6-diphenyl- and 3,6-di(2-thienyl)thieno[3,4-c]thiophenes (2a,b)were synthesized from 2-(tert-butylthio)-3-phenyl- and 3-(2-thienyl)cyclopropenethiones (1a,b) and triphenylphosphine in dry benzene at 50 degrees C, although similar treatment of 2,4,6-triisopropylphenyl, N,N-diethylamino, pyrrolidino, and diphenyl-substituted cyclopropenethiones (1c-h) did not result in the production of the corresponding thieno[3,4-c]thiophene derivatives. The possible reaction pathway for the formation of 2a,b is described. The protonation of 2a with trifluoroacetic acid (TFA) gave 4-(tert-butylthio)-3,6-diphenylthieno[3,4-c]thiophene-1(3H)-thione (13a), the treatment of which with sodium hydride and then isopropyl iodide led to 4-(tert-butylthio)-3,6-diphenyl-1-(isopropylthio)thieno[3,4-c]thiophene (16) by the regeneration of the thieno[3,4-c]thiophene ring system, this making possible the synthesis of other alkylthio-substituted thieno[3,4-c]thiophene derivatives. The reactions of 2a,b with N-phenylmaleimide (NPM) gave predominantly the endo-cycloadducts (17a,b) at the 1- and 3-positions, and that of 2a with dimethyl acetylenedicarboxylate (DMAD) led to the benzo[c]thiophene derivative (19) by desulfurization.