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Thermal reaction of 1,8-diketone: A computational study
Computational and Theoretical Chemistry ( IF 2.8 ) Pub Date : 2019-11-08 , DOI: 10.1016/j.comptc.2019.112641
M. Emin Cinar

Thermal reaction of 1,8-diketone in presence of Lawesson's reagent (LR) or P4S10 under toluene reflux condition provided expected fused five-membered thiophene and dithiin compounds along with 2,4-diphenylthiophene (2,4-DPT), 2,5-diphenylthiophene (2,5-DPT) and 3,6-diphenylthieno[3,2-b][1,4]dithiine (3,6-DPTDT). DFT level computations conducted to shed light on this intriguing mechanism indicate in situ generation of phenylthiirene from phenylthiiran analogue, which leads to the formation of the 2,4-DPT and 2,5-DPT based on the literature. Phenylthiiran undergoes successive intramolecular reactions yielding a precursor 3-phenyl-1,2-dithiete, which renders 2,5- and 2-6-diphenyl-1,4-dithiin. These 1,4-dithiins result in 2,4-DPT and 2,5-DPT by overcoming relatively high activation barriers. On the other hand, acid catalyzed ring opening reactions of two phenylthiirenes followed by intramolecular reactions yield the 2,4-DPT and 2,5-DPT. Formation of the fused five-membered thiophene and 3,6-DPTDT takes place in successive reactions of 1,4-dithiin. These results decipher the intricate mechanism of thermal reaction of 1,8-diketone in presence of P4S10.



中文翻译:

1,8-二酮的热反应:计算研究

1,8-二酮在Lawesson试剂(LR)或P 4 S 10的存在下在甲苯回流条件下的热反应提供了预期的稠合五元噻吩和二噻吩化合物以及2,4-二苯噻吩(2,4-DPT), 2,5-二苯基噻吩(2,5-DPT)和3,6-二苯基噻吩并[3,2- b ] [1,4]二硫氨酸(3,6-DPTDT)。传导到在这个有趣的机制阐明DFT水平计算指示原位根据文献,由苯基噻喃类似物生成苯基噻吩烯,导致2,4-DPT和2,5-DPT的形成。苯噻喃经历连续的分子内反应,产生前体3-苯基-1,2-二硫代双(diethiete),其生成2,5-和2-6-二苯基-1,4-二硫代双胍。这些1,4-二硫辛素通过克服相对较高的激活屏障而产生2,4-DPT和2,5-DPT。另一方面,两个苯基噻吩的酸催化的开环反应,然后进行分子内反应,产生2,4-DPT和2,5-DPT。稠合的五元噻吩和3,6-DPTDT的形成发生在1,4-二硫精的连续反应中。这些结果破译了在P 4 S 10存在下1,8-二酮的热反应的复杂机理。

更新日期:2019-11-08
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