Cross-coupling polymerization of organosodium for polythiophene synthesis
Cross-coupling polymerization of organosodium for polythiophene synthesis
复制标题
有机钠交叉偶联聚合合成聚噻吩
DOI：
10.1021/acs.organomet.1c00508
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发表时间：
2021
期刊：
影响因子：
2.8
通讯作者：
Atsunori Mori
中科院分区：
文献类型：
--
作者：
Tomoki Inoue;Sonoka Yamamoto;Yuma Sakagami;Masaki Horie;Kentaro Okano;Atsunori Mori
在己烷中用2，2，6，6-四甲基哌啶-1-基钠（TMPNa）处理2-氯-3-己基噻吩导致在5-位去质子化，得到噻吩-钠物质，其形成通过用碘猝灭来证实，导致以85%产率的2-氯-3-己基-5-碘噻吩。在环戊基甲基醚中，将带有N-杂环卡宾（NHC）的镍催化剂加入到由此形成的噻吩-钠物质中，在−20 °C下诱导交叉偶联聚合。将反应混合物搅拌24小时后，以56%的产率获得聚（3-己基噻吩-2，5-二基）。平均分子量Mn显示为9700，其接近基于单体进料/催化剂负载比（2.0摩尔%）的理论分子量（M= 8500），并且发现分子量分布为2.1。
Treatment of 2-chloro-3-hexylthiophene with sodium 2,2,6,6-tetramethylpiperidin-1-yl (TMPNa) in hexane resulted in deprotonation at the 5-position to afford the thiophene–sodium species, whose formation was confirmed by quenching with iodine, leading to 2-chloro-3-hexyl-5-iodothiophene in 85% yield. Addition of a nickel catalyst bearing an N-heterocyclic carbene (NHC) to the thus-formed thiophene–sodium species in cyclopentyl methyl ether induced a cross-coupling polymerization at −20 °C. After the reaction mixture was stirred for 24 h, poly(3-hexylthiophen-2,5-diyl) was obtained in 56% yield. The average molecular weightMnwas revealed to be 9700, which was close to the theoretical molecular weight (M= 8500) on the basis of the monomer feed/catalyst loading ratio (2.0 mol %), and the molecular weight distribution was found to be 2.1.