Studies on the Generation of Metalating Species Equivalent to the Knochel–Hauser Base in the Dehydrobrominative Polymerization of Thiophene Derivatives
2012; American Chemical Society; Volume: 31; Issue: 6 Linguagem: Inglês
10.1021/om201209z
ISSN1520-6041
AutoresShunsuke Tamba, Shinobu Mitsuda, Fujimaru Tanaka, Atsushi Sugie, Atsunori Mori,
Tópico(s)Synthetic Organic Chemistry Methods
ResumoDehydrobrominative polycondensation of 2-bromo-3-hexylthiophene proceeded with TMPMgBr·LiBr and (TMP)2Mg·2LiBr, formed by LiTMP and MgBr2, which was found to serve as a surrogate of the Knochel–Hauser base TMPMgCl·LiCl, and head-to-tail-type regioregular poly(3-hexylthiophene) was obtained with high efficiency. The regioregular poly(3-hexylthiophene) was also found to be obtained by one-shot addition of 2-bromo-3-hexylthiophene as a monomer, magnesium amide, and a nickel catalyst, suggesting that complete formation of metalated thiophene species is not an essential requisite for the successful polymerization with a nickel catalyst. This method was employed for the preparation of tolyl-terminated polythiophene by an aryl group with narrow molecular weight distribution using (o-tolyl)NiCldppp as a catalyst.
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