5632-29-1Relevant articles and documents
A new method of using supercritical carbon dioxide as a green solvent for synthesis and purification of 5,5?-bis(tridecafluorohexyl)-2,2′:5′,2″:5″,2?-quaterthiophene, which is one of n-type organic semiconducting materials
Hirase, Ryuji,Honda, Koji,Ishihara, Mari,Yoshioka, Hideki,Monobe, Hirosato
, p. 469 - 472 (2018/01/04)
We have investigated synthesis as well as purification of 5,5?-bis(tridecafluorohexyl)-2,2′:5′,2″:5″,2?-quaterthiophene (BFH-4 T, n-type organic semiconducting material) using supercritical carbon dioxide (scCO2) as a green solvent. BFH-4T was obtained in good selectivity and high yield by TDAE/PdCl2-catalyzed reductive coupling reaction of 5-bromo-5′-(tridecafluorohexyl)-2,2′-bithiophene in scCO2. We have also successfully established purification of the reaction mixture by passing scCO2 in the reaction vessel. The product was yellow powder of BFH-4T with purity of more than 99% and Pd catalyst was not contained.
Meta-substituted thienyl benzenes: A comparative Synthetic, structural and computational study
Cornacchio, Angelica L. P.,Price, Jacquelyn T.,Jennings, Michael C.,McDonald, Robert,Staroverov, Viktor N.,Jones, Nathan D.
experimental part, p. 530 - 544 (2009/06/28)
A selection of metal-catalyzed C-C bond-forming strategies has been evaluated in the synthesis of a series of meta-substituted thienylbenzenes, (Tn)2C6H4 and (Tn) 3C6H3 (n = 1, 2; T1 = 2-thienyl; T2 = 2, 2′-bithien-5-yl). Kumada coupling reactions catalyzed by PdCl2(dppf) between the appropriate thienyl Grignard and either 1, 3- or 1, 3, 5-bromo- or iodobenzenes were found to be the most reliable in terms of convenience, selectivity and yield (dppf = 1, 1′- bis(diphenylphosphino)ferrocene). These conditions also allowed the optimized syntheses of mixed (thienyl)(halo)benzenes, (Tn)C6H 3X2 and (Tn)2C6H 3X(X = Br, I); the latter bromides could be further elaborated in subsequent Stille, Sonogashira, or Kumada reactions to furnish bis(thienyl) compounds bearing electron-donating or -withdrawing groups in the third meta position, (Tn)2C6H3R (R= Ph, p-MeOC6H4, p-FC6H4; n = 1, 2) and (T1)2C6H3R′ (R′ = Me, C=CPh, Fc; Fc = ferrocenyl). The relative effects of R, R′, and n were evaluated by electronic spectroscopy, cyclic voltammetry and calculation. The absorption and emission characteristics and calculated ionization potentials and HOMO-LUMO gaps of these compounds were strongly dependent on n and largely insensitive to R/R′. These measured and calculated properties were also found to be largely invariant with respect to the degree of substitution about the central ring in the meta-substituted benzenes (Tn) mX3-mC6H3 (m = 1-3; n = 1, 2; X = Br, H), although in the case of n = 1, there was a smooth, albeit small, increase in the emission maximum with increasing thienyl substitution. These findings essentially confirmed earlier theoretical predictions that the thienyl "arms" of meta-substituted phenyl-cored dendrimers were predominantly responsible for absorption and that excitons were localized to the "arms" without any electronic coupling between them, but also introduced the caveat that there was a minimum of two contiguous thiophene rings required for strict exciton localization to the arms. The oxidation potentials of the compounds in solution ranged from 0.9 to 1.6 V and were not rationally dependent on the degree of substitution or the nature of R/R′.
Inter- and Intramolecular Biaryl Couplings Via Cyanocuprate Intermediates
Lipshutz, Bruce H.,Kayser, Frank,Maullin, Nathalie
, p. 815 - 818 (2007/10/02)
Low temperature oxidations of selected higher order cyanocuprates composed of one or two heteroaromatic ligands can be oxidatively coupled in an inter- or intramolecular fashion to afford unsymmetrical biaryls.Non-heteroaromatic systems have also been studied in related intramolecular processes.
