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.
One-step simple preparation of catalytic initiators for catalyst-transfer Kumada polymerization: Synthesis of defect-free polythiophenes
Chavez, Carlos A.,Choi, Jinwoo,Nesterov, Evgueni E.
, p. 506 - 516 (2014/02/14)
Externally initiated living catalyst-transfer polymerization based on Ni(II)-catalyzed Kumada coupling of aromatic halogen-substituted Grignard monomers is an established and highly efficient method for the controlled preparation of conjugated polymers such as polythiophenes and poly(p-phenylenes). In this contribution, we report a simple preparation of external catalytic initiators for such a polymerization based on oxidative addition between a readily available Ni(0) complex Ni(dppp)2 (where dppp is 1,3-bis(diphenylphosphino)propane) and various aryl halides. As a direct challenge to previous reports and established opinion that such a reaction would be impossible, this clean and efficient oxidative addition enables simple preparation of highly reactive catalytic initiators for the catalyst-transfer polymerization. In particular, we demonstrated that polymerization of 5-halo-2-thienylmagnesium monomers initiated by these catalysts produced highly regioregular, defect-free polythiophenes and block copolymers with high molecular weight and low polydispersity. We also found that the polymers prepared using this catalytic system showed a uniform end-group composition with one end terminated with an aryl group from the catalytic initiator and the other end with Br. The bromine termination could potentially allow further synthetic manipulations with the polymers. Overall, this convenient and advantageous method for the preparation of external catalytic initiators provides a simple and straightforward approach to controlled synthesis of polythiophenes and other conjugated polymers.
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′.
A novel approach to a one-pot synthesis of unsubstituted oligo(α-thiophenes)
Buzhansky, Ludmila,Feit, Ben-Ami
, p. 7523 - 7525 (2007/10/03)
Oligo(α-thiophenes) α-4T and α-8T were prepared by the following one-pot sequential conversions: thiophene (T) → α-2T → α-4T → α-8T. PdCl2-induced coupling of a mono-α-mercuration derivative of each of the n-mers T, α-2T, and α-4T was applied in these conversions.
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.
Radical Cations and Anions from Some Simple Polythiophenes: an ESR Investigation
Alberti, Angelo,Favaretto, Laura,Seconi, Giancarlo,Pedulli, Gian Franco
, p. 931 - 935 (2007/10/02)
The radical cations and anions of the four lower oligomers of thiophene have been generated and characterized by means of ESR spectroscopy, with the exception of bi- and quinque-thienyl radical cations. cis-trans isomerism about the interannular bonds, similar to that previously reported for the 2,2'-dithienyl radical anion, has been observed for terthienyl cation and anion radicals, while no direct evidence of such isomerism could be obtained for quaterthienyl and quinquethienyl.
SYNTHESIS AND CHARACTERIZATION OF 2,2':5',2''-TERTHIOPHENE DERIVATIVES OF POSSIBLE THERAPEUTIC USE
Rossi, Renzo,Carpita, Adriano,Ciofalo, Maurizio,Houben, Julien L.
, p. 793 - 803 (2007/10/02)
Several derivatives of 2,2':5',2''-terthiophene, 1a, and a structural analogue of this natural phototoxin, i.e. 5--2,2'-bithiophene, 2, have been conveniently synthesized on a medium scale using a general approach which involves palladium-catalyzed carbon-carbon bond forming reactions between (hetero)aryl halides and heteroaryl organometallics such as Grignard reagents, organozinc and organotin compounds.These 2,2':5',2''-terthiophene derivatives, which include some naturally-occurring compounds, have been characterized by EIMS spectrometry , 1H and 13C NMR spectroscopy as well as by absorption and fluorescence measurements.Four of these phototoxins exhibit considerable antibiotic and antiviral properties in the presence of UVA light and are cytotoxic against the P 815 mouse mastocytoma cell line.
