- Rational Design of an Iron-Based Catalyst for Suzuki–Miyaura Cross-Couplings Involving Heteroaromatic Boronic Esters and Tertiary Alkyl Electrophiles
-
Suzuki–Miyaura cross-coupling reactions between a variety of alkyl halides and unactivated aryl boronic esters using a rationally designed iron-based catalyst supported by β-diketiminate ligands are described. High catalyst activity resulted in a broad substrate scope that included tertiary alkyl halides and heteroaromatic boronic esters. Mechanistic experiments revealed that the iron-based catalyst benefited from the propensity for β-diketiminate ligands to support low-coordinate and highly reducing iron amide intermediates, which are very efficient for effecting the transmetalation step required for the Suzuki–Miyaura cross-coupling reaction.
- Byers, Jeffery A.,Crockett, Michael P.,Li, Bo,Wong, Alexander S.
-
supporting information
p. 5392 - 5397
(2020/03/04)
-
- Synthesis of 1,3,6,8-tetra-substituted pyrene derivatives and application of pyrene derivatives in organic field-effect transistors
-
The invention aims to develop synthesis of 1,3,6,8-tetra-substituted pyrene derivatives of the same category having semiconductor properties and application of the derivatives in organic field-effecttransistors. Series thiophene units are introduced into positions 1, 3, 6 and 8 of pyrene to construct the tetra-substituted pyrene derivatives, and material preparation is performed by utilizing a chemical reaction. Moreover, a silicon wafer serves as a gate, and the pyrene derivatives serve as organic semiconductor materials, so that bottom-gate top-contact field-effect transistors are prepared.R refers to the following groups as shown in the specification.
- -
-
-
- 1,8-Substituted Pyrene Derivatives for High-Performance Organic Field-Effect Transistors
-
There have been many reports on the application of pyrene derivatives as organic semiconductors, but 1,8-subsituted pyrene semiconductors are less well-developed. Two p-type 1,8-substituted pyrene derivatives were synthesized that were composed of a pyrene core, thiophene or bithiophene arms, and end-capped octyl chains. These structures were not completely symmetrical and the dihedral angles between the pyrene core and the adjacent thiophene units had a difference of approximately two degrees. The field-effect performance of these materials was tested on a variety of dielectric surfaces. The performance of both materials with a spin-coated polystyrene layer on SiO2 (PS-treated SiO2) was better than that with an octadecyltrichlorosilane self-assembled monolayer on SiO2 (OTS-treated SiO2), which was mainly attributed to the presence of large grains on the low-leakage and high-capacitance PS films. The thiophene-contained compound presented a hole mobility of up to 0.18 cm2 V?1 s?1 on PS-treated SiO2, which was 45 times that of the bithiophene-contained compound, owing to less steric hindrance, high crystallinity, and large grain size.
- Gong, Xiaojie,Zheng, Chaoyue,Feng, Xingcui,Huan, Yihong,Li, Jiewei,Yi, Mingdong,Fu, Zhenqian,Huang, Wei,Gao, Deqing
-
p. 3920 - 3927
(2018/11/23)
-
- Cross-coupling reaction of alkyl halides with alkyl grignard reagents catalyzed by cp-iron complexes in the presence of 1,3-butadiene
-
Iron-catalyzed cross-coupling reaction of alkyl halides with alkyl Grignard reagents by the combined use of cyclopentadienyl ligand and 1,3-butadiene additive is described. The reaction smoothly proceeds at room temperature using unactivated alkyl bromides and fluorides via non-radical mechanism, which is in sharp contrast with hitherto known Fe-catalyzed cross-coupling reactions of alkyl halides.
- Iwasaki, Takanori,Shimizu, Ryohei,Imanishi, Reiko,Kuniyasu, Hitoshi,Kambe, Nobuaki
-
supporting information
p. 763 - 766
(2018/05/29)
-
- Thiophene-containing thiolato dimers, oxygen inserted Cu(II) complex, crystal structures, molecular docking and theoretical studies
-
Reactions of n-butyl- and n-octyl-thiophene with CS2 at 0?°C resulted in thiolate dimers 1 and 2, respectively. The reaction of 1 with Cu(NO3)2·3H2O in methanol under ambient reaction conditions yielded monomeric [CuII{(n-C4H9(C4H2S)CS2O}2] (3). 1 and 3 were authenticated by their single-crystal X-ray crystal structures. Crystal structure of 3 revealed cleavage of the S-S bond of 1 followed by insertion of O-atom, forming a new five-membered Cu–O–S–C–S metallacycle. 1, 2, and 3 were further investigated for their bioactivity through molecular docking with nine different proteins having medicinal implications. Molecular docking of 1, 2 and 3 revealed considerable interaction with different proteins viz. cancer protein Tankyrase 2, influenza viral protein Polymerase subunit PAC–PB1N complex (H5N1), Polymerase subunit PA endonuclease (H1N1), Polymerase subunit PAn Apo(avian influenza), and FTSZ (Bacillus subtilis). Comparatively, 1 has promising application in therapeutics as compared to 2 and 3 based on its inhibitory constant and binding energy. Density functional theory calculations were performed to better understand the bonding of complex using MO diagram in 1–3. Moreover, TDDFT calculations were performed to facilitate the assignment of electronic transitions of UV–Vis spectra.
- Mobin, Shaikh M.,Tauqeer, Mohd.,Mohammad, Akbar,Mishra, Veenu,Kumari, Pratibha
-
p. 2015 - 2023
(2016/07/20)
-
- Boron fluoride complexing bi-pyrrole methylidyne derivative substituted by meso-position alkyl thiophene and 3,5-position electron-donating group and preparation method of derivative
-
The invention discloses a boron fluoride complexing bi-pyrrole methylidyne derivative substituted by meso-position alkyl thiophene and a 3,5-position electron-donating group and a preparation method of the derivative. According to the method, 2-bromothiophene serves as a starting raw material, dipyrrylmethanes substituted by meso-position alkyl thiophene is synthesized through a series of reactions, NBS bromination is conducted, and 3,5-dibromo bi-pyrrolidine is obtained; then, TCQ oxidation and boron trifluoride ether complexing are conducted, a 3,5-boron dibromo fluorine intermediate with the meso-position containing alkyl thiophene is obtained, then the intermediate is utilized to conduct an Suzuki/Stille coupled reaction with a variety of modification groups, the boron fluoride complexing bi-pyrrole methylidyne derivative substituted by a 3,5-position donor unit is obtained, and the structural formula can be found in formula I. The boron fluoride complexing bi-pyrrole methylidyne derivative substituted by meso-position alkyl thiophene and the 3,5-position electron-donating group has good stability and has potential application value in the fields of life science, solar cells, environment, energy and the like.
- -
-
Paragraph 0070; 0071
(2016/10/08)
-
- Metal complex, and dye sensitizing oxide semiconductor dye-sensitized solar power cell (by machine translation)
-
PROBLEM TO BE SOLVED: To provide a photoelectric conversion element using new dye, having sensitivity to light in a long-wavelength region, being stable, and having the conversion efficiency higher than that of the Black dye. SOLUTION: As the dye, a metal complex uses an organic metal dye represented by the following general formula (1): MLZX (1). In the formula, M represents a group VIII to X metal element, Z represents a 2,2'-6',2"-terpyridine dielectric having one to three carboxyl groups, X represents a halogen atom and a cyano group and the like, and L represents a 1,3-butanedione dielectric. COPYRIGHT: (C)2012,JPO&INPIT
- -
-
Paragraph 0071; 0072; 0073
(2016/12/01)
-
- Synthesis and characterization of two new benzothiadiazole- and fused bithiophene based low band-gap D-A copolymers: Application as donor bulk heterojunction polymer solar cells
-
Two new narrow bandgap D-A conjugated copolymers P1 and P2 containing different fused thiophene donor unit and same benzothiadiazole acceptor unit were synthesized by Stille cross-coupling polymerization, and characterized by 1H NMR, elemental analysis and GPC, TGA, DSC. Cyclic voltammetry measurement showed that the HOMO energy level both copolymers is deep lying (-5.10 and -5.35 eV for P1 and P2, respectively) which show that copolymers has good stability in the air and assured a higher open circuit voltage when it photovoltaic application. These copolymer were used as donor along with PC71BM and the BHJ polymer solar cells based on P1:PC71BM and P2:PC71BM processed with chloroform (CF) solvent showed over all PCE of 4.54% and 4.36%, respectively. Additionally, the PCE was improved up to 5.62% and 5.24% for P1:PC71BM and P2:PC71BM active layer processed with DIO (4 v%)/CF solvent. The enhancement in the PCE has been attributed to improved nanoscale morphology and crystalline nature of active layer as well as charge transport in the device with the addition of DIO, due to the higher boiling point of DIO causing slow evaporation rate during the film formation.
- Keshtov,Sharma,Kuklin,Ostapov,Godovsky,Khokhlov,Chen
-
p. 193 - 201
(2016/01/30)
-
- Copper-catalyzed alkyl-alkyl cross-coupling reactions using hydrocarbon additives: Efficiency of catalyst and roles of additives
-
Cross-coupling of alkyl halides with alkyl Grignard reagents proceeds with extremely high TONs of up to 1230000 using a Cu/unsaturated hydrocarbon catalytic system. Alkyl fluorides, chlorides, bromides, and tosylates are all suitable electrophiles, and a TOF as high as 31200 h-1 was attained using an alkyl iodide. Side reactions of this catalytic system, i.e., reduction, dehydrohalogenation (elimination), and the homocoupling of alkyl halides, occur in the absence of additives. It appears that the reaction involves the β-hydrogen elimination of alkylcopper intermediates, giving rise to olefins and Cu-H species, and that this process triggers both side reactions and the degradation of the Cu catalyst. The formed Cu-H promotes the reduction of alkyl halides to give alkanes and Cu-X or the generation of Cu(0), probably by disproportionation, which can oxidatively add to alkyl halides to yield olefins and, in some cases, homocoupling products. Unsaturated hydrocarbon additives such as 1,3-butadiene and phenylpropyne play important roles in achieving highly efficient cross-coupling by suppressing β-hydrogen elimination, which inhibits both the degradation of the Cu catalyst and undesirable side reactions.
- Iwasaki, Takanori,Imanishi, Reiko,Shimizu, Ryohei,Kuniyasu, Hitoshi,Terao, Jun,Kambe, Nobuaki
-
p. 8522 - 8532
(2015/01/08)
-
- OLIGOTHIOPHENES DERIVATIVES
-
The present invention is directed to new oligothiophene derivatives and their use as a semiconductor material in electronic devices. More specifically, the present invention relates to new 3,4-dicyanooligothiophenes derivatives, processes for manufacturing thereof, and to their use as organic n-type (electron-transporting) semiconductors, in particular, in field-effect transistors (FET).
- -
-
Page/Page column 65-66
(2011/04/13)
-
- Synthesis and optical properties of soluble near-infrared arylene bisthienoimidazole dyes
-
Soluble, film-forming near-infrared arylene bisthienoimidazole dyes with a band gap of 1.2-1.3 eV are electrochromic and absorb strongly at the telecommunication wavelengths (1310 and 1550 nm) in the oxidized state.
- Luo, Min,Wang, Qun,Wang, Zhi Yuan
-
supporting information; scheme or table
p. 4092 - 4095
(2011/10/01)
-
- Organic semiconductor material, organic semiconductor structure and organic semiconductor apparatus
-
The present invention is directed to the provision of a novel liquid crystalline organic semiconductor material that is highly stable under an film forming environment and, at the same time, can easily form a film, for example, by coating. The liquid crystalline organic semiconductor material is represented by chemical formula 1 wherein R1 and R2 represent an identical alkyl group having 7 to 20 carbon atoms: There is also provided a liquid crystalline organic semiconductor material characterized by being represented by chemical formula 2 wherein R3 and R4 represent an identical alkyl group having 7 to 20 carbon atoms:
- -
-
-
- Bent-core mesogens with thiophene units
-
Bent-core mesogens with thiophene and 2,2′-bithiophene units at the periphery of the aromatic core were synthesized and investigated by polarizing microscopy, XRD and electrooptical methods. Resorcinol, 2,7-naphthalenediol and 3,4′-biphenyldiol were used as bent units, phenyl thiophene-2-carboxylates form the rod-like wings and n-alkyl chains as well as olefin- and silylated-terminated alkyl chains were attached as flexible end-groups. A broad variety of different mesophase structures, incorporating ferroelectric and antiferroelectric switching smectic as well as modulated smectic phases, was obtained. Compared with the corresponding benzoates, these thiophene derived compounds form nearly identical LC phase structures, but have significantly reduced transition temperatures, which make them advantageous for applications.
- Geese, Karina,Prehm, Marko,Tschierske, Carsten
-
supporting information; experimental part
p. 9658 - 9665
(2011/06/09)
-
- Synthesis of soluble oligothiophenes bearing cyano groups, their optical and electrochemical properties
-
The synthesis and the characterization of twelve new soluble oligothiophenes, possessing two to four 3,4-dicyanothiophene units in their backbone, are described. These semiconductors are prepared through Stille coupling and/or homo-coupling reactions. Cyclic voltammetry studies have been performed to evaluate their stability as n-type semiconducting materials under ambient conditions. The measured electrochemical and optical properties are fully supported by quantum-chemical calculations.
- Balandier, Jean-Yves,Quist, Florence,Amato, Claire,Bouzakraoui, Sa?d,Cornil, Jér?me,Sergeyev, Sergey,Geerts, Yves
-
scheme or table
p. 9560 - 9572
(2011/01/12)
-
- ORGANIC SEMICONDUCTOR MATERIAL, ORGANIC SEMICONDUCTOR STRUCTURE AND ORGANIC SEMICONDUCTOR APPARATUS
-
The present invention is directed to the provision of a liquid crystalline organic semiconductor material, which is highly stable under a film forming environment and, at the same time, can easily form a film, for example, by coating. The liquid crystalline organic semiconductor material comprises: a thiophene skeleton comprising 3 to 6 thiophenes linearly connected to each other; and an identical alkyl group having 1 to 20 carbon atoms located on both sides of the thiophene skeleton, wherein acetylene skeletons each have been introduced into between the thiophene skeleton and the alkyl group, or acetylene skeletons have been introduced symmetrically into the thiophene skeleton.
- -
-
-
- Photochromism of 1,2-bis(2-n-alkyl-5-formyl-3-thienyl)perfluorocyclopentene derivatives
-
Photochromic diarylethene derivatives 1o-6o bearing long alkyl chains (≥seven carbon atoms) have been synthesized and their structures with the exception of compound 3o have been determined by single-crystal X-ray diffraction analysis. The effect of alkyl chain length on their properties, including photochromism both in solution and in PMMA film and their electrochemical properties were investigated in detail. All of these diarylethenes showed good photochromism both in solution and in PMMA film. The diarylethene derivatives with n-heptyl and n-octyl substituents at the 2-positions of the two thiophene rings exhibit photochromism even in the single-crystalline phase, but those with n-decyl, n-undecyl and n-dodecyl groups showed no photochromism in the single-crystalline phase. Compared to the photochromic features of 1,2-bis(2-methyl-5-formyl-3-thienyl)perfluorocyclopentene, introduction of the long alkyl groups was found to decrease the cycloreversion quantum yield and induce bathochromic shifts of the absorption spectra of the closed-ring isomers. The absorption coefficients of both open- and closed-ring isomers increased remarkably when replacing the methyl groups at 2-positions of the two thiophene rings with n-heptyl ones. However, further increase was not observed the alkyl chain becoming longer from n-heptyl to n-dodecyl groups. The cyclic voltammetry indicated that the HOMO and LUMO energy levels of these diarylethenes increased with the increase of the carbon numbers of alkyl chains from n-heptyl to n-dodecyl groups, but their band gaps were essentially not influenced by the alkyl chain length.
- Pu, Shouzhi,Zhu, Shengsheng,Rao, Yi,Liu, Gang,Wei, Huizhen
-
experimental part
p. 89 - 100
(2009/08/15)
-
- Iron-catalyzed cross-coupling of alkyl sulfonates with arylzinc reagents
-
Iron-catalyzed cross-coupling reactions of primary and secondary alkyl sulfonates with arylzinc reagents proceed smoothly In the presence of excess TMEDA and a concomitant magnesium salt. The arylzinc reagents are prepared from the corresponding aryllithium or magnesium reagents with ZnI2. The In situ formation of alkyl Iodides and consecutive rapid cross-coupling avoids discrete preparation of the unstable secondary alkyl halides and also achieves high product selectivity.
- Ito, Shingo,Fujiwara, Yu-Ichi,Nakamura, Eiichi,Nakamura, Masaharu
-
supporting information; experimental part
p. 4306 - 4309
(2009/12/26)
-
- Poly[3-(5-octyl-thienylene-vinyl)-thiophene]: A side-chain conjugated polymer with very broad absorption band
-
A novel polythiophene derivative, poly[3-(5-octyl-thienylene-vinyl)- thiophene] (POTVT) with conjugated thienylene vinyl side-chain, was synthesized, and the POTVT film shows a very broad absorption band-width covering from 300 nm to 700 nm after thermal annealing at 130°C for 10 min. The Royal Society of Chemistry 2006.
- Hou, Jianhui,Yang, Chunhe,He, Chang,Li, Yongfang
-
p. 871 - 873
(2008/02/08)
-
- 1,4-DITHIENYLBENZENE DERIVATIVE
-
A novel compound having a mesophase forming property or liquid crystallinity and a high level of electric charge mobility, a liquid crystal composition comprising said compound and a charge transfer material comprising the same, and various element using said charge transfer material. The novel compound is a 1,4-dithienylbenzene derivative represented by general formula (I): (I) wherein R1 and R2 each independently represent a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, provided that R1 and R2 do not simultaneously represent a hydrogen atom; and A represents a benzene ring optionally having a substituent.
- -
-
Page/Page column 12
(2010/10/20)
-
- Cobalt(diamine)-catalyzed cross-coupling reaction of alkyl halides with arylmagnesium reagents: Stereoselective constructions of arylated asymmetric carbons and application to total synthesis of AH13205
-
A cobalt-diamine complex catalyzes the cross-coupling reactions of primary and secondary alkyl halides with aryl Grignard reagents. It is confirmed that oxidative addition of alkyl halide to cobalt proceeds via a radical process. Optically pure Ueno-Stork halo acetals undergo diastereoselective cross-coupling reactions, the products of which are transformed into optically active THF derivatives. A sequential radical cyclization/arylation reaction under cobalt catalysis provides extremely short access to a synthetic prostaglandin AH13205.
- Ohmiya, Hirohisa,Yorimitsu, Hideki,Oshima, Koichiro
-
p. 1886 - 1889
(2007/10/03)
-
- Cobalt-catalyzed cross-coupling reactions of alkyl halides with aryl Grignard reagents and their application to sequential radical cyclization/cross-coupling reactions
-
Reactions of alkyl halides with arylmagnesium bromides in the presence of cobalt(II)(diphosphine) complexes are discussed. Treatment of 1-bromooctane with phenylmagnesium bromide with the aid of a catalytic amount of CoCl 2(dppp) [DPPP=1,3-bis(diphenylphosphino)propane] yielded octylbenzene in good yield. The reaction mechanism would include single electron transfer from an electron-rich cobalt complex to alkyl halide to generate the corresponding alkyl radical. The mechanism was justified by CoCl 2(dppe)-catalyzed [DPPE=1,2-bis(diphenylphosphino)ethane] sequential radical cyclization/cross-coupling reactions of 6-halo-1-hexene derivatives that yielded benzyl-substituted cyclopentane skeletons.
- Ohmiya, Hirohisa,Wakabayashi, Katsuyu,Yorimitsu, Hideki,Oshima, Koichiro
-
p. 2207 - 2213
(2007/10/03)
-
- Synthesis of C3-symmetric nano-sized polyaromatic compounds by trimerization and Suzuki-Miyaura cross-coupling reactions
-
Various C3-symmetric molecules were prepared by trimerization of acetyl aromatic compounds and subsequently coupled with various boronic acids under Pd0 catalysis conditions to generate oligoaryl/-heteroaryl C3-symmetric molecules. Several furan- and thiophene-containing star-shaped molecules were prepared by the use of Suzuki-Miyaura cross-coupling as a key step. Structural and conformational details were explored by semi-empirical molecular orbital theory using the AM1 method. Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2004.
- Kotha, Sambasivarao,Kashinath, Dhurke,Lahiri, Kakali,Sunoj, Raghavan B.
-
p. 4003 - 4013
(2007/10/03)
-
- Synthesis of Functionalized Carbon-Sulfur [5]Helicene: Pd-Catalyzed Negishi Cross-Coupling between the β-Positions of Thiophenes
-
Octyl- and bromo-substituted carbon-sulfur [5]helicene was prepared in several steps starting from either thiophene or 3-bromothiophene. Pd-catalyzed Negishi cross-coupling between the β-positions of thiophenes was one of the key steps in the synthesis.
- Miyasaka, Makoto,Rajca, Andrzej
-
p. 177 - 181
(2007/10/03)
-
- Synthesis, polymerization and characterization of substituted dithieno [3,4-b: 3',4'-d] thiophenes
-
Chemical or electrochemical oxidation of substituted dithieno [3,4- b:3',4'-d]thiophenes provides polymers with defined regiochemical structures. These materials have lower bandgaps (0.7-0.9 eV) than the unsubstituted fused heteroarene. Potential cycling of the 1,3-dimethyl substituted polymer film shows repetitive p- and n-dopability. The chemically-prepared dioctyl analog is soluble in common solvents such as chloroform, dichloromethane and THF. However, overoxidation of the polymers at an electrode surface presents a limitation to the polymerization of substituted analogs of the parent fused heteroarene.
- Inaoka, Seiji,Collard, David M.
-
p. 1719 - 1725
(2007/10/03)
-
- Sulfonation of aromatic compounds in the presence of solvents
-
A process for the sulfonation of aromatic compounds wherein an aromatic substance consisting of one or more aromatic compounds susceptible to the action of sulfur trioxide is formed into a reactant by admixture with one or more organic liquids, substantially inert to sulfur trioxide under the conditions of the process, which reactant is brought to boiling at a temperature not greater than 100° C under a pressure of from 0.1 mm Hg to atmospheric pressure, gaseous sulfur trioxide is introduced thereinto thereby causing it to continue to boil, the component or components of the reactant thus volatilized is or are reconverted to liquid in a heat-exchanger and recycled to the reaction chamber, and the pressure in the reaction chamber and the rate at which the gaseous sulfur trioxide is introduced into the reactant are controlled so as to ensure that there is always present in the reaction chamber an amount of volatilizable matter exceeding that amount volatilizable by the heat of reaction of the aromatic substance present in the reaction chamber with the gaseous sulfur trioxide in contact with said aromatic substance and that the temperature of the reaction mixture is a temperature of 100° C or below.
- -
-
-