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61.
Mechanistic Investigation of Catalyst‐Transfer Suzuki–Miyaura Condensation Polymerization of Thiophene–Pyridine Biaryl Monomers with the Aid of Model Reactions 下载免费PDF全文
Yu Tokita Masaru Katoh Dr. Yoshihiro Ohta Prof. Tsutomu Yokozawa 《Chemistry (Weinheim an der Bergstrasse, Germany)》2016,22(48):17436-17444
We have investigated the requirements for efficient Pd‐catalyzed Suzuki–Miyaura catalyst‐transfer condensation polymerization (Pd‐CTCP) reactions of 2‐alkoxypropyl‐6‐(5‐bromothiophen‐2‐yl)‐3‐(4,4,5,5‐tetramethyl‐1,3,2‐dioxaborolan‐2‐yl)pyridine ( 12 ) as a donor–acceptor (D –A) biaryl monomer. As model reactions, we first carried out the Suzuki–Miyaura coupling reaction of X–Py–Th–X′ (Th=thiophene, Py=pyridine, X, X′=Br or I) 1 with phenylboronic acid ester 2 by using tBu3PPd0 as the catalyst. Monosubstitution with a phenyl group at Th‐I mainly took place in the reaction of Br–Py–Th–I ( 1 b ) with 2 , whereas disubstitution selectively occurred in the reaction of I–Py–Th–Br ( 1 c ) with 2 , indicating that the Pd catalyst is intramolecularly transferred from acceptor Py to donor Th. Therefore, we synthesized monomer 12 by introduction of a boronate moiety and bromine into Py and Th, respectively. However, examination of the relationship between monomer conversion and the Mn of the obtained polymer, as well as the matrix‐assisted laser desorption ionization time‐of‐flight (MALDI‐TOF) mass spectra, indicated that Suzuki–Miyaura coupling polymerization of 12 with (o‐tolyl)tBu3PPdBr initiator 13 proceeded in a step‐growth polymerization manner through intermolecular transfer of the Pd catalyst. To understand the discrepancy between the model reactions and polymerization reaction, Suzuki–Miyaura coupling reactions of 1 c with thiopheneboronic acid ester instead of 2 were carried out. This resulted in a decrease of the disubstitution product. Therefore, step‐growth polymerization appears to be due to intermolecular transfer of the Pd catalyst from Th after reductive elimination of the Th‐Pd‐Py complex formed by transmetalation of polymer Th–Br with (Pin)B–Py–Th–Br monomer 12 (Pin=pinacol). Catalysts with similar stabilization energies of metal–arene η2‐coordination for D and A monomers may be needed for CTCP reactions of biaryl D–A monomers. 相似文献
62.
Yoshihiro Ohta Makoto Karasawa Tetsurou Niiyama Akihiro Yokoyama Tsutomu Yokozawa 《Journal of polymer science. Part A, Polymer chemistry》2014,52(3):360-365
Well‐defined poly(3‐alkyl‐4‐benzamide) was synthesized by means of chain‐growth condensation polymerization of phenyl 3‐octyl‐4‐(4‐octyloxybenzyl(OOB)amino)benzoate ( 1c ) from initiator 2 , followed by removal of the OOB groups on amide nitrogen of poly 1c . Polymerization of 1c with phenyl 4‐(trifluoromethyl)benzoate ( 2b ) in the presence of 1,1,1,3,3,3‐hexamethyldisilazide (LiHMDS) and LiCl in THF at ?10 °C gave poly 1c with a narrow molecular weight distribution (Mw/Mn ≤ 1.08) and a well‐defined molecular weight (Mn = 4480–12,700) determined by the feed ratio of monomer to initiator (from 10 to 30). The OOB groups of poly 1c were removed with H2SO4 to give the corresponding N‐unsubstituted poly(p‐benzamide) (poly 1c′ ) with low polydispersity. The solublity of poly 1c′ in polar organic solvents was dramatically higher than that of poly(p‐benzamide), demonstrating that introduction of an alkyl group on the aromatic ring is very effective for improving the solubility of poly(p‐benzamide). © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2014 , 52, 360–365 相似文献
63.
Yasuhito Tanaka 《Operations Research Letters》2019,47(5):406-409
We study a dynamic free-entry oligopoly with sluggish entry and exit of firms under general demand and cost functions. We show that the number of firms in a steady-state open-loop solution for a dynamic free-entry oligopoly is smaller than that at static equilibrium and that the number of firms in a steady-state memoryless closed-loop solution is larger than that in an open-loop solution. 相似文献
64.
65.
Abstract Oligomerization of butadiene with the catalyst system of nickel(II)chloride, electron donor, and lithium aluminum hydride or sodium borohydride has been studied. Most oligomers obtained with this catalyst were linear, and dihydrogenated dimers, trimers, and tetramers. They were n-octa-1,6-diene, n-octa-1,7-diene, n-dodeca-1,6,10-triene, and n-hexadeca-1,6,10,14-tetraene, which were identified by means of infrared, nuclear magnetic resonance, and mass spectrometry. Yields of each oligomer were strongly affected by the nature of the electron donors used. The hydrogen required for the formation of the hydrooligomers was assumed to originate from the lithium aluminum hydride or sodium borohydride used as a reducing agent. A proposed mechanism for the hydrooligomerization is that butadiene is oligomerized on the nickel atom, and the produced oligoolefins, bonded to the nickel by two terminal π-allylic bonds, are dihydrogenated to linear hydrooligomers. 相似文献
66.
Reductive dehalogenation of aryl halides was achieved using hydrogen and a palladium catalyst. By using deuterium gas, the deuterated arenes were readily prepared. 相似文献
67.
Kiyofumi Katagiri Keiko Ohta Kunihito Koumoto Kei Kurosu Yoshihiro Sasaki Kazunari Akiyoshi 《Colloid and polymer science》2013,291(6):1375-1380
Novel organic–inorganic hybrid nanoparticles consisting of polymer–hydrogel nanoparticles (nanogels) and iron oxide were developed for potential biomedical applications. Hybrid nanoparticles were prepared by a simple procedure using polysaccharide nanogels as a reactive site for iron oxide formation. The hybrid nanoparticles have a narrow size distribution with a diameter of approximately 30 nm and show high colloidal stability. These nanohybrid particles could be used as a contrast medium for magnetic resonance imaging or for magnetic hyperthermia therapy. 相似文献
68.
Dr. Kazukuni Tahara Yuki Yamamoto Dr. Dustin E. Gross Hiroyoshi Kozuma Yoko Arikuma Dr. Koji Ohta Dr. Yoshiko Koizumi Yuan Gao Dr. Yo Shimizu Prof. Shu Seki Dr. Kenji Kamada Prof. Jeffrey S. Moore Prof. Yoshito Tobe 《Chemistry (Weinheim an der Bergstrasse, Germany)》2013,19(34):11251-11260
We present herein the synthesis and properties of the largest hitherto unknown graphyne fragment, namely trigonally expanded tetrakis(dehydrobenzo[12]annulene)s (tetrakis‐DBAs). Intramolecular three‐fold alkyne metathesis reactions of hexakis(arylethynyl)DBAs 9 a and 9 b using Fürstner’s Mo catalyst furnished tetrakis‐DBAs 8 a and 8 b substituted with tert‐butyl or branched alkyl ester groups in moderate and fair yields, respectively, demonstrating that the metathesis reaction of this protocol is a powerful tool for the construction of graphyne fragment backbones. For comparison, hexakis(arylethynyl)DBAs 9 c – g have also been prepared. The one‐photon absorption spectrum of tetrakis‐DBA 8 a bearing tert‐butyl groups revealed a remarkable bathochromic shift of the absorption cut‐off (λcutoff) compared with those of previously reported graphyne fragments due to extended π‐conjugation. Moreover, in the two‐photon absorption spectrum, 8 a showed a large cross‐section for a pure hydrocarbon because of the planar para‐phenylene‐ethynylene conjugation pathways. Hexakis(arylethynyl)‐DBAs 9 c – e and 9 g and tetrakis‐DBA 8 b bearing electron‐withdrawing groups aggregated in chloroform solutions. Comparison between the free energies of 9 e and 8 b bearing the same substituents revealed the more favorable association of the latter due to stronger π–π interactions between the extended π‐cores. Polarized optical microscopy observations, DSC, and XRD measurements showed that 8 b and 9 e with branched alkyl ester groups displayed columnar rectangular mesophases. By the time‐resolved microwave conductivity method, the columnar rectangular phase of 8 b was shown to exhibit a moderate charge‐carrier mobility of 0.12 cm2 V?1 s?1. These results indicate that large graphyne fragments can serve as good organic semiconductors. 相似文献
69.
Co–Pd bimetallic alloy nanoparticle catalysts were prepared from CoCl2, Pd(OAc)2 and several capping agents with Li(C2H5)3BH. The nanoparticle catalysts were applied to the aerobic oxidation of a variety of alcohols in water to give the corresponding carbonyl products. The catalyst was magnetically recovered and reused for further oxidation. The nanoparticle catalysts were characterized with TEM, ICP, and XPS analyses. 相似文献
70.
Akemi Umeyama Chihiro Ohta Yukari Shino Minori Okada Yukari Nakamura Tatsuya Hamagaki Hiroshi Imagawa Masami Tanaka Aki Ishiyama Masato Iwatsuki Kazuhiko Otoguro Satoshi Ōmura Toshihiro Hashimoto 《Tetrahedron》2014
During the search for new antitrypanosomal drug leads, three new antitrypanosomal compounds, hexatenuins A–C (1–3), were isolated from the fruiting body of Hexagonia tenuis. 1 and 3 possessed an unusual malonate half-ester functional group at C-3 position, and 1 and 2 had a spirostructure in the side-chain. Their structures were elucidated using MS analyses, extensive 2D-heteronuclear NMR data interpretation. Compounds 1–3 showed in vitro antitrypanosomal activity against Trypanosoma brucei brucei with IC50 values of 0.57, 8.60 and 5.62 μg/ml, respectively. 相似文献