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971.
Maciej Krzeszewski Takuya Kodama Eli M. Espinoza Prof. Dr. Valentine I. Vullev Prof. Dr. Takashi Kubo Prof. Dr. Daniel T. Gryko 《Chemistry (Weinheim an der Bergstrasse, Germany)》2016,22(46):16478-16488
Large aza‐analogues of curved polycyclic aromatic hydrocarbons with a double‐helicene structure present unique features for molecular photonics. We present the preparation and characterization of three such structures. The synthesis of these heterocyclic nanographenes involves only a few high‐yield steps that use readily available starting materials. X‐ray analysis revealed that each of these new dyes has three conformational isomers: one diastereoisomer in a meso form and two enantiomers in twisted forms [(P,P)] and [(M,M)]. The low energy barriers between the conformers, however, prevent their separation by using chiral HPLC, and the NMR spectra show only one set of signals for each of these curved compounds. Density functional theory (DFT) calculations quantify the small energy difference and the small energy barriers between the chiral and meso forms, which fully supports the experimental results. Their optical absorption lacks any sensitivity to the solvent environment, whereas their fluorescence features exhibit pronounced solvatochromism. This rarely observed solvatofluorochromism of centrosymmetric molecules without either electron‐withdrawing groups or ‐donating substituents was probed by using time‐resolved spectroscopy. These studies suggest that, similar to 9,9′‐bianthryl, the nonpolar locally excited state shows negligible solvatochromism, whereas the charge‐transfer state is sensitive to solvent polarity. 相似文献
972.
973.
J. Taprogge A. Jungclaus H. Grawe I. N. Borzov S. Nishimura P. Doornenbal G. Lorusso G. S. Simpson P. -A. Söderström T. Sumikama Z. Y. Xu H. Baba F. Browne N. Fukuda R. Gernhäuser G. Gey N. Inabe T. Isobe H. S. Jung D. Kameda G. D. Kim Y. -K. Kim I. Kojouharov T. Kubo N. Kurz Y. K. Kwon Z. Li H. Sakurai H. Schaffner Y. Shimizu K. Steiger H. Suzuki H. Takeda Zs. Vajta H. Watanabe J. Wu A. Yagi K. Yoshinaga G. Benzoni S. Bönig K. Y. Chae L. Coraggio J. -M. Daugas F. Drouet A. Gadea A. Gargano S. Ilieva N. Itaco F. G. Kondev T. Kröll G. J. Lane A. Montaner-Pizá K. Moschner D. Mücher F. Naqvi M. Niikura H. Nishibata A. Odahara R. Orlandi Z. Patel Zs. Podolyák A. Wendt 《The European Physical Journal A - Hadrons and Nuclei》2016,52(12):375
974.
The line shape of a multiplet proton resonance changes greatly as the rate of relaxation of a nuclear spin I to which the proton is coupled increases. In order to show that such complex line shapes are generally accessible to theoretical analysis, examples of line contours are calculated and shown graphically for I = 1, 3/2, 2, 5/2 and 3. 相似文献
975.
976.
Preparation and characterization of novel transparent plasticized poly(butylene terephthalate)‐co‐poly(alkylene glycol terephthalate) gel
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Hong Xia Yoshio Hashimoto Toshihiro Hirai 《Journal of Polymer Science.Polymer Physics》2015,53(12):829-832
Transparent plasticized gels with good mechanical, optical, and dielectric properties have important applications in various fields. We prepared a new gel using a poly(butylene terephthalate)‐co‐poly(alkylene glycol terephthalate) (PBT‐co‐PAGT) copolymer and a plasticizer, dibutyl adipate (DBA). This method improved the polymer crystallinity, and suppressed particle formation in cast‐films when the polymer was dissolved in 1,1,1,3,3,3‐hexafluoro‐2‐propanol, followed by solvent evaporation, and enabled uniform swelling of the polymer network by the plasticizer to form a transparent and flexible gel. The dielectric constants of the developed PBT‐co‐PAGT/DBA gels are much higher than those of PBT‐co‐PAGT films at low frequency. We believe that these PBT‐co‐PAGT/DBA gels could be used as photovoltaic, dielectric, and actuator materials. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2015 , 53, 829–832 相似文献
977.
Shigeyasu Motohashi Ken Yasukawa Michio Takido Toshihiro Akihisa Torn Takagi Ryota Nishioka 《合成通讯》2013,43(24):4467-4472
The asymmetric synthesis of (6S,8R)-, (6S,8S)-, (6R,8S)- and (6R,8R)-heptacosane-6,8-diols from (2S)-, (2R)-1-[(R)-p-tolylsulfinyl]-2-heptanols and 1-icosanal is described. 相似文献
978.
Asymmetric anionic polymerizations of 7‐(o‐substituted phenyl)‐2,6‐dimethyl‐1,4‐benzoquinone methides: Electrostatic interaction and steric,inductive, and resonance effects of the ortho‐substituent on the optical activity
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Takahiro Uno Shuhei Yamamoto Atsushi Yamane Masataka Kubo Takahito Itoh 《Journal of polymer science. Part A, Polymer chemistry》2017,55(6):1048-1058
7‐(o‐Substituted phenyl)‐2,6‐dimethyl‐1,4‐benzoquinone methides which have an electron‐donating methoxy‐(o‐OMe, 2a ) and methyl‐ (o‐Me, 2b ) substituents or an electron‐withdrawing cyano‐ (o‐CN, 2c ) and trifluoromethyl‐ (o‐CF3, 2d ) substituents at the ortho‐position of the aromatic ring and 7‐(m‐substituted phenyl)‐2,6‐dimethyl‐1,4‐benzoquinone methide with an electron‐withdrawing trifluoromethyl‐ (m‐CF3, 2e ) substituent at the meta‐position of the aromatic ring were synthesized, and their asymmetric anionic polymerizations using the complex of lithium 4‐isopropylphenoxide with (?)‐sparteine were carried out in toluene at 0 °C. The polymers with negative optical activity were obtained for all of five monomers, and their specific rotation values largely changed depending upon the substituents of the monomers. On the basis of the comparison of various substituents effects, it was found that the specific rotation of obtained polymers is significantly affected by the electronic effects such as inductive and resonance effects rather than the steric and electrostatic effects of the substituent. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2017 , 55 , 1048–1058 相似文献
979.
Yoshio Nishimura Takanori Kubo Yasuko Okamoto Hidetsura Cho 《Tetrahedron letters》2017,58(45):4236-4239
A method of convergent synthesis of novel 4,6-unsubstituted 5-acyl-2-aminodihydropyrimidines 7 is developed. The synthetic intermediate of 7, 4,6-unsubstituted 2-aminodihydropyrimidines 9 having a Weinreb amide at the 5-position, is prepared by the sequential Staudinger/aza-Wittig/cyclization reactions of (E)-tert-butyl{3-azido-2-[methoxy(methyl)carbamoyl]allyl}carbamate (E)-10. The transformation of the Weinreb amide of 9 to an acyl group proceeds smoothly by a substitution reaction using aryllithiums or alkyllithiums in the presence of a catalytic amount of BF3 etherate, affording 7 in good to high yield. The N-protecting group of 7 can be easily removed to obtain N-unsubstituted 2-amino-5-acyldihydropyrimidines 8, and the derivatives are observed as a single isomer in 1H NMR spectroscopy. All dihydropyrimidines in this study were hitherto unavailable and difficult to synthesize by conventional methods. 相似文献
980.
A Divergent Synthesis of Spiropyrazole Derivatives Containing Iminolactone and/or Cyclic Imide Moiety
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Eiichi Masumoto Hiroshi Maruoka Fumi Okabe Toshihiro Fujioka Kenji Yamagata 《Journal of heterocyclic chemistry》2015,52(1):48-53
An approach to spiropyrazole derivatives containing iminolactone and/or cyclic imide moiety starting from 1H‐pyrazole‐4‐acetic acid derivative is described. Hydrolysis of C‐cyanomethylated 1H‐pyrazole‐4‐acetic acid methyl ester ( 1 ), which was easily prepared from 1H‐pyrazole‐4‐acetic acid derivative by a C‐cyanomethylation, led to the C‐cyanomethylated 1H‐pyrazole‐4‐acetic acid ( 2 ). Compound 2 was reacted with ethanol in the presence of tin(IV) chloride in refluxing chloroform to give the key intermediate ethyl imidate ( 3 ). Sodium hydride‐assisted lactonization of 3 in N,N‐dimethylformamide afforded the spiropyrazole derivative containing iminolactone moiety ( 4 ). On the other hand, thermal treatment of 3 with sodium acetate in the absence of solvent caused another intramolecular cyclization to yield the spiropyrazole derivative containing cyclic imide moiety ( 6 ). 相似文献