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41.
Otera J Fujita Y Sakuta N Fujita M Fukuzumi S 《The Journal of organic chemistry》1996,61(9):2951-2962
Mechanism of Mukaiyama-Michael reaction of ketene silyl acetal has been discussed. The competition reaction employing various types of ketene silyl acetals reveals that those bearing more substituents at the beta-position react preferentially over less substituted ones. However, when ketene silyl acetals involve bulky siloxy and/or alkoxy group(s), less substituted compounds react preferentially. The Lewis acids play an important role in these reactions. Enhanced preference for the more sterically demanding Michael adducts is obtained with Bu(2)Sn(OTf)(2), SnCl(4), and Et(3)SiClO(4) in the former reaction while TiCl(4) gives the highest selectivity for the less sterically demanding products in the latter case. These results are interpreted in terms of alternative reaction mechanisms. The reaction of less bulky ketene silyl acetals are initiated by electron transfer from these compounds to a Lewis acid. On the other hand, bulkier ketene silyl acetals undergo a ubiquitous nucleophilic reaction. Such a mechanistic change is discussed based on a variety of experimental results as well as the semiempirical PM3 MO calculations. 相似文献
42.
Oike T Kurata T Takimiya K Otsubo T Aso Y Zhang H Araki Y Ito O 《Journal of the American Chemical Society》2005,127(44):15372-15373
The porphyrin-sexithiophene-fullerene triad 2, where the two central thiophene units of the sexithiophene spacer are bridged with a crown-ether-like polyether chain, undergoes efficient intramolecular electron transfer from the photoexcited porphyrin moiety to the fullerene through the sexithiophene. However, complexation with a sodium cation in the crown ether ring causes complete suppression of electron transfer as a result of a drastic conformational change of the sexithiophene backbone. Furthermore, decomplexation resumes the photoinduced electron transfer. This on/off switching phenomenon indicates that the polyether-bridged sexithiophene can function as a complexation-gated molecular wire. 相似文献
43.
[reaction: see text] A new class of molecular machine exhibits a hingelike motion upon photoirradiation. The motion (close and open) can be operated by alternate irradiation with UV and visible light. The trans/trans and cis/cis isomers are thermally stable at 40 degrees C, and the photochemical closure reaction (from trans/trans to cis/cis isomer) is dependent on the intensity of the light used because of the short-lived intermediate (trans/cis isomer). 相似文献
44.
Sadayuki Mori Tetsuya Karita Koichi Komatsu Nobuyuki Sugita Terence S. M. Wan 《合成通讯》2013,43(9):1475-1482
Under high pressure conditions, fullerene C60 smoothly reacts with 2H-pyran-2-one to give a [4+2] cycloadduct, which can be reduced to an alcohol derivative. 相似文献
45.
Plasma-enhanced MOCVD in which metal-organic compounds are sublimated directly into the growth chamber is studied for the first time as a new low-temperature process for growing superconducting YBa2Cu3O--x thin films. Y(THD)3, Ba(THD)2, Cu(THD)2 and oxygen are used as metal sources and oxydizing agent. Emission spectroscopy reveals that activated metal-organic compounds and activated oxygen species are present during film growth. Superconducting YBa2Cu3O7-x films whose zero-resistivity temperature are 50 K and 82 K are grown at 550°C and 600°C. 相似文献
46.
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48.
This paper presents some new characterizations of Euclidean distance matrices (EDMs) of special structures. More specifically, we discuss multispherical and block-structured EDMs, each of which can be viewed as a generalization of spherical EDM. We focus on a well-known inequality that characterizes spherical EDMs and extend it to the sets of multispherical and block-structured EDMs. Some related results are also presented. 相似文献
49.
Mohammad Nasir Uddin Zainul Abedin Siddique Nobuyuki Mase Monir Uzzaman Wahhida Shumi 《应用有机金属化学》2019,33(6)
A number of oxotitanium(IV) complexes of the type TiOL with bis‐unsymmetric dibasic tetradentate Schiff base (LH2) containing ONNO donor atoms have been synthesized. Mono‐Schiff base (OPD‐HNP) was prepared by the condensation of 1:3 molar ratio of 2‐hydroxy‐1‐naphthaldehyde (HNP) with o‐phenylenediamine (OPD). Dibasic unsymmetric tetradentate diamine Schiff bases were prepared by the reaction of OPD‐HNP with 2‐hydroxyacetophenone, 2‐hydroxypropeophenone, benzoylacetone, acetylacetone and ethylacetoacetate. Further, titanylacetylacetonate was reacted with these ligands to obtain their metal complexes. On the basis of analytical and physiochemical data, the formation of complexes as TiOL was suggested having square pyramidal geometry. Quantum mechanical approach also confirmed this geometry. The assessment of the synthesized ligands and their complexes showed that some behave as good inhibitors of mycelial growth against selected phytopathogic fungi but weak inhibitors against some selected bacteria. A few of them also showed antioxidant properties. 相似文献
50.
Nobuyuki Otozawa Rio Hamajima Masataka Yoshioka Raito Kato Arisa Tanaka Hiroto Fukuma Toshiki Terao Kei Manabe Syuji Fujii Yoshinobu Nakamura Atsushi Takahara Tomoyasu Hirai 《Journal of polymer science. Part A, Polymer chemistry》2020,58(14):1960-1964
This study investigates the effect of ionic liquids (ILs) on the anionic polymerization of methyl methacrylate (MMA). Polymethyl methacrylate (PMMA), an isotactic polymer, is prepared by anionic polymerization at a high reaction temperature with an IL that acts as both solvent and additive. The most plausible reaction mechanism is determined using 1H NMR and Fourier-transform infrared spectroscopy. The electrostatic interaction between MMA and the IL increases the apparent steric hindrance in MMA, resulting in the isotactic PMMA. 相似文献