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111.
Photochemistry of α,α-bisulfenylated ketone has been investigated. Irradiation of 2-phenylthiodihydrothiophen-3-one (1) in benzene gave the radical recombination products 9 (63%) and 10 (49%). In a polar solvent, the ionic chemistry became predominant. Brief irradiation of 1 in acetonitrile and methanol gave the cis-fused dihydrothiophene 11 as the major product in 43% and 20% yields, respectively. The stereoselective photocyclization was generally observed for other ketones (2–8) in acetonitrile solution (Table 1). The photo-products were easily dehydrated by treating with boron trifluoride etherate to give the corresponding benzothiophenes in high yields. Simple α-phenylthioketones are photoinert under the same conditions. The mechanism of this novel photocyclization of bisulfenylated ketones is also discussed. 相似文献
112.
Kaizaki Sumio Kita Przemyslaw Wiśniewska Joanna Sakagami Narumi 《Transition Metal Chemistry》1998,23(4):511-515
Three new complex ions, [Cr(NCS)(R-pdtrp)]-, [Cr(R-pdtrp)(NCSHg)]+ and [Cr(edtrp)(NCSHg)]+, that are derivatives of the trans-equatorial isomers of [Cr(R-pdtrp)(H2O)]0 and [Cr(edtrp)(H2O)]0 (edtrp= ethylenediamine-N,N,N-tripropionate, R-pdtrp= R-propane-1,2-diamine-N,N,N-tripropionate) have been obtained and characterized in solution. Rate constants and activation parameters, including, in two cases, volumes of activation, have been determined. Rate retardation for NCS- ligand release has been observed with increasing acidity within the pH 0–2 range. The mechanism of the reactions has been discussed. 相似文献
113.
Grubišic Sonja Gruden-Pavlović Maja Niketić Svetozar R. Sakagami-Yoshida Narumi Kaizaki Sumio 《Transition Metal Chemistry》2003,28(1):37-42
The structure of trans-equatorial [Cr(edtrp)(H2O)] · 3H2O (edtrp3– is the anion of ethylenediamine-N,N,N-tripropionic acid) was determined by single crystal X-ray diffraction. The chromium(III) ion is surrounded octahedrally by the two nitrogen and three oxygen atoms of the quinquedentate edtrp3–, forming a five-membered diamine ring and the three six-membered -propionato chelate rings. The remaining coordination position is occupied by the H2O ligand. The crystal structure conformation is compared to the result of recent molecular mechanics analysis. The ring strain of R and G chelate rings was found to be in agreement with the previously proposed mechanisms for the C—N bond cleavage and recombination. 相似文献
114.
Yamada Ji Satoki S Mishima S Akashi N Takahashi K Masuda N Nishimoto Y Takasaki S Anzai H 《The Journal of organic chemistry》1996,61(12):3987-3995
Efficient synthetic methods for the construction of a wide variety of unsymmetrical tetrathiafulvalenes (TTFs) via the Me(3)Al-promoted reactions of organotin thiolates or selenolates with esters are described. Reaction of tin thiolates (3a-c and 10) and selenolates (3d, 5, and 7) with esters (11a,b) in the presence of Me(3)Al as a Lewis acid gave dihydrotetrathiafulvalene derivatives (12, 14, 15, and 17-20) and 1,3-dithiane derivatives (13 and 16). In addition, the synthesis of diselenadithiafulvalene derivatives (25-28) could be accomplished by Me(3)Al-mediated reaction of tin thiolate (2a) or selenolates (3d and 5) with esters (22a, 22d, and 24). Furthermore, the application of the Me(3)Al-promoted reaction of tin thiolate (34) with esters (11a-b, 22a-d, and 35a-b) for the synthesis of unsymmetrical TTFs-fused donors enabled us to obtain various TTFs-fused systems (29-33) in short steps. 相似文献
115.
Fumio Hamazu Sumio Akashi Tatsuya Koizumi Toshikazu Takata Takeshi Endo 《Journal of polymer science. Part A, Polymer chemistry》1991,29(11):1675-1680
Three benzyl p-hydroxyphenyl methylsulfonium salts with different counter anions were synthesized as novel latent thermal initiators. Syntheses of the sulfonium salts ( 2 ) were performed by the reaction of p-hydroxyphenyl methyl sulfide with benzyl chloride followed by exchange of the counter anion (Cl?) with SbF?6 ( 2a ), PF?6 ( 2b ), or BF?4 ( 2c ). In the bulk polymerization of glycidyl phenyl ether (PGE) with 2 , initiator activity of the sulfonium salts was evaluated by comparison with that of benzyl tetramethylenesulfonium hexafluoroantimonate ( 1 , R = H). Among the initiators, 2a showed the highest activity, and was much more active than 1 (R = H). Since the polymerization of PGE with 2a proceeded efficiently at more than 80°C but not at all at less than 60°C, 2a was suggested to be a good latent thermal initiator. 相似文献
116.
Nakano K Suemura N Kawata S Fuyuhiro A Yagi T Nasu S Morimoto S Kaizaki S 《Dalton transactions (Cambridge, England : 2003)》2004,(7):982-988
The synthesis and characterization of new spin-crossover pyrazolato bridged dinuclear [(FeII(NCS)(py))2(mu-bpypz)2] and the corresponding cyanotrihydroborato-kappaN complexes are described together with the X-ray crystal analysis of the latter in both the high-spin and low-spin states as well as the variable temperature magnetic susceptibility and/or Mossbauer spectra demonstrating the spin-crossover which exhibits an one-step process, but not a two-step one characteristic of the known bpym bridged dinuclear complexes. 相似文献
117.
Kimiaki Imafuku Miyuki Sumio Hisashi Matsumura 《Journal of heterocyclic chemistry》1980,17(5):1057-1059
3-Methyl-1,8-dihydrocycloheptapyrazol-8-one hydrazone ( 5 ) reacted with triethyl ortho-formate, orthoacetate and orthopropionate to afford 2,2a,4,5-tetraazabenz[cd]azulene derivatives ( 7a-c ). 3-Methyl- ( 7b ) and 3-phenyl-substituted compounds ( 7d ) were also obtained by the reactions of 5 with acetyl and benzoyl chlorides, respectively. 相似文献
118.
Sumio AisawaHidetoshi Hirahara Hiroaki UchiyamaSatoshi Takahashi Eiichi Narita 《Journal of solid state chemistry》2002,167(1):152-159
In this paper, the synthesis and thermal decomposition behavior of hydrotalcite-like Mn-Al layered double hydroxide (LDH) have been investigated. First, the Mn-Al LDH was synthesized by the coprecipitation method using various anions such as Cl−, CO2−3, NO−3, SO2−4 or dicarboxylic acids (DCA). The single phase of the Mn-Al LDH was obtained when Cl−, NO−3 or DCA was used as a guest anion. In the case of CO2−3 or SO2−4, the solid products included MnCO3 or shigaite as a by-product. The crystallinity of the Cl/Mn-Al LDH was greatly influenced by a drying temperature and that the crystallinity of the Cl/Mn-Al LDH dried at room temperature was found to rise about 6 times in comparison with that dried at 333 K. The DCA/Mn-Al LDH was found to have an expanding LDH structure, supporting that the LDH basal layers were bridged by the intercalated DCA anion. Then, the thermal decomposition of the DCA/Mn-Al LDH has been examined, and the intercalated DCA was found to be decomposed at lower temperature than DCA itself. The oxidation number of Mn ion rose with increasing the heat treatment temperature and was +2.70 with crystallizing Mn3O4 after being heated at 973 K. The thermal decomposition of guest DCA was thought to be accelerated by the strong catalytic action of Mn ion in the host hydroxide basal layers. 相似文献
119.
Toyonobu Yoshida Kunihiko Nakagawa Toshiya Harada Kazuo Akashi 《Plasma Chemistry and Plasma Processing》1981,1(1):113-129
A numerical model has been developed for predicting the two-dimensional flow and temperature fields in a radio-frequency (rf) plasma torch. The method employed here is based on Boulos' model with the exception of the boundary conditions for the electric and magnetic field equations. Calculations have been made for the confirmation of a new sample injection method, which is capable of completely evaporating refractory materials at high feeding rates without interfering with the stability of the plasma. In the newly designed torch, the reagent is radially injected into the hottest part of the plasma through quartz capillary tubes set symmetrically between an inductor coil. Experimental investigations have also been performed for verifying the proper function of the design. These results provide evidence that our radial injection method developed here is more effective in practical processing than the conventional axial injection methods. 相似文献
120.
Several trifluoromethanesulfonyl(TFMS) derivatives of sugars were prepared and treated with sodium in liquid ammonia or subjected to ultraviolet irradiation. Three 3--TFMS derivatives gave the corresponding 3-deoxy compounds, but a 2--TFMS derivative gave a branched-chain sugar. 相似文献