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71.
72.
Takushi Kurihara Mariko Sugiyama Hiroshi Hirano Ken-Ichi Tomita Masayoshi Sakaki 《Journal of heterocyclic chemistry》1975,12(3):541-545
Reaction of o-nitrobenzylideneacetylacetone ( 1a ) with hydrazine dihydrochloride in methanol gave 4-(α-methoxy-o-nitrobenzyl)-3,5-dimethylpyrazole hydrochloride ( 4a ), whose structure was unambigously confirmed by an X-ray crystallographic analysis, via 4-(o-nitrobenzylidene)-3,5-dimethylisopyrazole ( 2a ). Compound 2a was synthesized by condensation of 1a with hydrazine dihydrochloride in acetonitrile. Analogously the corresponding o-chloro derivatives ( 2b, 4b ) were obtained. These were converted to N-methyl ( 6b ) and N-acetyl ( 7a,b ) derivatives and the behaviors on bromination and pyrolysis were investigated. 相似文献
73.
Four new cycloartane glycosides from Aquilegia vulgaris 总被引:2,自引:0,他引:2
Four new cycloartane glycosides, named aquilegiosides G-J, were isolated from the dried aerial parts of Aquilegia vulgaris. Their structures were determined by spectroscopic analysis and chemical evidence. 相似文献
74.
Shokyoku Kanaoka Nobuyuki Ikeda Akira Tanaka Hitoshi Yamaoka Toshinobu Higashimura 《Journal of polymer science. Part A, Polymer chemistry》2002,40(14):2449-2457
Random copolymers with high molecular weights of indene and p‐methylstyrene (pMeSt) were synthesized by cationic polymerization with trichloroacetic acid/tin tetrachloride in CH2Cl2 at low temperatures. When indene and pMeSt (1:1 v/v), for example, were polymerized at ?40 °C, both monomers were consumed at very similar rates to give a copolymer with high molecular weight [number‐average molecular weight (Mn): 8–9 × 104]. This is indeed quite unexpected behavior for the combination of these two monomers because pMeSt polymerized over 1000 times faster than indene in the homopolymerization under the reaction conditions previously described. The product copolymer of indene and pMeSt had a random monomer sequence in it that was confirmed by NMR analyses and thermal‐property measurements. In sharp contrast with pMeSt, styrene and p‐chlorostyrene, which have no electron‐donating groups on the phenyl ring, led to low molecular weight polymers (Mn < 10,000) in the copolymerization with indene (1:1 v/v). © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 2449–2457, 2002 相似文献
75.
Extraction equilibria for the 4-(2-Pyridylazo)-Resorcinol-Nickel(II)-Quaternary-Ammonium salt system
The extraction equilibria of nickel(II)-PAR complexes with tetradecyldimethylbenzylammonium chloride(Q+Cl?) are investigated. Two kinds of nickel complex are extracted by chloroform: Ni(HR)2,nQ+Cl?(0)(?500 = 3.73·104l mol?1cm?1) at about pH 5 and 2Q+ NiR2-2(o)(?500 = 8.08·104 l mol?1 cm?1) at above pH 8.5. The extraction constant for 2Q+ NiR2-2(o) was evaluated as [2Q+ NiR2-2]0/[NiR2-2] [Q+]2 = 1011.16 at μ = 0.1 (Na2SO4. Synergic extraction studies of the Ni(HR)2 species under slightly acidic conditions show that the species is Ni(HR)2(H2O)2in auqeous solution and is extracted into chloroform as the adduct Ni(HR)2(TBP)2 (?535 = 3.57·104 l mol?1 cm?1. Based on the extraction behavior of these complexes, the structures of the Ni2+—PAR complexes are discussed. 相似文献
76.
ESTIMATION OF AN INDEX OF HYDROPHOBICITY OF DNA INTERIOR USING 5-METHOXYPSORALEN AS A FLUORESCENT PROBE 总被引:1,自引:0,他引:1
Masako Sasaki Isao Nakasato Hiroyuki Sugiura Hitoshi Fujita Toshibumi Sakata 《Photochemistry and photobiology》1987,46(4):551-555
The index of hydrophobicity of DNA interior was estimated by measuring fluorescence spectra of psoralen derivatives associated with DNA. The environment around 5-MOP associated with DNA was as hydrophobic (Dk = 34) as methanol, suggesting that the molecules reside at the space between the base-pairs in B-form DNA. This is also true for 8-MOP. Thus, planar and aromatic molecules of 5- and 8-MOP are more stable in the interior of DNA than in aqueous medium due to hydrophobic affinity. 相似文献
77.
Todoroki K Hayama T Ijiri S Kazuta A Yoshida H Nohta H Yamaguchi M 《Journal of chromatography. A》2004,1038(1-2):113-120
6-Rhodamine B amine functions as a highly sensitive fluorescence derivatization reagent for mono- and oligosaccharides; it reacts with the reducing end of saccharides under acidic conditions. The fluorescent derivatives of five monosaccharides can be separated within 25 min by reversed-phase liquid chromatography with isocratic elution. The detection limits (S/N = 3) for mono-, di-, and oligosaccharides are 7-51, 13, and 9-35 fmol/20 microl injection, which correspond to analyte concentrations of 35-255, 65, 45-175 nM, respectively. We have applied this derivatization method successfully to the analysis of the components of oligosaccharides in glycoproteins (ribonuclease B and fetuin) following their acidic or enzymatic hydrolysis. The results from these analyses are in good agreements with the reported values established previously. 相似文献
78.
Yutaka T Mori I Kurihara M Mizutani J Kubo K Furusho S Matsumura K Tamai N Nishihara H 《Inorganic chemistry》2001,40(19):4986-4995
We synthesized azobenzene-conjugated bis(terpyridine) Ru(II) and Rh(III) mononuclear and dinuclear complexes and investigated their photochemical properties on excitation of the azo pi-pi band upon 366 nm light irradiation. The Ru mononuclear complex underwent trans-to-cis photoisomerization to reach the photostationary state with only 20% of the cis form, while the Ru dinuclear complex did not isomerize at all photochemically. On the other hand, the mononuclear and dinuclear Rh complexes showed almost complete trans-to-cis photoisomerization behavior. Cis forms of the Rh complexes thermally returned to the trans form at a much slower rate than those of organic azobenzenes, but they did not isomerize photochemically. The reduction potential of the cis forms was 80 mV more negative than that of the trans forms. The photoisomerization quantum yields of the Rh complexes were strongly dependent on the polarity, viscosity, and donor site of the solvents as well as the size of the counterions. We investigated the photoisomerization process of these complexes using femtosecond absorption spectroscopy. For the Rh complexes, we observed S(n) <-- S(2) and S(n) <-- S(1) absorption bands similar to those of organic azobenzenes. For the Ru complexes, we observed very fast bleaching of the MLCT band of the Ru complex, which indicated that the energy transfer pathway to the MLCT was the primary cause of the depressed photoisomerization. The electronic structures, which were estimated from ZINDO molecular orbital calculation, supported the different photochemical reaction behavior between the Ru and Rh complexes. 相似文献
79.
Tsuneyuki Sato Naoki Morita Hitoshi Tanaka Tadatoshi Ota 《Journal of polymer science. Part A, Polymer chemistry》1989,27(8):2497-2508
Solvent effect on the polymerization of di-n-butyl itaconate (DBI) with dimethyl azobisisobutyrate (MAIB) was investigated at 50 and 61°C. The solvents used were found to affect significantly the polymerization. The polymerization rate (Rp) and the molecular weight of the resulting polymer are lower in more polar solvents. The initiation rate (Ri) by MAIB, however, shows a trend of being rather higher in polar solvents. The stationary state concentration of propagating poly(DBI) radical was determined by ESR in seven solvents. The rate constants of propagation (kp) and termination (kt) were evaluated by using Rp, Ri, and the polymer radical concentration observed. The kp value decreases fairly with increasing polarity of the solvent used, whereas kt is not so influenced by the solvents. The solvent effect on kp is explained in terms of a difference in the environment around the terminal radical center of the growing chain. Copolymerization of DBI with styrene (St) was also examined in three solvents with different physical properties. The poly(DBI) radical shows a lower reactivity toward St in a more polar solvent. 相似文献
80.
Harayama T Akiyama T Nakano Y Nishioka H Abe H Takeuchi Y 《Chemical & pharmaceutical bulletin》2002,50(4):519-522
A palladium-assisted coupling reaction of aryl triflate with arene was investigated, and a novel Pd reagent prepared from equimolar Pd(OAc)2, 1,3-Bis[diphenylphosphino]propane (DPPP), and Bu3P was developed. This method is useful for intramolecular biaryl coupling reactions, not only between aryl triflate and arene (triflate-amide), but also between aryl halide and arene (halo-amide). 相似文献