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11.
12.
Toshio Matsushita Ken Hirotsu Taiichi Higuchi Kichisuke Nishimoto Masaaki Yoshifuji Katsuhiro Shibayama Naoki Inamoto 《Tetrahedron letters》1984,25(31):3321-3324
Ab initio Calculations of the isomerization reaction of diphosphene 1-sulfide (2′) to thiadiphosphirane (3′) suggest that the energy barrier of the reaction in the ground state is 25 kcal/mol and that 2′ lies 21 kcal/mol above 3′, while the calculations show that there exists one local minimum on the lowest triplet energy surface. 相似文献
13.
Effects of metal surfaces, such as aluminium, silver and gold, on the melting behavior and thermal polymerization of long-chain diynoic acids having a diacetylene group at different positions were investigated by thermal analyses using DSC, TG and other methods. The surface effects of metals were significant in the order of Ag, Al and Au. These effects are attributable to the anchoring of carboxyl group on the surface by chemisorption, which leads to unfavorable condition for polymerization of heptadeca-2,4-diynoic acid. In the case of tricosa-10,12-diynoic acid, containing a flexible methylene chain, inserted between COOH and C≡C?C≡C groups, the anchoring of COOH on the metal surface causes rather favorable effect on the polymerization. 相似文献
14.
A novel type of heterogenized CuCl2 catalysts was designed for the oxidative carbonylation of methanol to dimethyl carbonate (DMC) taking account of the plausible reaction mechanism and intermediates. To prevent severe corrosion of the reaction equipment materials due to Cl– while keeping the catalytic activity of the homogeneous CuCl2 catalyst, we adopted, as supports (or ligands) of CuCl2, four polymers, bearing a 2,2-bipyridine (bpy) or pyridine (py) unit, namely, poly(2,2-bipyridine-5,5-diyl) (Pbpy), poly(pyridine-2,5-diyl) (Ppy), poly(N,N-bisphenylene-2,2-bipyridine-4,4-dicarboxylic amide) (Bpya), and poly(4-methyl-4-vinyl-2,2-bipyridine) (Pvbpy), together with one chelate compound, 8-quinolinol. The catalytic activity, stability of heterogenized CuCl2 and their corrosivities to stainless steels were examined in the liquid-phase reaction of the oxidative carbonylation of methanol. These polymer-supported catalysts showed considerable catalytic activity and stability for the DMC synthesis. In particular, the Pbpy-CuCl2 and Ppy-CuCl2 catalysts exhibited high DMC yields and selectivity comparable to those of the homogeneous CuCl2 catalyst. This high activity appears to be associated with the presence of the -conjugated system in the polymers, which affect the redox reactions of Cu involved in the catalytic reaction. All of the polymer-supported CuCl2 catalysts could be easily recycled after filtration, and the initial catalytic activity was maintained after three times of use. The corrosive characters of the catalysts were closely related to CuCl2 leaching from the supports, which reflects the ability of supports to coordinate Cu. These experimental results suggest that both the electronic structure and the coordination ability of the polymer supports are key factors for the development of an effective catalytic system. 相似文献
15.
[reaction: see text] A newly developed strategy for construction of eight-membered carbocycles via [6 + 2] annulation that involves the combination of beta-alkenoyl acylsilanes and a vinyllithium derivative is described. A unique feature of this annulative approach is that it enables in one operation and a stereoselective manner construction of eight-membered ring systems containing useful functionalities for further synthetic elaboration from readily available six- and two-carbon components. 相似文献
16.
Nishimoto A Narita K Ohmoto S Takahashi Y Yoshizumi S Yoshida T Kado N Okezaki E Kato H 《Chemical & pharmaceutical bulletin》2001,49(9):1120-1127
A series of erythromycin A 9-O-substituted oxime ether derivatives have been synthesized and evaluated for antibacterial activity against Mycobacterium avium complex (MAC) and Staphylococcus aureus. These compounds possessed stronger in vitro activity against MAC including macrolide-resistant strains than clarithromycin (2), although in vitro antibacterial activities of these compounds were less than that of 2 against Staphylococcus aureus. Our studies found that several factors contribute to the antibacterial activity against MAC. The length and spatial orientation of the substituent at 9-position were found to significantly influenced the anti-MAC activity, especially against macrolide-resistant strains. Of all the compounds prepared, erythromycin A 9-[O-(4-phenylbutyl)oxime] (12q) and erythromycin A 9-[O-(3-phenoxypropyl)oxime] (12t) possessed 16 times stronger antibacterial activity than 2 against clarithromycin-resistant strains. Surprisingly, the minimum inhibitory concentrations (MICs) of 12q and 12t against the resistant strains were almost same as those against the susceptible strains. These results suggest that the erythromycin A 9-O-substituted oxime ether derivatives would be promising macrolide antibiotics. 相似文献
17.
Synthesis and photochemical properties of photoactivated antitumor prodrugs releasing 5-fluorouracil
A new family of antitumor prodrugs (1-3) of 5-fluorouracil (5-FU) possessing photolabile 2-nitrobenzyl chromophores have been designed and synthesized to investigate the efficiency and mechanism of photoactivated 5-FU release upon UV-irradiation at lambda(ex)= 365 nm. The photoactivated prodrug 3 derived from conjugation of 2 with a tumor-homing cyclic peptide Cys-Asn-Gly-Arg-Cys (CNGRC) was so designed as to manifest a tumor-targeting function. 相似文献
18.
We developed a rapid, microscale and reliable analytical method for binding of drugs to plasma proteins using capillary electrophoresis (CE) with ionic cyclodextrins (CD) combined with frontal analysis. These CDs were used as pseudostationary phases of electrokinetic chromatography (EKC). The CD-modified EKC (CDEKC) approach allowed us to separate anionic drugs from plasma proteins, whereas CZE could not separate these drugs from plasma proteins because they had a similar mobility like plasma proteins. CDs uniquely interact with these drugs but not with plasma proteins. Therefore, CDEKC could be coupled with frontal analysis to measure the binding of anionic drugs to plasma proteins. The binding values obtained by CDEKC were highly consistent with those determined by the ultrafiltration method. Our CDEKC approach should expand the applicability of CE to protein binding analysis. 相似文献
19.
Yasushi Arakawa Tomoaki MurakamiFumiko Ozawa Yukimi ArakawaShigeyuki Yoshifuji 《Tetrahedron》2003,59(38):7555-7563
Diels-Alder adducts of 1,2-dihydropyridine with maleic and acrylic acid derivatives were stereospecifically converted by way of RuO4 oxidation into new r-2,c-3,c-4,c-5-piperidinetetracarboxylic acid, r-2,t-3,t-4,c-5-piperidinetetracarboxylic acid, r-2,c-3,c-5-piperidinetricarboxylic acid, and r-2,t-3,c-5-piperidinetricarboxylic acid. 相似文献
20.
Kashiwagi T Ohkoshi S Seino H Mizobe Y Hashimoto K 《Journal of the American Chemical Society》2004,126(16):5024-5025
We have prepared a pillared layer magnetic material containing a noncoordinated aromatic molecule, [{MnII(pyrimidine)(H2O)}2{MnII(H2O)2}{WV(CN)8}2](pyrimidine)2.2H2O. This compound has one-dimensional channels (6.2 x 2.1 A) that are occupied by noncoordinated pyrimidine. The magnetization versus temperature plots showed the magnetic phased transition temperature (TC) was 47 K. The magnetization versus external magnetic field plots showed that the saturation magnetization (MS) value was 13.0 muB at 2 K. This MS value indicates that an antiferromagnetic interaction operates between the WV (S = 1/2) and MnII (S = 5/2) ions. The magnetic hysteresis loop showed that the coercive field (HC) was 17 G at 2 K. 相似文献