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51.
The pinacol reaction of beta-halogenated alpha,beta-unsaturated aldehydes was promoted by titanium tetraiodide to give coupling products in good yields with high dl-selectivity. Subsequent reduction with H(2)/Pd-C gave saturated vic-diols in good yields. Heck coupling reaction enabled the displacement of halogens with vinyl groups without the loss of stereochemical integrities. [reaction: see text] 相似文献
52.
Mikio Hori Tadashi Kataoka Hiroshi Shimizu Akihiko Tomoto 《Tetrahedron letters》1981,22(37):3629-3632
1-Benzoyl-2-methy1-3,4-dihydro-2-thianaphthalene () underwent novel intermolecular 1,4-rearrangement in refluxing toluene to give an enol ether , while rearrangement of 2-phenyl derivative proceeded intramolecularly in refluxing xylene to afford a 1,4-rearranged enol ether . On the other hand, ylides were refluxed in alcohols to afford some ring-opened products . 相似文献
53.
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
54.
The photoisomerization properties of tris(bipyridine)cobalt complexes containing six or three azobenzene moieties, namely, [Co(II)(dmAB)3](BF4)2 [dmAB = 4,4'-bis[3'-(4'-tolylazo)phenyl]-2,2'-bipyridine], [Co(III)(dmAB)3](BF4)3, [Co(II)(mAB)3](BF4)2 [mAB = 4-[3' '-(4' '-tolylazo)phenyl]-2,2'-bipyridine], and [Co(III)(dmAB)3](BF4)3, derived from the effect of gathering azobenzenes in one molecule and the effect of the cobalt(II) or cobalt(III) ion were investigated using UV-vis absorption spectroscopy, femtosecond transient spectroscopy, and 1H NMR spectroscopy. In the photostationary state of these four complexes, nearly 50% of the trans-azobenzene moieties of the Co(II) complexes were converted to the cis isomer, and nearly 10% of the trans-azobenzene moieties of the Co(III) complexes isomerized to the cis isomer, implying that the cis isomer ratio in the photostationary state upon irradiation at 365 nm is controlled not by the number of azobenzene moieties in one molecule but rather by the oxidation state of the cobalt ions. The femtosecond transient absorption spectra of the ligands and the complexes suggested that the photoexcited states of the azobenzene moieties in the Co(III) complexes were strongly deactivated by electron transfer from the azobenzene moiety to the cobalt center to form an azobenzene radical cation and a Co(II) center. The cooperation among the photochemical structural changes of six azobenzene moieties in [Co(II)(dmAB)3](BF4)2 was investigated with 1H NMR spectroscopy. The time-course change in the 1H NMR signals of the methyl protons indicated that each azobenzene moiety in [Co(II)(dmAB)3](BF4)2 isomerized to a cis isomer with a random probability of 50% and without interactions among the azobenzene moieties. 相似文献
55.
Goto S Masuda K Miura M Kanazawa K Sasaki M Masui M Shiramizu M Terada H Chuman H 《Chemical & pharmaceutical bulletin》2002,50(4):445-449
We measured the affinity of more than 20 sugars with concanavalin A (ConA) by an optical biosensor (surface plasmon resonance sensor) using asialofetuin (ASF) as an immobilized binding partner of ConA. We determined kinetic parameters of the effects of sugars on the dissociation of ConA from ASF quantitatively, and the structural requirements of the functional groups of sugars for binding with ConA. We found that the affinity of ConA for sugars is dependent on its conformation induced by interaction with the binding partner. In addition, the results showed that optical biosensor system is well mimics the interaction of ConA with sugars in biomembrane. 相似文献
56.
2-Alkyl-1-alkylthioisoquinolinium salts were readily prepared from 2-alkyl-1(2H)-isoquinolones via 2-alkyl1(2H)-thioisoquinolones in two steps. Under mild conditions, the reaction of 2-alkyl-1-alkylthioisoquinolinium salts with active methylene compounds in the presence of sodium hydride afforded 2-alkyl-1-(substituted methylene)iso-quinolines in good yields. Pyrrolo[2,1-a]isoquinolines were synthesized by the cyclization of 2-benzyl-1-(substituted methylene)isoquinolines using acetic anhydride. 相似文献
57.
Production of polyacrylonitrile particles by precipitation polymerization in supercritical carbon dioxide 总被引:2,自引:0,他引:2
Masayoshi?OkuboEmail author Syuji?Fujii Hiroshi?Maenaka Hideto?Minami 《Colloid and polymer science》2003,281(10):964-972
Polyacrylonitrile particles were produced by precipitation polymerization of acrylonitrile (AN) without any colloidal stabilizer in supercritical carbon dioxide as a polymerization medium at about 30 MPa for 24 h at 65 °C at different initiator concentrations (0.8–45.2 mmol/l) and at different AN concentrations (10–40% w/v). An increase in the initiator concentration led to increases in the conversion and in the degree of coagulation and to a decrease in the molecular weight. At AN concentration of 20% w/v, micron-sized, relatively monodisperse polyacrylonitrile particles with clean and uneven surfaces were produced. 相似文献
58.
Minimal contracted Gaussian basis sets are presented for Ga through Cd. Characteristically these Gaussian-based minimal sets give far better d orbital energies than those by minimal STO basis sets. These new basis sets were tested on Br2 for which a new benchmark calculation was also performed. The test result is satisfactory in that these basis sets produce good general agreement with the near Hartree–Fock calculation with respect to the molecular spectroscopic constants. 相似文献
59.
Mariko Kusabe Hiromitsu Kozuka Satoru Abe Hiroshi Suzuki 《Journal of Sol-Gel Science and Technology》2007,44(2):111-118
Hydroxypropylcellulose (HPC)–titania hybrid thin films were prepared by sol–gel method where titanium tetraisopropoxide Ti(OC3H7
i
)4 was hydrolyzed under acidic conditions in the presence of HPC, followed by dip-coating and drying at 120 °C for 24 h. The
viscosity average molecular weight of HPC was 55,000–70,000 or 110,000–150,000, and the TiO2/(HPC + TiO2) mass ratio ranged from 0 to 1, which was calculated on the assumption that all Ti(OC3H7
i
)4 is converted into TiO2. The films were 0.35–1.0 μm thick, transparent in visible region and opaque in ultraviolet (UV) region, where the optical
absorption coefficient in UV region increased with increasing titania content. The refractive index increased with increasing
titania content, ranging from 1.6 to 1.8 for the hybrid thin films. The pencil hardness increased from 6B to 5H, the durability
in hot water significantly increased and the contact angle of water on films increased from 35° to 89° with increasing titania
content. Crack-free films could be deposited on organic polymer substrates irrespective of titania or HPC contents, where
cracking did not occur at higher HPC contents even when the substrate was bent. 相似文献
60.
The H2 and CH4 chemical ionization mass spectra of a series of series of substituted benzoic acids and substituted benzyl alcohols have been determined. For the benzoic acids the major fragmentation reactions of the protonated molecule involve elimination of H2O or elimination of CO2, the latter reaction involving migration of the carboxylic hydrogen to the aromatic ring. For the benzyl alcohols the major fragmentation reactions of [MH]+ involve loss of H2O or CH2O, analogous to the CO2 elimination reaction for the benzoic acids. It is shown that the CO2 and CH2O elimination reactions occur only when a conjugated aromatic ring system is present, and that for the carboxylic acid systems, methyl groups and, to a lesser extent, phenyl groups are capable of migrating. The only discernible effect of substituents on the fragmentation of [MH]+ is an enhancement of the H2O loss reaction in the benzoic acid system when an amino, hydroxyl, or halogen substituent is ortho to the carboxyl function. This ‘ortho’ effect, which differs in scope from that observed in electron impact mass spectra, is attributed to an intramolecular catalysis by the ortho substituent of the 1,3 hydrogen migration in the carbonyl protonated acid followed by H2O elimination. Apparently, this route is favoured over the direct elimination of H2O from the carbonyl protonated acid, since the latter has a high activation energy barrier because of unfavourable orbital symmetry restrictions. 相似文献