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41.
Kazuhisha Hiratani Shamsun Naher Michinori Karikomi Kazuo Haga 《Journal of heterocyclic chemistry》2005,42(4):575-582
Novel crownophanes with 27‐ and 28‐membered rings having two hydroxyl groups, two amide groups, and aromatic moieties such as naphthalene, pyridine, and phenyl rings were successfully synthesized by a one‐step reaction from the corresponding macrocyclic polyethers via “tandem Claisen rearrengement” in moderate yields. They can solubilize urea and its derivatives into chloroform solution, while the corresponding macrocyclic polyethers do not solubilize them. According to NMR studies, crownophanes 1 and 2 interact with urea and its derivatives forming 1:1 complexes. 相似文献
42.
Palladium-diethylzinc or palladium-triethylborane catalytically promotes self-allylation of 2-(allyloxy)tetrahydrofurans, 2-(allyloxy)tetrahydropyrans, and their hydroxy derivatives on the rings (ribose, glucose, mannose, deoxyribose, deoxyglucose). All the reactions proceed at room temperature and provide polyhydroxyl products, sharing a structural motif of a homoallyl alcohol, in good to excellent yields with high levels of stereoselectivity. Useful C3-unit elongation, which makes the best use of an allyl ether as a protecting group and a nucleophilic allylation agent, is demonstrated. Mechanisms for the umpolung reaction (of an allyl ether into an allylic anion) and stereoselectivity associated with allylation of aldehydes are discussed. 相似文献
43.
A reliable and sensitive capillary gas chromatographic-mass spectrometric method was developed for the detection and determination of diazepam and its major metabolite, N-desmethyldiazepam, in human material. Medazepam served as the internal standard. Quantitative determination was achieved using mass fragmentography with selected ions of m/z 256 for diazepam and m/z 242 for N-desmethyldiazepam and medazepam. The limit of detection was 1 ng/g and the recoveries were 98.54 +/- 3.95% for diazepam and 98.66 +/- 6.48% for N-desmethyldiazepam. The calibration graph was linear over the concentration range from 1.0 ng/g to 1.0 microgram/g for diazepam and N-desmethyldiazepam. Using this method, trace amounts of diazepam and N-desmethyldiazepam were detected in the tissues of an autopsied individual. 相似文献
44.
[structure: see text] A highly convergent synthetic route to the FGHIJKLM ring fragment of ciguatoxins has been developed, which relied on extensive use of the B-alkyl Suzuki-Miyaura coupling reaction. 相似文献
45.
Shi-jun Zheng Kazuo Akagi Qun Xu Shao-kui Cao Qi-feng Zhou 《高分子科学》2006,(4):353-361
Novel shish-kebab type liquid crystalline poly(p-phenylenevinylene) derivatives were synthesized by Stille coupling reaction from 2,5-bis[(4-n-alkoxyl)benzoyloxy]1,4-dibromobenzene (monomer l) and 1,2-bis(tributylstannyl) ethylene (monomer 2). The polymers with alkoxy groups are soluble in common organic solvents and exhibit blue fluorescence. Both the cast film and the annealed film have large red-shifts in fluorescence spectra and show yellow fluorescence. The polymers with CN and NO2 groups show poor solubility and green fluorescence. All the polymers possess liquid crystalline smectic phases. The melting point (Tm) of the polymers decreases when the length of the alkoxy tails of the mesogenic units increases. The polymers are easily aligned under a magnetic field of 10 Tesla. It is found that the conjugated backbone and LC side chain are aligned perpendicular and parallel to the magnetic field, respectively. The polymers show optical dichroism in fluorescence spectra, suggesting that they are available for advance materials with linear optical polarization. 相似文献
46.
Tomoya Kinumi Kazuo Tsujimoto Mamoru Ohashi Reiko Hara Tomiyuki Hara Koichi Ozaki Miho Saka Yuko Katsuta Akimori Wada Masayoshi Ito 《Photochemistry and photobiology》1993,58(3):409-412
Abstract— 3, 7-Dimethyl-2, 4, 6, 8, 10-dodecapentaenal was synthesized for reconstitution of the retinochrome analog. Its opsin shift was 1000 cm 1 smaller than that of native retinochrome, whose chromophore contains the same number of double bonds. The conformational change from 6-s-trans to 6-s-cis , as figured in a retinal molecule, plays an important role in the formation of the retinochrome analog, based on the estimation of opsin shifts for retinal analogs locked in the 6-s conformation. Thus the conformation of the 6–7 single bond in the native retinochrome was suggested to be 6 -cis . Analysis of the circular dichroic spectra of retinochrome analogs revealed that the 6-s conformation is independent of the appearance of the β-band. The stereoselectivity in the photoisomerization of the retinal analogs by a retinochrome template depends on the hydrophobic binding in the region of the β-ionone ring. 相似文献
47.
Hiizu Iwamura Tadashi Sugawara Yuzo Kawada Kazuo Tori Ryonosuke Muneyuki Ryoji Noyori 《Tetrahedron letters》1979,20(36):3449-3452
Natural-abundance 17O NMR spectra have been measured for twenty one oxiranes. Their chemical shifts covering a 100 ppm range were interpreted in terms of the paramagnetic β- and diamagnetic γ-effects. In addition, through-space orbital interaction between the ethylenic π and the Walsh orbitals of the oxirane ring was suggested by a lowfield shift in norbornadiene -oxide. 相似文献
48.
[structure: see text] The first total synthesis of gambierol, a marine polycyclic ether toxin, has been achieved. The synthesis features the Pd(PPh3)4/CuCl/LiCl-promoted Stille coupling for the stereoselective construction of the sensitive triene side chain that includes a conjugated (Z,Z)-diene moiety. 相似文献
49.
Yoshitaka Ogiwara Hitoshi Kubota Yuji Kimura 《Journal of polymer science. Part A, Polymer chemistry》1978,16(11):2865-2873
The influence of ferric acetylacetonate [Fe(acac)3] on the photodegradation of model compounds of polyethylene (PE) was examined. By studying electron-spin-resonance (ESR) spectra of photoirradiated compounds such as 1-octene and 1,7-octadiene, which contain carbon double bonds, Fe(acac)3 was found to accelerate the formation of allyl radical by contact with them. On the other hand, Fe(acac)3 suppressed the radical formation based on Norrish type I reaction in a carbonyl group of compounds such as 2-octanone and 3-octanone. Based on the study of ultraviolet (UV) spectra as well as ESR spectra on photoirradiated samples, the influence of Fe(acac)3 on the photodecomposition of model compounds of PE was discussed. Finally, the discussion turned to the mechanism of photodecomposition of PE in the presence of ferric salt. 相似文献
50.
Naganawa H Suzuki H Noro J Kimura T 《Chemical communications (Cambridge, England)》2005,(23):2963-2965
The weakly coordinating hydrophobic anion TFPB-, whose surface is covered with a hydrophobic field, gives rise to a selective separation of Am(III) from lanthanides(III) in their solvent extraction even with a hard-donor extractant that shows no selectivity for Am(III) in traditional solvent extraction. 相似文献