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61.
The complete structure of palytoxin (1) was elucidated by us in 1982.1 Our continuous interests in palytoxin led us to examine minor constituents of Okinawan Palythoa tuberculosa. In this paper, we describe successful isolation and structural elucidation of four minor toxins, which were named homopalytoxin (2), bishomopalytoxin (3), neopalytoxin (4) and deoxypalytoxin (5). 相似文献
62.
Di-tert-butyl ether was synthesized in good yields by the SN reactions of lithium tert-butoxide with tosyl and p-bromobenzenesulfonyl chlorides under mild conditions. 相似文献
63.
[reaction: see text] A formal total synthesis of the sex attractant of male dried bean beetle, methyl (R,E)-(-)-tetradeca-2,4,5-trienoate, was achieved by a new efficient route utilizing the Pd-catalyzed asymmetric allene synthesis reaction. It was found that the atropisomeric biaryl bisphosphine (R)-segphos showed better enantioselectivity than (R)-binap in the Pd-catalyzed reaction for preparing alkyl-substituted axially chiral allenes. 相似文献
64.
Tadatomi Nishikubo Takashi Iizawa Seiji Saita 《Journal of polymer science. Part A, Polymer chemistry》1986,24(7):1685-1695
Addition reactions of pendant epoxide groups in poly(glycidyl methacrylate) (PGMA) with various active esters such as 1-benzotriazolyl benzoate, S-(2-benzoxazolyl) thiobenzoate, S-(2-benzothiazolyl) thiobenzoate, 4-nitrophenyl benzoate (4NPB), and S-phenyl thiobenzoate (PTB) were carried out using quaternary salts as catalysts. The reactions of PGMA with those active esters proceeded in diglyme at 100°C for 24 h quantitatively without the formation of 2-hydroxyl pendant groups in the polymer when 10 mol % of tetraethylammonium bromide was used as a catalyst. Furthermore, it was found that the respective quaternary salts have higher catalytic activity than tertiary amines in the reaction of PGMA with the active esters, and the reaction of PGMA with 4NPB gave the corresponding polymer with the highest conversion by addition of tetrabutylammonium bromide as a catalyst, while tetraethylammonium chloride showed the highest activity for the reaction of PGMA with PTB. In addition, the rate of reaction of PGMA with 4NPB was proportional to third order kinetics of the epoxide concentration, the ester concentration and the catalyst concentration as follows: ?d[Epoxide]/dt = ?[Ester]/dt = k3[Epoxide] [Ester] [Catalyst]. 相似文献
65.
Yoshinori Kadoma Takashi Toida Kenji Takeda Keikichi Uno Yoshio Iwakura 《Journal of polymer science. Part A, Polymer chemistry》1975,13(3):707-716
The polymerization of picryl (PMA), 2,4-dinitrophenyl (2,4-DNMA),2,6-dinitrophenyl (2,6-DNMA), 2-methyl-4,6-dinitrophenyl (MDNMA), and 2,6-dimethylphenyl methacrylates (DMMA) was carried out in benzene at 60°C. PMA, 2,6-DNMA, and MDNMA did not undergo radical homopolymerization, while 2,4-DNMA and DMMA did. The results suggest that the growing radical readily attacks the oxygen atom of the nitro group at the 2 position of the terminal phenyl group due to the steric effect of the substituent at the 6 position, resulting in chain termination. PMA formed a charge-transfer complex with 2-naphthyl methacrylate (NMA). The stoichiometric composition of this complex was shown to be 1:1 molar complex. PMA was readily copolymerized with NMA. The amount of solvent affected the composition of the copolymer obtained at a given same mole fraction in feed. The results suggest that charge-transfer interaction between the ester groups affects the copolymerization mechanism. 相似文献
66.
Tabushi Iwao Kuroda Yasuhisa Yamada Masahiko Sera Takashi 《Journal of inclusion phenomena and macrocyclic chemistry》1988,6(6):599-603
Deuterium relaxation times ofd- andl--d-tryptophan included in -cyclodextrin derivatives were directly measured by deuterium NMR spectroscopy. The results showed that the molecular motion of the tryptophan molecule was strongly restricted even in the cavity of unmodified -cyclodextrin and the additional recognition groupings — ammonium and carboxylate — on -cyclodextrin did not affect the molecular motion of tryptophan, though the association constants were significantly enhanced.Deceased on March 22, 1987. 相似文献
67.
In the reaction of soybean lipoxygenase (EC 1.13.11.12) with polyunsaturated fatty acids such as linoleic, linolenic and arachidonic acids, some radical species were detected using the electron spin resonance (ESR) spin-trapping technique. The radical species derived from the three polyunsaturated fatty acids were not distinguishable because the ESR spectra of the spin adducts of nitrosobenzene with their three radical species showed no difference in their hyperfine splittings. To overcome this defect of the spin-trapping technique, these spin-adducts were separated by employing high-performance liquid chromatography (HPLC) combined with ESR spectroscopy. The spin adducts were eluted from a C18 reversed-phase column in the order linolenic acid, linoleic acid and arachidonic acid. The half-lives of the spin adducts separated by HPLC-ESR were determined as linoleic acid 600 min, linolenic acid 360 min and arachidonic acid 160 min. The use of an ultraviolet detector together with the HPLC-ESR technique resulted in a 500-fold increase in sensitivity in the detection of the radical species. 相似文献
68.
Makoto Minato Takefumi Kaneko Shogo Masauji Takashi Ito 《Journal of organometallic chemistry》2006,691(11):2483-2488
We describe the synthesis of a new asymmetric P,N,N′-tridentate ligand (bis(pyrid-2-ylethyl) menthylphosphine, BPEMP), containing two pyridyl rings and (1S,2R,5S)-menthylphosphino group. The ligand is obtained in five steps from natural abundant l-menthol. The coordination behavior of the ligand toward cationic (allylic)Pd(II) moiety and its first application in palladium-catalyzed asymmetric allylic alkylation are presented. Crystallographic and spectroscopic analyses reveal that [(η3-allylic)Pd(BPEMP)]+ complex forms only one isomer in the solid state as well as in solution. 相似文献
69.
Masafumi Kobayashi Tetsuya Inoguchi Takashi Iida Takashi Tanioka Hiroshi Kumase Yasushi Fukai 《Journal of fluorine chemistry》2003,120(2):2838-110
Direct fluorination of 1,3-dioxolan-2-one with elemental fluorine was successfully carried out to provide 4-fluoro-1,3-dioxolan-2-one, which was expected as an additive for lithium ion secondary battery. 4-Fluoro-1,3-dioxolan-2-one was also further fluorinated with elemental fluorine to give three isomers of difluoro derivatives by the same methodology. Another topic is the preparation of trifluoromethanesulfonyl fluoride, an intermediate of lithium battery electrolyte, by the reaction of methanesulfonyl fluoride with elemental fluorine. The use of perfluoro-2-methylpentane as a solvent gave satisfactory selectivity of trifluoromethanesulfonyl fluoride. 相似文献
70.
The cycloaddition reaction of N-ethoxycarbonyl-1H-azepine with 2,5-dimethoxycarbonyl-3,4-diphenylcyclopentadienone gave anti-endo [4+2]π and exo [6+4]π cycloadducts. These structures were fully identified by X-ray crystallographic techniques. Mechanism for their cycloaddition reactions are also discussed. 相似文献