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41.
42.
Jacques E. Desnoyers Gérald Perron Sylvain Léger Byron Y. Okamoto Terrence H. Lilley Robert H. Wood 《Journal of solution chemistry》1978,7(3):165-178
The freezing-point depression of the ternary systems tetraalkylammonium bromides-t-butanol-water for the first five homologs of R4NBr was measured. In the case of Bu4NBr, the effect of size of the alcohol (methahol ton-butanol) was also investigated. From the corresponding freezing-point data for the binary systems the apparent salting constants
were calculated. The true salting constantsk
s were obtained by extrapolation to infinite dilution. These are all very close to zero at the freezing temperature. From the
corresponding thermochemical data the temperature dependence ofk
s was calculated, and above 5°C all the R4NBr salts int-butanol; the salting-in increases with temperature and with the size of the hydrophobic cations. The scaled-particle theory
is at present the only one which can account semiquantitatively for the temperature dependence of the salting-in effect.
On leave of absence from Chemistry Department, The University, Sheffield S3 7HF, England
To whom correspondence should be addressed. 相似文献
43.
Treatment of 3,4-alkadienyl carbonates 2a-i with a low-valent titanium reagent diisopropoxy(eta(2)-propene)titanium (1), readily generated by the reaction of Ti(O-i-Pr)(4) with 2 i-PrMgCl, resulted in an intramolecular nucleophilic acyl substitution (INAS) reaction to afford vinyltitanium compounds 3 which, in turn, reacted with H(3)O(+), D(2)O, or iodine to give alpha-substituted beta,gamma-unsaturated esters 4 in good to excellent yields. The olefin moiety of the hydrolysis product 4 has (Z)-geometry mainly except for 4h. Starting from chiral 2f or 2g, the reaction proceeded stereospecifically to give optically active alpha-substituted beta,gamma-unsaturated ester 4f or 4g having (Z)-olefin geometry exclusively. 相似文献
44.
Simple syntheses of syncarpurea (1) from syncarpic acid and the amino acids ornithine or citrulline are presented. 相似文献
45.
Yoshihisa Kurasawa Tomoyoshi Hosaka Kazue Ikeda Yuko Matsumoto Aiko Ishikura Atsushi Takada Ho Sik Kim Yoshihisa Okamoto 《Journal of heterocyclic chemistry》1994,31(2):527-533
The 3-(arylhydrazono)methyl-2-oxo-1,2-dihydroquinoxalines 9–11 were synthesized by the reaction of the quinoxalines 6–8 with various p-substituted benzenediazonium salts. Compounds 9–11 showed the tautomeric equilibria between the hydrazone imine A and diazenyl enamine B forms in dimethyl sulfoxide media. The substituent effect on the tautomer ratios of A to B was studied by the nmr spectroscopy to clarify that the presence of the ester group R2 on the hydrazone carbon and electron-donating p-substituent R1 on the side chain benzene ring exhibited a tendency to increase the ratios of the tautomer A . 相似文献
46.
47.
A rhodium-catalyzed isomerization of alpha-arylpropargyl alcohols to indanones has been developed under mild conditions. Considering the ease of preparation of these propargyl alcohols (terminal alkynes + aromatic aldehydes), this method provides a new way of constructing indanones with high efficiency. By the mechanistic investigations using deuterium-labeled substrates, it has also been demonstrated that the reaction goes through an unexpected cascade, with a 1,4-hydrogen shift being the turnover-limiting step of the catalytic cycle. 相似文献
48.
Akiko Tsuhako Jing-Qian He Mariko Mihara Naoko Saino Sentaro Okamoto 《Tetrahedron letters》2007,48(52):9120-9123
Ketones and aldehydes were effectively reduced to the corresponding alcohols (or their silyl ethers) by the reaction with CaH2 and R3SiCl in the presence of a catalytic amount of ZnCl2. In the absence of the carbonyl substrate, the reagent reduced R3SiCl to the corresponding hydrosilane under mild reaction conditions. 相似文献
49.
Organotrichlorogermanes were synthesized by the reaction of elemental germanium, tetrachlorogermane and organic chlorides, methyl, propyl, isopropyl and allyl chlorides. Dichlorogermylene formed by the reaction of elemental germanium with tetrachlorogermane was the reaction intermediate, which was inserted into the carbon-chlorine bond of the organic chloride to give organotrichlorogermane. When isopropyl or allyl chloride was used as an organic chloride, organotrichlorogermane was formed also in the absence of tetrachlorogermane. These chlorides were converted to hydrogen chloride, which subsequently reacted with elemental germanium to give the dichlorogermylene intermediate. The reaction of elemental germanium, tetrachlorogermane and organic chlorides provides a simple and easy method for synthesizing organotrichlorogermanes, and all the raw materials are easily available. 相似文献
50.
Cordonier CE Satake K Atarashi M Kawamoto Y Okamoto H Kimura M 《The Journal of organic chemistry》2005,70(9):3425-3436
[reaction: see text] The reaction of 2-methoxy-3H-azepines, in the presence or absence of a nucleophile, with N-bromosuccinimide (NBS) gave a regioselective 1,4-adduct from which the corresponding 2H-azepine derivatives were formed via base-promoted hydrogen bromide elimination, generally in moderate to quantitative yield. Competitive formation of 4-bromo-2-methoxy-3H-azepine by electrophilic substitutuion or 3H-azepin-2-yl 2H-azepin-2-yl ether by transetherification was minimized at lower reaction temperatures. Quantitative substitution of 2-(2',4',6'-trichlorophenoxy)-2H-azepine derivatives, formed in moderate yield from the respective 3H-azepine and NBS in the presence of 2,4,6-trichlorophenol (TCP), by various nucleophiles gave the corresponding 2-substituted 2H-azepine. Among these nucleophiles were alkanethiol and alkylamine that are not tolerated in the reaction of 3H-azepine and NBS. 相似文献