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121.
A novel method for the synthesis of gem-dialkoxycarbonylcyclopropane derivatives is reported which involves the reaction of olefins with dibromomalonic esters and Cu in dimethyl sulphoxide. The reaction was applicable to a wide range of olefins and proceeded smoothly at moderate temperature to give the cyclopropane derivatives often in good yields. Cu was converted to Cu(II) bromide during the reaction. The reaction was weakly electrophilic and proceeded non-stereospecifically, and a stepwise mechanism involving addition and elimination appeared favourable for the reaction. In contrast, in the previously reported examples of the cyclopropanation of olefins by organic gem-dihalides and Cu in an aromatic hydrocarbon, Cu was converted to Cu(I) halides and a concerted cycloaddition of carbenoid intermediates appeared favourable. 相似文献
122.
A potent ACAT (acyl-CoA: cholesterol acyltransferase) inhibitor SMP-797 was effectively synthesized by the urea formation of 3-amino-4-aryl-1,8-naphthyridin-2(1H)-one and 4-amino-2,6-diisopropylamine. The synthesis of the former compound involved the Suzuki coupling reaction as a key step, and the latter was prepared by the 4-selective nitration of 2,6-diisopropylaniline using 2,3,5,6-tetrabromo-4-methyl-4-nitro-2,5-cyclohexadienone. 相似文献
123.
Iwao Amada Minoru Yamaji Masami Sase Haruo Shizuka Takuji Shimokage Shozo Tero-Kubota 《Research on Chemical Intermediates》1998,24(1):81-104
Investigations using CIDEP techniques showed that an H-atom abstraction from phenol and the electron transfer from 1,2,4,5-tetramethoxybenzene
to photoexcited 2,3-dibromo-1,4-naphthoquinone (DBNQ) and 2,3-dichloro-1,4-naphthoquinone (DCNQ) in the polar media originated
from their triplet states. Nanosecond laser photolysis at 355 nm was carried out to determine the absorption spectra and coefficients
of the corresponding triplet states, semiquinone, and anion radicals for a quantitative investigation of the mechanisms involved
in the H-atom abstraction and the electron transfer. The steric hindrance of the substituted groups was indifferent to H-atom
abstraction. The electronic structures of triplet DBNQ and DCNQ at 295 K were both revealed to be the mixed states of 3(n,π*) with a 3(π,π*) character. 相似文献
124.
Naomichi Furukawa Toshiaki Yoshimura Masami Ohtsu Takeshi Akasaka Shigeru Oae 《Tetrahedron》1980,36(1):73-80
The Michael type additions of diphenyl N-unsubstituted sulfimide (free sulfimide) to various electrophilic olefins were carried out. The reaction with cis- and trans-dibenzoylethylene, dimethyl-fumarate, dimethylmaleate, benzalacetophenone and benzalacetone gave mainly the corresponding trans-2-acylaziridines and trans-enaminoketones. However, phenyl vinyl sulfone or acrylonitrile afforded not the corresponding aziridine but diphenyl-N-2-cyano or N-2-phenylsulfonylethylsulfimide, a simple Michael adduct When optically active (+)-(R)-o-methoxyphenyiphenyl free sulfimide was treated with such an α,β-unsaturated carbonyl compound as benzalacetopbenone, an optically active 2-acylazindine, i.e., (-)-trans-2-benzoyl-3-phenylaziridine was obtained in ca 30% optical purity and its absolute configuration was assigned as (2R,3S) upon chemical transformation to the configuration-ally known 2-phenyl-2-benzoylamino-1-ethanol or by comparing its CD spectrum with that of (1R,2R)-1-phenyl-2-benzoyl-cyclopropane. Meanwhile, (-)-(S)-o-methoxyphenylphenyl free sulfimide was found to react with benzalacetophenone to afford (+)-trans-2-benzoyl-3-phenylaziridine of 25% optical purity. Effects of solvent and temperature on both die distribution of the products ratio and the optical yield were examined. 相似文献
125.
Issei Kasahara Masami Kanai Masako Taniguchi Ayako Kakeba Noriko Hata Shigeru Taguchi Katsumi Goto 《Analytica chimica acta》1989
The singly charged complex anion bis[2-(5-bromo-2-pyridylazo)-5-(N-propyl-N-sulphopropylamino)phenolato]cobaltate(III) is intensely purple-violet and is stable over the pH range 1–13. Its absorption spectrum remains the same over this pH range. At pH2, it forms extractable ion pairs with long-chain quaternary ammonium ions and protonated alkylamines. Only the quaternary ammonium ions are extracted into chloroform at pH 11, hence separate extractions allow both types to be determined. The absorbance of the organic phase is measured at 594 nm. The apparent molar absorptivity is 7.0 × 104 l mol?1 cm?1. Calibration graphs for zephiramine, benzethonium and hexadecylpyridinium ions are linear over the range 0.1–2 × 10?6 M. The only interference found was from anionic surfactants. The method is applied to hair and fabric conditioners. 相似文献
126.
The calcium salts of -sulfonated fatty acid methyl esters were prepared, and the physico-chemical properties such as solubility, critical micelle concentration, aggregation number, and precipitation phase boundary were studied to clarify the reasons for the good hardness tolerance manifested by -sulfonated fatty acid methyl esters.The Krafft point of the calcium salts of -sulfonated fatty acid methyl esters were not necessarily lower than room temperature, but the rate of crystallization in hard water was extremely slow compared with the calcium salt of dodecyl sulfate, which has been known as an insufficient surfactant in terms of hardness tolerance. 相似文献
127.
Yarita T Nakajima R Otsuka S Ihara TA Takatsu A Shibukawa M 《Journal of chromatography. A》2002,976(1-2):387-391
A method for the determination of ethanol in alcoholic beverages by high-performance liquid chromatography-flame ionization detection (HPLC-FID) was developed. An FID system could be directly connected to an HPLC system using pure water as a mobile phase. In a durability test using triacontylsilyl (C30)-silica gel stationary phase for 96 h, no significant change in the retention time of four alcohol compounds was observed. So the HPLC separation of alcoholic beverages was carried out on the C30-silica gel stationary phase. On application to the analysis of six kinds of alcoholic beverages, ethanol could be determined accurately by the proposed method. 相似文献
128.
129.
γ,δ-Epoxy tin compounds underwent divergent reactions depending upon the substitution pattern of the substrates as well as upon Lewis acids used as the indueer. 相似文献
130.
Abstract Block polymerization of methyl methacrylate initiated with monohalo-terminated polystyrene/manganese carbonyl systems were investigated. The rate of polymerization was lower than that of the trihalo-terminated polystyrenelmanganese carbonyl system. The molecular weight of the block copolymers obtained was independent of the conversion. To define the polymerization mechanism, 1-bromobutane was employed as a model compound for monohalo-terminated polystyrene. Polymerization kinetics followed a modified rate equation based on the Michaelis-Menten mechanism. The molecular weight of the block co-polymer could be regulated by varying the ratio of monohalo-terminated polymer to methyl methacrylate. Graft polymerization of methyl methacrylate initiated with chloromethylstyrene-styrene copolymer/ manganese carbonyl was also carried out. The polymerization behavior was strongly affected by the concentration of manganese carbonyl. Characterization of graft copolymers by GPC and halogen analysis showed that the number of grafting points per backbone polymer molecule increased when the concentration of manganese carbonyl was raised, but that the branches became shorter. 相似文献