巻号一覧
59 巻, 1 号
選択された号の論文の7件中1～7を表示しています
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石井 康敬2001 年 59 巻 1 号 p. 2-10
発行日: 2001/01/01
公開日: 2009/11/13
ジャーナル フリーA novel strategy for organic synthesis via radical intermediates was developed by using N-hydroxyphthalimide (NHPI) as the key catalyst. Carbon radicals were successfully generated from various hydrocarbons under the influence of NHPI combined with Co (II) salt and dioxygen, and the carbon radicals thus formed were applied to a variety of synthetic reactions. Firstly, in the reaction with alkanes, oxygen-containing compounds such as alcohols, ketones and carboxylic acids were produced through the formation of alkyl radicals in good yields. Secondary, the treatment of alkenes with hydroperoxides, which are derived from the reaction of alkyl radicals thus generated with dioxygen, afforded epoxides in good yields. In contrast, the trapping of alkyl radicals prepared by the present method by NO2 and SO2 under mild conditions provided an efficient method for the synthesis of nitroalkanes and sulfonic acids, respectively. Finally, the generation of α-hydroxy carbon radicals from alcohols was also successful, and the synthesis of α-hydroxy-γ-lactones, which so far had been difficult to prepare by the conventional methods, was achieved in high yields by allowing them to react with acrylates.抄録全体を表示PDF形式でダウンロード (1332K) -
大下 浄治2001 年 59 巻 1 号 p. 11-22
発行日: 2001/01/01
公開日: 2009/11/13
ジャーナル フリーOrganosilicon compounds, in which π-conjugated carbon units are linked by a silicon bridge, are of current interest. They represent a new class of conjugated compounds and the interaction between the silicon σ-orbital and π-electron system, namely σ-π conjugation, provides the opportunities to use them as functionality materials. In particular, polymers composed of a regularly alternating arrangement of organosilicon and π-conjugated carbon units have been extensively studied and it has been demonstrated that they can be used as photoresists, organic semiconductors, and precursors of silicon carbide. This paper deals with the synthesis and properties of novel σ-π conjugated compounds. In addition, our recent efforts to understand the nature of σ-π conjugation in the compounds and find out the relationship between the functionality and the structures of the compounds, are described. This would provide important information to design the σ-π conjugated compounds with higher functionalities.抄録全体を表示PDF形式でダウンロード (1752K) -
菅沼 弘之2001 年 59 巻 1 号 p. 23-32
発行日: 2001/01/01
公開日: 2010/01/22
ジャーナル フリー2-Acetoxy-3-dodecyl-1, 4-naphthoquinone (Acequinocyl) was acaricide which originated by Du Pont in 1975. Kawasaki Kasei Chemical Ltd. developed a new industrial production process of Acequinocyl, starting from 1, 4-naphthoquinone which is known as a widely used industrial raw material produced only by us in the world. The key technique of this new process was how to introduce a dodecyl group on 3-position of 2-hydroxy-1, 4-naphthoquinone. In the process of research, we discovered that 3- (1-dodecenyl) -2-hydroxy-1, 4-naphthoquinone could be easily obtained with over 90% of yield from ammonium salt of 3- (1-alkylaminododecyl) -2-hydroxy-1, 4-naphthoquinone under thermal decomposition condition. We also developed a convenient production process of high purity 2-hydroxy-1, 4-naphthoquinone from 1, 4-naphthoquinone. This new synthetic route was extremely useful as an industrial process compared with the conventional processes.
In this paper we report the development course of high yield and low cost production processes of Acequinocyl from 1, 4-naphthoquinone.抄録全体を表示PDF形式でダウンロード (1412K) -
宮部 豪人, 内藤 猛章2001 年 59 巻 1 号 p. 33-39
発行日: 2001/01/01
公開日: 2009/11/13
ジャーナル フリーThis review summarizes the recent progress in the field of radical reaction of imine derivatives, and focuses on the new carbon-carbon bond constructing-methods especially based on intermolecular carbon radical addition to imine derivatives. Among the wide range of radical acceptors containing a carbon-nitrogen double bond, it was revealed that the oxime ethers were excellent radical acceptors, and a lot of studies have been explored by using oxime ethers. Reactivity of imine derivatives and possible reaction pathways have also been presented. The reaction was extended to one-pot and/or multi-component reactions. Moreover, a high degree of stereocontrol in reaction of acyclic and cyclic imine derivatives was achieved by using triethylborane and diethylzinc.抄録全体を表示PDF形式でダウンロード (988K) -
片山 博之, 小澤 文幸2001 年 59 巻 1 号 p. 40-51
発行日: 2001/01/01
公開日: 2009/11/13
ジャーナル フリーThis article summarizes recent progress in transition-metal catalysts for olefin metathesis reactions, in terms of their catalytic activity, stability, and accessibility. Catalytic olefin metathesis reactions are now being one of the most efficient methods of constructing C-C bonds in organic and polymer synthesis. Since Grubbs et al. have discovered that alkylideneruthenium complexes possess high catalytic activity and wide tolerance of functional groups, a number of well-defined ruthenium-based catalysts have been developed. Some of them show greatly enhanced activity and thermal stability, as compared with the original Grubbs' catalyst. In addition, the complexes having a metal-carbon unsaturated bond, including vinylidene, allenylidene, Fischer-type carbene, and carbyne complexes, are found to be active for olefin metathesis catalysts (or catalyst precursors).抄録全体を表示PDF形式でダウンロード (1674K) -
中沢 浩, 三吉 克彦2001 年 59 巻 1 号 p. 52-61
発行日: 2001/01/01
公開日: 2009/11/13
ジャーナル フリーIn this review, a new and general method for the preparation of phosphenium complexes of transition metals has been reported. The stability of phosphenium complexes increases with going to a heavier congener among group 6 transition metals, and with increasing the number of amino substituents on the phosphenium phosphorus. The X-ray structures, 31P NMR and 95Mo NMR studies, and theoretical calculations have revealed that r back donation from a filled d orbital of a transition metal to an empty p orbital of a phosphenium phosphorus is a dominant contribution. Unique reactivities of phosphenium complexes have been developed : (i) heteroatom migration from a tertiary phosphorus to a phosphenium phosphorus in a coordination sphere, (ii) migratory insertion of a phosphenium ligand into a carbon-transition metal bond, (iii) 1, 3-migration of an alkyl group from a stannyl ligand to a phosphenium phosphorus. Activation parameters concerning phosphenium ligand rotation along the P-M axis have been estimated.抄録全体を表示PDF形式でダウンロード (1613K) -
大下 浄治, 片山 博之, 中沢 浩2001 年 59 巻 1 号 p. 62
発行日: 2001/01/01
公開日: 2009/11/13
ジャーナル フリーPDF形式でダウンロード (170K)
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