著者
海野 雅史 松本 英之
出版者
The Society of Synthetic Organic Chemistry, Japan
雑誌
有機合成化学協会誌 (ISSN:00379980)
巻号頁・発行日
vol.62, no.2, pp.107-115, 2004-02-01 (Released:2009-11-13)
参考文献数
36
被引用文献数
2 4

Octasilacubane is an intriguing polyhedral polysilane because of its unique electronic properties arising from highly strained Si-Si σ-bonded framework. The first octasilacubane, octakis (t-butyldimethylsilyl) octasilacubane was reported by our group in 1988, as the first example of Platonic solid compounds comprising Group 14 elements other than carbon. We then prepared the alkyl-substituted one (ThexSi)8 (Thex = 1, 1, 2-trimethylpropyl) in 1992. These octasilacubanes are fairly stable, and various reactions, e.g., halogenation, oxidation, and photoreaction have been reported. Thus, the reaction of (ThexSi)8 with PCl5 leading to dichlorides via skeletal, rearrangement, the halogenation with Br2 or I2 leading to dibromides or diiodides, and the reductive dehalogenation of these dihalides with sodium to regenerate (ThexSi)8. Photo-initiated partial oxidation with DMSO gave monooxaoctasilahomocubane and dioxaoctasilabishomocubane. In this paper, in addition to these reactions, structure, thermal property, photoluminescent property, and UV property of octasilacubanes were summarized.
著者
西川 剛 大内 誠
出版者
公益社団法人 有機合成化学協会
雑誌
有機合成化学協会誌 (ISSN:00379980)
巻号頁・発行日
vol.81, no.4, pp.313-323, 2023-04-01 (Released:2023-04-08)
参考文献数
59

In chain-growth polymerization, (co)polymerization abilities of monomers are heavily dependent on the element or functional group attaching to vinyl moiety, resulting in the limitation of accessible polymers. The replacement of the element on the polymer main chain could lead to access new class of polymers with overcoming the synthetic limitations. Herein, we describe the usability of alkenylboronic acid derivatives as the monomers for radical polymerization and post-polymerization transformation through carbon-boron bond-cleaving side-chain replacement. The key for radical polymerization ability of alkenyl boronate was vacant p-orbital of boron for moderate stabilization of chain growth radical. The alkenyl boronate monomers are usable for copolymerization with common monomers as well as for RAFT polymerization. The C-B bond transformation allows syntheses of conventionally inaccessible polymers, such as poly(α-methyl vinyl alcohol), poly(α-methyl vinyl amine), styrene-vinyl alcohol copolymer, and ethylene-acrylate copolymer. Boron on the polymer main chain was also used as the trigger for stimuli-responsive backbone degradation of methacrylate polymer through C-B bond homolysis and β-scission. Thus, alkenyl boronate monomers have an impact on not only breakthrough of the limitation in polymer synthesis but also development of novel polymer functions.
著者
納谷 洋子
出版者
The Society of Synthetic Organic Chemistry, Japan
雑誌
有機合成化学協会誌 (ISSN:00379980)
巻号頁・発行日
vol.46, no.5, pp.447-454, 1988-05-01 (Released:2010-01-22)
参考文献数
18
被引用文献数
1

The presence of a molt-inhibiting hormone (MIH) in crustaceans versus the molting hormone (ecdysteroids) has been biologically demonstrated, however, only a little of the chemical nature of MIH is known so far Our attempt to isolate MIH produced in the X-organ of the eyestalks (ES) resulted in the characterization of xanthurenic acid as an ecdysone biosynthesis inhibitor (EBI) In addition, it was found that 3-hydroxy-L-kynurenine (3-OH-K) present in the X-organ of ES was also biotransformed into xanthurenic acid. The inhibitory action was shown in the cultured Y-organ-complex homogenate as well as in the crayfish by injection of 3-OH-K that revealed the delay of ecdysis. The preliminary study of ED50 of the active compounds appeared to account for most of but not the full potency of ES extract. Therefore, a molt-inhibiting phenomena is probably the result of the action by the multiple factors including EBI. After the mode of inhibitory action of the recently isolated sinusgland neuropeptide is shown, the involvement of a hormone in the negative control of molting will be clarified.
著者
Yohsuke Yamamoto Kin-ya Akiba
出版者
The Society of Synthetic Organic Chemistry, Japan
雑誌
有機合成化学協会誌 (ISSN:00379980)
巻号頁・発行日
vol.62, no.11, pp.1128-1137, 2004-11-01 (Released:2009-11-13)
参考文献数
31
被引用文献数
15 21

Various carbon and boron compounds bearing a 1, 8-disubstituted anthracene skeleton were synthesized and characterized by X-ray analysis. They showed three types of structures based on the kinds of substituents. The first one is symmetrical and is a loose pentacoordinate structure, which has the sp2 carbon or boron atom and the two weak apical interactions. The next one is an unsymmetrical tetracoordinate structure, which has the sp3 central atom. The last one is symmetrical and is a tight pentacoordinate structure, which resulted from the special feature of the fluorine substituents on the boron. The existence of hypervalent interaction was proved by the Atoms In Molecules Theory, experimental electron distribution analysis and a comparison among the structures of tight and loose pentacoordinate species. The synthesis and structures of hypervalent carbon compounds with a 2, 6-bis (aryloxymethyl) benzene ligand are also discussed.
著者
岡本 佳男 八島 栄次
出版者
The Society of Synthetic Organic Chemistry, Japan
雑誌
有機合成化学協会誌 (ISSN:00379980)
巻号頁・発行日
vol.45, no.8, pp.792-804, 1987-08-01 (Released:2010-01-22)
参考文献数
68

Three different types of asymmetric polymerizaitons of methacrylates have been achieved successfully. Racemic α-substituted benzyl methacrylates were polymerized with a high enantiomer-selectivity over 90% in the polymerization by (-) -sparteine-Grignard reagent complexes. Optically active polymethacrylates with nearly 100% one-handed helicity were obtained in the polymerization of such bulky esters as triphenylmethyl methacrylate with chiral anionic initiators. These chiral polymers were found to be very effective in separating the optical isomers under HPLC conditions. A very high enantiomer selection by the growing chain end with a stable helical structure was also attained in the polymerization of a bulky racemic monomer phenyl-2-pyridyl-ο-tolylmethyl methacrylate.
著者
小方 芳郎 木村 眞
出版者
The Society of Synthetic Organic Chemistry, Japan
雑誌
有機合成化学協会誌 (ISSN:00379980)
巻号頁・発行日
vol.37, no.7, pp.581-594, 1979-07-01 (Released:2009-11-13)
参考文献数
85
被引用文献数
3 8

Metal hypohalites (e. g. NaOCl) can be used not only for selective oxidation and halogenation of organic compounds, but also for oxidative removal of pollutants such as aromatic compounds and surfactants, especially nitrogen compounds which results in the eutrophication of sees and lakes.The present article reviews the properties and oxidative preparation, reactions of hydrocarbons (aliphatic and aromatic), alcohols, aldehydes, ketones, ethers, carboxylic acids, ammonia, amines, amides (including urea), and sulfur compounds (including sulfonic acids) with the hypohalites. On UV irradiation hypohalites delivers atomic oxygen and HO·which are highly active oxidants, thus initiate a chain reaction by abstracting hydrogen atom, and can be used for removal of pollutants. The review emphasizes the mechanisms for hypohalite oxidation and photo-oxidation of compounds polluting waste water.