著者

上原 忠夫 齋藤 研一 山本 嘉則

出版者

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.47, no.4, pp.321-329, 1989-04-01 (Released:2010-01-22)

参考文献数

79

被引用文献数

2 3

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High-pressure technique is a practical method for laboratory organic synthesis since simple equipment has become available in this decade. Pressure accelerates reactions if their values of 'the volume of activation' are negative, such as cycloaddition reactions and reactions through dipolar transition states. Especially, this technique is useful to drive reactions with steric hindrance. In this article are reviewed recent developments of substitution reactions, addition reactions to a carbonyl group, conjugated addition reactions, Deils-Alder reactions, 1, 4-cycloaddition reactions, other pericyclic reactions, and organometallic reactions since 1985.

著者

上原 忠夫 大沼 俊雄 鈴木 赳 加藤 忠弘 吉田 利男 高橋 勝宏

出版者

天然有機化合物討論会

雑誌

天然有機化合物討論会講演要旨集

巻号頁・発行日

no.22, pp.235-242, 1979-09-20

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From a higher boiling fraction (Bp>100℃/8 Torr) of peppermint oil (Mentha piperia L.) was isolated a white crystalline (mp 59-61℃, 300 mg from 80 g of the fraction) having a molecular formula of C_<15>H_<24>S. The structure of the crystalline was unequivocally determined by X-ray crystallographic analysis and we named it mintsulfide (1)(abbreviated as MS). Ultraviolet irradiation (Pyrex filter) of (-)-germacrene D (2)(abbreviated as GD), one of the major components of the oil, in the presence of sulfur powder afforded the mintsulfide (1), thus demonstrating the absolute configuration of MS. The mintsulfide was converted into the isomer (4). Both 1 and 4 were oxidized to give the products (5〜10), which showed the chemical shifts in the NMR spectra as summarized in table 1 and 2. Table 3 indicates the results of photochemical conversion of GD (2), giving MS (1) and/or β-bourbonene (3) under the various conditions. The evidence in table 3 suggests that activated sulfur (sulfur atom ?) is generated first under the Pyrex filtered irradiation. The activated sulfur reacts with GD, leading the formation of MS (1). This novel photoreaction is substrate specific since presence of caryophyllene (12) or β-bourbonene (3) affects no influence. The preliminary experiments revealed that myrcene (13) and tenmembered diene (14) also react with the photo-activated sulfur.