| Co-Investigator(Kenkyū-buntansha) |
OGAWA Akiya Osaka Univ., Faculty of Engineering, Research Assistant, 工学部, 助手 (30183031)
RYU Ilhyong Osaka Univ., Faculty of Engineering, Research Assistant, 工学部, 助手 (80210821)
KAMBE Nobuaki Osaka Univ., Faculty of Engineering, Associate Professor, 工学部, 助教授 (60144432)
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| Budget Amount *help |
¥14,400,000 (Direct Cost: ¥14,400,000)
Fiscal Year 1994: ¥5,000,000 (Direct Cost: ¥5,000,000)
Fiscal Year 1993: ¥9,400,000 (Direct Cost: ¥9,400,000)
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| Research Abstract |
Radical reactions between organic dichalcogenides and carbon-carbon unsaturated compounds have been investigated precisely. Based on the relative reactivities of organic dichalcogenides and chalcogen-centered radicals, it has become apparent that two different chalcogeno-groups can be introduced simultaneously into a variety of carbon-carbon multiple bonds with excellent selectivity. Upon irradiation with the light of wavelength over 300 nm, the reaction of acetylenes with organic disulfides and diselenides takes place smoothly to provide the corresponding thioselenation products regioselectively. Similar additions can be employed with allenes and 1,3-dienes, affording beta-selenoallylic sulfieds and gamma- (selenomethyl) -allylic sulfides, respectively, in good yields. With vinylcyclopropanes, thioselenation via ring-opening of cyclopropane occurs to give gamma- (selenomethyl) allylic sulfides. With enynes, thioselenation via radical cyclization is demonstrated successfully. In additi
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on, novel mixed systems of organic dichalcogenides, i.e., a disulfide-ditelluride mixed system and a diselenide-ditelluride mixed system have been developed. Both systems require the irradiation with light of wavelength over 400nm, because UV or near UV light causes the decomposition of the products bearing a photo-sensitive C-Te bond. From acetylenes are thus obtained beta-thio-and beta-selenovinylic tellurides, respectively. With allenes and 1,3-dienes, however, the desired thiotelluration products are not formed at all, but instead dithiolation products are obtained. Further investigation on this disulfide-ditelluride-allene system leads to successful development of a novel telluride-catalyzed dithiolation reaction of allenes with disulfides. Similary, a selenide-catalyzed dithiolation of 1,3-dienes to give 1,4-dithiolation products are disclosed. Both systems has enabled the efficient dithiolation of allenes and 1,3-dienes, which is difficult to be attained by using a disulfide single system. Less
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