Selective Addition of Polyhalides to Different Double Bonds by Semiconductor Catalyst under Photoirradiatior.

• Project/Area Number: 07651028
• Research Category: Grant-in-Aid for Scientific Research (C)
• Allocation Type: Single-year Grants
• Section: 一般
• Research Field: 有機工業化学
• Research Institution: Shinshu University
• Principal Investigator: MITANI Michiharu Engineering., Shinshu University Professor, 工学部, 教授 (20021016)
• Co-Investigator(Kenkyū-buntansha): MITANI Michiharu Engineering., Shinshu University Professor (20021016)
• Project Period (FY): 1995 – 1996
• Project Status: Completed (Fiscal Year 1996)
• Budget Amount: ¥2,100,000 (Direct Cost: ¥2,100,000); Fiscal Year 1996: ¥700,000 (Direct Cost: ¥700,000); Fiscal Year 1995: ¥1,400,000 (Direct Cost: ¥1,400,000)
• Keywords: Semiconductor Catalyst / Photoreaction / Polyhalide / Chemo-selective Addition / Olefin / Modified Semiconductor

Research Abstract

Polyhalides were added to non-polar olefins in the photoreaction catalyzed by Ag-doped titanium oxide particles, meanwhile polar olefins did not almost undergo the addition reaction with polyhalides under these conditions. Use of titanium oxide catalysts impregnated with the polar groups such as an amine or cyanoacetic group furnished a little, not remarkable, enhancement of the addition reaction to the polar olefins, compared with the unmodified titanium oxide catalyst. When the substrates which possesses both the polar and non-polar carbon-carbon double bonds in the molecule, i. e., omega-alkenyl acrylates, omega-alkenyl vinyl ketones, omega-alkenyl vinyl ethers, omega-alkenyl allyl ethers, vinyl undecylate and allyl undecylate were subjected to the TiO_2-catalyzed photoreaction with carbon tetrachloride or bromoform, those carrying the methylene groups below four units between the polar and non-polar carbon-carbon double bonds afforded the complex mixture in the low yields while tho se carrying the methylene groups over six units between the polar and non-polar double bonds brought about the enhanced formation of the selective addition products to the non-ploar double bonds. The selective adducts thus obtained were subjected to subsequent transformation as follows ; (1)formation of the nitrogen-containing macrocyclic lactones or ketones through the addition reaction of benzyl or butylamine to the remaining polar double bonds of the adducts of omega-alkenyl acrylates or omega-alkenyl vinyl ketones with carbon tetrachloride followed by treatment with silver nitrate, (2)formation of the polymers bearing the CHClCH_2CCl_3 group as a pendant by trestment of the adducts obtained from carbon tetrachloride and omega-alkenyl vinyl ethers with boron trifluoride, (3)formation of the polymers bearing the CHClCH_2CCl_3 group as a pendant by treatment of the adducts obtained from carbon tetrachloride and omega-alkenyl acrylate or omega-alkenyl vinyl ketones with sodium naphthalide.