| Budget Amount *help |
¥12,200,000 (Direct Cost: ¥12,200,000)
Fiscal Year 2004: ¥2,700,000 (Direct Cost: ¥2,700,000)
Fiscal Year 2003: ¥3,400,000 (Direct Cost: ¥3,400,000)
Fiscal Year 2002: ¥6,100,000 (Direct Cost: ¥6,100,000)
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| Research Abstract |
We have reported that dicyanoketene acetals (DCKA), in which gem-dicyano groups of tetracyanoethylene (TCNE) are displaced with alkoxyl groups, function as π-acid catalysts, and that a polymer derived from a monomer, in which the alkoxyl group at the ω-position is modified with styrene moiety, also shows high level of activities as an acid. In this research, polymers previously developed and new monomers, in which the alkoxyl group at the ω-position is modified with ethereal moiety and the corresponding polymers were investigated on catalytic activities. Synthsis of the corresponding catalysts having a fluorus tag was also studied.
(1) 5-Benzyl-1, 3-dioxane type DCKA (2) was synthesized from TCNE and 2-benzyl-1, 3-propanediol (1) prepared starting with diethyl malonate. 5-Hydroxymethyl-5-ethyl-1, 3-dioxane of cyclic acetal type DCKA (3) was synthesized from commercially available 1, 1, 1-tris (hydroxymethyl) ethane and TCNE. A monomeric DCKA (4) was synthesized by benzylation of hydroxy
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l group at the ω-position on the side chain.
(2) Monomeric DCKAs (5,6) bearing 4-vinylbenzyl group prepared analogously was heated with ethyleneglycol dimethacrylate (EGDMA) in the presence of AIBN as a catalyst to give polymeric DCKAs (7,8).
(3) monomeric DCKA (2,4) and polymeric DCKA (7,8) thus obtained was examined on catalytic activities in the two component Mannich type C-C bond forming reaction of benzylidene aniline (9) and dimethylketene O-TMS-O-ethyl acetal (10) and in the three component one using benzaldehyde, aniline, and acetal (10) in acetonitrile and water at room temperature. The DCKAs except for a polymer (8) showed higher activities in water than acetonitrile, and excellent activities were observed especially for a polymer (7).
(4) Polymeric DCK (7) was recycled without loss of activities in three times experiments of the two component and three component reactions above.
(5) In order to make DCKAs with fluorus tag which are expected to function in super critical CO_2, a novel fluorus tag of [BrCH_2C_6H_4-3,5-(C_<10>F_<21>)_2] (11) was synthesized from 3,5-diiodobenzylmethyl ether and C_<10>F_<21>-I.
(6) Fluorus DCKAs (12,13) were synthesized by using the fluorus tag (11), and examination of those catalytic activities in regular solvents and fluorus solvents are in progress. Less
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