Development of Recyclable π-Acid Catalyst

我们已经报道了四氰乙烯（TCNE）的双氰基被烷氧基取代的二氰烯缩醛（DCKA）作为π酸催化剂的作用，以及一种由单体衍生的聚合物，其中ω位置的烷氧基被苯乙烯部分修饰，也显示出高水平的酸活性。在本研究中，研究了前人开发的聚合物和用醚基团修饰ω位烷氧基的新单体，并对相应聚合物的催化活性进行了研究。并研究了相应的含氟催化剂的合成。(1)以TCNE为原料合成5-苄基- 1,3 -二恶烷型DCKA(2)，以丙二酸二乙酯为起始原料制备2-苄基- 1,3 -丙二醇(1)。以市售的1,1,1 -三（羟甲基）乙烷和TCNE为原料合成了环缩醛型DCKA(3)的5-羟甲基-5-乙基- 1,3 -二恶烷。以侧链上ω位的羟基为甲基，合成了单体DCKA(4)。(2)在AIBN存在下，以乙二醇二甲基丙烯酸酯（EGDMA）为催化剂，用类似方法制备了含4-乙烯基苯基的单体DCKAs(5,6)，得到了聚合DCKAs（7,8）。(3)考察了由此得到的单体DCKA（2,4）和聚合DCKA（7,8）在苯基苯胺(9)和二甲基乙烯烯o - tms - o -乙基缩醛（10）的双组份Mannich型C-C成键反应中的催化活性。和缩醛（10）在乙腈和水的室温下。除聚合物(8)外，DCK(7)在水中的活性高于乙腈，特别是聚合物(7)的活性优异。(4)聚合物DCK(7)在上述两组份和三组份反应的三次实验中均无活性损失。(5)以3,5-二碘苄基甲基醚和C_<10>F_<21>- 1为原料，合成了一种新型的[brch_2c_6h_4 -3,5-(C_<10>F_<21>)_2]（11）的含氟标记物[brch_2c_6h_4 -3,5]。(6)利用氟标记物（11）合成了含氟DCKAs(12、13)，并对其在常规溶剂和含氟溶剂中的催化活性进行了研究。少

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 … More 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