Development of Recyclable π-Acid Catalyst

可回收π酸催化剂的开发

• 批准号: 14370724
• 负责人: MASAKI Yukio
• 金额: $ 7.81万
• 依托单位: Gifu Pharmaceutical University
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (B)
• 财政年份: 2002
• 资助国家: 日本
• 起止时间: 2002 至 2004
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/en/grant/KAKENHI-PROJECT-14370724/
• 关键词: π-acid catalyst; polymeric dicyanoketene acetal; recycle; Mannich reaction; dicyanoketene acetal; aqueous reaction; three component binding reaction; fluorus catalyst; 高分子ジシアンケテンアセタール; 高分子化ジシアノケテンアセタール

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

我们已经报道了二氰基酮缩醛(DCKA)，其中四氰乙烯的二氰基被烷氧基取代，用作π酸催化剂，以及由单体衍生的聚合物，其中ω位的烷氧基被苯乙烯部分修饰，也显示出较高的酸活性。在本研究中，对已开发的聚合物和新单体进行了催化活性研究，其中ω-位的烷氧基被醚化修饰，相应的聚合物具有催化活性。(1)以丙二酸二乙酯为起始原料合成了5-苄基-1，3-二氧六环型DCKA(2)和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DCKA(3)型5-羟甲基-5-乙基-1，3-二氧六环。通过对羟基…的苄基化反应合成了一种单体DCKA(4)(2)类似合成的含4-乙烯基苄基的单体DCKA(5，6)在AIBN催化下与乙二醇二甲基丙烯酸酯(EGDMA)反应生成聚合物DCKA(7，8)。(3)考察了所得单体DCKA(2，4)和聚合物DCKA(7，8)在苯亚甲基苯胺(9)和二甲基酮O-TMS-O-乙缩醛(10)两组分Mannich C-C键形成反应中的催化活性。(4)聚合物DCK(7)在上述两个组分和三个组分的三次反应实验中活性没有损失。(5)为了制备有望在超临界CO_2中起作用的带氟标签的DCKA，合成了一种新型的氟标签[BrCH_2C_6H_4-3，5-(C&lt；10&gt；F_&lt；21&gt；以3，5-二碘苯甲基甲醚为原料，与C_&lt；10&gt；F_&lt；21&gt；-I反应，合成了3，5-二碘苯甲醚[2](11)(11)。(6)用氟标记(11)合成了含氟DCKAs(12，13)，并对其在常规溶剂和氟溶剂中的催化活性进行了考察。较少