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

本文报道了烷氧基取代四氰基乙烯（TCNE）的偕-二氰基的双氰基烯酮缩醛（DCKA）作为π-酸催化剂的作用，以及由ω-位烷氧基用苯乙烯部分修饰的单体衍生的聚合物作为酸也表现出高水平的活性。本研究对已开发的聚合物和ω-位烷氧基经醚基改性的新单体及相应聚合物的催化活性进行了研究。还研究了具有氟标记的相应催化剂的合成。(1)以丙二酸二乙酯为起始原料，合成了2-苄基-1，3-丙二醇（1）和TCNE，合成了5-苄基-1，3-二氧六环型DCKA（2）。以1，1，1-三羟甲基乙烷和TCNE为原料，合成了DCKA（3）型环缩醛5-羟甲基-5-乙基-1，3-二氧六环。通过羟基苄基化反应合成了单体DCKA（4 ...更多信息 L基团在侧链上的ω-位置处。(2)类似地制备的带有4-乙烯基苄基的单体DCKAs（5，6）与乙二醇二甲基丙烯酸酯（EGDMA）在作为催化剂的AIBN存在下加热以得到聚合DCKAs（7，8）。(3)考察了单体DCKA（2，4）和聚合DCKA（7，8）在室温下在苄叉苯胺（9）和二甲基乙烯酮O-TMS-O-乙缩醛（10）的双组分Mannich型C-C键形成反应和在苯甲醛、苯胺和乙缩醛（10）的三组分Mannich型C-C键形成反应中的催化活性。除了聚合物（8）之外，DCKAs在水中显示出比乙腈更高的活性，特别是聚合物（7）观察到优异的活性。(4)聚合物DCK（7）在上述两组分和三组分反应的三次实验中循环使用而没有活性损失。(5)为了制备有望在超临界CO_2中发挥作用的含氟DCKAs，<10><21>以3，5-二碘苄基甲醚和CF-I为原料，合成了一种新型的含氟DCKAs [BrCH_2C_6H_4- 3，5-（CF_）_2]（11）<10><21>。(6)通过使用氟标记（11）合成氟DCKAs（12，13），并且正在进行在常规溶剂和氟溶剂中的这些催化活性的检测。少