酞菁锌高效催化以二氧化碳、含氢硅烷和有机胺为原料合成甲酰胺类衍生物

催化学报 ›› 2017, Vol. 38 ›› Issue (8): 1382-1389.

酞菁锌高效催化以二氧化碳、含氢硅烷和有机胺为原料合成甲酰胺类衍生物

罗荣昌^a, 林小微^a, 鲁静^b, 周贤太^c, 纪红兵^a

a 中山大学化学学院, 广东省低碳化学与过程节能重点实验室, 广东广州 510275;
b 广州市天河中学猎德实验学校, 广东广州 510623;
c 中山大学化学工程与技术学院, 广东珠海 519000

收稿日期:2017-05-12 修回日期:2017-06-18 出版日期:2017-08-18 发布日期:2017-08-04
通讯作者: 纪红兵
基金资助:
国家自然科学基金（21676306，21425627）；国家重点研发计划（2016YFA0602900）；广东省自然科学基金（2016A030310211）；广东省普通高校特色创新类项目（自然科学类）.

Zinc phthalocyanine as an efficient catalyst for halogen-free synthesis of formamides from amines via carbon dioxide hydrosilylation under mild conditions

Rongchang Luo^a, Xiaowei Lin^a, Jing Lu^b, Xiantai Zhou^c, Hongbing Ji^a

a School of Chemistry, Key Laboratory of Low-Carbon Chemistry & Energy Conservation of Guangdong Province, Sun Yat-sen University, Guangzhou 510275, Guangdong, China;
b Liede Experimental School of Guangzhou Tianhe High School, Guangzhou 510623, Guangdong, China;
c School of Chemical Engineering and Technology, Sun Yat-sen University, Zhuhai 519000, Guangdong, China

Received:2017-05-12 Revised:2017-06-18 Online:2017-08-18 Published:2017-08-04
Supported by:
This work was supported by the National Natural Science Foundation of China (21676306, 21425627), the National Key Research and Development Program of China (2016YFA0602900), the Natural Science Foundation of Guangdong Province (2016A030310211), and the Characteristic Innovation Project (Natural Science) of Guangdong Colleges and Universities.

摘要/Abstract

摘要：

目前为了有效地利用好CO₂，主要策略有以下几种：（1）“水平途径”——无价态及能量变化，譬如生成尿素、环状碳酸酯、聚碳酸酯及噁唑烷酮类衍生物等；（2）“垂直途径”——有价态及能量变化，譬如直接加氢转化成碳一产品（甲酸、甲醛、甲醇、甲烷）等；（3）“对角线途径”——有价态及能量变化，即结合石油化工原料将CO₂还原生成醇、醚、羧酸、亚胺、酰胺、酯等系列高附加值的精细有机化工产品.其中以二氧化碳和含氢硅烷为原料，通过有机胺的N-甲酰化反应合成甲酰胺类衍生物符合绿色化学和可持续发展的要求.
基于仿生催化CO₂分子活化的基本理论，我们借鉴强极性的有机溶剂可有效活化硅氢键的性质，创新性地将廉价易得的酞菁锌（ZnPc）作为类酶催化剂，并以化学计量的N，N'-二甲基甲酰胺（DMF）为添加剂，构成组分新颖并高效绿色的类酶协同催化体系，实现了在温和反应条件下高效高选择性地合成甲酰胺类衍生物.研究发现：以苯硅烷作为还原剂，当加入0.5 mol% ZnPc和2 mmol DMF，在25℃和0.5 MPa下仅需反应6 h，可得到收率为99%的N-甲基甲酰苯胺.更值得注意的是，当以更易得的聚甲基氢硅烷（PMHS）为还原剂时，加入5 mol% ZnPc和1 mL DMF，在80℃和1 MPa下反应8 h，N-甲基甲酰苯胺的收率也高达99%.实验结果表明：添加剂DMF可以通过溶剂化和强极性作用高效活化含氢硅烷中的Si-H键，然后具有亲电性的金属活性中心能够稳定氢负离子生成高活性锌氢中间体.即ZnPc/DMF之间的协同催化作用能够促进氢化物从含氢硅烷转移到CO₂分子，进而有利于CO₂分子的高效活化.
综上所述，利用类酶催化剂反应专一性的特点，通过有机胺的N-甲酰化反应，实现了以CO₂和含氢硅烷为原料在温和条件下甲酰胺类衍生物的绿色高效合成.这对于设计和开发更加高效的催化体系具有一定的指导作用和借鉴意义.

关键词: 二氧化碳, 酞菁锌, 协同作用, N-甲酰化, 含氢硅烷

Abstract:

The combination of a zinc phthalocyanine (ZnPc) catalyst and a stoichiometric amount of dimethyl formamide (DMF) provided a simple route to formamide derivatives from amines, CO₂, and hydrosilanes under mild conditions. We deduced that formation of an active zinc-hydrogen (Zn-H) species promoted hydride transfer from the hydrosilane to CO₂. The cooperative activation of the Lewis acidic ZnPc by strongly polar DMF, led to formation of activated amines and hydrosilanes, which promoted the chemical reduction of CO₂. Consequently, the binary ZnPc/DMF catalytic system showed excellent yields and superior chemoselectivity, representing a simple and sustainable pathway for the reductive transformation of CO₂ into valuable chemicals as an alternative to conventional halogen-containing process.

Key words: Carbon dioxide, Zinc phthalocyanine, Cooperative effect, N-formylation, Hydrosilanes

罗荣昌, 林小微, 鲁静, 周贤太, 纪红兵. 酞菁锌高效催化以二氧化碳、含氢硅烷和有机胺为原料合成甲酰胺类衍生物[J]. 催化学报, 2017, 38(8): 1382-1389.

Rongchang Luo, Xiaowei Lin, Jing Lu, Xiantai Zhou, Hongbing Ji. Zinc phthalocyanine as an efficient catalyst for halogen-free synthesis of formamides from amines via carbon dioxide hydrosilylation under mild conditions[J]. Chinese Journal of Catalysis, 2017, 38(8): 1382-1389.

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