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铜配合物Cu（5-CH₃-1,10-phenanthroline）Br₂催化甲醇氧化羰基化

Oxidative Carbonylation of Methanol Catalyzed by Cu（5-CH₃-1,10-phenanthroline）Br₂

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【Author】 XIAO Yan-hua;SUN Zhi-kang;WEN Wu-qiang;DING Yi-gang;WU Yuan-xin;WANG Gong-ying;DU Zhi-ping;Key Laboratory for Green Chemical Process of Ministry of Education,Hubei Key Laboratory of Novel Chemical Reactor and Green Chemical Technology,School of Chemical Engineering & Pharmacy,Wuhan Institute of Technology;Chengdu Institute of Organic Chemistry,Chinese Academy of Sciences;

【机构】绿色化工过程教育部重点实验室湖北省新型反应器与绿色化学工艺重点实验室武汉工程大学化工与制药学院；中国科学院成都有机化学研究所；

【摘要】以R-phen（R=5-NH₂、5-CH₃、5-H、5-Cl、5-NO₂,2-CH₃、4-CH₃、2,9-dimethyl、4,7-dimethyl、5,6-dimethyl;phen=1,10-邻菲啰啉）和溴化铜为原料,通过沉淀反应制备了铜配合物Cu（R-phen）Br₂。在甲醇氧化羰基化反应中,以Cu（OCH₃）₂和卤化亚铜/卤化铜为催化剂考察了卤素离子的作用机理,以Cu（R-phen）Br₂为催化剂探究了催化剂的构效关系,以及工艺条件对甲醇氧化羰基化反应的影响。结果表明:卤素离子主要起桥联作用,其催化活性顺序为交界碱Br->硬碱Cl->软碱I-;Cu（R-phen）Br₂中,催化活性顺序为Cu（5-NO₂-phen）Br₂<Cu（5-NH₂-phen）Br₂<Cu（5-Cl-phen）Br₂<Cu（phen）Br₂<Cu（5-CH₃-phen）Br₂;含单甲基phen的Cu配合物的催化活性顺序是Cu（5-CH₃-phen）Br₂>Cu（4-CH₃-phen）Br₂>Cu（2-CH₃-phen）Br₂,且比相应的含双甲基phen的Cu配合物的催化活性高。以Cu（5-CH₃-phen）Br₂催化甲醇氧化羰基化的优化工艺条件为:总压力4 MPa、CO与O₂的分压比为19∶1、反应时间4 h、反应温度130℃、催化剂浓度0.0110 mol/L（以甲醇体积计）。在此条件下,碳酸二甲酯（DMC）的TON[n（DMC）/n（Cu）]值为67.2,DMC的选择性为96.9%。更多还原

【Abstract】 A series of Cu complexes,Cu（ R-phen） Br₂（ R = 5-NH₂,5-CH₃,5-H,5-Cl,5-NO₂,2-CH₃,4-CH₃,2,9-dimethyl,4,7-dimethyl,5,6-dimethyl,phen = 1,10-phenanthroline）,were synthesized by the precipitation reaction of 1,10-phenanthroline containing different substituent group and cupric bromide. In the oxidative carbonylation of methanol to dimethyl carbonate（ DMC）,the mixture of Cu（ OCH₃）2and cuprous halides/cupric halides was used as catalysts to study the mechanism of halogen ions,and Cu（ R-phen） Br₂ was used to investigate its structure-activity relationship and its influence on the reaction. The results showed that halogen ions played bridging roles,and their catalytic activity order was border base Br-> hard base Cl-> soft base I-. Among the prepared complexes,the catalytic activity of Cu（ 5-NO₂-phen） Br₂,Cu（ 5-NH₂-phen） Br₂,Cu（ 5-Cl-phen） Br₂,Cu（ phen） Br₂ and Cu（ 5-CH₃-phen） Br₂ increased in turn. In addition,the catalytic activity of the Cu complexes containing mono-methyl phen ligands displayed the following order: Cu（ 5-CH₃-phen） Br₂> Cu（ 4-CH₃-phen） Br₂> Cu（ 2-CH₃-phen） Br₂,which were higher than that of the complexes containing dimethyl phen ligands. Under the optimized process conditions of total pressure 4. 0 MPa,ratio of partial pressure of CO to O₂19 ∶ 1 at 130 ℃ for 4 h,Cu（ 5-CH₃-phen） Br₂ concentration in methanol 0. 011 mol/L,the turnover number（ TON） could reach 67. 2 mol of DMC per mol of Cu and the selectivity of DMC was up to 96. 9%.更多还原