应用化学

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金属次卟啉二甲酯催化氧化苯乙烯制苯甲醛

赵东辉,胡炳成*,孙呈郭,邓全知   

  1. (南京理工大学化工学院 南京 210094)
  • 收稿日期:2012-02-28 修回日期:2012-05-17 出版日期:2013-01-10 发布日期:2013-01-10
  • 通讯作者: 胡炳成,教授; Tel/Fax:025-8431503; E-mail:hubingcheng@yahoo.com; 研究方向:有机合成和绿色催化
  • 作者简介:作者:赵东辉,男,汉族,在读硕士,目前就读于南京理工大学化工学院应用化学专业。研究方向:有机合成及绿色催化。邮箱:zdh1949@126.com, 联系电话:15295588290;
  • 基金资助:
    江苏省自然科学基金(BK2009386)江苏省研究生创新基金(CXZZ11_0263)资助项目

Preparation of Benzaldehyde through Oxidation of Styrene Catalyzed by Metallo-deuteroporphyrin Dimethyl Esters

ZHAO Donghui, HU Bingcheng*, SUN Chengguo, DENG Quanzhi   

  1. (College of Chemical Engineering,Nanjing University of Science and Technology,Nanjing 210094,China)
  • Received:2012-02-28 Revised:2012-05-17 Published:2013-01-10 Online:2013-01-10
  • Contact: Hu BingCheng
  • About author:Author: Zhao dong hui, male, a master studying in the College of Chemical Engineering, Nanjing University of Science and Technology. Research direction: organic synthesis and green catalysis. Email: zdh1949@126.com, Tel: 15295588290.

摘要: 将金属次卟啉二甲酯用作叔丁基过氧化氢(TBHP)氧化苯乙烯制苯甲醛的催化剂。 考察了催化剂、氧化剂用量、反应温度、时间、溶剂和不同金属次卟啉二甲酯[M(DPDME)]对苯乙烯转化率及苯甲醛选择性的影响,初步探索了反应机理。 结果表明,金属次卟啉二甲酯能够顺利地选择性催化氧化苯乙烯生成苯甲醛。 以0.002 mmol锰次卟啉二甲酯[ClMn(DPDME)]为催化剂,0.4 mmol TBHP为氧化剂,1 mmol苯乙烯为底物,5 mL CH3CN/H2O(体积比4∶1)为溶剂,反应温度75 ℃,常压反应20 h,苯乙烯的转化率达到98.3%,苯甲醛的选择性为92.7%。

关键词: 金属次卟啉二甲酯, 苯乙烯, 催化氧化

Abstract: In the presence of tert-butyl hydroperoxide(TBHP), metallo-deuteroporphyrin dimethyl esters[M(DPDME)] were used as catalysts in the oxidation of styrene. We have investigated the effects of the amount of the catalyst, the amount of the oxidant, reaction temperature, time, solvents and metallo-deuteroporphyrin dimethyl esters with different central metals on the conversion of styrene and the selectivity of benzaldehyde. The mechanism of the reaction was also discussed. The results indicated that the M(DPDME) could efficiently catalyze selective oxidation of styrene to benzaldehyde in good yields. Under the conditions of 0.002 mmol ClMn(DPDME) as the catalyst, 0.4 mmol TBHP as the oxidatant, 1 mmol styrene as the substrate, CH3CN(4 mL)/H2O(1 mL) as the solvent, reaction temperature of 75 ℃, atmospheric pressure, and a reaction time of 20 h, the conversion of styrene reached 98.3% with the benzaldehyde selectivity of 92.7%.

Key words: metallo-deuteroporphyrin dimethyl esters, styrene, catalytic oxidation

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