化工学报 ›› 2019, Vol. 70 ›› Issue (3): 929-936.DOI: 10.11949/j.issn.0438-1157.20181322

• 催化、动力学与反应器 • 上一篇    下一篇

交联菲罗啉负载铜催化剂用于合成三甲基苯醌

郭婉婉(),李如月,黄军()   

  1. 1. 南京工业大学化工学院,江苏 南京 211816
  • 收稿日期:2018-11-12 修回日期:2018-12-05 出版日期:2019-03-05 发布日期:2019-03-05
  • 通讯作者: 黄军
  • 作者简介:<named-content content-type="corresp-name">郭婉婉</named-content>(1993—),女,硕士研究生,<email>13770635576@163.com</email>|黄军(1973—),男,博士,教授,<email>junhuang@njtech.edu.cn</email>
  • 基金资助:
    国家自然科学基金项目(21676140)

Copper catalyst supported on cross-linked phenanthroline for oxidative synthesis of 2,3,5-trimethyl-1,4-benzoquinone

Wanwan GUO(),Ruyue LI,Jun HUANG()   

  1. 1. College of Chemical Engineering, Nanjing Tech University, Nanjing 211816, Jiangsu, China
  • Received:2018-11-12 Revised:2018-12-05 Online:2019-03-05 Published:2019-03-05
  • Contact: Jun HUANG

摘要:

烷基取代的苯醌可用作多种生物活性化合物的功能结构单元。提出了一种在温和条件下,用氧气氧化2,3,6-三甲基苯酚(TMP)得到2,3,5-三甲基-1,4-苯醌(TMQ,维生素E前体)的方法。利用Friedel-Crafts烷基化反应,成功制备了一种基于1,10-菲罗啉的交联多孔聚合物负载铜催化剂Cu/PPhen。采用氮气吸附脱附、SEM、FTIR和XPS对催化剂Cu/PPhen-4进行了一系列的表征,获得了催化剂的基本结构特征。并考察了催化剂的加入量、溶剂、氧气压力、反应温度以及反应时间等因素对Cu/PPhen-4催化氧化制备2,3,5-三甲基-1,4-苯醌的影响,得到最佳的工艺条件。当2,3,6-三甲基苯酚的加入量为136 mg时,催化剂量为150 mg,乙腈量为2 ml,0.5 MPa的氧气,40℃下反应4 h,2,3,5-三甲基-1,4-苯醌的收率可以达到99%。催化剂Cu/PPhen-4具有较好的稳定性,可以回收至少五次,活性几乎没有下降。

关键词: 铜催化剂, 2,3,5-三甲基-1,4-苯醌, 氧化, 反应, 聚合物

Abstract:

Alkyl-substituted benzoquinones were versatile building blocks for a variety of biologically active compounds. The catalytic oxidation of 2,3,6-trimethylphenol (TMP) to 2,3,5-trimethyl-1,4-benzoquinone (TMQ, vitamin E precursor) with oxygen gas was proposed under mild conditions. The cross-linked porous polymer (PPhen) was synthesized by Friedel-Crafts alkylation of 1,10-phenanthroline, and the related Cu catalysts (Cu/PPhen) were prepared. The prepared Cu/PPhen catalysts were characterized by nitrogen adsorption and desorption isotherms, scanning electron microscope (SEM), Fourier transform infrared spectroscopy (FTIR), and X-ray photoelectron spectroscopy (XPS) .The basic structure of the Cu/PPhen catalysts were obtained. Reaction conditions, such as catalyst loading, solvent, oxygen pressure, reaction temperature and reaction time were studied, and 2,3,5-trimethyl-1,4-benzoquinone was obtained in 99% yield with the optimized reaction conditions. The optimized reaction conditions were achieved as 136 mg 2,3,6-trimethylphenol with 150 mg the Cu/PPhen-4 catalyst in 2 ml acetonitrile, under 0.5 MPa O2 at 40℃ for 4 h. The Cu/PPhen-4 catalyst has good stability and can be recovered at least five times with almost no decrease in activity.

Key words: coper catalyst, 2,3,5-trimethyl-1,4-benzoquinone, oxidation, reaction, polymers

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