松香基氮杂环卡宾催化剂的制备及其对芳基加成反应的催化性能

doi:10.3969/j.issn.0253-2417.2018.02.006

林产化学与工业 ›› 2018, Vol. 38 ›› Issue (2): 46-50.doi: 10.3969/j.issn.0253-2417.2018.02.006

松香基氮杂环卡宾催化剂的制备及其对芳基加成反应的催化性能

李健¹, 张军华¹, 宋湛谦², 商士斌²

1. 西北农林科技大学林学院, 陕西杨凌 712100;
2. 中国林业科学研究院林产化学工业研究所, 江苏南京 210042

收稿日期:2017-09-14 出版日期:2018-04-25 发布日期:2018-04-28
通讯作者: 商士斌,研究员,博士生导师,研究领域为生物质化学与利用;E-mail:shangsb@hotmail.com。 E-mail:shangsb@hotmail.com
作者简介:李健(1983-),男,山东单县人,副教授,博士,主要从事萜烯化学的研究工作
基金资助:
国家自然科学基金资助项目（31400509）；西北农林科技大学林学院“优秀青年教师人才培育计划”（Z111021604）

Preparation of Rosin-based N-Heterocyclic Carbene Catalyst and Its Catalytic Properties for Addition Reaction of Aryl

LI Jian¹, ZHANG Junhua¹, SONG Zhanqian², SHANG Shibin²

1. College of Forestry, Northwest Agriculture and Forestry University, Yangling 712100, China;
2. Institute of Chemical Industry of Forest Products, Chinese Academy of Forestry, Nanjing 210042, China

Received:2017-09-14 Online:2018-04-25 Published:2018-04-28

摘要/Abstract

摘要： 以脱氢枞胺和丙烯海松胺为主要原料，设计合成了两类松香基N-杂环卡宾（NHC）分子，并通过FT-IR、¹H NMR、¹³C NMR、MS和元素分析等进行了结构鉴定。以制备的新型松香基NHC分子催化芳香醛和芳基硼酸的加成反应，来筛选催化剂和进行活性评价。结果表明：丙烯海松基NHC（Ap-NHC）的催化活性优于脱氢枞基NHC（Da-NHC），以1，4-二氧杂环己烷（DOA）/H₂O体积比6：1为溶剂、催化剂用量为2.5%，叔丁醇钾作碱性助剂时，并在反应温度为60℃、反应时间4 h时催化效果最佳，产物得率最高达到95%。最后研究了不同结构的底物对反应活性大小的影响，当芳硼酸与带有吸电基的芳香醛加成时，反应产率最高，而芳基硼酸上的取代基对反应的产率影响不大。

关键词: 脱氢枞胺, 丙烯海松胺, 氮杂环卡宾, 催化, 加成反应

Abstract: Two kinds of rosin-based N-heterocyclic carbene (NHC) from dehydroabietylamine and acrypimaric amine were designed and synthesized, and their structures were identified by FT-IR, ¹H NMR, ¹³C NMR, MS and elemental analysis. For screening the catalysts and evaluating their activity, the novel rosin-based NHC molecules were used to catalyze the addition reaction of aromatic aldehydes and aryl boronic acids. The results showed that catalytic activity of the acrypimaric-based NHC(Ap-NHC) was better than that of dehydroabietic-based NHC(Da-NHC), and the optimal catalytic effect was presented at reaction conditions of reaction temperature 60℃, the reaction time 4 h, the amount of catalyst 2.5% and potassium tert-butoxide as alkali, and the yield reached to 95%. Finally, the influence of different substituent groups on the reactant was studied. When the aryl boronic acid reacted with the aromatic aldehyde with electron withdrawing group, the yield was the highest, while the substituent on the boric acid had little effect on the reaction.

Key words: dehydroabietylamine, acrypimaric amine, N-heterocyclic carbine, catalysis, addition reaction

中图分类号:

TQ35

李健, 张军华, 宋湛谦, 商士斌. 松香基氮杂环卡宾催化剂的制备及其对芳基加成反应的催化性能[J]. 林产化学与工业, 2018, 38(2): 46-50.

LI Jian, ZHANG Junhua, SONG Zhanqian, SHANG Shibin. Preparation of Rosin-based N-Heterocyclic Carbene Catalyst and Its Catalytic Properties for Addition Reaction of Aryl[J]. Chemistry and Industry of Forest Products, 2018, 38(2): 46-50.

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松香基氮杂环卡宾催化剂的制备及其对芳基加成反应的催化性能

Preparation of Rosin-based N-Heterocyclic Carbene Catalyst and Its Catalytic Properties for Addition Reaction of Aryl

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