Page 125 - 《精细化工》2020年第9期

第 37 卷第 9 期 精 细 化 工 Vol.37, No.9
202 0 年 9 月 FINE CHEMICALS Sept. 2020

催化与分离提纯技术
HKUST-1 单位点铜催化 CO /CS 成环
2
2
耦合三氟甲基化反应

*
臧瀚彬，李莫尘，张铁欣 ，段春迎
（大连理工大学 精细化工国家重点实验室，辽宁 大连 116024）

摘要：以烯丙基胺类化合物为底物，Togni′s Reagent Ⅱ〔1-（三氟甲基）-1,2-苯碘酰-3(1H)-酮〕为三氟甲基源，
CO 2 或 CS 2 为 C1 合成子，高稳定性金属有机框架 HKUST-1 的 Cu 2 (O 2 C) 4 双轮桨节点的单位点铜为催化剂，在
温和条件下耦合 CO 2 /CS 2 成环与三氟甲基化反应。对碱性添加剂、溶剂、反应温度、催化剂负载量等反应条件
进行了优化。结果表明，在 5%的 HKUST-1〔以底物 N-苄基-2-苯基丙烯-2-烯-1-胺（1a）的物质的量为基准计算
得到。HKUST-1 的添加量基于 Cu 2 (O 2 C) 4 双轮桨节点（催化剂最简分子结构式为 Cu 2 (BTC) 4/3 •2H 2 O，摩尔质量
为 439.28 g/mol）的摩尔质量计算，下同〕、CO 2 压力为 101.325 kPa、45 ℃的最佳反应条件下，含不同取代基
的底物能以 69%~87%的产率得到三氟甲基-唑烷酮医药中间体。自由基捕获实验验证了该反应可能的反应机
理。催化剂 HKUST-1 可循环使用 4 次仍保持良好催化活性和晶态结构。使用 CS 2 替代 CO 2 时，可得到具有中枢
神经调节作用的三氟甲基-噻唑烷硫酮衍生物，体现出该体系对硫毒化的耐受性。
关键词：金属有机框架；铜催化；三氟甲基化；二氧化碳；二硫化碳；唑烷酮；噻唑烷硫酮；催化技术
中图分类号：TQ426.61 文献标识码：A 文章编号：1003-5214 (2020) 09-1839-08

Cyclization of CO 2/CS 2 coupled with trifluoromethylation catalyzed

by single-site copper within HKUST-1

*
ZANG Hanbin, LI Mochen, ZHANG Tiexin , DUAN Chunying
（State Key Laboratory of Fine Chemicals, Dalian University of Technology, Dalian 116024, Liaoning, China）

Abstract: Cyclization of CO 2 (or CS 2) coupled with trifluoromethylation was carried out taking allylamine
as substrate, Togni's Reagent Ⅱ[1-(trifluoromethyl)-1,2-benziodoxol-3(1H)-one] as source of trifluoromethyl,
single-site copper of highly stable metal-organic framework (MOF) HKUST-1[based upon the Cu 2(O 2C) 4
bis-paddelwheel, the simplest molecular structure of catalyst is Cu 2(BTC) 4/3 •2H 2O, and the relative
molecular weight is about 439.28 g/mol] as catalyst. The factors affecting the reaction such as basic additive,
solvent, reaction temperature, loading amount of HKUST-1 were optimized. The results showed that
allylamine substrates bearing different substituent groups could been transformed into bioactive
trifluoromethylated 2-oxazolidones in yields of 69%~87% under the optimal conditions of 5% HKUST-
1[based on the molar mass of substance 3-benzyl-5-phenyl-5-(2,2,2-trifluoroethyl)oxazolidin-2-one (1a)],
CO 2 pressure 101.325 kPa, reaction temperature 45 ℃. The possible mechanism of the reaction was
verified by free radical trapping experiment. The catalyst HKUST-1 could be easily recovered and reused
for at least four times and still had good catalytic activity and crystal structure. When CS 2 was used as C1
source instead of CO 2, the analogue of central nervous system agent, trifluoromethylated 2-
thiazolidinethione could be obtained, reflecting the durability of this heterogeneous catalytic system against
sulfur-poisoning effect.

收稿日期：2020-04-20; 定用日期：2020-05-19; DOI: 10.13550/j.jxhg.20200335
基金项目：国家自然科学基金（21971031、21890381、U1608224）
作者简介： 臧瀚彬（1993—），男，硕士生，E-mail：911323626@qq.com。联系人：张铁欣（1983—），男，副教授，E-mail：
zhangtiexin@dlut.edu.cn。