铜(I)催化生物质基平台化合物糠醛与直链醇的氧化-缩合反应

doi:10.6023/cjoc202107039

摘要/Abstract

作为已实现工业化生产的生物质平台化合物, 糠醛的高质化应用研究是当前能源化工领域的热点之一. 本工作以廉价易得的铜盐作为催化剂, 使用氧气为氧源, 实现了糠醛与直链醇的氧化-缩合反应过程. 其中, 在糠醛与正丙醇进行反应时, 糠醛的转化率和主产物3-(2-呋喃基)-2-甲基-2-丙烯醛选择性分别达94%和99%以上. 该方法具有反应温度较低、可操作性强和普适性好等优点, 通过“一锅法”串联过程实现了糠醛绿色、高效利用.

关键词: 糠醛, 氧化-缩合, 卤代铜盐, 氧气

In the face of the continuous consumption of fossil energy and the increasingly serious ecological damage, the synthesis of liquid fuels and high value-added fine chemicals from biomass-derived furfural has become one of the research hotspots in the field of energy and chemical industry. In this work, a highly efficient and selective aerobic oxidative condensation of furfural with straight-chain alcohol is achieved with simple copper(I) chloride as the catalyst. Therein, 3-(2- furanyl)-2-methyl-2-acrolein was synthesized by the oxidative condensation reaction of furfural with n-propanol under the mild conditions. As a result, it is found that the conversion of furfural and the selectivity of main product reached 94% and more than 99.9% in the presence of molecular oxygen, respectively. Moreover, the effects of basic additive, reaction time and temperature were further investigated in detail. In addition, oxidative condensation of different substrates was also successfully performed. This catalytic method provides a promising, green and sustainable technology for the valorization of biomass and biomass-based platform compounds.

Key words: furfural, oxidative condensation, halogenated copper salt, oxygen

引用此文

师静, 郭鹏飞, 李蔚, 孙海静, 孟令武, 仝新利. 铜(I)催化生物质基平台化合物糠醛与直链醇的氧化-缩合反应[J]. 有机化学, 2022, 42(3): 905-909.

Jing Shi, Pengfei Guo, Wei Li, Haijing Sun, Lingwu Meng, Xinli Tong. Copper(I)-Catalyzed Aerobic Oxidative Condensation of Biomass-Based Platform Compound Furfurals with Straight-Chain Alcohols[J]. Chinese Journal of Organic Chemistry, 2022, 42(3): 905-909.

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图/表 7

图式1. 糠醛与直链醇的氧化缩合反应

Scheme 1. Oxidative condensation reaction of the furfural and straight-chain alcohols

Entry^a	Catalysis	Conv.^b/%	Product^b/%
Entry^a	Catalysis	Conv.^b/%	3	4	Others
1	CuCl+LiOH	94	99.7	—	—
2	CuCl₂+LiOH	61	74	26	—
3	FeCl₃+LiOH	25	14	6	80
4	MnCl₂+LiOH	11	92	8	—
5	CuBr+LiOH	94	96	4	—
6	CuBr₂+LiOH	84	67	33	—
7	CuI+LiOH	95	87	13	—
8	CrCl₃+LiOH	23	62	34	4
9	LiOH	76	36	64	—
10	CuCl	32	—	—	100
11	None	20	—	—	100

表1. 糠醛与正丙醇氧化缩合反应的初步研究

Table 1. Preliminary study on the oxidation condensation reaction of the furfural with n-propanol

Entry^a	Basic additive	Conversion^b/%	Selectivity of 3^b/%
1	LiOH	94	99.7
2	NaOH	95	90
3	KOH	65	62
4	Ca(OH)₂	0	—
5	Na₂CO₃	8	—
6	K₂CO₃	7	—
7	CaCO₃	23	—
8	Li₂CO₃	15	—

表2. 不同助剂对氧化缩合反应的影响

Table 2. The impact of various additives on the oxidation condensation reaction

Entry ^a	Temp./℃	Time/h	Conversion^b/%	Selectivity of 3^b/%
1	100	4	94	99.1
2	80	4	94	99.7
3	60	4	94	99
4	40	4	58	92
5	20	4	35	69
6	60	0.5	68	86
7	60	1	69	>99.9
8	60	2	94	>99.9
9	60	6	95	99

表3. 反应条件优化

Table 3. Optimization of reaction conditions

图式2. 底物普适性研究

Scheme 2. Universal research of substrate

Entry	Catalytic systems	Reactants	Conversion^b/%	Selectivity of 3^b/%
1	CuCl+LiOH	FUR+n-propanol	94	99.7
2^c	CuCl+LiOH	FUR+n-propanol	68	55
3^d	CuCl+LiOH	FUR+propanal	89	>99.9
4^d	LiOH	FUR+propanal	86	>99.9
5^d	CuCl	FUR+propanal	50	—

表4. 糠醛和正丙醇间氧化-缩合反应的机理研究a

Table 4. Investigations on reaction mechanism of the oxidative condensation of furfural with n-propanol

图式3. 铜盐催化糠醛与正丙醇的氧化-缩合反应机理示意图

Scheme 3. Schematic diagram of oxidation condensation reaction mechanism between furfural and n-propanol catalyzed by copper salt

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