Copper(I)-Catalyzed Aerobic Oxidative Condensation of Biomass-Based Platform Compound Furfurals with Straight-Chain Alcohols

doi:10.6023/cjoc202107039

Chinese Journal of Organic Chemistry ›› 2022, Vol. 42 ›› Issue (3): 905-909.DOI: 10.6023/cjoc202107039 Previous Articles Next Articles

NOTES

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

师静, 郭鹏飞, 李蔚^*(), 孙海静, 孟令武, 仝新利^*()

天津理工大学化学化工学院天津 300384

收稿日期:2021-07-18 修回日期:2021-09-15 发布日期:2021-11-03
通讯作者: 李蔚, 仝新利
基金资助:
国家自然科学基金(21878235); 天津市研究生科研创新(2019YJSS058)

Copper(I)-Catalyzed Aerobic Oxidative Condensation of Biomass-Based Platform Compound Furfurals with Straight-Chain Alcohols

Jing Shi, Pengfei Guo, Wei Li(), Haijing Sun, Lingwu Meng, Xinli Tong()

School of Chemistry and Chemical Engineering, Tianjin University of Technology, Tianjin 300384

Received:2021-07-18 Revised:2021-09-15 Published:2021-11-03
Contact: Wei Li, Xinli Tong
Supported by:
National Natural Science Foundation of China(21878235); Research Innovation Program of Graduate Students in Tianjin(2019YJSS058)

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Abstract

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

Cite this article

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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Fig. & Tab. 7

References 24

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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

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

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	—

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	—

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	—

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

Copper(I)-Catalyzed Aerobic Oxidative Condensation of Biomass-Based Platform Compound Furfurals with Straight-Chain Alcohols

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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

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