Direct synthesis of α,ω-dicarboxylic acids via dicarbonylation of cyclic ethers

doi:10.1016/S1872-2067(23)64577-2

Abstract

Abstract:

α,ω-Dicarboxylic acids are important intermediates for the preparation of polyamides, polyesters and polyurethanes. However, their production pathways are limited and usually suffer from low efficiency and environmental problems. Here, we report an innovative approach to synthesize C+2 dicarboxylic acids directly from cyclic ethers by dicarbonylation. Different from the general findings that C+1 monocarboxylic acids are produced by carbonylation of cyclic ethers involving alkene intermediates, in this work, by manipulating the reaction system with RhCl₃ and iodine in acetic acid, diiodide-substituted intermediates were selectively formed and subsequently converted to dicarboxylic acids in the presence of H₂ and CO. As high as 84% yield of adipic acid was obtained directly from tetrahydrofuran. This catalytic system is applicable not only to a wide variety of cyclic ethers but also to different primary diols to synthesize C2-elongated α,ω-dicarboxylic acids. This work provides a novel dicarbonylation strategy for the efficient synthesis of adipic acid, glutaric acid and other important α,ω-dicarboxylic acids (such as 1,7-heptanedioic acid and 1,8-octanedioic acid) that are still not easily synthesized by other methods.

Key words: α,ω-Dicarboxylic acid, Dicarbonylation, Cyclic ethers, Polyols, Adipic acid

Changpo Ma, Ying Lai, Tiange Zhao, Xiaoxuan Zhang, Haichao Liu, Weiran Yang. Direct synthesis of α,ω-dicarboxylic acids via dicarbonylation of cyclic ethers[J]. Chinese Journal of Catalysis, 2024, 56: 122-129.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(23)64577-2

https://www.cjcatal.com/EN/Y2024/V56/I1/122

Figures/Tables 9

Fig. 1. Main synthesis methods of adipic acid, as an representative example of α,ω-dicarboxylic acids.

Table 1 Catalytic system exploration for adipic acid synthesis from THF.


Entry	Catalyst	Promoter	Solvent	Conversion (%)	Yield of adipic acid (%)
1	RhCl₃	I₂	AcOH/H₂O	100	84.3
2	IrCl₃	I₂	AcOH/H₂O	98.1	6.1
3	RuCl₃	I₂	AcOH/H₂O	83.5	N. D
4	PdCl₂	I₂	AcOH/H₂O	80.3	N. D
5	NiCl₂	I₂	AcOH/H₂O	77.5	N. D
6	CoCl₂	I₂	AcOH/H₂O	70.2	N. D
7	[RhCl(COD)]₂	I₂	AcOH/H₂O	100	72.3
8	[RhCl(CO)₂]₂	I₂	AcOH/H₂O	100	80.9
9	RhCl₃	LiI	AcOH/H₂O	71.1	12.2
10	RhCl₃	NaI	AcOH/H₂O	69.8	11.4
11	RhCl₃	MgI₂	AcOH/H₂O	65.2	5.5
12	RhCl₃	CH₃I	AcOH/H₂O	49.6	8.6
13	RhCl₃	HI	AcOH/H₂O	100	84.5
14	RhCl₃	HCl	AcOH/H₂O	55.5	N. D
15	RhCl₃	HBr	AcOH/H₂O	63.4	N. D
16 ^a	RhCl₃	I₂	AcOH	100	50.0
17	RhCl₃	I₂	Propionic acid/H₂O	100	50.5
18	RhCl₃	I₂	CF₃COOH/H₂O	100	83.1
19	RhCl₃	I₂	DMI/H₂O	68.3	N. D

Fig. 2. (a) Effect of I2 amount on the reaction. Reaction conditions: 90 μmol Rh catalyst (based on the metal), I2, 1 mmol THF, 3 mL AcOH, 2 mL H2O, 3 MPa H2, 3 MPa CO, 170 °C, 10 h. (b) Effect of ratio of acetic acid to water on the reaction. Reaction conditions: 90 μmol Rh catalyst (based on the metal), 1 mmol I2, 1 mmol THF, AcOH+H2O 5 mL, 3 MPa H2, 3 MPa CO, 170 °C, 10 h. (c) Effect of temperature on the reaction. Reaction conditions: 90 μmol Rh catalyst (based on the metal), 1 mmol I2, 1 mmol THF, 3 mL AcOH, 2 mL H2O, 3 MPa H2, 3 MPa CO, 10 h. (d) Effect of H2 and CO pressure on the reaction. Reaction conditions: 90 μmol Rh catalyst (based on the metal), 1 mmol I2, 1 mmol THF, 3 mL AcOH, 2 mL H2O, H2, CO, 170 °C, 10 h. (ADA: adipic acid, VA: valeric acid, 2-MA: 2-methylbutanoic acid).

Table 2 Synthesis of dicarboxylic acids using various cyclic ethers and diols.

Entry	Substrate	Yield^a (%)	Product
1		80.4
2		84.3
3		73.5
4		72.9
5		81.1
6		78.9
7		79.1
8		79.3

Table 3 Synthesis of carboxylic acids using various ether substrates.

Entry	Yield^a (mol%)	Yield distribution
1	199	—
2	59.4	—
3	92.7	1:2 = 62:38
4	99	—
5	56.8	—
6	18	1:2 = 67:33
6	55	1:2 = 60:40
7	199	—
8	180	1:2 = 79:21
9	99	—
10	94.1	1:2 = 79:21

Fig. 3. Time course study of the reaction. Reaction conditions: 90 μmol Rh catalyst (based on the metal), 1 mmol I2, 1 mmol THF, 3 mL AcOH, 2 mL H2O, 3 MPa H2, 3 MPa CO, 170 °C. THF: tetrahydrofuran; ADA: adipic acid; VA: valeric acid; 2-MA: 2-methylbutyric acid.

Fig. 4. Mechanistic study. Reaction conditions: (a) 90 μmol Rh catalyst, 1 mmol THF, 2 mmol HI, 3 mL AcOH, 2 mL H2O, 3 MPa CO, 170 °C, 10 h. (b) 2 mmol THF, 4 mmol HI, 2 mL AcOH, 3 MPa H2, 100 °C, 3 h. (c) 50 μmol Rh catalyst, 0.3 mmol 4-iodo-1-butanol, 0.6 mmol I2, 5 mL AcOH, 3 MPa H2, 170 °C, 2 h. (d) 90 μmol Rh catalyst, 1 mmol 1,4-diiodobutane, 3 mL AcOH, 2 mL H2O, 3 MPa CO, 170 °C, 10 h. Source analysis of monocarboxylic acid byproducts. Reaction conditions: (e) 50 μmol Rh catalyst, 2 mmol THF, 2 mmol I2, 5 mL AcOH, 3 MPa H2, 170 °C, 2 h. (f) 50 μmol Rh catalyst, 2 mmol 1-butylene, 2 mmol I2, 5 mL AcOH, 3 MPa H2, 170 °C, 2 h. (g) 90 μmol Rh catalyst, 1 mmol 1-iodobutane, 3 mL AcOH, 2 mL H2O, 3 MPa CO, 170 °C, 10 h. (h) 90 μmol Rh catalyst, 1 mmol 2-iodobutane, 3 mL AcOH, 2 mL H2O, 3 MPa CO, 170 °C, 10 h.

Fig. 5. Source analysis of monoiodide intermediate. Reaction conditions: (a) 50 μmol Rh catalyst, 2 mmol ethylene glycol, 1.5 mmol I2, 5 mL AcOH, 3 MPa H2, 170 °C, 2 h. (b) 50 μmol Rh catalyst, 1 mmol 1,3-butanediol, 1 mmol I2, 5 mL AcOH, 3 MPa H2, 170 °C, 4 h.

Fig. 6. Proposed dicarbonylation mechanism for adipic acid synthesis from THF (Note: Rh represents the rhodium active center).

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