环醚直接双羰基化合成α,ω-二元羧酸

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

摘要/Abstract

摘要：

二元羧酸是制备聚酰胺、聚酯和聚氨酯的重要中间体, 其传统合成途径具有一定的局限性. 以己二酸为例, 其主要工业生产工艺是利用硝酸氧化KA油, 该方法存在KA油产量低和产生大量温室气体N₂O等问题. 因此, 探索工艺绿色、原子有效和采用可再生原料的二元羧酸制备方法具有重要意义. 环醚和多元醇很容易从生物质原料中得到, 以它们为原料, 通过双羰基化直接制备二元羧酸, 是一种非常有潜力的反应途径. 但目前大多数文献报道由环醚或多元醇通过羰基化反应生成的产物主要是C+1单羧酸.

本课题组一直致力于碘催化生物质衍生的多元醇的加氢脱氧, 研究发现, 在特定的反应条件下, 多元醇可以选择性地形成多碘取代化合物的中间体. 受此启发, 本文报道了一种由环醚或多元醇形成二碘代物中间体, 然后直接通过双羰基化反应生成对应的C+2二羧酸的新策略. 由于己二酸是最重要的二元羧酸之一, 且四氢呋喃(THF)可以从丰富的生物质衍生的糠醛中获得, 本文重点研究了通过双羰基化反应直接利用THF合成己二酸. 在优化的反应条件下, 以铑盐为催化剂, 碘为促进剂, 乙酸和水为混合溶剂, 在170 °C, CO和H₂条件下, THF可以84%的产率转化为己二酸. 循环实验结果表明, 该催化体系在5次循环后仍能够稳定运行. 该催化体系不仅适用于各种环醚, 也适用于不同的伯二醇合成对应的C+2 α,ω-二元羧酸. 通过对反应中间体进行检测以及控制实验研究发现, 选择性生成1,4-二碘丁烷中间体是进一步双羰基化制备己二酸的关键, 而生成烯烃中间体和单碘代物中间体是形成副产物戊酸的主要原因. 在实验结果和文献研究基础上, 提出了THF转化为己二酸的反应机理. 在反应中, 活性铑常以Rh(I)的形式存在, 并且从质谱中观察到了[Rh(CO)₂I₂]⁻阴离子, 它可以在羰基化条件下由不同的铑前体(例如RhCl₃)经过CO和碘还原后衍生. 具体反应步骤为, 首先铑催化剂催化H₂和I₂生成HI, 然后THF与HI反应生成1,4-二碘丁烷中间体, 此中间体经过铑催化活化在两端分别进行羰基化反应, 最终生成产物己二酸. 通过质谱检测到两个推测的中间体, 进一步证实该反应机理.

综上, 本文为己二酸、戊二酸和其他重要的二羧酸(如1,7-庚二酸和1,8-辛二酸)的有效合成提供了一种新策略, 为二元羧酸的高效、绿色合成提供参考.

关键词: α,ω-二元羧酸, 双羰基化, 环醚, 多元醇, 己二酸

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

马长坡, 赖楹, 赵天歌, 张小炫, 刘海超, 杨维冉. 环醚直接双羰基化合成α,ω-二元羧酸[J]. 催化学报, 2024, 56: 122-129.

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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链接本文: https://www.cjcatal.com/CN/10.1016/S1872-2067(23)64577-2

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

图/表 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).

参考文献

[1]	R. Sang, P. Kucmierczyk, R. Duhren, R. Razzaq, K. Dong, J. Liu, R. Franke, R. Jackstell, M. Beller, Angew. Chem. Int. Ed., 2019, 58, 14365-14373.
[2]	M. T. Sabatini, L. T. Boulton, T. D. Sheppard, Sci. Adv., 2017, 3, e1701028.
[3]	J. Yang, J. Liu, Y. Ge, W. Huang, H. Neumann, R. Jackstell, M. Beller, Angew. Chem. Int. Ed., 2020, 59, 20394-20398.
[4]	X. Fang, H. Li, R. Jackstell, M. Beller, Angew. Chem. Int. Ed., 2014, 53, 9030-9034.
[5]	A. Tortajada, R. Ninokata, R. Martin, J. Am. Chem. Soc., 2018, 140, 2050-2053.
[6]	J. Han, Energy Convers. Manage., 2016, 129, 75-80.
[7]	Y. Wan, J.-M. Lee, ACS Catal., 2021, 11, 2524-2560.
[8]	D. R. Vardon, M. A. Franden, C. W. Johnson, E. M. Karp, M. T. Guarnieri, J. G. Linger, M. J. Salm, T. J. Strathmann, G. T. Beckham, Energy Environ. Sci., 2015, 8, 617-628.
[9]	R. T. Larson, A. Samant, J. Chen, W. Lee, M. A. Bohn, D. M. Ohlmann, S. J. Zuend, F. D. Toste, J. Am. Chem. Soc., 2017, 139, 14001-14004.
[10]	L. Zhao, B. Pudasaini, A. Genest, J. D. Nobbs, C. H. Low, L. P. Stubbs, M. van Meurs, N. Roesch, ACS Catal., 2017, 7, 7070-7080.
[11]	B. Xiao, M. Zheng, X. Li, J. Pang, R. Sun, H. Wang, X. Pang, A. Wang, X. Wang, T. Zhang, Green Chem., 2016, 18, 2175-2184.
[12]	G. S. Zhang, M. M. Zhu, Q. Zhang, Y. M. Liu, H. Y. He, Y. Cao, Green Chem., 2016, 18, 2155-2164.
[13]	G. Toyooka, K. I. Fujita, ChemSusChem, 2020, 13, 3820-3824.
[14]	W. Deng, L. Yan, B. Wang, Q. Zhang, H. Song, S. Wang, Q. Zhang, Y. Wang, Angew. Chem. Int. Ed., 2021, 60, 4712-4719.
[15]	M. J. Gilkey, A. V. Mironenko, D. G. Vlachos, B. Xu, ACS Catal., 2017, 7, 6619-6634.
[16]	L. Zhang, C. Ma, C. Wang, G. Sun, Y. Shu, W. Zou, T. Yang, W. Yang, Green Chem., 2022, 24, 7644-7651.
[17]	K. Cao, D. Fan, S. Zeng, B. Fan, N. Chen, M. Gao, D. Zhu, L. Wang, P. Tian, Z. Liu, Chin. J. Catal., 2021, 42, 1468-1477.
[18]	S. M. Xia, Z. W. Yang, K. H. Chen, N. Wang, L.-N. He, Chin. J. Catal., 2022, 43, 1642-1651.
[19]	J. B. Peng, H. Q. Geng, X. F. Wu, Chem, 2019, 5, 526-552.
[20]	J. B. Peng, F. P. Wu, X. F. Wu, Chem. Rev., 2019, 119, 2090-2127.
[21]	J. Yang, J. Liu., H. Neumann, R. Franke, R. Jackstell, M. Beller, Science, 2019, 366, 1514-1517.
[22]	Y. Wang, Q. Qian, J. Zhang, B. B. A. Bediako, Z. Wang, H. Liu, B. Han, Nat. Commun., 2019, 10, 5395.
[23]	B. B. Asare Bediako, Q. Qian, Y. Wang, J. Zhang, Z. Wang, S. Li, H. Liu, T. Wu, M. Ge, B. Han, Chem Catal., 2022, 2, 114-124.
[24]	T Li, P. Jin., Y. Zhang, K. Huang, J. Long, J. Jiang, S. Liu, A. Sen, W. Yang, Ind. Eng. Chem. Res., 2020, 59, 17173-17181.
[25]	T. Li, S. Liu, B. Wang, J. Long, J. Jiang, P. Jin, Y. Fu, H. Yu, W. Yang, Green Chem., 2019, 21, 4434-4442.
[26]	W. Yang, M. R. Grochowski, A. Sen, ChemSusChem, 2012, 5, 1218-1222.
[27]	Y. Zhu, J. Yang, F. Mei, X. Li, C. Zhao, Green Chem., 2022, 24, 6450-6466.
[28]	J. Zhan, R. Hu, X. Luo, C. Zhang, G. Luo, J. Fan, J. H. Clark, S. Zhang, Green Chem., 2022, 24, 1152-1164.
[29]	K. Tomishige, M. Yabushita, J. Cao, Y. Nakagawa, Green Chem., 2022, 24, 5652-5690.
[30]	H. Choi,N. E. Soland, B. L. Buss, N. C. Honeycutt, E. G. Tomashek, S. J. Haugen, K. J. Ramirez, J. Miscall, E. C. D. Tan, T. N. Smith, P. O. Saboe, E. M. Karp, Green Chem., 2022, 24, 1350-1361.
[31]	M. Besson, P. Gallezot, C. Pinel, Chem. Rev., 2014, 114, 1827-1870.
[32]	S. Chen, R. Wojcieszak, F. Dumeignil, E. Marceau, S. Royer, Chem. Rev., 2018, 118, 11023-11117.
[33]	L. Zhou, Y. Li, Y. Lu, S. Wang, Y. Zou, Chin. J. Catal., 2022, 43, 3142-3153.
[34]	W. Zhang, Y. Shi, Y. Yang, J. Tan, Q. Gao, Chin. J. Catal., 2022, 43, 3116-3125.
[35]	E. J. García-Suárez, A. M. Balu, M. Tristany, A. B. García, K. Philippot, R. Luque, Green Chem., 2012, 14, 1434-1439.
[36]	N. S. Biradar, A. A. Hengne, S. N. Birajdar, R. Swami, C. V. Rode, Org. Process. Res. Dev., 2014, 18, 1434-1442.
[37]	S. Sitthisa, D. E. Resasco, Catal. Lett., 2011, 141, 784-791.
[38]	Q. Qian, M. Cui, J. Zhang, J. Xiang, J. Song, G. Yang, B. Han, Green Chem., 2018, 20, 206-213.
[39]	Q. L. Qian, J. J. Zhang, M. Cui, B. X. Han, Nat. Commun., 2016, 7, 11481.
[40]	M. Cui, Q. Qian, J. Zhang, C. Chen, B. Han, Green Chem., 2017, 19, 3558-3565.
[41]	Q. Mei, H. Liu, X. Shen, Q. Meng, H. Liu, J. Xiang, B. Han, Angew. Chem. Int. Ed., 2017, 56, 14868-14872.
[42]	T. C. Wang, and W. H. Hu, J. Chem. Eng. Data, 2017, 62, 931-937.
[43]	Y. J. Sohn, M. Kang, M.-H. Ryu, S. Lee, K. H. Kang, Y. Hong, B. K. Song, K. Park, S. J. Park, J. C. Joo, H. T. Kim, Green Chem., 2022, 24, 1590-1602.
[44]	T. Coskun, C. M. Conifer, L. C. Stevenson, G. J. Britovsek, Chem. Eur. J., 2013, 19, 6840-6844.
[45]	K. X. Wang, H. F. Xu, W. S. Li, C. T. Au, X. P. Zhou, Appl. Catal. A, 2006, 304, 168-177.
[46]	Q. Mei, Y. Yang, H. Liu, S. Li, H. Liu, B. Han, Sci. Adv., 2018, 4, eaaq0266.