电子和空间位阻效应促进铱配合物催化1-丁醇经Guerbet反应选择制备2-乙基己醇

doi:10.1016/S1872-2067(20)63772-X

催化学报 ›› 2021, Vol. 42 ›› Issue (9): 1586-1592.DOI: 10.1016/S1872-2067(20)63772-X

电子和空间位阻效应促进铱配合物催化1-丁醇经Guerbet反应选择制备2-乙基己醇

许占威^a, 颜佩芳^a, 梁长慧^a^,^b, 贾松岩^c, 刘秀梅^a, 张宗超^a^,^*()

^a中国科学院大连化学物理研究所, 洁净能源国家实验室(筹), 催化国家重点实验室, 辽宁大连110623
^b中国科学院大学, 北京100049
^c沈阳化工大学化工学院, 辽宁沈阳110142

收稿日期:2020-12-25 接受日期:2021-01-22 出版日期:2021-09-18 发布日期:2021-05-16
通讯作者: 张宗超
作者简介:^* 电话/传真: (0411)84379462; 电子信箱: zczhang@yahoo.com
基金资助:
国家自然科学基金(21706255);国家自然科学基金(21932005);国家自然科学基金(21690084)

Electronic and steric factors for enhanced selective synthesis of 2-ethyl-1-hexanol in the Ir-complex-catalyzed Guerbet reaction of 1-butanol

Zhanwei Xu^a, Peifang Yan^a, Changhui Liang^a^,^b, Songyan Jia^c, Xiumei Liu^a, Z. Conrad Zhang^a^,^*()

^aState Key Laboratory of Catalysis, Dalian National Laboratory for Clean Energy, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023, Liaoning, China
^bUniversity of Chinese Academy of Sciences, Beijing 100049, China
^cCollege of Chemical Engineering, Shenyang University of Chemical Technology, Shenyang 110142, Liaoning, China

Received:2020-12-25 Accepted:2021-01-22 Online:2021-09-18 Published:2021-05-16
Contact: Z. Conrad Zhang
About author:^* Tel/Fax: +86-411-84379462; E-mail: zczhang@yahoo.com
Supported by:
National Natural Science Foundation of China(21706255);National Natural Science Foundation of China(21932005);National Natural Science Foundation of China(21690084)

摘要/Abstract

摘要：

2-乙基己醇是一种增塑剂醇, 可用于合成增塑剂、表面活性剂和溶剂等诸多化工领域. 目前工业上2-乙基己醇的合成是以化石资源丙烯为原料,与氢气和一氧化碳通过氢甲酰化反应制备1-丁醛, 后者经羟醛缩合和催化加氢反应生成2-乙基己醇. 由生物质发酵产生的1-丁醇为原料, 只需要经Guerbet反应可一步直接生成2-乙基己醇. 比较而言, Guerbet反应路线步骤更少, 且1-丁醇原位脱氢产生的氢为氢源, 无需额外氢, 因此比化石资源丙烯路线对环境友好. 目前, 文献报道的非均相催化1-丁醇Guerbet反应条件苛刻(如温度 > 170°C), 副产物多(如烯烃、醚和高碳醇等), 且均相催化剂的活性低.
本文报道了一类Cp*Ir(Cp*为1,2,3,4,5-五甲基环戊二烯基)配合物用于该Guerbet反应. 当Cp*Ir配合物的配体上修饰给电子基N,N-二甲基氨基和邻羟基时, Cp*Ir配合物的催化活性增强, 催化剂的转化数最高达到了14047. 当氢氧化钾和 Cp*Ir配合物(配体上修饰了N,N-二甲基氨基和邻羟基官能团)在1-丁醇中的浓度分别为1.7 mol%和0.04 wt%时, 在130°C反应48 h, 产物2-乙基己醇收率为23.9%, 选择性为89.5%. 核磁(NMR)研究结果表明, Cp*Ir配合物配体上的邻羟基与氢氧化钾反应脱除质子, 生成了羰基结构配体配位的Cp*Ir配合物, 继续催化1-丁醇脱氢反应. 机理研究表明, 中间产物2-乙基己醛α-碳上乙基的位阻效应和2-乙基己烯醛本身的共轭效应抑制了其继续发生羟醛反应, 从而提高了目标产物的选择性.

关键词: 2-乙基己醇, Guerbet反应, 1-丁醇, 铱, 加氢

Abstract:

1-Butanol is a potential bio-based fermentation product obtained from cellulosic biomass. As a value-added chemical, 2-ethyl-1-hexanol (2-EH) can be produced by Guerbet conversion from 1-butanol. This work reports the enhanced catalytic Guerbet reaction of 1-butanol to 2-EH by a series of Cp*Ir complexes (Cp*: 1,2,3,4,5-pentamethylcyclopenta-1,3-diene) coordinated to bipyridine-type ligands bearing an ortho-hydroxypyridine group with an electron-donating group and a Cl^- anion. The catalytic activity of the Cp*Ir complex increased by increasing the electron density of the bipyridine ligand when functionalized with the para-NMe₂ and ortho-hydroxypyridine groups. A record turnover number of 14047 was attained. A mechanistic study indicated that the steric effect of the ethyl group on the α-C of 2-ethylhexanal (2-EHA) and the conjugation effect of C=C-C=O in 2-ethylhex-2-enal (2-EEA) benefits the high selectivity of 2-EH from 1-butanol by inhibiting the cross-aldol reaction of 2-EHA and 2-EEA with butyraldehyde. Nuclear magnetic resonance study revealed the formation of a carbonyl group in the bipyridine-type ligand via the reaction of the Cp*Ir complex with KOH.

Key words: 2-Ethyl-1-hexanol, Guerbet reaction, 1-Butanol, Iridium, Hydrogenation

许占威, 颜佩芳, 梁长慧, 贾松岩, 刘秀梅, 张宗超. 电子和空间位阻效应促进铱配合物催化1-丁醇经Guerbet反应选择制备2-乙基己醇[J]. 催化学报, 2021, 42(9): 1586-1592.

Zhanwei Xu, Peifang Yan, Changhui Liang, Songyan Jia, Xiumei Liu, Z. Conrad Zhang. Electronic and steric factors for enhanced selective synthesis of 2-ethyl-1-hexanol in the Ir-complex-catalyzed Guerbet reaction of 1-butanol[J]. Chinese Journal of Catalysis, 2021, 42(9): 1586-1592.

×
扫码分享

导出引用管理器 EndNote|Ris|BibTeX

链接本文: https://www.cjcatal.com/CN/10.1016/S1872-2067(20)63772-X

https://www.cjcatal.com/CN/Y2021/V42/I9/1586

图/表 10

Scheme 1. Alternative route for the synthesis of 2-ethyl-1-hexanol.

Scheme 2. Chemical structures of Cp*Ir complexes in this work.

Table 1 Guerbet reaction of 1-butanol to 2-EH by using a Cp*Ir complex as catalyst.


Entry	Catalyst	T (°C )	TON	Selectivity (%)
Entry	Catalyst	T (°C )	TON	2-EHA	2-EEA	2-EHE	2-EH
1	[Cp*IrCl₂]₂	120	411	4.1	2.9	18.7	74.3
2	[Cp*IrClL1]Cl	120	629	3.8	7.6	26.6	62.0
3	[Cp*IrClL2]Cl	120	1124	3.5	6.9	27.6	62.0
4	[Cp*IrClL3]Cl	120	2900	1.1	6.1	15.0	77.8
5	[Cp*IrClL4]Cl	120	2192	1.3	5.4	17.7	75.6
6	[Cp*IrClL3]Cl	130	3492	0.7	4.5	8.4	86.4

Fig. 1. (a) Effect of the amount of KOH on TON by using the [Cp*IrClL3]Cl complex as the catalyst (conditions: 0.5 μmol of [Cp*IrClL3]Cl, and 2 g of 1-butanol under 10 bar of N2 atmosphere at 120 °C for 6 h); (b) The effect of the amount of KOH on the selectivity by using [Cp*IrClL3]Cl as the catalyst (conditions: 0.5 μmol of [Cp*IrClL3]Cl and 2 g of 1-butanol under 10 bar of N2 atmosphere at 120 °C for 6 h).

Scheme 3. Proposed pathways of the Guerbet reaction of 1-butanol to 2-EH.

Scheme 4. Steric and conjugation effects on product selectivity in the aldol reactions of butyraldehyde, 2-EHA, and 2-EEA. Reaction conditions: butyraldehyde (1 mmol), 2-EHA (0.5 mmol), 2-EEA (0.5 mmol), KOH (30 mg), 1-butanol (2 g), at 25 °C for 5 min.

Table 2 Control experiments for the hydrogenation of 2-EHA and 2-EHE.

Entry	Substrate	TOF (h^-1)	Selectivity (%)
1	—	—	—
2		1409	92.6
3		56	> 99

Scheme 5. The proposed reaction of [Cp*IrClL3]Cl complex with KOH.

Fig. 2. The 1H NMR and 13C NMR spectra of the [Cp*IrClL3]Cl complex with/without KOH. (a) The 1H NMR spectrum of [Cp*IrClL3]Cl without KOH; (b) The 1H NMR spectrum of [Cp*IrClL3]Cl with KOH; (c) The 13C NMR spectrum of [Cp*IrClL3]Cl without KOH; (d) The 13C NMR spectrum of [Cp*IrClL3]Cl with KOH.

Scheme 6. The proposed mechanism of the Guerbet reaction of 1-butanol to 2-EH.

参考文献

[1]	J. Ma, L. Xu, L. Xu, H. Wang, S. Xu, H. Li, S. Xie, H. Li, ACS Catal., 2013,3, 985-992.
[2]	S. K. Sharma, R. V. Jasra, Ind. Eng. Chem. Res., 2011,50, 2815-2821.
[3]	L. Zhao, Y. Wang, H. An, X. Zhao, Y. Wang, Catal. Commun., 2018,103, 74-77.
[4]	G. M. Torres, R. Frauenlob, R. Franke, A. Börner, Catal. Sci. Technol., 2015,5, 34-54.
[5]	Y. Li, X. Liu, H. An, X. Zhao, Y. Wang, Ind. Eng. Chem. Res., 2016,55, 6293-6299.
[6]	N. Liang, X. Zhang, H. An, X. Zhao, Y. Wang, Green Chem., 2015,17, 2959-2972.
[7]	R. L. Wingad, P. J. Gates, S. T. G. Street, D. F. Wass, ACS Catal., 2015,5, 5822-5826.
[8]	R. Mazzoni, C. Cesari, V. Zanotti, C. Lucarelli, T. Tabanelli, F. Puzzo, F. Passarini, E. Neri, G. Marani, R. Prati, F. Viganò, A. Conversano, F. Cavani, ACS Sustainable Chem. Eng., 2019,7, 224-237.
[9]	V. N. Panchenko, E. A. Paukshtis, D. Y. Murzin, I. L. Simakova, Ind. Eng. Chem. Res., 2017,56, 13310-13321.
[10]	G. R. M. Dowson, M. F. Haddow, J. Lee, R. L. Wingad, D. F. Wass, Angew. Chem. Int. Ed., 2013,52, 9005-9008.
[11]	R. L. Wingad, E. J. E. Bergström, M. Everett, K. J. Pellow, D. F. Wass, Chem. Commun., 2016,52, 5202-5204.
[12]	T. Moteki, D. W. Flaherty, ACS Catal., 2016,6, 4170-4183.
[13]	C. N. Neumann, S. J. Rozeveld, M. Yu, A. J. Rieth, M. Dincă, J. Am. Chem. Soc., 2019,141, 17477-17481.
[14]	K.-N. T. Tseng, S. Lin, J. W. Kampf, N. K. Szymczak, Chem. Commun., 2016,52, 2901-2904.
[15]	H. Aitchison, R. L. Wingad, D. F. Wass, ACS Catal., 2016,6, 7125-7132.
[16]	Y. Xie, Y. Ben-David, L. J. W. Shimon, D. Milstein, J. Am. Chem. Soc., 2016,138, 9077-9080.
[17]	H. Li, A. Riisager, S. Saravanamurugan, A. Pandey, R. S. Sangwan, S. Yang, R. Luque, ACS Catal., 2018,8, 148-187.
[18]	Q. Liu, G. Xu, X. Wang, X. Liu, X. Mu, ChemSusChem, 2016,9, 3465-3472.
[19]	G. Xu, T. Lammens, Q. Liu, X. Wang, L. Dong, A. Caiazzo, N. Ashraf, J. Guana, X. Mu, Green Chem., 2014,16, 3971-3977.
[20]	S. Chakraborty, P. E. Piszel, C. E. Hayes, R. T. Baker, W. D. Jones, J. Am. Chem. Soc., 2015,137, 14264-14267.
[21]	E. M. Green, Curr. Opin. Biotechnol., 2011,22, 337-343.
[22]	C. Jin, M. Yao, H. Liu, C.-F. Lee, J. Ji, Renew. Sust. Energy Rev., 2011,15, 4080-4106.
[23]	A. Prakash, R. Dhabhai, V. Sharma, Curr. Biochem. Eng., 2015,3, 37-46.
[24]	J. C. Liao, L. Mi, S. Pontrelli, S. Luo, Nat. Rev. Microbiol., 2016,14, 288-304.
[25]	M. H. S. A. Hamid, P. A. Slatford, J. M. J. Williams, Adv. Synth. Catal., 2007,349, 1555-1575.
[26]	G. E. Dobereiner, R. H. Crabtree, Chem. Rev., 2010,110, 681-703.
[27]	D. Liu, X. Chen, G. Xu, J. Guan, Q. Cao, B. Dong, Y. Qi, C. Li, X. Mu, Sci. Rep., 2016,6, 21365.
[28]	C. Carlini, A. Macinai, A. M. R. Galletti, G. Sbrana, J. Mol. Catal. A, 2004,212, 65-70.
[29]	V. N. Panchenko, E. A. Paukshtis, D. Yu. Murzin, I. L. Simakova, Ind. Eng. Chem. Res., 2017,56, 13310-13321.
[30]	T. Matsu-ura, S. Sakaguchi, Y. Obora, Y. Ishii, J. Org. Chem., 2006,71, 8306-8308.
[31]	G. Xu, T. Lammens, Q. Liu, X. Wang, L. Dong, A. Caiazzo, N. Ashraf, J. Guana, X. Mu, Green Chem., 2014,16, 3971-3977.
[32]	S. Hanspal, Z. D. Young, J. T. Prillaman, R. J. Davis, J. Catal., 2017,352, 182-190.
[33]	A. V. Chistyakov, P. A. Zharova, S. A. Nikolaev, M. V. Tsodikov, Catal. Today, 2017,279, 124-132
[34]	W. Y. Hernández, K. De Vlieger, S. Clerick, P. Van Der Voort, A. Verberckmoes, Catal. Commun., 2017,98, 94-97.
[35]	K. Sordakis, C. Tang, L. K. Vogt, H. Junge, P. J. Dyson, M. Beller, G. Laurenczy, Chem. Rev., 2018,118, 372-433.
[36]	K. Fujita, R. Kawahara, T. Aikawa, R. Yamaguchi, Angew. Chem. Int. Ed., 2015,54, 9057-9060.
[37]	K. Fujita, Y. Tanaka, M. Kobayashi, R. Yamaguchi, J. Am. Chem. Soc., 2014,136, 4829-4832.
[38]	W. P. Wu, Y. J. Xu, R. Zhu, M. S. Cui, X. L. Li, J. Deng, Y. Fu, ChemSusChem, 2016,9, 1209-1215.
[39]	Z. Xu, P. Yan, W. Xu, X. Liu, Z. Xia, B. Chung, S. Jia, Z. C. Zhang, ACS Catal., 2015,5, 788-792.
[40]	Z. Xu, P. Yan, H. Li, K. Liu, X. Liu, S. Jia, Z. C. Zhang, ACS Catal., 2016,6, 3784-3788.
[41]	N. Onishi, S. Xu, Y. Manaka, Y. Suna, W.-H. Wang, J. T. Muckerman, E. Fujita, Y. Himeda, Inorg. Chem., 2015,54, 5114-5123.
[42]	J. F. Hull, Y. Himeda, W.-H. Wang, B. Hashiguchi, R. Periana, D. J. Szalda, J. T. Muckerman, E. Fujita, Nat. Chem., 2012,4, 383-388.
[43]	W.-H. Wang, S. Xu, Y. Manaka, Y. Suna, H. Kambayashi, J. T. Muckerman, E. Fujita, Y. Himeda, ChemSusChem, 2014,7, 1976-1983.
[44]	W.-H. Wang, J. F. Hull, J. T. Muckerman, E. Fujita, Y. Himeda, Energy Environ. Sci., 2012,5, 7923-7926.
[45]	Y. Suna, M. Z. Ertem, W.-H. Wang, H. Kambayashi, Y. Manaka, J. T. Muckerman, E. Fujita, Y. Himeda, Organometallics, 2014,33, 6519-6530.
[46]	W.-H. Wang, M. Z. Ertem, S. Xu, N. Onishi, Y. Manaka, Y. Suna, H. Kambayashi, J. T. Muckerman, E. Fujita, Y. Himeda, ACS Catal., 2015,5, 5496-5504.
[47]	W.-H. Wang, J. T. Muckerman, E. Fujita, Y. Himeda, ACS Catal., 2013,3, 856-860.
[48]	W.-H. Wang, Y. Himeda, J. T. Muckerman, G. F. Manbeck, E. Fujita, Chem. Rev., 2015,115, 12936-12973.
[49]	K.-I. Fujita, N. Tanino, R. Yamaguchi, Org. Lett., 2007,9, 109-111.

电子和空间位阻效应促进铱配合物催化1-丁醇经Guerbet反应选择制备2-乙基己醇

Electronic and steric factors for enhanced selective synthesis of 2-ethyl-1-hexanol in the Ir-complex-catalyzed Guerbet reaction of 1-butanol

RichHTML

PDF

Supporting Information

可视化

摘要/Abstract

引用本文

使用本文

扫码分享

图/表 10

参考文献

相关文章 15

编辑推荐

Metrics

[1]	刘诗瑶, 巩玉同, 杨晓, 张楠楠, 刘会斌, 梁长海, 陈霄. 具有富电子镍位点的耐酸金属间化合物CaNi₂Si₂催化剂用于不饱和有机酸酐/酸的水相加氢[J]. 催化学报, 2023, 50(7): 260-272.
[2]	夏思源, 李奇远, 张仕楠, 许冬, 林秀, 孙露菡, 许景三, 陈接胜, 李国栋, 李新昊. Pd纳米立方体异质结尺寸依赖的电子界面效应对苯酚加氢反应的促进作用[J]. 催化学报, 2023, 49(6): 180-187.
[3]	张锋伟, 郭河芳, 刘萌萌, 赵阳, 洪峰, 李静静, 董正平, 乔波涛. 表面应力介导的碳基Pt纳米催化剂用于硝基芳烃的高选择性加氢[J]. 催化学报, 2023, 48(5): 195-204.
[4]	曾严, 王慧, 杨惠茹, 隽超, 李丹, 温晓东, 张帆, 邹吉军, 彭冲, 胡常伟. 镍纳米粒子耦合氧空位高效催化转化棕榈酸制备烷烃[J]. 催化学报, 2023, 47(4): 229-242.
[5]	Eun Hyup Kim, Min Hee Lee, Jeehye Kim, Eun Cheol Ra, Ju Hyeong Lee, Jae Sung Lee. 无碱CO₂加氢高效制甲酸Pd/g-C₃N₄催化剂的单原子和纳米簇的协同作用[J]. 催化学报, 2023, 47(4): 214-221.
[6]	杨成功, 王冬娥, 黄蓉, 韩健强, 塔娜, 马怀军, 曲炜, 潘振栋, 王从新, 田志坚. 高效稳定的MoS₂-TiO₂纳米复合催化剂用于浆态床菲催化加氢[J]. 催化学报, 2023, 46(3): 125-136.
[7]	刘玥, 章伟, 刘海超. 三氧化钨基催化剂在纤维素选择性转化合成二元醇反应中的活性相态[J]. 催化学报, 2023, 46(3): 56-63.
[8]	聂超, 龙向东, 刘琪, 王嘉, 展飞, 赵泽伦, 李炯, 席永杰, 李福伟. 原子分散Ru-P-Ru催化剂的制备及其在多类加氢中的高效应用[J]. 催化学报, 2023, 45(2): 107-119.
[9]	沙峰, 唐珊, 汤驰洲, 冯振东, 王集杰, 李灿. ZnZrO_x固溶体催化剂表面羟基在CO₂加氢制甲醇中的作用[J]. 催化学报, 2023, 45(2): 162-173.
[10]	李航杰, 肖月华, 肖佳乐, 范凯, 李炳宽, 李晓龙, 王亮, 肖丰收. 镓改性的铜基疏水催化剂用于CO₂选择性加氢制二甲醚的研究[J]. 催化学报, 2023, 54(11): 178-187.
[11]	顾宇, 王磊, 徐柏庆, 施慧. 金属-水界面催化的分子机制: 加氢与氧化反应[J]. 催化学报, 2023, 54(11): 1-55.
[12]	张宁, 杜家毅, 周纳, 王德鹏, 鲍迪, 钟海霞, 张新波. 高价金属钽掺杂无定型氧化铱用于酸性氧析出反应[J]. 催化学报, 2023, 53(10): 134-142.
[13]	周紫璇, 高鹏. 多相催化CO₂加氢直接合成大宗化学品与液体燃料[J]. 催化学报, 2022, 43(8): 2045-2056.
[14]	高广, 赵泽伦, 王嘉, 席永杰, 孙鹏, 李福伟. PtReO_x/TiO₂金属-氧化物-载体相互作用增强手性羧酸选择性加氢[J]. 催化学报, 2022, 43(8): 2034-2044.
[15]	王梦茹, 王奕, 牟效玲, 林荣和, 丁云杰. 1,3-丁二烯选择性加氢催化剂的设计策略以及构效关系[J]. 催化学报, 2022, 43(4): 1017-1041.