三齿P配体钌络合物催化脂肪醇胺N-烷基化反应研究

doi:10.6023/cjoc202412019

有机化学 ›› 2025, Vol. 45 ›› Issue (8): 2983-2988.DOI: 10.6023/cjoc202412019 上一篇下一篇

研究论文

三齿P配体钌络合物催化脂肪醇胺N-烷基化反应研究

刘丽强^a, 南军^a^,^*(), 段兴宇^a, 王昊龙^a, 蔡巷^a, 王梓诚^a, 张恩泽^b, 孙彦民^a

^a 中海油天津化工研究设计院有限公司天津 300131
^b 天津工业大学化学工程与技术学院天津 300387

收稿日期:2024-12-23 修回日期:2025-02-24 发布日期:2025-03-13
基金资助:
中国海洋石油集团有限公司重大科技(CNOOC-KJ 145 FZDXM 00 TJY 001 TJY 2021)

N-Alkylation of Aliphatic Alcohol Amine Catalyzed by Tridentate P Ligand Ruthenium Complex

Liqiang Liu^a, Jun Nan^a^,^*(), Xingyu Duan^a, Haolong Wang^a, Xiang Cai^a, Zicheng Wang^a, Enze Zhang^b, Yanmin Sun^a

^a CNOOC Tianjin Chemical Research and Design Institute Co., Ltd., Tianjin 300131
^b School of Chemical Engineering and Technology, Tiangong University, Tianjin 300387

Received:2024-12-23 Revised:2025-02-24 Published:2025-03-13
Contact: *E-mail:nanjun@cnooc.com.cn
Supported by:
Major Scientific and Technological Projects of China National Offshore Oil Corporation(CNOOC-KJ 145 FZDXM 00 TJY 001 TJY 2021)

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摘要/Abstract

过渡金属配合物催化醇与胺的N-烷基化反应已成为制备含氮化合物的重要方法之一. 报道了一种三齿膦配体钌络合物催化的乙醇胺分子间的高效N-烷基化反应, 成功制备出了多乙烯多胺. 考察了催化剂投料比、反应温度及反应时间等因素对反应性能的影响, 得到了最佳工艺条件: 催化剂用量为0.20 mol%, 在四氢呋喃溶剂中于150 ℃反应24 h, 反应转化率高达99%. 此外, 对反应催化机理进行了深入分析, 探讨了催化剂的活化与失活过程, 并预测了反应循环机制, 为脂肪族多元醇胺通过缩聚反应制备高分子含氮化合物的合成提供了借鉴和理论依据.

关键词: 三齿P配体, 钌络合物, 脂肪族醇胺, N-烷基化

The N-alkylation reaction of alcohols and amines catalyzed by transition metal complexes has emerged as an important repertoire for the synthesis of nitrogen-containing compounds. An efficient intermolecular N-alkylation reaction of ethanol amines catalyzed by a tridentate phosphine ligand ruthenium complex to successfully prepare polyethylene polyamines was reported. The effects of factors such as catalyst feed ratio, reaction temperature, and reaction time on the reaction performance were studied, and the optimal process conditions were obtained. Using 0.20 mol% catalyst, the reaction was carried out at 150 ℃ for 24 h with tetrahydrofuran as solvent, and the reaction conversion rate was as high as 99%. In addition, the catalytic mechanism of the reaction was analyzed, the deactivation and activation process of the catalyst was investigated, and the reaction cycle mechanism was predicted, which provided a reference and theoretical basis for the synthesis of polymeric nitrogen-containing compound prepared by polycondensation of aliphatic polyol amines.

Key words: tridentate P ligand, ruthenium complex, aliphatic alcohol amine, N-alkylation

引用此文

刘丽强, 南军, 段兴宇, 王昊龙, 蔡巷, 王梓诚, 张恩泽, 孙彦民. 三齿P配体钌络合物催化脂肪醇胺N-烷基化反应研究[J]. 有机化学, 2025, 45(8): 2983-2988.

Liqiang Liu, Jun Nan, Xingyu Duan, Haolong Wang, Xiang Cai, Zicheng Wang, Enze Zhang, Yanmin Sun. N-Alkylation of Aliphatic Alcohol Amine Catalyzed by Tridentate P Ligand Ruthenium Complex[J]. Chinese Journal of Organic Chemistry, 2025, 45(8): 2983-2988.

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参考文献 41

[1]	Bähn, S.; Imm, S.; Neubert, L.; Zhang, M.; Neumann, H.; Beller, M. ChemCatChem. 2011, 3, 1853.
[2]	Abdel-Magid, A. F.; Mehrman, S. J. Org. Process Res. Dev. 2006, 10, 971.
[3]	Salvatore, R. N.; Yoon, C. H.; Jung, K. W. Tetrahedron 2001, 57, 7785.
[4]	Prabha, D.; Pachisia, S.; Gupta, R. Inorg. Chem. Front. 2021, 8, 1599.
[5]	Huang, M.; Li, Y.; Lan, X.-B.; Liu, J.; Zhao, C.; Liu, Y.; Ke, Z. Org. Biomol. Chem. 2021, 19, 3451. doi: 10.1039/d1ob00362c pmid: 33899900
[6]	Midya, S. P.; Mondal, A.; Begum, A.; Balaraman, E. Synthesis 2017, 49, 3957.
[7]	Junge, K.; Wendt, B.; Shaikh, N.; Beller, M. Chem. Commun. 2010, 46, 1769.
[8]	Yeung, C. S.; Dong, V. M. Chem. Rev. 2011, 111, 1215.
[9]	Castillo, J.-C.; Orrego-Hernández, J.; Portilla, J. Eur. J. Org. Chem. 2016, 2016, 3824.
[10]	Yang, Q.; Wang, Q.; Yu, Z. Chem. Soc. Rev. 2015, 44, 2305. doi: 10.1039/c4cs00496e pmid: 25661436
[11]	Elangovan, S.; Neumann, J.; Sortais, J. B.; Junge, K.; Darcel, C.; Beller, M. Nat. Commun. 2016, 7, 12641.
[12]	Crabtree, R. H. Organometallics 2011, 30, 17.
[13]	Leonard, J.; Blacker, A. J.; Marsden, S. P.; Jones, M. F.; Mulholland, K. R.; Newton, R. Org. Process Res. Dev. 2015, 19, 1400.
[14]	Nandakumar, A.; Midya, S. P.; Landge, V. G.; Balaraman, E. Angew. Chem., Int. Ed. 2015, 54, 11022.
[15]	Huang, M.; Li, Y.; Liu, J.; Lan, X.-B.; Liu, Y.; Zhao, C.; Ke, Z. Green Chem. 2019, 21, 219. doi: 10.1039/c8gc02298d
[16]	Ramachandran, R.; Prakash, G.; Vijayan, P.; Viswanathamurthi, P.; Malecki, J. G. Inorg. Chim. Acta 2017, 464, 88.
[17]	Ranjan, R.; Chakraborty, A.; Kyarikwal, R.; Ganguly, R.; Mukhopadhyay, S. Dalton Trans. 2022, 51, 13288.
[18]	Chen, H.; Wang, Q.; Liu, T.; Chen, H.; Zhou, D.; Qu, F. J. Coord. Chem. 2021, 74, 877. doi: 10.1080/00958972.2021.1881066
[19]	Ghanimati, M.; Abdoli Senejani, M.; Isfahani, T. M.; Bodaghifard, M. A. Appl. Organomet. Chem. 2018, 32, e4591.
[20]	Panigrahi, D.; Mondal, M.; Gupta, R.; Mani, G. RSC Adv. 2022, 12, 4510. doi: 10.1039/d1ra08961g pmid: 35425522
[21]	Zhang, C.; Liang, Q.; Yang, W.; Zhang, G.; Hu, M.; Zhang, G. Green Chem. 2022, 24, 7368.
[22]	Balamurugan, G.; Ramesh, R.; Malecki, J. G. J. Org. Chem. 2020, 85, 7125.
[23]	Huang, M.; Li, Y.; Li, Y.; Liu, J.; Shu, S.; Liu, Y.; Ke, Z. Chem. Commun. 2019, 55, 6213.
[24]	Fertig, R.; Irrgang, T.; Freitag, F.; Zander, J.; Kempe, R. ACS Catal. 2018, 8, 8525.
[25]	Savela, R.; Vogt, D.; Leino, R. Eur. J. Org. Chem. 2020, 2020, 3030.
[26]	Moutaoukil, Z.; Serrano-Díez, E.; Collado, I. G.; Jiménez-Tenorio, M.; Botubol-Ares, J. M. Org. Biomol. Chem. 2022, 20, 831. doi: 10.1039/d1ob02214h pmid: 35018948
[27]	Guin, A. K.; Pal, S.; Chakraborty, S.; Chakraborty, S.; Paul, N. D. J. Org. Chem. 2023, 88, 5944.
[28]	Ramachandran, R.; Prakash, G.; Selvamurugan, S.; Viswana- thamurthi, P.; Malecki, J. G.; Ramkumar, V. Dalton Trans. 2014, 43, 7889. doi: 10.1039/c4dt00006d pmid: 24705796
[29]	Blank, B.; Madalska, M.; Kempe, R. Adv. Synth. Catal. 2008, 350, 749.
[30]	Chakraborty, S.; Mondal, R.; Pal, S.; Guin, A. K.; Roy, L.; Paul, N. D. J. Org. Chem. 2023, 88, 771. doi: 10.1021/acs.joc.2c01773 pmid: 36577023
[31]	Jafarzadeh, M.; Sobhani, S. H.; Gajewski, K.; Kianmehr, E. Org. Biomol. Chem. 2022, 20, 7713.
[32]	Strautmann, J.; Schaub, T.; Hueffer, S.; Maas, S.; Wood, C. US 9550725, 2017.
[33]	Pingen, D.; Lutz, M.; Vogt, D. Organometallics 2014, 33, 1623.
[34]	Bakhmutov, V. I.; Bakhmutova, E. V.; Belkova, N. V.; Bianchini, C.; Epstein, L. M.; Masi, D.; Peruzzini, M.; Shubina, E. S.; Vorontsov, E. V.; Zanobini, F. Can. J. Chem. 2001, 79, 479.
[35]	Ye, X.; Plessow, P. N.; Brinks, M. K.; Schelwies, M.; Schaub, T.; Rominger, F.; Paciello, R.; Limbach, M.; Hofmann, P. J. Am. Chem. Soc. 2014, 136, 5923.
[36]	Pingen, D.; Lebl, T.; Lutz, M.; Nichol, G. S.; Kamer, P. C. J.; Vogt, D. Organometallics 2014, 33, 2798.
[37]	Derrah, E. J.; Hanauer, M.; Plessow, P. N.; Schelwies, M.; Da Silva, M. K.; Schaub, T. Organometallics 2015, 34, 1872.
[38]	Celaje, J. J. A.; Zhang, X.; Zhang, F.; Kam, L.; Herron, J. R.; Williams, T. J. ACS Catal. 2017, 7, 1136.
[39]	Nakagawa, N.; Derrah, E. J.; Schelwies, M.; Rominger, F.; Trapp, O.; Schaub, T. Dalton Trans. 2016, 45, 6856. doi: 10.1039/c5dt04870b pmid: 26880661
[40]	Gnanaprakasam, B.; Zhang, J.; Milstein, D. Angew. Chem., Int. Ed. 2010, 49, 1468.
[41]	Han, Z.; Rong, L.; Wu, J.; Zhang, L.; Wang, Z.; Ding, K. Angew. Chem., Int. Ed. 2012, 51, 13041.

Entry	Cat.	Dosage of Cat./mol%	Time/h	Conv.^b/%
1	Cat.1	0.25	24	10
2	Cat.2	0.25	24	>99
3	Cat.3	0.25	24	8
4	Cat.4	0.25	24	—
5	Cat.5	0.25	24	5

Entry	Cat.	Dosage of Cat./mol%	Time/h	Conv.^b/%
1	Cat.1	0.25	24	10
2	Cat.2	0.25	24	>99
3	Cat.3	0.25	24	8
4	Cat.4	0.25	24	—
5	Cat.5	0.25	24	5

Entry	Dosage of Cat./mol%	Conv.^b/%	M_w^c	PDI
1	0.25	>99	1607	2.20
2	0.20	>99	1555	2.18
3	0.10	70	1026	2.58
4	0.05	30	380	3.19
5	0.02	—	—

Entry	Dosage of Cat./mol%	Conv.^b/%	M_w^c	PDI
1	0.25	>99	1607	2.20
2	0.20	>99	1555	2.18
3	0.10	70	1026	2.58
4	0.05	30	380	3.19
5	0.02	—	—

Entry	Temp./℃	Conv.^b/%	M_w^c	PDI
1	70	—	—	—
2	110	10	166	3.22
3	150	>99	1555	2.18
4	170	>99	1234	2.34

三齿P配体钌络合物催化脂肪醇胺N-烷基化反应研究

N-Alkylation of Aliphatic Alcohol Amine Catalyzed by Tridentate P Ligand Ruthenium Complex

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Entry	Base	Additive	Conv.^b/%	M_w^c	PDI
1	—	—	>99	1555	2.18
2	^tBuOK	—	—	—	—
3	^tBuOK	2-Aminoethanol hydrochloride	>98	1346	2.42

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