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

doi:10.6023/cjoc202412019

Chinese Journal of Organic Chemistry ›› 2025, Vol. 45 ›› Issue (8): 2983-2988.DOI: 10.6023/cjoc202412019 Previous Articles Next Articles

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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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Abstract

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

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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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Fig. & Tab. 7

References 41

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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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