均相催化丙二酸二甲酯加氢制1,3-丙二醇的研究

doi:10.6023/cjoc202202034

摘要/Abstract

将系列o-二苯基膦苯胺配体构成的Ru(II)配合物[(PPh₃)(o-PPh₂C₆H₄NH₂)RuCl₂]₂ (1)、(o-PPh₂C₆H₄NHR)₂RuCl₂ (R=H, 2; Me, 3; Et, 4; CH₂Ph, 5)和(o-PPh₂C₆H₄NH₂)[(CH₂NHR)₂]RuCl₂ (R=H, 6; Me, 7; Et, 8; ⁱPr, 9)应用于催化丙二酸二甲酯加氢制3-羟基丙酸甲酯或1,3-丙二醇. 围绕催化加氢性能, 系统探究了配合物结构、助剂种类及用量以及溶剂等反应条件对底物转化率和目标产物收率的影响. 研究发现, 配合物8性能最优. 同时, 配合物8在催化丙二酸二乙酯等二酯类分子加氢制醇反应中也表现出一定的催化活性.

关键词: 钌, o-二苯基膦苯胺, 丙二酸二甲酯, 1,3-丙二醇

Ruthenium complexes [(PPh₃)(o-PPh₂C₆H₄NH₂)RuCl₂]₂ (1), (o-PPh₂C₆H₄NHR)₂RuCl₂ (R=H, 2; Me, 3; Et, 4; CH₂Ph, 5) and (o-PPh₂C₆H₄NH₂)[(CH₂NHR)₂]RuCl₂ (R=H, 6; Me, 7; Et, 8; ⁱPr, 9) were applied to the catalytic hydrogenation of dimethyl malonate into methyl 3-hydroxypropanoate or 1,3-propanediol. Targeting on the objective of the catalytic hydrogenation efficiency, the influence factors on the dimethyl malonate conversion and methyl 3-hydroxypropanoate or 1,3-propanediol selectivity, such as the structure of the ruthenium complex, the type and amount of the catalyst assistant and solvent, were well investigated. The results revealed that complex 8 resulted in the best catalytic results. Meanwhile, complex 8 could also catalyze the hydrogenation of diesters such as diethyl malonate.

Key words: ruthenium, o-(diphenylphosphino)aniline, dimethyl malonate, 1,3-propanediol

引用此文

方霄龙, 李斌, 金杰, 段宁. 均相催化丙二酸二甲酯加氢制1,3-丙二醇的研究[J]. 有机化学, 2022, 42(5): 1407-1413.

Xiaolong Fang, Bin Li, Jie Jin, Ning Duan. Homogeneous Catalytic Hydrogenation of Dimethyl Malonate into 1,3-Propanediol[J]. Chinese Journal of Organic Chemistry, 2022, 42(5): 1407-1413.

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Entry	Ru/mol%	p(H₂)/MPa	Time/h	Conv.^b/%	Yield^b/%
Entry	Ru/mol%	p(H₂)/MPa	Time/h	Conv.^b/%	3-HPM	1,3-PDO	MP	Others^c
1	2	5	16	100	37	57	2	4
2	2	5	24	100	0	92 (84)^d	2	6
3^e	1	5	16	100	—	95	2	3
4	1	2	24	85	74	4	4	3
5	1	5	24	100	40	52	1	7
6	0.4	5	24	88	72	8	2	6

Entry	Ru/mol%	p(H₂)/MPa	Time/h	Conv.^b/%	Yield^b/%
Entry	Ru/mol%	p(H₂)/MPa	Time/h	Conv.^b/%	3-HPM	1,3-PDO	MP	Others^c
1	2	5	16	100	37	57	2	4
2	2	5	24	100	0	92 (84)^d	2	6
3^e	1	5	16	100	—	95	2	3
4	1	2	24	85	74	4	4	3
5	1	5	24	100	40	52	1	7
6	0.4	5	24	88	72	8	2	6