Homogeneous Catalytic Hydrogenation of Dimethyl Malonate into 1,3-Propanediol

doi:10.6023/cjoc202202034

Abstract

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

Cite this article

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

均相催化丙二酸二甲酯加氢制1,3-丙二醇的研究