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A kind of method of ruthenium complex selective hydrogenation of dienone

Active Publication Date: 2022-03-11
WANHUA CHEM GRP CO LTD
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

[0007] To sum up, the selective hydrogenation of α, β-carbon-carbon double bonds of conjugated α, γ-dienones can facilitate the synthesis of a variety of important synthetic intermediates, but currently there is a lack of general and feasible methods in the known technical literature. Advanced technology, high yield, high selectivity to achieve the above conversion

Method used

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  • A kind of method of ruthenium complex selective hydrogenation of dienone
  • A kind of method of ruthenium complex selective hydrogenation of dienone
  • A kind of method of ruthenium complex selective hydrogenation of dienone

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Embodiment 1～12

[0036] Optimization of Conditions for Selective Hydrogenation of β-Ionone to Synthesis of Dihydroβ-Ionone

[0037] In the glove box, [Ru(COD)Cl 2 ] (57mg, 0.2mmol), BINAP (0.138g, 0.22mmol) and ethanol (10.0g) were added to a single-necked bottle equipped with a magnetic stirrer, and the stirring was started, and the metal precursor and the ligand were dissolved and coordinated for 10 minutes. , to obtain a light yellow catalyst solution, seal the one-mouth bottle, go out of the glove box, and inject it into the autoclave with a parallel flow pump under the protection of nitrogen. The autoclave has been replaced with nitrogen in advance, and the substrate β-ionone (19.622g, 0.1 mol), poisoning agent quinoline (261mg, 2.0mmol) and solvent ethanol (29.244g). After the catalyst is added, replace the nitrogen with hydrogen three times, 2.0MPa each time, and finally fill in 2.0MPa of hydrogen, turn on the autoclave for stirring and heat tracing, when the inner temperature of the r...

Embodiment 16

[0042] Selective Hydrogenation of β-Ionone to Synthesis of Dihydro β-Ionone

[0043] In the glove box, [Ru(COD)Cl 2] (57mg, 0.2mmol), dppf (0.123g, 0.22mmol) and acetone (10.0g) were added to a single-necked bottle equipped with a magnetic stirrer, and the stirring was started, and the metal precursor and the ligand were dissolved and coordinated for 10 minutes. , to obtain a light yellow catalyst solution, seal the one-mouth bottle, go out of the glove box, and inject it into the autoclave with a parallel flow pump under the protection of nitrogen. The autoclave has been replaced with nitrogen in advance, and the substrate β-ionone (19.622g, 0.1 mol), poisoning agent quinoline (261mg, 2.0mmol) and solvent acetone (29.244g). After the catalyst is added, replace the nitrogen with hydrogen three times, 2.0MPa each time, and finally fill in 2.0MPa of hydrogen, start the autoclave to stir, keep the inner temperature of the reactor at 20°C, start timing, keep the reaction for 3 ho...

Embodiment 17

[0045] Selective Hydrogenation of β-Ionone to Synthesis of Dihydro β-Ionone

[0046] In the glove box, [Ru(COD)Cl 2 ] (57mg, 0.2mmol), dppf (0.123g, 0.22mmol) and tetrahydrofuran (10.0g) were added to a single-necked bottle equipped with a magnetic stirrer, and the stirring was started, and the metal precursor and ligand were dissolved and coordinated for 10 minutes. , to obtain a light yellow catalyst solution, seal the one-mouth bottle, go out of the glove box, and inject it into the autoclave with a parallel flow pump under the protection of nitrogen. The autoclave has been replaced with nitrogen in advance, and the substrate β-ionone (19.622g, 0.1 mol), poisoning agent quinoline (261mg, 2.0mmol) and solvent tetrahydrofuran (29.244g). After the catalyst is added, replace the nitrogen with hydrogen three times, 2.0MPa each time, and finally fill in 4.0MPa of hydrogen, turn on the autoclave to stir, and keep the inner temperature of the reactor at 60°C, start timing, keep th...

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Abstract

The invention provides a method for selectively hydrogenating α, γ-unsaturated dienone with a ruthenium complex, in particular to a method for reducing α, γ-unsaturated dienone to the corresponding hydrogen under the action of a catalyst In the method for γ-unsaturated ketones, the catalyst used is a ruthenium complex, which is prepared in situ from a ruthenium precursor and a ligand. The main advantage of the present invention is that the catalyst is prepared in situ from metal precursors and ligands, and is easy to operate and has high catalyst activity; the addition of nitrogen-containing aromatic heterocyclic poisoning agents such as pyridine and quinoline effectively inhibits the production of γ-unsaturated ketones. Transition hydrogenation side reaction, good selectivity and low cost.

Description

technical field [0001] The invention belongs to the fields of fine chemicals and flavors and fragrances, and in particular relates to a method for selectively hydrogenating α, γ-diketenes from homogeneous ruthenium complexes to obtain γ-ketenes. Background technique [0002] Selective hydrogenation of α, β-carbon-carbon double bonds of conjugated α, γ-dienones is an important class of reactions. For example, selective hydrogenation of 6-methyl-3,5-heptadien-2-one can Obtain 6-methyl-5-hepten-2-one, which is an important synthetic intermediate of spices such as linalool, citral, citronellal, and ionone; β-ionone is selectively hydrogenated to dihydroβ - Ionone, which is a key intermediate in the synthesis of ambergris. Because α, γ-dienone contains three unsaturated double bonds, there are many different hydrogenation products in theory, and it is extremely challenging to control the selectivity of this type of reaction and realize the hydrogenation of α, β-carbon-carbon dou...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): C07C45/62C07C49/21C07C49/203
Inventor 沈稳黄文学张永振谢硕朱小瑞苏黎明
Owner WANHUA CHEM GRP CO LTD