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Metal complex catalyst, and preparation method and application thereof

A technology of metal complexes and preparation methods, which can be applied in the directions of organic compound/hydride/coordination complex catalysts, physical/chemical process catalysts, catalytic reactions, etc., can solve the problems of increased production cost, difficult separation, etc., and achieve excellent catalysis The effect of hydrogenation performance

Inactive Publication Date: 2019-07-12
CHIZHOU UNIV
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

[0006] The present invention aims at the use of a large number of additives in the actual application of traditional M-NH catalysts, which on the one hand leads to an increase in production costs, and on the other hand causes difficulties in subsequent separations and other related problems, and provides a class of phosphine amines and diamine complexes containing secondary amine functional groups. Bulk transition metal complex catalyst, which can efficiently catalyze the hydrogenation of carbonyl derivatives such as aldehydes, ketones, esters, etc.

Method used

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  • Metal complex catalyst, and preparation method and application thereof
  • Metal complex catalyst, and preparation method and application thereof
  • Metal complex catalyst, and preparation method and application thereof

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0036] metal complex catalyst (o-PPh 2 C 6 h 4 NH 2 ) 2 RuCl 2 Preparation of (I-A-1):

[0037] Step (1): under an inert atmosphere, weigh 0.48g (PPh 3 ) 3 RuCl 2 (0.5mmol) and 0.14g o-Ph 2 PC 6 h 4 NH 2 (0.5 mmol) in a Schlenk bottle (100 mL) containing about 40 mL of toluene, and heated to 70° C. in a sealed manner. After reacting overnight, the reaction solution was cooled to room temperature, collected by filtration and washed with n-hexane to generate precipitates, dried under reduced pressure, weighed 0.31g (yield 87%), and obtained intermediate i[(PPh 3 )(o-Ph 2 PC 6 h 4 NH 2 )RuCl 2 ] 2 ;

[0038] Step (2): Under an inert atmosphere, weigh 0.29g of intermediate i (0.2mmol) obtained in step 1 and 0.11g of o-Ph 2 PC 6 h 4 NH 2 (0.4 mmol) in a Schlenk bottle (100 mL) containing about 30 mL of toluene, and heated to 100°C in a sealed manner. After one day of reaction, the resulting yellow-green solid precipitate was collected by filtration and washe...

Embodiment 2

[0043] metal complex catalyst (o-PPh 2 C 6 h 4 NHMe) 2 RuCl 2 Preparation of (I-A-2):

[0044] Step (1): Under an inert atmosphere, weigh 0.48g RuCl 2 (DMSO) 4 (1.0mmol) and 0.29g o-Ph 2 PC 6 h 4 NHMe (1.0 mmol) was placed in a Schlenk bottle (100 mL) containing about 40 mL of tetrahydrofuran, and heated to 70°C in a sealed manner. After reacting overnight, the resulting precipitate was collected by filtration and washed with n-hexane, dried under reduced pressure, and weighed 0.40 g (yield 64%) to obtain the intermediate i(o-Ph 2 PC 6 h 4 NHMe)RuCl 2 (DMSO) 2 ;

[0045] Step (2): Under an inert atmosphere, weigh 0.18g of intermediate i (0.3mmol) obtained in step 1 and 87.0mg of o-Ph 2 PC 6 h 4 NHMe (0.3 mmol) was placed in a Schlenk bottle (100 mL) containing about 30 mL of toluene, and heated to 100°C in a sealed manner. After one day of reaction, the reaction solution was concentrated to about 1 mL and then about 5 mL of n-hexane was added. The orange prec...

Embodiment 3

[0050] metal complex catalyst (o-PPh 2 C 6 h 4 NHEt) 2 RuCl 2 Preparation of (I-A-3):

[0051] Step (1): Under an inert atmosphere, weigh 0.48g RuCl 2 (DMSO) 4 (1.0mmol) and 0.30g o-Ph 2 PC 6 h 4 NHEt (1.0 mmol) was heated to 70°C in a Schlenk bottle (100 mL) containing about 40 mL of tetrahydrofuran. After reacting overnight, the resulting precipitate was collected by filtration and washed with n-hexane, dried under reduced pressure, and weighed 0.44 g (yield 70%) to obtain intermediate i(o-Ph 2 PC 6 h 4 NHEt)RuCl 2 (DMSO) 2 ;

[0052] Step (2): Under an inert atmosphere, weigh 0.19g of intermediate i (0.3mmol) obtained in step 1 and 91.6mg of o-Ph 2 PC 6 h 4 NHEt (0.3 mmol) was heated to 100°C in a Schlenk bottle (100 mL) containing about 30 mL of toluene. After reacting for four days, the reaction solution was concentrated to about 1 mL and then 5 mL of n-hexane was added. The resulting pale orange precipitate was collected by filtration and washed with n-...

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Abstract

The invention provides a secondary amine functional group-containing phosphonamine and diamine ligand transition metal complex catalyst, and a preparation method and an application thereof, and relates to a metal complex catalyst capable of efficiently catalyzing hydrogenation of esters, aldehydes, ketones and other carbonyl derivative molecules at a low dosage of an assistant to produce alcohols.The metal center of the catalyst is coordinated with an o-PPh2C6H4NHR1 ligand and an o-PPh2C6H4NHR2 ligand or o-PPh2C6H4NHR1 ligand and an R2HNCH2CH2NHR3 ligand, and the catalyst can be prepared by asimple two-step synthesis method. The catalyst can achieve an excellent catalytic hydrogenation performance only through using a small amount of the assistant alkali when participating in the catalytic hydrogenation reaction, and effectively overcomes the defect of a large amount of the assistant needed by conventional catalysts composed of primary amine ligands.

Description

technical field [0001] The invention relates to a phosphine amine containing a secondary amine functional group, a diamine ligand transition metal complex catalyst and a preparation method and application thereof, belonging to the technical field of industrial catalytic carbonyl derivative molecule hydrogenation to alcohol. Background technique [0002] Since Noyori et al. reported in 1995 that adding 1 times the equivalent of ethylenediamine ligands in the reaction system can significantly improve the reactivity of the phosphine-Ru(II) catalyst system to catalyze the hydrogenation of aromatic ketones (J.Am.Chem.Soc.1995 , 117, 2675-2676), M-NH complex catalysts based on diphosphine, diamine and phosphoamine ligands (M is a late transition metal, such as Ru, Os, Ir, etc.) Significant progress has been made in the study of derivatives hydrogenation to alcohols (WO2006106483, WO 2006106484, Org. Process Res. Dev. 2014, 18, 289-302). Theoretical and experimental results show t...

Claims

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Application Information

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IPC IPC(8): C07F15/00B01J31/24C07C67/31C07C69/675
CPCB01J31/2404B01J2231/641B01J2531/0241B01J2531/821C07C67/31C07F15/0053C07C69/675
Inventor 方霄龙汪新段宁
Owner CHIZHOU UNIV
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