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Phosphine-ruthenium functionalized ionic liquid and preparation method thereof, catalyst and preparation method for 4-acetoxybutyraldehyde

An ionic liquid and acetoxy technology, which is applied in the preparation of organic compounds, physical/chemical process catalysts, organic compound/hydride/coordination complex catalysts, etc., can solve the problems of easy hydrolysis, weak coordination, and easy catalyst Inactivation and other problems, to achieve high conversion rate, high reaction conversion rate effect

Active Publication Date: 2019-04-02
WANHUA CHEM GRP CO LTD
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

However, this phosphite ligand has the disadvantages of instability and easy hydrolysis, and its coordination with rhodium is not strong, so the formed catalyst is easily deactivated at high temperature, which affects the separation and application of the catalyst.

Method used

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  • Phosphine-ruthenium functionalized ionic liquid and preparation method thereof, catalyst and preparation method for 4-acetoxybutyraldehyde
  • Phosphine-ruthenium functionalized ionic liquid and preparation method thereof, catalyst and preparation method for 4-acetoxybutyraldehyde
  • Phosphine-ruthenium functionalized ionic liquid and preparation method thereof, catalyst and preparation method for 4-acetoxybutyraldehyde

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Experimental program
Comparison scheme
Effect test

Embodiment 1

[0057] To prepare phosphine-ruthenium functionalized ionic liquid IL1, proceed as follows:

[0058] (1), under nitrogen protection, 3-picoline (13.97g, 0.15mol) was dissolved in tetrahydrofuran (540.83g, 7.5mol), and n-butyllithium hexane solution was added dropwise at -70°C ( 2M, 90mL) for 5 hours, followed by adding diphenylphosphine chloride (39.72g, 0.18mol) for 1.5 hours, and then warming up to room temperature for 12 hours. After the reaction, it was quenched with ammonium chloride. Spin dry under reduced pressure under the protection of nitrogen, and recrystallize with dichloromethane / methanol solution with a volume ratio of 1:10 to obtain a white solid Its nuclear magnetic analysis data are as follows: 1 H NMR (400MHz, CDCl 3 ,298K)δ=8.7(1H,dd,J=8.6Hz,2.4Hz, N CH =CH),8.0(1H,dd,J=8.6Hz,2.4Hz,CH 3 -C CH =CH), 7.2-7.5(11H, m, NCH= CH , Phenyl -P),2.3(3H,s, CH 3 ).

[0059] (2), (37.44g, 0.135mol) the product of step (1) was mixed with bromomethane tetrahydro...

Embodiment 2

[0066] Preparation of phosphine-ruthenium functionalized ionic liquid IL2 is carried out according to the following steps:

[0067] (1) Under nitrogen protection, dissolve 3-phenylpyridine (15.52g, 0.1mol) in tetrahydrofuran (1081.65g, 15mol), and add n-butyllithium hexane solution (2M , 100mL) to keep warm for 3h, then add diphenylphosphine chloride (44.13g, 0.2mol) to keep warm for 1h, then warm up to room temperature and react for 10h, after the reaction, quench with ammonium chloride, and the reaction solution is protected under nitrogen Spin dry under reduced pressure, and recrystallize with a dichloromethane methanol solution with a volume ratio of 10:1 to obtain a white solid Its nuclear magnetic analysis data are as follows: 1 H NMR (400MHz, CDCl 3 ,298K)δ=8.7(1H,dd,J=8.6Hz,2.5Hz, N CH =CH), 8.3(1H, dd, J=8.6Hz, 2.5Hz, Phenyl-C CH =CH),7.8(1H,t,J=8.6Hz, NCH CH =CH),7.3-7.5(15H,m, Phenyl group ).

[0068] (2), (31.22g, 0.09mol) step (1) product is mixed with mo...

Embodiment 3

[0074] Preparation of phosphine-ruthenium functionalized ionic liquid IL3 is carried out according to the following steps:

[0075] (1), under the protection of nitrogen, dissolve 3-picoline (9.31g, 0.1mol) in tetrahydrofuran (721.10g, 10mol), and add n-butyllithium hexane solution (2M , 80mL) to keep warm for 4h, then add diphenylphosphine chloride (35.30g, 0.16mol) to keep warm for 1h, then warm up to room temperature and react for 9h, after the reaction, quench with ammonium chloride, and the reaction solution is protected under nitrogen Spin dry under reduced pressure, and recrystallize with a dichloromethane / methanol solution with a volume ratio of 1:1 to obtain a white solid Its nuclear magnetic analysis data are as follows: 1 H NMR (400MHz, CDCl 3 ,298K)δ=8.7(1H,dd,J=8.6Hz,2.4Hz,N CH =CH),8.0(1H,dd,J=8.6Hz,2.4Hz,CH 3 -C CH =CH), 7.2-7.5(11H, m, NCH= CH , Phenyl -P),2.3(3H, s, CH 3 ).

[0076] (2), (25.79g, 0.09mol) the product of step (1) is mixed with mono...

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Abstract

The invention relates to a phosphine-ruthenium functionalized ionic liquid and a preparation method thereof, a catalyst and a preparation method for 4-acetoxybutyraldehyde. The catalyst containing thephosphine-ruthenium functionalized ionic liquid is utilized to catalyze a hydroformylation reaction of allyl acetate to generate the 4-acetoxybutyraldehyde, wherein the conversion rate of the reaction is up to 99%, and the yield of the 4-acetoxybutyraldehyde is up to 95.17% to 98.57%. The catalyst provided by the invention can be separated from a product only with the need of simple extraction and phase separation, can be directly used for a next reaction, and still can maintain high reaction conversion rate (larger than 99%) and high yield (larger than 95%) after being separated and reused for a plurality of times.

Description

technical field [0001] The invention relates to the field of hydroformylation reaction catalysts, in particular to a hydroformylation catalyst containing phosphine-ruthenium functionalized ionic liquid, and a method for using the catalyst to catalyze allyl acetate to generate 4-acetoxybutyraldehyde. Background technique [0002] 1,4-Butanediol (BDO for short) is an important organic and fine chemical raw material, which is widely used in the fields of medicine, chemical industry, textile, papermaking, automobile and daily chemical industry. BDO can produce polybutylene terephthalate (PBT), γ-butyrolactone (GBL) and polyurethane resin (PU Resin), coatings and plasticizers, etc., as well as solvents and brighteners in the electroplating industry Wait. [0003] The current industrial production process of BDO is that allyl alcohol undergoes a liquid-phase hydroformylation reaction to generate 4-hydroxybutyraldehyde under the action of a rhodium-triphenylphosphine system cataly...

Claims

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Application Information

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IPC IPC(8): B01J31/02B01J31/24C07C67/293C07C69/14
CPCB01J31/0285B01J31/2404B01J2231/321B01J2531/821C07C67/293C07C69/14Y02P20/584
Inventor 林龙黄真真张涛吕英东杨宗龙黎源朱龙龙程晓波王延斌张旭
Owner WANHUA CHEM GRP CO LTD
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