CN101003456A - Method for preparing Beta, Gamma unsaturated ester - Google Patents
Method for preparing Beta, Gamma unsaturated ester Download PDFInfo
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- CN101003456A CN101003456A CN 200610000886 CN200610000886A CN101003456A CN 101003456 A CN101003456 A CN 101003456A CN 200610000886 CN200610000886 CN 200610000886 CN 200610000886 A CN200610000886 A CN 200610000886A CN 101003456 A CN101003456 A CN 101003456A
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Abstract
This invention discloses a method for preparing beta-gamma unsaturated ester from conjugated olefin. The method adopts conjugated olefin, CO and hydroxyl-containing compound as the raw materials, as well as palladium compound and diphosphine compound as the catalysts. The raw materials react in nonpolar or weak polar solvent to obtain beta-gamma unsaturated ester. Under optimized reaction conditions, the conjugated olefin can be converted completely, and the selectivity of the target product is higher than 96%. Besides, the catalysts can be recycled, and the TOF value of the catalyst system in a single use is up to 1432 h-1.
Description
Technical field
The present invention relates to a kind of conjugated alkene be carried out the method that carbonylation prepares Beta, Gamma unsaturated ester.Exactly (but being not limited thereto), the present invention relates to 1,3-butadiene, carbon monoxide and methyl alcohol is raw material, forms catalyzer with palladium compound and bidentate phosphine compound, in non-polar solvent or weak polar solvent, react, make the method for 3-amylene-4 acid methyl ester.
Background technology
External in recent years each big chemical company and some research institutions (for example DSM N. V., Shell company, DuPont company, BASF AG and Taiwan industrial research institute etc.) are when actively improving the prior art route of producing hexanolactam, having carried out is the research that starting raw material is produced hexanolactam with the divinyl, has obtained certain achievement.Wherein the Altam route of developing jointly with DSM N. V. and Shell company has application prospect most.
First segment process of Altam route is feedstock production 3-amylene-4 acid methyl ester and 4-amylene-4 acid methyl ester with 1,3-butadiene, carbon monoxide and methyl alcohol.3-and 4-amylene-4 acid methyl ester in fact all are the intermediate raw materials that utilizes Altam path of preparing hexanolactam, therefore utilize divinyl extremely important through the method that carbonylation reaction prepares amylene-4 acid methyl ester.For example United States Patent (USP) the 5th, 028, No. 734 (1991 years, Shell company), the 5th, 495, No. 041 (1996 years, DSM N. V. and DuPont company), the 6th, 010, No. 975 (2000 years, Taiwan industrial research institute), the 6th, No. 232262 (calendar year 2001, DSM N. V.) and the 6th, 737, No. 542 (2004, Shell company) all relate to the synthetic of amylene-4 acid methyl ester.Concrete outcome is as follows: at United States Patent (USP) the 5th, 028, in No. 734, the yield of 3-amylene-4 acid methyl ester is 75%, and a certain amount of 2-amylene-4 acid methyl ester of by-product simultaneously is so the catalyst system selectivity is not high; United States Patent (USP) the 5th, 495, the transformation efficiency of divinyl has only about 80% in No. 041, and the selectivity of 3-amylene-4 acid methyl ester is below 50%, so target product yield is low; United States Patent (USP) the 6th, 010, all about 92%, the TOF value of catalyst system therefor system is all at 212h for the selectivity of the transformation efficiency of divinyl and 3-amylene-4 acid methyl ester in No. 975
-1, below, so the efficient of catalyst system is low; United States Patent (USP) also exists the low problem of 3-amylene-4 acid methyl ester yield, the highest yield 75% for the 6th, No. 232262.At United States Patent (USP) the 6th, 737, the 3-amylene-4 acid methyl ester is a by product in No. 542, and its target product is two carbonylation products.This several patents is all formed catalyzer with palladium compound and bidentate phosphine compound basically.
Summary of the invention
The object of the present invention is to provide and a kind of conjugated alkene is carried out the method that carbonylation prepares Beta, Gamma unsaturated ester.
Preparation method provided by the invention, the selectivity of its target product 3-amylene-4 acid methyl ester reaches more than 96%, and the TOF value that the catalyst system single uses is up to 1432h
-1
For achieving the above object, the method for preparing Beta, Gamma unsaturated ester provided by the invention, with conjugated alkene, carbon monoxide and hydroxy-containing compounds are raw material, form catalyzer with palladium compound and bidentate phosphine compound, the consumption of bidentate phosphine compound in catalyzed reaction is 0.1-20 times of palladium compound mole dosage, in non-polar solvent or weak polar solvent, react, temperature of reaction system is 50-400 ℃, initial carbon monoxide pressure is 1-30 MPa, solvent is 10 with the mol ratio of conjugated alkene: 1-0.1: 1, the mol ratio of hydroxy-containing compounds and conjugated alkene is 0.1: 1-10: 1, conjugated alkene is 100 with the mol ratio of catalyzer: 1-100000: 1, reaction times be 1 minute to 20 hours, make Beta, Gamma unsaturated ester; Reaction formula is as follows:
Wherein, R and R ' are for replacing or non-substituted alkyl, and R ' can also be hydrogen (H); Catalyzer is made of following a, b two portions or by a, b, c three parts constitute:
A) palladium compound;
B) bidentate phosphine compound;
C) organic acid auxiliary agent;
The bidentate phosphine compound satisfies general formula I
The bidentate phosphine compound contains two phosphorus atom; R wherein
1-R
4Be C identical or different, that replace or do not have to replace
5-C
10Aryl, alicyclic group or C
5-C
10Alkyl; Be bridge linkage group between two phosphorus atom, X is heteroatomss such as N, O, S; Ar is the C that replaces or do not have to replace
5-C
10Aryl, especially C
6Phenyl ring; Except that the X bridging, two Ar bases can also be linked at together with other bridge linkage group (as alkyl carbon atoms) simultaneously; X encircles last two adjacent carbon atoms with Ar respectively with P and links to each other.The specific example of these compounds includes but not limited to: 4,5-two (diphenyl phosphine)-9,9-dimethyl-xanthene (Xantphos) and α, α '-two (diphenyl phosphine) phenylate, its structural formula respectively suc as formula 1 and formula 2 shown in.
The consumption of bidentate phosphine compound in catalyzed reaction generally is 0.1 to 20 times of used palladium compound mole dosage, and more excellent consumption is 1 to 10 times of palladium compound mole dosage, especially 1 to 3 times.
Palladium compound used among the present invention can provide from any source.The material that can be used as the palladium catalyst source comprises coordination compound of palladium salt, palladium oxide, organic palladium compound, palladium and composition thereof.The specific example of these compounds includes but not limited to: palladium Pd (OAc)
2, acetopyruvic acid palladium, hexafluoroacetylacetone acid palladium, Palladous chloride PdCl
2Deng.The preferred source of palladium catalyst comprises palladium Pd (OAc)
2, Palladous chloride PdCl
2Deng.
Used organic acid auxiliary agent is the phenylformic acid that replaces among the present invention.The specific example of these compounds includes but not limited to: 2, and 6-dimethoxybenzoic acid, 2,4,6-triisopropyl phenylformic acid, 2,4,6-tri-tert phenylformic acid, 2,6-di-isopropyl phenylformic acid, 2, the bigger substituted benzoyl acid compounds of spatial volume such as 6-di-tert-butyl benzoic acid.
Used conjugated alkene is C among the present invention
4-C
20Diolefine.The specific example of these compounds includes but not limited to 1,3-butadiene.
Used hydroxy-containing compounds is the alcohol that contains 1 to 20 carbon atom among the present invention, and can contain a plurality of oh groups.Especially straight or branched alkyl alcohol.The specific example of these compounds includes but not limited to methyl alcohol and ethanol.In reaction system, the mol ratio of pure and mild conjugated alkene is between 0.1: 1 to 10: 1, especially below 2: 1.
Catalyst body among the present invention has very high catalytic activity, and in the start material, conjugated alkene can be between 100: 1 to 100000: 1, especially between 3000: 1 to 50000: 1 with the mol ratio of catalyzer.
Catalyzed reaction among the present invention can be carried out in 50-400 ℃ temperature range, and it is too slow to be lower than 50 ℃ of reactions, infeasible on industrial application; Being higher than 300 ℃ has undesirable product to generate.Preferable reaction temperature is between 100-300 ℃, most preferably between 150-250 ℃.
The initial stagnation pressure that catalyzed reaction among the present invention is fit to is in 1-30 MPa scope, and preferred pressure is between 1-10 MPa, and most preferably pressure is between 3-8 MPa.
The suitable solvent of present method be those under reaction conditions with reactant and the compatible material of catalyst system.Such solvent comprises aromatic hydrocarbon solvent, halogenated hydrocarbon solvent, ether, ester or its mixed solvent.The benzene that replaces as benzene,toluene,xylene, trimethylbenzene and other alkyl, methyl-phenoxide, phenyl ether, 3-amylene-4 acid methyl ester, valerolactone etc.The higher organic solvent of boiling point such as methyl-phenoxide, phenyl ether preferably.
The reaction times of the catalyzed reaction among the present invention can be changed, and how it depend on selective reaction thing, solvent, catalyzer and organic acid auxiliary agent to also have their concentration and reaction conditionss separately, as temperature, pressure.Reaction times all was acceptable at 1 minute to 20 hours.
Reaction of the present invention can be carried out with intermittence or continuous mode.Product can with in the prior art by people general any technology of separating carry out Separation and Recovery, comprise as extraction, distillation etc., but be not limited only to this.
Embodiment
The following examples are in order to further specify special character of the present invention and favourable part, but scope not thereby limiting the invention.The data of being reported are based on the gas-chromatography yield of 3-amylene-4 acid methyl ester, i.e. the 3-amylene-4 acid methyl ester that reaction obtains after finishing is with the percentage ratio of the ratio of the 3-amylene-4 acid methyl ester that obtains for the benchmark Theoretical Calculation with the 1,3-butadiene.
Embodiment 1
Under nitrogen protection; in the 250ml autoclave, add 0.05mmol palladium, 0.11mmol α α '-two (diphenyl phosphine) phenylate (Oxydi-2; 1-phenylene) bis (diphenylphosphine), 328.00mmol methyl alcohol, the positive nonane of 0.718g (interior mark) and 50ml phenyl ether or methyl-phenoxide; add 286.50mmol 1 then; the 3-divinyl charges into carbon monoxide to pressure 5MPa.Stirring reaction is 4 hours in 230 ℃ of oil baths.Reaction is cooled to room temperature after finishing, and product is through the gas chromatograph-mass spectrometer analysis.The result transforms fully for 1,3-butadiene, and the selectivity of 3-amylene-4 acid methyl ester (3-MP) is more than 96%, and the gas-chromatography yield is 96%.
Embodiment 2
Under nitrogen protection, in the 250ml autoclave, add 0.05mmol palladium, 0.4mmol α α '-two (diphenyl phosphine) phenylate, other reaction conditions is with embodiment 1.Reaction is cooled to room temperature after finishing, and product is through the gas chromatograph-mass spectrometer analysis, and the gas-chromatography yield of 3-amylene-4 acid methyl ester is 84.8%.
Embodiment 3
Under nitrogen protection; in the 250ml autoclave, add 0.05mmol palladium, 0.06mmol α α '-two (diphenyl phosphine) phenylate, 328.00mmol methyl alcohol, the positive nonane of 0.072g (interior mark) and 10ml methyl-phenoxide; add 286.50mmol 1 then; the 3-divinyl charges into carbon monoxide to pressure 3MPa.Stirring reaction is 4 hours in 230 ℃ of oil baths.Reaction is cooled to room temperature after finishing, and product is through the gas chromatograph-mass spectrometer analysis, and the gas-chromatography yield of 3-amylene-4 acid methyl ester is 35.4%.
Embodiment 4
Under nitrogen protection; in the 250ml autoclave, add 0.05mmol palladium, 0.06mmol4; 5-two (diphenyl phosphine)-9; 9-dimethyl-xanthene (Xantphos), 328.00mmol methyl alcohol, the positive nonane of 0.718g (interior mark) and 50ml methyl-phenoxide; add 286.50mmol 1 then; the 3-divinyl charges into carbon monoxide to pressure 5MPa.Stirring reaction is 4 hours in 230 ℃ of oil baths.Reaction is cooled to room temperature after finishing, and product is through the gas chromatograph-mass spectrometer analysis.The result is the approaching conversion fully of 1,3-butadiene, and the selectivity of 3-amylene-4 acid methyl ester is 92.2%, and promptly the gas-chromatography yield is 92.2%.
Embodiment 5
Under nitrogen protection; in the 250ml autoclave, add 0.05mmol palladium, 0.06mmol4; 5-two (diphenyl phosphine)-9; 9-dimethyl oxa-anthracene (Xantphos), 65.60mmol methyl alcohol, the positive nonane of 0.072g (interior mark) and 10ml methyl-phenoxide; add 57.30mmol 1 then; the 3-divinyl charges into carbon monoxide to pressure 2MPa.Stirring reaction is 4 hours in 230 ℃ of oil baths.Reaction is cooled to room temperature after finishing, and product is through the gas chromatograph-mass spectrometer analysis, and the gas-chromatography yield of 3-amylene-4 acid methyl ester is 48.5%.
Embodiment 6
Under nitrogen protection, in the 250ml autoclave, charge into carbon monoxide to pressure 3MPa, other reaction conditions is with embodiment 5.Reaction is cooled to room temperature after finishing, and product is through the gas chromatograph-mass spectrometer analysis, and the gas-chromatography yield of 3-amylene-4 acid methyl ester is 59.9%.
Embodiment 7
Under nitrogen protection, in the 250ml autoclave, add 0.05mmol palladium, 0.03mmol4,5-two (diphenyl phosphine)-9,9-dimethyl-xanthene (Xantphos) charges into carbon monoxide to pressure 5MPa, and other reaction conditions is with embodiment 5.Reaction is cooled to room temperature after finishing, and product is through the gas chromatograph-mass spectrometer analysis, and the gas-chromatography yield of 3-amylene-4 acid methyl ester is 34.2%.
Embodiment 8
Under nitrogen protection, in the 250ml autoclave, add the 0.05mmol palladium, 0.20mmol4,5-two (diphenyl phosphine)-9,9-dimethyl-xanthene (Xantphos), other reaction conditions is with embodiment 7.Reaction is cooled to room temperature after finishing, and product is through the gas chromatograph-mass spectrometer analysis, and the gas-chromatography yield of 3-amylene-4 acid methyl ester is 36.1%.
Embodiment 9
In nitrogen protection, under 200 ℃ of oil bath temperatures, charge into carbon monoxide to pressure 5MPa, other reaction conditions is with embodiment 5.Reaction is cooled to room temperature after finishing, and product is through the gas chromatograph-mass spectrometer analysis, and the gas-chromatography yield of 3-amylene-4 acid methyl ester is 15.6%.
Embodiment 10
In nitrogen protection, under 250 ℃ of oil bath temperatures, other reaction conditions is with embodiment 9.Reaction is cooled to room temperature after finishing, and product is through the gas chromatograph-mass spectrometer analysis, and the gas-chromatography yield of 3-amylene-4 acid methyl ester is 28.5%.
Embodiment 11
Under nitrogen protection; in the 75ml autoclave, add 0.05mmol palladium, 0.06mmol4; 5-two (diphenyl phosphine)-9; 9-dimethyl oxa-anthracene (Xantphos), 39.5mmol methyl alcohol, 0.7mmol2; 6-dimethoxybenzoic acid, the positive nonane of 0.072 g (interior mark) and 10ml methyl-phenoxide; add the 23.0mmol 1,3-butadiene then, charge into carbon monoxide to pressure 5MPa.Stirring reaction is 5 hours in 230 ℃ of oil baths.Reaction is cooled to room temperature after finishing, and product is through the gas chromatograph-mass spectrometer analysis, and 1,3-butadiene is near reacting completely, and the gas-chromatography yield of 3-amylene-4 acid methyl ester is 91.0%.
Embodiment 12
Under nitrogen protection; in the 75ml autoclave, add 0.27mmol palladium, 1.08mmol4; 5-two (diphenyl phosphine)-9; 9-dimethyl oxa-anthracene (Xantphos), 65.60mmol methyl alcohol, 1.89mmol 2; 6-dimethoxybenzoic acid, the positive nonane of 0.072g (interior mark) and 20ml phenyl ether; add the 57.30mmol 1,3-butadiene then, charge into carbon monoxide to pressure 5MPa.Stirring reaction is 6 hours in 230 ℃ of oil baths.Reaction is cooled to room temperature after finishing, and product is through the gas chromatograph-mass spectrometer analysis, and 1,3-butadiene is near reacting completely, and the gas-chromatography yield of 3-amylene-4 acid methyl ester is more than 95.0%.
Embodiment 13
Product among the embodiment 1 under nitrogen protection, adds 300.00mmol methyl alcohol again after volatile components, product and interior mark are removed in underpressure distillation; 0.718g positive nonane (interior mark); add the 286.50mmol 1,3-butadiene then, charge into carbon monoxide to pressure 5 MPa.Stirring reaction is 4 hours in 230 ℃ of oil baths.Reaction is cooled to room temperature after finishing, and product is through the gas chromatograph-mass spectrometer analysis.Operation cycle is four times equally, comes the stability of catalyst testing system, and the results are shown in Table 1.The result shows that this catalyst system has satisfactory stability.
Table 1
Sequence number 3-MP yield (%) TOF (h
-1)
1 95.0 1360
2 96.6 1375
3 99.5 1418
4 97.0 1390
Comparison example 1
Under nitrogen protection; in the 75ml autoclave, add 0.05mmol palladium, a certain amount of bidentate phosphine ligands, 65.60mmol methyl alcohol, the positive nonane of 0.072g (interior mark) and 10ml phenyl ether; add the 57.30mmol 1,3-butadiene then, charge into carbon monoxide to pressure 5MPa.Stirring reaction is 4 hours in 230 ℃ of oil baths.Reaction is cooled to room temperature after finishing, and product is through the gas chromatograph-mass spectrometer analysis, and the results are shown in Table 2.
Table 2
Sequence number bidentate phosphine ligands phosphine part consumption 3-MP yield (%)
11,1 '-two (diphenyl phosphine) ferrocene 0.06mmol 41.6
21,4-two (diphenyl phosphine) butane 0.06mmol 43.2
31,4-two (diphenyl phosphine)-2-butylene 0.10mmol 31.7
Method set forth in the present invention is very useful for the preparation Beta, Gamma unsaturated ester, particularly for being that raw material prepares the 3-amylene-4 acid methyl ester with carbon monoxide, 1,3-butadiene and methyl alcohol.Such product can be used as the raw material of synthesis of caprolactam.
After the present invention has been done description like this and illustrates, should be appreciated that claim subsequently is not to limit, but require to provide a scope suitable with the description of the integral part of claim and equivalent thereof.
Claims (13)
1, a kind of conjugated alkene that is used for carries out the method that carbonylation prepares Beta, Gamma unsaturated ester, with conjugated alkene, carbon monoxide and hydroxy-containing compounds are raw material, form catalyzer with palladium compound and bidentate phosphine compound, the consumption of bidentate phosphine compound in catalyzed reaction is 0.1-20 times of palladium compound mole dosage, in non-polar solvent or weak polar solvent, react, temperature of reaction system is 50-400 ℃, initial carbon monoxide pressure is 1-30MPa, solvent is 10 with the mol ratio of conjugated alkene: 1-0.1: 1, the mol ratio of hydroxy-containing compounds and conjugated alkene is 0.1: 1-10: 1, conjugated alkene is 100 with the mol ratio of catalyzer: 1-100000: 1, reaction times be 1 minute to 20 hours, make Beta, Gamma unsaturated ester; Reaction formula is as follows:
Wherein, R and R ' are for replacing or non-substituted alkyl, and R ' can also be hydrogen (H); Catalyzer is made of following a, b two portions or by a, b, c three parts constitute:
A) palladium compound;
B) bidentate phosphine compound;
C) organic acid auxiliary agent;
The bidentate phosphine compound satisfies general formula I
R wherein
1-R
4Represent identical or different aryl or alkyl; X is N, O or S heteroatoms; Ar is phenyl ring or substituted benzene ring; Except that the X bridging, two Ar bases can also be linked at together with other bridge linkage group simultaneously; X encircles last two adjacent carbon atoms with Ar respectively with P and links to each other;
Described conjugated alkene is C
4-C
20Alkene;
Described hydroxy-containing compounds is the alcohol that contains 1 to 20 carbon atom;
Described organic acid auxiliary agent is the substituted benzoyl acid compounds.
2, in accordance with the method for claim 1, it is characterized in that described conjugated alkene is a 1,3-butadiene.
3, in accordance with the method for claim 1, it is characterized in that described hydroxy-containing compounds is methyl alcohol or ethanol.
4, in accordance with the method for claim 1, it is characterized in that described palladium compound is coordination compound of palladium salt, palladium oxide, organic palladium compound, palladium and composition thereof.
According to claim 1 or 4 described methods, it is characterized in that 5, described palladium compound is palladium Pd (OAc)
2With Palladous chloride PdCl
2
6, in accordance with the method for claim 1, it is characterized in that R in the used bidentate phosphine compound molecule
1-R
4Be C identical or different, that replace or do not have to replace
5-C
10Aryl, alicyclic group or C
1-C
10Alkyl.
7, in accordance with the method for claim 1, it is characterized in that Ar is the C that replaces or do not have to replace in the used bidentate phosphine compound
5-C
10Aryl, especially C
6The aryl phenyl ring.
8, in accordance with the method for claim 1, it is characterized in that X is the O atom in the used bidentate phosphine compound.
According to claim 1,6,7 or 8 described methods, it is characterized in that 9, used bidentate phosphine compound is 4,5-two (diphenyl phosphine)-9,9-dimethyl oxa-anthracene or α, α '-two (diphenyl phosphine) phenylate.
10, in accordance with the method for claim 1, it is characterized in that described organic acid auxiliary agent is 2,6-dimethoxybenzoic acid, 2,4,6-triisopropyl phenylformic acid, 2,4,6-tri-tert phenylformic acid, 2,6-di-isopropyl phenylformic acid or 2,6-di-tert-butyl benzoic acid.
11, in accordance with the method for claim 1, it is characterized in that described solvent is methyl-phenoxide, phenyl ether, toluene, dimethylbenzene and mixed solvent thereof.
12, in accordance with the method for claim 1, it is characterized in that, temperature of reaction system is 150-300 ℃, initial carbon monoxide pressure is 3-8MPa, solvent is 2 with the mol ratio of conjugated alkene: 1-0.2: 1, the mol ratio of hydroxy-containing compounds and conjugated alkene is below 2: 1, and conjugated alkene is 3000 with the mol ratio of catalyzer: 1-50000: 1, and bidentate phosphine compound consumption is 1-3 a times of palladium compound mole dosage.
13, in accordance with the method for claim 1, it is characterized in that 1,3-butadiene, carbon monoxide and methyl alcohol are converted into 3-amylene-4 acid methyl ester (3-MP) and 4-amylene-4 acid methyl ester (4-MP); The 3-amylene-4 acid methyl ester is a primary product, and the 4-amylene-4 acid methyl ester is a secondary product.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103142569A (en) * | 2013-02-27 | 2013-06-12 | 南京医科大学 | 2, 6-diisopropyl benzoic acid and application of 2, 6-diisopropyl benzoic acid derivative serving as neuroprotective agent |
| CN107915630A (en) * | 2017-11-23 | 2018-04-17 | 华东师范大学 | A kind of preparation method of succinic diester or succinic diester derivative |
| CN111087306A (en) * | 2019-12-27 | 2020-05-01 | 南京诚志清洁能源有限公司 | Method for preparing organic carboxylic ester by aryl bidentate phosphine ligand combined catalysis |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0977628B1 (en) * | 1997-04-07 | 2001-06-20 | Dsm N.V. | Carbonylation catalyst system |
| US6010975A (en) * | 1998-06-19 | 2000-01-04 | Industrial Technology Research Institute | Catalyst composition for preparing 3-pentenoic ester from butadiene |
| TW524801B (en) * | 1999-03-22 | 2003-03-21 | Shell Int Research | Process for the carbonylation of conjugated dienes |
-
2006
- 2006-01-16 CN CN2006100008865A patent/CN101003456B/en active Active
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103142569A (en) * | 2013-02-27 | 2013-06-12 | 南京医科大学 | 2, 6-diisopropyl benzoic acid and application of 2, 6-diisopropyl benzoic acid derivative serving as neuroprotective agent |
| CN107915630A (en) * | 2017-11-23 | 2018-04-17 | 华东师范大学 | A kind of preparation method of succinic diester or succinic diester derivative |
| CN107915630B (en) * | 2017-11-23 | 2021-01-01 | 华东师范大学 | Preparation method of succinic acid diester or succinic acid diester derivative |
| CN111087306A (en) * | 2019-12-27 | 2020-05-01 | 南京诚志清洁能源有限公司 | Method for preparing organic carboxylic ester by aryl bidentate phosphine ligand combined catalysis |
| WO2021129138A1 (en) * | 2019-12-27 | 2021-07-01 | 南京诚志清洁能源有限公司 | Method for preparing organic carboxylic ester by means of combinatorial catalysis with aryl bidentate phosphine ligand |
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