Bisphenol-derived bidentate phosphine ligand, synthesis method and application thereof

Abstract

The present invention relates to a bidentate phosphine ligand derived from bisphenol, wherein the ligand has a structure shown in the general formula (I): wherein: R 1 、R 2 is an alkyl group, an aryl group or a hydrogen atom, and R 1 、R 2 Same or different; R 3 、R 4 is one of alkyl, aryl, alkoxy or aryloxy, and R 3 、R 4 The invention also discloses a synthesis method and application of the ligand. The invention introduces an oxygen-containing functional group to regulate the properties of the bidentate phosphine ligand, providing more possibilities for hydroformylation and hydroesterification reactions.

Description

Technical Field

[0001] The present invention relates to the field of homogeneous catalysis, and in particular to a bidentate phosphine ligand derived from bisphenol, a synthesis method thereof and an application thereof. Background Art

[0002] Ligands are the core components of homogeneous catalysts, and synthesizing new ligands is an important approach to creating homogeneous catalysts. Among them, bidentate phosphine ligands have long held a dominant position in homogeneous catalysis, playing a crucial role in catalyst efficiency, selectivity, and lifespan (Chem. Rev. 2000, 100, 2741). Xantphos, a prominent representative bidentate phosphine ligand, has the following structural formula:

[0003]

[0004] Since its discovery in 1994, it has been widely used in a variety of reactions, such as hydroformylation and hydroesterification (Catal. Sci. Technol., 2018, 8, 26; BE patent appl., 9400470).

[0005] Currently, the synthesis of Xantphos primarily involves the reaction of xanthone with a methylaluminum reagent to yield the intermediate xanthene, followed by the introduction of a phosphorus-containing functional group via lithiation. This synthetic strategy allows for the introduction of functional groups at the meta-position (2,7-positions) adjacent to the phosphorus atom on the xanthene ring, but the ortho-positions (3,6-positions) are currently unattainable, limiting the structural diversity of these bidentate phosphine ligands (Acc. Chem. Res., 2001, 34, 895).

[0006]

[0007] In order to introduce an oxygen-containing functional group at the ortho position of the carbon adjacent to the phosphorus atom, Paul Kamer et al. reported a method for synthesizing bidentate phosphine ligands using fluorine-substituted diphenyl ether as a raw material (Organometallics 2015, 34, 1608). This synthesis method can introduce an oxygen-containing functional group at the ortho position of the carbon adjacent to the phosphorus atom.

[0008]

[0009] However, compared to the xanthene skeleton, the diphenyl ether skeleton is not rigid, and the introduction of oxygen-containing functional groups into the xanthene skeleton has not been reported so far. Summary of the Invention

[0010] The technical problem to be solved by the present invention is to provide a bidentate phosphine ligand derived from bisphenol.

[0011] Another technical problem to be solved by the present invention is to provide a method for synthesizing the bidentate phosphine ligand derived from bisphenol.

[0012] The third technical problem to be solved by the present invention is to provide an application of the bidentate phosphine ligand derived from bisphenol.

[0013] To solve the above problems, the present invention provides a bidentate phosphine ligand derived from bisphenol, characterized in that the ligand has a structure represented by the general formula (I):

[0014]

[0015] Where: R 1 、R 2 is an alkyl group, an aryl group or a hydrogen atom, and R 1 、R 2 Same or different; R 3 、R 4 is one of alkyl, aryl, alkoxy or aryloxy, and R 3 、R 4 Same or different.

[0016] The method for synthesizing a bidentate phosphine ligand derived from bisphenol is characterized in that: a compound 1 containing a bisphenol structure is reacted with a halogenated hydrocarbon in the presence of a solvent A and a base to obtain a compound 2 containing a bisphenol ether structure; the compound 2 is then reacted with an alkyl lithium reagent in a solvent B for lithiation; and after complete lithiation, the compound 2 is reacted with a chlorophosphine compound to obtain a bidentate phosphine ligand derived from bisphenol;

[0017] The structural formula of the compound 1 is ; The structural formula of the compound 2 is Where: R 1 、R 2 is an alkyl group, an aryl group or a hydrogen atom, and R 1 、R 2 Same or different.

[0018] The base is selected from one of sodium hydride, potassium hydride, potassium carbonate, sodium carbonate, and cesium carbonate; the molar ratio of the base to the compound 1 is 2.5:1.

[0019] The halogenated hydrocarbon is selected from one of methyl iodide, allyl chloride, benzyl bromide, and tert-butyl chloride; and the molar ratio of the halogenated hydrocarbon to the compound 1 is 2.5:1.

[0020] The alkyl lithium reagent is selected from one of n-butyl lithium, sec-butyl lithium and tert-butyl lithium.

[0021] The chlorophosphine compound is selected from diphenylphosphine chloride, dimethylphosphine chloride, di-tert-butylphosphine chloride, diethylphosphite chloride, di-tert-butylphosphite chloride, phenyl-1,2-dimethylphosphite chloride, biphenyl-2,2 ’ -One of the phosphorus oxychlorides.

[0022] The use of the bidentate phosphine ligand derived from bisphenol in a hydroformylation reaction is characterized in that synthesis gas and olefin are used as raw materials for the hydroformylation reaction, a combination of a rhodium compound and the bidentate phosphine ligand derived from bisphenol is used as a catalyst; and the olefin is selected from one of hexene, octene, and styrene.

[0023] The use of a bisphenol-derived bidentate phosphine ligand in a hydroesterification reaction as described above is characterized in that: carbon monoxide, olefin and alcohol are used as raw materials, and a combination of a palladium compound and the bisphenol-derived bidentate phosphine ligand is used as a catalyst; the olefin is selected from one of hexene, octene and styrene; and the alcohol is selected from one of methanol, ethanol and butanol.

[0024] Compared with the prior art, the present invention has the following advantages:

[0025] 1. The present invention uses a bisphenol compound as a starting material and reacts it with a halogenated hydrocarbon under the action of a base to obtain a compound containing a bisphenol ether structure. A phosphorus-containing functional group is then introduced through a lithiation reaction to obtain a bidentate phosphine ligand. This method can introduce an oxygen-containing functional group at the ortho position of the carbon adjacent to the phosphorus atom on the xanthene ring, providing a site for structural modification of the phosphine ligand, deriving more bidentate phosphine ligands, enriching the types of catalysts containing bidentate phosphine ligand structures, and providing more powerful ligand tools for homogeneous catalysis.

[0026] 2. The present invention introduces oxygen-containing functional groups, which can regulate the properties of bidentate phosphine ligands and provide more possibilities for hydroformylation and hydroesterification reactions. BRIEF DESCRIPTION OF THE DRAWINGS

[0027] The specific embodiments of the present invention will be further described in detail below with reference to the accompanying drawings.

[0028] Figure 1 This is the hydrogen nuclear magnetic resonance spectrum of the product Ia of Example 1 of the present invention.

[0029] Figure 2 This is the nuclear magnetic resonance phosphorus spectrum of the product Ia of Example 1 of the present invention. DETAILED DESCRIPTION

[0030] A bidentate phosphine ligand derived from bisphenol, wherein the ligand has a structure represented by the general formula (I):

[0031]

[0032] Where: R1 、R 2 is an alkyl group, an aryl group or a hydrogen atom, and R 1 、R 2 Same or different; R 3 、R 4 is one of alkyl, aryl, alkoxy or aryloxy, and R 3 、R 4 The same or different. That is, its structure contains two phosphorus atoms, and the adjacent carbon positions of the phosphorus atoms in the xanthene skeleton structure contain oxygen-containing functional groups (OR 1 , OR 2 ); phosphorus atoms contain functional groups (R 3 、R 4 ).

[0033] A method for synthesizing a bidentate phosphine ligand derived from bisphenol: the method uses a compound 1 containing a bisphenol structure as a raw material, reacts with a halogenated hydrocarbon in the presence of solvent A and a base to obtain a compound 2 containing a bisphenol ether structure; the compound 2 reacts with an alkyl lithium reagent in solvent B for lithiation, and after complete lithiation, reacts with a chlorophosphine compound to obtain a bidentate phosphine ligand derived from bisphenol.

[0034] Wherein: The structural formula of compound 1 is ; The structural formula of compound 2 is Where: R 1 、R 2 is an alkyl group, an aryl group or a hydrogen atom, and R 1 、R 2 Same or different.

[0035] The base is selected from one of sodium hydride, potassium hydride, potassium carbonate, sodium carbonate, and cesium carbonate; and the molar ratio of the base to the compound 1 is 2.5:1.

[0036] The halogenated hydrocarbon is selected from one of iodomethane, allyl chloride, benzyl bromide and tert-butyl chloride; the molar ratio of the halogenated hydrocarbon to the compound 1 is 2.5:1.

[0037] The alkyl lithium reagent is selected from one of n-butyl lithium, sec-butyl lithium and tert-butyl lithium.

[0038] The phosphine chloride compound is selected from diphenylphosphine chloride, dimethylphosphine chloride, di-tert-butylphosphine chloride, diethylphosphine chloride, di-tert-butylphosphine chloride, phenyl-1,2-dimethylphosphine chloride, biphenyl-2,2 ’ -One of the phosphorus oxychlorides.

[0039] Solvent A and solvent B are both commonly used solvents in the art.

[0040] Its synthetic route is as follows:

[0041]

[0042] The specific process is as follows:

[0043] In a flask, add 1 equivalent of compound 1 containing a bisphenol structure and 100 equivalents of anhydrous acetonitrile solvent, based on a mol / mol ratio. Stir to mix thoroughly, then slowly add 2.5 equivalents of a base. Continue stirring for 1 hour, then slowly add 2.5 equivalents of an alkyl halide dropwise while continuing to stir. Monitor the reaction by thin-layer chromatography (TLC). Once the reaction is complete, discontinue stirring, remove the acetonitrile solvent by vacuum distillation, wash with water, and extract the crude solid with dichloromethane. Recrystallize or separate by column chromatography to obtain compound 2 containing a bisphenol ether structure.

[0044] To a flask, add 1 equivalent of compound 2 and 50 equivalents of anhydrous tetrahydrofuran solvent, stir and mix thoroughly. Slowly add 2.5 equivalents (based on the alkyl lithium) of alkyl lithium solution dropwise, continue stirring, and after complete lithiation, slowly add 2.5 equivalents of a phosphine chloride compound. Continue stirring until the reaction is complete. Remove the tetrahydrofuran solvent by distillation under reduced pressure, wash with water to remove the lithium chloride, and then wash the crude solid product with n-hexane. Recrystallize from ethanol to obtain a bisphenol-derived bidentate phosphine ligand, the structure of which is shown in Formula (I).

[0045] The invention discloses an application of a bidentate phosphine ligand derived from bisphenol in a hydroformylation reaction: synthesis gas and olefin are used as raw materials for the hydroformylation reaction; a combination of a rhodium compound and a bidentate phosphine ligand derived from bisphenol is used as a catalyst; the olefin is selected from hexene, octene, and styrene.

[0046] The specific process is as follows:

[0047] To a reactor, add 1 equivalent of a rhodium compound and 2 equivalents of a bisphenol-derived bidentate phosphine ligand, measured in mol / mol. Then, add 5,000 equivalents of an olefin and 25,000 equivalents of toluene. The reactor is sealed. After purging the air with inert gas, 2 MPa of synthesis gas is introduced. The reactor is heated to the reaction temperature. After the reaction is complete, the reaction is cooled to room temperature. The synthesis gas is slowly vented, the reactor is opened, and a liquid sample is taken. After dilution, the sample is analyzed by gas chromatography.

[0048] The invention discloses an application of a bidentate phosphine ligand derived from bisphenol in a hydroesterification reaction. The invention uses carbon monoxide, olefins and alcohols as raw materials, and a combination of a palladium compound and a bidentate phosphine ligand derived from bisphenols as a catalyst. The olefin is selected from one of hexene, octene and styrene. The alcohol is selected from one of methanol, ethanol and butanol.

[0049] The specific process is as follows:

[0050] To a reactor, add 1 equivalent of a palladium compound and 2 equivalents of a bisphenol-derived bidentate phosphine ligand, based on a mol / mol ratio. Then, add 1000 equivalents of an olefin and 5000 equivalents of an alcohol. The reactor is sealed. After purging the air with inert gas, 5 MPa of carbon monoxide is introduced. The reaction is heated to the reaction temperature. After the reaction is complete, the reaction is cooled to room temperature. The carbon monoxide is slowly vented, the reactor is opened, and a liquid sample is taken. After dilution, the sample is analyzed by gas chromatography.

[0051] Example 1

[0052] To a flask, 10 mmol of compound 1 containing a bisphenol structure and 1 mol of anhydrous acetonitrile solvent were added and stirred to mix thoroughly. 25 mmol of sodium hydride was then added portionwise. After stirring for 1 hour, 25 mmol of methyl iodide was slowly added dropwise with continued stirring. The reaction was monitored by TLC. Once the reaction was complete, stirring was stopped and the acetonitrile solvent was removed by vacuum distillation. After washing with water, the crude solid product was extracted with 20 ml of dichloromethane and recrystallized from n-hexane to obtain compound 2a containing a bisphenol ether structure. The structural formula is shown below:

[0053]

[0054] To a flask, add 10 mmol of compound 2a and 500 mmol (approximately 20 ml) of anhydrous tetrahydrofuran. Stir and mix thoroughly. Slowly add 25 mmol (based on the alkyl lithium) of n-butyllithium solution dropwise. Continue stirring. After complete lithiation, slowly add 25 mmol of diphenylphosphine chloride. Continue stirring until the reaction is complete. Remove the tetrahydrofuran solvent by distillation under reduced pressure, wash with water to remove the lithium chloride, and then wash the crude solid with n-hexane. Recrystallize from ethanol to obtain the bidentate phosphine ligand Ia, whose structure is shown below:

[0055]

[0056] Its NMR information is as follows Figures 1 and 2 As shown:

[0057] 1 H NMR (400 MHz, Chloroform-d) δ 7.29 (d, J = 8.7 Hz, 1H), 7.27-7.22(m, 4H), 7.07–6.96 (m, 6H), 6.45 (d, J = 8.7 Hz, 1H), 3.09 (s, 3H), 1.50 (s,3H).

[0058] 31 P NMR (162 MHz, Chloroform-d) δ -24.07.

[0059] Example 2

[0060] To a flask, 10 mmol of compound 1 containing a bisphenol structure and 1 mol of anhydrous acetonitrile solvent were added and stirred to mix thoroughly. 25 mmol of potassium hydride was then added portionwise. After stirring for 1 hour, 25 mmol of allyl chloride was slowly added dropwise with continued stirring. The reaction was monitored by TLC. Upon completion, stirring was stopped and the acetonitrile solvent was removed by vacuum distillation. After washing with water, the crude solid product was extracted with 20 ml of dichloromethane and separated by column chromatography to yield compound 2b containing a bisphenol ether structure. The structural formula is shown below:

[0061]

[0062] To a flask, add 10 mmol of compound 2b and 500 mmol (approximately 20 ml) of anhydrous tetrahydrofuran. Stir to mix thoroughly. Slowly add 25 mmol (based on the alkyl lithium) of sec-butyllithium solution dropwise. Continue stirring. After lithiation is complete, slowly add 25 mmol of dimethylphosphine chloride. Continue stirring until the reaction is complete. Remove the tetrahydrofuran solvent by distillation under reduced pressure, wash with water to remove the lithium chloride, and then wash the crude solid with n-hexane. Recrystallize from ethanol to obtain the bidentate phosphine ligand Ib, whose structure is shown below:

[0063]

[0064] Its NMR information is as follows: 31 P NMR (162 MHz, Chloroform-d) δ -46.32.

[0065] Example 3

[0066] To a flask, 10 mmol of compound 1 containing a bisphenol structure and 1 mol of anhydrous acetonitrile solvent were added and stirred to mix thoroughly. 25 mmol of potassium carbonate was then added portionwise. After stirring for 1 hour, 25 mmol of benzyl bromide was slowly added dropwise with continued stirring. The reaction was monitored by TLC. Upon completion, stirring was stopped and the acetonitrile solvent was removed by vacuum distillation. After washing with water, the crude solid product was extracted with 20 ml of dichloromethane and separated by column chromatography to yield compound 2c containing a bisphenol ether structure. The structural formula is shown below:

[0067]

[0068] To a flask, add 10 mmol of compound 2c and 500 mmol (approximately 20 ml) of anhydrous tetrahydrofuran. Stir to mix thoroughly. Slowly add 25 mmol (based on the alkyl lithium) of tert-butyllithium solution dropwise. Continue stirring. After complete lithiation, slowly add 25 mmol of di-tert-butylphosphine chloride. Continue stirring until the reaction is complete. Remove the tetrahydrofuran solvent by distillation under reduced pressure, wash with water to remove the lithium chloride, and then wash the crude solid with n-hexane. Recrystallize from ethanol to obtain the bidentate phosphine ligand Ic, whose structure is shown below:

[0069]

[0070] Example 4

[0071] To a flask, 10 mmol of compound 1 containing a bisphenol structure and 1 mol of anhydrous acetonitrile solvent were added and stirred to mix thoroughly. Then, 25 mmol of sodium carbonate was added portionwise. After stirring for 1 hour, 25 mmol of tert-butyl chloride was slowly added dropwise with continued stirring. The reaction was monitored by TLC. After completion, stirring was stopped and the acetonitrile solvent was removed by vacuum distillation. After washing with water, the crude solid product was extracted with 20 ml of dichloromethane and separated by column chromatography to obtain compound 2d containing a bisphenol ether structure. The structural formula is shown below:

[0072]

[0073] To a flask, add 10 mmol of compound 2d and 500 mmol (approximately 20 ml) of anhydrous tetrahydrofuran. Stir to mix thoroughly. Slowly add 25 mmol (based on the alkyl lithium) of tert-butyllithium solution dropwise. Continue stirring. After complete lithiation, slowly add 25 mmol of diethylphosphite chloride. Continue stirring until the reaction is complete. Remove the tetrahydrofuran solvent by distillation under reduced pressure, wash with water to remove lithium chloride, and continue washing the crude solid with n-hexane. Recrystallize from ethanol to obtain the bidentate phosphine ligand Id, whose structure is shown below:

[0074]

[0075] Example 5

[0076] To a flask, 10 mmol of compound 1 containing a bisphenol structure and 1 mol of anhydrous acetonitrile solvent were added and stirred to mix evenly. 25 mmol of cesium carbonate was added in batches. After stirring for 1 hour, 12.5 mmol of iodomethane was slowly added dropwise and stirring was continued. The reaction was monitored by TLC until the reaction was complete. 12.5 mmol of tert-butyl chloride was added and stirring was continued. The reaction was monitored by TLC until the reaction was complete. The solvent acetonitrile was removed by vacuum distillation. After washing with water, the crude solid product was extracted with 20 ml of dichloromethane and separated by column chromatography to obtain compound 2e containing a bisphenol ether structure. The structural formula is shown below:

[0077]

[0078] To a flask, add 10 mmol of compound 2e and 500 mmol (approximately 20 ml) of anhydrous tetrahydrofuran. Stir to mix thoroughly. Slowly add 25 mmol (based on the alkyl lithium) of n-butyllithium solution dropwise. Continue stirring. After complete lithiation, slowly add 25 mmol of di-tert-butylphosphite chloride. Continue stirring until the reaction is complete. Remove the tetrahydrofuran solvent by distillation under reduced pressure, wash with water to remove the lithium chloride, and continue washing the crude solid with n-hexane. Recrystallize from ethanol to obtain the bidentate phosphine ligand Ie, whose structure is shown below:

[0079]

[0080] Its NMR information is as follows: 31 P NMR (162 MHz, Chloroform-d) δ 132.43, 133.56.

[0081] Example 6

[0082] To a flask, add 10 mmol of compound 2a and 500 mmol (approximately 20 ml) of anhydrous tetrahydrofuran. Stir to mix thoroughly. Slowly add 25 mmol (based on the alkyl lithium) of n-butyllithium solution dropwise. Continue stirring. After lithiation is complete, slowly add 25 mmol of phenyl-1,2-dimethylphosphite chloride. Continue stirring until the reaction is complete. Remove the tetrahydrofuran solvent by distillation under reduced pressure, wash with water to remove lithium chloride, and continue washing the crude solid with n-hexane. Recrystallize from ethanol to obtain the bidentate phosphine ligand If, whose structure is shown below:

[0083]

[0084] Its NMR information is as follows: 31 P NMR (162 MHz, Chloroform-d) δ 132.82.

[0085] Example 7

[0086] To a flask, add 10 mmol of compound 2a and 500 mmol (approximately 20 ml) of anhydrous tetrahydrofuran solvent. Stir to mix thoroughly. Slowly add 25 mmol (based on the alkyl lithium) of n-butyllithium solution dropwise. Continue stirring. After lithiation is complete, slowly add 25 mmol of biphenyl-2,2'-phosphite chloride. Continue stirring until the reaction is complete. Remove the tetrahydrofuran solvent by distillation under reduced pressure. Wash with water to remove lithium chloride. Wash the crude solid with n-hexane and recrystallize from ethanol to obtain the bidentate phosphine ligand Ig, whose structure is shown below:

[0087]

[0088] Its NMR information is as follows: 31P NMR (162 MHz, Chloroform-d) δ 123.86.

[0089] Example 8

[0090] At low temperature, add 10 mmol of compound Ia and 100 mmol of dichloromethane to a flask. Stir and mix thoroughly. Slowly add 20 mmol (based on boron tribromide) of a dichloromethane solution dropwise. Continue stirring until the reaction is complete. The reaction mixture is slowly added dropwise to an ice-water mixture. The product is extracted with dichloromethane, and the solvent is removed under reduced pressure to yield bidentate phosphine ligand Ih, the structure of which is shown below:

[0091]

[0092] Its NMR information is as follows: 31 P NMR (162 MHz, Chloroform-d) δ -23.66.

[0093] Example 9

[0094] A 150 mL autoclave was charged with 0.02 mmol of dicarbonyl acetylacetonate rhodium and 0.04 mmol of compound Ia, followed by 0.1 mol of hexene and 0.5 mol of toluene. The reactor was then sealed. After the inert gas was purged from the air, 2 MPa of synthesis gas (a mixture of carbon monoxide and hydrogen) was introduced. The reaction mixture was heated to 130°C, allowed to react for 12 hours, and then cooled to room temperature. The synthesis gas was slowly vented, the reactor was opened, and a liquid sample was taken. After dilution, gas chromatography revealed a hexene conversion of 95% and a heptanal yield of 91%.

[0095] Example 10

[0096] A 150 mL autoclave was charged with 0.02 mmol of rhodium chloride and 0.04 mmol of compound Id, followed by 0.1 mol of octene and 0.5 mol of toluene. The reactor was then sealed. After the inert gas was purged from the air, 2 MPa of synthesis gas (a mixture of carbon monoxide and hydrogen) was introduced. The reaction was heated to 120°C, allowed to react for 6 hours, and then cooled to room temperature. The synthesis gas was slowly vented, the reactor was opened, and a liquid sample was taken. After dilution, gas chromatography revealed an octene conversion of 92% and a nonanal yield of 89%.

[0097] Example 11

[0098] A 150 mL autoclave was charged with 0.02 mmol (calculated as rhodium atoms) of tetrarhodium dodecacarbonyl and 0.04 mmol of compound If. Subsequently, 0.1 mol of styrene and 0.5 mol of toluene were added, and the reactor was sealed. After the inert gas was purged from the air, 2 MPa of synthesis gas (a mixture of carbon monoxide and hydrogen) was introduced. The reactor was heated to 100°C, reacted for 24 hours, and then cooled to room temperature. The synthesis gas was slowly vented, the reactor was opened, and a liquid sample was taken. After dilution, gas chromatography revealed a styrene conversion of 99% and a phenylpropionaldehyde yield of 85%.

[0099] Example 12

[0100] To a 50 mL autoclave, 0.1 mmol of palladium acetate, 0.2 mmol of compound Ib, and 0.4 mmol of p-toluenesulfonic acid were added. Subsequently, 0.1 mol of hexene and 0.5 mol of methanol were added, and the reactor was sealed. After the inert gas was purged from the air, 5 MPa of carbon monoxide was introduced. The reactor was heated to 130°C, reacted for 18 hours, and then cooled to room temperature. The carbon monoxide was slowly vented, the reactor was opened, and a liquid sample was taken. After dilution, gas chromatography revealed a hexene conversion of 91% and an 87% yield of methyl heptanoate.

[0101] Example 13

[0102] To a 50 mL autoclave, 0.1 mmol of palladium chloride, 0.2 mmol of compound Ic, and 0.4 mmol of methanesulfonic acid were added. Subsequently, 0.1 mol of octene and 0.5 mol of ethanol were added, and the reactor was sealed. After the inert gas was purged from the air, 5 MPa of carbon monoxide was introduced. The reactor was heated to 120°C, reacted for 24 hours, and then cooled to room temperature. The carbon monoxide was slowly vented, the reactor was opened, and a liquid sample was taken. After dilution, gas chromatography revealed an octene conversion of 85% and an ethyl nonanoate yield of 82%.

[0103] Example 14

[0104] To a 150 mL autoclave, 0.1 mmol of palladium chloride, 0.2 mmol of compound Ia, and 0.4 mmol of sulfuric acid were added. Subsequently, 0.1 mol of styrene and 0.5 mol of butanol were added, and the reactor was sealed. After the inert gas was purged from the air, 5 MPa of carbon monoxide was introduced. The reactor was heated to 120°C, allowed to react for 24 hours, and then cooled to room temperature. The carbon monoxide was slowly vented, the reactor was opened, and a liquid sample was taken. After dilution, gas chromatography revealed a styrene conversion of 93% and a yield of butyl phenylpropionate of 76%.

Claims

1. A bidentate phosphine ligand derived from bisphenol, characterized in that: The ligand has the structure shown below: ； ； ； ； ； ； 。 2. The method for synthesizing a bisphenol-derived bidentate phosphine ligand according to claim 1, wherein: The method uses a compound 1 containing a bisphenol structure as a raw material, reacts with a halogenated hydrocarbon in the presence of a solvent A and a base to obtain a compound 2 containing a bisphenol ether structure; the compound 2 reacts with an alkyl lithium reagent in a solvent B for lithiation, and after complete lithiation, reacts with a chlorophosphine compound to obtain a bidentate phosphine ligand derived from the bisphenol; The structural formula of the compound 1 is ; The structural formula of the compound 2 is ; The halogenated hydrocarbon is selected from one of iodomethane, allyl chloride, benzyl bromide, and tert-butyl chloride; the molar ratio of the halogenated hydrocarbon to the compound 1 is 2.5:1; the chlorophosphine compound is selected from one of diphenylphosphine chloride, dimethylphosphine chloride, di-tert-butylphosphine chloride, diethylphosphite chloride, di-tert-butylphosphite chloride, and phenyl-1,2-dimethylphosphite chloride.

3. The method for synthesizing a bisphenol-derived bidentate phosphine ligand according to claim 2, wherein: The base is selected from one of sodium hydride, potassium hydride, potassium carbonate, sodium carbonate, and cesium carbonate; the molar ratio of the base to the compound 1 is 2.5:

1.

4. The method for synthesizing a bisphenol-derived bidentate phosphine ligand according to claim 2, wherein: The alkyl lithium reagent is selected from one of n-butyl lithium, sec-butyl lithium and tert-butyl lithium.

5. Use of a bisphenol-derived bidentate phosphine ligand in a hydroformylation reaction according to claim 1, characterized in that: Synthesis gas and olefins are used as raw materials for hydroformylation reaction, and a combination of a rhodium compound and a bidentate phosphine ligand derived from bisphenol is used as a catalyst; the olefin is selected from one of hexene, octene and styrene.

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