A method for synthesizing carboxylic compounds by hydrocarboxylating olefins

Abstract

The application discloses a method for synthesizing carboxylic acid compounds by olefin hydrocarboxylation, which comprises the following steps: under the action of a combined catalytic system of a bidentate phosphine ligand, a palladium compound and an acidic additive, performing hydrocarboxylation reaction on olefin, carbon monoxide, water and a non-alcohol organic solvent to generate carboxylic acid with one more carbon than the olefin. The method of the application adopts the combined catalytic system of the bidentate phosphine ligand, the palladium compound and the acidic additive, can efficiently catalyze the hydrocarboxylation reaction of the olefin under relatively mild conditions, and can obtain the carboxylic acid product with one more carbon with high selectivity, has few by-products, has low product separation and purification difficulty, reduces the preparation cost of the carboxylic acid compounds, and is suitable for industrialized production and application.

Description

Technical Field

[0001] This invention belongs to the field of organic synthesis technology, specifically relating to a method for synthesizing carboxylic acid compounds by hydrogen carboxylation of olefins. Background Technology

[0002] Carboxylic acid compounds are an important class of chemicals, widely used in pharmaceuticals, pesticides, materials, food additives, and lubricants. The main industrial method for synthesizing carboxylic acids often employs a two-step hydroformylation-oxidation process: first, an aldehyde is generated by the hydroformylation of an olefin, and then the aldehyde is oxidized to obtain the carboxylic acid. In this method, the first step of hydroformylation typically requires an expensive rhodium catalyst, while the second step of oxidation poses safety risks. In contrast, the hydrocarboxylation of olefins allows for the direct, one-step synthesis of carboxylic acid compounds from olefins. This route (as shown below) offers significant advantages such as shorter reaction steps, higher atom utilization, lower catalyst cost, and the elimination of multiple separation steps.

[0003] In 1973, Fenton reported palladium-catalyzed olefin hydrocarboxylation, discovering that phosphine ligands were crucial for reactivity and selectivity. Since then, scientists have shifted their focus to ligand development, resulting in a variety of phosphine ligands for palladium-catalyzed terminal olefin hydrocarboxylation. However, the hydrocarboxylation of internal alkenes and sterically hindered alkenes still faces significant challenges.

[0004] In 2019, Professor Beller's team in Germany developed the 1,2-bis((tert-butyl(pyridin-2-yl)phosphoryl)methyl)benzene (pytbpx) ligand for the efficient hydrocarboxylation of various alkenes (including internal alkenes, sterically hindered alkenes, and terminal alkenes) to synthesize carboxylic acids using palladium catalysis (Angew. Chem. Int. Ed. 2019, 58 (40), 14365-14373). However, this ligand suffers from drawbacks such as complex synthetic routes, high costs, and susceptibility to oxidation. Moreover, when water is used as the solvent in this reaction, the yield of the target compound is very low; for example, the yield of 3,5,5-trimethylhexanoic acid is only 16%, requiring the addition of acetic acid in amounts three times that of water to improve the yield of the target compound. The influence of the solvent is also mentioned in Fenton's reported technique. In industrial practice, the product acid is usually chosen as the solvent, and acetic acid is chosen as the main solvent due to its ease of use. Furthermore, the available palladium catalysts are limited. The yields using PdCl2, Pd(TFA)2, Pd(OAc)2, and Pd2(dba)3 are all unsatisfactory, with only Pd(acac)2 showing good catalytic performance. This severely restricts the range of catalysts available, making it difficult to adapt to the needs of different production scenarios. Therefore, there is an urgent need to develop a highly efficient, low-cost combinatorial catalytic system with simple ligand structures for palladium-catalyzed hydrogen carbonylation of olefins, particularly internally derived and sterically hindered olefins.

[0005] It should be noted that the information disclosed in the background section above is only used to enhance the understanding of the background of this disclosure, and therefore may include information that does not constitute prior art known to those skilled in the art. Summary of the Invention

[0006] The purpose of this invention is to provide a method for synthesizing carboxylic acid compounds by olefin hydrocarboxylation, which solves the problems of high difficulty and cost in ligand synthesis, many restrictions on catalyst selection in the catalytic system, and low yield of internal olefins with large steric hindrance in the prior art. The method of this invention can efficiently realize the hydrocarboxylation of various olefins under mild conditions to obtain carboxylic acid products with one more carbon than the starting olefin.

[0007] To achieve the above objectives, the present invention provides a method for synthesizing carboxylic acid compounds by hydrocarboxylation of olefins. The method comprises: a hydrocarboxylation reaction of an olefin, carbon monoxide, water, and a non-alcoholic organic solvent under the action of a combined catalytic system of a bidentate phosphine ligand, a palladium compound, and an acidic additive as shown in Formula I, to generate a carboxylic acid having one more carbon atom than the olefin. In formula I, R 1 R 2 R 3 and R 4Each is independently selected from: substituted or unsubstituted C1~C 12 Alkyl or heteroalkyl, substituted or unsubstituted C3~C 12 cycloalkyl or heterocycloalkyl, substituted or unsubstituted C6~C 20 aryl or heteroaryl; A is selected from: a straight-chain alkyl group with a total number of 5 atoms, containing or not containing heteroatoms, or the structure shown in Formula II; In Formula II, X is selected from carbon and oxygen; R 5 and R 6 Each is independently selected from: H, C1~C5 alkyl groups, and C1~C5 alkoxy groups; This indicates the position where the ligand is attached to the bidentate phosphine ligand shown in Formula I.

[0008] Preferably, R 1 R 2 R 3 and R 4 Selected from the same group.

[0009] Preferably, the substituted or unsubstituted C1~C 12 The alkyl or heteroalkyl groups are selected from: -(C1~C1) 12 )alkyl, -O-(C1~C 12 )alkyl, -S-(C1-C 12 )alkyl, -N-[(C1-C 12 )alkyl]2、-COO-(C1-C 12 )alkyl, -CONH-(C1-C 12 )alkyl, -CO-(C1-C 12 )alkyl; the substituted or unsubstituted C3~C 12 The cycloalkyl or heterocycloalkyl groups are selected from: -(C3-C 12 )cycloalkyl, -(C3-C 12 Heterocyclic alkyl groups, -O-(C3-C 12 )cycloalkyl, -O-(C3-C 12 Heterocyclic alkyl groups, -S-(C3-C 12 )cycloalkyl, -S-(C3-C 12 Heterocyclic alkyl groups, -COO-(C3-C 12 )cycloalkyl, -COO-(C3-C 12 Heterocyclic alkyl groups, -CONH-(C3-C 12 )cycloalkyl, -CONH-(C3-C 12 Heterocyclic alkyl groups, -CO-(C3-C 12 )cycloalkyl, -CO-(C3-C 12Heterocyclic alkyl groups; the substituted or unsubstituted C6~C 20 The aryl or heteroaryl groups are selected from: -(C6~C 20 )Aryl, -(C6~C 20 ) heteroaryl, -(C6~C 20 )Aryl-(C1~C 12 -alkyl, -(C6~C 20 )heteroaryl-(C1~C 12 -alkyl, -(C6~C 20 )Aryl-O-(C1~C 12 )alkyl, -(C6~C 20 )heteroaryl-O-(C1~C 12 )alkyl, -O-(C1-C 12 )-alkyl-(C6-C 20 )-Aryl.

[0010] More preferably, the R 1 R 2 R 3 and R 4 Each is independently selected from: -(C1~C 12 )alkyl, C6~C 20 The aryl group. More preferably, the R 1 R 2 R 3 and R 4 Each is independently selected from: -(C1~C5)alkyl, phenyl.

[0011] Preferably, the bidentate phosphine ligand is selected from any one or more of the following structures: .

[0012] Preferably, the palladium compound is selected from at least one of palladium chloride, palladium acetate, palladium trifluoroacetate, bis(triphenylphosphine)palladium chloride, bis(acetonitrile)palladium chloride, (1,5-cyclooctadiene)palladium chloride, allyl palladium chloride, tetratriphenylphosphine palladium, palladium acetylacetonate, bis(dibenzylacetonate)palladium, and tri(dibenzylacetonate)palladium.

[0013] Preferably, the acidic additive is selected from at least one of perchloric acid, sulfuric acid, phosphoric acid, hydrochloric acid, formic acid, acetic acid, oxalic acid, methanesulfonic acid, trifluoromethanesulfonic acid, tert-butanesulfonic acid, p-toluenesulfonic acid, dodecyl sulfonic acid, and aluminum trifluoromethanesulfonate.

[0014] Preferably, the non-alcoholic organic solvent is selected from at least one of dioxane, tetrahydrofuran, ethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, 1,2-diethoxyethane ether, ethyl acetate, benzene, toluene, xylene, anisole, N,N-dimethylformamide, dichloromethane, and chloroform.

[0015] Preferably, the hydrogen carboxylation reaction is carried out at a temperature of 60-180°C. More preferably, the reaction temperature is 130-150°C.

[0016] Preferably, the carbon monoxide pressure during the hydrogen carboxylation reaction is 0.5~8 MPa. More preferably, the carbon monoxide pressure is 3~5 MPa.

[0017] Preferably, in the combined catalytic system, the molar ratio of the bidentate phosphine ligand to the palladium compound is 0.5~50:1. More preferably, the molar ratio of the bidentate phosphine ligand to the palladium compound is 1~40:1.

[0018] Preferably, in the combined catalytic system, the molar ratio of the acidic additive to the palladium compound is 0.5 to 100:1. More preferably, the molar ratio of the acidic additive to the palladium compound is 1 to 100:1.

[0019] Preferably, in the system of the hydrocarboxylation reaction, the molar ratio of the palladium compound to the olefin is 0.001 to 0.1:1.

[0020] Preferably, the molar ratio of water to olefin is 1.2 to 50:1. More preferably, the molar ratio of water to olefin is 1.2 to 30:1.

[0021] Preferably, the volume ratio of water to non-alcoholic organic solvent is 0.036~0.270 : 1.

[0022] Preferably, the structure of the olefin is shown in Formula III: In Equation III, R 7 R 8 R 9 and R 10 Each is independently selected from H, C1~C 16 alkyl, olefinic, aryl, aralkyl, or R 7 and R 10 Forming a quinary or hexacyclic ring; the R 7 R 8 R 9 and R 10 They cannot both be H.

[0023] The method for synthesizing carboxylic acid compounds by olefin hydrocarboxylation of the present invention solves the problems of high difficulty and cost in ligand synthesis, numerous restrictions on catalyst selection in the catalytic system, and low yield of sterically hindered internal olefins in the prior art, and has the following advantages: In the combined catalytic system employed in this invention, the 4 or 5 carbon atoms (or heteroatoms) spaced between the two phosphorus atoms of the bidentate phosphine ligand facilitate the formation of an optimal coordination bite angle, thereby enabling the generated palladium active species to exhibit excellent catalytic activity in the hydrocarboxylation reaction of olefins. The method of this invention demonstrates broad compatibility with a wide range of olefin substrates, including aliphatic olefins, aromatic olefins, terminal olefins, internal olefins, and sterically hindered olefins. Even for sterically hindered olefins and internal olefins, this catalytic system can successfully react to generate the corresponding carboxylic acids, exhibiting advantages such as high catalytic efficiency, wide substrate applicability, simple ligand structure, and low cost. Detailed Implementation

[0024] The technical solutions in the embodiments of the present invention will be clearly and completely described below. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.

[0025] It should be noted that: Unless otherwise specified in the examples, conditions should be followed according to standard conditions or the manufacturer's recommendations. Instruments whose manufacturers are not specified are all commercially available products. Raw materials and reagents whose manufacturers are not specified are all commercially available goods or can be prepared using known methods.

[0026] In this invention, all features defined in the form of numerical ranges or percentage ranges, such as numerical values, quantities, contents, and concentrations, are used only for simplicity and convenience. Accordingly, the description of numerical ranges or percentage ranges should be considered as covering and specifically disclosing all possible sub-ranges and individual numerical values ​​(including integers and fractions) within those ranges.

[0027] The features mentioned in this invention can be combined arbitrarily, and all possible combinations should be considered within the scope of this specification, provided that there is no contradiction in the combination of these features. Each feature disclosed in the specification can be replaced by any alternative feature that provides the same, equivalent, or similar purpose. Therefore, unless otherwise specified, the disclosed features are merely general examples of equivalent or similar features.

[0028] In the description of this invention, it should be noted that the terms "comprising," "including," or any other variations thereof are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements includes not only those elements but also other elements not expressly listed, or elements inherent to such a process, method, article, or apparatus. Those skilled in the art will understand the specific meaning of the above terms in this invention according to the specific circumstances.

[0029] The following is a detailed explanation of some of the technical terms used in this invention: “C n ": Represents a carbon chain with a total number of carbon atoms of number n. For example, C1~C 12 Alkyl groups refer to alkyl groups with a total number of carbon atoms of 1 to 12; C6 to C6. 20 The aryl group refers to an aryl group with a total number of carbon atoms of 6 to 20.

[0030] "Substitution" refers to the replacement of hydrogen atoms in a molecule by other different atoms or groups.

[0031] "Alkyl": refers to the hydrocarbon group remaining after an alkane molecule loses one hydrogen atom.

[0032] "Heteroalkyl": refers to a group in which one or more carbon atoms in the carbon chain skeleton of an alkyl group are replaced by heteroatoms.

[0033] "Cycloalkyl": refers to the hydrocarbon group remaining after a cycloalkane molecule loses one hydrogen atom.

[0034] "Heterocyclic alkyl": refers to a group in which one or more carbon atoms in the cyclic skeleton of a cycloalkyl group are replaced by heteroatoms.

[0035] "Aryl": refers to the hydrocarbon group remaining after an aromatic hydrocarbon molecule loses a hydrogen atom from its aromatic ring.

[0036] "Heteroaryl": refers to a group obtained by replacing one or more carbon atoms in the aromatic ring skeleton of an aryl group with heteroatoms.

[0037] "Aryl group": refers to a group obtained by substituting the hydrogen atom of an alkyl group with an aryl group.

[0038] The following examples illustrate a method for synthesizing carboxylic acid compounds by olefin hydrocarboxylation according to the present invention, but do not limit the scope of the invention.

[0039] In the following examples, diisobutylene refers to a mixture of 2,4,4-trimethyl-1-pentene and 2,4,4-trimethyl-2-pentene in a molar ratio of 81:19.

[0040] Example 1 A method for synthesizing carboxylic acid compounds by hydrogen carboxylation of olefins, comprising: In a 100 mL high-pressure reactor, 2.0 mmol diisobutylene, 8.0 mmol water, 0.008 mmol palladium chloride, 0.032 mmol bidentate phosphine ligand a, 0.08 mmol p-toluenesulfonic acid, and 4.0 mL dioxane were added. After sealing the reactor, it was purged three times with carbon monoxide, and then purged with 4.0 MPa of carbon monoxide. The temperature was raised to 140 °C and the reaction was carried out for 16 h. After the reaction was completed, the reactor was cooled to room temperature, the gas was slowly released, and the reactor was unloaded.

[0041] The reaction solution was analyzed using an Agilent 6890 / 5973 gas chromatograph-mass spectrometer. The reaction mixture was alkalized, washed with ethyl acetate, acidified, extracted, and concentrated to obtain the target product 3,5,5-trimethylhexanoic acid. The yield of the target product 3,5,5-trimethylhexanoic acid was 97%, and the positive-to-iso ratio was 99:1.

[0042] The structural formula of the above-mentioned bidentate phosphine ligand a is as follows: Example 2 A method for synthesizing carboxylic acid compounds by hydrogen carboxylation of olefins differs from Example 1 only in that: Bidentate phosphine ligand b was used instead of bidentate phosphine ligand a, and everything else was the same as in Example 1.

[0043] The yield of the target product 3,5,5-trimethylhexanoic acid was 89%, with an iso-to-normal ratio of 99:1.

[0044] The structural formula of the above-mentioned bidentate phosphine ligand b is as follows: Example 3 A method for synthesizing carboxylic acid compounds by hydrogen carboxylation of olefins differs from Example 1 only in that: Bidentate phosphine ligand c was used instead of bidentate phosphine ligand a, and everything else was the same as in Example 1.

[0045] The yield of the target product 3,5,5-trimethylhexanoic acid was 74%, with an iso-to-normal ratio of 99:1.

[0046] The structural formula of the bidentate phosphine ligand c is as follows: Example 4 A method for synthesizing carboxylic acid compounds by hydrogen carboxylation of olefins differs from Example 1 only in that: Bidentate phosphine ligand d was used instead of bidentate phosphine ligand a, and everything else was the same as in Example 1.

[0047] The yield of the target product 3,5,5-trimethylhexanoic acid was 78%, with an iso-to-normal ratio of 99:1.

[0048] The structural formula of the above bidentate phosphine ligand d is as follows: Example 5 A method for synthesizing carboxylic acid compounds by hydrogen carboxylation of olefins differs from Example 1 only in that: Bidentate phosphine ligand e was used instead of bidentate phosphine ligand a, and everything else was the same as in Example 1.

[0049] The yield of the target product 3,5,5-trimethylhexanoic acid was 86%, with an iso-to-normal ratio of 99:1.

[0050] The structural formula of the above bidentate phosphine ligand e is as follows: Example 6 A method for synthesizing carboxylic acid compounds by hydrogen carboxylation of olefins differs from Example 1 only in that: (1,5-cyclooctadiene)palladium dichloride was used instead of palladium chloride, and everything else was the same as in Example 1.

[0051] The yield of the target product 3,5,5-trimethylhexanoic acid was 94%, with an iso-to-normal ratio of 99:1.

[0052] Example 7 A method for synthesizing carboxylic acid compounds by hydrogen carboxylation of olefins differs from Example 1 only in that: Allyl palladium chloride was used instead of palladium chloride, and everything else was the same as in Example 1.

[0053] The yield of the target product 3,5,5-trimethylhexanoic acid was 85%, with an iso-to-normal ratio of 99:1.

[0054] Example 8 A method for synthesizing carboxylic acid compounds by hydrogen carboxylation of olefins differs from Example 1 only in that: The amount of water used was 60 mmol, perchloric acid was used instead of p-toluenesulfonic acid, and ethylene glycol dimethyl ether was used instead of dioxane. Everything else was the same as in Example 1.

[0055] The yield of the target product 3,5,5-trimethylhexanoic acid was 76%, with an iso-to-normal ratio of 99:1.

[0056] Example 9 A method for synthesizing carboxylic acid compounds by hydrogen carboxylation of olefins differs from Example 1 only in that: The amount of diisobutylene used was 8.0 mmol, and the amount of water used was 10.0 mmol; carbon monoxide was introduced at 8 MPa; and the temperature was raised to 180°C. Everything else was the same as in Example 1.

[0057] The yield of the target product 3,5,5-trimethylhexanoic acid was 81%, with an iso-to-normal ratio of 99:1.

[0058] Example 10 A method for synthesizing carboxylic acid compounds by hydrogen carboxylation of olefins differs from Example 1 only in that: 0.20 mmol PdCl2 was used instead of 0.008 mmol palladium chloride, ligand a was used at 0.20 mmol, and p-toluenesulfonic acid was used at 0.20 mmol; carbon monoxide was introduced at 2 MPa; and the temperature was raised to 80°C. Everything else was the same as in Example 1.

[0059] The yield of the target product 3,5,5-trimethylhexanoic acid was 93%, with an iso-to-normal ratio of 99:1.

[0060] Example 11 The only difference from Example 1 is that 0.32 mmol ligand a, 0.80 mmol methanesulfonic acid, 5 MPa, 130 °C, and tetrahydrofuran were used instead of 0.032 mmol ligand a, 4 MPa, 140 °C, and dioxane. Everything else was the same as in Example 1. The yield of 3,5,5-trimethylhexanoic acid was 84%, with a positive-to-iso ratio of 99:1.

[0061] Comparative Example 1 The only difference from Example 1 is: Bidentate phosphine ligand f was used instead of bidentate phosphine ligand a, and everything else was the same as in Example 1.

[0062] The yield of the target product 3,5,5-trimethylhexanoic acid was 62%, with an iso-to-normal ratio of 99:1.

[0063] The structural formula of the above bidentate phosphine ligand f is as follows: Comparative Example 2 The only difference from Example 1 is: Bidentate phosphine ligand g was used instead of bidentate phosphine ligand a, and everything else was the same as in Example 1.

[0064] The yield of the target product 3,5,5-trimethylhexanoic acid was 39%, with an iso-to-normal ratio of 99:1.

[0065] The structural formula of the above-mentioned bidentate phosphine ligand g is as follows: Compared with Comparative Examples 1 and 2, Example 1 of this application shows that having 5 atoms between two phosphines results in better catalytic performance than having 4 or 6 atoms between two phosphines.

[0066] Application example: substrate adaptability Using the catalyst system and reaction conditions in Example 1 as an example, the catalytic performance in different olefin carboxylation reactions is demonstrated. The reaction process was the same as in Example 1, except that 2.0 mmol of other olefin substrates were used to replace 2.0 mmol of diisobutylene. Specific reaction results are shown in Table 1.

[0067] Table 1 Results of hydrocarboxylation reactions with different olefin substrates As shown in Table 1, the combined catalytic system of this invention can be applied to the hydrocarboxylation reaction of different types of olefin substrates. Aliphatic olefins, aromatic olefins, terminal olefins, intermediate olefins, cyclic olefins, and sterically hindered olefins can all generate carboxylic acid compounds in good yields.

[0068] Although the present invention has been described in detail through the preferred embodiments above, it should be understood that the above description should not be considered as a limitation of the present invention. Various modifications and substitutions to the present invention will be apparent to those skilled in the art after reading the above description. Therefore, the scope of protection of the present invention should be defined by the appended claims.

Claims

1. A method for synthesizing carboxylic acid compounds by hydrogen carboxylation of olefins, characterized in that, The method includes: Under the combined catalytic system of bidentate phosphine ligand, palladium compound and acidic additive shown in Formula I, olefins, carbon monoxide, water and non-alcoholic organic solvents undergo a hydrocarboxylation reaction to generate a carboxylic acid with one more carbon than the olefin. In formula I, R 1 R 2 R 3 and R 4 Each is independently selected from: substituted or unsubstituted C1~C 12 Alkyl or heteroalkyl, substituted or unsubstituted C3~C 12 cycloalkyl or heterocycloalkyl, substituted or unsubstituted C6~C 20 aryl or heteroaryl; A is selected from: a straight-chain alkyl group with a total number of 5 atoms, containing or not containing heteroatoms, or the structure shown in Formula II; In Formula II, X is selected from carbon and oxygen; R 5 and R 6 Each is independently selected from: H, C1~C5 alkyl groups, and C1~C5 alkoxy groups; This indicates the position where the ligand is attached to the bidentate phosphine ligand shown in Formula I.

2. The method according to claim 1, characterized in that, The substituted or unsubstituted C1~C 12 The alkyl or heteroalkyl groups are selected from: -(C1~C1) 12 )alkyl, -O-(C1~C 12 )alkyl, -S-(C1-C 12 )alkyl, -N-[(C1-C 12 )alkyl]2、-COO-(C1-C 12 )alkyl, -CONH-(C1-C 12 )alkyl, -CO-(C1-C 12 )alkyl; The substituted or unsubstituted C3~C 12 The cycloalkyl or heterocycloalkyl groups are selected from: -(C3-C 12 )cycloalkyl, -(C3-C 12 Heterocyclic alkyl groups, -O-(C3-C 12 )cycloalkyl, -O-(C3-C 12 Heterocyclic alkyl groups, -S-(C3-C 12 )cycloalkyl, -S-(C3-C 12 Heterocyclic alkyl groups, -COO-(C3-C 12 )cycloalkyl, -COO-(C3-C 12 Heterocyclic alkyl groups, -CONH-(C3-C 12 )cycloalkyl, -CONH-(C3-C 12 Heterocyclic alkyl groups, -CO-(C3-C 12 )cycloalkyl, -CO-(C3-C 12 Heterocyclic alkyl groups; The substituted or unsubstituted C6~C 20 The aryl or heteroaryl groups are selected from: -(C6~C 20 )Aryl, -(C6~C 20 ) heteroaryl, -(C6~C 20 )Aryl-(C1~C 12 -alkyl, -(C6~C 20 )heteroaryl-(C1~C 12 -alkyl, -(C6~C 20 )Aryl-O-(C1~C 12 )alkyl, -(C6~C 20 )heteroaryl-O-(C1~C 12 )alkyl, -O-(C1-C 12 )-alkyl-(C6-C 20 )-Aryl.

3. The method according to claim 1, characterized in that, The bidentate phosphine ligand is selected from any one or more of the following structures: 。 4. The method according to claim 1, characterized in that, The palladium compound is selected from at least one of palladium chloride, palladium acetate, palladium trifluoroacetate, bis(triphenylphosphine)palladium dichloride, bis(acetonitrile)palladium dichloride, (1,5-cyclooctadiene)palladium dichloride, allyl palladium chloride, tetratriphenylphosphine palladium, palladium acetylacetonate, bis(dibenzylacetonate)palladium, and tri(dibenzylacetonate)palladium.

5. The method according to claim 1, characterized in that, The acidic additive is selected from at least one of perchloric acid, sulfuric acid, phosphoric acid, hydrochloric acid, formic acid, acetic acid, oxalic acid, methanesulfonic acid, trifluoromethanesulfonic acid, tert-butanesulfonic acid, p-toluenesulfonic acid, dodecyl sulfonic acid, and aluminum trifluoromethanesulfonate.

6. The method according to claim 1, characterized in that, The non-alcoholic organic solvent is selected from at least one of dioxane, tetrahydrofuran, ethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, 1,2-diethoxyethane ether, ethyl acetate, benzene, toluene, xylene, anisole, N,N-dimethylformamide, dichloromethane, and chloroform.

7. The method according to claim 1, characterized in that, The hydrogen carboxylation reaction is carried out at a temperature of 60~180℃; or / and the hydrogen carboxylation reaction is carried out at a carbon monoxide pressure of 0.5~8MPa.

8. The method according to claim 1, characterized in that, In the combined catalytic system, the molar ratio of the bidentate phosphine ligand to the palladium compound is 0.5~50:1; or / and the molar ratio of the acidic additive to the palladium compound is 0.5~100:

1.

9. The method according to claim 1, characterized in that, In the system of the hydrocarboxylation reaction, the molar ratio of the palladium compound to the olefin is 0.001~0.1:1; or / and, the molar ratio of water to the olefin is 1.2~50:1; or / and, the volume ratio of water to the non-alcoholic organic solvent is 0.036~0.270:

1.

10. The method according to any one of claims 1 to 9, characterized in that, The structure of the olefin is shown in Formula III below: In Equation III, R 7 R 8 R 9 and R 10 Each is independently selected from H, C1~C 16 alkyl, olefinic, aryl, aralkyl, or R 7 and R 10 Forming a quinary or hexacyclic ring; the R 7 R 8 R 9 and R 10 They cannot both be H.

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