Phosphite bidentate phosphine ligand, synthesis method and application thereof

Abstract

The present invention provides a phosphite bidentate phosphine ligand having the following structure: wherein X 1 is oxygen or sulfur, R 1 、R 2 、R 3 、R 4 、R 5 、R 6 、R 7 、R 8 、R 9 、R 10 、R 11 、R 12 、R 13 、R 14 、R 15 、R 16 、R 17 、R 18 、R 19 、R 20 、R 21 、R 22 、R 23 and R 24 Each is independently selected from hydrogen, halogen, substituted or unsubstituted C1-C30 alkyl, and substituted or unsubstituted C6-C30 aryl. The above-mentioned phosphite bidentate phosphine ligand provided by the present invention has a special structural fragment of diphenyl ether or diphenyl sulfide, in which the unique oxygen or sulfur can enhance the catalytic activity of the bidentate phosphine ligand and also make the coordination between it and the catalytically active metal more stable, thereby improving the structural stability of the catalyst system including the ligand and enhancing the catalytic effect.

Description

Technical Field

[0001] The present invention relates to the technical field of organic ligand synthesis, and in particular to a phosphite bidentate phosphine ligand, a synthesis method and application thereof. Background Art

[0002] Olefin hydroformylation is an important method for the industrial preparation of aldehydes, which can be converted into chemicals such as alcohols, acids, and esters, finding widespread application in pharmaceuticals, fine chemicals, and dyes. One of the most important requirements for a successful chemical reaction is the presence of a catalyst. Consequently, for many years, research in olefin hydroformylation has focused on complex catalytic systems with high activity, excellent selectivity, and mild operating conditions. In particular, the successful synthesis of phosphine ligands with various structures has further promoted the development of highly active and selective rhodium-phosphine complex catalysts.

[0003] Phosphine ligands and phosphite ligands are widely used in organic reactions. Phosphite ligands can be divided into bidentate phosphine phosphite ligands and monodentate phosphine phosphite ligands. Compared with monodentate phosphine phosphite ligands, bidentate phosphine phosphite ligands have the advantages of simple synthesis, stable properties in air, high structural controllability, and tight chelation with metals. They can better catalyze reactions. Therefore, the different structures of bidentate phosphine phosphite ligands and the corresponding synthesis methods have become a research hotspot among scholars.

[0004] Patent application CN202310392185.4 provides a bidentate phosphite polymer, its preparation method and application, and a method for olefin carbonyl synthesis reaction. The polymer is formed by copolymerizing a specific bidentate phosphite ligand with 2-vinylnaphthalene. It can be used to catalyze olefin carbonyl synthesis reaction, not only ensuring the catalytic performance of olefin carbonyl synthesis reaction, but also improving the polymer's resistance to solvent swelling, thereby facilitating the stability of the catalyst morphology and, in turn, facilitating the stable production of olefin carbonyl synthesis aldehydes; Patent application CN202010832618.X discloses a bidentate phosphite ligand, its preparation method and application. The preparation method comprises the following steps: (1) mixing phosphorus trichloride with a biphenol compound shown in formula I and performing a first reaction to obtain an intermediate; (2) mixing the intermediate with a solution containing a biphenol compound shown in formula II, an acid binding agent, N,N-dimethylformamide and a solvent and performing a second reaction to produce a bidentate phosphite ligand shown in formula III. This method can improve product yield and reduce production costs. However, existing bidentate phosphine phosphite ligands generally have a binaphthalene and / or biphenyl bridge group in their structure. Their use as olefin hydroformylation catalyst ligands suffers from harsh reaction conditions, complex processes, poor catalytic effect on carbonyl synthesis reactions, low raw material yields, and poor selectivity due to the harsh reaction conditions and complex processes.

[0005] Based on this, how to provide a bidentate phosphine phosphite ligand with a novel structure and optimize its synthesis and preparation reaction conditions accordingly so that the resulting bidentate phosphine phosphite ligand exhibits higher catalytic activity when used as a catalyst ligand for olefin hydroformylation reaction, thereby improving the conversion rate and the yield of the catalytic reaction product, is one of the technical problems to be solved in this field. Summary of the Invention

[0006] The main purpose of the present invention is to provide a phosphite bidentate phosphine ligand, a synthesis method and application thereof, so as to solve the problems in the prior art of poor catalytic activity, low catalytic conversion rate and low yield of reaction products when the bidentate phosphine phosphite ligand is used as a ligand for olefin hydroformylation reaction catalyst.

[0007] In order to achieve the above object, the present invention provides a phosphite bidentate phosphine ligand on one hand, wherein the phosphite bidentate phosphine ligand has a structure as shown in the following formula I:

[0008]

[0009] Among them, X 1 is oxygen or sulfur; R 1 、R 2 、R 3 、R 4 、R 5 、R 6 、R 7 、R 8 、R 9 、R 10 、R 11 、R 12 、R 13 、R 14 、R 15 、R 16 、R 17 、R 18 、R 19 、R 20 、R 21 、R 22 、R 23 and R 24 Each is independently selected from hydrogen, halogen, substituted or unsubstituted C1-C30 alkyl, and substituted or unsubstituted C6-C30 aryl.

[0010] Furthermore, R 1 、R 3 、R 6 and R 84 are each independently selected from substituted or unsubstituted C5-C20 cycloalkyl, substituted or unsubstituted C6-C20 aryl, R 2 、R 4 、R 5、R 7 、R 9 、R 10 、R 11 、R 12 、R 13 、R 14 、R 15 、R 16 、R 17 、R 18 、R 19 、R 20 、R 21 、R 22 、R 23 and R 24 Each is independently selected from hydrogen, and a substituted or unsubstituted C1-C20 linear or branched alkyl group.

[0011] Furthermore, R 1 、R 3 、R 6 and R 84 are each independently a substituted or unsubstituted C5-C12 cycloalkyl group, R 2 、R 4 、R 5 、R 7 、R 9 、R 10 、R 11 、R 12 、R 13 、R 14 、R 15 、R 16 、R 17 、R 18 、R 19 、R 20 、R 21 、R 22 、R 23 and R 24 Each is independently hydrogen, substituted or unsubstituted C1-C12 straight or branched alkyl; preferably, R 1 、R 3 、R 6 and R 84 Each is independently cyclopentyl, cyclohexyl, cycloheptyl, or adamantyl, R 2 、R 4 、R 5 、R 7 、R 9 、R 10 、R 11 、R 12 、R 13 、R 14 、R 15 、R 16 、R17 、R 18 、R 19 、R 20 、R 21 、R 22 、R 23 and R 24 are each independently hydrogen, methyl or ethyl.

[0012] Furthermore, the structure of the phosphite bidentate phosphine ligand is:

[0013]

[0014] Alternatively, the structure of the phosphite bidentate phosphine ligand is:

[0015]

[0016] Another aspect of the present invention provides a method for synthesizing the above-mentioned phosphite bidentate phosphine ligand, which comprises: step S1, mixing a first substrate, a first solvent, a first base compound, and a halide, and subjecting the mixture to a first stirring reaction to obtain a first mixed solution, wherein the first mixed solution includes a first product; step S2, adding a second solvent to the first mixed solution to dissolve the first product to obtain a second mixed solution; step S3, subjecting the second mixed solution to a first extraction, a first concentration, and a purification to obtain a second product; step S4, mixing a second substrate, a third solvent, a second base compound, and phosphorus trichloride, and subjecting the mixture to a second stirring reaction to obtain a third mixed solution; step S5, mixing the second product, a fourth solvent, and a catalyst to obtain a fourth mixed solution; step S6, adding the fourth mixed solution to the third mixed solution to obtain a fifth mixed solution, adding the third base compound to the fifth mixed solution, and subjecting the mixture to a third stirring reaction to obtain a sixth mixed solution containing the phosphite bidentate phosphine ligand, thereby obtaining the phosphite bidentate phosphine ligand; the structural formula of the first substrate is:

[0017]

[0018] The structural formula of the halogenated compound is:

[0019]

[0020] The structural formula of the second product is:

[0021]

[0022] The structural formula of the second substrate is:

[0023] And the equivalent numbers of the two are the same; among them, X 2 is selected from F, Cl, Br or I, X 1 、R 1、R 2 、R 3 、R 4 、R 5 、R 6 、R 7 、R 8 、R 9 、R 10 、R 11 、R 12 、R 13 、R 14 、R 15 、R 16 、R 17 、R 18 、R 19 、R 20 、R 21 、R 22 、R 23 and R 24 It has the structure as described above.

[0024] Furthermore, in step S1, the ratio of the equivalent numbers of the first substrate and the halide is (1.2-1.3):1; preferably, the reaction conditions of the first stirring reaction are: 30-120°C, 10-24h.

[0025] Furthermore, in step S4, the ratio of the equivalents of the second substrate, the second base compound and phosphorus trichloride is 2:(2.5-2.6):(2.00-2.05); preferably, the reaction conditions of the second stirring reaction are: 23±2° C., 16-18 h.

[0026] Furthermore, in step S5, the ratio of the equivalents of the second product and the third base compound is 1:(1.5-2.5), and the equivalent of the catalyst added is 0.1-0.12; preferably, in step S6, the reaction conditions of the third stirring reaction are: 23±2°C, 16-18h.

[0027] Further, the first substrate is 3,5-bis(adamantan-1-yl)catechol and / or 3,5-bis(adamantan-1-yl)2-hydroxythiophenol; and / or, the halide is selected from one or more of 2,4-bis(adamantan-1-yl)-6-bromophenol, 2,4-bis(adamantan-1-yl)-6-chlorophenol and 2,4-bis(adamantan-1-yl)-6-trifluoromethanesulfonylphenol; and / or, the first base compound is selected from potassium carbonate, sodium carbonate, cesium carbonate, NaH, sodium hydroxide, potassium hydroxide, tert-butyl benzoate, benzophenone ... One or more of potassium butoxide t-BuOK, potassium sodium tert-butoxide t-BuONa, triethylamine TEA, N,N-diisopropylethylamine DIEA, 4-dimethylaminopyridine DMAP and 1,8-diazabicyclo[5.4.0]undec-7-ene DBU; and / or the second substrate is 2,2'-biphenol, the second base compound and the third base compound are each independently triethylamine and / or ammonia; and / or the catalyst is selected from one or more of sodium alkoxide, organic base and copper halide, preferably 4-pyrrolidinopyridine.

[0028] Further, the first solvent is selected from one or more of methanol, ethanol, dichloromethane, chloroform, ethyl acetate, benzene, toluene, n-hexane, tetrahydrofuran, acetonitrile, dioxane, N,N-dimethylformamide and dimethyl sulfoxide; and / or, the second solvent is selected from one or more of water, acetonitrile and DMF; and / or, the third solvent is selected from one or more of dichloromethane, benzene, n-hexane and carbon tetrachloride; and / or, the fourth solvent is selected from one or more of methanol, ethanol, dichloromethane, chloroform, ethyl acetate, benzene, toluene, n-hexane, tetrahydrofuran, acetonitrile, N,N-dimethylformamide and dimethyl sulfoxide.

[0029] Furthermore, the first substrate is 3,5-di(adamantan-1-yl)catechol, and the structure of the second product is:

[0030]

[0031] The structure of the phosphite bidentate phosphine ligand is:

[0032]

[0033] Alternatively, the first substrate is 3,5-bis(adamantan-1-yl)2-hydroxythiophenol, and the structure of the second product is:

[0034]

[0035] The structure of the phosphite bidentate phosphine ligand is:

[0036]

[0037] Furthermore, the purification in step S3 is carried out by column chromatography, and the loading method of the column chromatography is dry loading; preferably, the eluent of the column chromatography is selected from one or more of methanol, ethanol, dichloromethane, chloroform, ethyl acetate, n-hexane and petroleum ether; preferably, the eluent is dichloromethane and methanol, and the volume ratio of dichloromethane to methanol is (4-6):1; or, the eluent is ethyl acetate and petroleum ether, and the volume ratio of ethyl acetate to petroleum ether is (18-22):1.

[0038] Furthermore, step S6 also includes: step S6-1, washing, second extraction and second concentration treatment of the sixth mixed liquid to obtain a third product; step S6-2, recrystallizing the third product to obtain a phosphite bidentate phosphine ligand.

[0039] Furthermore, the recrystallization treatment in step S6-1 includes: dissolving the third product in a good recrystallization solvent and heating to reflux; adding a poor recrystallization solvent after cooling, stirring, and filtering to obtain a phosphite bidentate phosphine ligand; preferably, the good recrystallization solvent is selected from one or more of methanol, ethanol, dichloromethane, chloroform and tetrahydrofuran, and the poor recrystallization solvent is selected from one or more of n-hexane, ether, petroleum ether and methyl ethyl ether.

[0040] Another aspect of the present invention provides the use of the aforementioned bidentate phosphite ligand in an olefin hydroformylation reaction, which comprises converting an olefin, hydrogen, and carbon monoxide into an aldehyde compound. The aforementioned bidentate phosphite ligand is complexed with a rhodium-containing compound and used as a catalyst for the olefin hydroformylation reaction; the olefin is selected from a C4-C12 normal olefin or an isoolefin.

[0041] The technical solution of the present invention provides a phosphite bidentate phosphine ligand with a unique structure. The bidentate ligand comprises a special structural fragment of diphenyl ether or diphenyl sulfide. The unique oxygen or sulfur in the bidentate phosphine ligand enhances the catalytic activity of the bidentate phosphine ligand and also stabilizes its coordination with the catalytically active metal, thereby improving the structural stability of the catalyst system including the ligand and enhancing the catalytic effect. DETAILED DESCRIPTION

[0042] It should be noted that, in the absence of conflict, the embodiments and features in the embodiments of the present application can be combined with each other. The present invention will be described in detail below with reference to the embodiments.

[0043] As described in the background art, the bidentate phosphine phosphite ligands in the prior art have poor catalytic activity when used as olefin hydroformylation catalyst ligands, resulting in low catalytic conversion and reaction product yields. In order to solve the above technical problems, the present invention provides a phosphite bidentate phosphine ligand having a structure shown in the following formula I:

[0044]

[0045] Among them, X 1 is oxygen or sulfur; R 1 、R 2 、R 3 、R 4 、R 5 、R 6 、R 7 、R 8 、R 9 、R 10 、R 11 、R 12 、R 13 、R 14 、R 15 、R 16 、R 17 、R 18 、R 19 、R 20 、R 21 、R 22 、R 23 and R 24 Each is independently selected from hydrogen, halogen, substituted or unsubstituted C1-C30 alkyl, and substituted or unsubstituted C6-C30 aryl.

[0046] The special phosphite bidentate phosphine ligand including diphenyl ether or diphenyl sulfide provided by the present invention, because there is a special oxygen or sulfur atom in the structure, there is a lone pair of electrons in the electronic structure of the two, the electron cloud density of the overall structure of the ligand can be improved, the rich electric property of the obtained phosphite bidentate phosphine ligand is enhanced, so that the phosphite bidentate phosphine ligand can more significantly enhance the catalytic activity of the metal active center in many reactions, such as catalytic hydrogenation and hydroformylation. And, the introduction of oxygen or sulfur atom can also increase the steric hindrance of the obtained phosphine ligand, and when it is used in hydroformylation, the formation of carbonyl dimers in the reaction can be suppressed, thereby effectively improving the yield of aldehyde compounds. The phosphite bidentate phosphine ligand with the above-mentioned special structural fragment has good universality, can produce stable coordination with rhodium and its various homologous metals, and obtain a more stable metal / phosphine ligand structure, further improving the catalytic effect.

[0047] Furthermore, R 1 、R 3 、R6 and R 84 are each independently selected from substituted or unsubstituted C5-C20 cycloalkyl, substituted or unsubstituted C6-C20 aryl, R 2 、R 4 、R 5 、R 7 、R 9 、R 10 、R 11 、R 12 、R 13 、R 14 、R 15 、R 16 、R 17 、R 18 、R 19 、R 20 、R 21 、R 22 、R 23 and R 24 Each is independently selected from hydrogen, and a substituted or unsubstituted C1-C20 linear or branched alkyl group.

[0048] Furthermore, R 1 、R 3 、R 6 and R 84 are each independently a substituted or unsubstituted C5-C12 cycloalkyl group, R 2 、R 4 、R 5 、R 7 、R 9 、R 10 、R 11 、R 12 、R 13 、R 14 、R 15 、R 16 、R 17 、R 18 、R 19 、R 20 、R 21 、R 22 、R 23 and R 24 Each is independently hydrogen, substituted or unsubstituted C1-C12 straight or branched alkyl; preferably, R 1 、R 3 、R 6 and R 84 Each is independently cyclopentyl, cyclohexyl, cycloheptyl, or adamantyl, R 2 、R 4 、R 5 、R 7 、R 9、R 10 、R 11 、R 12 、R 13 、R 14 、R 15 、R 16 、R 17 、R 18 、R 19 、R 20 、R 21 、R 22 、R 23 and R 24 are each independently hydrogen, methyl or ethyl.

[0049] In several preferred embodiments, the structure of the phosphite bidentate phosphine ligand is:

[0050]

[0051] Alternatively, the structure of the phosphite bidentate phosphine ligand is:

[0052] The inventor has conducted a lot of experiments on R 1 、R 2 、R 3 、R 4 、R 5 、R 6 、R 7 、R 8 、R 9 、R 10 、R 11 、R 12 、R 13 、R 14 、R 15 、R 16 、R 17 、R 18 、R 19 、R 20 、R 21 、R 22 、R 23 and R 24 The group types were optimized and it was found that when the final structures were When the phosphine is used as a catalyst, the catalytic activity is higher and it can better chelate with the active metal to form a metal / phosphine complex with higher activity and more stable structure, which is less likely to deactivate when used as a catalyst in various reactions.

[0053] Another aspect of the present invention provides a method for synthesizing the above-mentioned phosphite bidentate phosphine ligand, which comprises: step S1, mixing a first substrate, a first solvent, a first base compound, and a halide, and subjecting the mixture to a first stirring reaction to obtain a first mixed solution, wherein the first mixed solution includes a first product; step S2, adding a second solvent to the first mixed solution to dissolve the first product to obtain a second mixed solution; step S3, subjecting the second mixed solution to a first extraction, a first concentration, and a purification to obtain a second product; step S4, mixing a second substrate, a third solvent, a second base compound, and phosphorus trichloride, and subjecting the mixture to a second stirring reaction to obtain a third mixed solution; step S5, mixing the second product, a fourth solvent, and a catalyst to obtain a fourth mixed solution; step S6, adding the fourth mixed solution to the third mixed solution to obtain a fifth mixed solution, adding the third base compound to the fifth mixed solution, and subjecting the mixture to a third stirring reaction to obtain a sixth mixed solution containing the phosphite bidentate phosphine ligand, thereby obtaining the phosphite bidentate phosphine ligand; the structural formula of the first substrate is:

[0054]

[0055] The structural formula of the halogenated compound is:

[0056]

[0057] The structural formula of the second product is:

[0058]

[0059] The structural formula of the second substrate is:

[0060] And the equivalent numbers of the two are the same; among them, X 2 is selected from F, Cl, Br or I, X 1 、R 1 、R 2 、R 3 、R 4 、R 5 、R 6 、R 7 、R 8 、R 9 、R 10 、R 11 、R 12 、R 13 、R 14 、R 15 、R 16 、R 17 、R 18 、R 19 、R 20 、R 21 、R 22 、R 23 and R24 It has the structure as described above.

[0061] The present invention is directed to the above-mentioned phosphite bidentate phosphine ligand with a special structure, and accordingly provides a preparation method suitable therefor. Among them, first a first substrate, a first solvent, a first base compound and a halide are mixed and reacted to obtain a first product contained in the structure, and the first product is separated and purified to obtain a second product for use. Thereafter, a fourth mixed solution is obtained by reacting a second substrate, a third solvent, a second base compound and phosphorus trichloride, wherein the intermediate product contains a chlorine atom substituent. After that, the second solvent and the catalyst are dissolved in the fourth solvent, and then reacted with the third mixed solution containing the intermediate product in the presence of a base to obtain a sixth mixed solution containing the final phosphine ligand structure, and the phosphite bidentate phosphine ligand is obtained after separation and purification. The present invention synthesizes the novel phosphite bidentate phosphine ligand described above by using the above-mentioned simpler and more efficient method. The above-mentioned method provided by the present invention has simpler and milder synthesis conditions, is more economical and more in line with the principles of green chemistry, and the obtained product has higher purity and higher catalytic activity.

[0062] In a preferred embodiment, in step S1, the ratio of the equivalents of the first substrate to the halide is (1.2-1.3):1. Regarding the novel phosphite bidentate phosphine ligand provided by the present invention, the inventors optimized the ratio of the equivalents of the first substrate to the halide during the formation of its structure through extensive experiments and found that when the equivalent ratio is within this range, the provided phosphine ligand structure can be better formed. On this basis, the inventors further preferred the reaction conditions for the first stirring reaction to be: 30-120°C, 10-24h, and found that under these conditions, the phosphine ligand structure can be formed more efficiently, thereby improving its yield.

[0063] Furthermore, in step S4, the ratio of the equivalents of the second substrate, the second base compound, and phosphorus trichloride is 2: (2.5-2.6): (2.00-2.05). After a large number of experiments, the inventors optimized the ratio of the equivalents of the second substrate, the second base compound, and phosphorus trichloride involved in the reaction to this range so as to prepare the intermediate product with higher purity. On this basis, the reaction conditions are further optimized to be: 23±2°C, 16-18h, thereby improving the yield of the intermediate product.

[0064] In a preferred embodiment, the ratio of the equivalents of the second product to the third base compound in step S5 is 1:(1.5-2.5), and the equivalent of the catalyst added is 0.1-0.12, so as to generate an active intermediate and thus accelerate the reaction. Preferably, in step S6, the reaction conditions for the third stirring reaction are: 23±2°C for 16-18 hours. Through extensive experiments, the inventors optimized the reaction conditions involved in the step of ultimately forming the novel phosphite bidentate phosphine ligand structure and found that a temperature of 23±2°C and a reaction time of 16-18 hours resulted in a higher yield of the bidentate phosphine ligand.

[0065] In several typical embodiments, the first substrate is 3,5-bis(adamantan-1-yl)catechol and / or 3,5-bis(adamantan-1-yl)2-hydroxythiophenol; and / or the halide is selected from one or more of 2,4-bis(adamantan-1-yl)-6-bromophenol, 2,4-bis(adamantan-1-yl)-6-chlorophenol and 2,4-bis(adamantan-1-yl)-6-trifluoromethanesulfonate phenol; and / or the first base compound is selected from potassium carbonate, sodium carbonate, cesium carbonate, NaH, sodium hydroxide, potassium hydroxide, potassium tert-butoxide t-BuOK, potassium sodium tert-butoxide t-BuONa, triethylamine TEA, N,N-diisopropylethylamine DIEA, 4-dimethylaminopyridine DMAP and 1,8-

[0066] One or more of diazabicyclo[5.4.0]undec-7-ene (DBU). Regarding the phosphite bidentate phosphine ligand structure provided by the present invention, because the molecular structure of the first substrate significantly influences the final structure, the inventors, through extensive experimentation, optimized the aforementioned raw material types and successfully developed a special phosphite bidentate phosphine ligand comprising diphenyl ether or diphenyl sulfide. Based on the aforementioned raw material types, and / or, the second substrate is 2,2'-biphenol, the second base compound and the third base compound are each independently triethylamine and / or ammonia; and / or, the catalyst is selected from one or more of sodium alkoxide, an organic base, and a copper halide, preferably 4-pyrrolidinylpyridine. Through extensive experimentation, the inventors optimized the second substrate, second and third base compounds, and catalyst types for this special novel bidentate phosphine ligand to minimize byproducts during the synthesis of the bidentate phosphine ligand and improve its purity.

[0067] Furthermore, with respect to the solvent system used in each step of the present method, the inventors have optimized it based on the above-mentioned special products and intermediates, namely: the first solvent is selected from one or more of methanol, ethanol, dichloromethane, chloroform, ethyl acetate, benzene, toluene, n-hexane, tetrahydrofuran, acetonitrile, dioxane, N,N-dimethylformamide and dimethyl sulfoxide; and / or, the second solvent is selected from one or more of water, acetonitrile and DMF; and / or, the third solvent is selected from one or more of dichloromethane, benzene, n-hexane and carbon tetrachloride; and / or, the fourth solvent is selected from one or more of methanol, ethanol, dichloromethane, chloroform, ethyl acetate, benzene, toluene, n-hexane, tetrahydrofuran, acetonitrile, N,N-dimethylformamide and dimethyl sulfoxide. The types of solvents used in each step of the above-mentioned type are optimized by the inventors through a large number of experiments, and it is found that using the above-mentioned types of compounds as solvents used in each step can better adapt to the synthesis method system provided by the present invention, thereby better achieving the smooth progress of each step, improving the reaction efficiency, while also reducing the difficulty of separation, and ultimately enhancing the catalytic reaction activity of the resulting bidentate phosphine ligand.

[0068] In several typical embodiments, when the first substrate is 3,5-di(adamantan-1-yl)catechol, the first solvent is toluene, and the reaction conditions of the first stirring reaction are: 100°C, 24h, and the extractant used for the first extraction is dichloromethane; or, the first solvent is tetrahydrofuran, and the reaction conditions of the first stirring reaction are: 30°C, 24h, and the extractant used for the first extraction is ethyl acetate; or, the first solvent is n-butanol, and the reaction conditions of the first stirring reaction are: 120°C, 16h, and the extractant used for the first extraction is dichloromethane; or, the first solvent is dioxane, and the reaction conditions of the first stirring reaction are: 110°C, 16h, and the extractant used for the first extraction is dichloromethane. After a large number of experiments, the inventors optimized the first substrate, the first solvent and the corresponding reaction conditions used in the reaction, and obtained the above-mentioned schemes. It was also found that when the synthesis is carried out according to the above scheme, it can be obtained more efficiently, that is, with a higher yield and liquid chromatography purity. These two intermediates can improve the reaction yield of the final phosphite bidentate phosphine ligand.

[0069] In several preferred embodiments, the first substrate is 3,5-di(adamantan-1-yl)catechol, and the structure of the second product is:

[0070]

[0071] The structure of the phosphite bidentate phosphine ligand is:

[0072]

[0073] Alternatively, the first substrate is 3,5-bis(adamantan-1-yl)2-hydroxythiophenol, and the structure of the second product is:

[0074]

[0075] The structure of the phosphite bidentate phosphine ligand is:

[0076] After extensive experiments, the inventors optimized the type of the first substrate and found that when it is the two types mentioned above, the corresponding phosphite bidentate phosphine ligand can be prepared with higher yield and purity. Furthermore, the two structures obtained have higher catalytic activity and are better able to chelate with active metals, forming more active and structurally stable metal / phosphine complexes, which are less likely to deactivate when used as catalysts in various reactions.

[0077] In the method provided by the present invention, step S3 involves The first product is purified. Furthermore, in step S3, the purification is carried out by column chromatography, and the loading method of the column chromatography is dry loading. With respect to the above-mentioned intermediate product, considering its special structure and the system to be separated, the inventors prefer to separate it by column chromatography with dry loading to improve the purity of the product, and based on the polarity of the two products, the eluent used for the column chromatography is preferably one or more of methanol, ethanol, dichloromethane, chloroform, ethyl acetate, n-hexane and petroleum ether. In several typical embodiments, the eluent is dichloromethane and methanol, and the volume ratio of dichloromethane to methanol is (4-6):1; or, the eluent is ethyl acetate and petroleum ether, and the volume ratio of ethyl acetate to petroleum ether is (18-22):1. After a large number of experiments and comparisons, the inventors optimized the eluent system used in this separation step and found that the above two eluent systems are more adaptable to the polarity of these two intermediate products. The bands during the separation process are clearer and the intervals are larger. At the same time, they can also better suppress the side reactions that may occur in the separation column, thereby better improving the purity and yield of the final phosphite bidentate phosphine ligand product.

[0078] Furthermore, step S6 also includes: step S6-1, washing, second extraction and second concentration treatment of the sixth mixed liquid to obtain a third product; step S6-2, recrystallizing the third product to obtain a phosphite bidentate phosphine ligand.

[0079] Furthermore, the recrystallization treatment in step S6-1 includes: dissolving the third product in a good recrystallization solvent and heating to reflux; adding a poor recrystallization solvent after cooling, stirring, and filtering to obtain a phosphite bidentate phosphine ligand to improve the purity of the phosphite bidentate phosphine ligand. In view of the solubility characteristics of the phosphite bidentate phosphine ligand provided by the present invention, the inventors, after a large number of experiments, selected the recrystallization good solvent from one or more of methanol, ethanol, dichloromethane, chloroform, and tetrahydrofuran, and the recrystallization poor solvent from one or more of n-hexane, ether, petroleum ether, and methyl ethyl ether, thereby further improving the purity of the obtained phosphite bidentate phosphine ligand product.

[0080] Another aspect of the present invention provides the use of the aforementioned bidentate phosphite ligand in an olefin hydroformylation reaction, which comprises converting an olefin, hydrogen, and carbon monoxide into an aldehyde compound. The aforementioned bidentate phosphite ligand is complexed with a rhodium-containing compound and used as a catalyst for the olefin hydroformylation reaction; the olefin is selected from a C4-C12 normal olefin or an isoolefin.

[0081] The phosphite bidentate phosphine ligand provided by the present invention, when used as a catalyst component, exhibits enhanced catalytic activity for olefin hydroformylation reactions, resulting in high conversion rates of the catalytic reaction feedstock and high product yields, while also exhibiting high selectivity for aldehyde products. After complexation with a rhodium-containing compound, the phosphite bidentate phosphine ligand participates in the olefin hydroformylation reaction with a stable structure and is not easily deactivated during use.

[0082] The present application is further described in detail below with reference to specific embodiments. These embodiments should not be construed as limiting the scope of protection claimed in this application.

[0083] Unless otherwise defined, all technical terms used hereinafter have the same meanings as those generally understood by those skilled in the art. The technical terms used herein are only for the purpose of describing specific embodiments and are not intended to limit the scope of protection of the present invention.

[0084] Preparation Example 1

[0085] A method for preparing a phosphite bidentate phosphine ligand:

[0086] A dry 250 mL round-bottom flask was placed under a magnetic stirrer. 2,4-di(adamantan-1-yl)-6-bromophenol (0.884 g) was added, followed by 60 mL of toluene, CsCO₃ (1.303 g), and finally 3,5-di(adamantan-1-yl)catechol (0.910 g). The mixture was stirred at 100°C for 24 hours before the reaction was complete. After cooling, 20 mL of water was added to dissolve the solid, and the aqueous phase was extracted with 40 mL of dichloromethane. This extraction was repeated twice, and the organic phase was concentrated to yield 1.331 g of a pale yellow solid. The crude product was dry-applied onto a column chromatography column and eluted with dichloromethane / methanol (5:1). After concentration, 1.257 g of product C, a white solid powder, was obtained, with a yield of 85% and a liquid chromatography purity of 99.6%.

[0087] To a dry 50 mL two-necked flask, add 2,2'-biphenol (0.748 g), 10 mL of a toluene solution containing 0.53 g of triethylamine, and freshly distilled PCl3 (0.567 g). Stir overnight at 25°C (16 h, the same below) to obtain product D. After completion of the reaction, use it directly in the next step without further treatment.

[0088] Take a dry 100mL two-necked flask and add product C (1.479g), add 15mL of toluene, and add 0.03g of 4-pyrrolidinylpyridine. Add the above solution to the reaction bottle of product D, then add 0.408g of triethylamine, and stir at room temperature of 25℃ for 24 hours. The resulting reaction solution was washed with water and extracted with 30mL of dichloromethane. The extraction was repeated twice. After concentration, the solid was a yellow-white solid. The crude product weighed 2.1g.

[0089] To a 100mL single-necked round-bottom flask, add 30mL of methanol, heat to reflux for 30 minutes, cool to room temperature (25°C), then slowly add 15mL of n-hexane, stir for 2 hours, and filter. The resulting solid is the bidentate phosphite ligand of Formula Ia. After drying, it weighs 2.01g, with an 86% yield and a liquid chromatography purity of 99.6%. The overall reaction yield is 73%.

[0090] The specific reaction route is:

[0091]

[0092] Preparation Example 2

[0093] A method for preparing a phosphite bidentate phosphine ligand:

[0094] A dry 250 mL round-bottom flask was placed under a magnetic stirrer. 2,4-di(adamantan-1-yl)-6-bromophenol (0.884 g) was added, followed by 60 mL of acetonitrile, then Na₂CO₃ (0.552 g), and finally 3,5-di(adamantan-1-yl)catechol (0.910 g). The mixture was stirred at 80°C for 24 hours before the reaction was complete. After cooling, 20 mL of water was added to dissolve the solid, and the aqueous phase was extracted with 40 mL of ethyl acetate. This extraction was repeated twice, and the organic phase was concentrated to yield 1.103 g of a pale yellow solid. The crude product was dry-applied onto a column chromatography column and eluted with ethyl acetate / petroleum ether (20:1). After concentration, 0.808 g of Product C, a white solid powder, was obtained, with a yield of 55% and a liquid chromatography purity of 98.6%.

[0095] In a dry 50 mL two-necked flask, add 2,2'-biphenol (0.748 g), 10 mL of a toluene solution containing 0.53 g of triethylamine, and freshly distilled PCl3 (0.567 g). Stir overnight at 25°C to obtain product D. After the reaction is complete, use it directly in the next step without further treatment.

[0096] Take a dry 100mL two-necked flask and add product C (1.479g), add 15mL of toluene, and add 0.03g of 4-pyrrolidinylpyridine. Add the above solution to the reaction bottle of product D, then add 0.408g of triethylamine, and stir at room temperature 25°C for 24 hours. The resulting reaction solution was washed with water and extracted with 30mL of dichloromethane. The extraction was repeated twice. After concentration, the solid was a yellow-white solid. The crude product weighed 2.05g.

[0097] To a 100 mL single-necked round-bottom flask, add 30 mL of methanol, heat to reflux for 30 minutes, cool to room temperature (25°C), then slowly add 15 mL of n-hexane, stir for 2 hours, and filter. The resulting solid is a phosphite bidentate phosphine ligand of Formula Ia. After drying, the solid weighs 1.89 g, with an 81% yield and 96.7% liquid chromatography purity. The overall reaction yield is 44.6%. This yield is lower than that of Preparation Example 1.

[0098] Preparation Example 3

[0099] A method for preparing a phosphite bidentate phosphine ligand:

[0100] A dry 250 mL round-bottom flask was placed under a magnetic stirrer. 2,4-di(adamantan-1-yl)-6-bromophenol (0.884 g) was added, followed by 60 mL of tetrahydrofuran, KOH (0.224 g), and finally 3,5-di(adamantan-1-yl)catechol (0.910 g). The reaction was stirred at 30°C for 24 hours and allowed to complete. After cooling, 20 mL of water was added to dissolve the solid, and the aqueous phase was extracted with 40 mL of ethyl acetate. This extraction was repeated twice, and the organic phase was concentrated to yield 1.294 g of a pale yellow solid. The crude product was dry-applied onto a column chromatography column and eluted with ethyl acetate / petroleum ether (20:1). After concentration, 1.216 g of product C, a white solid powder, was obtained, with a yield of 82% and a liquid chromatography purity of 99.1%.

[0101] In a dry 50 mL two-necked flask, add 2,2'-biphenol (0.748 g), 10 mL of a toluene solution containing 0.53 g of triethylamine, and freshly distilled PCl3 (0.567 g). Stir overnight at 25°C to obtain product D. After the reaction is complete, use it directly in the next step without further treatment.

[0102] Take a dry 100mL two-necked flask and add product C (1.479g), add 15mL of toluene, and add 0.03g of 4-pyrrolidinylpyridine. Add the above solution to the reaction bottle of product D, then add 0.408g of triethylamine, and stir at room temperature of 25℃ for 24 hours. The resulting reaction solution was washed with water and extracted with 30mL of dichloromethane. The extraction was repeated twice. After concentration, the solid was a yellow-white solid. The crude product weighed 2.1g.

[0103] To a 100mL single-necked round-bottom flask, add 30mL of methanol, heat to reflux for 30 minutes, cool to room temperature (25°C), then slowly add 15mL of n-hexane, stir for 2 hours, and filter. The resulting solid is the bidentate phosphite ligand of Formula Ia. After drying, it weighs 2.03g, with a yield of 86% and a liquid chromatography purity of 99.7%. The overall reaction yield is 70.5%.

[0104] Preparation Example 4

[0105] A method for preparing a phosphite bidentate phosphine ligand:

[0106] A dry 250 mL round-bottom flask was placed in a magnetic stirrer. 2,4-di(adamantan-1-yl)-6-bromophenol (0.884 g) was added, followed by 60 mL of tetrahydrofuran, followed by KOH (0.168 g), and finally 3,5-di(adamantan-1-yl)catechol (0.910 g). The reaction was stirred at 30°C for 10 hours. After cooling, 20 mL of water was added to dissolve the solid, and the aqueous phase was extracted with 40 mL of ethyl acetate. This extraction was repeated twice, and the organic phase was concentrated to yield 1.029 g of a pale yellow solid.

[0107] The crude product was loaded onto a column chromatography column by dry method, and the sample was eluted with dichloromethane / methanol (5:1). After concentration, 0.926 g of white solid powder product C was obtained with a yield of 63% and a liquid chromatography purity of 98.4%.

[0108] In a dry 50 mL two-necked flask, add 2,2'-biphenol (0.748 g), 10 mL of a toluene solution containing 0.53 g of triethylamine, and freshly distilled PCl3 (0.567 g). Stir overnight at 25°C to obtain product D. After the reaction is complete, use it directly in the next step without further treatment.

[0109] Take a dry 100mL two-necked flask and add product C (1.479g), add 15mL of toluene, and add 0.03g of 4-pyrrolidinylpyridine. Add the above solution to the reaction bottle of product D, then add 0.408g of triethylamine, and stir at room temperature of 25°C for 24 hours. The reaction solution obtained above was washed with water and extracted with 30mL of dichloromethane. The extraction was repeated twice. After concentration, the solid was a yellow-white solid. The crude product weighed 1.98g.

[0110] To a 100 mL single-necked round-bottom flask, add 30 mL of methanol, heat to reflux for 30 minutes, cool to room temperature (25°C), then slowly add 15 mL of n-hexane, stir for 2 hours, and filter. The resulting solid is a phosphite bidentate phosphine ligand of Formula Ia. After drying, the solid weighs 1.74 g, with a single-step reaction yield of 74.4%, a liquid chromatography purity of 97.7%, and an overall reaction yield of 46.8%. This yield is lower than that of Preparation Example 3.

[0111] Preparation Example 5

[0112] A method for preparing a phosphite bidentate phosphine ligand:

[0113] A dry 250 mL round-bottom flask was placed under a magnetic stirrer. 1.022 g of 2,4-di(adamantan-1-yl)-6-trifluoromethanesulfonate phenol was added, followed by 20 mL of n-butanol, 0.516 g of DIEA, and finally 0.910 g of 3,5-di(adamantan-1-yl)catechol. The reaction was stirred at 120°C for 16 hours, and the reaction was complete. After cooling, 10 mL of water was added to dissolve the solid, and the aqueous phase was extracted with 30 mL of dichloromethane. This extraction was repeated twice, and the organic phase was concentrated to yield 1.308 g of a pale yellow solid. The crude product was dry-applied onto a column chromatography column and eluted with dichloromethane / methanol (5:1). After concentration, 1.217 g of product C, a white solid powder, was obtained, with a yield of 82.2% and a liquid chromatography purity of 98.6%.

[0114] In a dry 50 mL two-necked flask, add 2,2'-biphenol (0.748 g), 10 mL of a toluene solution containing 0.53 g of triethylamine, and freshly distilled PCl3 (0.567 g). Stir overnight at 25°C to obtain product D. After the reaction is complete, use it directly in the next step without further treatment.

[0115] Take a dry 100mL two-necked flask and add product C (1.479g), add 15mL of toluene, and add 0.03g of 4-pyrrolidinylpyridine. Add the above solution to the reaction bottle of product D, then add 0.408g of triethylamine, and stir at room temperature at 25°C for 24 hours. The resulting reaction solution was washed with water and extracted with 30mL of dichloromethane. The extraction was repeated twice. After concentration, the solid was a yellow-white solid. The crude product weighed 2.03g.

[0116] To a 100mL single-necked round-bottom flask, add 30mL of methanol, heat to reflux for 30 minutes, cool to room temperature (25°C), then slowly add 15mL of n-hexane, stir for 2 hours, and filter. The resulting solid is the bidentate phosphite ligand of Formula Ia. After oven drying, it weighs 1.88g, with a yield of 80.3% and a liquid chromatography purity of 99.7%. The overall reaction yield is 66.00%.

[0117] Preparation Example 6

[0118] A method for preparing a phosphite bidentate phosphine ligand:

[0119] A dry 250 mL round-bottom flask was placed under a magnetic stirrer. 1.022 g of 2,4-di(adamantan-1-yl)-6-trifluoromethanesulfonate phenol was added, followed by 20 mL of toluene, followed by 0.384 g of sodium tert-butoxide, and finally 0.910 g of 3,5-di(adamantan-1-yl)catechol. The reaction was stirred at 110°C for 16 hours, and the mixture was allowed to complete. After cooling, 10 mL of water was added to dissolve the solid, and the aqueous phase was extracted with 30 mL of dichloromethane. This extraction was repeated twice, and the organic phase was concentrated to yield 1.176 g of a pale yellow solid. The crude product was dry-applied onto a column chromatography column, eluted with dichloromethane / methanol (5:1), and concentrated to yield 0.882 g of Product C, a white solid powder with a yield of 59.6% and a liquid chromatography purity of 97.5%.

[0120] In a dry 50 mL two-necked flask, add 2,2'-biphenol (0.748 g), 10 mL of a toluene solution containing 0.53 g of triethylamine, and freshly distilled PCl3 (0.567 g). Stir overnight at 25°C to obtain product D. After the reaction is complete, use it directly in the next step without further treatment.

[0121] Take a dry 100mL two-necked flask and add product C (1.479g), add 15mL of toluene, and add 0.03g of 4-pyrrolidinylpyridine. Add the above solution to the reaction bottle of product D, then add 0.408g of triethylamine, and stir at room temperature of 25℃ for 24 hours. The resulting reaction solution was washed with water and extracted with 30mL of dichloromethane. The extraction was repeated twice. After concentration, the solid was a yellow-white solid. The crude product weighed 2.1g.

[0122] To a 100mL single-necked round-bottom flask, add 30mL of methanol, heat to reflux for 30 minutes, cool to room temperature (25°C), then slowly add 15mL of n-hexane, stir for 2 hours, and filter. The resulting solid is a phosphite bidentate phosphine ligand of Formula Ia. After drying, the solid weighs 1.91g, with a yield of 81.6%, a liquid chromatography purity of 49.1%, and an overall reaction yield of 48.6%. This yield is lower than that of Preparation Example 5.

[0123] Preparation Example 7

[0124] A method for preparing a phosphite bidentate phosphine ligand:

[0125] A dry 250 mL round-bottom flask was placed under a magnetic stirrer. 2,4-di(adamantan-1-yl)-6-chlorophenol (0.884 g) and 0.796 g) were added, followed by 20 mL of dioxane and sodium tert-butoxide (0.384 g). Finally, 3,5-di(adamantan-1-yl)catechol (0.910 g) was added and stirred at 110°C for 16 hours to complete the reaction. After cooling, the filtrate was filtered, and 10 mL of water was added to dissolve the solid. The aqueous phase was then extracted with 30 mL of dichloromethane. This extraction was repeated twice, and the organic phase was concentrated to yield 1.338 g of a pale yellow solid. The crude product was dry-applied onto a column chromatography column and eluted with dichloromethane / methanol (5:1). After concentration, 1.244 g of product C, a white solid powder, was obtained, with a yield of 84.1% and a liquid chromatography purity of 98.7%.

[0126] In a dry 50 mL two-necked flask, add 2,2'-biphenol (0.748 g), 10 mL of a toluene solution containing 0.53 g of triethylamine, and freshly distilled PCl3 (0.567 g). Stir overnight at 25°C to obtain product D. After the reaction is complete, use it directly in the next step without further treatment.

[0127] Take a dry 100mL two-necked flask and add product C (1.479g), add 15mL of toluene, and add 0.03g of 4-pyrrolidinylpyridine. Add the above solution to the reaction bottle of product D, then add 0.408g of triethylamine, and stir at room temperature of 25℃ for 24 hours. The resulting reaction solution was washed with water and extracted with 30mL of dichloromethane. The extraction was repeated twice. After concentration, the solid was a yellow-white solid. The crude product weighed 2.1g.

[0128] To a 100mL single-necked round-bottom flask, add 30mL of methanol, heat to reflux for 30 minutes, cool to room temperature (25°C), then slowly add 15mL of n-hexane, stir for 2 hours, and filter. The resulting solid is the bidentate phosphite ligand of Formula Ia. After drying, it weighs 2.02g, with a single-step reaction yield of 86.3% and a liquid chromatography purity of 99.9%. The overall reaction yield is 72.57%.

[0129] Preparation Example 8

[0130] A method for preparing a phosphite bidentate phosphine ligand:

[0131] A dry 250 mL round-bottom flask was placed under a magnetic stirrer. 2,4-di(adamantan-1-yl)-6-chlorophenol (0.884 g) and 0.796 g) were added, followed by 20 mL of dioxane and sodium tert-butoxide (0.384 g). Finally, 3,5-di(adamantan-1-yl)catechol (0.910 g) was added and stirred at 110°C for 16 hours to complete the reaction. After cooling, the filtrate was filtered, and 10 mL of water was added to dissolve the solid. The aqueous phase was then extracted with 30 mL of dichloromethane. This extraction was repeated twice, and the organic phase was concentrated to yield 1.19 g of a pale yellow solid. The crude product was dry-applied onto a column chromatography column and eluted with dichloromethane / methanol (5:1). After concentration, 0.857 g of Product C, a white solid powder, was obtained, with a single-step overall yield of 57.9% and a liquid chromatography purity of 94.7%.

[0132] In a dry 50 mL two-necked flask, add 2,2'-biphenol (0.748 g), 10 mL of a toluene solution containing 0.53 g of triethylamine, and freshly distilled PCl3 (0.567 g). Stir overnight at 25°C to obtain product D. After the reaction is complete, use it directly in the next step without further treatment.

[0133] Take a dry 100mL two-necked flask and add product C (1.479g), add 15mL of toluene, and add 0.03g of 4-pyrrolidinylpyridine. Add the above solution to the reaction bottle of product D, then add 0.408g of triethylamine, and stir at room temperature 25°C for 24 hours. The resulting reaction solution was washed with water and extracted with 30mL of dichloromethane. The extraction was repeated twice. After concentration, the solid was a yellow-white solid. The crude product weighed 1.29g.

[0134] To a 100 mL single-necked round-bottom flask, add 30 mL of methanol, heat to reflux for 30 minutes, cool to room temperature (25°C), then slowly add 15 mL of n-hexane, stir for 2 hours, and filter. The resulting solid is a phosphite bidentate phosphine ligand of Formula Ia. After drying, the solid weighs 2.02 g, with a yield of 86.3%, a liquid chromatography purity of 98.4%, and an overall reaction yield of 49.9%. This yield is lower than that of Preparation Example 7.

[0135] Preparation Example 9

[0136] A method for preparing a phosphite bidentate phosphine ligand:

[0137] Take a dry 250mL round-bottom flask, put in a magnetic bar, add 2,4-di(adamantan-1-yl)-6-bromophenol (0.884g), then add 60mL of toluene, add CsCO3 (1.303g) again, and finally add 3,5-di(adamantan-1-yl) 2-hydroxybenzenethiol (1.01g) and stir at 100℃ for 24 hours to complete the reaction. After cooling, add 20mL of water to dissolve the solid, and then add 40mL

[0138] The aqueous phase was extracted with dichloromethane, repeated twice, and the organic phase was concentrated to yield 1.292 g of a pale yellow solid. The crude product was dry-loaded onto a column chromatography column, eluted with dichloromethane / methanol (5:1), and concentrated to yield 1.137 g of product C, a white solid powder, with a yield of 74.8% and a liquid chromatography purity of 98.9%.

[0139] In a dry 50 mL two-necked flask, add 2,2'-biphenol (0.748 g), 10 mL of a toluene solution containing 0.53 g of triethylamine, and freshly distilled PCl3 (0.567 g). Stir overnight at 25°C to obtain product D. After the reaction is complete, use it directly in the next step without further treatment.

[0140] Take a dry 100mL two-necked flask and add product C (1.52g), add 15mL of toluene, and add 0.03g of 4-pyrrolidinylpyridine. Add the above solution to the reaction bottle of product D, then add 0.408g of triethylamine, and stir at room temperature 25°C for 24 hours. The resulting reaction solution was washed with water and extracted with 30mL of dichloromethane. The extraction was repeated twice. After concentration, the solid was a yellow-white solid. The crude product weighed 2.2g.

[0141] To a 100mL single-necked round-bottom flask, add 30mL of methanol, heat to reflux for 30 minutes, cool to room temperature (25°C), then slowly add 15mL of n-hexane, stir for 2 hours, and filter. The resulting solid is the bidentate phosphite ligand of Formula Ib. After drying, it weighs 1.95g, with a single-step reaction yield of 82% and a liquid chromatography purity of 98.5%. The overall reaction yield is 61.3%.

[0142] The specific reaction route is as follows:

[0143]

[0144] Preparation Example 10

[0145] A method for preparing a phosphite bidentate phosphine ligand:

[0146] A dry 250 mL round-bottom flask was placed under a magnetic stirrer. 2,4-di(adamantan-1-yl)-6-bromophenol (0.884 g) was added, followed by 60 mL of acetonitrile, then Na₂CO₃ (0.552 g), and finally 3,5-di(adamantan-1-yl)-2-hydroxythiophenol (1.01 g). The reaction was stirred at 80°C for 24 hours and the reaction was complete. After cooling, 20 mL of water was added to dissolve the solid, and the aqueous phase was extracted with 40 mL of ethyl acetate. This extraction was repeated twice, and the organic phase was concentrated to yield 0.912 g of a pale yellow solid. The crude product was dry-applied onto a column chromatography column, eluted with ethyl acetate / petroleum ether (20:1), and concentrated to yield 0.638 g of Product C as a white solid powder. The overall yield for the single-step reaction was 42%, and the liquid chromatography purity was 97.9%.

[0147] In a dry 50 mL two-necked flask, add 2,2'-biphenol (0.748 g), 10 mL of a toluene solution containing 0.53 g of triethylamine, and freshly distilled PCl3 (0.567 g). Stir overnight at 25°C to obtain product D. After the reaction is complete, use it directly in the next step without further treatment.

[0148] Take a dry 100mL two-necked flask and add product C (1.52g), add 15mL of toluene, and add 0.03g of 4-pyrrolidinylpyridine. Add the above solution to the reaction bottle of product D, then add 0.408g of triethylamine, and stir at room temperature at 25°C for 24 hours. The resulting reaction solution was washed with water and extracted with 30mL of dichloromethane. The extraction was repeated twice. After concentration, the solid was a yellow-white solid. The crude product weighed 2.00g.

[0149] To a 100 mL single-necked round-bottom flask, add 30 mL of methanol, heat to reflux for 30 minutes, cool to room temperature (25°C), then slowly add 15 mL of n-hexane, stir for 2 hours, and filter. The resulting solid is a phosphite bidentate phosphine ligand of Formula Ib. After drying, the solid weighs 1.88 g, with a single-step reaction yield of 79% and a liquid chromatography purity of 96.1%. The overall reaction yield is 33.2%. This yield is lower than that of Preparation Example 9.

[0150] Preparation Example 11

[0151] A method for preparing a phosphite bidentate phosphine ligand:

[0152] A dry 250 mL round-bottom flask was placed under a magnetic stirrer. 2,4-di(adamantan-1-yl)-6-bromophenol (0.884 g) was added, followed by 60 mL of tetrahydrofuran, KOH (0.224 g), and finally 3,5-di(adamantan-1-yl)-2-hydroxythiophenol (1.01 g). The reaction was stirred at 30°C for 24 hours and then terminated. After cooling, 20 mL of water was added to dissolve the solid, and the aqueous phase was extracted with 40 mL of ethyl acetate. This extraction was repeated twice, and the organic phase was concentrated to yield 1.353 g of a pale yellow solid. The crude product was dry-applied onto a column chromatography column and eluted with ethyl acetate / petroleum ether (20:1). After concentration, 1.177 g of product C, a white solid powder, was obtained, with a single-step overall yield of 77% and a liquid chromatography purity of 98.7%.

[0153] In a dry 50 mL two-necked flask, add 2,2'-biphenol (0.748 g), 10 mL of a toluene solution containing 0.53 g of triethylamine, and freshly distilled PCl3 (0.567 g). Stir overnight at 25°C to obtain product D. After the reaction is complete, use it directly in the next step without further treatment.

[0154] Take a dry 100mL two-necked flask and add product C (1.52g), add 15mL of toluene, and add 0.03g of 4-pyrrolidinylpyridine. Add the above solution to the reaction bottle of product D, then add 0.408g of triethylamine, and stir at room temperature 25°C for 24 hours. The resulting reaction solution was washed with water and extracted with 30mL of dichloromethane. The extraction was repeated twice. After concentration, the solid was a yellow-white solid. The crude product weighed 2.05g.

[0155] To a 100mL single-necked round-bottom flask, add 30mL of methanol, heat to reflux for 30 minutes, cool to room temperature (25°C), then slowly add 15mL of n-hexane, stir for 2 hours, and filter. The resulting solid is the bidentate phosphite ligand of Formula Ib. After drying, it weighs 1.845g, with a single-step reaction yield of 90% and a liquid chromatography purity of 99.0%. The overall reaction yield is 69.3%.

[0156] Preparation Example 12

[0157] A method for preparing a phosphite bidentate phosphine ligand:

[0158] A dry 250 mL round-bottom flask was placed under a magnetic stirrer. 2,4-di(adamantan-1-yl)-6-bromophenol (0.884 g) was added, followed by 60 mL of tetrahydrofuran, KOH (0.168 g), and finally 3,5-di(adamantan-1-yl)-2-hydroxythiophenol (1.01 g). The reaction was stirred at 30°C for 10 hours and the mixture was allowed to complete. After cooling, 20 mL of water was added to dissolve the solid, and the aqueous phase was extracted with 40 mL of ethyl acetate. This extraction was repeated twice, and the organic phase was concentrated to yield 1.094 g of a pale yellow solid. The crude product was dry-applied onto a column chromatography column and eluted with dichloromethane / methanol (5:1). After concentration, 0.547 g of Product C, a white solid powder, was obtained, with a single-step overall yield of 36% and a liquid chromatography purity of 98.0%.

[0159] In a dry 50 mL two-necked flask, add 2,2'-biphenol (0.748 g), 10 mL of a toluene solution containing 0.53 g of triethylamine, and freshly distilled PCl3 (0.567 g). Stir overnight at 25°C to obtain product D. After the reaction is complete, use it directly in the next step without further treatment.

[0160] Take a dry 100mL two-necked flask and add product C (1.52g), add 15mL of toluene, and add 0.03g of 4-pyrrolidinylpyridine. Add the above solution to the reaction bottle of product D, then add 0.408g of triethylamine, and stir at room temperature 25°C for 24 hours. The resulting reaction solution was washed with water and extracted with 30mL of dichloromethane. The extraction was repeated twice. After concentration, the solid was a yellow-white solid. The crude product weighed 1.76g.

[0161] To a 100 mL single-necked round-bottom flask, add 30 mL of methanol, heat to reflux for 30 minutes, cool to room temperature (25°C), then slowly add 15 mL of n-hexane, stir for 2 hours, and filter. The resulting solid is a phosphite bidentate phosphine ligand of Formula Ib. After drying, the solid weighs 1.144 g, with a yield of 64%, a liquid chromatography purity of 97.7%, and an overall reaction yield of 23.0%. This yield is lower than that of Preparation Example 11.

[0162] Preparation Example 13

[0163] A method for preparing a phosphite bidentate phosphine ligand:

[0164] A dry 250 mL round-bottom flask was placed under a magnetic stirrer. 2,4-di(adamantan-1-yl)-6-bromophenol (0.884 g) was added, followed by 60 mL of tetrahydrofuran, KOH (0.224 g), and finally 3,5-di(adamantan-1-yl)-2-hydroxythiophenol (0.95 g). The reaction was stirred at 130°C for 8 hours and the reaction was complete. After cooling, 20 mL of water was added to dissolve the solid, and the aqueous phase was extracted with 40 mL of ethyl acetate. This extraction was repeated twice, and the organic phase was concentrated to yield 1.25 g of a pale yellow solid. The crude product was dry-applied onto a column chromatography column and eluted with ethyl acetate / petroleum ether (20:1). After concentration, 0.912 g of Product C, a white solid powder, was obtained, with a single-step overall yield of 60% and a liquid chromatography purity of 98.3%.

[0165] In a dry 50 mL two-necked flask, add 2,2'-biphenol (0.748 g), 10 mL of a toluene solution containing 0.53 g of triethylamine, and freshly distilled PCl3 (0.567 g). Stir overnight at 25°C to obtain product D. After the reaction is complete, use it directly in the next step without further treatment.

[0166] Take a dry 100mL two-necked flask and add product C (1.52g), add 15mL of toluene, and add 0.03g of 4-pyrrolidinylpyridine. Add the above solution to the reaction bottle of product D, then add 0.408g of triethylamine, and stir at room temperature at 25°C for 24 hours. The resulting reaction solution was washed with water and extracted with 30mL of dichloromethane. The extraction was repeated twice. After concentration, the solid was a yellow-white solid. The crude product weighed 2.00g.

[0167] To a 100mL single-necked round-bottom flask, add 30mL of methanol, heat to reflux for 30 minutes, cool to room temperature (25°C), then slowly add 15mL of n-hexane, stir for 2 hours, and filter. The resulting solid is the bidentate phosphite ligand of Formula Ib. After drying, it weighs 1.74g, with a single-step reaction yield of 85%, a liquid chromatography purity of 99.2%, and an overall reaction yield of 51%.

[0168] Preparation Example 14

[0169] A method for preparing a phosphite bidentate phosphine ligand:

[0170] Take a dry 250mL round-bottom flask, place a magnetic bar, add 2,4-di(adamantan-1-yl)-6-bromophenol (0.884g), then add 60mL of tetrahydrofuran, add KOH (0.224g) again, and finally add 3,5-di(adamantan-1-yl) 2-hydroxybenzenethiol (1.01g). Stir at 25℃ for 26 hours and the reaction is complete. After cooling, add 20mL of water to dissolve the solid and add

[0171] The aqueous phase was extracted with 40 mL of ethyl acetate, repeated twice, and the organic phase was concentrated to obtain a pale yellow solid g. The crude product was dry-loaded onto a column chromatography column and eluted with ethyl acetate / petroleum ether (20:1). After concentration, 0.988 g of product C, a white solid powder, was obtained. The overall yield for the single-step reaction was 65%, and the liquid chromatography purity was 98.9%.

[0172] In a dry 50 mL two-necked flask, add 2,2'-biphenol (0.748 g), 10 mL of a toluene solution containing 0.53 g of triethylamine, and freshly distilled PCl3 (0.567 g). Stir overnight at 25°C to obtain product D. After the reaction is complete, use it directly in the next step without further treatment.

[0173] Take a dry 100mL two-necked flask and add product C (1.52g), add 15mL of toluene, and add 0.03g of 4-pyrrolidinylpyridine. Add the above solution to the reaction bottle of product D, then add 0.408g of triethylamine, and stir at room temperature at 25°C for 24 hours. The resulting reaction solution was washed with water and extracted with 30mL of dichloromethane. The extraction was repeated twice. After concentration, the solid was a yellow-white solid. The crude product weighed 2.01g.

[0174] To a 100mL single-necked round-bottom flask, add 30mL of methanol, heat to reflux for 30 minutes, cool to room temperature (25°C), then slowly add 15mL of n-hexane, stir for 2 hours, and filter. The resulting solid is the bidentate phosphite ligand of Formula Ib. After drying, it weighs 1.82g, with a single-step reaction yield of 89% and a liquid chromatography purity of 97.5%. The overall reaction yield is 57.8%.

[0175] Preparation Example 15

[0176] A method for preparing a phosphite bidentate phosphine ligand:

[0177] A dry 250 mL round-bottom flask was placed under a magnetic stirrer. 2,4-di(adamantan-1-yl)-6-bromophenol (0.884 g) was added, followed by 60 mL of tetrahydrofuran, KOH (0.224 g), and finally 3,5-di(adamantan-1-yl)-2-hydroxythiophenol (1.01 g). The reaction was stirred at 30°C for 24 hours and then terminated. After cooling, 20 mL of water was added to dissolve the solid, and the aqueous phase was extracted with 40 mL of ethyl acetate. This extraction was repeated twice, and the organic phase was concentrated to yield 1.353 g of a pale yellow solid. The crude product was dry-applied onto a column chromatography column and eluted with ethyl acetate / petroleum ether (20:1). After concentration, 1.177 g of product C, a white solid powder, was obtained, with a single-step overall yield of 77% and a liquid chromatography purity of 98.7%.

[0178] In a dry 50 mL two-necked flask, add 2,2'-biphenol (0.748 g), 10 mL of a toluene solution containing 0.53 g of triethylamine, and freshly distilled PCl3 (0.567 g). Stir overnight at 25°C to obtain product D. After the reaction is complete, use it directly in the next step without further treatment.

[0179] Take a dry 100mL two-necked flask and add product C (1.52g), add 15mL of toluene, and add 0.042g of 4-pyrrolidinylpyridine. Add the above solution to the reaction bottle of product D, then add 0.306g of triethylamine, and stir at room temperature at 25°C for 24 hours. The resulting reaction solution was washed with water and extracted with 30mL of dichloromethane. The extraction was repeated twice. After concentration, the solid was a yellow-white solid. The crude product weighed 1.85g.

[0180] To a 100mL single-necked round-bottom flask, add 30mL of methanol, heat to reflux for 30 minutes, cool to room temperature (25°C), then slowly add 15mL of n-hexane, stir for 2 hours, and filter. The resulting solid is the bidentate phosphite ligand of Formula Ib. After drying, it weighs 1.54g, with a single-step reaction yield of 0.75% and a liquid chromatography purity of 98.5%. The overall reaction yield is 57.8%.

[0181] Preparation Example 16

[0182] A method for preparing a phosphite bidentate phosphine ligand:

[0183] A dry 250 mL round-bottom flask was placed under a magnetic stirrer. 2,4-di(adamantan-1-yl)-6-bromophenol (0.884 g) was added, followed by 60 mL of tetrahydrofuran, KOH (0.224 g), and finally 3,5-di(adamantan-1-yl)-2-hydroxythiophenol (1.01 g). The reaction was stirred at 30°C for 24 hours and then terminated. After cooling, 20 mL of water was added to dissolve the solid, and the aqueous phase was extracted with 40 mL of ethyl acetate. This extraction was repeated twice, and the organic phase was concentrated to yield 1.353 g of a pale yellow solid. The crude product was dry-applied onto a column chromatography column and eluted with ethyl acetate / petroleum ether (20:1). After concentration, 1.177 g of product C, a white solid powder, was obtained, with a single-step overall yield of 77% and a liquid chromatography purity of 98.7%.

[0184] In a dry 50 mL two-necked flask, add 2,2'-biphenol (0.748 g), 10 mL of a toluene solution containing 0.53 g of triethylamine, and freshly distilled PCl3 (0.567 g). Stir overnight at 25°C to obtain product D. After the reaction is complete, use it directly in the next step without further treatment.

[0185] Take a dry 100mL two-necked flask and add product C (1.52g), add 15mL of toluene, and add 0.024g of 4-pyrrolidinylpyridine. Add the above solution to the reaction bottle of product D, then add 0.51g of triethylamine, and stir at room temperature at 25°C for 24 hours. The resulting reaction solution was washed with water and extracted with 30mL of dichloromethane. The extraction was repeated twice. After concentration, the solid was a yellow-white solid. The crude product weighed 1.81g.

[0186] To a 100mL single-necked round-bottom flask, add 30mL of methanol, heat to reflux for 30 minutes, cool to room temperature (25°C), then slowly add 15mL of n-hexane, stir for 2 hours, and filter. The resulting solid is the bidentate phosphite ligand of Formula Ib. After drying, it weighs 1.44g, with a single-step reaction yield of 70% and a liquid chromatography purity of 98.1%. The overall reaction yield is 54%.

[0187] Preparation Example 17

[0188] A method for preparing a phosphite bidentate phosphine ligand:

[0189] A dry 250 mL round-bottom flask was placed under a magnetic stirrer. 2,4-di(adamantan-1-yl)-6-bromophenol (0.884 g) was added, followed by 60 mL of tetrahydrofuran, KOH (0.224 g), and finally 3,5-di(adamantan-1-yl)-2-hydroxythiophenol (1.01 g). The reaction was stirred at 30°C for 24 hours and then terminated. After cooling, 20 mL of water was added to dissolve the solid, and the aqueous phase was extracted with 40 mL of ethyl acetate. This extraction was repeated twice, and the organic phase was concentrated to yield 1.353 g of a pale yellow solid. The crude product was dry-applied onto a column chromatography column using a 10 / 1 dichloromethane / methanol system. After elution and concentration, 0.912 g of Product C, a white solid powder, was obtained. The overall yield for the single-step reaction was 85%, and the liquid chromatography purity was 85.6%.

[0190] In a dry 50 mL two-necked flask, add 2,2'-biphenol (0.748 g), 10 mL of a toluene solution containing 0.53 g of triethylamine, and freshly distilled PCl3 (0.567 g). Stir overnight at 25°C to obtain product D. After the reaction is complete, use it directly in the next step without further treatment.

[0191] Take a dry 100mL two-necked flask and add product C (1.52g), add 15mL of toluene, and add 0.03g of 4-pyrrolidinylpyridine. Add the above solution to the reaction bottle of product D, then add 0.408g of triethylamine, and stir at room temperature at 25°C for 24 hours. The resulting reaction solution was washed with water and extracted with 30mL of dichloromethane. The extraction was repeated twice. After concentration, the solid was a yellow-white solid. The crude product weighed 1.75g.

[0192] To a 100mL single-necked round-bottom flask, add 30mL of methanol, heat to reflux for 30 minutes, cool to room temperature (25°C), then slowly add 15mL of n-hexane, stir for 2 hours, and filter. The resulting solid is the bidentate phosphite ligand of Formula Ib. After drying, it weighs 1.74g, with a single-step reaction yield of 0.85% and a liquid chromatography purity of 99.0%. The overall reaction yield is 51%.

[0193] Application Example 1

[0194] Application of a phosphite bidentate phosphine ligand in the olefin hydroformylation reaction of butene:

[0195] A magnet was placed in a 1 L autoclave, 21 g of butene was added, 2.2 g of the above-obtained bidentate phosphine ligand of formula Ia, and 0.105 g of acetylacetonatodicarbonylrhodium were added, hydrogen and carbon monoxide were pressurized to 1 MPa each, and the reaction was carried out at 100° C. for 10 hours.

[0196] Chromatographic analysis of the catalytic reaction products showed that the butene conversion rate was 90% and the valeraldehyde yield was 85%.

[0197] Application Example 2

[0198] Application of a phosphite bidentate phosphine ligand in the olefin hydroformylation reaction of butene:

[0199] A magnet was placed in a 1 L autoclave, 21 g of butene was added, 2.2 g of the above-obtained bidentate phosphine ligand of formula Ib, and 0.105 g of acetylacetonatodicarbonylrhodium were added, hydrogen and carbon monoxide were pressurized to 1 MPa each, and the reaction was carried out at 100° C. for 10 hours.

[0200] Chromatographic analysis of the catalytic reaction products showed that the butene conversion was 88% and the valeraldehyde yield was 82.5%.

[0201] Comparative Example 1

[0202] A phosphite bidentate phosphine ligand PH3P, whose structural formula is:

[0203]

[0204] Application of a phosphite bidentate phosphine ligand in the olefin hydroformylation reaction of butene:

[0205] A magnet was placed in a 1 L autoclave, 21 g of butene, 1.05 g of the above-mentioned PH3P phosphite bidentate phosphine ligand, and 0.105 g of acetylacetonatodicarbonyl rhodium were added, and the hydrogen and carbon monoxide were pressurized to 1 MPa each, and the reaction was carried out at 100° C. for 10 hours.

[0206] Chromatographic analysis of the catalytic reaction products showed that the butene conversion rate was 50% and the valeraldehyde yield was 35%.

[0207] Comparative Example 2

[0208] A phosphite bidentate phosphine ligand Biphephos, whose structural formula is:

[0209]

[0210] Application of a phosphite bidentate phosphine ligand in the olefin hydroformylation reaction of butene:

[0211] A magnet was placed in a 1 L autoclave, 21 g of butene, 2.1 g of the above-mentioned Biphephos phosphite bidentate phosphine ligand, and 0.105 g of acetylacetonatodicarbonyl rhodium were added, and the hydrogen and carbon monoxide were pressurized to 1 MPa each, and the reaction was carried out at 100° C. for 10 hours.

[0212] Chromatographic analysis of the catalytic reaction products showed that the butene conversion rate was 45% and the valeraldehyde yield was 30%.

[0213] From the above description, it can be seen that the above-mentioned embodiments of the present invention adopt suitable reaction temperature, appropriate reaction time, and trace amount of catalyst to synthesize a new type of ligand under simple and easy-to-operate conditions. This structure has excellent properties in the catalytic reaction and has higher conversion rate and better selectivity compared with existing ligands.

[0214] It should be noted that the terms "first," "second," and the like in the specification and claims of this application are used to distinguish similar objects, and are not necessarily used to describe a specific order or precedence. It should be understood that the terms used in this manner are interchangeable where appropriate, so that the embodiments of the application described herein can, for example, be implemented in an order other than that described herein.

[0215] The foregoing description is merely a preferred embodiment of the present invention and is not intended to limit the present invention. Those skilled in the art will readily appreciate that various modifications and variations of the present invention are possible. Any modifications, equivalent substitutions, or improvements made within the spirit and principles of the present invention are intended to be within the scope of protection of the present invention.

Claims

1. A phosphite bidentate phosphine ligand, characterized in that The structure of the phosphite bidentate phosphine ligand is: Formula Ia; Alternatively, the structure of the phosphite bidentate phosphine ligand is: Formula Ib.

2. A method for synthesizing the phosphite bidentate phosphine ligand according to claim 1, characterized in that: The synthesis method comprises: Step S1, mixing a first substrate, a first solvent, a first base compound, and a halide, and performing a first stirring reaction to obtain a first mixed solution, wherein the first mixed solution includes a first product; Step S2, adding a second solvent to the first mixed solution to dissolve the first product to obtain a second mixed solution; Step S3, obtaining a second product by subjecting the second mixed solution to a first extraction, a first concentration, and purification; Step S4, mixing the second substrate, the third solvent, the second base compound and phosphorus trichloride, and performing a second stirring reaction to obtain a third mixed solution; Step S5, mixing the second product, a fourth solvent and a catalyst to obtain a fourth mixed solution; Step S6, adding the fourth mixed solution to the third mixed solution to obtain a fifth mixed solution, adding a third base compound to the fifth mixed solution, and after a third stirring reaction, obtaining a sixth mixed solution containing the phosphite bidentate phosphine ligand, thereby obtaining the phosphite bidentate phosphine ligand; The first substrate is 3,5-di(adamantan-1-yl)catechol, and the structure of the second product is: ， The structure of the phosphite bidentate phosphine ligand is: ； Alternatively, the first substrate is 3,5-bis(adamantan-1-yl)-2-hydroxythiophenol, and the structure of the second product is: ， The structure of the phosphite bidentate phosphine ligand is: ； The halide is selected from one or more of 2,4-di(adamantan-1-yl)-6-bromophenol, 2,4-di(adamantan-1-yl)-6-chlorophenol and 2,4-di(adamantan-1-yl)-6-trifluoromethanesulfonylphenol; The second substrate is 2,2'-biphenol.

3. The synthetic method of the phosphite bidentate phosphine ligand according to claim 2, characterized in that, In step S1, the ratio of the equivalent numbers of the first substrate and the halide is (1.2-1.3):

1.

4. The method for synthesizing the phosphite bidentate phosphine ligand according to claim 2, wherein The reaction conditions of the first stirring reaction are: 30-120° C., 10-24 h.

5. The method for synthesizing the bidentate phosphite ligand according to any one of claims 2 to 4, characterized in that: In step S4, the ratio of the equivalents of the second substrate, the second base compound, and the phosphorus trichloride is 2:(2.5-2.6):(2.00-2.05).

6. The method for synthesizing the phosphite bidentate phosphine ligand according to claim 5, wherein The reaction conditions of the second stirring reaction are: 23±2° C., 16-18 h.

7. The method for synthesizing the bidentate phosphite ligand according to any one of claims 2 to 4, characterized in that: In step S5, the ratio of the equivalents of the second product to the third base compound is 1:(1.5-2.5), and the equivalent of the added catalyst is 0.1-0.

12.

8. The method for synthesizing the phosphite bidentate phosphine ligand according to claim 7, wherein: In step S6, the reaction conditions of the third stirring reaction are: 23±2° C., 16-18 h.

9. The method for synthesizing the bidentate phosphite ligand according to any one of claims 2 to 4, characterized in that: The first base compound is selected from one or more of potassium carbonate, sodium carbonate, cesium carbonate, NaH, sodium hydroxide, potassium hydroxide, potassium tert-butoxide t-BuOK, potassium sodium tert-butoxide t-BuONa, triethylamine TEA, N,N-diisopropylethylamine DIEA, 4-dimethylaminopyridine DMAP and 1,8-diazabicyclo[5.4.0]undec-7-ene DBU; and / or, The second base compound and the third base compound are each independently triethylamine and / or ammonia; and / or, The catalyst is selected from one or more of sodium alkoxide, organic base and copper halide.

10. The method for synthesizing the phosphite bidentate phosphine ligand according to claim 9, characterized in that: The catalyst is 4-pyrrolidinopyridine.

11. The method for synthesizing the bidentate phosphite ligand according to any one of claims 2 to 4, characterized in that: The first solvent is selected from one or more of methanol, ethanol, dichloromethane, chloroform, ethyl acetate, benzene, toluene, n-hexane, tetrahydrofuran, acetonitrile, dioxane, N,N-dimethylformamide and dimethyl sulfoxide; and / or, The second solvent is selected from one or more of water, acetonitrile and DMF; and / or, The third solvent is selected from one or more of dichloromethane, benzene, n-hexane and carbon tetrachloride; and / or, The fourth solvent is selected from one or more of methanol, ethanol, dichloromethane, chloroform, ethyl acetate, benzene, toluene, n-hexane, tetrahydrofuran, acetonitrile, N,N-dimethylformamide and dimethyl sulfoxide.

12. The method for synthesizing the bidentate phosphite ligand according to any one of claims 2 to 4, characterized in that: The purification in step S3 is performed by column chromatography, and the column chromatography is loaded by dry loading.

13. The method for synthesizing the phosphite bidentate phosphine ligand according to claim 12, characterized in that: The eluent of the column chromatography method is selected from one or more of methanol, ethanol, dichloromethane, chloroform, ethyl acetate, n-hexane and petroleum ether.

14. The method for synthesizing the phosphite bidentate phosphine ligand according to claim 13, characterized in that: The eluent is dichloromethane and methanol, and the volume ratio of the dichloromethane to the methanol is (4-6):1; or, the eluent is ethyl acetate and petroleum ether, and the volume ratio of the ethyl acetate to the petroleum ether is (18-22):

1.

15. The method for synthesizing the phosphite bidentate phosphine ligand according to any one of claims 2 to 4, characterized in that: Step S6 further includes: Step S6-1, washing, second extraction, and second concentration are performed on the sixth mixed liquid to obtain a third product; Step S6-2: Recrystallize the third product to obtain the phosphite bidentate phosphine ligand.

16. The method for synthesizing the phosphite bidentate phosphine ligand according to claim 15, characterized in that: The recrystallization treatment in step S6-1 includes: dissolving the third product in a good recrystallization solvent and heating to reflux, adding a poor recrystallization solvent after cooling, stirring, and filtering to obtain the phosphite bidentate phosphine ligand.

17. The method for synthesizing the phosphite bidentate phosphine ligand according to claim 16, characterized in that: The good solvent for recrystallization is selected from one or more of methanol, ethanol, dichloromethane, chloroform and tetrahydrofuran, and the poor solvent for recrystallization is selected from one or more of n-hexane, ethyl ether, petroleum ether and methyl ethyl ether.

18. Use of the phosphite bidentate phosphine ligand according to claim 1 in an olefin hydroformylation reaction, wherein the olefin hydroformylation reaction comprises converting olefin, hydrogen and carbon monoxide into aldehyde compounds, characterized in that: The phosphite bidentate phosphine ligand according to claim 1 is complexed with a rhodium-containing compound and used as a reaction catalyst for olefin hydroformylation; the olefin is selected from one of C4~C12 normal olefins or isoolefins.

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