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CN116655686A - Synthesis method and application of pentavalent and trivalent tridentate phosphine ligand - Google Patents

Synthesis method and application of pentavalent and trivalent tridentate phosphine ligand Download PDF

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Publication number
CN116655686A
CN116655686A CN202310491726.9A CN202310491726A CN116655686A CN 116655686 A CN116655686 A CN 116655686A CN 202310491726 A CN202310491726 A CN 202310491726A CN 116655686 A CN116655686 A CN 116655686A
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ligand
reaction
pentavalent
trivalent
tridentate
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张润通
彭江华
王勇
钟剑平
方丽娜
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Guangdong Oukai New Material Co ltd
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Guangdong Oukai New Material Co ltd
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    • B01J31/2457—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring comprising condensed ring systems and phosphine-P atoms as substituents on a ring of the condensed system or on a further attached ring with more than one complexing phosphine-P atom comprising aliphatic or saturated rings, e.g. Xantphos
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Abstract

The invention discloses a synthesis method of pentavalent and trivalent tridentate phosphine oxide ligand, and the pentavalent phosphine oxide ligand and trivalent tridentate phosphine oxide ligand after reductionThe dentate phosphine ligand has a structure shown in general formulas I and II. In formulae I and II, R may be tert-butyl, isopropyl, phenyl, pyridinyl or adamantyl. The phosphorus-oxygen ligand has excellent catalytic effect and application prospect in olefin hydroformylation, alkoxyl carbonylation and hydrocarboxylation.

Description

Synthesis method and application of pentavalent and trivalent tridentate phosphine ligand
Technical Field
The invention relates to a synthesis method and application of a pentavalent tridentate phosphine oxide ligand and a trivalent tridentate phosphine ligand after reduction thereof.
Background
The hydroformylation reaction has found tremendous use in industry since 1938 as taught by Otto Roelen (Chem Abstr,1994, 38-550). Since aldehydes can be very easily converted into compounds having important uses in organic synthesis, corresponding alcohols, carboxylic acids, esters, imines, etc., aldehydes synthesized by hydroformylation are synthesized on a large scale in industrial production. The production of aldehydes by hydroformylation in industrial production per year is now up to 1500 ten thousand tons. The general reaction equation for hydroformylation is shown below:
in the hydroformylation reaction, while bidentate phosphine ligands and tetradentate phosphine ligands are widely reported and patented by large chemical companies such as BASF, dow, shell and Eastman and some research groups abroad, multidentate phosphine ligands are rarely reported. Therefore, the development of the novel efficient multidentate phosphine ligand in the hydroformylation reaction and the preparation method thereof have important significance.
The hydroesterization of olefins is carried out by reacting olefins with carbon monoxide and alcohols under the action of metal compounds/phosphine ligands to give esters having one more carbon atom than olefins. Among the numerous methods for synthesizing organic carboxylic acid esters, this is the most atom-economical, simple method. The following scheme shows the general reaction equation for the transesterification of olefins: the alkoxycarbonylation of olefinic compounds is a process of increasing importance. Alkoxycarbonylations refer to the reaction of an olefin with carbon monoxide and an alcohol in the presence of a metal complex to form the corresponding ester. Typically, palladium is used as the metal. The following scheme shows the general reaction equation for oxycarbonylation:
organic carboxylic acid esters are an important class of oxygen-containing compounds and are widely applied to the fields of fine chemical products, medicines, pesticides, food additives, perfumes, coatings, paints and the like. For example, methyl propionate is widely used in the food, feed, and cosmetic industries as a solvent, an additive, a preservative, or a fragrance. In addition, it is an important chemical intermediate, which is a key raw material for producing polymethyl methacrylate (PMMA). PMMA has the advantages of good weather resistance, moderate density, rigidity, stability, transparency and the like, and is widely applied to the fields of automobiles, LED core original materials, buildings, aviation and the like. Therefore, the development of an efficient synthesis method of organic carboxylic acid esters is of great significance.
The invention develops a pentavalent tridentate phosphine oxide ligand and a synthetic method of the tridentate phosphine oxide ligand after reduction. The synthesized phosphorus-oxygen ligand has the characteristics of short route, higher yield, extremely stable water-oxygen, difficult decomposition and the like. The reaction activity of hydroformylation, carbonyl esterification and carboxylation is good, and the yield of linear aldehyde, ester or carboxylic acid products is high. Has great potential and practical value.
Disclosure of Invention
The invention aims to develop a pentavalent tridentate phosphine oxide ligand and a method for synthesizing the trivalent tridentate phosphine oxide ligand after reduction. The preparation is easy to synthesize, has higher yield and can amplify synthesis. The structure of the tridentate phosphine oxide compound and the derivative thereof is represented as follows:
a synthesis method and application of pentavalent tridentate phosphine oxide ligand and trivalent tridentate phosphine ligand are characterized by comprising the following synthesis routes:
wherein, the pentavalent phosphine and trivalent tridentate phosphine ligand represented by substituent R has the following structure:
from pentavalent phosphine oxide 3 to trivalent phosphorus oxide 4, only one reduction is needed, the steps are as follows:
further, compound 3 can also be achieved by the method of the grignard reagent:
the above reaction is characterized in that the reducing agent used for the reaction may be: any one of triethylsilane, phenylsilane, diphenylsilane, triphenylsilane, triethoxysilane, tetramethyldisiloxane, polymethylhydrosiloxane, trichlorosilane, hexachlorodisilane, hexamethyldisilane, lithium aluminum hydride, or hydrogen. The catalyst can be any one of copper chloride, triphenylphosphine, trifluoroacetic acid, stannic chloride, tetraisopropyl titanate, trifluoromethanesulfonic acid or p-toluenesulfonic acid.
Further, the complex formed by the pentavalent phosphine and the trivalent phosphine ligand L1-L5 synthesized by the method, pd salt and acid can be used for preparing ester or carboxylic acid by catalyzing olefin hydroformylation, alkoxycarbonylation or hydrocarboxylation, and the reaction equation is as follows:
further, catalytic methods are included, where the ligand is used in the hydroformylation reaction, the molar ratio of olefin to cobalt or rhodium salt is between 100:1 and 1000:1; when the ligand is used in an alkoxycarbonylation or hydrocarboxylation reaction, the molar ratio of olefin to palladium salt is between 100:1 and 100000:1, and the molar ratio of acidic additive to palladium salt is 6:1.
Further, the method comprises a catalytic method, when the ligand is used for hydroformylation reaction, the reaction temperature is 40-100 ℃, the cobalt salt/ligand reaction pressure is 4.0-8.0MPa, and the reaction time is 12-24 hours; rhodium salt/ligand reaction pressure is 1.0-2.0MPa, and reaction time is 4-8 hours; when the ligand is used for alkoxycarbonylating or hydrocarboxylating reaction, the reaction temperature is 80-140 ℃, the reaction pressure is 1.0-4.0MPa, and the reaction time is 4-24 hours;
further, including catalytic methods, when the ligand is used in a hydroformylation reaction, the reaction solvent may be benzene, toluene, tetrahydrofuran, or the corresponding product aldehyde, the solvent to substrate volume ratio being from 1:5 to 1:25; when the ligand is used in an alkoxycarbonylation or hydrocarboxylation reaction, the molar ratio of methanol to olefin is 1.5:1 and the molar ratio of acetic acid to water to olefin is 2:1:1.
Further, the olefin may be a terminal olefin, an internal olefin, a disproportionated olefin, or a polysubstituted olefin, for example: the terminal alkene includes ethylene, propylene, butene or C5-C10 terminal alkene; the internal olefins include 2-butene, 2-octene, 3-octene, 4-octene or C5-C10 internal olefins; the disproportionated or polysubstituted olefins include 2, 4-trimethyl-1-pentene, 2, 4-trimethyl-2-pentene, 2, 3-dimethyl-2-butene or diisobutene. .
The invention aims to provide a multidentate phosphine oxide ligand for hydroformylation, alkoxycarbonylation or hydrocarboxylation and a product after reduction thereof, wherein the pentavalent phosphine ligand can be placed in the air for a long time and is suitable for large-scale industrial production and amplification. When coordination complex is carried out with cobalt salts, rhodium salts or palladium salts/acids, high catalytic activity species can be obtained without or with only one reduction step, which makes it possible to achieve higher olefin conversion, better regioselectivity and higher aldehyde or ester or carboxylic acid yields.
Detailed Description
The above route of the present invention will be specifically described by way of examples, which are provided for further illustration of the present invention, but are not to be construed as limiting the present invention in any way. Some insubstantial improvements and modifications in light of the teachings of this invention may occur to those skilled in the art.
Example 1: preparation of 1,2, 3-trichlorobenzene
1,2, 3-trimethylbenzene (20.0 g), 80, g N-chlorosuccinimide, 242mg of dibenzoyl peroxide and 500ml of methylene chloride were successively added to a 1L reaction flask, followed by stirring, refluxing under heating, and irradiation with a 100W 395nm ultraviolet lamp to react overnight. The reaction solution was filtered, the filtrate was washed with saturated sodium carbonate, dried over anhydrous sodium sulfate, and the solvent was dried by spin-drying, and recrystallized twice from methylene chloride/n-hexane to give 26.4g of a solid in 71% yield.
Example 1-a: preparation of tert-butyl R-based phosphine oxide (1 bb-ff):
1. di-tert-butylphosphine oxide (1 bb):
50g of tert-butyldichloride are introduced into a dry 1L Schlenk flask under inert gasPhosphine (P)And 300ml of anhydrous tetrahydrofuran, stirring uniformly and cooling to-20 ℃. Subsequently, 1.5M t-butylmagnesium chloride-format reagent solution (210 ml) was slowly added dropwise at-20℃and after completion of the addition, the reaction was allowed to proceed to room temperature overnight at 50 ℃. The inorganic salt in the system was filtered off, the organic phase was removed by rotary evaporation, and 31.2g of di-t-butylphosphine chloride was obtained by distillation under reduced pressure at 150℃in 55% yield.
In a dry 250mL Schlenk flask under inert gas, 10g of t-butyldichloride was addedPhosphine (P)And 80ml of anhydrous tetrahydrofuran, stirred well and cooled to-50 ℃. Subsequently, a 2.5M solution of lithium aluminum hydride in tetrahydrofuran (23.5 ml) was slowly added dropwise at-50℃and, after completion of the addition, the reaction was allowed to proceed to room temperature overnight at room temperature. After quenching with deoxygenated water, extraction with ethyl acetateThe organic phase was dried over anhydrous sodium sulfate, the organic phase was removed by rotary evaporation, and 7.0g of di-t-butylphosphine was obtained by distillation under reduced pressure at 210℃in 86% yield.
In a dry 250mL Schlenk flask under inert gas, 5g of di-tert-butyl are addedPhosphine (P)Hydrogen and 100ml of deoxygenated glacial acetic acid and heated to 85 ℃. Subsequently, 30% H was slowly added dropwise to the flask 2 O 2 24.5ml of the solution was added dropwise and reacted at 80℃overnight. The organic phase was dried over anhydrous sodium sulfate and distilled under reduced pressure to give 5.1g of a white solid of di-t-butylphosphine oxide in 92% yield.
A dry 250mL reaction flask was charged with 5g of di-tert-butylphosphine hydrogen and 100mL of a deoxygenated dichloromethane and methanol mixed solution and heated to 50deg.C. Subsequently, pure oxygen was continuously introduced into the flask, and the reaction was carried out at 50℃overnight. After rotary evaporation under reduced pressure, 4.9g of white solid of di-tert-butylphosphine oxide was obtained in 88% yield.
Into a dry 250mL reaction flask was added 5g of di-tert-butylphosphine hydrogen and 100mL of dichloromethane and cooled to-20 ℃. Then, continuously introducing ozone into the bottle, reacting for 1 hour at the temperature of minus 20 ℃, introducing the unreacted ozone into a potassium iodide trap for quenching, and introducing oxygen until no ozone remains. After rotary evaporation under reduced pressure, 5.4g of white solid of di-tert-butylphosphine oxide was obtained in 98% yield.
2. Tert-butyl isopropyl phosphine oxide (1 cc):
The operation steps are the same as those of 1b and 1bb, 34.1g of tert-butyl isopropyl phosphine chloride, and the yield is 65%; 6.3g of tert-butyl isopropyl phosphine and the yield is 79%; 5.4g of tert-butyl isopropyl phosphine oxide and the yield is 97%.
3. Tert-butylphenyl phosphine oxide (1 dd):
The operation steps are the same as those of 1b and 1bb, 46.1g of tert-butylphenyl phosphine chloride, and the yield is 73%; 7.0g of tert-butylphenyl phosphine and 84% yield; 5.2g of tert-butylphenyl phosphine oxide and the yield is 95%.
4. Tert-butylpyridylphosphine oxide (1 ee):
The operation steps are the same as those of 1b and 1bb, the tertiary butyl pyridylphosphine chloride is 30.4g, and the yield is 48%; 6.3g of tert-butylpyridylphosphine hydrogen, yield 76%; 4.7g of tert-butylpyridylphosphine oxide, and the yield is 85%.
5. Tertiary butyl adamantyl phosphine oxide (1 ff):
The operation steps are the same as those of 1b and 1bb, the yield is 33% and the tert-butyl adamantyl phosphine chloride is 26.9 g; 7.5g of tertiary butyl adamantyl phosphine and the yield is 87%; 4.1g of tertiary butyl adamantyl phosphine oxide and the yield is 77%.
Example 2: preparation of 1,2, 3-tris (di-tert-butylmethylenephosphinyloxy) benzene
4.5g of 1,2, 3-tris (chloromethyl) benzene and 100ml of anhydrous tetrahydrofuran are added into a 1L Schlenk reaction flask in sequence under the protection of inert gas, stirred uniformly and cooled to 0 ℃. In a separate dry and nitrogen-replaced 500mL Schlenk flask, 16.3g (5.0 eq.) of a solution of di-tert-butylphosphine oxide in anhydrous tetrahydrofuran (200 mL) was added at-40℃and 2.5M solution of n-butyllithium (40.7 mL) was slowly added dropwise to the flask and the flask was returned to room temperature after the dropwise addition. The lithiated di-tert-butylphosphine oxide solution was slowly added dropwise to a bottle containing 1,2, 3-tris (chloromethyl) benzene at-20℃and the reaction was stirred at 60℃overnight. After quenching with water, the organic phase was dried over anhydrous sodium sulfate, the solvent was removed by rotary evaporation, and after flash column chromatography 9.6g of a white solid was obtained in 79% yield.
Example 3: preparation of 1,2, 3-tris (t-butylisopropylmethylenephosphinyloxy) benzene
5.1g of 1,2, 3-tris (chloromethyl) benzene and 110ml of anhydrous tetrahydrofuran are added into a 1L Schlenk reaction flask in sequence under the protection of inert gas, stirred uniformly and cooled to 0 ℃. In a separate dry and nitrogen-replaced 500mL Schlenk reaction flask, 16.9g (5.0 eq.) of tert-butylisopropyl phosphine oxide in anhydrous tetrahydrofuran (200 mL) was added at-40℃and 2.5M n-butyllithium solution (50.7 mL) was slowly added dropwise to the flask and the flask was returned to room temperature after the dropwise addition. The lithiated tert-butyl isopropyl phosphine oxide solution was slowly added dropwise to a bottle containing 1,2, 3-tris (chloromethyl) benzene at-20 ℃. After quenching with water, the organic phase was dried over anhydrous sodium sulfate, the solvent was removed by rotary evaporation, and after flash column chromatography, 10.7g of a white solid was obtained in 84% yield.
Example 4: preparation of 1,2, 3-tris (tert-butylphenylmethylene phosphinyloxy) benzene
5.7g of 1,2, 3-tris (chloromethyl) benzene and 100ml of anhydrous tetrahydrofuran are added into a 1L Schlenk reaction flask in sequence under the protection of inert gas, stirred uniformly and cooled to 0 ℃. In a separate dry and nitrogen-replaced 500mL Schlenk reaction flask, 23.2g (3.5 eq.) of tert-butylphenyl phosphine oxide in anhydrous tetrahydrofuran (220 mL) was added at-40℃and 2.5M n-butyllithium solution (56.6 mL) was slowly added dropwise to the flask and the flask was returned to room temperature after the dropwise addition. The lithiated tert-butylphenylphosphino-oxy solution was slowly added dropwise to a bottle containing 1,2, 3-tris (chloromethyl) benzene at-20℃and the reaction was stirred at 60℃overnight. After quenching with water, the organic phase was dried over anhydrous sodium sulfate, the solvent was removed by rotary evaporation, and after flash column chromatography, 15.0g of a white solid was obtained in 89% yield.
Example 5: preparation of 1,2, 3-tris (tert-butylpyridylmethylene phosphinyloxy) benzene
4.9g of 1,2, 3-tris (chloromethyl) benzene and 100ml of anhydrous tetrahydrofuran are added into a 1L Schlenk reaction flask in sequence under the protection of inert gas, stirred uniformly and cooled to 0 ℃. In a separate dry and nitrogen-replaced 500mL Schlenk reaction flask, 20.1g (5.0 eq.) of a solution of tert-butylpyridinylphosphine oxide in anhydrous tetrahydrofuran (200 mL) was added at-40℃and 2.5M solution of n-butyllithium (48.7 mL) was slowly added dropwise to the flask and the flask was returned to room temperature after the dropwise addition. The lithiated tert-butylpyridinium phosphine oxide solution was slowly added dropwise to a bottle containing 1,2, 3-tris (chloromethyl) benzene at-20 ℃ and the reaction was stirred at 60 ℃ overnight. After quenching with water, the organic phase was dried over anhydrous sodium sulfate, the solvent was removed by rotary evaporation, and 13.5g of a white solid was obtained after flash column chromatography in 93% yield.
Example 6: preparation of 1,2, 3-tris (t-butyladamantylmethylene phosphinyloxy) benzene
6.0g of 1,2, 3-tris (chloromethyl) benzene and 100ml of anhydrous tetrahydrofuran are added into a 1L Schlenk reaction flask in sequence under the protection of inert gas, stirred uniformly and cooled to 0 ℃. In a separate dry and nitrogen-replaced 500mL Schlenk flask, 32.3g (5.0 eq.) of a solution of t-butyladamantylphosphine oxide in anhydrous tetrahydrofuran (320 mL) was added at-40℃and 2.5M solution of n-butyllithium (59.6 mL) was slowly added dropwise to the flask and the flask was returned to room temperature after the dropwise addition. The lithiated tert-butyl adamantylphosphino oxygen solution was slowly added dropwise to a bottle containing 1,2, 3-tris (chloromethyl) benzene at-20℃and the reaction was stirred at 60℃overnight. After quenching with water, the organic phase was dried over anhydrous sodium sulfate, the solvent was removed by rotary evaporation, and 17.0g of a white solid was obtained after flash column chromatography in 76% yield.
Example 7: preparation of 1,2, 3-tris (di-tert-butylmethylenephosphinyloxy) benzene
Under the protection of inert gas, 500ml of 0.08M 2' -anhydrous tetrahydrofuran is added into a dry 1.5L three-mouth bottle, stirred uniformly and cooled to-20 ℃. Subsequently, 25.3g (3.5 eq.) of a solution of di-tert-butylphosphine chloride in anhydrous tetrahydrofuran (400 ml) was added and the reaction was stirred at room temperature overnight. Filtering inorganic salt, continuously introducing ozone into the bottle at-20 ℃ for reaction for 1 hour, introducing unreacted ozone into a potassium iodide trap for quenching, and introducing oxygen until no ozone remains. The solvent was removed by rotary evaporation under reduced pressure, and 13.9g of a white solid was obtained after flash column chromatography in 61% yield.
Comparative example 1: silane reagent and catalyst in the reduction of 1,2, 3-tris (t-butylpyridylmethylene phosphino)
Effect in benzene
To a 1L Schlenk flask, 3 (10 mmol), a silane reagent, a catalyst and toluene (200 ml) were added in this order under inert gas. After the addition was completed, the reaction was carried out at 80℃for 24 hours. The solvent was dried under reduced pressure and flash column chromatography was performed under an argon atmosphere with deoxygenated ethyl acetate. The resulting organic phase was concentrated and then added with methanol, stirred at 0 ℃ until white solid 4 precipitated, collected by filtration, and the yields are shown in table 1:
TABLE 1
PMHS polymethylsiloxane
TMHS Tetramethyldisiloxane
LAH lithium aluminum tetrahydroide
Comparative example 2: triethylsilane and catalyst in the reduction of 1,2, 3-tris (t-butylpyridylmethylene phosphine oxide Radical) effect in benzene
To a 1L Schlenk flask, 3 (10 mmol), triethylsilane (6.0 eq.), catalyst and toluene (200 ml) were added in this order under inert gas. After the addition was completed, the reaction was carried out at 80℃for 24 hours. The solvent was dried under reduced pressure and flash column chromatography was performed under an argon atmosphere with deoxygenated ethyl acetate. The resulting organic phase was concentrated and then added with methanol, stirred at 0 ℃ until a white solid precipitated, collected by filtration, and the yields are shown in table 2:
TABLE 2
Comparative example 3: cobalt and tridentate phosphorus-oxygen (pentavalent) ligand catalytic olefin hydroformylation reaction result
Under argon atmosphere, adding a certain amount of Co into a stainless steel high-pressure reaction kettle 2 (CO) 8 (0.04 mmol,1.4 mg) and a certain amount of phosphine oxide ligand 3, L1-L5 (0.008-0.02 mmol), a certain volume of toluene and an internal standard n-decane were added, and the mixture was subjected to complexing for 30 minutes with stirring with a magnet to give a complex of cobalt and phosphine oxide (V-valent) ligand. Then, after connecting the gas pipeline and fully replacing, adding a certain proportion of liquefied terminal alkene or internal alkene into the reaction kettle, controlling the concentration of the cobalt catalyst in the total solution to be about 100ppm, and uniformly stirring for 5-10 minutes at room temperature. After stirring uniformly, the mixed gas (1:1) of carbon monoxide and hydrogen is filled into the reaction device until the total pressure is 4.0MPa. The reaction vessel was raised to the desired temperature (70-115 ℃) and the total pressure was kept constant at 4.0MPa by continuous air make-up during the reaction. After 24-48 hours of reaction, the reaction kettle is connected into a cold sleeve at the temperature of minus 40 ℃ for cooling, and the kettle temperature is cooled toAfter room temperature, the gas in the reaction vessel was completely released in a fume hood, the vessel was opened to sample, and the normal-to-iso ratio (the ratio of linear aldehyde to branched aldehyde) and the conversion were measured by a Gas Chromatograph (GC), and the results are shown in table 3.
TABLE 3 Table 3
Diisobutylene:2, 4-trimethyl-1-pentene and 2, 4-trimethyl-2-pentene mixture (80:20)
Comparative example 4: rhodium and tridentate phosphine (trivalent) ligand catalyzed olefin hydroformylation reaction result
Under argon atmosphere, adding a certain amount of Rhacac (CO) into a stainless steel high-pressure reaction kettle 2 (0.004 mmol,1.0 mg) and a certain amount of ligand 4L1-4L5 (0.008-0.02 mmol), a certain volume of toluene and an internal standard n-decane were added, and the mixture was subjected to complexing with stirring with a magnet for 30 minutes to give a rhodium-phosphine ligand (III-valent) complex. Then, after connecting the gas pipeline and fully replacing, adding a certain proportion of liquefied terminal alkene or internal alkene into the reaction kettle, controlling the concentration of the rhodium catalyst in the total solution to be about 90ppm, and uniformly stirring for 5-10 minutes at room temperature. After stirring evenly, the mixed gas (1:1) of carbon monoxide and hydrogen is filled into the reaction device until the total pressure is 1.0-2.5MPa. The reaction kettle is raised to the required temperature (70-110 ℃), and the total pressure is kept constant at 1.0-2.5MPa by continuously supplementing air in the reaction. After 2-8 hours of reaction, the reaction kettle is connected into a-40 ℃ cold sleeve for cooling, after the kettle temperature is reduced to normal temperature, the gas in the reaction kettle is completely released in a fume hood, the kettle is opened for sampling, and a Gas Chromatograph (GC) is used for measuring the normal-to-iso ratio (the ratio of linear aldehyde to branched aldehyde) and the conversion rate, and the results are shown in Table 4.
TABLE 4 Table 4
Comparative example 5: palladium and tridentate phosphine (trivalent) ligand catalyzed diisobutylene alkoxycarbonyl reaction comparison test：
To a 1000ml Parr stainless steel autoclave was added tridentate phosphine ligand 4L1-4L5 (0.6 mmol), pd (acac) under argon atmosphere 2 (0.1 mmol,30.3 mg) and an excess of PTSA (2.0 mmol), 400ml of a mixed solution of diisobutylene and methanol (volume ratio: 19:21) were added, and the mixture was stirred and complexed for 1 hour to give a complex of palladium and 4L1-4L 5. And then, after connecting a gas pipeline and fully replacing, heating the reaction kettle to 120 ℃, then filling carbon monoxide into the reaction kettle, keeping the total pressure at about 3.5MPa for reaction for 12 hours, cooling to room temperature, discharging the pressure in the kettle, distilling the product isononanoate under reduced pressure, and then, keeping the catalyst in the reaction kettle for repeated use, wherein the reaction conditions are the same as above. The reaction mixture was sampled and the conversion and selectivity were measured by Gas Chromatography (GC), and the results are shown in table 5.
TABLE 5
Comparative example 6: comparative test of palladium and tridentate phosphine (trivalent) ligand catalyzed diisobutylene hydrocarboxylation：
To a 1000ml Parr stainless steel autoclave was added a decaborane ligand 4L1-4L5 (0.6 mmol), pd (acac) under an argon atmosphere 2 (0.1 mmol,30.3 mg) and an excess of PTSA (2.0 mmol), 400ml of a mixed solution of diisobutylene, water and acetic acid (volume ratio: 2:5:5) were added, and the mixture was stirred and complexed for 1 hour to give a catalytic complex of palladium and ligand. And then, after connecting a gas pipeline and fully replacing, heating the reaction kettle to 120 ℃, then filling carbon monoxide into the reaction kettle, keeping the total pressure at about 35bar for reaction for 12 hours, cooling to room temperature, discharging the pressure in the kettle, decompressing and distilling out the isononanoate product, and then, keeping the catalyst in the reaction kettle for repeated use, wherein the reaction conditions are the same as above. The reaction mixture was sampled and the conversion and selectivity were measured by Gas Chromatography (GC), and the results are shown in table 3.
TABLE 6
Palladium/ligand Conversion (%) Carboxylic acid selectivity TON
Pd/4L1 45.8 >99 1832
Pd/4L2 32.1 >99 1284
Pd/4L3 73.2 >99 2928
Pd/4L4 96.4 >99 3856
Pd/4L5 92.5 >99 3700

Claims (10)

1. A method for synthesizing a pentavalent tridentate phosphine oxide ligand and a trivalent tridentate phosphine ligand after reduction is characterized by comprising the following synthetic routes:
wherein, the pentavalent phosphine and trivalent tridentate phosphine ligand represented by substituent R has the following structure:
2. the method for synthesizing a pentavalent tridentate phosphine oxide ligand and a reduced trivalent tridentate phosphine ligand according to claim 1, wherein the phosphorus oxide intermediate is realized by an oxidation method:
3. the method for synthesizing a pentavalent tridentate phosphine oxide ligand and a reduced trivalent tridentate phosphine ligand according to claim 1, wherein the compound 3 can be realized by a method of a format reagent:
4. the synthesis method of a pentavalent tridentate phosphine oxide ligand and a trivalent tridentate phosphine ligand after reduction according to claim 1, wherein the reduction of pentavalent phosphine compound 3 into trivalent phosphine compound 4 is achieved by the following reaction:
wherein the above reaction is characterized in that the reducing agent used for the reaction may be: any one of triethylsilane, phenylsilane, diphenylsilane, triphenylsilane, triethoxysilane, tetramethyldisiloxane, polymethylhydrosiloxane, trichlorosilane, hexachlorodisilane, hexamethyldisilane, lithium aluminum hydride, or hydrogen. The catalyst can be any one of copper chloride, triphenylphosphine, trifluoroacetic acid, stannic chloride, tetraisopropyl titanate, trifluoromethanesulfonic acid or p-toluenesulfonic acid.
5. The method for synthesizing pentavalent tridentate phosphine oxide ligand and reduced trivalent tridentate phosphine ligand thereof, wherein the complex formed by pentavalent tridentate phosphine synthesized by the method, trivalent tridentate phosphine ligand L1-L5, pd salt and acid can be used for preparing ester or carboxylic acid by catalyzing olefin hydroformylation, alkoxycarbonylating or hydrocarboxylation, and the reaction equation is as follows:
6. the method for synthesizing a pentavalent tridentate phosphine oxide ligand and its reduced trivalent tridentate phosphine oxide ligand according to claim 4, wherein the method comprises a catalytic method, and when the ligand is used for hydroformylation, the molar ratio of olefin to cobalt salt or rhodium salt is 100:1-1000:1; when the ligand is used in an alkoxycarbonylation or hydrocarboxylation reaction, the molar ratio of olefin to palladium salt is between 100:1 and 100000:1, and the molar ratio of acidic additive to palladium salt is 6:1.
7. The method for synthesizing a pentavalent tridentate phosphine oxide ligand and a trivalent tridentate phosphine ligand after reduction according to claim 4, wherein the method comprises a catalytic method, when the ligand is used for hydroformylation, the reaction temperature is 40-100 ℃, the cobalt salt/ligand reaction pressure is 4.0-8.0MPa, and the reaction time is 12-24 hours; rhodium salt/ligand reaction pressure is 1.0-2.0MPa, and reaction time is 4-8 hours; when the ligand is used for alkoxycarbonylating or hydrocarboxylating reaction, the reaction temperature is 80-140 ℃, the reaction pressure is 1.0-4.0MPa, and the reaction time is 4-24 hours.
8. The method for synthesizing a pentavalent tridentate phosphine oxide ligand and its reduced trivalent tridentate phosphine oxide ligand according to claim 4, wherein the method comprises a catalytic method, and when the ligand is used for hydroformylation reaction, the reaction solvent can be benzene, toluene, tetrahydrofuran or corresponding product aldehyde, and the volume ratio of the solvent to the substrate is 1:5 to 1:25; when the ligand is used in an alkoxycarbonylation or hydrocarboxylation reaction, the molar ratio of methanol to olefin is 1.5:1 and the molar ratio of acetic acid to water to olefin is 2:1:1.
9. The method for synthesizing a pentavalent tridentate phosphine oxide ligand and its reduced trivalent tridentate phosphine oxide ligand according to claim 4, wherein the olefin is terminal olefin, internal olefin, disproportionated olefin or polysubstituted olefin.
10. The method for synthesizing a pentavalent tridentate phosphine oxide ligand and a reduced trivalent tridentate phosphine oxide ligand thereof according to claim 9, wherein the terminal alkene comprises ethylene, propylene, butylene or C5-C10 terminal alkene; the internal olefins include 2-butene, 2-octene, 3-octene, 4-octene or C5-C10 internal olefins; the disproportionated or polysubstituted olefins include 2, 4-trimethyl-1-pentene, 2, 4-trimethyl-2-pentene, 2, 3-dimethyl-2-butene or diisobutene.
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