CN114835746A - Novel tetradentate phosphine ligand compound and synthetic method and application thereof - Google Patents

Novel tetradentate phosphine ligand compound and synthetic method and application thereof Download PDF

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CN114835746A
CN114835746A CN202110137485.9A CN202110137485A CN114835746A CN 114835746 A CN114835746 A CN 114835746A CN 202110137485 A CN202110137485 A CN 202110137485A CN 114835746 A CN114835746 A CN 114835746A
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张润通
王建新
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Huizhou Kailisi Technology Co ltd
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Abstract

The invention discloses a preparation method of benzene-based tetraphosphine ligand 1,2,4, 5-tetra (di-tert-butylphosphine methyl) benzene and derivatives thereof. The novel tetradentate phosphine ligand has a structure shown as a general formula I, wherein a substituent R1 and R2 in the general formula I can be respectively selected from alkyl, cycloalkyl or aryl. Meanwhile, the invention discloses a synthesis method of the novel tetrakisphosphine ligand, and a complex of the novel tetrakisphosphine ligand and a metal palladium precursor as a catalyst in an alkene alkoxycarbonylation or hydrocarboxylation reactionThe use of (1).
Figure DDA0002927275180000011

Description

Novel tetradentate phosphine ligand compound and synthetic method and application thereof
Technical Field
The invention relates to the technical field of chemical synthesis, in particular to a novel tetradentate phosphine ligand, a synthesis method thereof and application thereof in olefin alkoxy carbonylation (or hydrocarboxylation) reaction.
Background
The hydroesterification reaction of olefin is to react olefin with carbon monoxide and alcohol under the action of metal compound/phosphine ligand to obtain ester with one more carbon atom than olefin. This is the most atomic, economical and convenient method among the many methods for synthesizing organic carboxylic acid esters. The following scheme shows the general reaction equation for the olefin hydroasterification reaction: the alkoxycarbonylation of olefinic compounds is a process of increasing importance. By alkoxycarbonylation is meant 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 general reaction equation for the oxycarbonylation is shown below:
Figure BDA0002927275160000011
hydrocarboxylation refers to the reaction of an olefin with carbon monoxide and a carboxylic acid in the presence of a metal complex to form the corresponding carboxylic acid. Typically, palladium is used as the metal. The general reaction equation for the hydrocarboxylation reaction is shown below:
Figure BDA0002927275160000012
the organic carboxylic ester is an important oxygen-containing compound and is widely applied to the fields of fine chemical products, medicines, pesticides, food additives, spices, coatings, paints and the like. For example, methyl propionate is widely used in the industries of food, feed and cosmetics as a solvent, an additive, a preservative or a spice. 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 a high-efficiency synthesis method of the organic carboxylic ester has important significance.
At present, the reported catalyst system mainly consists of a central metal, related phosphine ligands and an acid additive. The central metal is viii, transition metals of subgroup x such as Rh, Pd, Ni, Co, Cu, etc., of which the most studied is Pd. The study of related phosphine ligands such as alkyl phosphines, cycloalkyl phosphines, bidentate phosphines etc. has been described in a number of patents, such as EPA04489472, EPA0499329, EPA0495547, US2005085671a1, US6284919B1, US2001051745a1, US6476255B1 etc. In particular, the company cellulosate (Lucite) discloses a group of bidentate phosphides with substituted aryl bridges, 1, 2-bis (di-t-butylphosphinomethyl) benzene (dtbpx), which provides significantly higher reaction rates and produces little or no impurities than those previously disclosed, and has high conversion (chem. Commun.,1999, 1877-1878; WO 96/19434; WO2004/014552A 1). Furthermore, the company Evonik-Degusa also discloses 1, 1' -bis (tert-butylphenyl phosphino) -ferrocene ligands having high catalytic performance for the alkoxycarbonylation of olefins (Angew. chem. int. Ed.,2017,56(19), 5267-5271; US2017/0022234 Al).
Figure BDA0002927275160000021
These two ligands are the most efficient ligands in the current olefin hydroesterification reaction. These cases indicate that an important factor for high activity derives from the tertiary alkyl phosphine ligand structure. Although these two ligands show good performance in hydroesterification reactions, it is of great importance in alkoxycarbonylation reactions, in particular the reaction of ethylene with methanol to 3-methylpropionate (ethylene-methoxycarbonylation) as an intermediate step in the preparation of Methyl Methacrylate (MMA) (cata. The ethylene methoxycarbonylation reaction is carried out under mild conditions using methanol as a solvent using a ligand-modified palladium catalyst.
The object of the present invention is to provide novel bodies for alkoxycarbonylation with which better l/b selectivity, higher ester yields and milder reaction conditions can be achieved. In particular, the ligands of the present invention should also be suitable for hydroformylation, hydroaminomethylation of olefinic compounds. The presence of other functional groups on the olefin is also suitable.
Disclosure of Invention
The invention aims to develop a high-efficiency synthesis method of a novel tetradentate phosphine ligand and a derivative thereof. It is especially easy to synthesize, high in yield and capable of being synthesized in large scale. The structures of the compound and its derivatives are shown below:
Figure BDA0002927275160000031
in the structure of formula I, R 1 、R 2 Each independently optionally substituted organic group, as shown above. The synthetic route of the tetraphosphine ligand is as follows:
Figure BDA0002927275160000041
drawings
FIG. 1, preparation of ligand Compound L1 of the present invention 1 H NMR(400MHz,CDCl 3 ) A schematic diagram;
FIG. 2, preparation of ligand Compound L1 of the present invention 31 P NMR(400MHz,CDCl 3 ) A schematic diagram;
FIG. 3, of the ligand Compound L1 of the present invention 13 C NMR(400MHz,CDCl 3 ) Schematic representation.
Detailed Description
The above route of the present invention is described in detail by the following examples, which should be noted that the present invention is only for further illustration and not limited to the present invention. Those skilled in the art may make insubstantial modifications and adaptations to the present invention.
Example 1
Preparation of 1,2,4, 5-tetrabromomethylbenzene (scheme 1)
Figure BDA0002927275160000042
Into a 1L reaction flask were successively charged 13.4g (100mmol) of durene and 75g (420mmol) of NBromosuccinimide, 80mg dibenzoyl peroxide, 300ml carbon tetrachloride, stirred, heated to reflux and irradiated with 100W of 395nm ultraviolet lamp for overnight reaction. The reaction solution was filtered, the filtrate was washed with saturated sodium carbonate, dried over anhydrous sodium sulfate, the solvent was dried by spinning, and recrystallized twice from methylene chloride/n-hexane to obtain 21.6g of a solid. 1 H NMR(400MHz；CDCl 3 )δ:4.60(s,8H),7.37(s,2H).
Example 2
Preparation of di-tert-butylphosphine borane complex (route 1)
Figure BDA0002927275160000051
400ml of tetrahydrofuran and 25.0g (156.5mmol) of di-tert-butyl phosphine chloride are added into a 1000ml Schlenk reaction bottle in sequence under anhydrous and oxygen-free atmosphere, stirred, cooled to 0 ℃, added with 23.5 g (750mmol) of sodium borohydride and heated to room temperature for reaction overnight. Filtering after complete reaction, carrying out rotary evaporation on the filtrate to obtain a white solid, adding 250ml of distilled water, stirring for 1 hour, extracting for 2 times by using dichloromethane, combining organic phases, adding anhydrous sodium sulfate, drying, filtering, carrying out rotary evaporation to obtain a transparent oily liquid, and recrystallizing by using normal hexane to obtain 20.5 g of white crystals. 1 H NMR(400MHz；CDCl 3 )δ:0.4(m br w,3H),1.2(d,18H),3.9(d q, 1H). 31 P NMR(121.5MHz；CDCl 3 )δ:49.5(m).
Example 3
Preparation of lithiated di-tert-butylphosphine borane Complex (route 1)
Figure BDA0002927275160000052
Under the anhydrous and oxygen-free atmosphere, 150ml of n-hexane and 21.1g (126mmol) of di-tert-butylphosphine borane complex are sequentially added into a 500ml Schlenk bottle and stirred, the temperature is reduced to-78 ℃, 54ml (1M) of n-butyllithium tetrahydrofuran solution is dropwise added, the temperature is raised to the room temperature for reaction for 2 hours, and the mixture is stored at the low temperature for standby.
Example 4
Preparation of borane-protected 1,2,4, 5-tetrakis (di-tert-butylphosphinomethyl) benzene (scheme 1)
Figure BDA0002927275160000061
Under the protection of nitrogen or argon, 125ml (0.1M) lithiated di-tert-butylphosphine borane complex/tetrahydrofuran is added into a 500ml Schlenk reaction flask, stirred and cooled to-78 ℃, and then a solution of 5.4g (12 mmol) of 1,2,4, 5-tetrabromomethylbenzene and 150ml of tetrahydrofuran is added dropwise, and the temperature is raised to room temperature for reaction for 5 hours. Removing the solvent by rotary evaporation, adding 300ml of saturated NaCl aqueous solution/dichloromethane at a ratio of 1:1, stirring for 30 minutes, carrying out phase separation, extracting the water phase once with dichloromethane, combining the organic phases, drying with anhydrous sodium sulfate, filtering, carrying out rotary evaporation to obtain a light yellow solid, and pulping with ethyl acetate to obtain 8.4g of a white solid. 1 H NMR(400MHz,CDCl 3 ) δ:7.88(s,2H),3.23(d,8H),1.18(d,72H),0.75-0.10(bs,12H). 31 P NMR(162MHz, CDCl 3 )δ:49.43.
Example 5
Preparation of 1,2,4, 5-tetrakis (di-tert-butylphosphinomethyl) benzene (scheme 1)
Figure BDA0002927275160000062
Under nitrogen or argon atmosphere, 12.4g (16.2mmol) of 3, 14.52 g (130mmol) of DABCO and 200ml of toluene were charged into a 500ml reaction flask, and the reaction was stirred at 80 ℃ for 10 hours. N is a radical of 2 Under protection, rotary evaporation to obtain light white solid, adding degassed distilled water/ethyl acetate, stirring for 30 min, sucking organic phase with syringe needle, drying with anhydrous sodium sulfate, rotary evaporation, and final recrystallization with degassed methanol to obtain 7.6g white solid. 1 H NMR(400 MHz,CDCl 3 )δ:7.48(s,2H),3.03(s,8H),1.09-1.11(d,72H). 31 P NMR(162MHz, CDCl 3 )δ:28.65.
Example 6
Preparation of lithium reagent for 1,2,4, 5-tetramethylbenzene (route 2)
Figure BDA0002927275160000071
A1000 ml Schlenk reaction flask was charged under an anhydrous and oxygen-free atmosphere with 17.29g (180mmol) of sodium tert-butoxide, 27.1ml (180mmol) of tetramethylethylenediamine, 200ml of heptane and 4.03g (30mmol) of durene in succession. While stirring, 72.0ml (2.5M) of n-butyllithium was slowly added to the reaction system, and the temperature was raised to 80 ℃ for 6 hours. A grayish red precipitate formed which was separated by filtration and washed with 100ml of heptane and then resuspended in 200ml of heptane until use.
Example 7
Preparation of 1,2,4, 5-tetrakis (di-tert-butylphosphinomethyl) benzene (scheme 2)
Figure BDA0002927275160000072
A1000 ml Schlenk reaction flask was charged with 200ml (0.1M) of a 2' heptane suspension, 30.33ml (120mol) of di-t-butylphosphine chloride under anhydrous and oxygen-free atmosphere, and stirred at 60 ℃ for reaction overnight. The next day 50ml of degassed distilled water was added to quench the reaction, the organic phase was separated, the solvent removed by rotary evaporation and recrystallised from degassed methanol at-20 ℃ to give 13.4g of a white solid. 1 HNMR(400MHz,CDCl 3 )δ:7.48(s,2H), 3.03(s,8H),1.09-1.11(d,72H). 31 P-NMR(162MHz,CDCl 3 )δ:28.65.
In a preferred embodiment of the present invention, the method for preparing the organic carboxylic acid ester (or carboxylic acid) by olefin hydroesterification (or hydrocarboxylation) reaction is to perform a hydroesterification (or hydrocarboxylation) reaction on the terminal olefin, carbon monoxide and alcohol (or carboxylic acid) in an organic solvent under the action of a palladium compound/tetradentate phosphine ligand/acidic additive combined catalyst to generate the organic carboxylic acid ester (or carboxylic acid) with one more carbon than the olefin.
Comparative example 1: comparative test for alkoxycarbonylation reaction
The novel tetraphosphine ligand dttpx, namely: (1,2,4, 5-Tetrakis (di-tert-butylphosphinomethyl) benzene) as the ligand compound of comparative example 1, cellulosateCompany commercializes ligand dtbpx as a comparison ligand, i.e.: 1, 2-bis (di-tert-butylphosphinomethyl) benzene. Under argon atmosphere, adding a certain amount of Pd (OAc) into a 200ml stainless steel high-pressure reaction kettle provided with a pressure sensor, a temperature probe, an online sampling port, a safety relief valve and the like 2 (0.26. mu. mol, 0.06mg), a certain amount of ligand dttpx or dtbpx (0.52-2.08. mu. mol) and excess methanesulfonic acid (2.6-5.2. mu. mol), adding a certain volume of methanol (5ml) and an internal standard toluene, and stirring and complexing for 30 minutes with a magneton to generate a catalytic complex of palladium and ligand. Subsequently, after connecting a gas line and sufficiently replacing the gas line, a certain proportion of liquefied ethylene (26mmol) was added to the reaction vessel by a plunger pump having a metering function under switching of a two-position four-way valve. Carbon monoxide was charged into the reactor to 4.5 MPa. The reaction kettle is heated to the required temperature of 80 ℃, and carbon monoxide is continuously supplemented in the reaction to keep the total pressure constant at about 4.5 MPa. After 8 hours of reaction, the reaction kettle is connected into a-40 ℃ cold sleeve for cooling, after the temperature of the kettle is reduced to normal temperature, an online sampling port is opened for sampling under the condition that the kettle is not opened, and after the online sampling port is diluted by chromatographic grade ethyl acetate, a Gas Chromatograph (GC) is used for measuring the normal-to-abnormal ratio and the conversion rate. And after the kettle is opened, completely releasing the gas in the high-pressure reaction kettle in a fume hood, and sampling and weighing. The results are shown in Table 1.
Figure BDA0002927275160000081
Figure BDA0002927275160000082
＊ Reaction conditions：45bar，80℃，8h.
[b]Conversionand//bratio is determined by GC.
[c]TON is calculated by conversion×100000.
From the above experimental results, it can be seen that with the ligand of the present invention, the reaction time is 8 hours at S/C100000, the TON is as high as 92600, and the TOF is about 12000S- 1 Nearly one-fold higher activity than the commercial ligand, dtbpx,and the positive contrast ratio dtbpx is better.
Comparative example 2: hydrocarboxylation reaction comparative experiment
The novel tetraphosphine ligand dttpx, namely: (1,2,4, 5-tetrakis (di-tert-butylphosphinomethyl) benzene) as the ligand compound of comparative example 1, and celluloid corporation's commercial ligand dtbpx as the comparative ligand, namely: 1, 2-bis (di-tert-butylphosphinomethyl) benzene. Under argon atmosphere, adding a certain amount of Pd (acac) into a 200ml stainless steel high-pressure reaction kettle provided with a pressure sensor, a temperature probe, an online sampling port, a safety relief valve and the like 2 (10. mu. mol, 3.0mg), a certain amount of ligand dttpx or dtbpx (20-80. mu. mol) and excess p-toluenesulfonic acid (0.15-0.4mmol), adding a certain volume of acetic acid (2.0ml) and an internal standard toluene, and stirring and complexing for 30 minutes by using a magneton to generate a catalytic complex of palladium and the ligand. Subsequently, after connecting a gas line and sufficiently replacing, a plunger pump with a metering function was used to add a certain proportion of liquefied ethylene (4mmol) into the reaction kettle under the switching of a two-position four-way valve. Carbon monoxide was charged into the reactor to 5.0 MPa. The reaction kettle is heated to the required temperature of 80 ℃, and carbon monoxide is continuously supplemented in the reaction to keep the total pressure constant at about 5.0 MPa. After reacting for 10 hours, the reaction kettle is connected into a-40 ℃ cold sleeve for cooling, after the temperature of the kettle is reduced to normal temperature, an online sampling port is opened for sampling under the condition of not opening the kettle, and after the online sampling port is diluted by chromatographic grade ethyl acetate, a Gas Chromatograph (GC) is used for measuring the normal-to-abnormal ratio. And after the kettle is opened, completely releasing the gas in the high-pressure reaction kettle in a fume hood, and sampling and weighing. The results are shown in Table 2.
Figure BDA0002927275160000091
Figure BDA0002927275160000092
＊ Reaction conditions：50bar，100℃，10h.
[b]Conversion and//bratio is determined by GC.
[c]TON is calculated by conversion×400.
From the above experimental results, it can be seen that with the ligand of the present invention, the TON is 302, nearly three times higher than that of the commercial ligand, dtbpx, and the positive-iso ratio is better than dtbpx at S/C400 and 10 hours reaction time.
Figure BDA0002927275160000093
The foregoing is a more detailed description of the invention in connection with specific preferred embodiments and it is not intended that the invention be limited to these specific details. For those skilled in the art to which the invention pertains, several simple deductions or substitutions can be made without departing from the spirit of the invention, and all shall be considered as belonging to the protection scope of the invention.

Claims (10)

1. A preparation method of benzene-based tetraphosphine ligand 1,2,4, 5-tetra (di-tert-butylphosphine methyl) benzene and derivatives thereof is characterized by comprising the following synthetic routes:
Figure FDA0002927275150000011
or by a method of directly lithiating 1,2,4, 5-tetramethylbenzene (durene) (1), 1,2,4, 5-tetra (di-tert-butylphosphinomethyl) benzene (4) is obtained in two steps:
Figure FDA0002927275150000012
wherein, the structure of the novel tetraphosphorus ligand represented by the general formula I is as follows:
Figure FDA0002927275150000013
Figure FDA0002927275150000021
。
2. the method for preparing benzene-based tetraphosphine ligand 1,2,4, 5-tetrakis (di-tert-butylphosphinomethyl) benzene and its derivatives according to claim 1, wherein the backbone synthesis is performed by the following reaction.
Figure FDA0002927275150000022
Preparation of 1,2,4, 5-tetrabromomethyl benzene.
3. The process for preparing benzene-based tetraphosphine ligand 1,2,4, 5-tetrakis (di-t-butylphosphinomethyl) benzene and its derivatives according to claim 1, wherein the borane-protected phosphine hydride is obtained by the following reaction.
Figure FDA0002927275150000023
Preparation of di-tert-butylphosphine borane complex.
4. The process for preparing a benzene-based tetraphosphine ligand 1,2,4, 5-tetrakis (di-tert-butylphosphinomethyl) benzene and its derivatives as claimed in claim 1, wherein the lithiated di-tert-butylphosphine borane complex is obtained by the following reaction.
Figure FDA0002927275150000031
Preparation of lithiated di-tert-butylphosphine borane complex.
5. The process for preparing benzene-based tetraphosphine ligand 1,2,4, 5-tetrakis (di-t-butylphosphinomethyl) benzene and its derivatives as claimed in claim 1, wherein the borane-protected tetraphosphine ligand is obtained by the following reaction.
Figure FDA0002927275150000032
Preparation of borane-protected 1,2,4, 5-tetrakis (di-tert-butylphosphinomethyl) benzene.
6. The process for preparing benzene-based tetraphosphine ligand 1,2,4, 5-tetrakis (di-t-butylphosphinomethyl) benzene and its derivatives according to claim 1, wherein the borane-removed protected tetraphosphine ligand is obtained by the following reaction.
Figure FDA0002927275150000033
Preparation of 1,2,4, 5-tetra (di-tert-butylphosphinomethyl) benzene
Wherein the above reaction is characterized in that the ether solvent used in the reaction may be any one of anisole, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, tetrahydrofuran, methyl tert-butyl ether, ethyl tert-butyl ether, diethyl ether, isopropyl ether, dibutyl ether, 2-methyl tetrahydrofuran or dioxane.
7. The method for preparing benzene-based tetraphosphine ligand 1,2,4, 5-tetrakis (di-tert-butylphosphinomethyl) benzene and its derivatives according to claim 1, wherein the backbone synthesis is performed by the following reaction.
Figure FDA0002927275150000041
Preparation of lithium reagent for 1,2,4, 5-tetramethylbenzene.
8. The method for preparing benzene-based tetraphosphine ligand 1,2,4, 5-tetrakis (di-tert-butylphosphinomethyl) benzene and its derivatives according to claim 1, wherein the backbone synthesis is performed by the following reaction.
Figure FDA0002927275150000042
Preparation of 1,2,4, 5-tetra (di-tert-butylphosphinomethyl) benzene
Meanwhile, the ether solvent used in the reaction may be any one of anisole, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, tetrahydrofuran, methyl tert-butyl ether, ethyl tert-butyl ether, diethyl ether, isopropyl ether, dibutyl ether, 2-methyl tetrahydrofuran, or dioxane.
9. A novel tetraphosphine compound is used as a ligand in the methoxy carbonylation (or hydrocarboxylation) reaction of olefin. The method is characterized in that olefin, carbon monoxide and alcohol (or carboxylic acid) are subjected to a hydroesterification (or hydrocarboxylation) reaction to produce an organic carboxylic acid ester (or carboxylic acid) having one more carbon than the olefin in an organic solvent using a complex of the compound of claim 1 and a metallic palladium precursor as a catalyst.
The olefin used in the above-mentioned alkoxycarbonylation or hydrocarboxylation reaction is an olefin having 2 to 19 carbon atoms, such as ethylene, propylene, 1-butene, cis-and/or trans-2-butene, isobutylene, 1, 3-butadiene, 1-pentene, cis-and/or trans-2-pentene, 2,4, 4-trimethyl-1-pentene, 2,4, 4-trimethyl-2-pentene, 2-methyl-1-butene, 3-methyl-1-butene, 2-methyl-2-butene, 3, 3-dimethyl-1-butene, 2,3, 3-trimethyl-1-butene, 2, 3-dimethyl-1-butene, 2-methyl-1-butene, 2-dimethyl-1-butene, 2-methyl-2-pentene, 2-methyl-1-pentene, 2-methyl-2-pentene, 3-dimethyl-1-butene, 2-methyl-pentene, 2-butene, 2, 3-methyl-2-pentene, 2, and mixtures thereof, 2, 3-dimethyl-2-butene, hexene, tetramethylethylene, heptene, 1-octene, 2-octene, di-n-butene, diisobutylene, n-decene, cyclohexene, cycloheptene, cyclooctene, methyl 3-pentenoate, methyl 4-pentenoate, methyl 2-hexenoate, methyl 3-hexenoate, methyl 5-hexenoate, methyl 2-heptenoate, methyl (E) -2-octenoate, methyl (E) -2-nonenoic acid, methyl 10-enoate, methyl 11-enoate, methyl (Z) -oleate, methyl (E) -oleate or a mixture thereof.
The alcohol used in the above alkoxycarbonylation reaction is an aliphatic alcohol compound or a cycloaliphatic alcohol compound having 1 to 20 carbon atoms, such as methanol, ethanol, 1-propanol, isopropanol, isobutanol, t-butanol, 1-butanol, 2-butanol, 1-pentanol, 2-pentanol, 3-pentanol, 1-hexanol, cyclohexanol, 2-ethylhexanol, isononyl alcohol, 2-propylheptanol, cyclohexane-1, 2-diol, 1, 2-ethanediol, 1, 3-propanediol, glycerol, 1,2, 4-butanetriol, 2-hydroxymethyl-1, 3-propanediol, pentaerythritol, 1,2, 6-trihydroxyhexane, 1,1, 1-tris (hydroxymethyl) ethane, or a mixture thereof.
The carboxylic acid used in the above hydrocarboxylation reaction is an aliphatic or aromatic poly-or monocarboxylic acid compound having 1 to 20 carbon atoms, such as oxalic acid, malonic acid, succinic acid, adipic acid, azelaic acid, maleic acid, fumaric acid, citraconic acid, etc.; aromatic polycarboxylic acids such as phthalic acid, isophthalic acid, terephthalic acid, naphthalenedicarboxylic acid, benzenetricarboxylic acid, etc.; alicyclic polycarboxylic acids such as cyclopentanedicarboxylic acid, cyclohexanedicarboxylic acid, cycloheptanedicarboxylic acid, and the like. Examples of the organic carboxylic acids and derivatives thereof which can be used for the hydrocarboxylation reaction in addition to the polybasic acid include aliphatic monocarboxylic acids such as formic acid, acetic acid, propionic acid, butyric acid, valeric acid, lauric acid, stearic acid, phenylacetic acid, bromoacetic acid, acrylic acid, methacrylic acid and the like; aromatic monocarboxylic acids such as benzoic acid, methylbenzoic acid, naphthoic acid, bibenzoic acid, and the like; alicyclic monocarboxylic acids such as cyclopentanecarboxylic acid, cyclohexanecarboxylic acid, cycloheptanecarboxylic acid and the like. Among these compounds, acetic acid, propionic acid, methacrylic acid, benzoic acid and the like are preferable.
10. A novel tetraphosphinic compound as claimed in claim 9, for use as a ligand in the methoxycarbonylation (or hydrocarboxylation) reaction of an olefin. The method is characterized by being realized according to the following process steps and parameters.
(1) Sequentially adding a palladium compound, a tetradentate phosphine ligand and an acidic additive into a reaction kettle with a polytetrafluoroethylene lining in a reaction device under the protection of inert gas in a certain proportion, wherein the molar ratio of the tetradentate phosphine ligand to the palladium compound is 0.2: 1-120: 1 (preferably 1: 1-20: 1); the molar ratio of the acidic additive to the palladium compound is 0.2:1 to 200:1 (preferably 1:1 to 50: 1); the combined catalyst is used in an amount of the palladium compound relative to the olefin: the molar amount of the palladium compound is 0.000001 to 1% (preferably 0.00005 to 0.001%) of the molar amount of the olefin.
(2) Then, under the protection of inert gas, adding a certain proportion of liquid mixed olefin and a certain proportion of methanol (or acetic acid) into the reaction kettle by using a plunger pump with a metering function, controlling the total solution concentration of the rhodium catalyst to be about 10-200 ppm, and uniformly stirring at room temperature for 5-10 minutes.
(3) After stirring evenly, filling CO with a certain pressure into the reaction device, and controlling the total reaction pressure between 1.0MPa and 15.0 MPa; the reaction temperature is controlled to be 40-200 ℃, and the reaction time is controlled to be 4-20 hours.
In the above reaction, the palladium compound is one selected from the group consisting of palladium acetate, palladium chloride, bis (triphenylphosphine) palladium dichloride, bis (acetonitrile) palladium dichloride, (1, 5-cyclooctadiene) palladium dichloride, allylpalladium chloride, tetratriphenylphosphine palladium, palladium acetylacetonate, bis (dibenzylideneacetone) palladium and tris (dibenzylideneacetone) dipalladium. Preferably PdCl 2 、Pd(acac) 2 Bis (acetonitrile) palladium dichloride, (1, 5-cyclooctadiene) palladium dichloride, allylpalladium chloride, palladium iodide, palladium bromide.
In the above reaction, the acidic additive is one selected from perchloric acid, sulfuric acid, phosphoric acid, hydrochloric acid, formic acid, acetic acid, oxalic acid, methanesulfonic acid (MsOH), trifluoromethanesulfonic acid (TfOH), tert-butanesulfonic acid, p-toluenesulfonic acid (PTSA), 2-hydroxy-phenylpropane-2-sulfonic acid, 2,4, 6-trimethylbenzenesulfonic acid and dodecylsulfonic acid, aluminum trifluoromethanesulfonate. Preference is given to p-toluenesulfonic acid, methanesulfonic acid, trifluoromethanesulfonic acid, tert-butanesulfonic acid, 2,4, 6-trimethylbenzenesulfonic acid, dodecylsulfonic acid.
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