CN112442087A - Preparation method and application of ionic phosphoramidite ligand - Google Patents

Preparation method and application of ionic phosphoramidite ligand Download PDF

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CN112442087A
CN112442087A CN202011342977.3A CN202011342977A CN112442087A CN 112442087 A CN112442087 A CN 112442087A CN 202011342977 A CN202011342977 A CN 202011342977A CN 112442087 A CN112442087 A CN 112442087A
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phosphoramidite
reaction
ionic
solvent
ligand
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孙予罕
王慧
王栋梁
马春辉
宋文越
杜洋
袁湘琦
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Shanghai Cluster Rui Low Carbon Energy Technology Co ltd
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Abstract

The invention discloses an ionic phosphoramidite ligand, a preparation method and application thereof in hydroformylation reaction. The general formula of the structure is
Figure DDA0002799055950000011
Or

Description

Preparation method and application of ionic phosphoramidite ligand
Technical Field
The invention relates to a preparation method and application of an ionic phosphoramidite ligand, and the catalyst has the advantages of simple synthesis process, unique physical and chemical properties, and higher industrial application prospect in hydroformylation and other reactions, and belongs to the technical field of metal organic and homogeneous catalysis.
Background
The hydroformylation reaction is also called oxo reaction, and is characterized in that under the action of a catalyst, olefin and synthesis gas (CO + H)2) Catalytic reaction process for generating aldehyde or alcohol. The yield of aldehydes and alcohols produced by hydroformylation reactions has exceeded 1000 million tons per year.
In the early hydroformylation, a Co metal complex is used as a catalyst, but the reaction condition is harsh, the product selectivity is poor, and the Co complex is very toxic (Angew. chem. int. Ed.,1994,33, 2144). With the progress of research, it was found that the catalytic activity of Rh metal complexes is much higher than that of Co metal complexes, and thus Rh metal complexes gradually become the main catalyst of hydroformylation reaction.
The ligand is an important factor influencing the catalytic activity of the transition metal catalyst, and the phosphine ligand becomes the ligand which is most researched and widely applied so far due to the structural diversity and unique effect of the phosphine ligand. Depending on the atom to which P is bonded, phosphine ligands can be further divided into three classes, organic phosphine ligands (P bonded to three carbon atoms), phosphite ligands (P bonded to one or more O atoms), and phosphoramidite ligands (P bonded to one or more N atoms). The phosphoramidite ligand has the advantages of simple synthesis, easy modification and unique effect, and compared with tertiary phosphine ligands and phosphite ligands, the phosphoramidite is a stronger pi electron acceptor, which is favorable for separating CO from a catalyst and is favorable for the reaction rate of hydroformylation, however, the research on the phosphoramidite ligand is less at present. Patent CN106000470A designs and synthesizes phosphoramidite ligands of binaphthol skeleton, and the phosphoramidite ligands are used for catalyzing the hydroformylation reaction of olefin, so that the conversion rate is higher, but the method needs larger ligand dosage which needs to reach 100 times of the mole number of rhodium. Patent CN102746338A designs and synthesizes bidentate phosphoramidite ligands with spiroketal frameworks, and the ligands are applied to hydroformylation of olefins, have better catalytic activity, but the cost of the ligand synthesis raw materials is higher, which is not beneficial to industrial application.
In addition, the design and use of the water-soluble ligand can realize the hydroformylation reaction of water and oil phases, and improve the separation and recovery efficiency of the catalyst. A breakthrough of the ligand is sulfonated aryl phosphine TPPTS (3, 3' -phosphinylidyne tris (benzenesulfonic acid) trisodium salt), however, the preparation process of the ligand is complex, the reaction conditions are harsh, and the existence of oxygen needs to be strictly eliminated, so that the development of a novel water-soluble ligand by a simple and efficient method is favorable for promoting the further development of hydroformylation reaction, and the ligand has a good industrial application prospect.
Although phosphoramidite ligands have been reported, most of the work is focused on pyrrole, indole and the like as modifying groups, and the synthesis method of the phosphoramidite ligands taking imidazole as a group is yet to be designed and optimized. In addition, the imidazole group can be subjected to quaternization modification so as to change the electronic effect, water solubility and other characteristics of the ligand, thereby regulating and controlling the catalytic effect of the transition metal catalyst and having the potential of realizing water-oil two-phase hydroformylation reaction.
The research on the phosphoramidite ligand is relatively limited compared with the synthesis application of the phosphite ligand, and the water-soluble phosphoramidite ligand is more rarely reported.
Disclosure of Invention
The technical problem to be solved by the invention is as follows: provides a series of ionic phosphoramidite ligands modified by imidazole groups, a method for efficiently synthesizing the ligands and application of the ligands in hydroformylation.
In order to solve the technical problems, the invention provides an ionic phosphoramidite ligand, which is characterized in that the structural general formula is as follows:
Figure BDA0002799055940000021
or
Figure BDA0002799055940000022
In the above formula, R1、R2Independently of one another is hydrogen, C1-C 6Alkyl or C1-C 6Alkoxy radical, R3Independently is C1-C18Alkyl or sultone.
The invention also provides the preparation method, which is characterized by comprising the following steps:
step 1): dissolving phosphorus trichloride and imidazole in a solvent, stirring for reaction, filtering, dissolving substituted biphenol in the solvent, dropwise adding the substituted biphenol into the filtrate for reaction, and purifying the obtained product to obtain monodentate phosphoramidite;
step 2): reacting monodentate phosphoramidite with a quaternizing agent in a solvent to obtain a product, and purifying the product to obtain an ionic monodentate phosphoramidite ligand shown in a formula I;
step 3): dissolving phosphorus trichloride and imidazole in a solvent, stirring for reaction under an alkaline condition, filtering, dissolving substituted biphenol in the solvent, dropwise adding the substituted biphenol into the filtrate for reaction, and purifying the obtained product to obtain the bidentate phosphoramidite.
Step 4): reacting the bidentate phosphoramidite with a quaternary amination reagent in a solvent to obtain a product, and purifying the product to obtain the ionic bidentate phosphoramidite ligand shown in the formula II.
The principle of the steps 1) and 2) is as follows:
Figure BDA0002799055940000031
the principles of the steps 3) and 4) are as follows:
Figure BDA0002799055940000041
preferably, the solvent is at least one of dichloromethane, tetrahydrofuran, chloroform, toluene, dimethyl sulfoxide, acetonitrile and deionized water; the purification means may be any post-treatment of the resulting product by various post-treatment methods conventionally used in the art. Methods of such post-processing include, but are not limited to: extraction, recrystallization, washing, drying, filtration, and the like.
Preferably, in the step 2) and 4), the quaternizing agent is at least one of halogenated hydrocarbon, a methanesulfonic acid ester derivative and a sultone derivative; the reaction temperature is 25-150 deg.C, and the reaction time is 0.5-48h, preferably 24 h.
More preferably, the quaternizing agent is at least one of n-butyl chloride, chloroethyl piperidine hydrochloride, methyl trifluoromethanesulfonate and 1, 3-propane sultone.
Preferably, the molar ratio of the phosphorus trichloride to the imidazole in the step 1) is 1:6-1:10, preferably 1: 7; the molar ratio of phosphorus trichloride to imidazole in the step 3) is 1: 2; the alkali adopted under the alkaline condition is organic alkali or inorganic alkali; the molar ratio of phosphorus trichloride to base is from 1:2 to 1:6, preferably 1: 3.
Preferably, the base used in the alkaline condition is at least one of triethylamine, pyridine, 4-dimethylaminopyridine, diisopropylethylamine and potassium carbonate, preferably any one or two of triethylamine and 4-dimethylaminopyridine.
Preferably, the reaction in step 1) and 3) is carried out at a temperature of 0-100 ℃, preferably 25 ℃ for 0.5-24h, preferably 1 h.
The invention also provides application of the ionic type phosphoramidite ligand in hydroformylation reaction, which is characterized in that a rhodium catalytic precursor, the ionic type phosphoramidite ligand and an organic solvent are added into a reaction kettle, olefin is added, then gas is filled, and the reaction kettle is heated for reaction.
Preferably, the rhodium catalytic precursor is rhodium acetylacetonate dicarbonyl, rhodium acetylacetonate triphenylphosphine carbonyl, rhodium triphenylphosphine hydride, Rh (OAc)3、Rh2O3、Rh4(CO)12And Rh6(CO)16At least one of; the organic solvent is at least one of benzene, toluene, xylene, valeraldehyde, dimethyl sulfoxide, dichloromethane, dichloroethane, acetonitrile, hexane, ethyl acetate, dioxane, tetrahydrofuran, methanol, ethanol, n-propanol, isopropanol and n-butanol; the olefin is C2-C18Preferably propylene, butene, octene, styrene; the molar ratio of the rhodium catalytic precursor to the ionic phosphoramidite ligand is 1: 1-1: 50, preferably in a molar ratio of rhodium catalytic precursor to monodentate phosphoramidite ligand of 1:10, the molar ratio of rhodium catalytic precursor to bidentate phosphoramidite ligand is 1: 5; the molar ratio of the rhodium catalytic precursor to the olefin is 1: 100-1: 10000; the volume ratio of the organic solvent to the olefin is 1: 1-20: 1; the gas is CO and H2In a molar ratio of 1:1, the pressure of the reaction kettle after being filled with gas is 2-8MPa, preferably 3-5 MPa.
Preferably, the heating reaction is carried out at a temperature of 80-180 ℃, preferably 90-120 ℃ for 0.5-10h, preferably 2 h.
The method provided by the invention can be used for conveniently synthesizing a series of neutral phosphoramidite ligands and efficiently synthesizing a series of ionic phosphoramidite ligands with different physicochemical properties by a quaternization method.
Compared with the prior art, the invention has the following advantages:
(1) the novel ionic phosphoramidite ligand provided by the invention has high pi electron accepting capacity and is favorable for the reaction rate of hydroformylation;
(2) the invention can change the characteristics of water solubility, oil solubility and the like of the obtained phosphoramidite ligand through simple quaternization, realizes the high-efficiency preparation and functional modification of the water-soluble phosphoramidite ligand, and has good application prospect in hydroformylation reaction.
Detailed Description
In order to make the invention more comprehensible, preferred embodiments are described in detail below.
Example 1
A preparation method of ionic monodentate phosphoramidite with a structural formula A and an application thereof in butene hydroformylation are disclosed:
Figure BDA0002799055940000061
dissolving 2.04g of imidazole in 50mL of ultra-dry dichloromethane under the protection of nitrogen, dropwise adding 0.43mL of phosphorus trichloride under ice bath, reacting for 30min, filtering, and protecting the filtrate with nitrogen. Dissolving 0.93g of diphenol in 10mL of ultra-dry dichloromethane, dropwise adding the solution into the filtrate, reacting at room temperature for 1h, filtering, spin-drying the solvent, and purifying the obtained product by column chromatography, wherein an eluent is ethyl acetate: n-hexane ═ 1:10, obtaining the monodentate phosphoramidite product. Under the protection of nitrogen, dissolving 1.41g of the obtained monodentate phosphoramidite in 20mL of toluene, adding 0.52mL of n-butyl chloride, heating to 110 ℃, refluxing for 12h, cooling, precipitating crystals, quickly filtering, washing the crystals with diethyl ether, dissolving the obtained crystals in deionized water, and adding NaBF40.55g is stirred at room temperature for 24 h. And (3) after the reaction is finished, removing water by rotary evaporation, extracting the product by using dichloromethane, drying the product by using anhydrous sodium sulfate, and then carrying out rotary drying to obtain the ionic phosphoramidite product A with the yield of 85%.
0.02mmol of Rh (acac) (CO)20.2mmol of phosphoramidite ligand A was charged into a 100mL reaction vessel, 40mL of a toluene solvent was added, followed by three-time replacement with a synthetic gas, 20mmol (1.72g) of n-butene was added, and the reaction was carried out at 120 ℃ with purging of the synthetic gas to 4 MPa. After 4h, the reaction kettle is cooled, the reaction liquid is washed out by toluene, an internal standard substance is added, and gas chromatography analysis is carried out, so that the n-butene conversion rate is 35%, the aldehyde selectivity is 91%, and the normal-iso ratio is 4.5.
Example 2
A preparation method of ionic monodentate phosphoramidite with a structural formula B and an application thereof in butene hydroformylation are disclosed:
Figure BDA0002799055940000071
dissolving 2.04g of imidazole in 50mL of ultra-dry dichloromethane under the protection of nitrogen, dropwise adding 0.43mL of phosphorus trichloride under ice bath, reacting for 30min, filtering, and protecting the filtrate with nitrogen. Dissolving 0.93g of diphenol in 10mL of ultra-dry dichloromethane, dropwise adding the solution into the filtrate, reacting at room temperature for 1h, filtering, spin-drying the solvent, and purifying the obtained product by column chromatography, wherein an eluent is ethyl acetate: n-hexane ═ 1:10, obtaining the monodentate phosphoramidite product. Under the protection of nitrogen, 1.41g of the obtained monodentate phosphoramidite is dissolved in 20mL of toluene, 0.61g of 1, 3-propane sultone is added, the temperature is raised to 110 ℃, reflux is carried out for 12h, crystals are separated out after cooling, the crystals are quickly filtered, washed by ether and dried to obtain the ionic phosphoramidite product B, and the yield is 79%.
0.02mmol of Rh (acac) (CO)20.2mmol of phosphoramidite ligand B was charged into a 100mL reaction vessel, 40mL of a toluene solvent was added, followed by three-time replacement with a synthetic gas, 20mmol (1.72g) of n-butene was added, and the reaction was carried out at 120 ℃ with purging of the synthetic gas to 4 MPa. After 4h, the reaction kettle is cooled, the reaction liquid is washed out by toluene, an internal standard substance is added, and gas chromatography analysis is carried out, so that the n-butene conversion rate is 70%, the aldehyde selectivity is 94%, and the n-iso ratio is 5.4.
Example 3
A preparation method of ionic monodentate phosphoramidite with a structural formula of C and an application thereof in butene hydroformylation are disclosed:
Figure BDA0002799055940000081
dissolving 2.04g of imidazole in 50mL of ultra-dry dichloromethane under the protection of nitrogen, dropwise adding 0.43mL of phosphorus trichloride under ice bath, reacting for 30min, filtering, and protecting the filtrate with nitrogen. Dissolving 2.05g of 3,3 ' -5,5 ' -tetra-tert-butyl-2, 2 ' -biphenol in 10mL of ultra-dry dichloromethane, dropwise adding the solution into the filtrate, reacting at room temperature for 1h, filtering, spin-drying the solvent, and purifying the obtained product by column chromatography, wherein the eluent is ethyl acetate: n-hexane ═ 1:10, obtaining the monodentate phosphoramidite product. Under the protection of nitrogen, 2.53g of the obtained monodentate phosphoramidite is dissolved in 20mL of toluene, 0.61g of 1, 3-propane sultone is added, the temperature is raised to 110 ℃, reflux is carried out for 12h, crystals are separated out after cooling, the crystals are quickly filtered, washed by ether and dried to obtain the ionic phosphoramidite product C, and the yield is 75%.
0.02mmol of Rh (acac) (CO)20.1mmol of phosphoramidite ligand C was charged into a 100mL reaction vessel, 40mL of a toluene solvent was added, followed by three-time replacement with syngas, 20mmol (1.72g) of n-butene was added, and syngas was purged to 4MPa to conduct a reaction at 120 ℃. After 4h, the reaction kettle is cooled, toluene is used for washing out reaction liquid, an internal standard substance is added, and gas chromatography analysis is carried out, so that the n-butene conversion rate is 80%, the aldehyde selectivity is 94%, and the normal-iso ratio is 6.
Example 4
Preparation method of bidentate phosphoramidite with structural formula D and application of bidentate phosphoramidite in butene hydroformylation reaction
Figure BDA0002799055940000091
Dissolving 2.04g of imidazole and 1.39mL of triethylamine in 50mL of ultra-dry dichloromethane under the protection of nitrogen, dropwise adding 1.29mL of phosphorus trichloride under ice bath, reacting for 30min, filtering, and protecting the filtrate with nitrogen. Dissolving 0.93g of diphenol in 10mL of ultra-dry dichloromethane, dropwise adding the solution into the filtrate, reacting at room temperature for 1h, filtering, spin-drying the solvent, and purifying the obtained product by column chromatography, wherein an eluent is ethyl acetate: n-hexane ═ 1:6, obtaining the bidentate phosphoramidite product. Dissolving 2.57g of the obtained bidentate phosphoramidite in 40mL of toluene, adding 0.52mL of n-butyl chloride, heating to 110 ℃, refluxing for 12h, cooling, precipitating crystals, rapidly performing suction filtration, washing the crystals with diethyl ether, dissolving the obtained crystals in deionized water, and adding NaBF42.20g are stirred at room temperature for 24 h. And (3) after the reaction is finished, removing water by rotary evaporation, extracting the product by using dichloromethane, drying the product by using anhydrous sodium sulfate, and then carrying out rotary drying to obtain the ionic phosphoramidite product D with the yield of 74%.
0.02mmol of Rh (acac) (CO)20.1mmol of phosphoramidite ligand D, into a 100mL reaction vessel, 40mL of toluene solvent was added, followed by three times of replacement with syngas, 20mmol of n-butene was added, and syngas was purged to 4MPa to conduct the reaction at 120 ℃. After 4h, the reaction is finished, the reaction kettle is cooled, toluene is used for washing out reaction liquid, an internal standard substance is added, and gas chromatography analysis is carried out, so that the n-butene conversion rate is 90%, the aldehyde selectivity is 97%, and the normal-iso ratio is 11.
Example 5
A preparation method of ionic bidentate phosphoramidite with a structural formula of E and an application thereof in butene hydroformylation reaction are disclosed:
Figure BDA0002799055940000101
dissolving 2.04g of imidazole and 1.39mL of triethylamine in 50mL of ultra-dry dichloromethane under the protection of nitrogen, dropwise adding 1.29mL of phosphorus trichloride under ice bath, reacting for 30min, filtering, and protecting the filtrate with nitrogen. Dissolving 0.93g of diphenol in 10mL of ultra-dry dichloromethane, dropwise adding the solution into the filtrate, reacting at room temperature for 1h, filtering, spin-drying the solvent, and purifying the obtained product by column chromatography, wherein an eluent is ethyl acetate: n-hexane ═ 1:6, obtaining the bidentate phosphoramidite product. Dissolving 2.57g of the obtained bidentate phosphoramidite in 40mL of toluene, refluxing 0.61g of 1, 3-propane sultone at 110 ℃ for 12h, cooling, separating out crystals, quickly filtering, washing the crystals with diethyl ether, and drying to obtain the ionic phosphoramidite product E with the yield of 70%.
0.02mmol of Rh (acac) (CO)20.1mmol of phosphoramidite ligand E, into a 100mL reaction vessel, 40mL of toluene solvent was added, followed by three times of replacement with syngas, 20mmol of n-butene was added, and syngas was purged to 4MPa to conduct the reaction at 120 ℃. After 4h, the reaction is finished, and the reaction kettle is cooledThe reaction solution was washed out with toluene, and an internal standard was added to conduct gas chromatography, whereby the n-butene conversion was 84%, the aldehyde selectivity was 95%, and the n-iso ratio was 10.
Example 6
A preparation method of ionic bidentate phosphoramidite with a structural formula of F and an application thereof in butene hydroformylation reaction are disclosed:
Figure BDA0002799055940000111
dissolving 2.04g of imidazole and 1.39mL of triethylamine in 50mL of ultra-dry dichloromethane under the protection of nitrogen, dropwise adding 1.29mL of phosphorus trichloride under ice bath, reacting for 30min, filtering, and protecting the filtrate with nitrogen. Dissolving 2.05g of 3,3 ' -5,5 ' -tetra-tert-butyl-2, 2 ' -biphenol in 10mL of ultra-dry dichloromethane, dropwise adding the solution into the filtrate, reacting at room temperature for 1h, filtering, spin-drying the solvent, and purifying the obtained product by column chromatography, wherein the eluent is ethyl acetate: n-hexane ═ 1:6, obtaining the bidentate phosphoramidite product. Dissolving 3.69g of the obtained bidentate phosphoramidite in 40mL of toluene, refluxing 0.61g of 1, 3-propane sultone at 110 ℃ for 12h, cooling, separating out crystals, quickly filtering, washing the crystals with diethyl ether, and drying to obtain the ionic phosphoramidite product F with the yield of 65%.
0.02mmol of Rh (acac) (CO)20.1mmol of phosphoramidite ligand F, into a 100mL reaction vessel, 40mL of toluene solvent was added, followed by three times of replacement with syngas, 20mmol of n-butene was added, and syngas was purged to 4MPa to conduct the reaction at 120 ℃. After 4h, the reaction is finished, the reaction kettle is cooled, toluene is used for washing out reaction liquid, an internal standard substance is added, and gas chromatography analysis is carried out, so that the n-butene conversion rate is 95%, the aldehyde selectivity is 99%, and the normal-iso ratio is 15.

Claims (11)

1. An ionic phosphoramidite ligand is characterized by having a structural general formula:
Figure FDA0002799055930000011
in the above formula, R1、R2Independently of one another is hydrogen, C1-C 6Alkyl or C1-C 6Alkoxy radical, R3Independently is C1-C18Alkyl or sultone.
2. The process for preparing ionic phosphoramidite ligands according to claim 1, comprising the steps of:
step 1): dissolving phosphorus trichloride and imidazole in a solvent, stirring for reaction, filtering, dissolving substituted biphenol in the solvent, dropwise adding the substituted biphenol into the filtrate for reaction, and purifying the obtained product to obtain monodentate phosphoramidite;
step 2): reacting monodentate phosphoramidite with a quaternizing agent in a solvent to obtain a product, and purifying the product to obtain an ionic monodentate phosphoramidite ligand shown in a formula I;
step 3): dissolving phosphorus trichloride and imidazole in a solvent, stirring for reaction under an alkaline condition, filtering, dissolving substituted biphenol in the solvent, dropwise adding the substituted biphenol into the filtrate for reaction, and purifying the obtained product to obtain the bidentate phosphoramidite.
Step 4): reacting the bidentate phosphoramidite with a quaternary amination reagent in a solvent to obtain a product, and purifying the product to obtain the ionic bidentate phosphoramidite ligand shown in the formula II.
3. The method of claim 2, wherein the solvent is at least one of dichloromethane, tetrahydrofuran, chloroform, toluene, dimethylsulfoxide, acetonitrile, and deionized water.
4. The method of claim 2, wherein in the steps 2) and 4), the quaternizing agent is at least one of a halogenated hydrocarbon, a methanesulfonic acid ester derivative and a sultone derivative; the reaction temperature is 25-150 ℃ and the reaction time is 0.5-48 h.
5. The method of claim 4, wherein the quaternizing agent is at least one of n-butyl chloride, chloroethyl piperidine hydrochloride, methyl trifluoromethanesulfonate, and 1, 3-propane sultone.
6. The method for preparing ionic phosphoramidite ligands according to claim 2, wherein the molar ratio of phosphorus trichloride to imidazole in step 1) is from 1:6 to 1: 10; the molar ratio of phosphorus trichloride to imidazole in the step 3) is 1: 2; the alkali adopted under the alkaline condition is organic alkali or inorganic alkali; the molar ratio of the phosphorus trichloride to the alkali is 1:2-1: 6.
7. The method of claim 6, wherein the basic conditions are performed using at least one base selected from the group consisting of triethylamine, pyridine, 4-dimethylaminopyridine, diisopropylethylamine, and potassium carbonate.
8. The process for preparing ionic phosphoramidite ligands according to claim 2, wherein the reaction in steps 1) and 3) is carried out at a temperature of 0 to 100 ℃ for a time of 0.5 to 24 hours.
9. The use of the ionic phosphoramidite ligand of claim 1 in hydroformylation reactions, wherein the rhodium catalytic precursor, the ionic phosphoramidite ligand and an organic solvent are added into a reaction vessel, an olefin is added, then a gas is introduced, and the reaction vessel is heated for reaction.
10. The use of claim 9 wherein the rhodium catalytic precursor is rhodium dicarbonyl acetylacetonate, rhodium triphenylphosphine carbonyl acetylacetonate, rhodium triphenylphosphine hydride, Rh (OAc)3、Rh2O3、Rh4(CO)12And Rh6(CO)16At least one of; the organic solvent is benzene, toluene, xylene, valeraldehyde, dimethyl sulfoxide or dimethyl sulfoxideAt least one of methyl chloride, dichloroethane, acetonitrile, hexane, ethyl acetate, dioxane, tetrahydrofuran, methanol, ethanol, n-propanol, isopropanol, and n-butanol; the olefin is C2-C18A monoolefin of (a); the molar ratio of the rhodium catalytic precursor to the ionic phosphoramidite ligand is 1: 1-1: 50; the molar ratio of the rhodium catalytic precursor to the olefin is 1: 100-1: 10000; the volume ratio of the organic solvent to the olefin is 1: 1-20: 1; the gas is CO and H2In a molar ratio of 1:1, the pressure of the reaction kettle filled with gas is 2-8 MPa.
11. The use according to claim 9, wherein the heating reaction is carried out at a temperature of 80 to 180 ℃ for a time of 0.5 to 10 hours.
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