Method for synthesizing methyl 3-hydroxypropionate by cobalt catalysis with TADDOL skeleton as ligand

Abstract

The invention discloses a method for synthesizing methyl 3-hydroxypropionate through cobalt catalysis by taking a TADDOL framework as a ligand, and the methyl 3-hydroxypropionate is obtained by catalyzing ethylene oxide esterification reaction by taking a phosphine-containing ligand of the TADDOL framework and a cobalt catalyst. The phosphine-containing ligand with a TADDOL skeleton is matched with the cobalt catalyst, and the ligand and the cobalt catalyst have a good coordination relationship, so that the dissolution of the cobalt catalyst can be promoted, the activity of the catalyst is improved, the reaction time is shortened, and the conversion rate of ethylene oxide and the selectivity and yield of methyl 3-hydroxypropionate are improved; meanwhile, the ligand system has a very good catalytic circulation effect, can keep activity after being circulated for multiple times, is suitable for industrial application, and has a wide application prospect.

Description

Technical Field

[0001] The invention relates to the technical field of organic synthesis, in particular to a method for synthesizing methyl 3-hydroxypropionate by cobalt catalysis using a TADDOL skeleton as a ligand. Background Art

[0002] 1,3-Propanediol (1,3-PDO) is an important organic fine chemical with a wide range of industrial applications. It is a key raw material for the production of antifreeze agents, plasticizers, cosmetics, and surfactants. In the polyurethane industry, it is primarily used as an initiator or chain extender for polyester polyols. Its primary application is as a polymerization monomer, reacting with terephthalic acid to form poly(trimethylene terephthalate) (PTT). As a key raw material for PTT polyester fibers, 1,3-PDO is irreplaceable, and the development of an efficient method for its synthesis has become a research priority.

[0003] The key intermediate of the ethylene oxide hydroesterification method is 3-hydroxymethyl propionate (3-HPM), and its reaction equation is as follows:

[0004] US Patent No. 4973741 discloses the use of precious metal rhodium and triphenylphosphine ligands to prepare methyl 3-hydroxypropionate from ethylene oxide at a pressure of 14 MPa. However, the ethylene oxide conversion and selectivity for the target product are relatively low. US Patent No. 6191321 discloses the use of Co2(CO)8 and 1,10-phenanthroline as catalysts, with a reaction temperature of 90°C and 7.8 MPa for 18 hours. The ethylene oxide conversion is 11%, and the selectivity for 3-HPM is 74%. US Patent No. 6521801 discloses the use of Co2(CO)8 and imidazole as catalysts, with a reaction temperature of 70-80°C and 3.4-8 MPa for 2-4 hours. The reaction temperature is 94%, and the selectivity for 3-HPM is 78%. Patent CN101020635A discloses a system using a cobalt salt as a catalyst, a nitrogen-containing compound as a ligand, and an alkali metal or alkaline earth metal as a cocatalyst at 50-100°C and 3-7 MPa for 3-5 hours, achieving a 90% selectivity for 3-HPM. Patent CN101973881A discloses a system using Co2(CO)8 / ionic liquids, using a nitrogen-containing heterocycle or an organophosphine as a ligand, at 50-100°C and 3-7 MPa for 6-18 hours, achieving an ethylene oxide conversion of 98.1% and a 3-HPM selectivity of 90.8%. Patent CN105233830A discloses a system using a soluble cobalt salt as a catalyst, 3-hydroxypyridine as a ligand, and cobalt powder as a reducing agent, achieving a maximum ethylene oxide conversion of 99.73%, a 3-HPM selectivity of 97.72%, and a yield of 75.38%. However, the above-mentioned application systems have exposed the problem of insufficient cycle stability in actual operation, and the cycle evaluation results of their catalytic systems are also unsatisfactory, which has greatly hindered their industrialization process.

[0005] Current research progress shows that designing and synthesizing ligands with high stability and efficiency to significantly improve the conversion rate of ethylene oxide and methyl 3-hydroxypropionate and achieve industrial-scale production is the key to promoting the maturity and application of ethylene oxide hydroesterification technology. Summary of the Invention

[0006] The present invention aims to overcome the above-mentioned problems existing in the synthesis reaction of methyl 3-hydroxypropionate in the prior art and provides a method for synthesizing methyl 3-hydroxypropionate using cobalt as a TADDOL skeleton ligand. The method adopts a high-efficiency catalytic system based on a TADDOL skeleton and a phosphine-containing ligand for the hydromethylation reaction of ethylene oxide. The method can significantly improve the activity, selectivity and stability of the reaction under mild catalytic conditions, thereby significantly shortening the reaction time and significantly improving the conversion rate of ethylene oxide as well as the selectivity and yield of methyl 3-hydroxypropionate.

[0007] In order to achieve the above object, the present invention adopts the following technical solutions: A method for synthesizing methyl 3-hydroxypropionate using a TADDOL skeleton as a ligand and cobalt as a catalyst, comprising the following steps: catalyzing an ethylene oxide esterification reaction using a TADDOL skeleton-containing phosphine ligand and a cobalt catalyst to obtain methyl 3-hydroxypropionate; The structural formula of the TADDOL framework phosphine-containing ligand is: Among them, R 1 is a C1-C4 alkyl or phenyl group; R 2 is one of hydrogen, C1-C4 alkyl, phenyl, and substituted phenyl; The bridging group X is selected from one of C, N, O, and S; R 3 is one of hydrogen, C1-C4 alkyl, phenyl, substituted phenyl, heteroaryl, and substituted heteroaryl.

[0008] As a preference, R 1 is methyl; R 2 is one of phenyl and p-methylphenyl; X is one of N and O; R 3 It is one of hydrogen, methyl, ethyl, propyl, butyl, phenyl, and substituted phenyl.

[0009] Preferably, the cobalt catalyst is dicobalt octacarbonyl.

[0010] Preferably, the molar concentration of the TADDOL framework phosphine-containing ligand added during the reaction is 0.001-100 mmol / L; the molar concentration of the cobalt catalyst is 0.001-100 mmol / L.

[0011] Preferably, the molar concentration of the TADDOL framework phosphine-containing ligand added during the reaction is 1-100 mmol / L; the molar concentration of the cobalt catalyst is 1-100 mmol / L.

[0012] Preferably, the raw materials for the ethylene oxide esterification reaction are ethylene oxide, carbon monoxide, organic alcohol or organic phenol.

[0013] Preferably, the ethylene oxide esterification reaction is carried out in an organic solvent, wherein the organic solvent is selected from one or more of organic alcohols, phenols, ethers, and aromatic solvents.

[0014] Preferably, the organic solvent is selected from one or more of methanol, ethanol, propanol, butanol, pentanol, hexanol, heptanol, octanol, nonanol, decanol, cyclopentanol, cyclohexanol, benzyl alcohol, phenol, benzene, toluene, ether, tetrahydrofuran, and 1,4-dioxane.

[0015] Preferably, the reaction temperature of the ethylene oxide esterification reaction is 0-250° C., the reaction pressure is 0.1-20 MPa, and the reaction time is 0.01-100 h.

[0016] Preferably, the reaction temperature of the ethylene oxide esterification reaction is 60-120° C., the reaction pressure is 2-8 MPa, and the reaction time is 0.5-4 h.

[0017] Therefore, the present invention has the following beneficial effects: the present invention adopts a phosphine-containing ligand with a TADDOL skeleton to cooperate with a cobalt catalyst, and the ligand has a good coordination relationship with the cobalt catalyst, which can promote the dissolution of the cobalt catalyst, improve the activity of the catalyst, shorten the reaction time, and improve the conversion rate of ethylene oxide, the selectivity and yield of methyl 3-hydroxypropionate; at the same time, the ligand system has a good catalytic cycle effect, can maintain activity after multiple cycles, is suitable for industrial applications, and has broad application prospects. BRIEF DESCRIPTION OF THE DRAWINGS

[0018] Figure 1 It is a gas chromatogram of the product obtained in Example 2 of the present invention. DETAILED DESCRIPTION

[0019] The present invention will be further described below with reference to the accompanying drawings and specific embodiments.

[0020] In the present invention, unless otherwise specified, all equipment and raw materials can be purchased from the market or are commonly used in the industry. The methods in the following embodiments, unless otherwise specified, are all conventional methods in the art.

[0021] In order to further understand the present invention, preferred embodiments of the present invention are described below in conjunction with specific implementation methods. However, it should be understood that these descriptions are only for further illustrating the features and advantages of the present invention rather than limiting the claims of the present invention.

[0022] In the following description, many specific details are set forth to facilitate a full understanding of the present invention, but the present invention may also be implemented in other ways different from those described herein, and those skilled in the art may make similar generalizations without violating the connotation of the present invention. Therefore, the present invention is not limited to the specific embodiments disclosed below.

[0023] Secondly, the term "one embodiment" or "embodiment" herein refers to a specific feature, structure, or characteristic that may be included in at least one implementation of the present invention. The phrase "in one embodiment" appearing in various places throughout this specification does not necessarily refer to the same embodiment, nor does it refer to a separate or selective embodiment that is mutually exclusive of other embodiments.

[0024] Overall embodiment: A method for synthesizing methyl 3-hydroxypropionate using a TADDOL skeleton as a ligand and cobalt as a catalyst, comprising the following steps: catalyzing an ethylene oxide esterification reaction using a TADDOL skeleton-containing phosphine ligand and a cobalt catalyst to obtain methyl 3-hydroxypropionate; The structural formula of the TADDOL framework phosphine-containing ligand is: Among them, R 1 is a C1-C4 alkyl or phenyl group; R 2 is one of hydrogen, C1-C4 alkyl, phenyl, and substituted phenyl; The bridging group X is selected from one of C, N, O, and S; R 3 is one of hydrogen, C1-C4 alkyl, phenyl, substituted phenyl, heteroaryl, and substituted heteroaryl.

[0025] As a specific embodiment, R 1 is methyl; R 2 is one of phenyl and p-methylphenyl; X is one of N and O; R 3 It is one of hydrogen, methyl, ethyl, propyl, butyl, phenyl, and substituted phenyl.

[0026] As a specific embodiment, the cobalt catalyst is dicobalt octacarbonyl.

[0027] As a specific embodiment, the molar concentration of the TADDOL framework phosphine-containing ligand added during the reaction is 0.001-100 mmol / L; the molar concentration of the cobalt catalyst is 0.001-100 mmol / L.

[0028] As a specific embodiment, the molar concentration of the TADDOL framework phosphine-containing ligand added during the reaction is 1-100 mmol / L; the molar concentration of the cobalt catalyst is 1-100 mmol / L.

[0029] As a specific embodiment, the raw materials for the ethylene oxide esterification reaction are ethylene oxide, carbon monoxide, organic alcohol or organic phenol.

[0030] As a specific embodiment, the ethylene oxide esterification reaction is carried out in an organic solvent, and the organic solvent is selected from one or more of organic alcohols, phenols, ethers, and aromatic solvents.

[0031] As a specific embodiment, the organic solvent is selected from one or more of methanol, ethanol, propanol, butanol, pentanol, hexanol, heptanol, octanol, nonanol, decanol, cyclopentanol, cyclohexanol, benzyl alcohol, phenol, benzene, toluene, ether, tetrahydrofuran, and 1,4-dioxane.

[0032] As a specific embodiment, the reaction temperature of the ethylene oxide esterification reaction is 0-250° C., the reaction pressure is 0.1-20 MPa, and the reaction time is 0.01-100 h.

[0033] As a specific embodiment, the reaction temperature of the ethylene oxide esterification reaction is 60-120° C., the reaction pressure is 2-8 MPa, and the reaction time is 0.5-4 h.

[0034] Example 1: A method for synthesizing methyl 3-hydroxypropionate using a cobalt-catalyzed TADDOL skeleton as a ligand, comprising the following steps: To a 100 mL reactor, 136.8 mg (0.4 mmol) of Co2(CO)8 and 431.2 mg (0.8 mmol) of ligand 1 were added, and 1760 mg (40 mmol) of ethylene oxide and 40 mL of methanol were injected through a metering pump. After the reactor was purged with carbon monoxide three times, the carbon monoxide was pressurized to 8 MPa and stirred at 60°C for 1 hour. The reactor was fully cooled to 0°C, slowly depressurized to normal pressure, and the reactor was purged with nitrogen three times. Sampling and analysis were performed, and the conversion of ethylene oxide and the selectivity and yield of methyl 3-hydroxypropionate were calculated. The results are shown in Table 1.

[0035] The structural formula of ligand 1 is:

[0036] Example 2: A method for synthesizing methyl 3-hydroxypropionate using a cobalt-catalyzed TADDOL skeleton as a ligand, comprising the following steps: To a 100 mL reactor, 136.8 mg (0.4 mmol) of Co2(CO)8 and 453.6 mg (0.8 mmol) of ligand 2 were added, and 1760 mg (40 mmol) of ethylene oxide and 40 mL of methanol were injected through a metering pump. After the reactor was purged with carbon monoxide three times, the carbon monoxide was pressurized to 8 MPa and stirred at 60°C for 1 hour. The reactor was fully cooled to 0°C, the pressure was slowly released to normal pressure, and the reactor was purged with nitrogen three times. Samples were taken for analysis, and the gas chromatogram of the product was as shown below. Figure 1 The conversion of ethylene oxide and the selectivity and yield of methyl 3-hydroxypropionate were calculated, and the results are shown in Table 1.

[0037] The structural formula of ligand 2 is:

[0038] Example 3: A method for synthesizing methyl 3-hydroxypropionate using a cobalt-catalyzed TADDOL skeleton as a ligand, comprising the following steps: To a 100 mL reactor, 136.8 mg (0.4 mmol) of Co2(CO)8 and 530.4 mg (0.8 mmol) of ligand 3 were added, and 1760 mg (40 mmol) of ethylene oxide and 40 mL of methanol were injected through a metering pump. After the reactor was purged with carbon monoxide three times, the carbon monoxide was pressurized to 8 MPa and stirred at 60°C for 1 hour. The reactor was fully cooled to 0°C, slowly depressurized to normal pressure, and the reactor was purged with nitrogen three times. Sampling and analysis were performed, and the conversion of ethylene oxide and the selectivity and yield of methyl 3-hydroxypropionate were calculated. The results are shown in Table 1.

[0039] The structural formula of ligand 3 is:

[0040] Example 4: A method for synthesizing methyl 3-hydroxypropionate using a cobalt-catalyzed TADDOL skeleton as a ligand, comprising the following steps: To a 100 mL reactor, 136.8 mg (0.4 mmol) of Co2(CO)8 and 452.0 mg (0.8 mmol) of ligand 4 were added, and 1760 mg (40 mmol) of ethylene oxide and 40 mL of methanol were injected through a metering pump. After the reactor was purged with carbon monoxide three times, the carbon monoxide was pressurized to 8 MPa and stirred at 60°C for 1 hour. The reactor was fully cooled to 0°C, slowly depressurized to normal pressure, and the reactor was purged with nitrogen three times. Sampling and analysis were performed, and the conversion of ethylene oxide and the selectivity and yield of methyl 3-hydroxypropionate were calculated. The results are shown in Table 1.

[0041] The structural formula of ligand 4 is:

[0042] Example 5: A method for synthesizing methyl 3-hydroxypropionate using a cobalt-catalyzed TADDOL skeleton as a ligand, comprising the following steps: To a 100 mL reactor, 136.8 mg (0.4 mmol) of Co2(CO)8 and 476.1 mg (0.8 mmol) of ligand 5 were added, and 1760 mg (40 mmol) of ethylene oxide and 40 mL of methanol were injected through a metering pump. After the reactor was purged with carbon monoxide three times, the carbon monoxide was pressurized to 8 MPa and stirred at 60°C for 1 hour. The reactor was fully cooled to 0°C, slowly depressurized to normal pressure, and the reactor was purged with nitrogen three times. Sampling and analysis were performed, and the conversion of ethylene oxide and the selectivity and yield of methyl 3-hydroxypropionate were calculated. The results are shown in Table 1.

[0043] The structural formula of ligand 5 is:

[0044] Example 6: A method for synthesizing methyl 3-hydroxypropionate using a cobalt-catalyzed TADDOL skeleton as a ligand, comprising the following steps: To a 100 mL reactor, 136.8 mg (0.4 mmol) of Co2(CO)8 and 409.6 mg (0.8 mmol) of ligand 6 were added, and 1760 mg (40 mmol) of ethylene oxide and 40 mL of methanol were injected through a metering pump. After the reactor was purged with carbon monoxide three times, the carbon monoxide was pressurized to 8 MPa and stirred at 60°C for 1 hour. The reactor was fully cooled to 0°C, slowly depressurized to normal pressure, and the reactor was purged with nitrogen three times. Sampling and analysis were performed, and the conversion of ethylene oxide and the selectivity and yield of methyl 3-hydroxypropionate were calculated. The results are shown in Table 1.

[0045] The structural formula of ligand 6 is:

[0046] Example 7: A method for synthesizing methyl 3-hydroxypropionate using a cobalt-catalyzed TADDOL skeleton as a ligand, comprising the following steps: To a 100 mL reactor, 136.8 mg (0.4 mmol) of Co2(CO)8 and 420.8 mg (0.8 mmol) of ligand 7 were added, and 1760 mg (40 mmol) of ethylene oxide and 40 mL of methanol were injected through a metering pump. After the reactor was purged with carbon monoxide three times, the carbon monoxide was pressurized to 8 MPa and stirred at 60°C for 1 hour. The reactor was fully cooled to 0°C, slowly depressurized to normal pressure, and the reactor was purged with nitrogen three times. Sampling and analysis were performed, and the conversion of ethylene oxide and the selectivity and yield of methyl 3-hydroxypropionate were calculated. The results are shown in Table 1.

[0047] The structural formula of ligand 7 is:

[0048] Example 8: A method for synthesizing methyl 3-hydroxypropionate using a cobalt-catalyzed TADDOL skeleton as a ligand, comprising the following steps: To a 100 mL reactor, 136.8 mg (0.4 mmol) of Co2(CO)8 and 470.4 mg (0.8 mmol) of ligand 8 were added, and 1760 mg (40 mmol) of ethylene oxide and 40 mL of methanol were injected through a metering pump. After the reactor was purged with carbon monoxide three times, the carbon monoxide was pressurized to 8 MPa and stirred at 60°C for 1 hour. The reactor was fully cooled to 0°C, slowly depressurized to normal pressure, and the reactor was purged with nitrogen three times. Sampling and analysis were performed, and the conversion of ethylene oxide and the selectivity and yield of methyl 3-hydroxypropionate were calculated. The results are shown in Table 1.

[0049] The structural formula of ligand 8 is:

[0050] Example 9: A method for synthesizing methyl 3-hydroxypropionate using a cobalt-catalyzed TADDOL skeleton as a ligand, comprising the following steps: To a 100 mL reactor, 136.8 mg (0.4 mmol) of Co2(CO)8 and 454.4 mg (0.8 mmol) of ligand 9 were added, and 1760 mg (40 mmol) of ethylene oxide and 40 mL of methanol were injected through a metering pump. After the reactor was purged with carbon monoxide three times, the carbon monoxide was pressurized to 8 MPa and stirred at 60°C for 1 hour. The reactor was fully cooled to 0°C, slowly depressurized to normal pressure, and the reactor was purged with nitrogen three times. Sampling and analysis were performed, and the conversion of ethylene oxide and the selectivity and yield of methyl 3-hydroxypropionate were calculated. The results are shown in Table 1.

[0051] The structural formula of ligand 9 is:

[0052] Example 10: A method for synthesizing methyl 3-hydroxypropionate using a cobalt-catalyzed TADDOL skeleton as a ligand, comprising the following steps: To a 100 mL reactor, 136.8 mg (0.4 mmol) of Co2(CO)8 and 409.6 mg (0.4 mmol) of ligand 6 were added, and 1760 mg (40 mmol) of ethylene oxide and 40 mL of methanol were injected through a metering pump. After the reactor was purged with carbon monoxide three times, the carbon monoxide was pressurized to 8 MPa and stirred at 60°C for 1 hour. The reactor was fully cooled to 0°C, slowly depressurized to normal pressure, and the reactor was purged with nitrogen three times. Sampling and analysis were performed, and the conversion of ethylene oxide and the selectivity and yield of methyl 3-hydroxypropionate were calculated. The results are shown in Table 1.

[0053] The structural formula of ligand 6 is:

[0054] Example 11: A method for synthesizing methyl 3-hydroxypropionate using a cobalt-catalyzed TADDOL skeleton as a ligand, comprising the following steps: To a 100 mL reactor, 136.8 mg (0.4 mmol) of Co2(CO)8 and 409.6 mg (2.0 mmol) of ligand 6 were added, and 1760 mg (40 mmol) of ethylene oxide and 40 mL of methanol were injected through a metering pump. After the reactor was purged with carbon monoxide three times, the carbon monoxide was pressurized to 8 MPa and stirred at 60°C for 1 hour. The reactor was fully cooled to 0°C, slowly depressurized to normal pressure, and the reactor was purged with nitrogen three times. Sampling and analysis were performed, and the conversion of ethylene oxide and the selectivity and yield of methyl 3-hydroxypropionate were calculated. The results are shown in Table 1.

[0055] The structural formula of ligand 6 is:

[0056] Example 12: A method for synthesizing methyl 3-hydroxypropionate using a cobalt-catalyzed TADDOL skeleton as a ligand, comprising the following steps: To a 100 mL reactor, 136.8 mg (0.1 mmol) of Co2(CO)8 and 409.6 mg (0.8 mmol) of ligand 6 were added, and 1760 mg (40 mmol) of ethylene oxide and 40 mL of methanol were injected through a metering pump. After the reactor was purged with carbon monoxide three times, the carbon monoxide was pressurized to 8 MPa and stirred at 60°C for 1 hour. The reactor was fully cooled to 0°C, slowly depressurized to normal pressure, and the reactor was purged with nitrogen three times. Sampling and analysis were performed, and the conversion of ethylene oxide and the selectivity and yield of methyl 3-hydroxypropionate were calculated. The results are shown in Table 1.

[0057] The structural formula of ligand 6 is:

[0058] Example 13: A method for synthesizing methyl 3-hydroxypropionate using a cobalt-catalyzed TADDOL skeleton as a ligand, comprising the following steps: To a 100 mL reactor, 136.8 mg (0.8 mmol) of Co2(CO)8 and 409.6 mg (0.8 mmol) of ligand 6 were added, and 1760 mg (40 mmol) of ethylene oxide and 40 mL of methanol were injected through a metering pump. After the reactor was purged with carbon monoxide three times, the carbon monoxide was pressurized to 8 MPa and stirred at 60°C for 1 hour. The reactor was fully cooled to 0°C, slowly depressurized to normal pressure, and the reactor was purged with nitrogen three times. Sampling and analysis were performed, and the conversion of ethylene oxide and the selectivity and yield of methyl 3-hydroxypropionate were calculated. The results are shown in Table 1.

[0059] The structural formula of ligand 6 is:

[0060] Comparative Example 1 (without adding TADDOL skeleton phosphine-containing ligand): A method for synthesizing methyl 3-hydroxypropionate catalyzed by cobalt, comprising the following steps: 136.8 mg (0.4 mmol) of Co2(CO)8 was added to a 100 mL reactor, and 1760 mg (40 mmol) of ethylene oxide and 40 mL of methanol were injected through a metering pump. After the reactor was purged with carbon monoxide three times, the carbon monoxide was pressurized to 8 MPa and stirred at 60°C for 1 hour. The reactor was fully cooled to 0°C, slowly depressurized to normal pressure, and the reactor was purged with nitrogen three times. Sampling was performed and analyzed, and the conversion of ethylene oxide and the selectivity of methyl 3-hydroxypropionate were calculated. The results are shown in Table 1.

[0061] Table 1: Product analysis results.

[0062] As can be seen from the data in Table 1, the use of a TADDOL framework phosphine-containing ligand and a cobalt catalyst to catalyze the ethylene oxide esterification reaction in Examples 1 to 9 significantly improves the activity, selectivity, and stability of the reaction, compared with Comparative Example 1 in which no TADDOL framework phosphine-containing ligand is added, thereby significantly improving the conversion rate of ethylene oxide and the selectivity and yield of methyl 3-hydroxypropionate.

[0063] The ligand system in Example 6 was distilled under reduced pressure to obtain the desired product, and the mother liquor containing the catalyst and the ligand was then subjected to a catalytic cycle effect test. The results are shown in Table 2.

[0064] Table 2: Cyclic performance test results. Number of cycles EO conversion rate / % 3-HMP selectivity / % 3-HMP yield / % 1 98 93 91.14 2 97 94 91.18 3 97 93 90.21 4 97 93 90.21 5 97 92 89.24 6 96 93 89.28

[0065] As can be seen from Table 2, the catalytic system of the present invention using the TADDOL framework phosphine-containing ligand and the cobalt catalyst has a good catalytic cycle effect and can maintain activity after multiple cycles. It is suitable for industrial applications and has broad application prospects.

[0066] The above embodiments are only used to illustrate the technical solutions of the present invention and are not intended to limit the present invention. Although the present invention has been described in detail with reference to the preferred embodiments, those skilled in the art should understand that the technical solutions of the present invention may be modified or replaced by equivalents without departing from the purpose and scope of the technical solutions, which should all be included in the scope of the claims of the present invention.

Claims

1. A method for synthesizing methyl 3-hydroxypropionate using cobalt as a TADDOL skeleton ligand, characterized in that the steps The method comprises the following steps: catalyzing the esterification of ethylene oxide with a TADDOL skeleton-containing phosphine ligand and a cobalt catalyst to obtain methyl 3-hydroxypropionate; The structural formula of the TADDOL framework phosphine-containing ligand is: Among them, R 1 is a C1-C4 alkyl or phenyl group; R 2 is one of hydrogen, C1-C4 alkyl, phenyl, and substituted phenyl; The bridging group X is selected from one of C, N, O, and S; R 3 is one of hydrogen, C1-C4 alkyl, phenyl, substituted phenyl, heteroaryl, and substituted heteroaryl.

2. The method for synthesizing methyl 3-hydroxypropionate by cobalt catalysis with a TADDOL skeleton as a ligand according to claim 1, wherein: R 1 is methyl; R 2 is one of phenyl and p-methylphenyl; X is one of N and O; R 3 It is one of hydrogen, methyl, ethyl, propyl, butyl, phenyl, and substituted phenyl.

3. The method for synthesizing methyl 3-hydroxypropionate by cobalt catalysis with a TADDOL skeleton as a ligand according to claim 1, wherein: The cobalt catalyst is dicobalt octacarbonyl.

4. The method for synthesizing methyl 3-hydroxypropionate by cobalt catalysis with a TADDOL skeleton as a ligand according to claim 1, 2 or 3, wherein: The molar concentration of the TADDOL framework phosphine-containing ligand added during the reaction is 0.001-100 mmol / L; the molar concentration of the cobalt catalyst is 0.001-100 mmol / L.

5. The method for synthesizing methyl 3-hydroxypropionate by cobalt catalysis with a TADDOL skeleton as a ligand according to claim 4, wherein: The molar concentration of the TADDOL framework phosphine-containing ligand added during the reaction is 1-100 mmol / L; the molar concentration of the cobalt catalyst is 1-100 mmol / L.

6. The method for synthesizing methyl 3-hydroxypropionate by cobalt catalysis with a TADDOL skeleton as a ligand according to claim 1, wherein: The raw materials for ethylene oxide esterification reaction are ethylene oxide, carbon monoxide, organic alcohol or organic phenol.

7. The method for synthesizing methyl 3-hydroxypropionate by cobalt catalysis with a TADDOL skeleton as a ligand according to claim 1 or 5, characterized in that: The ethylene oxide esterification reaction is carried out in an organic solvent, and the organic solvent is selected from one or more of organic alcohols, phenols, ethers, and aromatic solvents.

8. The method for synthesizing methyl 3-hydroxypropionate by cobalt catalysis with a TADDOL skeleton as a ligand according to claim 7, wherein: The organic solvent is selected from one or more of methanol, ethanol, propanol, butanol, pentanol, hexanol, heptanol, octanol, nonanol, decanol, cyclopentanol, cyclohexanol, benzyl alcohol, phenol, benzene, toluene, ether, tetrahydrofuran, and 1,4-dioxane.

9. The method for synthesizing methyl 3-hydroxypropionate by cobalt catalysis with a TADDOL skeleton as a ligand according to claim 1, wherein: The reaction temperature of the ethylene oxide esterification reaction is 0-250° C., the reaction pressure is 0.1-20 MPa, and the reaction time is 0.01-100 h.

10. The method for synthesizing methyl 3-hydroxypropionate by cobalt catalysis with a TADDOL skeleton as a ligand according to claim 9, characterized in that: The reaction temperature of the ethylene oxide esterification reaction is 60-120° C., the reaction pressure is 2-8 MPa, and the reaction time is 0.5-4 h.

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