CN106431921A - Synthesis method of 3-hydroxy propionate - Google Patents
Synthesis method of 3-hydroxy propionate Download PDFInfo
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- CN106431921A CN106431921A CN201510493269.2A CN201510493269A CN106431921A CN 106431921 A CN106431921 A CN 106431921A CN 201510493269 A CN201510493269 A CN 201510493269A CN 106431921 A CN106431921 A CN 106431921A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/36—Preparation of carboxylic acid esters by reaction with carbon monoxide or formates
- C07C67/37—Preparation of carboxylic acid esters by reaction with carbon monoxide or formates by reaction of ethers with carbon monoxide
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
- B01J31/1805—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing nitrogen
- B01J31/181—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine
- B01J31/1815—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine with more than one complexing nitrogen atom, e.g. bipyridyl, 2-aminopyridine
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
- C07D401/14—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing three or more hetero rings
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/02—Compositional aspects of complexes used, e.g. polynuclearity
- B01J2531/0213—Complexes without C-metal linkages
- B01J2531/0219—Bimetallic complexes, i.e. comprising one or more units of two metals, with metal-metal bonds but no all-metal (M)n rings, e.g. Cr2(OAc)4
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/02—Compositional aspects of complexes used, e.g. polynuclearity
- B01J2531/0238—Complexes comprising multidentate ligands, i.e. more than 2 ionic or coordinative bonds from the central metal to the ligand, the latter having at least two donor atoms, e.g. N, O, S, P
Abstract
The invention relates to a synthesis method of 3-hydroxy propionate. The method mainly solves the problem that the selectivity of the 3-hydroxy propionate in the prior art is low. The synthesis method of the 3-hydroxy propionate comprises the following steps: i, enabling the ligand as shown in the formula (I) to perform the complexing reaction with cobalt carbonyl in a solvent to obtain a catalyst solution, wherein the solvent is the alcohol or the solvent containing the alcohol; R1 to R3 are independently selected from one of alkyl or alkenyl, aryl or substituted aryl, and heterocyclo, and R1 to R3 independently contain 1 to 6 carbon atoms; ii, adding ethylene oxide and carbon monoxide in the catalyst solution, reacting to obtain the 3-hydroxy propionate. The technical scheme well solves the technical problem, and can be used for the industrial production of the 3-hydroxy propionate. The the formula (I) is shown in the description.
Description
Technical field
The present invention relates to a kind of synthetic method of 3- hydroxy propionate.
Background technology
1, ammediol is a kind of important organic fine chemicals, can be used as producing antifreezing agent, plasticizer, preservative and the raw material of emulsifying agent, also it is widely used in food, the industry such as cosmetics and pharmacy, its most important application is to synthesize PTT (PTT) polyester fiber as monomer, compared with conventional polyethylene terephthalate (PET) fiber, ptt fiber had both had light resistance, water suction is few, the premium properties such as good stability, there is resilience good simultaneously again, the advantages of easily biological-degradable and environmental pollution are little, it is with a wide range of applications, it is the focus of current research and development.
3- hydroxy propionate is the important intermediate of synthesis 1,3-PD, and it hydrogenates under appropriate conditions and can get 1,3-PD.3- hydroxy propionate can be prepared by oxirane hydroesterification reaction, and, its synthetic reaction is expressed as follows taking 3- hydroxy methyl propionate as a example:
The major progress obtaining at present is as follows:
Nineteen ninety, US4973741 discloses using Noble Metal Rhodium catalyst and triphenylphosphine ligand, and oxirane hydrogen carbomethoxy is combined to 3- hydroxy methyl propionate, but reaction needs the high pressure of 14MPa, and the selectivity of oxirane conversion ratio and target product is relatively low.
Calendar year 2001, US6191321 discloses and uses Co2(CO)8The catalyst system of/1,10- adjacent phenanthrene quinoline, methyl tertiary butyl ether(MTBE) is solvent, at 90 DEG C, reacts 18 hours under conditions of 7.8MPa, and oxirane conversion ratio is only 11%, and the selectivity of target product 3- hydroxy methyl propionate is 74%.
2002, EP1179524A1 disclosed with cobalt salt as catalyst, and N- alkyl azole compounds are part, the method that methanol synthesizes 3- hydroxy methyl propionate for solvent, and wherein target product selectivity is up to 90%.
2003, US6521801 disclosed with cobalt salt as catalyst, and nitrogen-containing heterocycle compound is part, it is 6MPa in carbon monoxide pressure, reaction temperature is under 75 DEG C of reaction condition, and oxirane conversion ratio is 94%, and the selectivity of target product 3- hydroxy methyl propionate is 78%.
2007, CN101020635A (3- hydroxy propionate and 1, the preparation method of ammediol) disclose with cobalt salt as catalyst, pyridine, quinoline and its respective derivant are part, alkaline or alkaline-earth salts are accelerator, and pressure is 3.0MPa~7.0MPa, and reaction temperature is 50 DEG C~100 DEG C, reaction 3 hours~5 hours, the selectivity of target product 3- hydroxy methyl propionate is up to 90%.
2011, CN101973881A discloses with carbonyl cobalt functionalized ion liquid as catalyst, with nitrogen-containing heterocycle compound or organic phosphine as part, the pressure of carbon monoxide is 3.0MPa~7.0MPa, reaction temperature is 50 DEG C~100 DEG C, response time is 6 hours~18 hours, and, up to 98.1%, the yield of target product 3- hydroxy methyl propionate is up to 90.8% for the conversion ratio of oxirane.
But prior art reaction temperature is of a relatively high, energy consumption is big, and the selectivity of 3- hydroxy propionate is still relatively low.
Content of the invention
The technical problem to be solved is the low problem of selectivity of 3- hydroxy propionate in prior art, provides a kind of synthetic method of new 3- hydroxy propionate, the method has the advantages that 3- hydroxy propionate selectivity is high.
For solving above-mentioned technical problem, technical scheme is as follows:The synthetic method of 3- hydroxy propionate, comprises the steps:
I, the part shown in formula (I) and carbonyl cobalt is made to carry out complexation reaction in a solvent and obtain catalyst solution, described solvent is the solvent of alcohol or containing alcohol;
Wherein R1~R3It is independently selected from one of alkyl or alkenyl, aryl or substituted aryl, Azacyclyl, and R1~R3Middle independently contain 1~6 carbon atom;
Ii, in above-mentioned catalyst solution, add oxirane and carbon monoxide, reaction obtains described 3- hydroxy propionate.
In technique scheme, described alcohol is preferably the straight or branched alcohol of C1~C5, such as but not limited to methanol, ethanol.
In technique scheme, R1~R3Independently it preferably is selected from methyl, isopropyl, the tert-butyl group, pi-allyl, phenyl, 2,4,6- trimethylphenyl, 2,6- diisopropyl phenyl, benzyl, 2- pyrimidine radicals, 2- pyridine radicals or 2- picolyl.
In technique scheme, described part is preferably (1~5) with carbonyl cobalt molar ratio:1.
In technique scheme, the solvent of described containing alcohol is optional to include alcohol and at least one in methyl tertiary butyl ether(MTBE), oxolane, Isosorbide-5-Nitrae-dioxane, DOX, toluene and chlorobenzene.
In technique scheme, described methanol is preferably (2~25) with the mol ratio of oxirane:1.
In technique scheme, reaction pressure is preferably 3MPa~8MPa.
In technique scheme, reaction temperature is preferably 45 DEG C~100 DEG C;More preferably 50 DEG C~80 DEG C.
In technique scheme, the response time is preferably 3 hours~8 hours.
The present invention passes through to design multiple tooth cheland, many coordination sites and Co2(CO)8Collaborative coordination, improves the stability of catalyst further, passes through to change the auxiliary group of part, the space of regulation and control part and electronic property simultaneously, increases the activity of catalyst, improve the conversion ratio of oxirane and the selectivity of target product.
The present invention can specifically be carried out as follows:
The multiple tooth cheland of i and Co2(CO)8Complexation reaction in the solvent of containing alcohol, obtains the solution of catalyst, and this solution is transferred in reactor;
Ii nitrogen purging reactor three times, adds oxirane and CO to be reacted;
Iii reaction terminates, and kettle is cooled sufficiently to 0 DEG C, slow pressure release to normal pressure, with nitrogen purging reactor three times;
Iv sample analysis, the conversion ratio of oxirane, the yield of 3- hydroxy propionate use gas chromatogram quantitative.
Co2(CO)8There is toxicity and easy decomposition, the therefore preparation of catalyst are preferably carried out under the protection of the argon of glove box.
Improve the selectivity of 3- hydroxy propionate using the inventive method.Experiment shows, is 1 in carbonyl cobalt, part F (see embodiment 6), oxirane, Methanol Molar ratio:3:50:Under 740 ratio, reaction pressure is 4MPa, reacts 4 hours, the selectivity of 3- hydroxy propionate is up to 95%, achieves preferable technique effect, can be used in the commercial production of 3- hydroxy propionate at 50 DEG C.
Give further instruction below by example to the present invention, but do not limit present disclosure.
Specific embodiment
Embodiment 1
1st, synthetic ligands A
1312mg (10mmol) three propargyl amine, 2988mg (36mmol) pi-allyl nitrine, 250mg (1mmol) hydrated copper sulfate (CuSO is added in 100mL reaction tube4·5H2O), 200mg (1mmol) sodium ascorbate, the 40mL tert-butyl alcohol and 10mL water, system nitrogen displacement three times, under nitrogen atmosphere, 60 DEG C are reacted 24 hours.Reaction finishes, and adds 100mL water, and dichloromethane extraction solution repeatedly, merges organic faciess, concentrates after being dried, and finally obtains 1900mg light yellow solid using pillar layer separation and is part A.
2nd, 3- hydroxy methyl propionate synthesis
Co by 342mg (1.0mmol)2(CO)8It is dissolved in 740mmol methanol, adds the part A of 3.0mmol, stir 2 hours under room temperature.Catalyst solution is transferred in the reactor of 100mL, with nitrogen purging reactor three times, adds oxirane, the carbon monoxide of 50mmol, make system pressure be 4.0MPa, react 4 hours at 50 DEG C.Kettle is cooled sufficiently to 0 DEG C, slow pressure release to normal pressure, and with nitrogen purging reactor three times, sample analysis, result shows:The conversion ratio of oxirane is the selectivity of 75%, 3- hydroxy methyl propionate is 81%.
For ease of comparing, by 3- hydroxy methyl propionate synthetic reaction, the results are shown in Table 1.
Embodiment 2
1st, synthetic ligands B
According to the experimentation of embodiment 1, with 1312mg (10mmol) three propargyl amine, 3564mg (36mmol) pi-allyl nitrine, 375mg (1.5mmol) hydrated copper sulfate (CuSO4·5H2O), 300mg (1.5mmol) sodium ascorbate is raw material, and synthesis obtains 1712mg brown solid and is part B.
2nd, 3- hydroxy methyl propionate synthesis
Co by 342mg (1.0mmol)2(CO)8It is dissolved in 740mmol methanol, adds the part B of 3.0mmol, stir 2 hours under room temperature.Catalyst solution is transferred in the reactor of 100mL, with nitrogen purging reactor three times, adds oxirane, the carbon monoxide of 50mmol, make system pressure be 4.0MPa, react 4 hours at 50 DEG C.Kettle is cooled sufficiently to 0 DEG C, slow pressure release to normal pressure, and with nitrogen purging reactor three times, sample analysis, result shows:The conversion ratio of oxirane is the selectivity of 83%, 3- hydroxy methyl propionate is 90%.
For ease of comparing, by 3- hydroxy methyl propionate synthetic reaction, the results are shown in Table 1.
Embodiment 3
1st, synthetic ligands C
According to the experimentation of embodiment 1, with 1312mg (10mmol) three propargyl amine, 4284mg (36mmol) aziminobenzene, 250mg (1mmol) hydrated copper sulfate (CuSO4·5H2O), 200mg (1mmol) sodium ascorbate is raw material, and synthesis obtains 2196mg white solid and is part C.
2nd, 3- hydroxy methyl propionate synthesis
Co by 342mg (1.0mmol)2(CO)8It is dissolved in 740mmol methanol, adds the part C of 3.0mmol, stir 2 hours under room temperature.Catalyst solution is transferred in the reactor of 100mL, with nitrogen purging reactor three times, adds oxirane, the carbon monoxide of 50mmol, make system pressure be 4.0MPa, react 4 hours at 50 DEG C.Kettle is cooled sufficiently to 0 DEG C, slow pressure release to normal pressure, and with nitrogen purging reactor three times, sample analysis, result shows:The conversion ratio of oxirane is the selectivity of 88%, 3- hydroxy methyl propionate is 74%.
For ease of comparing, by 3- hydroxy methyl propionate synthetic reaction, the results are shown in Table 1.
Embodiment 4
1st, synthetic ligands D
According to the experimentation of embodiment 1, with 1312mg (10mmol) three propargyl amine, 5796mg (36mmol) sym-trimethylbenzene. base nitrine, 500mg (2mmol) hydrated copper sulfate (CuSO4·5H2O), 400mg (2mmol) sodium ascorbate is raw material, obtains 1842mg yellow solid and is part D.
2nd, 3- hydroxy methyl propionate synthesis
Co by 342mg (1.0mmol)2(CO)8It is dissolved in 740mmol methanol, adds the part D of 3.0mmol, stir 2 hours under room temperature.Catalyst solution is transferred in the reactor of 100mL, with nitrogen purging reactor three times, adds oxirane, the carbon monoxide of 50mmol, make system pressure be 4.0MPa, react 4 hours at 50 DEG C.Kettle is cooled sufficiently to 0 DEG C, slow pressure release to normal pressure, and with nitrogen purging reactor three times, sample analysis, result shows:The conversion ratio of oxirane is the selectivity of 77%, 3- hydroxy methyl propionate is 91%.
For ease of comparing, by 3- hydroxy methyl propionate synthetic reaction, the results are shown in Table 1.
Embodiment 5
1st, synthetic ligands E
According to the experimentation of embodiment 1, with 1312mg (10mmol) three propargyl amine, 4788mg (36mmol) benzyl azide, 250mg (1mmol) hydrated copper sulfate (CuSO4·5H2O), 200mg (1mmol) sodium ascorbate is raw material, and synthesis obtains 2915mg light yellow solid and is part E.
2nd, 3- hydroxy methyl propionate synthesis
Co by 342mg (1.0mmol)2(CO)8It is dissolved in 740mmol methanol, adds the part E of 3.0mmol, stir 2 hours under room temperature.Catalyst solution is transferred in the reactor of 100mL, with nitrogen purging reactor three times, adds oxirane, the carbon monoxide of 50mmol, make system pressure be 4.0MPa, react 4 hours at 50 DEG C.Kettle is cooled sufficiently to 0 DEG C, slow pressure release to normal pressure, and with nitrogen purging reactor three times, sample analysis, result shows:The conversion ratio of oxirane is the selectivity of 84%, 3- hydroxy methyl propionate is 82%.
For ease of comparing, by 3- hydroxy methyl propionate synthetic reaction, the results are shown in Table 1.
Embodiment 6
1st, synthetic ligands F
According to the experimentation of embodiment 1, with 1312mg (10mmol) three propargyl amine, 4356mg (36mmol) pyrimidine radicals nitrine, 250mg (1mmol) hydrated copper sulfate (CuSO4·5H2O), 200mg (1mmol) sodium ascorbate is raw material, and synthesis obtains 2616mg brown solid and is part F.
2nd, 3- hydroxy methyl propionate synthesis
Co by 342mg (1.0mmol)2(CO)8It is dissolved in 740mmol methanol, adds the part F of 3.0mmol, stir 2 hours under room temperature.Catalyst solution is transferred in the reactor of 100mL, with nitrogen purging reactor three times, adds oxirane, the carbon monoxide of 50mmol, make system pressure be 4.0MPa, react 4 hours at 50 DEG C.Kettle is cooled sufficiently to 0 DEG C, slow pressure release to normal pressure, and with nitrogen purging reactor three times, sample analysis, result shows:The conversion ratio of oxirane is the selectivity of 92%, 3- hydroxy methyl propionate is 95%.
For ease of comparing, by 3- hydroxy methyl propionate synthetic reaction, the results are shown in Table 1.
Embodiment 7
1st, synthetic ligands G
According to the experimentation of embodiment 1, with 1312mg (10mmol) three propargyl amine, 4824mg (36mmol) picolyl nitrine, 250mg (1mmol) hydrated copper sulfate (CuSO4·5H2O), 200mg (1mmol) sodium ascorbate is raw material, and synthesis obtains 2140mg yellow solid and is part G.
2nd, 3- hydroxy methyl propionate synthesis
Co by 342mg (1.0mmol)2(CO)8It is dissolved in 740mmol methanol, adds the part G of 3.0mmol, stir 2 hours under room temperature.Catalyst solution is transferred in the reactor of 100mL, with nitrogen purging reactor three times, adds oxirane, the carbon monoxide of 50mmol, make system pressure be 4.0MPa, react 4 hours at 50 DEG C.Kettle is cooled sufficiently to 0 DEG C, slow pressure release to normal pressure, and with nitrogen purging reactor three times, sample analysis, result shows:The conversion ratio of oxirane is the selectivity of 89%, 3- hydroxy methyl propionate is 92%.
For ease of comparing, by 3- hydroxy methyl propionate synthetic reaction, the results are shown in Table 1.
【Comparative example 1】
In addition to replacing part A using pyridine, 3- hydroxy methyl propionate synthesis condition is same as Example 1, specially:
Co by 342mg (1.0mmol)2(CO)8It is dissolved in 740mmol methanol, adds the pyridine of 3.0mmol, stir 2 hours under room temperature.Catalyst solution is transferred in the reactor of 100mL, with nitrogen purging reactor three times, adds oxirane, the carbon monoxide of 50mmol, make system pressure be 4.0MPa, react 4 hours at 50 DEG C.Kettle is cooled sufficiently to 0 DEG C, slow pressure release to normal pressure, and with nitrogen purging reactor three times, sample analysis, result shows:The conversion ratio of oxirane is the selectivity of 81%, 3- hydroxy methyl propionate is 76%.
For ease of comparing, by 3- hydroxy methyl propionate synthetic reaction, the results are shown in Table 1.
【Comparative example 2】
Except adopting 2,2 '-bipyridyl replaces beyond part A, and 3- hydroxy methyl propionate synthesis condition is same as Example 1, specially:
Co by 342mg (1.0mmol)2(CO)8It is dissolved in 740mmol methanol, the 2 of addition 3.0mmol, 2 '-bipyridyl, stir 2 hours under room temperature.Catalyst solution is transferred in the reactor of 100mL, with nitrogen purging reactor three times, adds oxirane, the carbon monoxide of 50mmol, make system pressure be 4.0MPa, react 4 hours at 50 DEG C.Kettle is cooled sufficiently to 0 DEG C, slow pressure release to normal pressure, and with nitrogen purging reactor three times, sample analysis, result shows:The conversion ratio of oxirane is the selectivity of 53%, 3- hydroxy methyl propionate is 68%.
For ease of comparing, by 3- hydroxy methyl propionate synthetic reaction, the results are shown in Table 1.
【Comparative example 3】
Beyond adopting 1,10- adjacent phenanthrene quinoline to replace part A, 3- hydroxy methyl propionate synthesis condition is same as Example 1, specially:
Co by 342mg (1.0mmol)2(CO)8It is dissolved in 740mmol methanol, add 1, the 10- adjacent phenanthrene quinoline of 3.0mmol, stir 2 hours under room temperature.Catalyst solution is transferred in the reactor of 100mL, with nitrogen purging reactor three times, adds oxirane, the carbon monoxide of 50mmol, make system pressure be 4.0MPa, react 4 hours at 50 DEG C.Kettle is cooled sufficiently to 0 DEG C, slow pressure release to normal pressure, and with nitrogen purging reactor three times, sample analysis, result shows:The conversion ratio of oxirane is the selectivity of 62%, 3- hydroxy methyl propionate is 75%.
For ease of comparing, by 3- hydroxy methyl propionate synthetic reaction, the results are shown in Table 1.
【Comparative example 4】
In addition to replacing part A using N- Methylimidazole., 3- hydroxy methyl propionate synthesis condition is same as Example 1, specially:
Co by 342mg (1.0mmol)2(CO)8It is dissolved in 740mmol methanol, adds the N- Methylimidazole. of 3.0mmol, stir 2 hours under room temperature.Catalyst solution is transferred in the reactor of 100mL, with nitrogen purging reactor three times, adds oxirane, the carbon monoxide of 50mmol, make system pressure be 4.0MPa, react 4 hours at 50 DEG C.Kettle is cooled sufficiently to 0 DEG C, slow pressure release to normal pressure, and with nitrogen purging reactor three times, sample analysis, result shows:The conversion ratio of oxirane is the selectivity of 74%, 3- hydroxy methyl propionate is 80%.
For ease of comparing, by 3- hydroxy methyl propionate synthetic reaction, the results are shown in Table 1.
Data from table understands, the part commonly used with respect to prior art, and the multiple tooth cheland of our designs can significantly increase the activity of catalyst, and the selectivity of reaction is it is expected to be used in the commercial production of 3- hydroxy propionate.Table 1
Claims (9)
1. a kind of synthetic method of 3- hydroxy propionate, comprises the steps:
I, the part shown in formula (I) and carbonyl cobalt is made to carry out complexation reaction in a solvent and obtain catalyst solution, described
Solvent is the solvent of alcohol or containing alcohol;
Wherein R1~R3It is independently selected from one of alkyl or alkenyl, aryl or substituted aryl, Azacyclyl, and R1~R3
Middle independently contain 1~6 carbon atom;
Ii, in above-mentioned catalyst solution, add oxirane and carbon monoxide, reaction obtains described 3- hydracrylic acid
Ester.
2. synthetic method according to claim 1 is it is characterised in that alcohol is the straight or branched alcohol of C1~C5.
3. synthetic method according to claim 1 is it is characterised in that R1~R3Be independently selected from methyl, isopropyl,
The tert-butyl group, pi-allyl, phenyl, 2,4,6- trimethylphenyl, 2,6- diisopropyl phenyl, benzyl, 2- pyrimidine radicals,
2- pyridine radicals or 2- picolyl.
4. synthetic method according to claim 1 is it is characterised in that described part with carbonyl cobalt mol ratio is
(1~5):1.
5. synthetic method according to claim 1 is it is characterised in that the solvent of described containing alcohol includes alcohol and is selected from first
At least one in base tertbutyl ether, oxolane, 1,4- dioxane, 1,3- dioxolanes, toluene and chlorobenzene.
6. synthetic method according to claim 1 is it is characterised in that the mol ratio of described alcohol and oxirane
For (2~25):1.
7. synthetic method according to claim 1 is it is characterised in that reaction pressure is 3MPa~8MPa.
8. synthetic method according to claim 1 is it is characterised in that reaction temperature is 45 DEG C~100 DEG C.
9. synthetic method according to claim 1 is it is characterised in that the response time is 3 hours~8 hours.
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CN109678710A (en) * | 2017-10-19 | 2019-04-26 | 中国石油化工股份有限公司 | The synthetic method of 3- hydroxy methyl propionate |
CN114425451A (en) * | 2020-10-14 | 2022-05-03 | 中国石油化工股份有限公司 | Catalyst for synthesizing 3-hydroxy propionate and preparation and use methods thereof |
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Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
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CN109678710A (en) * | 2017-10-19 | 2019-04-26 | 中国石油化工股份有限公司 | The synthetic method of 3- hydroxy methyl propionate |
CN109678710B (en) * | 2017-10-19 | 2022-02-01 | 中国石油化工股份有限公司 | Synthesis method of methyl 3-hydroxypropionate |
CN114425451A (en) * | 2020-10-14 | 2022-05-03 | 中国石油化工股份有限公司 | Catalyst for synthesizing 3-hydroxy propionate and preparation and use methods thereof |
CN114425451B (en) * | 2020-10-14 | 2024-01-30 | 中国石油化工股份有限公司 | Catalyst for synthesizing 3-hydroxy propionate and preparation and use methods thereof |
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