CN115160119A - Method for preparing 4-methoxy-3-butene-2-ketone - Google Patents
Method for preparing 4-methoxy-3-butene-2-ketone Download PDFInfo
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- CN115160119A CN115160119A CN202210912703.6A CN202210912703A CN115160119A CN 115160119 A CN115160119 A CN 115160119A CN 202210912703 A CN202210912703 A CN 202210912703A CN 115160119 A CN115160119 A CN 115160119A
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- methyl formate
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- 238000000034 method Methods 0.000 title claims abstract description 27
- TZIHFWKZFHZASV-UHFFFAOYSA-N methyl formate Chemical compound COC=O TZIHFWKZFHZASV-UHFFFAOYSA-N 0.000 claims abstract description 52
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims abstract description 50
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 claims abstract description 34
- 238000006243 chemical reaction Methods 0.000 claims abstract description 16
- 239000003054 catalyst Substances 0.000 claims abstract description 10
- 239000002994 raw material Substances 0.000 claims abstract description 8
- 238000001816 cooling Methods 0.000 claims description 35
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 30
- 238000010438 heat treatment Methods 0.000 claims description 25
- 238000003756 stirring Methods 0.000 claims description 21
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 15
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 14
- 239000000243 solution Substances 0.000 claims description 14
- 239000002904 solvent Substances 0.000 claims description 14
- 239000007864 aqueous solution Substances 0.000 claims description 9
- 239000011541 reaction mixture Substances 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 6
- 239000011259 mixed solution Substances 0.000 claims description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 3
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 3
- DKAGJZJALZXOOV-UHFFFAOYSA-N hydrate;hydrochloride Chemical compound O.Cl DKAGJZJALZXOOV-UHFFFAOYSA-N 0.000 claims description 3
- FWFGVMYFCODZRD-UHFFFAOYSA-N oxidanium;hydrogen sulfate Chemical compound O.OS(O)(=O)=O FWFGVMYFCODZRD-UHFFFAOYSA-N 0.000 claims description 3
- 239000011260 aqueous acid Substances 0.000 claims 1
- VLLHEPHWWIDUSS-UHFFFAOYSA-N 4-methoxybut-3-en-2-one Chemical compound COC=CC(C)=O VLLHEPHWWIDUSS-UHFFFAOYSA-N 0.000 abstract description 4
- -1 acetyl methoxy ethanol sodium salt Chemical compound 0.000 abstract description 3
- 238000006482 condensation reaction Methods 0.000 abstract description 3
- 230000002378 acidificating effect Effects 0.000 abstract description 2
- 238000009833 condensation Methods 0.000 abstract description 2
- 230000005494 condensation Effects 0.000 abstract description 2
- 238000003541 multi-stage reaction Methods 0.000 abstract description 2
- 230000020477 pH reduction Effects 0.000 abstract description 2
- 238000004321 preservation Methods 0.000 abstract description 2
- 238000011031 large-scale manufacturing process Methods 0.000 abstract 1
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 27
- 239000000203 mixture Substances 0.000 description 12
- 239000000047 product Substances 0.000 description 12
- 238000001035 drying Methods 0.000 description 9
- 239000012044 organic layer Substances 0.000 description 9
- 238000002156 mixing Methods 0.000 description 8
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 150000002576 ketones Chemical class 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- PJCCSZUMZMCWSX-UHFFFAOYSA-N 4,4-Dimethoxy-2-butanone Chemical compound COC(OC)CC(C)=O PJCCSZUMZMCWSX-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- 238000007115 1,4-cycloaddition reaction Methods 0.000 description 1
- 238000006845 Michael addition reaction Methods 0.000 description 1
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 1
- 238000005882 aldol condensation reaction Methods 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Chemical group 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 208000012839 conversion disease Diseases 0.000 description 1
- 238000006352 cycloaddition reaction Methods 0.000 description 1
- 150000001993 dienes Chemical class 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000010606 normalization Methods 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000001632 sodium acetate Substances 0.000 description 1
- 235000017281 sodium acetate Nutrition 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
- C07C45/65—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by splitting-off hydrogen atoms or functional groups; by hydrogenolysis of functional groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
- C07C45/67—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton
- C07C45/68—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms
- C07C45/72—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms by reaction of compounds containing >C = O groups with the same or other compounds containing >C = O groups
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a method for preparing 4-methoxy-3-butene-2-ketone. The method comprises the steps of taking acetone and methyl formate as raw materials, taking sodium methoxide as a catalyst, preparing acetyl methoxy ethanol sodium salt through condensation reaction, and then carrying out heat preservation reaction under an acidic condition to obtain 4-methoxy-3-butene-2-one. The method has the advantages that the condensation, acidification and other multistep reaction processes are carried out in one reaction kettle, the operation is convenient, the raw materials are low in price and easy to obtain, the quality is controllable, the yield is high, the problem of low product purity in the market is solved, and the method is suitable for large-scale production.
Description
Technical Field
The invention relates to a preparation method of 4-methoxy-3-butene-2-ketone.
Background
4-methoxy-3-butene-2-ketone is an important organic synthesis intermediate and is widely applied to the synthesis of medicines and fine chemical products. The alpha, beta-unsaturated ketone is an alpha, beta-unsaturated ketone, carbon-carbon double bonds are conjugated with carbonyl, and the alpha, beta-unsaturated ketone has the properties of ketone, olefin and conjugated diene and has good reaction activity. It can produce important organic synthesis reactions such as aldol condensation, michael addition, [4+1] cycloaddition and [4+ 2] cycloaddition.
The literature reports less synthetic methods. The synthesis route is reported in 1978 by Helvetica Chimica Acta volume 61, 1609-1621, no. 26, no. 4197-4200 of 1993 Tetrahedron letters volume 34, 4,4-dimethoxy-2-butanone is used as a raw material, sodium acetate is added, one molecule of methanol is removed to generate a product, the method needs high temperature, the boiling point of the raw material is close to that of the product, the purification is difficult, and the purity of the obtained product is not high (less than 90%); 2. in 1981, polish Journal of Chemistry volume 55, no. 1, no. 79-88, reported that by using acetoacetal and methanol as raw materials and through condensation reaction, the by-product 4,4-dimethoxy-2-butanone is difficult to separate and the yield is not high (less than 50%).
Disclosure of Invention
The invention provides a method suitable for industrially preparing 4-methoxy-3-butene-2-one, which aims to solve the problems of high temperature, high requirement on production equipment, low product purity (less than 90%), low yield and the like of the existing method for preparing 4-methoxy-3-butene-2-one, reduce the production cost of the product and improve the market competitiveness of the product.
The preparation method of the 4-methoxy-3-butene-2-ketone takes acetone and methyl formate as raw materials, sodium methoxide as a catalyst, acetyl methoxy ethanol sodium salt is prepared through condensation reaction, and then the acetyl methoxy ethanol sodium salt is obtained through heat preservation reaction under the acidic condition.
The technical scheme of the invention is as follows:
the method comprises the following specific steps: .
(A) And (3) adding a catalyst and a solvent into the reaction kettle, and stirring. Cooling, and dropwise adding a mixed solution of acetone and methyl formate. After the dripping is finished, heating to a certain temperature and stirring for reaction for a period of time.
(B) Cooling, adjusting the pH value with acid water solution, heating to a certain temperature, stirring and reacting for a period of time.
(C) Cooling, extracting with dichloromethane, mixing organic layers, drying, concentrating, distilling under reduced pressure, and collecting the distillate.
The catalyst is one or more of sodium hydroxide and sodium methoxide, and sodium methoxide is preferred.
The solvent is one or more of tetrahydrofuran, acetone or anhydrous ether, and is preferably tetrahydrofuran.
The molar ratio of the catalyst to the methyl formate is 0.8 to 1.1, preferably 0.9.
The molar ratio of the acetone to the methyl formate is 1 to 1, preferably 1.5.
And B, heating to a certain temperature of 10-40 ℃, preferably 30 ℃.
And B, stirring and reacting for 6 to 16 hours, preferably 12 to 14 hours.
The acid water solution is one or more of hydrochloric acid water solution, sulfuric acid water solution or phosphoric acid water solution, and hydrochloric acid water solution is preferred.
And the step B is used for adjusting the pH to be 3~4. The reaction conversion rate is low when the pH is too high, and impurities are easily generated by polymerization when the pH is too low.
And B, heating to a certain temperature of 30-60 ℃, preferably 40 ℃.
And B, stirring and reacting for 1 to 10 hours, preferably 6 hours.
The invention has the advantages that: the condensation, acidification and other multistep reaction processes are carried out in a reaction kettle, the method has the advantages of convenient operation, low price and easy obtainment of raw materials, controllable quality and higher yield, and the product purity of more than 99 percent meets the requirements of the pharmaceutical industry, thereby being an ideal method for industrially producing the 4-methoxy-3-butene-2-one.
The specific implementation mode is as follows:
the following examples are intended to further illustrate the invention but not to limit the invention to these specific embodiments.
Example 1:
in a four-necked flask, sodium methoxide 24.3 g (0.45 mol) and tetrahydrofuran 125 mL were added and stirred. After cooling, a mixture of acetone 43.6 g (0.75 mol) and methyl formate 30.0 g (0.50 mol) was added dropwise. After dropping, the reaction mixture was stirred at 12h by heating to 30 ℃. Cooling, adjusting the pH to 3~4 by 10% hydrochloric acid aqueous solution, heating to 30 ℃, and stirring to react 6 h. And (6) cooling. Extracting with dichloromethane 300 mL by 3, mixing organic layers, drying, concentrating to recover solvent, distilling under reduced pressure (10 mmHg) to collect 58-59 deg.C fraction, weighing 42.9 g, yield 85.7% (based on methyl formate, the same below), and purity 99.1% (GC area normalization, the same below).
Example 2:
in a four-necked flask, sodium methoxide 27.0 g (0.5 mol), acetone 43.6 g (0.75 mol) and tetrahydrofuran 125 mL were added and stirred. After cooling, methyl formate 30.0 g (0.50 mol) was added dropwise. The other conditions were the same as in example 1, and the product 21.5 g was obtained in 42.9% yield and 96.4% purity.
Example 3:
in a four-necked flask, sodium methoxide 27.0 g (0.5 mol) and acetone 300 mL were added and stirred. After cooling, methyl formate 30.0 g (0.50 mol) was added dropwise, and the reaction mixture was stirred at 20 ℃ for 10h. The other conditions were the same as in example 1 to obtain 27.3 g with 54.5% yield and 97.4% purity.
Example 4:
in a four-necked flask, sodium methoxide 27.0 g (0.5 mol) and tetrahydrofuran 125 mL were added and stirred. After cooling, a mixed solution of acetone 75.1 g (1.5 mol) and methyl formate 30.0 g (0.50 mol) was added dropwise, and after the addition, 6 h was reacted with stirring by heating to 30 ℃. The other conditions were the same as in example 1 to obtain 37.9 g with a yield of 75.7% and a purity of 98.6%.
Example 5:
the anhydrous ether was used in place of tetrahydrofuran, and the other conditions were the same as in example 4, whereby 35.2 g was obtained in 70.3% yield and 98.1% purity.
Example 6:
in a four-necked flask, sodium methoxide 24.3 g (0.45 mol) and tetrahydrofuran 125 mL were added and stirred. After cooling, a mixture of acetone 75.1 g (1.5 mol) and methyl formate 30.0 g (0.50 mol) was added dropwise. After dropping, the reaction was stirred for 10h by heating to 20 ℃. Cooling, adjusting the pH to 3~4 by 10% hydrochloric acid aqueous solution, heating to 30 ℃, and stirring to react 6 h. And (6) cooling. Extracting with dichloromethane 300 mL by 3, combining organic layers, drying, concentrating and recovering the solvent, distilling under reduced pressure (10 mmHg) to collect the distillate at 58-59 ℃ to obtain the product, weighing 38.9 g, the yield is 77.8 percent, and the purity is 98.9 percent.
Example 7:
sodium methoxide 21.6 g (0.4 mol), other conditions were the same as in example 6, yielding 36.1g, with a yield of 72.1% and a purity of 98.9%.
Example 8:
acetone 100.2 g (2.0 mol), the other conditions are the same as in example 6, and the product 38.0 g is obtained with a yield of 76.0% and a purity of 98.7%.
Example 9:
acetone 50.1 g (1.0 mol), other conditions were the same as in example 6 to give product 40.9 g, yield 81.7%, purity 99.1%.
Example 10:
a mixture of acetone 25.0 g (0.5 mol) and methyl formate 30.0 g (0.50 mol) was added dropwise. After dropping, the mixture is stirred and reacted for 10 hours at 10 ℃. The other conditions were the same as in example 6, and 36.1g was obtained in 72.1% yield and 98.2% purity.
Example 11:
a mixture of acetone 100.2 g (2.0 mol) and methyl formate 30.0 g (0.50 mol) was added dropwise. After the dripping is finished, the mixture is stirred and reacted for 12 hours at the temperature of 30 ℃. The other conditions were the same as in example 6, and 41.7 g was obtained, with a yield of 72.1% and a purity of 99.3%.
Example 12:
in a four-necked flask, sodium methoxide 21.6 g (0.4 mol) and tetrahydrofuran 125 mL were added and stirred. After cooling, a mixture of acetone 43.6 g (0.75 mol) and methyl formate 30.0 g (0.50 mol) was added dropwise. After dropping, the reaction was stirred for 10h by heating to 20 ℃. Cooling, adjusting the pH to 3~4 by 10% hydrochloric acid aqueous solution, heating to 40 ℃, and stirring to react 4 h. And (6) cooling. Extracting with dichloromethane 300 mL by 3, mixing organic layers, drying, concentrating to recover solvent, and distilling under reduced pressure (10 mmHg) to collect 58-59 deg.C fraction, i.e. 41.2g, yield 82.4%, purity 99.2%.
Example 13:
in a four-necked flask, sodium methoxide 24.3 g (0.45 mol) and tetrahydrofuran 125 mL were added and stirred. After cooling, a mixture of acetone 43.6 g (0.75 mol) and methyl formate 30.0 g (0.50 mol) was added dropwise. After dropping, the reaction mixture 14 h was stirred with heating to 30 ℃. Cooling, adjusting pH to 3~4 with 10% hydrochloric acid aqueous solution, heating to 40 deg.C, and stirring to react 6 h. And (6) cooling. Extracting with dichloromethane 300 mL by 3, mixing organic layers, drying, concentrating to recover solvent, and distilling under reduced pressure (10 mmHg) to collect 58-59 deg.C fraction (43.8 g), with yield of 87.5% and purity of 99.5%.
Example 14:
in a four-necked flask, sodium methoxide 24.3 g (0.45 mol) and tetrahydrofuran 125 mL were added and stirred. After cooling, a mixture of acetone 50.1 g (1 mol) and methyl formate 30.0 g (0.50 mol) was added dropwise. After dropping, the reaction was stirred for 10h by heating to 40 ℃. Cooling, adjusting the pH to 3~4 by 10% hydrochloric acid aqueous solution, heating to 50 ℃, and stirring to react 1 h. And (6) cooling. Extracting with dichloromethane 300 mL by 3, mixing organic layers, drying, concentrating to recover solvent, and distilling under reduced pressure (10 mmHg) to collect 58-59 deg.C fraction, i.e. 42.1g, yield 84.1%, purity 99.2%.
Example 15:
in a four-necked flask, sodium methoxide 24.3 g (0.45 mol) and tetrahydrofuran 125 mL were added and stirred. After cooling, a mixture of acetone 62.6 g (1.25 mol) and methyl formate 30.0 g (0.50 mol) was added dropwise. After dropping, the reaction mixture was stirred at 12h by heating to 20 ℃. Cooling, adjusting the pH to 3~4 by 10% hydrochloric acid aqueous solution, heating to 40 ℃, and stirring to react 10h. And (6) cooling. Extracting with dichloromethane 300 mL by 3, mixing organic layers, drying, concentrating to recover solvent, and distilling under reduced pressure (10 mmHg) to collect 58-59 deg.C fraction, i.e. 42.8g, yield 85.5%, purity 99.3%.
Example 16:
in a four-necked flask, sodium methoxide 27.0 g (0.5 mol) and tetrahydrofuran 125 mL were added and stirred. After cooling, a mixture of acetone 43.6 g (0.75 mol) and methyl formate 30.0 g (0.50 mol) was added dropwise. After dropping, the reaction mixture was stirred at 40 ℃ for 12h. Cooling, adjusting the pH value to 1~2 by 10% sulfuric acid water solution, heating to 30 ℃, and stirring for reaction 4 h. And (6) cooling. Extracting with dichloromethane 300 mL by 3, mixing organic layers, drying, concentrating to recover solvent, and distilling under reduced pressure (10 mmHg) to collect 58-59 deg.C fraction (36.1 g), with yield of 72.1% and purity of 99.2%.
Example 17:
in a four-necked flask, sodium methoxide 29.7 g (0.55 mol) and tetrahydrofuran 125 mL were added and stirred. After cooling, a mixture of acetone 43.6 g (0.75 mol) and methyl formate 30.0 g (0.50 mol) was added dropwise. After dropping, the reaction mixture was stirred at 16 h by heating to 40 ℃. Cooling, adjusting the pH value to 5~6 by 10% phosphoric acid water solution, heating to 60 ℃, and stirring to react for 1 h. And (6) cooling. Extracting with dichloromethane 300 mL by 3, mixing organic layers, drying, concentrating to recover solvent, and distilling under reduced pressure (10 mmHg) to collect 58-59 deg.C fraction, which is 37.8g, yield 75.5%, and purity 99.1%.
Claims (10)
1. A method for preparing 4-methoxy-3-butene-2-ketone takes acetone and methyl formate as raw materials, and the reaction formula is as follows:
the steps of the method comprise that,
(A) Adding a catalyst and a solvent into a reaction kettle, and stirring; cooling, and dropwise adding a mixed solution of acetone and methyl formate; after dripping, heating to a certain temperature, stirring and reacting for a period of time;
(B) Cooling, adjusting the pH value with an acid aqueous solution, heating to a certain temperature, stirring and reacting for a period of time;
(C) Cooling, extracting, concentrating, distilling under reduced pressure and collecting fractions, namely the product;
the catalyst is sodium methoxide;
the solvent is one or more of tetrahydrofuran or anhydrous ether.
2. The method of claim 1, wherein: the method comprises the specific steps of carrying out the following steps,
(A) Adding a catalyst and a solvent into a reaction kettle, and stirring; cooling, and dropwise adding a mixed solution of acetone and methyl formate; after the dripping is finished, heating to 10-40 ℃, and stirring for reaction for 6-16 hours;
(B) Cooling, adjusting the pH value with an acid water solution, heating to 30-60 ℃, stirring and reacting for 1-10 hours.
3. The method of claim 2, wherein: the molar ratio of the catalyst to the methyl formate is 0.8 to 1.1; the molar ratio of the acetone to the methyl formate is 1 to 1.
4. The method according to any one of claims 1-3, wherein: the solvent is tetrahydrofuran.
5. The method of claim 4, wherein: the acid water solution is one or more of hydrochloric acid water solution, sulfuric acid water solution or phosphoric acid water solution.
6. The method of claim 5, wherein: the molar ratio of the catalyst to methyl formate is 0.9; the molar ratio of acetone to methyl formate is 1.
7. The method of claim 5, wherein: the method comprises the specific steps of carrying out the following steps,
(A) After the dripping is finished, heating to 30 ℃, and stirring for reaction for 12-14 hours;
(B) The pH of the aqueous acid solution was adjusted, and the reaction mixture was heated to 40 ℃ and stirred for 6 hours.
8. The method of any one of claims 1-3, 5-7, wherein: the acid aqueous solution is hydrochloric acid aqueous solution.
9. The method of any one of claims 1-3, 5-7, wherein: the pH was 3~4.
10. The method of any one of claims 1-3, 5-7, wherein: and distilling under reduced pressure (10 mmHg) to collect distillate at 58-59 ℃ to obtain the product.
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Application publication date: 20221011 |