CN117658812A - Preparation method of malonate - Google Patents
Preparation method of malonate Download PDFInfo
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- CN117658812A CN117658812A CN202211032833.7A CN202211032833A CN117658812A CN 117658812 A CN117658812 A CN 117658812A CN 202211032833 A CN202211032833 A CN 202211032833A CN 117658812 A CN117658812 A CN 117658812A
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- malonate
- chloroacetate
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- 238000002360 preparation method Methods 0.000 title claims abstract description 30
- OFOBLEOULBTSOW-UHFFFAOYSA-L Malonate Chemical compound [O-]C(=O)CC([O-])=O OFOBLEOULBTSOW-UHFFFAOYSA-L 0.000 title claims abstract description 29
- 238000006243 chemical reaction Methods 0.000 claims abstract description 53
- 239000003054 catalyst Substances 0.000 claims abstract description 40
- 239000002994 raw material Substances 0.000 claims abstract description 20
- 229940089960 chloroacetate Drugs 0.000 claims abstract description 17
- FOCAUTSVDIKZOP-UHFFFAOYSA-M chloroacetate Chemical compound [O-]C(=O)CCl FOCAUTSVDIKZOP-UHFFFAOYSA-M 0.000 claims abstract description 17
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 15
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 12
- 239000011574 phosphorus Substances 0.000 claims abstract description 12
- 239000002253 acid Substances 0.000 claims abstract description 9
- 238000000034 method Methods 0.000 claims description 22
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 16
- QABLOFMHHSOFRJ-UHFFFAOYSA-N methyl 2-chloroacetate Chemical compound COC(=O)CCl QABLOFMHHSOFRJ-UHFFFAOYSA-N 0.000 claims description 13
- YSHYEVBYOOFNLF-UHFFFAOYSA-N [Pt].C1(=CC=CC=C1)P(C1=CC=CC=C1)(C1=CC=CC=C1)C1=CC=CC=C1 Chemical compound [Pt].C1(=CC=CC=C1)P(C1=CC=CC=C1)(C1=CC=CC=C1)C1=CC=CC=C1 YSHYEVBYOOFNLF-UHFFFAOYSA-N 0.000 claims description 12
- UQPUONNXJVWHRM-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 UQPUONNXJVWHRM-UHFFFAOYSA-N 0.000 claims description 12
- 229910052763 palladium Inorganic materials 0.000 claims description 8
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 8
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 claims description 8
- 230000008569 process Effects 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 6
- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 6
- 239000003446 ligand Substances 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 6
- QOVUQHJLIWOBNB-UHFFFAOYSA-N C1=CC=CC=C1[P](C=1C=CC=CC=1)(C=1C=CC=CC=1)C1=CC=CC=C1 Chemical compound C1=CC=CC=C1[P](C=1C=CC=CC=1)(C=1C=CC=CC=1)C1=CC=CC=C1 QOVUQHJLIWOBNB-UHFFFAOYSA-N 0.000 claims description 4
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 4
- 239000002131 composite material Substances 0.000 claims description 4
- GPAYUJZHTULNBE-UHFFFAOYSA-N diphenylphosphine Chemical compound C=1C=CC=CC=1PC1=CC=CC=C1 GPAYUJZHTULNBE-UHFFFAOYSA-N 0.000 claims description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 4
- 229910052697 platinum Inorganic materials 0.000 claims description 4
- VEUUMBGHMNQHGO-UHFFFAOYSA-N ethyl chloroacetate Chemical compound CCOC(=O)CCl VEUUMBGHMNQHGO-UHFFFAOYSA-N 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- -1 tetraphenylphosphorus platinum Chemical compound 0.000 claims description 3
- 150000001298 alcohols Chemical class 0.000 claims description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 2
- 239000001569 carbon dioxide Substances 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims description 2
- 229910052751 metal Inorganic materials 0.000 claims description 2
- 239000002184 metal Substances 0.000 claims description 2
- RPGWZZNNEUHDAQ-UHFFFAOYSA-N phenylphosphine Chemical compound PC1=CC=CC=C1 RPGWZZNNEUHDAQ-UHFFFAOYSA-N 0.000 claims description 2
- QJZNRCWAXUGABH-UHFFFAOYSA-N propyl 2-chloroacetate Chemical compound CCCOC(=O)CCl QJZNRCWAXUGABH-UHFFFAOYSA-N 0.000 claims description 2
- 229910052703 rhodium Inorganic materials 0.000 claims description 2
- 239000010948 rhodium Substances 0.000 claims description 2
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims description 2
- 238000000926 separation method Methods 0.000 abstract description 7
- 238000000746 purification Methods 0.000 abstract description 5
- 230000000694 effects Effects 0.000 abstract description 3
- 230000007613 environmental effect Effects 0.000 abstract description 3
- 229910001385 heavy metal Inorganic materials 0.000 abstract description 3
- 238000004064 recycling Methods 0.000 abstract 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 24
- BEPAFCGSDWSTEL-UHFFFAOYSA-N dimethyl malonate Chemical compound COC(=O)CC(=O)OC BEPAFCGSDWSTEL-UHFFFAOYSA-N 0.000 description 21
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 15
- 239000000047 product Substances 0.000 description 14
- 230000003197 catalytic effect Effects 0.000 description 6
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 6
- 230000006315 carbonylation Effects 0.000 description 5
- 238000005810 carbonylation reaction Methods 0.000 description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 230000002194 synthesizing effect Effects 0.000 description 4
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 230000032050 esterification Effects 0.000 description 3
- 238000005886 esterification reaction Methods 0.000 description 3
- 230000006872 improvement Effects 0.000 description 3
- 150000002690 malonic acid derivatives Chemical class 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000012467 final product Substances 0.000 description 2
- 239000012046 mixed solvent Substances 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- 239000012074 organic phase Substances 0.000 description 2
- 231100000331 toxic Toxicity 0.000 description 2
- 230000002588 toxic effect Effects 0.000 description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- FOCAUTSVDIKZOP-UHFFFAOYSA-N chloroacetic acid Chemical compound OC(=O)CCl FOCAUTSVDIKZOP-UHFFFAOYSA-N 0.000 description 1
- 229940106681 chloroacetic acid Drugs 0.000 description 1
- 150000001868 cobalt Chemical class 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 239000002612 dispersion medium Substances 0.000 description 1
- 125000001183 hydrocarbyl group Chemical group 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 230000020477 pH reduction Effects 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
- C07C69/34—Esters of acyclic saturated polycarboxylic acids having an esterified carboxyl group bound to an acyclic carbon atom
- C07C69/38—Malonic acid esters
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention provides a preparation method of malonate, which mainly uses chloroacetate, alcohol and acid as raw materials, and uses a phosphorus ylide catalyst as the catalyst, wherein the phosphorus ylide catalyst has high activity, and the malonate with high yield can be prepared by adopting fewer catalysts, and meanwhile, the malonate has high purity. In addition, the preparation method has the advantages of lower reaction pressure and reaction temperature, safer reaction process, high conversion rate and selectivity, simple separation and purification of the catalyst, recycling, no discharge of heavy metals in the preparation process, and environmental protection.
Description
Technical Field
The invention belongs to the technical field of malonate preparation, and particularly relates to a method for synthesizing malonate by catalysis.
Background
1, 3-dicarbonyl compounds, particularly malonates, are important organic synthesis intermediates, are extremely important fine organic chemicals, and have wide application in the pharmaceutical, pesticide and dye industries. Therefore, the research of the synthetic route thereof, particularly the environment-friendly synthetic route, has great development prospects.
The main process in the prior art is a cyanidation esterification method, which is mainly used for synthesizing malonic acid diester by taking chloroacetic acid as a raw material through the steps of neutralization, cyanidation, acidification, dehydration, hydrolysis, esterification and the like, or the improvement on the process. However, these techniques are long in process, high in toxicity and high in strong acid. With the deepening of the awareness of green environmental protection at home and abroad, researchers have started the development work of green synthetic routes.
At present, the process route for synthesizing malonate by using the domestic carbonylation method is very rare, but the synthetic route using wittig as a catalytic principle is not reported yet. The reaction general formula of synthesizing malonate by using carbonylation catalytic system is as follows:
wherein r=c1 to C4 hydrocarbyl groups.
Synthesis of malonates Using a carbonyl catalytic System, R F Heek and D SBreslow published 1963 with the use of the catalyst NaCo (CO) 4 The experimental yield was only 20% as reported for the catalysis of methyl chloroacetate, carbon monoxide and methanol to dimethyl malonate.
In 2010, li Guangxing et al published that methyl chloroacetate, carbon monoxide and methanol are catalyzed to generate dimethyl malonate by using cobalt salt as a catalyst, the separation and purification process is complicated, and the resource consumption is large. Therefore, the improvement of the yield and the realization of the effective separation of the catalytic system are the important problems to be solved in the synthesis of malonate by carbonylation catalysis.
Disclosure of Invention
Based on the technical background, the inventor makes a keen approach, and found that: the preparation method has the advantages that chloroacetate and alcohol are used as raw materials, phosphorus ylide is used as a catalyst for preparing malonate, the catalyst has high reaction activity, the selectivity and conversion rate of the reaction can be effectively improved, meanwhile, the reaction temperature and the reaction pressure are low, the preparation process is mild and safe, no strong acid and toxic and harmful substances are generated, in addition, the separation and purification of the catalyst are simple, the catalyst can be recycled, the yield and purity of the prepared malonate are high, no heavy metal and toxic and harmful substances are discharged in the preparation process, the method is environment-friendly, and is suitable for large-scale industrial production, and the application prospect is good, so that the preparation method is completed.
The invention provides a preparation method of malonate, which takes chloroacetate and alcohol as raw materials and phosphorus ylide as a catalyst for preparation.
The preparation method provided by the invention has the following advantages:
(1) The preparation method has the advantages that the reaction pressure is low, and the safety of the reaction process is effectively improved;
(2) The reaction has higher conversion rate and selectivity, the raw material conversion rate is up to more than 94%, the selectivity of malonate can be up to more than 96%, and the purity of the malonate product is up to more than 97%;
(3) The catalyst can be effectively separated and recycled, and has the advantages of simple separation and purification process, short preparation flow, small resource consumption, no heavy metal emission in the preparation process, low toxicity, no generation of strong acid and environmental protection.
Drawings
FIG. 1 shows a gas chromatogram of dimethyl malonate produced in example 1;
FIG. 2 shows a gas chromatogram of dimethyl malonate produced in example 3.
Detailed Description
The features and advantages of the present invention will become more apparent and evident from the following detailed description of the invention.
The invention provides a preparation method of malonate, which takes chloroacetate and alcohol as raw materials and phosphorus ylide as a catalyst for preparation.
The chloroacetate is selected from one or more of methyl chloroacetate, ethyl chloroacetate and propyl chloroacetate, preferably one or two of methyl chloroacetate and ethyl chloroacetate, more preferably methyl chloroacetate.
Different malonates can be produced by selecting different chloroacetate as raw materials, such as dimethyl malonate by selecting methyl chloroacetate.
The phosphorus ylide catalyst is a coordination compound and comprises a central metal atom X and 1-4 ligands, wherein X is one or more of platinum, rhodium and palladium, and the ligands are one or more of phenylphosphine, diphenylphosphine and triphenylphosphine.
X is preferably one or two selected from platinum and palladium, and the ligand is one or more selected from diphenyl phosphine and triphenyl phosphine.
More preferably, the phosphorus ylide catalyst is one or more of tetraphenylphosphorus platinum, triphenylphosphine palladium, tetraphenylphosphorus palladium and tetraphenylphosphorus palladium.
The phosphorus ylide catalyst has high activity, and experiments show that the preparation of malonate by adopting the phosphorus ylide catalyst can improve the conversion rate and the reaction efficiency of raw materials, and simultaneously the reaction can be carried out under lower reaction pressure.
In the invention, the molar ratio of the catalyst to the chloroacetate is 1: (30 to 120), preferably the molar ratio is 1: (40 to 100), more preferably the molar ratio is 1: (45-85).
The addition amount of the catalyst is related to the yield and purity of the final product, and too little catalyst can reduce the yield and purity of the product, and too much catalyst can cause catalyst poisoning, which is also unfavorable for improving the yield and purity of the product.
In a preferred embodiment of the present invention, the catalyst is a composite catalyst of tetraphenylphosphine platinum and triphenylphosphine palladium.
Wherein, the mass ratio of the tetraphenylphosphine platinum to the triphenylphosphine palladium is (1-10): 1, preferably (1 to 8): 1, more preferably (1 to 6): 1.
experiments show that compared with a single-component catalyst, the composite catalyst can further improve the conversion rate of raw materials, improve the yield and purity of products, and meanwhile, the mass ratio of the two catalysts can also influence the yield and purity of the products.
The alcohol is selected from C 1 ～C 4 One or more of alcohols is preferably one or more selected from methanol, ethanol and propylene glycol, more preferably methanol.
The molar ratio of the alcohol to the chloroacetate is (0.5 to 10): 1, preferably (1 to 8): 1, more preferably (3 to 7): 1.
in the invention, the alcohol reacts with the chloroacetate to obtain a final product, the addition amount of the alcohol can influence the yield of the prepared product, the addition amount of the alcohol is too small or too large, the yield and purity of the product can be reduced, and the post-treatment process can be increased due to too large addition amount.
The preparation of malonate is carried out in a solvent selected from one or more of water and an acid selected from one or more of acetic acid, citric acid, oxalic acid, sulfuric acid, hydrochloric acid and nitric acid, preferably selected from one or more of water, citric acid, sulfuric acid, acetic acid and nitric acid, more preferably selected from a mixed solvent of water and acetic acid.
The carbonylation reagent obtained under anhydrous conditions is very active and unstable to water and air, and is therefore generally synthesized in the aqueous phase. In the reaction process, methanol can be catalyzed to add CO to generate acetic acid, and the solvent can inhibit the carbonylation phenomenon of the methanol to improve the conversion of the methanol in an esterification route.
The molar ratio of the acid to the chloroacetate is (0.1-2): 1, preferably the molar ratio is (0.2 to 1): 1, and preferably the molar ratio is (0.3 to 0.7): 1.
When the mixed solvent is selected, the mass ratio of water to acid is (2-5): 1, preferably the mass ratio is (3-4): 1.
The mass percentage of the chloroacetate in the solvent is 30-80%, preferably 35-70%. The mass percent of the raw materials in the solvent is too low, the reaction rate can be reduced, the mass percent of the raw materials in the solvent is too high, the raw materials are unevenly distributed, the reaction is not easy to carry out, and the product yield is improved.
The reaction temperature is 20 to 120 ℃, preferably 40 to 100 ℃, more preferably 50 to 70 ℃.
The reaction temperature is low, the catalyst shows excellent catalytic effect at the reaction temperature, the reaction is promoted, the reaction selectivity is high, and the reaction process is milder and safer.
The reaction time is 0.1 to 2 hours, preferably 0.2 to 1.5 hours, more preferably 0.4 to 1 hour. The reaction rate is high under the action of the catalyst, and the reaction can be completed in a short time.
In the preparation process, one or more of carbon monoxide, carbon dioxide and methane, preferably carbon monoxide, are also introduced into the reaction system. Carbon monoxide can be used as a dispersion medium to replace air in a system to ensure anaerobic environment conditions, can be used as a reaction raw material to realize carbonyl reaction more quickly under the condition of pressurization, and can not introduce other interference and impurities.
The reaction is preferably carried out in an autoclave, and after the introduction of the above-mentioned gas, the reaction pressure is 0.1 to 1.5MPa, preferably 0.2 to 1MPa, more preferably 0.3 to 0.7MPa.
Under the action of the catalyst, the reaction can be carried out under lower reaction pressure, the reaction is safe, and the yield and purity of the prepared product are higher.
After the reaction is completed, the product is kept stand for a period of time, wherein the standing time is 1-5 hours, preferably 2 hours. And (5) completely layering the reaction system.
The organic phase is separated by a siphon method and then is rectified and purified to obtain the product malonate. The catalyst has simple separation and purification process, and can be repeatedly recycled after separation.
The conversion rate of the raw material chloroacetate in the preparation method can reach more than 94%, the selectivity of malonate can reach more than 96%, and the purity of the prepared malonate is more than 97%.
In a second aspect, the invention provides a malonate prepared by the method for preparing a malonate according to the first aspect of the invention. The purity of the malonate is more than 97%.
Examples
The invention is further illustrated by the following specific examples, which are intended to be illustrative of the invention and are not intended to limit the scope of the invention.
Example 1
8g of water, 14.8g of methanol, 2.5g of acetic acid, 10g of methyl chloroacetate and 1.6g of tetraphenylphosphine platinum are added into a pressure kettle, the mixture is sequentially put into the pressure kettle, CO gas is introduced, the pressure is increased to 0.4MPa, the reaction temperature is 55 ℃, and the reaction time is 0.5 hour, so that the target product dimethyl malonate is produced. Standing the product for 2h, separating the organic phase by a siphon method, and then rectifying and purifying to obtain the product dimethyl malonate, wherein the catalyst separated by the catalytic system can be recycled.
The conversion rate of the raw material methyl chloroacetate reaches 95.7%, the selectivity of the dimethyl malonate reaches 96.5%, and the purity of the dimethyl malonate is 97.9%.
Example 2
The preparation of dimethyl malonate was carried out in a similar manner to example 1, except that: the addition amount of the tetraphenylphosphine platinum was 1.4g.
The conversion rate of the raw material methyl chloroacetate is 94.9%, the selectivity of the dimethyl malonate reaches 96.3%, and the purity of the dimethyl malonate is 97.1%.
Example 3
The preparation of dimethyl malonate was carried out in a similar manner to example 1, except that: the addition amount of the tetraphenylphosphine platinum and the triphenylphosphine palladium is 1.6g, wherein the mass ratio of the tetraphenylphosphine platinum to the triphenylphosphine palladium is 2.5:1.
The conversion rate of the raw material methyl chloroacetate is 96.9%, the selectivity of the dimethyl malonate reaches 97.1%, and the purity of the dimethyl malonate is 99.7%.
Example 4
The preparation of dimethyl malonate was carried out in a similar manner to example 1, except that: the addition amount of the tetraphenylphosphine platinum and the triphenylphosphine palladium is 1.6g, wherein the mass ratio of the tetraphenylphosphine platinum to the triphenylphosphine palladium is 2:1.
The conversion rate of the raw material methyl chloroacetate is 96.1%, and the selectivity of dimethyl malonate reaches 96.3%. The purity of dimethyl malonate was 99.5%.
Example 5
The preparation of dimethyl malonate was carried out in a similar manner to example 1, except that: the addition amount of the tetraphenylphosphine platinum and the triphenylphosphine palladium is 1.5g, wherein the mass ratio of the tetraphenylphosphine platinum to the triphenylphosphine palladium is 2.5:1.
The conversion rate of the raw material methyl chloroacetate is 95.0%, the selectivity of the dimethyl malonate reaches 96.0%, and the purity of the dimethyl malonate is 98.5%.
The invention has been described in detail in connection with the specific embodiments and exemplary examples thereof, but such description is not to be construed as limiting the invention. It will be understood by those skilled in the art that various equivalent substitutions, modifications or improvements may be made to the technical solution of the present invention and its embodiments without departing from the spirit and scope of the present invention, and these fall within the scope of the present invention. The scope of the invention is defined by the appended claims.
Claims (10)
1. The preparation method of the malonate is characterized in that chloroacetate, alcohol and acid are used as raw materials, and phosphorus ylide is used as a catalyst for preparation.
2. The method according to claim 1, wherein,
the chloroacetate is selected from one or more of methyl chloroacetate, ethyl chloroacetate and propyl chloroacetate;
the molar ratio of the catalyst to the chloroacetate is 1: (30-120).
3. The method according to claim 1, wherein,
the phosphorus ylide catalyst is a coordination compound and comprises a central metal atom X and 1-4 ligands, wherein X is one or more of platinum, rhodium and palladium, and the ligands are one or more of phenylphosphine, diphenylphosphine and triphenylphosphine;
x is preferably one or two selected from platinum and palladium, and the ligand is one or more selected from diphenyl phosphine and triphenylphosphine;
more preferably, the phosphorus ylide catalyst is one or more of tetraphenylphosphorus platinum, triphenylphosphine palladium, tetraphenylphosphorus palladium and tetraphenylphosphorus palladium.
4. A process according to claim 3, wherein,
the catalyst is a composite catalyst of tetraphenylphosphine platinum and triphenylphosphine palladium;
in the composite catalyst, the mass ratio of the tetraphenylphosphine platinum to the triphenylphosphine palladium is (1-10): 1.
5. the method according to claim 1, wherein,
the alcohol is selected from C 1 ～C 4 One or more of alcohols, wherein the molar ratio of the alcohol to the chloroacetate is (0.5-10): 1.
6. The method according to claim 1, wherein,
the preparation of malonate is carried out in a solvent selected from one or more of water and an acid.
7. The method according to claim 1, wherein,
the reaction temperature is 20-120 ℃ and the reaction time is 0.1-2 h.
8. The method according to claim 1, wherein,
in the preparation process, one or more of carbon monoxide, carbon dioxide and methane are also introduced into the reaction system;
the reaction pressure is 0.1-1.5 MPa.
9. The method according to claim 1, wherein,
the conversion rate of chloroacetate can reach more than 94%, the selectivity of malonate can reach more than 96%, and the purity of the malonate product is more than 97%.
10. A malonate obtainable by the process of any one of claims 1 to 9.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211032833.7A CN117658812A (en) | 2022-08-26 | 2022-08-26 | Preparation method of malonate |
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| Application Number | Priority Date | Filing Date | Title |
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| CN202211032833.7A CN117658812A (en) | 2022-08-26 | 2022-08-26 | Preparation method of malonate |
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| CN117658812A true CN117658812A (en) | 2024-03-08 |
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| CN202211032833.7A Pending CN117658812A (en) | 2022-08-26 | 2022-08-26 | Preparation method of malonate |
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