CN111470968B - Method for synthesizing methyl acetoacetate - Google Patents
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- CN111470968B CN111470968B CN202010300116.2A CN202010300116A CN111470968B CN 111470968 B CN111470968 B CN 111470968B CN 202010300116 A CN202010300116 A CN 202010300116A CN 111470968 B CN111470968 B CN 111470968B
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- methyl acetoacetate
- synthesizing methyl
- synthesizing
- methyl
- nickel chloride
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- WRQNANDWMGAFTP-UHFFFAOYSA-N Methylacetoacetic acid Chemical compound COC(=O)CC(C)=O WRQNANDWMGAFTP-UHFFFAOYSA-N 0.000 title claims abstract description 35
- 238000000034 method Methods 0.000 title claims abstract description 27
- 230000002194 synthesizing effect Effects 0.000 title claims abstract description 21
- 150000001412 amines Chemical class 0.000 claims abstract description 12
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims abstract description 11
- MCVVUJPXSBQTRZ-ONEGZZNKSA-N methyl (e)-but-2-enoate Chemical compound COC(=O)\C=C\C MCVVUJPXSBQTRZ-ONEGZZNKSA-N 0.000 claims abstract description 11
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims abstract description 11
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000001301 oxygen Substances 0.000 claims abstract description 6
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 18
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 claims description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 11
- 238000006243 chemical reaction Methods 0.000 claims description 11
- FKNQCJSGGFJEIZ-UHFFFAOYSA-N 4-methylpyridine Chemical compound CC1=CC=NC=C1 FKNQCJSGGFJEIZ-UHFFFAOYSA-N 0.000 claims description 8
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 6
- KWYHDKDOAIKMQN-UHFFFAOYSA-N N,N,N',N'-tetramethylethylenediamine Chemical compound CN(C)CCN(C)C KWYHDKDOAIKMQN-UHFFFAOYSA-N 0.000 claims description 5
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 4
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 claims description 4
- -1 diazabicyclo Chemical compound 0.000 claims description 4
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 4
- JUXXCHAGQCBNTI-UHFFFAOYSA-N 1-n,1-n,2-n,2-n-tetramethylpropane-1,2-diamine Chemical compound CN(C)C(C)CN(C)C JUXXCHAGQCBNTI-UHFFFAOYSA-N 0.000 claims description 2
- FNRMMDCDHWCQTH-UHFFFAOYSA-N 2-chloropyridine;3-chloropyridine;4-chloropyridine Chemical compound ClC1=CC=NC=C1.ClC1=CC=CN=C1.ClC1=CC=CC=N1 FNRMMDCDHWCQTH-UHFFFAOYSA-N 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 2
- IMFACGCPASFAPR-UHFFFAOYSA-N tributylamine Chemical compound CCCCN(CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-N 0.000 claims description 2
- YFTHZRPMJXBUME-UHFFFAOYSA-N tripropylamine Chemical compound CCCN(CCC)CCC YFTHZRPMJXBUME-UHFFFAOYSA-N 0.000 claims description 2
- 239000003054 catalyst Substances 0.000 abstract description 14
- WASQWSOJHCZDFK-UHFFFAOYSA-N diketene Chemical compound C=C1CC(=O)O1 WASQWSOJHCZDFK-UHFFFAOYSA-N 0.000 abstract description 5
- 239000002994 raw material Substances 0.000 abstract description 5
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 abstract description 4
- 239000003377 acid catalyst Substances 0.000 abstract description 3
- 239000003570 air Substances 0.000 abstract description 2
- 229910000510 noble metal Inorganic materials 0.000 abstract description 2
- 239000007800 oxidant agent Substances 0.000 abstract description 2
- 230000001590 oxidative effect Effects 0.000 abstract description 2
- 229910052763 palladium Inorganic materials 0.000 abstract description 2
- 238000001308 synthesis method Methods 0.000 abstract description 2
- 238000007254 oxidation reaction Methods 0.000 abstract 1
- 238000006555 catalytic reaction Methods 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- 239000002253 acid Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000010812 external standard method Methods 0.000 description 2
- 238000004817 gas chromatography Methods 0.000 description 2
- 239000012074 organic phase Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- 239000005794 Hymexazol Substances 0.000 description 1
- XVOKUMIPKHGGTN-UHFFFAOYSA-N Imazethapyr Chemical compound OC(=O)C1=CC(CC)=CN=C1C1=NC(C)(C(C)C)C(=O)N1 XVOKUMIPKHGGTN-UHFFFAOYSA-N 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 239000003899 bactericide agent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 229920003086 cellulose ether Polymers 0.000 description 1
- 239000012461 cellulose resin Substances 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 239000007810 chemical reaction solvent Substances 0.000 description 1
- BULLHNJGPPOUOX-UHFFFAOYSA-N chloroacetone Chemical compound CC(=O)CCl BULLHNJGPPOUOX-UHFFFAOYSA-N 0.000 description 1
- 208000012839 conversion disease Diseases 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- BXNANOICGRISHX-UHFFFAOYSA-N coumaphos Chemical compound CC1=C(Cl)C(=O)OC2=CC(OP(=S)(OCC)OCC)=CC=C21 BXNANOICGRISHX-UHFFFAOYSA-N 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- FHIVAFMUCKRCQO-UHFFFAOYSA-N diazinon Chemical compound CCOP(=S)(OCC)OC1=CC(C)=NC(C(C)C)=N1 FHIVAFMUCKRCQO-UHFFFAOYSA-N 0.000 description 1
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- BBXXLROWFHWFQY-UHFFFAOYSA-N ethirimol Chemical compound CCCCC1=C(C)NC(NCC)=NC1=O BBXXLROWFHWFQY-UHFFFAOYSA-N 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000002363 herbicidal effect Effects 0.000 description 1
- 239000004009 herbicide Substances 0.000 description 1
- KGVPNLBXJKTABS-UHFFFAOYSA-N hymexazol Chemical compound CC1=CC(O)=NO1 KGVPNLBXJKTABS-UHFFFAOYSA-N 0.000 description 1
- 239000002917 insecticide Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 150000007530 organic bases Chemical class 0.000 description 1
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 1
- JKDRQYIYVJVOPF-FDGPNNRMSA-L palladium(ii) acetylacetonate Chemical compound [Pd+2].C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O JKDRQYIYVJVOPF-FDGPNNRMSA-L 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 239000003128 rodenticide Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000011973 solid acid Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- PJVWKTKQMONHTI-UHFFFAOYSA-N warfarin Chemical compound OC=1C2=CC=CC=C2OC(=O)C=1C(CC(=O)C)C1=CC=CC=C1 PJVWKTKQMONHTI-UHFFFAOYSA-N 0.000 description 1
- 229960005080 warfarin Drugs 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/30—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group
- C07C67/313—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by introduction of doubly bound oxygen containing functional groups, e.g. carboxyl groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2531/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- C07C2531/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups C07C2531/02 - C07C2531/24
- C07C2531/28—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups C07C2531/02 - C07C2531/24 of the platinum group metals, iron group metals or copper
- C07C2531/30—Halides
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Abstract
The invention relates to a novel method for synthesizing methyl acetoacetate, which takes methyl crotonate as a raw material, oxygen or air as an oxidant, nickel chloride and organic amine as catalysts to carry out oxidation reaction and directly prepare the methyl acetoacetate from the methyl crotonate. Compared with the prior art for preparing methyl acetoacetate, the invention avoids the use of a strong acid catalyst in a diketene route, and provides a methyl acetoacetate synthesis method which has low cost and is environment-friendly and does not need noble metal palladium.
Description
Technical Field
The invention relates to a method for synthesizing methyl acetoacetate, belonging to the technical field of fine chemical engineering.
Background
Methyl acetoacetate (CAS number: 105-45-3) is an important intermediate of medicines and pesticides, is widely used for synthesizing substances such as bactericides hymexazol, dimetrimol, ethirimol, insecticide diazinon, coumaphos, pyriminophos, herbicide imazethapyr, rodenticide ether, warfarin and the like, and is also an excellent solvent of cellulose ether and cellulose resin.
The current industrial method for synthesizing methyl acetoacetate is mainly to react diketene and methanol in the presence of an acid catalyst and amine, and the method has the biggest limitation that strong acid is needed as the catalyst, the acid seriously corrodes equipment, and the catalyst is difficult to recover. For example, chinese patent publications CN101337890A and CN106748789A report the reaction process of methanol and diketene in the presence of concentrated sulfuric acid as a catalyst; chinese patent publication No. CN108586240A reports that p-toluenesulfonic acid is used as a catalyst to catalyze the conversion of diketene to methyl acetoacetate. Many methyl acetoacetate Synthesis methods independent of diketene are reported in succession, for example, a document of Advanced Synthesis & Catalysis reports a method for synthesizing methyl acetoacetate from monochloroacetone, carbon monoxide and methanol as raw materials and palladium acetylacetonate and furandiphenylphosphine as catalysts in the presence of an organic base (Advanced Synthesis & Catalysis,2012,354,3105-3114), which has the advantage of high yield but produces a large amount of organic salts as by-products, while expensive palladium catalysts lose the commercialization potential of the method; the literature of Catalysis Today and Catalysis Communications reports a method for catalyzing direct reaction of acetone and dimethyl carbonate to generate methyl acetoacetate by using solid acid as a catalyst, wherein the method has the advantages of simple process, cheap and easily available raw materials and low reaction conversion rate (the conversion rate is 18-32%) (Catalysis Communications,2008,9,680 and 684; Catalysis Today,2008,131,372 and 377); an article by Angewandte Chemie International Edition reports that methyl crotonate is used as a raw material, palladium chloride is used as a catalyst, N, N-dimethylacetamide is used as a solvent, and methyl crotonate is directly oxidized by oxygen to prepare methyl acetoacetate (Angew. chem. int. Ed.2013,52, 5961-containing 5964).
Disclosure of Invention
The invention aims to overcome the defects of a method for synthesizing methyl acetoacetate in the prior art, and provides a method for synthesizing methyl acetoacetate, which does not need strong acid or noble metal as a catalyst, avoids the corrosion of the traditional method acid catalyst to equipment from the source, and has the advantages of low cost and high reaction yield.
Technical scheme
A method for synthesizing methyl acetoacetate comprises the following steps: adding methyl crotonate, nickel chloride, organic amine, organic alcohol and water into an autoclave, then introducing oxygen or air of 0.1-2MPa, stirring and heating to 50-150 ℃ for reaction, and obtaining methyl acetoacetate solution after the reaction is finished.
Further, the mass ratio of the methyl crotonate to the nickel chloride is (100-5): 1.
Furthermore, the molar ratio of the nickel chloride to the organic amine is 1 (1-6).
Further, the amount of the water is 20% of the mass of the organic alcohol, and the purpose of adding the water is to adjust the polarity of the solvent.
Further, the organic amine is selected from any one of pyridine, 4-methylpyridine, chloropyridine, triethylamine, tripropylamine, tributylamine, diazabicyclo, tetramethylethylenediamine or tetramethylpropylenediamine. More preferably one of diazabicyclo, 4-methylpyridine or pyridine.
Further, all the organic alcohols are selected from any one of methanol, ethanol, propanol, butanol, pentanol or hexanol. More preferably hexanol.
The invention has the beneficial effects that: the invention provides a method for synthesizing methyl acetoacetate, which adopts methyl crotonate as a raw material, nickel chloride and organic amine as catalysts, alcohol as a reaction solvent and oxygen or air as an oxidant.
Detailed Description
The present invention will be described in detail with reference to the following embodiments.
Example 1
A method for synthesizing methyl acetoacetate comprises the following steps: 100g of methyl crotonate, 5.0g of nickel chloride, 6.7g of tetramethylethylenediamine, 100g of methanol and 20g of water are added into a 1000ml autoclave, then 1.0MPa of oxygen is introduced, the temperature is raised to 100 ℃ under stirring, and the reaction is carried out for 12 hours, thus obtaining the methyl acetoacetate solution. The organic phase was analyzed by gas chromatography, and calibration by an external standard method showed that the resulting solution contained 89.6g (yield: 77.2%) of methyl acetoacetate.
Example 2
A method for synthesizing methyl acetoacetate comprises the following steps: 100g of methyl crotonate, 5.0g of nickel chloride, 6.7g of tetramethylethylenediamine, 100g of hexanol and 20g of water were added to a 1000ml autoclave, and then 0.1MPa of air was bubbled through the mixture, and the temperature was raised to 80 ℃ with stirring to react for 12 hours, thereby obtaining a methyl acetoacetate solution. The organic phase was analyzed by gas chromatography, and calibration by an external standard method showed that the resulting solution contained 62.1g of methyl acetoacetate (yield: 53.5%).
Examples 3 to 9
In examples 3 to 9, the same procedure as in example 1 was repeated except for using the organic amine in an amount different from that used, and the results of the yield test are shown in Table 1:
TABLE 1 results of yield test using different organic amine reactions
Examples 10 to 13
In examples 10 to 13, the same procedure as in example 1 was repeated except that nickel chloride and tetramethylethylenediamine were used as catalysts, and the results of the productivity test are shown in Table 2:
TABLE 2 productivity test results with different amounts of catalyst
As can be seen from Table 2, the higher the amount of catalyst used, the higher the yield.
Examples 14 to 18
In examples 14 to 18, which were the same as in example 1 except that the solvents were different, the results of the yield test are shown in Table 3:
TABLE 3 results of yield test with different solvents
As can be seen from Table 3, the highest yield was obtained using hexanol as the solvent under otherwise identical conditions.
Claims (8)
1. A method for synthesizing methyl acetoacetate is characterized in that methyl crotonate, nickel chloride, organic amine, organic alcohol and water are added into a high-pressure kettle, then 0.1-2MPa of oxygen or air is introduced, the mixture is stirred and heated to 50-150 ℃ for reaction, and methyl acetoacetate solution is obtained after the reaction is finished.
2. The method for synthesizing methyl acetoacetate according to claim 1, wherein the mass ratio of the methyl crotonate to the nickel chloride is (100-5): 1.
3. The method for synthesizing methyl acetoacetate according to claim 1, wherein the molar ratio of the nickel chloride to the organic amine is 1 (1-6).
4. The method for synthesizing methyl acetoacetate according to claim 1, wherein the amount of water is 20% of the mass of the organic alcohol.
5. The method of synthesizing methyl acetoacetate according to claim 1, wherein the organic amine is selected from any one of pyridine, 4-methylpyridine, chloropyridine, triethylamine, tripropylamine, tributylamine, diazabicyclo, tetramethylethylenediamine or tetramethylpropylenediamine.
6. The method of synthesizing methyl acetoacetate according to claim 5, wherein the organic amine is one of diazabicyclo, 4-methylpyridine or pyridine.
7. The method for synthesizing methyl acetoacetate according to any one of claims 1 to 6, wherein the organic alcohol is selected from any one of methanol, ethanol, propanol, butanol, pentanol or hexanol.
8. The method of synthesizing methyl acetoacetate according to claim 7, wherein the organic alcohol is hexanol.
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| CN111470968B true CN111470968B (en) | 2022-04-22 |
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Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103450017A (en) * | 2012-12-21 | 2013-12-18 | 南通醋酸化工股份有限公司 | Preparation method of methyl acetoacetate |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103450017A (en) * | 2012-12-21 | 2013-12-18 | 南通醋酸化工股份有限公司 | Preparation method of methyl acetoacetate |
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Effective date of registration: 20231016 Address after: 730300 room 820, strategic emerging industry incubation base, Qinchuan Park, Lanzhou New Area, Lanzhou City, Gansu Province Patentee after: Baisheng New Materials (Gansu) Co.,Ltd. Address before: 226221 Binjiang fine chemical park, Qidong City, Nantong City, Jiangsu Province Patentee before: Nantong Baisheng Pharmaceutical Co.,Ltd. |