CN114163410A - Preparation method of 4, 6-dimethyl latissic acid methyl ester - Google Patents
Preparation method of 4, 6-dimethyl latissic acid methyl ester Download PDFInfo
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- CN114163410A CN114163410A CN202111507498.7A CN202111507498A CN114163410A CN 114163410 A CN114163410 A CN 114163410A CN 202111507498 A CN202111507498 A CN 202111507498A CN 114163410 A CN114163410 A CN 114163410A
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- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D309/00—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only ring hetero atom, not condensed with other rings
- C07D309/34—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only ring hetero atom, not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members
- C07D309/36—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only ring hetero atom, not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members with oxygen atoms directly attached to ring carbon atoms
- C07D309/38—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only ring hetero atom, not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members with oxygen atoms directly attached to ring carbon atoms one oxygen atom in position 2 or 4, e.g. pyrones
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Abstract
The invention discloses a preparation method of 4, 6-dimethyl latissic acid methyl ester, and raw materials used in the method comprise methyl acetoacetate, methanol, thionyl chloride and water. The preparation method of the 4, 6-dimethyl latissic acid methyl ester provided by the invention has the advantages that the reaction time is short, and the obtained 4, 6-dimethyl latissic acid methyl ester product has good purity and high yield.
Description
Technical Field
The invention relates to the technical field of synthesis, in particular to a preparation method of 4, 6-dimethyl latissic acid methyl ester.
Background
The 4, 6-dimethyl latissic acid methyl ester is an important organic intermediate, has lower production cost and higher profit margin. The conventional preparation method of methyl 4, 6-dimethyl latissinate is to add inorganic acid (HCl, concentrated sulfuric acid) into methyl acetoacetate at about 0 deg.C, and let it stand for about 2 weeks. The traditional preparation method has the defects of low yield and poor purity of the product obtained by the reaction.
Disclosure of Invention
Based on the technical problems in the background art, the invention provides a preparation method of 4, 6-dimethyl latissic acid methyl ester, the reaction time is short, and the obtained 4, 6-dimethyl latissic acid methyl ester product has good purity and high yield.
The invention provides a preparation method of 4, 6-dimethyl latissic acid methyl ester, which uses raw materials comprising methyl acetoacetate, methanol, thionyl chloride and water.
Preferably, the molar ratio of the methyl acetoacetate to the thionyl chloride is 2-3: 1.
preferably, the preparation method of the methyl 4, 6-dimethyl latissinate comprises the following steps:
s1, placing methyl acetoacetate and methanol in a glass lining reaction kettle, and uniformly stirring to obtain a mixed solution A;
s2, cooling the mixed solution A to below 5 ℃, dropwise adding thionyl chloride, controlling the temperature to be 0-5 ℃ in the dropwise adding process, dropwise adding water after the dropwise adding is finished, controlling the temperature to be 4-6 ℃ in the dropwise adding process, stirring at 15-20 ℃ after the dropwise adding is finished, and sampling and analyzing to be qualified to obtain a mixed solution B;
s3, heating the mixed solution B to 75-85 ℃ under normal pressure to concentrate the mixed solution B, cooling to 50-60 ℃, adding methanol, heating to 80-100 ℃ to concentrate the mixed solution B, and cooling to below 50 ℃ to obtain a mixed solution C;
s4, adding methanol into the mixed solution C, heating to reflux, keeping for 0.5-1.5h, cooling for crystallization, and centrifuging to obtain the methyl 4, 6-dimethyl latissilate.
Preferably, in S1, the weight ratio of methyl acetoacetate to methanol is 1: 0.55-0.85.
Preferably, in S2, mixed solution a is indirectly cooled to 5 ℃ or lower with frozen brine.
Preferably, in S2, a sample is taken for analysis after stirring for 1.5-2.5 h.
Preferably, in S4, the cooling crystallization time is 15-25 h.
Preferably, in S4, the time for the centrifugation is not less than 30 minutes.
Preferably, in S4, the method further comprises recrystallizing the centrifuged product.
Preferably, in S4, the method further comprises pumping the centrifuged liquid into the glass lining reactor in S1 by using a closed pipeline.
Preferably, in S2, the dropping time may be 2 to 3 hours during the dropping of thionyl chloride and the dropping of water.
Preferably, in S2, the molar ratio of dropwise added water to dropwise added thionyl chloride may be 1: 1.
preferably, the process of S2 is carried out under closed conditions, and a vent is provided at the top of the glass lining reaction kettle.
Preferably, in S2, water and thionyl chloride are added dropwise to the reaction kettle through the head tank.
The reaction formula of the preparation method of the methyl 4, 6-dimethyl latissinate is shown as follows:
in the preparation method of the methyl 4, 6-dimethyl latissinate, methyl acetoacetate is taken as a raw material, the reaction is carried out under the action of methanol, thionyl chloride and water, and the purity of the obtained methyl 4, 6-dimethyl latissinate is good by controlling the technological conditions of the reaction.
Detailed Description
The technical solution of the present invention will be described in detail below with reference to specific examples.
Example 1
The invention provides a preparation method of 4, 6-dimethyl latissic acid methyl ester, which comprises the following steps:
s1, placing methyl acetoacetate and methanol in a glass lining reaction kettle, and uniformly stirring to obtain a mixed solution A;
s2, cooling the mixed solution A to 3 ℃, dropwise adding thionyl chloride, controlling the temperature to be 0 ℃ in the dropwise adding process, dropwise adding water after the dropwise adding is finished, controlling the temperature to be 6 ℃ in the dropwise adding process, stirring at 15 ℃ after the dropwise adding is finished, and sampling and analyzing to obtain a mixed solution B;
s3, heating the mixed solution B to 80 ℃ under normal pressure to concentrate the mixed solution B, cooling to 55 ℃, adding methanol, heating to 100 ℃ to concentrate the mixed solution B, and cooling to 45 ℃ to obtain a mixed solution C;
s4, adding methanol into the mixed solution C, heating to reflux, keeping for 0.5h, cooling, crystallizing, and centrifuging to obtain the methyl 4, 6-dimethyl latissilate.
Example 2
The invention provides a preparation method of 4, 6-dimethyl latissic acid methyl ester, which comprises the following steps:
s1, placing methyl acetoacetate and methanol in a glass lining reaction kettle, wherein the weight ratio of methyl acetoacetate to methanol is 1: 0.85, uniformly stirring to obtain a mixed solution A;
s2, indirectly cooling the mixed solution A to 4 ℃ by using frozen saline, dropwise adding thionyl chloride, controlling the temperature to be 5 ℃ in the dropwise adding process, dropwise adding water after the dropwise adding is finished, controlling the temperature to be 4 ℃ in the dropwise adding process, stirring for 1.5 hours at 20 ℃ after the dropwise adding is finished, and sampling and analyzing to obtain a mixed solution B;
s3, heating the mixed solution B to 75 ℃ under normal pressure to concentrate the mixed solution B, cooling to 60 ℃, adding methanol, heating to 80 ℃ to concentrate the mixed solution B, and cooling to 40 ℃ to obtain a mixed solution C;
s4, adding methanol into the mixed solution C, heating to reflux, keeping for 1.5h, cooling for crystallization for 25h, centrifuging for 45min, and recrystallizing the centrifuged product to obtain the methyl 4, 6-dimethyl latissilate.
Example 3
The invention provides a preparation method of 4, 6-dimethyl latissic acid methyl ester, which comprises the following steps:
s1, placing methyl acetoacetate and methanol in a glass lining reaction kettle, wherein the weight ratio of methyl acetoacetate to methanol is 1: 0.55, uniformly stirring to obtain a mixed solution A;
s2, cooling the mixed solution A to 2 ℃ by using frozen saline water, dropwise adding thionyl chloride, controlling the temperature to be 1 ℃ in the dropwise adding process, dropwise adding water after the dropwise adding is finished, controlling the temperature to be 5 ℃ in the dropwise adding process, stirring for 2.5 hours at 18 ℃ after the dropwise adding is finished, and sampling and analyzing to obtain a mixed solution B;
s3, heating the mixed solution B to 85 ℃ under normal pressure to concentrate the mixed solution B, cooling to 50 ℃, adding methanol, heating to 82 ℃ to concentrate the mixed solution B, and cooling to 48 ℃ to obtain a mixed solution C;
s4, adding methanol into the mixed solution C, heating to reflux, keeping for 1h, cooling and crystallizing for 15h, centrifuging for 40min, and recrystallizing the centrifuged product to obtain the methyl 4, 6-dimethyl latissimate.
Example 4
The invention provides a preparation method of 4, 6-dimethyl latissic acid methyl ester, which comprises the following steps:
s1, placing methyl acetoacetate and methanol in a glass lining reaction kettle, wherein the weight ratio of methyl acetoacetate to methanol is 1: 0.6, uniformly stirring to obtain a mixed solution A;
s2, indirectly cooling the mixed solution A to 4 ℃ by using frozen saline, dropwise adding thionyl chloride, controlling the temperature to be 3 ℃ in the dropwise adding process, dropwise adding water after the dropwise adding is finished, controlling the temperature to be 5 ℃ in the dropwise adding process, stirring for 1.8 hours at 19 ℃ after the dropwise adding is finished, and sampling and analyzing to obtain a mixed solution B;
s3, heating the mixed solution B to 78 ℃ under normal pressure to concentrate the mixed solution B, cooling to 53 ℃, adding methanol, heating to 100 ℃ to concentrate the mixed solution B, and cooling to 35 ℃ to obtain a mixed solution C;
s4, adding methanol into the mixed solution C, heating to reflux, keeping for 0.5h, cooling for crystallization for 18h, separating for 50min, and recrystallizing the centrifuged product to obtain the methyl 4, 6-dimethyl latissilate; and pumping the centrifuged liquid into a glass lining reaction kettle in S1 by using a closed pipeline.
Example 5
The invention provides a preparation method of 4, 6-dimethyl latissic acid methyl ester, which comprises the following steps:
s1, placing methyl acetoacetate and methanol in a glass lining reaction kettle, wherein the weight ratio of methyl acetoacetate to methanol is 1: 0.7, uniformly stirring to obtain a mixed solution A;
s2, indirectly cooling the mixed solution A to 4 ℃ by using frozen saline, dropwise adding thionyl chloride, controlling the temperature to be 5 ℃ in the dropwise adding process, dropwise adding water after the dropwise adding is finished, controlling the temperature to be 6 ℃ in the dropwise adding process, stirring for 2.2 hours at 17 ℃ after the dropwise adding is finished, and sampling and analyzing to obtain a mixed solution B;
s3, heating the mixed solution B to 83 ℃ under the normal pressure condition to concentrate the mixed solution B, cooling to 55 ℃, adding methanol, heating to 100 ℃ to concentrate the mixed solution B, and cooling to 47 ℃ to obtain a mixed solution C;
s4, adding methanol into the mixed solution C, heating to reflux, keeping for 1.3h, cooling for crystallization for 18h, centrifuging for 50min, and recrystallizing the centrifuged product to obtain the methyl 4, 6-dimethyl latissilate; and pumping the centrifuged liquid into a glass lining reaction kettle in S1 by using a closed pipeline.
The 4, 6-dimethyl latissic acid methyl ester prepared by the embodiments 2-4 of the invention is detected, the yield is more than 85 percent, and the product purity is more than 99.7 percent.
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art should be considered to be within the technical scope of the present invention, and the technical solutions and the inventive concepts thereof according to the present invention should be equivalent or changed within the scope of the present invention.
Claims (10)
1. A process for preparing methyl 4, 6-dimethyl latissimate features that its raw materials include methyl acetoacetate, methanol, sulfoxide chloride and water.
2. The process for preparing methyl 4, 6-dimethyllatinate according to claim 1, wherein the molar ratio of methyl acetoacetate to thionyl chloride is 2-3: 1.
3. the process for the preparation of methyl 4, 6-dimethyllatinate according to claim 1 or 2, comprising the steps of:
s1, placing methyl acetoacetate and methanol in a glass lining reaction kettle, and uniformly stirring to obtain a mixed solution A;
s2, cooling the mixed solution A to below 5 ℃, dropwise adding thionyl chloride, controlling the temperature to be 0-5 ℃ in the dropwise adding process, dropwise adding water after the dropwise adding is finished, controlling the temperature to be 4-6 ℃ in the dropwise adding process, stirring at 15-20 ℃ after the dropwise adding is finished, and sampling and analyzing to be qualified to obtain a mixed solution B;
s3, heating the mixed solution B to 75-85 ℃ under normal pressure to concentrate the mixed solution B, cooling to 50-60 ℃, adding methanol, heating to 80-100 ℃ to concentrate the mixed solution B, and cooling to below 50 ℃ to obtain a mixed solution C;
s4, adding methanol into the mixed solution C, heating to reflux, keeping for 0.5-1.5h, cooling for crystallization, and centrifuging to obtain the methyl 4, 6-dimethyl latissilate.
4. The process of claim 3, wherein the weight ratio of methyl acetoacetate to methanol in S1 is 1: 0.55-0.85.
5. The process according to claim 3, wherein the temperature of mixed solution A in S2 is indirectly cooled to 5 ℃ or lower by using a frozen saline solution.
6. The process for preparing methyl 4, 6-dimethyllatinate according to claim 3, wherein the sample is taken out for analysis after stirring for 1.5 to 2.5 hours in S2.
7. The process of claim 3, wherein the cooling crystallization time in S4 is 15-25 h.
8. The process for producing methyl 4, 6-dimethyllatinate according to claim 3, wherein the centrifugation is carried out for not less than 30 minutes in S4.
9. The process of claim 3, wherein the step of S4 further comprises recrystallizing the centrifuged product.
10. The process for preparing methyl 4, 6-dimethyllatinate according to any one of claims 3 to 9, wherein the process further comprises pumping the centrifuged liquid into a glass-lined reactor of S1 by using a closed pipe at S4.
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| CN202111507498.7A CN114163410A (en) | 2021-12-10 | 2021-12-10 | Preparation method of 4, 6-dimethyl latissic acid methyl ester |
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| CN202111507498.7A CN114163410A (en) | 2021-12-10 | 2021-12-10 | Preparation method of 4, 6-dimethyl latissic acid methyl ester |
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| HU231014B1 (en) * | 2015-09-30 | 2019-11-28 | Első Vegyi Industria Zrt. | Simple industrial process for the preparation of isodehydroacetic acid ester |
| CN110922373A (en) * | 2018-09-19 | 2020-03-27 | 张家港九力新材料科技有限公司 | Synthesis method of methyl platinolate |
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- 2021-12-10 CN CN202111507498.7A patent/CN114163410A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| HU231014B1 (en) * | 2015-09-30 | 2019-11-28 | Első Vegyi Industria Zrt. | Simple industrial process for the preparation of isodehydroacetic acid ester |
| CN110922373A (en) * | 2018-09-19 | 2020-03-27 | 张家港九力新材料科技有限公司 | Synthesis method of methyl platinolate |
Non-Patent Citations (1)
| Title |
|---|
| 廖铁星 主编: "氯化亚砜", 《化学试剂危险物品 安全储存养护手册》, pages 140 - 141 * |
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