CN111018824A - Method for synthesizing 4, 5-dimethyl-1, 3-dioxol-2-one - Google Patents
Method for synthesizing 4, 5-dimethyl-1, 3-dioxol-2-one Download PDFInfo
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- CN111018824A CN111018824A CN201911254084.0A CN201911254084A CN111018824A CN 111018824 A CN111018824 A CN 111018824A CN 201911254084 A CN201911254084 A CN 201911254084A CN 111018824 A CN111018824 A CN 111018824A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D317/00—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms
- C07D317/08—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3
- C07D317/10—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 not condensed with other rings
- C07D317/32—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 not condensed with other rings with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D317/34—Oxygen atoms
- C07D317/40—Vinylene carbonate; Substituted vinylene carbonates
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- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
Abstract
The invention discloses a method for synthesizing 4, 5-dimethyl-1, 3-dioxole-2-ketone, which comprises the following steps: the method comprises the following steps: cyclizing 2, 3-butanedione and triphosgene to obtain 4, 5-dichloro-4, 5-dimethyl-1, 3-dioxolane-2-one; step two: dechlorinating 4, 5-dichloro-4, 5-dimethyl-1, 3-dioxol-2-one under the action of a reducing agent to prepare 4, 5-dimethyl-1, 3-dioxol-2-one. The method has mild conditions, and is simple and efficient.
Description
Technical Field
The invention relates to a new process for preparing 4, 5-dimethyl-1, 3-dioxol-2-one by using 2, 3-butanedione as a raw material.
Background
4, 5-dimethyl-1, 3-dioxol-2-one is an important pharmaceutical intermediate, and has been used in the synthesis of various drugs, such as olmesartan, quinolone antibacterial prulifloxacin, penicillin antibiotic, and penicillin.
The traditional process is to prepare 4, 5-dimethyl-1, 3-dioxol-2-one by taking 3-hydroxy-2-butanone and triphosgene as raw materials through the steps of acylation, cyclization, dehydrochlorination and the like.
Disclosure of Invention
The invention aims to provide a method for synthesizing 4, 5-dimethyl-1, 3-dioxol-2-one under mild conditions, simply and efficiently.
The technical solution of the invention is as follows:
a method of synthesizing 4, 5-dimethyl-1, 3-dioxol-2-one, the method comprising the steps of:
the method comprises the following steps: cyclizing 2, 3-butanedione and triphosgene to obtain 4, 5-dichloro-4, 5-dimethyl-1, 3-dioxolane-2-one;
step two: dechlorinating 4, 5-dichloro-4, 5-dimethyl-1, 3-dioxol-2-one under the action of a reducing agent to prepare 4, 5-dimethyl-1, 3-dioxol-2-one.
The operation of the first step is as follows: slowly dripping a dichloromethane solution of pyridine and triphosgene into a dichloromethane solution of 2, 3-butanedione at 0-30 ℃, stirring for 2-8 h, adding water for quenching reaction, extracting for phase separation, back extracting the water phase once by using dichloromethane, combining organic phases, and concentrating to obtain 4, 5-dichloro-4, 5-dimethyl-1, 3-dioxolane-2-one.
The molar ratio of the 2, 3-butanedione to the pyridine to the triphosgene is as follows: 1:0.5:0.4.
The operation of the second step is as follows: adding a reducing reagent into the solution of 4, 5-dichloro-4, 5-dimethyl-1, 3-dioxol-2-one in batches at the temperature of 20-80 ℃, stirring and reacting for 2-8 h, filtering after the reaction is finished, concentrating the filtrate, adding water, stirring and crystallizing, and filtering to obtain 4, 5-dimethyl-1, 3-dioxol-2-one.
Wherein the reducing reagent is zinc powder, iron powder, copper-zinc alloy and other reducing reagents; the solution is water, ethers, alkanes, aromatics, alcohols, acids, anhydrides, polar aprotic solutions and mixed solutions thereof, such as glycol dimethyl ether, n-heptane, toluene, ethanol, acetic acid, acetic anhydride, DMF and the like and mixed solutions thereof.
The molar ratio of the 4, 5-dichloro-4, 5-dimethyl-1, 3-dioxolane-2-one to the reducing agent is as follows: 1: (1-10).
The method has mild conditions, and is simple and efficient.
The present invention will be further described with reference to the following examples.
Detailed Description
Example 1
Slowly adding pyridine (4g) and triphosgene (11.8g) in dichloromethane (36mL) into 2, 3-butanedione (8.6g) at 10-20 ℃, stirring for 3h, adding water (50mL) to quench the reaction, extracting and separating phases, back-extracting the aqueous phase once with dichloromethane (50mL), combining organic phases, and concentrating to obtain 14.8g of 4, 5-dichloro-4, 5-dimethyl-1, 3-dioxolane-2-one with the yield of 80%.
Example 2
Adding zinc powder (7.8g) in batches into a solution of 4, 5-dichloro-4, 5-dimethyl-1, 3-dioxolane-2-one (7.4g) in ethanol (15mL) and acetic acid (15mL) at 40-50 ℃, and reacting for 4 hours at 60-70 ℃. After the reaction, the mixture is filtered, the filtrate is concentrated, 15mL of water is added, the mixture is stirred and crystallized, and 3.6g of 4, 5-dimethyl-1, 3-dioxol-2-one is obtained by filtration, and the yield is 79%.
Example 3
Adding zinc powder (9.1g) in batches into a toluene (15mL) and acetic anhydride (15mL) solution of 4, 5-dichloro-4, 5-dimethyl-1, 3-dioxolan-2-one (7.4g) at 30-40 ℃, and reacting for 6h at 70-80 ℃. After the reaction, the mixture was filtered, the filtrate was concentrated, 15mL of water was added, followed by crystallization with stirring and filtration to obtain 3.8g of 4, 5-dimethyl-1, 3-dioxol-2-one with a yield of 83%.
Claims (6)
1. A method for synthesizing 4, 5-dimethyl-1, 3-dioxol-2-one is characterized by comprising the following steps: the reaction formula is as follows:
the method comprises the following steps:
the method comprises the following steps: cyclizing 2, 3-butanedione and triphosgene to obtain 4, 5-dichloro-4, 5-dimethyl-1, 3-dioxolane-2-one;
step two: dechlorinating 4, 5-dichloro-4, 5-dimethyl-1, 3-dioxol-2-one under the action of a reducing agent to prepare 4, 5-dimethyl-1, 3-dioxol-2-one.
2. The method of claim 1, wherein the synthesis of 4, 5-dimethyl-1, 3-dioxol-2-one comprises: and in the second step, the reducing reagent is zinc powder, iron powder or a copper-zinc alloy agent.
3. The method of claim 1, wherein the synthesis of 4, 5-dimethyl-1, 3-dioxol-2-one comprises: the operation of the step one is as follows: slowly dripping a dichloromethane solution of pyridine and triphosgene into a dichloromethane solution of 2, 3-butanedione at 0-30 ℃, stirring for 2-8 h, adding water for quenching reaction, extracting for phase separation, back extracting the water phase once by using dichloromethane, combining organic phases, and concentrating to obtain 4, 5-dichloro-4, 5-dimethyl-1, 3-dioxolane-2-one.
4. The method of claim 3, wherein the synthesis of 4, 5-dimethyl-1, 3-dioxol-2-one comprises: the molar ratio of the 2, 3-butanedione to the pyridine to the triphosgene is as follows: 1:0.5:0.4.
5. The method of claim 1, wherein the synthesis of 4, 5-dimethyl-1, 3-dioxol-2-one comprises: the operation of the second step is as follows: adding a reducing reagent into the solution of 4, 5-dichloro-4, 5-dimethyl-1, 3-dioxol-2-one in batches at the temperature of 20-80 ℃, stirring and reacting for 2-8 h, filtering after the reaction is finished, concentrating the filtrate, adding water, stirring and crystallizing, and filtering to obtain 4, 5-dimethyl-1, 3-dioxol-2-one.
6. The method of claim 5, wherein the synthesis of 4, 5-dimethyl-1, 3-dioxol-2-one comprises: the molar ratio of the 4, 5-dichloro-4, 5-dimethyl-1, 3-dioxolane-2-one to the reducing agent is as follows: 1: (1-10).
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| Application Number | Priority Date | Filing Date | Title |
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| CN201911254084.0A CN111018824A (en) | 2019-12-10 | 2019-12-10 | Method for synthesizing 4, 5-dimethyl-1, 3-dioxol-2-one |
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| CN201911254084.0A CN111018824A (en) | 2019-12-10 | 2019-12-10 | Method for synthesizing 4, 5-dimethyl-1, 3-dioxol-2-one |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112480061A (en) * | 2020-12-27 | 2021-03-12 | 江苏瀚康新材料有限公司 | Method for preparing vinylene carbonate by using waste |
| CN115819394A (en) * | 2022-11-28 | 2023-03-21 | 江苏恒盛药业有限公司 | Synthesis process for preparing vinylene carbonate by using monochloroethylene carbonate byproduct |
-
2019
- 2019-12-10 CN CN201911254084.0A patent/CN111018824A/en not_active Withdrawn
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112480061A (en) * | 2020-12-27 | 2021-03-12 | 江苏瀚康新材料有限公司 | Method for preparing vinylene carbonate by using waste |
| CN115819394A (en) * | 2022-11-28 | 2023-03-21 | 江苏恒盛药业有限公司 | Synthesis process for preparing vinylene carbonate by using monochloroethylene carbonate byproduct |
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