Methyl 5-(methoxycarbonyl)-2-oxy-1, 3-dioxacyclopentane-4-formate and preparation method of methyl 5-(methoxycarbonyl)-2-oxy-1, 3-dioxacyclopentane-4-formate
Through a multi-step preparation method, the problems of complex process, insufficient purity and yield in the preparation of five-membered ring carbonate-related derivatives are solved, and efficient and simple preparation processes and high-purity and high-yield products are achieved.
Patent Information
- Application Number
- CN202311732572.4
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2023-12-17
- Publication Date
- 2025-06-17
AI Technical Summary
The prior art is difficult to effectively prepare five-membered ring carbonate-related derivatives, especially in terms of simple preparation process, easy operation and control, high product purity and good yield.
A preparation method is adopted, including adding tartaric acid, acid binding agent and a first organic solvent to the reaction vessel, and after cooling, adding a mixture of triphosgene and the first organic solvent dropwise, then heating up and stirring, suction filtration and concentration to obtain an intermediate. Then, an intermediate, a second organic solvent, a catalyst and methanol were added to the reflux reaction vessel with a water separator and condenser, and the reflux reaction was heated up, followed by filtration, crystallization and drying to obtain a finished methyl 5-(methoxycarbonyl)-2-oxy subunit-1,3-dioxolane-4-formate.
It has achieved efficient preparation of five-membered ring carbonate-related derivatives, with simple and easy-to-use technology, high product purity and good yield.
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Figure CN120157648A_ABST
Abstract
Description
Technical Field
[0001] The present invention relates to the technical field of organic synthesis, and particularly to a preparation method of five-membered cyclic carbonate related derivatives. Background Art
[0002] In recent years, the demand for electric vehicles has been increasing day by day. Developing lithium-ion batteries with high energy and high power density is the key to the large-scale commercialization of electric vehicles. Therefore, in order to continuously improve the battery performance, it is necessary to continuously research the electrolyte formula.
[0003] Five-membered cyclic carbonates have been widely studied as components of lithium-ion battery electrolytes. Ethylene carbonate is the parent compound of this type of compound. Due to its high polarity and the ability to form a solid electrolyte interphase layer, it is an indispensable part of the electrolyte. Therefore, the research on five-membered cyclic carbonates and related derivatives is of great significance for the research of lithium battery electrolytes. Summary of the Invention
[0004] The technical problem to be solved by the present invention is to provide methyl 5-(methoxycarbonyl)-2-oxo-1,3-dioxolane-4-carboxylate and its preparation method, which has a simple preparation process, is easy to operate and control, has high product purity and good yield.
[0005] To solve the above problems, the technical solution adopted by the present invention is: A five-membered cyclic carbonate derivative is methyl 5-(methoxycarbonyl)-2-oxo-1,3-dioxolane-4-carboxylate, and its structural formula is as follows: .
[0006] The preparation method of methyl 5-(methoxycarbonyl)-2-oxo-1,3-dioxolane-4-carboxylate includes the following steps.
[0007] I. Add tartaric acid, an acid-binding agent, and a first organic solvent into a reaction vessel, mix them evenly and then cool down. Dissolve triphosgene in the first organic solvent to form a mixed solution of triphosgene and the first organic solvent. Under the condition that the temperature does not exceed 10°C, usually controlled at 0°C - 10°C, dropwise add the mixed solution of triphosgene and the first solvent into the reaction vessel. After the dropping is completed, raise the temperature to room temperature and stir, filter off the insoluble substances, and concentrate the filtrate to dryness to obtain an intermediate; the acid-binding agent used is an organic weak base.
[0008] II. Add the intermediate obtained in the first step, a second organic solvent, a catalyst, and methanol into a reflux reaction vessel equipped with a water separator and a condenser. Heat the mixture to reflux for water separation. After the reaction is completed, concentrate the reaction solution to dryness to obtain a crude product. The catalyst is selected from one or two of p-toluenesulfonic acid and benzenesulfonic acid. Add the crude product to the first organic solvent, heat to reflux, filter while hot to remove insoluble substances, cool the filtrate to crystallize, filter by suction, and dry to obtain the finished product of methyl 5-(methoxycarbonyl)-2-oxo-1,3-dioxolane-4-carboxylate.
[0009] The reaction principle of the above preparation is as follows: 。
[0010] Further, in the above preparation method of methyl 5-(methoxycarbonyl)-2-oxo-1,3-dioxolane-4-carboxylate, in the first step, the molar ratio of tartaric acid, acid-binding agent, and triphosgene is 3:6~6.3:1~1.05.
[0011] Further, in the above preparation method of methyl 5-(methoxycarbonyl)-2-oxo-1,3-dioxolane-4-carboxylate, in the first step, the acid-binding agent is selected from one or more of triethylamine, pyridine, and imidazole.
[0012] Further, in the above preparation method of methyl 5-(methoxycarbonyl)-2-oxo-1,3-dioxolane-4-carboxylate, the first organic solvent is one or more of dichloromethane, dichloroethane, and chloroform, and the dosage is 1.5~2 times the weight of tartaric acid.
[0013] Further, in the above preparation method of methyl 5-(methoxycarbonyl)-2-oxo-1,3-dioxolane-4-carboxylate, in the second step, the molar ratio of the intermediate to methanol is 1:2~2.1.
[0014] Further, in the above preparation method of methyl 5-(methoxycarbonyl)-2-oxo-1,3-dioxolane-4-carboxylate, the dosage of the catalyst is 0.3%~0.5% of the mass of the intermediate.
[0015] Further, in the above preparation method of methyl 5-(methoxycarbonyl)-2-oxo-1,3-dioxolane-4-carboxylate, in the second step, the second organic solvent is selected from one or two of toluene and xylene, and the dosage is 2.5~4 times the mass of the intermediate.
[0016] Further, in the above preparation method of methyl 5-(methoxycarbonyl)-2-oxo-1,3-dioxolane-4-carboxylate, in the second step, the temperature is controlled at 0~5°C when the filtrate is cooled to crystallize.
[0017] The advantages of the present invention are as follows: A preparation method of methyl 5-(methoxycarbonyl)-2-oxo-1,3-dioxolane-4-carboxylate is provided. This synthesis method is simple and easy to implement, the post-treatment method is easy to operate, the product has high purity and good yield. Description of the Drawings
[0018] Figure 1 It is the carbon nuclear magnetic spectrum of the product prepared in Example 1.
[0019] Figure 2 It is the proton nuclear magnetic spectrum of the product prepared in Example 1. Embodiments
[0020] The present invention will be further described in detail below in conjunction with preferred embodiments.
[0021] Example 1: Add 300 g of tartaric acid, 404 g of triethylamine, and 300 g of dichloromethane into a 1000 ml jacketed flask equipped with a mechanical stirrer, a dropping funnel, and a thermometer. After mixing evenly, cool down to 5°C. Add 198 g of triphosgene and 200 g of dichloromethane into the dropping funnel. Under the condition of controlling the temperature not exceeding 10°C, drop the mixed solution of triphosgene and dichloromethane. After dropping, raise the temperature to room temperature and stir for 1 h. Filter off the insoluble substances by suction, and then concentrate the filtrate to dryness to obtain 330 g of white solid. Room temperature usually refers to 25°C, the same below.
[0022] Add 330 g of the white solid obtained in the first step, 1000 g of toluene, 120 g of methanol, and 1 g of p-toluenesulfonic acid into a 2000 ml three-necked flask equipped with a mechanical stirrer, a water separator, a condenser, and a thermometer. Heat up to reflux and react for 4 h. A total of 66 g of water is separated in the water separator. After the reaction is completed, concentrate the reaction solution to dryness to obtain 402 g of crude product. Add dichloromethane to the crude product, heat up to reflux, filter off the insoluble substances while it is hot, cool the filtrate to 5°C for crystallization, filter by suction, and dry to obtain 375 g of finished white solid, with a purity of 99.5% and a yield of 91.91%. The carbon nuclear magnetic spectrum of the product is shown in Figure 1 and the proton nuclear magnetic spectrum is shown in Figure 2 .
[0023] Example 2: Add 150 g of tartaric acid, 181.7 g of pyridine, and 150 g of dichloroethane into a 500 ml jacketed flask equipped with a mechanical stirrer, a dropping funnel, and a thermometer. After mixing evenly, cool down to 5°C. Add 103 g of triphosgene and 100 g of dichloroethane into the dropping funnel. Under the condition of controlling the temperature not exceeding 10°C, drop the mixed solution of triphosgene and dichloroethane. After dropping, raise the temperature to room temperature and stir for 1 h. Filter off the insoluble substances by suction, and then concentrate the filtrate to dryness to obtain 170 g of white solid.
[0024] In a 1000 ml three-necked flask equipped with a mechanical stirrer, a water separator, a condenser, and a thermometer, 170 g of the solid obtained in the first step, 510 g of xylene, 65 g of methanol, and 0.8 g of benzenesulfonic acid were added. The temperature was raised to reflux, and the reaction was carried out for 3 h. A total of 34 g of water was separated in the water separator. Then, the reaction solution was concentrated to dryness to obtain 200 g of a crude product. The crude product was added to dichloroethane and heated to reflux. Insoluble substances were filtered off while hot. The filtrate was cooled to 0 °C for crystallization, filtered by suction, and dried to obtain 192 g of a white solid product, with a purity of 99.3% and a yield of 94.1%.
[0025] Example 3: In a 1000 ml jacketed flask equipped with a mechanical stirrer, a dropping funnel, and a thermometer, 300 g of tartaric acid, 272 g of imidazole, and 300 g of chloroform were added. After mixing evenly, the temperature was lowered to 5 °C. In the dropping funnel, 205 g of triphosgene and 200 g of chloroform were added. The mixed solution of triphosgene and chloroform was added dropwise under the condition that the temperature was controlled not to exceed 10 °C. After the addition was completed, the temperature was raised to room temperature and stirred for 1 h. The insoluble substances were removed by suction filtration, and then the filtrate was concentrated to dryness to obtain 300 g of a white solid.
[0026] In a 2000 ml three-necked flask equipped with a mechanical stirrer, a water separator, a condenser, and a thermometer, 300 g of the white solid obtained in the first step, 1000 g of toluene, 110 g of methanol, and 1.5 g of p-toluenesulfonic acid were added. The temperature was raised to reflux, and the reaction was carried out for 6 h. A total of 60 g of water was separated in the water separator. Then, the reaction solution was concentrated to dryness to obtain 402 g of a crude product. The crude product was added to chloroform and heated to reflux. Insoluble substances were filtered off while hot. The filtrate was cooled to 0 °C for crystallization, filtered by suction, and dried to obtain 296 g of a white solid product, with a purity of 99.0% and a yield of 85.1%.
[0027] Example 4: In a 5000 ml jacketed flask equipped with a mechanical stirrer, a dropping funnel, and a thermometer, 1500 g of tartaric acid, 2300 g of triethylamine, and 1500 g of dichloromethane were added. After mixing evenly, the temperature was lowered to 5 °C. In the dropping funnel, 990 g of triphosgene and 1000 g of dichloromethane were added. The mixed solution of triphosgene and dichloromethane was added dropwise under the condition that the temperature was controlled not to exceed 10 °C. After the addition was completed, the temperature was raised to room temperature and stirred for 2 h. The insoluble substances were removed by suction filtration, and then the filtrate was concentrated to dryness to obtain 1700 g of a white solid.
[0028] In a 10000 ml three-necked flask equipped with a mechanical stirrer, a water separator, a condenser, and a thermometer, 1700 g of the white solid obtained in the first step, 4250 g of toluene, 649 g of methanol, and 5 g of p-toluenesulfonic acid were added. The temperature was raised to reflux, and the reaction was carried out for 4 h. A total of 340 g of water was separated in the water separator. Then, the reaction solution was concentrated to dryness to obtain 2010 g of a crude product. The crude product was added to dichloromethane and heated to reflux. Insoluble substances were filtered off while hot. The filtrate was cooled to 5 °C for crystallization, filtered by suction, and dried to obtain 1856 g of a white solid product, with a purity of 99.4% and a yield of 94.2%.
[0029] Example 5: Add 600 g of tartaric acid, 696 g of pyridine, and 600 g of dichloroethane into a 2000 ml jacketed flask equipped with mechanical stirring, dropping funnel, and thermometer. After mixing evenly, cool down to 5°C. Add 412 g of triphosgene and 400 g of dichloroethane into the dropping funnel. Dropwise add the mixture of triphosgene and dichloroethane under the condition that the temperature is controlled not exceeding 10°C. After the dropping is completed, raise the temperature to room temperature and stir for 1 h. Filter off the insoluble substances by suction, and then concentrate the filtrate to dryness to obtain 680 g of white solid.
[0030] Add 680 g of the white solid obtained in the first step, 2720 g of xylene, 256 g of methanol, and 3.2 g of benzenesulfonic acid into a 5000 ml three-necked flask equipped with mechanical stirring, water separator, condenser, and thermometer. Heat up to reflux and react for 5 h. A total of 136 g of water is separated out in the water separator. Then concentrate the reaction solution to dryness to obtain 800 g of crude product. Add the crude product into dichloroethane, heat up to reflux, filter off the insoluble substances while it is hot. Cool the filtrate to 5°C for crystallization, filter by suction, and dry to obtain 760 g of finished white solid, with a purity of 99.1% and a yield of 96.4%.
[0031] It can be obtained from the above examples that the present invention provides a compound - 5-(methoxycarbonyl)-2-oxo-1,3-dioxolane-4-carboxylic acid methyl ester, a related derivative of five-membered cyclic carbonate, and provides a preparation method thereof. The synthesis method is simple and easy to implement, the post-treatment method is easy to operate, the product has high purity and good yield.
Claims
1. A five-membered cyclic carbonate derivative is methyl 5-(methoxycarbonyl)-2-oxo-1,3-dioxolane-4-carboxylate, and its structural formula is as follows: 。 2. A preparation method of methyl 5-(methoxycarbonyl)-2-oxo-1,3-dioxolane-4-carboxylate, which is characterized in that: Comprising:
1. Add tartaric acid, acid-binding agent, and the first organic solvent into a reaction vessel, mix evenly and then cool down. Dissolve triphosgene in the first organic solvent to form a mixed solution of triphosgene and the first organic solvent. Under the condition that the temperature does not exceed 10°C, add the mixed solution of triphosgene and the first solvent dropwise into the reaction vessel. After the dropwise addition, raise the temperature to room temperature and stir. Filter by suction to remove insoluble substances, and concentrate the filtrate to dryness to obtain an intermediate; the acid-binding agent used is an organic weak base.
2. Add the intermediate obtained in the first step, the second organic solvent, a catalyst, and methanol into a reflux reaction vessel equipped with a water separator and a condenser, heat up to reflux for reaction to separate water. After the reaction ends, concentrate the reaction solution to dryness to obtain a crude product. The catalyst is selected from one or two of p-toluenesulfonic acid and benzenesulfonic acid; the crude product is added with the first organic solvent, heated to reflux, filtered while hot to remove insoluble substances, the filtrate is cooled for crystallization, filtered by suction, and dried to obtain the finished product of methyl 5-(methoxycarbonyl)-2-oxo-1,3-dioxolane-4-carboxylate.
3. The preparation method of methyl 5-(methoxycarbonyl)-2-oxo-1,3-dioxolane-4-carboxylate according to claim 2, which is characterized in that: In the first step, the molar ratio of tartaric acid, acid-binding agent, and triphosgene is 3:6 - 6.3:1 - 1.
05.
4. The preparation method of methyl 5-(methoxycarbonyl)-2-oxo-1,3-dioxolane-4-carboxylate according to claim 2, which is characterized in that: In the first step, the acid-binding agent is selected from one or more of triethylamine, pyridine, and imidazole.
5. The preparation method of methyl 5-(methoxycarbonyl)-2-oxo-1,3-dioxolane-4-carboxylate according to claim 2, which is characterized in that: The first organic solvent is one or more of dichloromethane, dichloroethane, and chloroform, and the dosage is 1.5 - 2 times the weight of tartaric acid.
6. The preparation method of methyl 5-(methoxycarbonyl)-2-oxo-1,3-dioxolane-4-carboxylate according to claim 2, which is characterized in that: In the second step, the molar ratio of the intermediate to methanol is 1:2 - 2.
1.
7. The preparation method of methyl 5-(methoxycarbonyl)-2-oxo-1,3-dioxolane-4-carboxylate according to claim 2, which is characterized in that: The dosage of the catalyst is 0.3% - 0.5% of the mass of the intermediate.
8. The preparation method of methyl 5-(methoxycarbonyl)-2-oxo-1,3-dioxolane-4-carboxylate according to claim 2, which is characterized in that: In the second step, the second organic solvent is selected from one or two of toluene and xylene, and the dosage is 2.5 - 4 times the mass of the intermediate.
9. The preparation method of methyl 5-(methoxycarbonyl)-2-oxo-1,3-dioxolane-4-carboxylate according to claim 2, which is characterized in that: In the second step, the temperature is controlled at 0 - 5°C when the filtrate is cooled for crystallization.