CN105152976A - Improved process of ethyl N-cyanoethanimideate preparation method - Google Patents
Improved process of ethyl N-cyanoethanimideate preparation method Download PDFInfo
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- CN105152976A CN105152976A CN201510448875.2A CN201510448875A CN105152976A CN 105152976 A CN105152976 A CN 105152976A CN 201510448875 A CN201510448875 A CN 201510448875A CN 105152976 A CN105152976 A CN 105152976A
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Abstract
The invention relates to the field of chemical engineering, and particularly relates to an improved process of an ethyl N-cyanoethanimideate preparation method. According to the process, acetonitrile, absolute ethanol, hydrogen chloride and a cyanamide aqueous solution having a concentration of 28 percent are mainly adopted as main reacting raw materials to react and prepare the ethyl N-cyanoethanimideate with high yield. The process has the advantages that the yield of the ethyl N-cyanoethanimideate is increased to 90 percent, the content of the ethyl N-cyanoethanimideate is more than or equal to 99.5 percent, and the reacting process is smooth and safe.
Description
technical field:
The present invention relates to chemical field, be specifically related to the improving technique of the preparation method of cyanaoethyl methacrylate.
Background technology
Cyanaoethyl methacrylate is a kind of important intermediate, and it is for the synthesis of the intermediate of agricultural chemicals acetamiprid.
Cyanaoethyl methacrylate reacts preparation by acetonitrile, ethanol, hydrogenchloride, cyanamide, and reaction principle is:
Acetonitrile ethanolic hydrogen chloride ethyliminum ether hydrochloride
Cyanamide cyanaoethyl methacrylate
From above reaction principle, reaction point two steps are carried out, the first step salt-forming reaction is under toluene solvant exists, carry out under anhydrous condition, high yield obtains ethyliminum ether hydrochloride, then in the first step reaction solution, adds the 28% cyanamide aqueous solution, carries out into ester reaction, regulate pH value during reaction, temperature of reaction of controlling well obtains product cyanaoethyl methacrylate.
Second step uses the 28% cyanamide aqueous solution in becoming ester to react, and now, ethyliminum ether hydrochloride is very easy to side reaction occurs, and cause product yield to reduce, therefore, improving technique condition, it is object of the present invention that high yield prepares cyanaoethyl methacrylate.
Summary of the invention
In order to solve above technical problem, the present invention proposes a kind of preparation technology of cyanaoethyl methacrylate, perfect technology, improving technique condition, and high yield prepares cyano methyl ester.
In order to reach foregoing invention object, the preparation technology of a kind of cyanaoethyl methacrylate of the present invention, is characterized in that: be mainly and adopt acetonitrile, dehydrated alcohol, hydrogenchloride, the 28% cyanamide aqueous solution to be principal reaction raw material, high yield reaction prepares cyanaoethyl methacrylate.
A preparation technology for cyanaoethyl methacrylate, concrete steps are as follows:
1) acetonitrile, dehydrated alcohol, solvent toluene are added in the synthesis reaction vessel of 3000L, open and stir and chilled brine, material in reactor is cooled to 0-5 DEG C, at the temperature disclosed above, starts to pass into hydrogen chloride gas, usually about need 9-10 hour; After ventilation terminates, material in reactor is raised to 25-30 DEG C gradually, start salify insulation reaction 7-8 hour, salt-forming reaction terminates;
2) under agitation, reaction solution is cooled to 0 DEG C, slowly adds volatile salt, then add the 28% cyanamide aqueous solution, regulate between pH value to 6-7 with 30% aqueous sodium hydroxide solution, at 20-25 DEG C of insulation reaction 0.5-1 hour, become ester reaction to terminate;
3) between 25-35 DEG C, leave standstill half an hour, organic layer is reclaimed in layering, and organic layer obtains product cyanaoethyl methacrylate through vacuum distilling, gc analysis content: 99.7%, molar yield: 91.65%.
The first step salt-forming reaction condition: logical hydrogen chloride gas temperature of reaction: 0-5 DEG C, salify leads to the hydrogenchloride time: 9-10 hour, salify insulation reaction temperature: 25-30 DEG C, salify insulation reaction time: 7-8 hour;
Second step becomes ester reaction conditions: control temperature at 20-25 DEG C, pH value: 6-7; Reaction times: 0.5-1 hour.
Further, the mol ratio of described acetonitrile, dehydrated alcohol, hydrogenchloride, 28% cyanamide is 1:1:1.05-1.1:1; The weight ratio of toluene and acetonitrile: 1:1.5-1.7.
Further, cushion PH with volatile salt, the physical properties of heat absorption when simultaneously utilizing volatile salt to dissolve, help to control well temperature of reaction, minimizing side reaction preferably.
The invention has the advantages that:
1. the improving technique of cyanaoethyl methacrylate preparation method, makes the yield of cyanaoethyl methacrylate bring up to 90%;
2. content >=99.5% of product cyanaoethyl methacrylate;
3. reaction process is mild, safety.
Embodiment
Embodiment 1: add in the synthesis reaction vessel of 3000L by 287Kg (7Kmol) acetonitrile, 322Kg (7Kmol) dehydrated alcohol, 430.5Kg solvent toluene, opens and stirs and chilled brine, material in reactor is cooled to 0-5 DEG C.At the temperature disclosed above, start to pass into hydrogen chloride gas 268.5Kg (7.36Kmol), usually about need 10 hours.After ventilation terminates, material in reactor is raised to 25-30 DEG C gradually, start salify insulation reaction 8 hours, salt-forming reaction terminates.
Under agitation, reaction solution is cooled to 0 DEG C, slowly adds volatile salt 50Kg, then 28% cyanamide aqueous solution 1050Kg (7Kmol) is added, regulate between pH value to 6.0-6.5 with 30% aqueous sodium hydroxide solution, 20-25 DEG C of insulation reaction 1 hour, become ester reaction to terminate.
Between 25-35 DEG C, leave standstill half an hour, organic layer is reclaimed in layering, and organic layer obtains product cyanaoethyl methacrylate through vacuum distilling: 718.5Kg, gc analysis content: 99.7%, molar yield: 91.65%.
Embodiment 2: add in the synthesis reaction vessel of 3000L by 287Kg (7Kmol) acetonitrile, 322Kg (7Kmol) dehydrated alcohol, 485Kg solvent toluene, opens and stirs and chilled brine, material in reactor is cooled to 0-5 DEG C.At the temperature disclosed above, start to pass into hydrogen chloride gas 270Kg (7.40Kmol), usually about need 9 hours.After ventilation terminates, material in reactor is raised to 25-30 DEG C gradually, start salify insulation reaction 7 hours, salt-forming reaction terminates.
Under agitation, reaction solution is cooled to 0 DEG C, slowly adds volatile salt 50Kg, then 28% cyanamide aqueous solution 1050Kg (7Kmol) is added, regulate between pH value to 6.0-6.5 with 30% aqueous sodium hydroxide solution, 20-25 DEG C of insulation reaction 1 hour, become ester reaction to terminate.
Between 25-35 DEG C, leave standstill half an hour, organic layer is reclaimed in layering, and organic layer obtains product cyanaoethyl methacrylate through vacuum distilling: 720Kg, gc analysis content: 99.6%, molar yield: 91.84%.
Claims (5)
1. a cyanaoethyl methacrylate preparation method's improving technique, is characterized in that: be mainly and adopt acetonitrile, ethanol, anhydrous hydrogen chloride, the 28% cyanamide aqueous solution to be principal reaction raw material, take toluene as solvent, high yield reaction prepares cyanaoethyl methacrylate.
2. the improving technique of a kind of cyanaoethyl methacrylate preparation method according to claim 1, is characterized in that:
1) acetonitrile, dehydrated alcohol, solvent toluene are added in the synthesis reaction vessel of 3000L, open and stir and chilled brine, material in reactor is cooled to 0-5 DEG C, at the temperature disclosed above, starts to pass into hydrogen chloride gas, usually about need 9-10 hour; After ventilation terminates, material in reactor is raised to 25-30 DEG C gradually, start salify insulation reaction 7-8 hour, salt-forming reaction terminates;
2) under agitation, reaction solution is cooled to 0 DEG C, slowly adds volatile salt, then add the 28% cyanamide aqueous solution, regulate between pH value to 6-7 with 30% aqueous sodium hydroxide solution, at 20-25 DEG C of insulation reaction 0.5-1 hour, become ester reaction to terminate;
3) between 25-35 DEG C, leave standstill half an hour, organic layer is reclaimed in layering, and organic layer obtains product cyanaoethyl methacrylate through vacuum distilling, gc analysis content: 99.7%, molar yield: 91.65%.
3. the improving technique of a kind of cyanaoethyl methacrylate preparation method according to claim 1, is characterized in that: the mol ratio of described acetonitrile, ethanol, anhydrous hydrogen chloride, 28% cyanamide is 1:1:1-1.05:1.
4. the improving technique of a kind of cyanaoethyl methacrylate preparation method according to claim 1, is characterized in that: the weight ratio of toluene and acetonitrile: 1:1.5-1.7.
5. the improving technique of a kind of cyanaoethyl methacrylate preparation method according to claim 1, is characterized in that: cushion pH value with volatile salt, the physical properties of heat absorption when simultaneously utilizing volatile salt to dissolve, and helps to control well temperature of reaction, minimizing side reaction preferably.
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| CN201510448875.2A CN105152976A (en) | 2015-07-28 | 2015-07-28 | Improved process of ethyl N-cyanoethanimideate preparation method |
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| CN201510448875.2A CN105152976A (en) | 2015-07-28 | 2015-07-28 | Improved process of ethyl N-cyanoethanimideate preparation method |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106187868A (en) * | 2016-07-15 | 2016-12-07 | 南通天泽化工有限公司 | A kind of preparation method of Acetamiprid |
| CN110256295A (en) * | 2019-07-03 | 2019-09-20 | 宁夏贝利特生物科技有限公司 | The synthetic method of N- cyan ethyl ethylimidoote |
| CN111072519A (en) * | 2019-12-17 | 2020-04-28 | 南通天泽化工有限公司 | Preparation method of cyanoethyl ester |
| CN111533669A (en) * | 2020-06-02 | 2020-08-14 | 宁夏东吴农化股份有限公司 | Continuous production process of cyanoethyl ester |
| CN112898183A (en) * | 2021-01-25 | 2021-06-04 | 宁夏东吴农化股份有限公司 | Method for synthesizing cyanoethyl ester by base catalysis in microchannel reactor |
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| US4587337A (en) * | 1984-03-27 | 1986-05-06 | Skw Trostberg Aktiengesellschaft | Process for the preparation of 2-amino-s-triazines |
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2015
- 2015-07-28 CN CN201510448875.2A patent/CN105152976A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4587337A (en) * | 1984-03-27 | 1986-05-06 | Skw Trostberg Aktiengesellschaft | Process for the preparation of 2-amino-s-triazines |
Non-Patent Citations (1)
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| 陆雪良 等: "乙亚氨酸乙酯盐酸盐的制备新工艺研究", 《应用化工》 * |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106187868A (en) * | 2016-07-15 | 2016-12-07 | 南通天泽化工有限公司 | A kind of preparation method of Acetamiprid |
| CN110256295A (en) * | 2019-07-03 | 2019-09-20 | 宁夏贝利特生物科技有限公司 | The synthetic method of N- cyan ethyl ethylimidoote |
| CN111072519A (en) * | 2019-12-17 | 2020-04-28 | 南通天泽化工有限公司 | Preparation method of cyanoethyl ester |
| CN111072519B (en) * | 2019-12-17 | 2022-05-27 | 南通天泽化工有限公司 | Preparation method of cyanoethyl ester |
| CN111533669A (en) * | 2020-06-02 | 2020-08-14 | 宁夏东吴农化股份有限公司 | Continuous production process of cyanoethyl ester |
| CN112898183A (en) * | 2021-01-25 | 2021-06-04 | 宁夏东吴农化股份有限公司 | Method for synthesizing cyanoethyl ester by base catalysis in microchannel reactor |
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Application publication date: 20151216 |