CN106117061B - The synthetic method of chloro-carbonic acid -2- chloroethene esters - Google Patents
The synthetic method of chloro-carbonic acid -2- chloroethene esters Download PDFInfo
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- CN106117061B CN106117061B CN201610447459.5A CN201610447459A CN106117061B CN 106117061 B CN106117061 B CN 106117061B CN 201610447459 A CN201610447459 A CN 201610447459A CN 106117061 B CN106117061 B CN 106117061B
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C68/00—Preparation of esters of carbonic or haloformic acids
- C07C68/02—Preparation of esters of carbonic or haloformic acids from phosgene or haloformates
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Abstract
The present invention provides a kind of synthetic method of 2 chloroethene ester of chloro-carbonic acid, includes the following steps：It is passed through phosgene in the solvent for being cooled to 10 DEG C ~ 5 DEG C, obtains gas-liquid mixture；The ethylene oxide being passed through in the gas-liquid mixture after phosgene and vaporization, reacts 2 hours at 0 DEG C ~ 10 DEG C, obtains reactant；Above-mentioned reactant is warming up to 20 DEG C ~ 40 DEG C, phosgene is removed, obtains 2 chloroethene ester of chloro-carbonic acid.The synthetic method of 2 chloroethene ester of above-mentioned chloro-carbonic acid does not generate that hydrogen chloride gas, product acidity are easily-controllable and yield is higher.
Description
Technical field
The present invention relates to the field of chemical synthesis, more particularly to the synthetic method of chloro-carbonic acid -2- chloroethene esters.
Background technology
Chloro-carbonic acid -2- chloroethene esters are used as medicine, pesticide intermediate, harsher to product quality requirement, especially product acid
Degree requires extremely stringent.The synthetic method of traditional chloro-carbonic acid -2- chloroethene esters is mainly chlorethanol phosgenation, and this method uses chloroethene
It is passed through phosgene after alcohol sub-cooled thereto again, then insulation reaction is complete, then heats up and catch up with light.But this method generates largely
Hydrogen chloride emission, product acidity is not easy to control, and yield is relatively low.
Invention content
Based on this, it is necessary to for traditional chloro-carbonic acid -2- chloroethene esters synthetic method generate a large amount of hydrogen chloride emission,
The problem that product acidity is not easy to control, yield is relatively low provides and a kind of does not generate that hydrogen chloride gas, product acidity is easily-controllable and yield
The synthetic method of higher chloro-carbonic acid -2- chloroethene esters.
A kind of synthetic method of chloro-carbonic acid -2- chloroethene esters, includes the following steps：
It is passed through phosgene in the solvent for being cooled to -10 DEG C ~ -5 DEG C, obtains gas-liquid mixture；
The ethylene oxide being passed through in the gas-liquid mixture after phosgene and vaporization, reacts 2 ~ 4 hours at 0 DEG C ~ 10 DEG C, obtains
To reactant；
The reactant is warming up to 20 DEG C ~ 40 DEG C, phosgene is removed, obtains chloro-carbonic acid -2- chloroethene esters.
The solvent is toluene, chlorobenzene or chloro-carbonic acid -2- chloroethene esters in one of the embodiments,.
The step of ethylene oxide being passed through in the gas-liquid mixture in one of the embodiments, after phosgene and vaporization
In, the mass ratio of the ethylene oxide and phosgene is 1:2.8~3.2.
The method for removing phosgene is specially in one of the embodiments,：It is passed through nitrogen and drives away phosgene, until phosgene
It eliminates.
The speed that is passed through of the nitrogen is 15L/h ~ 25L/h in one of the embodiments,.
In one of the embodiments, when the solvent is toluene or chlorobenzene, the step of the removings phosgene after and also
Include the following steps：
Rectifying removes solvent.
The synthetic method of above-mentioned chloro-carbonic acid -2- chloroethene esters carries out opening, no chlorine by ethylene oxide and phosgene
Change hydrogen to generate, and phosgene is easier than hydrogen chloride gas eliminates, acidity is easy to control.In addition, by the way that first a part of phosgene is dissolved in
In solvent, the utilization rate of phosgene can be improved, increases the yield of product.
Specific implementation mode
In order to make the foregoing objectives, features and advantages of the present invention clearer and more comprehensible, below to the specific reality of the present invention
The mode of applying is described in detail.Many details are elaborated in the following description in order to fully understand the present invention.But
The invention can be embodied in many other ways as described herein, and those skilled in the art can be without prejudice to this hair
Similar improvement is done in the case of bright intension, therefore the present invention is not limited to the specific embodiments disclosed below.
A kind of synthetic method of chloro-carbonic acid -2- chloroethene esters, includes the following steps：
S110, it is passed through phosgene in the solvent for being cooled to -10 DEG C ~ -5 DEG C, obtains gas-liquid mixture.
Wherein, solvent is toluene, chlorobenzene or chloro-carbonic acid -2- chloroethene esters.
Toluene, chlorobenzene can preferably absorb phosgene, improve the utilization rate of phosgene as solvent.Chloro-carbonic acid -2- chloroethene esters are made
For solvent, phosgene can not only be preferably absorbed, and subsequently no longer need to detach solvent, product quality is high, production cost is low.
The boiling point of phosgene is 8.2 DEG C, and solvent, which is cooled to -10 DEG C ~ -5 DEG C, so that phosgene is liquefied, be conducive to react into
Row increases product yield.
It should be noted that phosgene can be pure phosgene in step S110, can also be containing foreign gas（Carbon monoxide
And chlorine）Phosgene, the volume content of phosgene is 72% ~ 75% in the phosgene containing foreign gas.
S120, the ethylene oxide being passed through in above-mentioned gas-liquid mixture after phosgene and vaporization, it is small that 2 are reacted at 0 DEG C ~ 10 DEG C
When, obtain reactant.
Wherein, in the step of ethylene oxide being passed through in above-mentioned gas-liquid mixed after phosgene and vaporization, ethylene oxide and light
The mass ratio of gas is 1:2.8~3.2.
It should be noted that phosgene can be pure phosgene in step S120, can also be containing foreign gas（Carbon monoxide
And chlorine）Phosgene, the volume content of phosgene is 72% ~ 75% in the phosgene containing foreign gas.
S130, above-mentioned reactant is warming up to 20 DEG C ~ 40 DEG C, removes phosgene, obtains chloro-carbonic acid -2- chloroethene esters.
In the present embodiment, the method for removing phosgene is specially：It is passed through nitrogen and drives away phosgene, until phosgene eliminates.
Wherein, the speed that is passed through of nitrogen is 20L/h ~ 25L/h.
Further include after the step of being appreciated that when solvent is toluene or chlorobenzene, phosgene is removed in above-mentioned steps S130
Following steps：Rectifying removes solvent.
The synthetic method of above-mentioned chloro-carbonic acid -2- chloroethene esters carries out opening, no chlorine by ethylene oxide and phosgene
Change hydrogen to generate, and phosgene is easier than hydrogen chloride gas eliminates, acidity is easy to control.
It is specific embodiment below.
Embodiment 1
It is passed through the phosgene of 10L/h in the chloro-carbonic acid -2- chloroethene esters that 200g is cooled to -5 DEG C 1.5 hours, it is mixed to obtain gas-liquid
Close object.
The phosgene and the ethylene oxide 10 hours after 30L/h vaporizations that 40L/h is passed through in above-mentioned gas-liquid mixture, at 0 DEG C
Reaction 2 hours, obtains reactant.
Above-mentioned reactant is warming up to 20 DEG C, the nitrogen for being passed through 15L/h drives away phosgene, until phosgene eliminates, obtains 1670g
Chloro-carbonic acid -2- chloroethene esters（Contain the 200g chloro-carbonic acid -2- chloroethene esters as solvent）.
It is computed, the yield of chloro-carbonic acid -2- chloroethene esters is 99.1%.The mass concentration of product free acid is 0.07%.
Embodiment 2
It is passed through the phosgene of 10L/h in the chloro-carbonic acid -2- chloroethene esters that 200g is cooled to -10 DEG C 1.5 hours, it is mixed to obtain gas-liquid
Close object.
The phosgene and the ethylene oxide 10 hours after 30L/h vaporizations that 40L/h is passed through in above-mentioned gas-liquid mixture, at 10 DEG C
Reaction 4 hours, obtains reactant.
Above-mentioned reactant is warming up to 40 DEG C, the nitrogen for being passed through 25L/h drives away phosgene, until phosgene eliminates, obtains 1676g
Chloro-carbonic acid -2- chloroethene esters（Contain the 200g chloro-carbonic acid -2- chloroethene esters as solvent）.
It is computed, the yield of chloro-carbonic acid -2- chloroethene esters is 99.5%.The mass concentration of product free acid is 0.06%.
Embodiment 3
It is passed through the phosgene of 10L/h in the toluene that 200g is cooled to -5 DEG C 1.5 hours, obtains gas-liquid mixture.
The phosgene and the ethylene oxide 10 hours after 30L/h vaporizations that 40L/h is passed through in above-mentioned gas-liquid mixture, at 0 DEG C
Reaction 2 hours, obtains reactant.
Above-mentioned reactant is warming up to 20 DEG C, the nitrogen for being passed through 15L/h drives away phosgene, until phosgene eliminates, rectifying removes
Toluene obtains 1461g chloro-carbonic acid -2- chloroethene esters.
It is computed, the yield of chloro-carbonic acid -2- chloroethene esters is 98.5%.The mass concentration of product free acid is 0.08%.
Embodiment 4
It is passed through the phosgene of 10L/h in the chlorobenzene that 200g is cooled to -5 DEG C 1.5 hours, obtains gas-liquid mixture.
The phosgene and the ethylene oxide 10 hours after 30L/h vaporizations that 40L/h is passed through in above-mentioned gas-liquid mixture, at 0 DEG C
Reaction 2 hours, obtains reactant.
Above-mentioned reactant is warming up to 20 DEG C, the nitrogen for being passed through 20L/h drives away phosgene, until phosgene eliminates, rectifying removes
Chlorobenzene obtains 1463g chloro-carbonic acid -2- chloroethene esters.
It is computed, the yield of chloro-carbonic acid -2- chloroethene esters is 98.6%.The mass concentration of product free acid is 0.08%.
Several embodiments of the invention above described embodiment only expresses, the description thereof is more specific and detailed, but simultaneously
Cannot the limitation to the scope of the claims of the present invention therefore be interpreted as.It should be pointed out that for those of ordinary skill in the art
For, without departing from the inventive concept of the premise, various modifications and improvements can be made, these belong to the guarantor of the present invention
Protect range.Therefore, the protection domain of patent of the present invention should be determined by the appended claims.
Claims (6)
1. a kind of synthetic method of chloro-carbonic acid -2- chloroethene esters, which is characterized in that include the following steps：
It is passed through phosgene in the solvent for being cooled to -10 DEG C ~ -5 DEG C, obtains gas-liquid mixture；
The ethylene oxide being passed through in the gas-liquid mixture after phosgene and vaporization, reacts 2 ~ 4 hours at 0 DEG C ~ 10 DEG C, obtains anti-
Answer object；
The reactant is warming up to 20 DEG C ~ 40 DEG C, phosgene is removed, obtains chloro-carbonic acid -2- chloroethene esters.
2. the synthetic method of chloro-carbonic acid -2- chloroethene esters according to claim 1, which is characterized in that the solvent be toluene,
Chlorobenzene or chloro-carbonic acid -2- chloroethene esters.
3. the synthetic method of chloro-carbonic acid -2- chloroethene esters according to claim 1, which is characterized in that in the gas-liquid mixed
In the step of ethylene oxide being passed through in object after phosgene and vaporization, the mass ratio of the ethylene oxide and phosgene is 1:2.8~3.2.
4. the synthetic method of chloro-carbonic acid -2- chloroethene esters according to claim 1, which is characterized in that the removing phosgene
Method is specially：It is passed through nitrogen and drives away phosgene, until phosgene eliminates.
5. the synthetic method of chloro-carbonic acid -2- chloroethene esters according to claim 4, which is characterized in that the nitrogen is passed through
Speed is 15L/h ~ 25L/h.
6. the synthetic method of chloro-carbonic acid -2- chloroethene esters according to claim 2, which is characterized in that when the solvent is first
When benzene or chlorobenzene, the step of the removing phosgene after it is further comprising the steps of：
Rectifying removes solvent.
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| CN111662176B (en) * | 2020-06-10 | 2023-01-24 | 湖南维摩新材料有限公司 | Method for synthesizing n-hexyl chloroformate by phosgene method |
| CN111792996B (en) * | 2020-06-10 | 2022-12-13 | 湖南维摩新材料有限公司 | Method for synthesizing chloroformic acid-2-chloroethyl ester by phosgene method |
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| DE2346309A1 (en) * | 1973-09-14 | 1975-04-03 | Basf Ag | PROCESS FOR THE PREPARATION OF CHLORALKYL-CHLOROCARBON EASTERS |
| US4120888A (en) * | 1978-01-26 | 1978-10-17 | Minerec Corporation | Preparation of chlorine-substituted chloroformates |
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Denomination of invention: The synthetic method of chloroformic acid-2-chloroethyl ester Effective date of registration: 20220801 Granted publication date: 20180817 Pledgee: Hunan Linxiang rural commercial bank Limited by Share Ltd. Pledgor: HUNAN GOFAR FINE CHEMICAL TECH. CO.,LTD. Registration number: Y2022980011705 |