CN111978205A - Method and device for continuously synthesizing 4-chloro-2-methoxyimino ethyl acetoacetate - Google Patents
Method and device for continuously synthesizing 4-chloro-2-methoxyimino ethyl acetoacetate Download PDFInfo
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- CN111978205A CN111978205A CN202010807929.0A CN202010807929A CN111978205A CN 111978205 A CN111978205 A CN 111978205A CN 202010807929 A CN202010807929 A CN 202010807929A CN 111978205 A CN111978205 A CN 111978205A
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- C07C249/04—Preparation of compounds containing nitrogen atoms doubly-bound to a carbon skeleton of oximes
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- B01D53/14—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by absorption
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Abstract
The invention relates to a method and a device for continuously synthesizing 4-chloro-2-methoxyimino ethyl acetoacetate, wherein the method comprises the following steps: s1: pumping the ethanol solution of the 2-methoxy imino ethyl acetoacetate absorbing chlorine-containing gas into a nozzle, simultaneously, feeding chlorine into the nozzle, and uniformly mixing the two raw materials when flowing through the nozzle; s2: the mixed solution is uniformly formed into a film from the top of the falling film reactor, flows into the falling film reactor from the top of the falling film reactor and reacts in the falling film reactor; s3: the reaction liquid flows into the heat preservation kettle from the bottom of the falling film reactor to carry out heat preservation reaction; s4: and (3) removing chlorine-containing gas from the reaction solution after the temperature is kept for the target time through a degassing kettle to obtain an ethanol solution of the 4-chloro-2-methoxyimino ethyl acetoacetate. Compared with the prior art, the method obviously shortens the reaction time, improves the reaction efficiency, reduces the energy consumption, reduces the pollution, controls the polychlorinated substitute, finally reduces the cost and improves the reaction safety.
Description
Technical Field
The invention relates to the field of synthesis of medical intermediates, in particular to a method and a device for continuously synthesizing 4-chloro-2-methoxyimino acetoacetic acid ethyl ester.
Background
The aminothiovaleric acid is an important medical intermediate with high added value, and is mainly used for the synthesis of third-generation cephalosporin antibiotics. Ethyl 4-chloro-2-methoxyiminoacetoacetate is a key intermediate. The current industrial synthesis of 4-chloro-2-methoxyimino ethyl acetoacetate is mainly intermittent synthesis, and is obtained by chlorination of 2-methoxyimino ethyl acetoacetate with sulfonyl chloride or chlorine. (see journal of Chinese antibiotics 2012, 37(11), 837; intermediate of Fine chemical engineering 2012, (2) 27-29; CN1313452C)
4-chloro-2-methoxyiminoacetoacetate equation
The sulfonyl chloride method has high chlorination yield, but has large dosage, high raw material cost, long reaction time, bad smell of the sulfur-containing by-product, troublesome post-treatment, solvent recovery, complex operation and easy deterioration of chloride.
The chlorine method has low cost of raw materials for chlorination, but has lower yield and relatively more polychlorinated byproducts. At present, DMF is mostly used as a solvent, a nitrogen-containing alkaline catalyst is needed, operations such as water washing and the like are needed, and wastewater treatment is troublesome.
The two methods are intermittent reactions, the reaction is a strong exothermic reaction, a good coolant is required, and glycol cooling at the temperature of-10 to-20 ℃ is used in industrial production, so that chlorinated substances are separated out from the wall of a heat exchanger, the effect of the heat exchanger is influenced, and safety accidents are caused by over-temperature and over-pressure.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a method and a device for continuously synthesizing 4-chloro-2-methoxyimino ethyl acetoacetate.
The purpose of the invention can be realized by the following technical scheme:
the method for continuously synthesizing the 4-chloro-2-methoxyimino ethyl acetoacetate comprises the following steps:
s1: pumping the ethanol solution of the 2-methoxy imino ethyl acetoacetate absorbing chlorine-containing gas into a nozzle through a metering pump, simultaneously metering chlorine gas through a gas flow meter and then entering the nozzle, uniformly mixing the two raw materials when the two raw materials flow through the nozzle, and spraying the mixed solution to the top of the falling film reactor through the nozzle;
s2: the mixed solution is uniformly formed into a film from the top of the falling film reactor, flows into the falling film reactor from the top of the falling film reactor and reacts in the falling film reactor;
s3: the reaction liquid flows into the heat preservation kettle from the bottom of the falling film reactor to carry out heat preservation reaction;
s4: and (3) removing chlorine-containing gas from the reaction solution after the temperature is kept for the target time through a degassing kettle to obtain an ethanol solution of the 4-chloro-2-methoxyimino ethyl acetoacetate.
Further, chlorine-containing gases generated in the holding tank and the degassing tank were mixed with the raw material ethyl 2-methoxyiminoacetoacetate to obtain an ethanol solution of ethyl 2-methoxyiminoacetoacetate having absorbed chlorine-containing gases, which was used in S1.
Further, in the ethanol solution of ethyl 2-methoxyiminoacetoacetate in S1, the mass ratio of ethyl 2-methoxyiminoacetoacetate to ethanol is 1: (0.1 to 1);
the mol ratio of chlorine to 2-methoxy imino ethyl acetoacetate in S1 is 1: (1.1-1.3).
The ratio of ethyl 2-methoxyiminoacetoacetate to ethanol to chlorine is limited in a relatively strict range, and if the ratio is beyond the range, the quality of the final product is seriously affected.
Further, the falling film reactor in S1 is heated by a heating medium in an outer jacket, the temperature of the heating medium is 60-90 ℃, and the residence time of the reaction liquid in the falling film reactor is 60-240S.
Further, in S3, the reaction solution is kept warm by a heat preservation kettle, and the reaction solution is introduced into a degassing kettle until the content of the ethyl 2-methoxyiminoacetoacetate in the reaction solution is lower than 4%.
Further, the heat preservation temperature of the heat preservation kettle in the S3 is 20-30 ℃, and the heat preservation time is 10-20 hours.
Further, the degassing vessel in S4 was vacuum degassed by connecting a vacuum pump or by using a venturi device.
Further, the nozzle is made of one of engineering plastics, nickel alloy, hastelloy or 316L stainless steel.
The device for continuously synthesizing the 4-chloro-2-methoxyimino ethyl acetoacetate comprises a falling film reactor, a heat preservation kettle, a degassing kettle and an absorption assembly, wherein the device specifically comprises the following components:
the top of the falling film reactor is provided with a 2-methoxy imino ethyl acetoacetate inlet and a chlorine inlet, and the bottom of the falling film reactor is provided with a reaction liquid outlet;
the heat preservation kettle is provided with a heat preservation kettle inlet, a heat preservation kettle outlet and a heat preservation kettle exhaust port, and the heat preservation kettle inlet is connected with the reaction liquid outlet;
the degassing kettle is provided with a degassing kettle inlet, a degassing kettle outlet and a degassing kettle exhaust port;
the inlet of the degassing kettle is connected with the outlet of the heat preservation kettle, and the outlet of the degassing kettle continuously outputs a 4-chloro-2-methoxyimino ethyl acetoacetate product;
the absorption component is respectively connected with the exhaust port of the heat preservation kettle and the exhaust port of the degassing kettle, and 2-methoxyimino ethyl acetoacetate is introduced into the absorption component to be mixed with chlorine-containing gas from the exhaust port of the heat preservation kettle and the exhaust port of the degassing kettle in a gas-liquid manner, so that 2-methoxyimino ethyl acetoacetate absorbing the chlorine-containing gas is produced.
Further, the absorption assembly comprises three stages of countercurrent absorption towers which are connected in series in sequence;
the first-stage countercurrent absorption tower takes an ethanol solution of 2-methoxyimino ethyl acetoacetate as an absorbent;
the second stage countercurrent absorption tower takes water as an absorbent;
the third stage countercurrent absorption tower takes alkali solution as an absorbent.
Compared with the prior art, the invention has the following advantages:
1. according to the technical scheme, the heat exchange effect is improved through the falling film continuous reaction, the cooling temperature is increased, the product is prevented from being adhered to the wall of the heat exchanger, the energy consumption is reduced, and the safety is improved.
2. According to the technical scheme, the reaction temperature is improved, and meanwhile, a balanced heat transfer process is realized through the falling film reactor, so that the reaction time is greatly shortened, and the reaction efficiency is improved.
3. According to the technical scheme, the contact time of chlorine and the raw materials is shortened through the falling film continuous reaction, the generation of polychlorinated byproducts is reduced, and the reaction selectivity is improved.
4. According to the technical scheme, the residual chlorine is removed through further reaction of the heat-preservation kettle, otherwise, the quality and yield of the next reaction are influenced.
5. The technical scheme adopts ethanol as a solvent, does not need to be recycled or washed by water, and can be directly used for the next reaction.
6. The chlorine-containing gas collected and utilized in the invention contains chlorine and hydrogen chloride, and the redundant chlorine is absorbed by the raw materials, so that the utilization rate of the chlorine is improved, the pollution is reduced, and the reaction is autocatalytic by the hydrogen chloride, so that the reaction speed and selectivity are improved.
Drawings
FIG. 1 is a structural diagram of a device for continuously synthesizing ethyl 4-chloro-2-methoxyiminoacetoacetate.
In the figure: 1. a falling film reactor, 2, a heat preservation kettle, 3, a degassing kettle, 4, an absorption component, 41, a first-stage countercurrent absorption tower, 42, a second-stage countercurrent absorption tower, 43 and a third-stage countercurrent absorption tower.
Detailed Description
The invention is described in detail below with reference to the figures and specific embodiments.
The device for continuously synthesizing the 4-chloro-2-methoxyimino ethyl acetoacetate comprises a falling film reactor 1, a heat preservation kettle 2, a degassing kettle 3 and an absorption component 4, and is shown in figure 1.
The top of the falling film reactor 1 is provided with a 2-methoxy imino ethyl acetoacetate inlet and a chlorine inlet, and the bottom of the falling film reactor is provided with a reaction liquid outlet.
The heat preservation kettle 2 is provided with a heat preservation kettle inlet, a heat preservation kettle outlet and a heat preservation kettle exhaust port, the heat preservation kettle inlet is connected with the reaction liquid outlet, and the heat preservation kettle 2 realizes internal heat preservation through heating.
The degassing kettle 3 is provided with a degassing kettle inlet, a degassing kettle outlet and a degassing kettle exhaust port. And the inlet of the degassing kettle is connected with the outlet of the heat preservation kettle, and the outlet of the degassing kettle continuously outputs a 4-chloro-2-methoxyimino ethyl acetoacetate product.
The absorption component 4 is respectively connected with the exhaust port of the heat preservation kettle and the exhaust port of the degassing kettle, and 2-methoxyimino ethyl acetoacetate is introduced into the absorption component 4 to be mixed with chlorine-containing gas from the exhaust port of the heat preservation kettle and the exhaust port of the degassing kettle in a gas-liquid manner, so that 2-methoxyimino ethyl acetoacetate absorbing the chlorine-containing gas is produced. The absorption component 4 comprises three stages of countercurrent absorption towers which are sequentially connected in series, and the first stage of countercurrent absorption tower 41 takes 2-methoxyimino ethyl acetoacetate as an absorbent; the second stage countercurrent absorption tower 42 takes water as an absorbent; the third stage countercurrent absorption tower 43 uses an alkali solution as an absorbent.
Example 1
An ethanol solution which has absorbed a certain amount of 2-methoxyiminoacetoacetate of hydrogen chloride, 2-methoxyiminoacetoacetate and ethanol in a ratio of 1:0.2, was pumped into a nozzle by a pump, and the flow rate was controlled at 6kg/h (28.9 mol). Chlorine gas was passed through the nozzle and the chlorine flow rate was controlled at 783L/h (34.97 mol). The nozzle is made of engineering plastics, the temperature of an outer jacket of the falling film reactor is 85-90 ℃, and the reaction residence time is 60-65 seconds. The reaction solution enters a receiving heat preservation tank at 25-30 ℃. Degassing by a Venturi tube, and obtaining 4-chloro-2-methoxyimino acetoacetic ester ethanol solution after flowing out, wherein the 4-chloro-2-methoxyimino acetoacetic ester ethanol solution can be directly used for the next reaction without treatment, 7.21kg is obtained in 1 hour, the external standard content of HPLC is 77.4%, and the yield is 93.1%. Hydrochloric acid gas generated from the tail gas and redundant chlorine are absorbed by ethanol solution of raw material 2-methoxy imino ethyl acetoacetate, and the residual gas is absorbed by water and alkali. The absorbed raw material ethyl 2-methoxyiminoacetoacetate is returned to be used for the initial chlorination reaction.
Example 2
An ethanol solution which has absorbed a certain amount of 2-methoxyiminoacetoacetate of hydrogen chloride, 2-methoxyiminoacetoacetate and ethanol in a ratio of 1:0.1, was pumped into a nozzle by a pump, and the flow rate was controlled at 5.5kg/h (28.9 mol). Chlorine gas was passed through the nozzle and the chlorine flow rate was controlled at 712L/h (31.79 mol). The nozzle material is nickel alloy, the temperature of the outer jacket of the falling film reactor is 75-80 ℃, and the reaction residence time is 95-100 seconds. The reaction solution enters a receiving heat preservation tank at the temperature of between 20 and 25 ℃, vacuum degassing is carried out, and the 4-chloro-2-methoxyimino ethyl acetoacetate ethanol solution is obtained after flowing out and can be directly used for the next reaction without treatment, 6.56kg is obtained in 1 hour, the HPLC external standard quantitative content is 79.8 percent, and the yield is 87.3 percent. Hydrochloric acid gas generated from the tail gas and redundant chlorine are absorbed by ethanol solution of raw material 2-methoxy imino ethyl acetoacetate, and the residual gas is absorbed by water and alkali. The absorbed raw material ethyl 2-methoxyiminoacetoacetate is returned to be used for the initial chlorination reaction.
Example 3
The ethanol solution which has absorbed a certain amount of 2-methoxyiminoacetoacetate is pumped into a nozzle by a pump according to the ratio of 1:0.3 between 2-methoxyiminoacetoacetate and ethanol, and the flow rate is controlled to be 6.5kg/h (28.9 mol). Chlorine gas was fed into the nozzle and the chlorine flow rate was controlled at 841L/h (37.57 mol). The nozzle material is Hastelloy, the temperature of the outer jacket of the falling film reactor is 60-65 ℃, and the reaction residence time is 230-240 seconds. The reaction solution enters a receiving heat preservation tank at the temperature of between 20 and 25 ℃, vacuum degassing is carried out, and the 4-chloro-2-methoxyimino ethyl acetoacetate ethanol solution is obtained after flowing out and can be directly used for the next reaction without treatment, 7.62kg is obtained in 1 hour, the HPLC external standard quantitative content is 72.5 percent, and the yield is 92.2 percent. Hydrochloric acid gas generated from the tail gas and redundant chlorine are absorbed by ethanol solution of raw material 2-methoxy imino ethyl acetoacetate, and the residual gas is absorbed by water and alkali. The absorbed raw material ethyl 2-methoxyiminoacetoacetate is returned to be used for the initial chlorination reaction.
Example 4
The ethanol solution which has absorbed a certain amount of 2-methoxyiminoacetoacetate of hydrogen chloride, ethyl 2-methoxyiminoacetoacetate and ethanol in a ratio of 1:1, was pumped into a nozzle by a pump, and the flow rate was controlled at 10kg/h (28.9 mol). Chlorine gas was passed through the nozzle and the chlorine flow was controlled at 744.4L/h (33.23 mol). The nozzle is made of nickel, the temperature of an outer jacket of the falling film reactor is 70-75 ℃, and the reaction residence time is 160-165 seconds. The reaction solution enters a receiving heat preservation tank at 25-30 ℃. Degassing by a Venturi tube, and obtaining 4-chloro-2-methoxyimino acetoacetic acid ethyl ester ethanol solution after flowing out, wherein the ethanol solution can be directly used for the next reaction without treatment, 11.3kg is obtained in 1 hour, the HPLC external standard quantitative content is 49.2%, and the yield is 92.8%. Hydrochloric acid gas generated from the tail gas and redundant chlorine are absorbed by ethanol solution of raw material 2-methoxy imino ethyl acetoacetate, and the residual gas is absorbed by water and alkali. The absorbed raw material ethyl 2-methoxyiminoacetoacetate is returned to be used for the initial chlorination reaction.
The embodiments described above are described to facilitate an understanding and use of the invention by those skilled in the art. It will be readily apparent to those skilled in the art that various modifications to these embodiments may be made, and the generic principles described herein may be applied to other embodiments without the use of the inventive faculty. Therefore, the present invention is not limited to the above embodiments, and those skilled in the art should make improvements and modifications within the scope of the present invention based on the disclosure of the present invention.
Claims (10)
1. A method for continuously synthesizing 4-chloro-2-methoxyimino ethyl acetoacetate is characterized by comprising the following steps:
s1: pumping the ethanol solution of the 2-methoxyimino ethyl acetoacetate absorbing chlorine-containing gas into a nozzle through a metering pump, simultaneously metering chlorine gas through a gas flow meter and then feeding the chlorine gas into the nozzle, uniformly mixing the two raw materials when the two raw materials flow through the nozzle, and spraying the mixed solution to the top of a falling film reactor (1) through the nozzle;
s2: the mixed solution is uniformly formed into a film from the top of the falling film reactor (1), flows into the falling film reactor (1) from the top of the falling film reactor (1) and reacts in the falling film reactor (1);
s3: the reaction liquid flows into the heat preservation kettle (2) from the bottom of the falling film reactor to carry out heat preservation reaction;
s4: and (3) removing chlorine-containing gas from the reaction solution after the temperature is kept for the target time through a degassing kettle (3) to obtain an ethanol solution of the 4-chloro-2-methoxyimino ethyl acetoacetate.
2. The method for continuously synthesizing ethyl 4-chloro-2-methoxyiminoacetoacetate according to claim 1, wherein chlorine-containing gases generated in the holding tank (2) and the degassing tank (3) are mixed with the raw material ethyl 2-methoxyiminoacetoacetate to obtain an ethanol solution of ethyl 2-methoxyiminoacetoacetate absorbed with chlorine-containing gases, and the ethanol solution is used in S1.
3. The method for continuously synthesizing ethyl 4-chloro-2-methoxyiminoacetoacetate according to claim 1, wherein in the ethanol solution of ethyl 2-methoxyiminoacetoacetate in S1, the mass ratio of ethyl 2-methoxyiminoacetoacetate to ethanol is 1: (0.1 to 1);
the mol ratio of chlorine to 2-methoxy imino ethyl acetoacetate in S1 is 1: (1.1-1.3).
4. The method for continuously synthesizing ethyl 4-chloro-2-methoxyiminoacetoacetate according to claim 1, wherein the falling film reactor (1) in S1 is heated by a heating medium in an outer jacket, the temperature of the heating medium is 60-90 ℃, and the residence time of the reaction liquid in the falling film reactor (1) is 60-240S.
5. The method for continuously synthesizing ethyl 4-chloro-2-methoxyiminoacetoacetate according to claim 1, wherein the reaction solution is kept warm in the holding tank (2) in S3 until the content of ethyl 2-methoxyiminoacetoacetate in the reaction solution is lower than 4%, and the reaction solution is introduced into the degassing tank (3).
6. The method for continuously synthesizing ethyl 4-chloro-2-methoxyiminoacetoacetate according to claim 1, wherein the heat preservation temperature of the heat preservation kettle (2) in S3 is 20-30 ℃, and the heat preservation time is 10-20 h.
7. The method for continuously synthesizing ethyl 4-chloro-2-methoxyiminoacetoacetate according to claim 1, wherein the degassing kettle (3) in S4 is connected with a vacuum pump or vacuum degassing is carried out by adopting a Venturi device.
8. The method for continuously synthesizing ethyl 4-chloro-2-methoxyiminoacetoacetate according to claim 1, wherein the nozzle is made of one of engineering plastics, nickel alloy, Hastelloy or 316L stainless steel.
9. A device for continuously synthesizing 4-chloro-2-methoxyimino ethyl acetoacetate is characterized by comprising:
the top of the falling-film reactor (1) is provided with a 2-methoxyimino ethyl acetoacetate inlet and a chlorine inlet, and the bottom of the falling-film reactor is provided with a reaction liquid outlet;
the heat preservation kettle (2) is provided with a heat preservation kettle inlet, a heat preservation kettle outlet and a heat preservation kettle exhaust port, and the heat preservation kettle inlet is connected with the reaction liquid outlet;
the degassing kettle (3) is provided with a degassing kettle inlet, a degassing kettle outlet and a degassing kettle exhaust port;
the inlet of the degassing kettle is connected with the outlet of the heat preservation kettle, and the outlet of the degassing kettle continuously outputs a 4-chloro-2-methoxyimino ethyl acetoacetate product;
and the absorption component (4) is respectively connected with the exhaust port of the heat preservation kettle and the exhaust port of the degassing kettle, and 2-methoxyimino ethyl acetoacetate is introduced into the absorption component (4) to be mixed with chlorine-containing gas from the exhaust port of the heat preservation kettle and the exhaust port of the degassing kettle in a gas-liquid manner, so that 2-methoxyimino ethyl acetoacetate absorbing the chlorine-containing gas is produced.
10. The plant for the continuous synthesis of ethyl 4-chloro-2-methoxyiminoacetoacetate according to claim 9, wherein the absorption module (4) comprises three countercurrent absorption towers connected in series in turn;
the first-stage countercurrent absorption tower takes an ethanol solution of 2-methoxyimino ethyl acetoacetate as an absorbent;
the second stage countercurrent absorption tower takes water as an absorbent;
the third stage countercurrent absorption tower takes alkali solution as an absorbent.
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| CN107857741A (en) * | 2017-12-15 | 2018-03-30 | 山东金城医药化工有限公司 | The new technique for synthesizing of ainothiazoly loximate |
| CN109232470A (en) * | 2018-08-21 | 2019-01-18 | 山东金城柯瑞化学有限公司 | A kind of new process synthesizing ainothiazoly loximate |
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