CN111978205B - Method and device for continuously synthesizing 4-chloro-2-methoxyiminoacetoacetic acid ethyl ester - Google Patents
Method and device for continuously synthesizing 4-chloro-2-methoxyiminoacetoacetic acid ethyl ester Download PDFInfo
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- CN111978205B CN111978205B CN202010807929.0A CN202010807929A CN111978205B CN 111978205 B CN111978205 B CN 111978205B CN 202010807929 A CN202010807929 A CN 202010807929A CN 111978205 B CN111978205 B CN 111978205B
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
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- C07C249/04—Preparation of compounds containing nitrogen atoms doubly-bound to a carbon skeleton of oximes
- C07C249/12—Preparation of compounds containing nitrogen atoms doubly-bound to a carbon skeleton of oximes by reactions not involving the formation of oxyimino groups
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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-methoxyiminoacetoacetic acid ethyl ester, wherein the method comprises the following steps: s1: pumping the ethanol solution of the ethyl 2-methoxyiminoacetoacetate which absorbs chlorine-containing gas into a nozzle, and simultaneously, enabling chlorine to enter the nozzle, so that uniform mixing is realized when two raw materials flow through the nozzle; s2: the mixed solution uniformly forms a film from the top of the falling film reactor, flows down from the top of the falling film reactor to the inside of the falling film reactor, and reacts in the inside of 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 liquid after the heat preservation for target time through a degassing kettle to obtain an ethanol solution of 4-chloro-2-methoxyiminoacetoacetic acid ethyl ester. Compared with the prior art, the method has the advantages of obviously shortening the reaction time, improving the reaction efficiency, reducing the energy consumption, reducing the pollution, controlling the polychloride, finally reducing the cost and improving the safety of the reaction.
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-methoxyiminoacetoacetic acid ethyl ester.
Background
The amithiavaleric acid is an important medical intermediate with high added value, and is mainly used for synthesizing third-generation cephalosporin antibiotics. Ethyl 4-chloro-2-methoxyiminoacetoacetate is a key intermediate. At present, the industrialized synthesis of 4-chloro-2-methoxyiminoacetoacetate is mainly performed in batch, and is obtained by chloridizing 2-methoxyiminoacetoacetate with sulfonyl chloride or chlorine. ( See journal of chinese antibiotics 2012, 37 (11), 837; fine chemical intermediate 2012, (2) 27-29; CN1313452C )
4-chloro-2-methoxyiminoacetoacetic acid ethyl ester reaction equation
The sulfonyl chloride method has the advantages of high chlorination yield, high consumption, high raw material cost, long reaction time, bad smell of the sulfur-containing byproducts, troublesome post-treatment, solvent recovery, complex operation and easy degradation of the chloro.
The chlorine method has low cost of chlorinated raw materials but lower yield, and the polychlorinated byproducts are relatively more. At present, DMF is mostly used as a solvent, a nitrogenous basic catalyst is needed, washing and other operations are needed, and wastewater treatment is troublesome.
Both the above two methods are batch reactions, the reaction is a strong exothermic reaction, a good coolant is needed, and in the industrial production, ethylene glycol cooling at-10 to-20 ℃ can cause chloride to be separated out on the wall of a heat exchanger, the effect of the heat exchanger is affected, 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-methoxyiminoacetoacetic acid ethyl ester.
The aim of the invention can be achieved by the following technical scheme:
the method for continuously synthesizing the 4-chloro-2-methoxyiminoacetoacetic acid ethyl ester comprises the following steps:
s1: pumping an ethanol solution of the 2-methoxyiminoacetoacetic acid ethyl ester which absorbs chlorine-containing gas into a nozzle after passing through a metering pump, metering chlorine gas by a gas flowmeter, and then entering the nozzle, wherein two raw materials are uniformly mixed when flowing through the nozzle, and the mixed solution is sprayed to the top of a falling film reactor through the nozzle;
s2: the mixed solution uniformly forms a film from the top of the falling film reactor, flows down from the top of the falling film reactor to the inside of the falling film reactor, and reacts in the inside of 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 liquid after the heat preservation for target time through a degassing kettle to obtain an ethanol solution of 4-chloro-2-methoxyiminoacetoacetic acid ethyl ester.
Further, chlorine-containing gas generated in the heat preservation kettle and the degassing kettle is mixed with a raw material of the ethyl 2-methoxyiminoacetoacetate to obtain an ethanol solution of the ethyl 2-methoxyiminoacetoacetate absorbing the chlorine-containing gas, and the ethanol solution is used in S1.
Further, in the ethanol solution of the 2-methoxyiminoacetoacetate in the S1, the mass ratio of the 2-methoxyiminoacetoacetate to the ethanol is 1: (0.1 to 1);
the mol ratio of chlorine to 2-methoxyiminoacetoacetic acid ethyl ester in the S1 is 1: (1.1-1.3).
The ratio of the ethyl 2-methoxyiminoacetoacetate to ethanol and chlorine is severely limited, and once the ratio exceeds the secondary limited 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 solution in the falling film reactor is 60-240S.
And further, in the step S3, the reaction solution is subjected to heat preservation through a heat preservation kettle, and the reaction solution is introduced into a degassing kettle when the content of the 2-methoxyiminoacetoacetic acid ethyl ester in the reaction solution is lower than 4%.
Further, the heat preservation temperature of the heat preservation kettle in the step S3 is 20-30 ℃ and the heat preservation time is 10-20 h.
Further, the degassing kettle in S4 performs vacuum degassing by connecting a vacuum pump or using a venturi device.
Further, the nozzle is made of one of engineering plastics, nickel alloy, hastelloy or 316L stainless steel.
The invention relates to a device for continuously synthesizing 4-chloro-2-methoxyiminoacetoacetic acid ethyl ester, which comprises a falling film reactor, a heat preservation kettle, a degassing kettle and an absorption component, wherein the device comprises the following components:
the top of the falling film reactor is provided with a 2-methoxyiminoacetoacetic acid ethyl ester 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 4-chloro-2-methoxyiminoacetoacetic acid ethyl ester product is continuously output at the outlet of the degassing kettle;
the absorption component is respectively connected with the exhaust port of the heat preservation kettle and the exhaust port of the degassing kettle, and the 2-methoxyiminoacetoacetate 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 to produce the 2-methoxyiminoacetoacetate which absorbs the chlorine-containing gas.
Further, the absorption assembly comprises three stages of countercurrent absorption towers which are sequentially connected in series;
the first-stage countercurrent absorption tower takes an ethanol solution of 2-methoxyiminoacetoacetic acid ethyl ester as an absorbent;
the second stage countercurrent absorption tower takes water as absorbent;
the third stage countercurrent absorption tower uses alkali solution as absorbent.
Compared with the prior art, the invention has the following advantages:
1. according to the technical scheme, through continuous reaction of the falling film, the heat exchange effect is improved, the cooling temperature is improved, the product is prevented from being blocked at the heat exchanger, the energy consumption is reduced, and the safety is improved.
2. According to the technical scheme, when the reaction temperature is improved, the equilibrium 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 raw materials is shortened through falling film continuous reaction, the generation of polychlorinated byproducts is reduced, and the reaction selectivity is improved.
4. According to the technical scheme, residual chlorine is removed through further reaction in the heat preservation kettle, otherwise, the quality and the yield of the next reaction are affected.
5. The technical proposal adopts ethanol as solvent, does not need recovery or water washing, 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 redundant chlorine is absorbed by raw materials, so that the utilization rate of the chlorine is improved, the pollution is reduced, the reaction is automatically catalyzed by the hydrogen chloride, and the reaction speed and the reaction selectivity are improved.
Drawings
FIG. 1 is a block diagram of an apparatus for continuously synthesizing ethyl 4-chloro-2-methoxyiminoacetoacetate in the present technical scheme.
In the figure: 1. the device comprises a falling film reactor 2, a heat preservation kettle 3, a degassing kettle 4, an absorption assembly 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 will now be described in detail with reference to the drawings and specific examples.
The device for continuously synthesizing the 4-chloro-2-methoxyiminoacetoacetate comprises a falling film reactor 1, the falling film reactor 1, an insulating 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-methoxyiminoacetoacetic acid ethyl ester inlet and a chlorine inlet, and the bottom of the falling film reactor is provided with a reaction liquid outlet.
The heat preservation cauldron 2 is last to be equipped with heat preservation cauldron entry, heat preservation cauldron export and with heat preservation cauldron gas vent, heat preservation cauldron entry with reaction solution exit linkage, heat preservation cauldron 2 realize inside heat preservation through the heating.
The degasification kettle 3 is provided with a degasification kettle inlet, a degasification kettle outlet and a degasification 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 4-chloro-2-methoxyiminoacetoacetic acid ethyl ester product.
The absorption assembly 4 is respectively connected with the exhaust port of the heat preservation kettle and the exhaust port of the degassing kettle, and the 2-methoxyiminoacetoacetate is introduced into the absorption assembly 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 to produce the 2-methoxyiminoacetoacetate which absorbs the chlorine-containing gas. The absorption assembly 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-methoxyiminoacetoacetic acid ethyl ester as an absorbent; the second stage countercurrent absorption tower 42 uses water as absorbent; the third stage countercurrent absorption tower 43 uses an alkali solution as an absorbent.
Example 1
An ethanol solution of an amount of ethyl 2-methoxyiminoacetoacetate having absorbed hydrogen chloride was pumped into a nozzle by a pump in a ratio of 1:0.2, and the flow rate was controlled to 6kg/h (28.9 mol). Chlorine gas was introduced into the nozzle, and the flow rate of chlorine gas was controlled to 783L/h (34.97 mol). The nozzle is made of engineering plastics, the jacket temperature of the falling film reactor is 85-90 ℃, and the reaction residence time is 60-65 seconds. The reaction liquid enters a heat preservation groove at 25-30 ℃. Degassing by Venturi, and obtaining 4-chloro-2-methoxyiminoacetoacetic acid ethyl ester ethanol solution after outflow, wherein the ethanol solution can be directly used for the next reaction without treatment, 7.21kg of HPLC external calibration amount content is 77.4% and the yield is 93.1% is obtained in 1 hour. Hydrochloric acid gas generated by tail gas and redundant chlorine gas are absorbed by ethanol solution of raw material 2-methoxy iminoacetoacetic acid ethyl ester, and the residual gas is absorbed by water and alkali. The absorbed starting material ethyl 2-methoxyiminoacetoacetate was returned for the initial chlorination reaction.
Example 2
An ethanol solution of an amount of ethyl 2-methoxyiminoacetoacetate having absorbed hydrogen chloride was pumped into a nozzle by a pump in a ratio of 1:0.1, and the flow rate was controlled to 5.5kg/h (28.9 mol). Chlorine gas was introduced into the nozzle, and the flow rate of chlorine gas was controlled at 712L/h (31.79 mol). The nozzle is made of nickel alloy, the jacket temperature of the falling film reactor is 75-80 ℃, and the reaction residence time is 95-100 seconds. The reaction solution enters a heat preservation tank for 20-25 ℃, and is degassed by vacuum, and 4-chloro-2-methoxyiminoacetoacetic acid ethyl ester ethanol solution is obtained after outflow, and can be directly used for the next reaction without treatment, 6.56kg of HPLC external calibration amount content is 79.8% and the yield is 87.3%. Hydrochloric acid gas generated by tail gas and redundant chlorine gas are absorbed by ethanol solution of raw material 2-methoxy iminoacetoacetic acid ethyl ester, and the residual gas is absorbed by water and alkali. The absorbed starting material ethyl 2-methoxyiminoacetoacetate was returned for the initial chlorination reaction.
Example 3
An ethanol solution of an amount of ethyl 2-methoxyiminoacetoacetate having absorbed hydrogen chloride was pumped into a nozzle by a pump in a ratio of 1:0.3, and the flow rate was controlled to 6.5kg/h (28.9 mol). Chlorine gas was introduced into the nozzle, and the flow rate of chlorine gas 841L/h (37.57 mol) was controlled. The nozzle is made of hastelloy, the jacket temperature of the falling film reactor is 60-65 ℃, and the reaction residence time is 230-240 seconds. The reaction solution enters a heat preservation tank for 20-25 ℃, and is degassed by vacuum, and 4-chloro-2-methoxyiminoacetoacetic acid ethyl ester ethanol solution is obtained after outflow, and can be directly used for the next reaction without treatment, 7.62kg of HPLC external calibration amount content is obtained for 1 hour, and the yield is 92.2%. Hydrochloric acid gas generated by tail gas and redundant chlorine gas are absorbed by ethanol solution of raw material 2-methoxy iminoacetoacetic acid ethyl ester, and the residual gas is absorbed by water and alkali. The absorbed starting material ethyl 2-methoxyiminoacetoacetate was returned for the initial chlorination reaction.
Example 4
An ethanol solution of an amount of ethyl 2-methoxyiminoacetoacetate having absorbed hydrogen chloride was pumped into a nozzle by a pump in a ratio of 1:1, and the flow rate was controlled to 10kg/h (28.9 mol). Chlorine gas was introduced into the nozzle, and the flow rate of chlorine gas was controlled at 744.4L/h (33.23 mol). The nozzle is made of nickel, the jacket temperature of the falling film reactor is 70-75 ℃, and the reaction residence time is 160-165 seconds. The reaction liquid enters a heat preservation groove at 25-30 ℃. Degassing by Venturi, and obtaining 4-chloro-2-methoxyiminoacetoacetic acid ethyl ester ethanol solution after outflow, wherein the ethanol solution can be directly used for the next reaction without treatment, 11.3kg of HPLC external calibration content is 49.2% and yield is 92.8% is obtained in 1 hour. Hydrochloric acid gas generated by tail gas and redundant chlorine gas are absorbed by ethanol solution of raw material 2-methoxy iminoacetoacetic acid ethyl ester, and the residual gas is absorbed by water and alkali. The absorbed starting material ethyl 2-methoxyiminoacetoacetate was returned for the initial chlorination reaction.
The previous description of the embodiments is provided to facilitate a person of ordinary skill in the art in order to make and use the present invention. It will be apparent to those skilled in the art that various modifications can be readily made to these embodiments 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-described embodiments, and those skilled in the art, based on the present disclosure, should make improvements and modifications without departing from the scope of the present invention.
Claims (6)
1. A method for continuously synthesizing 4-chloro-2-methoxyiminoacetoacetic acid ethyl ester, which is characterized by comprising the following steps:
s1: pumping an ethanol solution of the 2-methoxyiminoacetoacetic acid ethyl ester which absorbs chlorine-containing gas into a nozzle after passing through a metering pump, metering chlorine gas into the nozzle after passing through a gas flowmeter, and uniformly mixing the two raw materials when flowing through the nozzle, wherein the mixed solution is sprayed to the top of a falling film reactor (1) through the nozzle;
s2: the mixed solution uniformly forms a film from the top of the falling film reactor (1), flows down from the top of the falling film reactor (1) to the inside of the falling film reactor (1), and reacts in the inside of 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: removing chlorine-containing gas from the reaction liquid after the heat preservation for target time through a degassing kettle (3) to obtain an ethanol solution of 4-chloro-2-methoxyiminoacetoacetic acid ethyl ester;
the chlorine-containing gas generated in the heat preservation kettle (2) and the degassing kettle (3) is mixed with the raw material of the 2-methoxy iminoacetoacetic acid ethyl ester to obtain an ethanol solution of the 2-methoxy iminoacetoacetic acid ethyl ester which absorbs the chlorine-containing gas, and the ethanol solution is used in S1;
in the ethanol solution of the 2-methoxyiminoacetoacetate in the S1, the mass ratio of the 2-methoxyiminoacetoacetate to the ethanol is 1: (0.1 to 1);
the mol ratio of chlorine to 2-methoxyiminoacetoacetic acid ethyl ester in the S1 is 1: (1.1-1.3);
the falling film reactor (1) in the 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 solution in the falling film reactor (1) is 60-240S;
and S3, preserving the temperature of the reaction liquid through a heat preservation kettle (2), and introducing the reaction liquid into a degassing kettle (3) when the content of the 2-methoxyiminoacetoacetic acid ethyl ester in the reaction liquid is lower than 4%.
2. The method for continuously synthesizing 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.
3. A method for continuously synthesizing ethyl 4-chloro-2-methoxyiminoacetoacetate according to claim 1, characterized in that the degassing vessel (3) in S4 is vacuum degassed by connecting a vacuum pump or using a venturi device.
4. The method for continuously synthesizing 4-chloro-2-methoxyiminoacetoacetate according to claim 1, wherein the nozzle is made of one of engineering plastic, nickel alloy, hastelloy or 316L stainless steel.
5. An apparatus for continuously synthesizing ethyl 4-chloro-2-methoxyiminoacetoacetate, comprising:
the falling film reactor (1) is provided with a 2-methoxyiminoacetoacetic acid ethyl ester inlet and a chlorine inlet at the top and a reaction liquid outlet at the bottom;
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;
a 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 4-chloro-2-methoxyiminoacetoacetic acid ethyl ester product is continuously output at the outlet of the degassing kettle;
and the absorption assembly (4) is respectively connected with the exhaust port of the heat preservation kettle and the exhaust port of the degassing kettle, and the 2-methoxyiminoacetoacetate is introduced into the absorption assembly (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 to produce the 2-methoxyiminoacetoacetate which absorbs the chlorine-containing gas.
6. An apparatus for the continuous synthesis of ethyl 4-chloro-2-methoxyiminoacetoacetate according to claim 5, wherein said absorption unit (4) comprises three countercurrent absorption columns in series;
the first-stage countercurrent absorption tower takes an ethanol solution of 2-methoxyiminoacetoacetic acid ethyl ester as an absorbent;
the second stage countercurrent absorption tower takes water as absorbent;
the third stage countercurrent absorption tower uses alkali solution as absorbent.
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| US4933486A (en) * | 1988-03-24 | 1990-06-12 | Hoechst Aktiengesellschaft | Process for the preparation of 4-halo-3-oxo-2-alkoxyaminobutyric esters |
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| CN105693509A (en) * | 2016-03-25 | 2016-06-22 | 上海应用技术学院 | Method for continuously synthesizing ethyl 4-chloroacetoacetates |
| 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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2020
- 2020-08-12 CN CN202010807929.0A patent/CN111978205B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4933486A (en) * | 1988-03-24 | 1990-06-12 | Hoechst Aktiengesellschaft | Process for the preparation of 4-halo-3-oxo-2-alkoxyaminobutyric esters |
| CN1462265A (en) * | 2001-04-26 | 2003-12-17 | 昭和电工株式会社 | Method for producing 2,3-dichloro-1-propahol and epiclorohyrin |
| CN1709879A (en) * | 2005-06-08 | 2005-12-21 | 浙江普洛化学有限公司 | Method for preparing (2)-2-(2-amino-4-thiazole)-2-hydroxy imine acetate and its derivative |
| CN105693509A (en) * | 2016-03-25 | 2016-06-22 | 上海应用技术学院 | Method for continuously synthesizing ethyl 4-chloroacetoacetates |
| 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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