CN107915622A - A kind of solvent-free 4 chlorine, 3 oxobutyric continuous stream synthetic method and system - Google Patents
A kind of solvent-free 4 chlorine, 3 oxobutyric continuous stream synthetic method and system Download PDFInfo
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- CN107915622A CN107915622A CN201711044031.7A CN201711044031A CN107915622A CN 107915622 A CN107915622 A CN 107915622A CN 201711044031 A CN201711044031 A CN 201711044031A CN 107915622 A CN107915622 A CN 107915622A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/58—Preparation of carboxylic acid halides
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J19/0093—Microreactors, e.g. miniaturised or microfabricated reactors
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/14—Preparation of carboxylic acid esters from carboxylic acid halides
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/48—Separation; Purification; Stabilisation; Use of additives
- C07C67/52—Separation; Purification; Stabilisation; Use of additives by change in the physical state, e.g. crystallisation
- C07C67/54—Separation; Purification; Stabilisation; Use of additives by change in the physical state, e.g. crystallisation by distillation
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Abstract
The invention belongs to chemical field, and in particular to a kind of solvent-free 4 chlorine, 3 oxobutyric continuous stream synthetic method and system.The reaction process of the present invention is that ketene dimer passes through the advanced chlorination reaction of micro passage reaction module 8 with liquid chlorine, reacted module 13 carries out esterification up to 4 chlorine, 3 oxobutyric crude product to chlorated liquid again with ethanol, up to 4 chlorine, 3 oxobutyric finished product after crude product rectification under vacuum.Since micro passage reaction has certain resistance, conventional feed arrangement can not realize that liquid chlorine is fed, in micro passage reaction, gas liquid reaction mixed effect does not have the reactive liquid solution effect good, and gas dosing poor accuracy, it may appear that the problems such as byproduct of reaction increases, and yield declines.
Description
Technical field
The invention belongs to chemical field, and in particular to a kind of solvent-free chloro- 3- oxobutyric acid ethyl esters continuous stream synthesis sides of 4-
Method and system.
Background technology
The chloro- 3- oxobutyric acid ethyl esters of 4- are colourless weak yellow liquid, molecular weight：164.59, fusing point：- 8 DEG C, boiling point：115
DEG C 14mmHg, density：1.218 flash-point：96 DEG C, water-soluble：47.5g/L(20℃).The chloro- 3- oxobutyric acid ethyl esters of 4- are one
The good medical synthetic intermediate of kind, is mainly used to produce Oxiracetam, and Oxiracetam belongs to the medicine for the treatment of cranial vascular disease,
It is the 4th generation intelligence development class medicine, the derivative of pyrrolidinone compounds, trade name is good for bright star, Ou Laining, neuromet and neupan
Deng.Oxiracetam is a kind of new medicine for central nervous system, can promote the functional rehabilitation of nerve cell, improves brain metabolism.
It has multi-efficiency, has significant curative effect to treatment amnesia, senile dementia, and toxicity is minimum, securely and reliably, adverse reaction compared with
It is few, therefore be with a wide range of applications, have a vast market prospect.
The conventional production process in industrial production is at present：Batch process produces, first by ketene dimer dissolving in a solvent
(quantity of solvent is usually m (solvent)：M (ketene dimer)=1:4~1：10) -30 DEG C~-10 DEG C are cooled to, and, unlatching is stirred
Mix, a certain amount of chlorine is passed through with certain flow into reaction kettle, 1~2h is kept the temperature at -30 DEG C~-10 DEG C, chlorination reaction terminates
Instill a certain amount of ethanol thereto afterwards, controlling reaction temperature is 0~5 DEG C, and drop, which finishes, is warming up to 20~25 DEG C, keeps the temperature 1h, esterification
After reaction, it is carried out that solvent is evaporated off, then is evaporated under reduced pressure, it is the chloro- 3- oxo-butynic acids of 4- to obtain colourless liquid product
Ethyl ester.
The shortcomings that technique is：Batch technology produces the chloro- 3- oxobutyric acid ethyl esters of 4-, and the reaction time is long, chlorination by-product
Should be excessive, product yield is relatively low, inferior quality；Not environmentally, solvent dosage is too big for production technology, and lock out operation is cumbersome, and is difficult to
Recycling is complete, and production cost is higher, and the solvent of use is generally monochloro methane, dichloromethane, chloroform, carbon tetrachloride etc.,
These solvent volatilities are strong, seriously pollute environment, and cause actual bodily harm to site operation personnel.
Chinese patent application Publication No. CN103787883A reports a kind of chloro- 3- oxobutyric acid ethyl esters preparation sides of 4-
Prepared by method, the batch process of use, stabilizer is added in chlorination reaction and suppresses chlorination side reaction generation, but repeats this technique lab scale
The effect of its narration is unable to reach, yield is only 74% after repeating.
One kind is reported in Chinese patent application Publication No. CN106748764A and uses the chloro- 3- oxobutyric acid ethyl esters of 4-
Synthesis system and method, its emphasis describe microreactor system and reaction process, this technique distinguishes chlorine and ketene dimer
Molten that successive reaction is carried out in micro- reaction as in solvent, the shortcomings that this technique is that solubility is limited in a solvent for chlorine, and pole
Unstable, easily effusion, and solvent usage amount is big, recycling cannot be complete, seriously pollutes environment.
The content of the invention
To solve the above-mentioned problems, the present invention provides the present invention provides a kind of solvent-free chloro- 3- oxo-butynic acids second of 4-
Ester continuous stream synthesis technique, has the characteristics such as solvent-free, continuous synthesis, and its object is to solve the production chloro- 3- oxygen of 4- at present
Not environmentally, product yield is relatively low for the technique of generation-ethyl butyrate, inferior quality, it is cumbersome the problems such as.
Technical scheme is as follows：
A kind of chloro- 3- oxobutyric acid ethyl esters continuous stream synthetic methods of solvent-free 4-, it is characterised in that：
1. opening inverted 1 valve of chlorine cylinder, and pipeline shut-off valve 3 is opened, releases liquid chlorine, import liquid chlorine booster jar 5,
After liquid level reaches 2/3,1 valve of chlorine cylinder and shut-off valve 3 are turned off, opens 2 valve of nitrogen cylinder and pipeline shut-off valve 4, it is right
Booster jar is pressurized；
2. opening pipeline shut-off valve 6, liquid chlorine and ketene dimer storage tank 9 enter chlorination at the same time by metering pump 7 and 10 respectively
Reaction module 8 carries out chlorination reaction, and the temperature range of chlorination reaction is -55 DEG C~25 DEG C, and the reaction time is 0.1s~55s, liquid
The reaction molar ratio of chlorine and ketene dimer is 0.8~2:1；
3. after chlorination reaction, the ethanol in ethanol storage tank 11 together enters esterification instead by metering pump 12 and chlorated liquid
Module 13 is answered to carry out esterification, the temperature range of esterification is -20 DEG C~40 DEG C, and the reaction time is 0.1s~50s, ethanol
Reaction molar ratio with ketene dimer is 0.9~1.5:1；
After 4. crude product is by 14 pressure release of pressure gauge counterbalance valve, into gas-liquid separation surge tank 15, tail gas, which enters, to be absorbed
Tank 16；
5. 3- oxobutyric acid ethyl esters chloro- to crude product 4- carry out rectification under vacuum, up to the chloro- 3- oxo-butynic acids second of product 4-
Ester.
Further, the step 2. middle chlorination reaction temperature range be -30 DEG C~15 DEG C, the reaction time for 5s~
40s。
Further, the step 2. middle liquid chlorine and ketene dimer reaction molar ratio be 1.0~1.1:1.
Further, the step 3. middle esterification temperature range be -10 DEG C~25 DEG C, the reaction time for 5s~
30s。
Further, the step 3. middle ethanol and ketene dimer reaction molar ratio be 1~1.1:1.
The present invention also provides a kind of solvent-free chloro- 3- oxobutyric acid ethyl esters continuous stream synthesis systems of 4-, the solvent-free 4-
Chloro- 3- oxobutyric acid ethyl esters continuous stream synthetic method is applied to the system, the solvent-free chloro- 3- oxobutyric acid ethyl esters of 4-
Continuous stream synthesis system includes chlorine cylinder 1, and the bottom of the chlorine cylinder 1 is connected by pipeline with the top of booster jar 5, institute
The upper end for stating booster jar 5 is also connected with nitrogen cylinder 2, and the top of the booster jar 5 is connected through metering pump 7 with chlorination reaction module 8,
The chlorination reaction module 8 is also connected with ketene dimer storage tank 9, the outlet connection esterification module 13 of chlorination reaction module 8,
The esterification module 13 is also connected through metering pump 12 with ethanol storage tank 11, the outlet and gas-liquid separation of esterification module 13
Surge tank 15 connects, and the gas-liquid separation surge tank 15 is connected with tourie 16.
Further, pipeline is set to end respectively on the pipeline behind the chlorine cylinder 1, nitrogen cylinder 2 and booster jar 5
Valve；Pressure gauge counterbalance valve 14 is set on the pipeline after the esterification module 13.
13 structure of the chlorination reaction module 8 and esterification module is the flat formula pipeline mixing of positive way pulse rectangle,
It is specifically shown in attached drawing 2.
A kind of solvent-free chloro- 3- oxobutyric acid ethyl esters continuous stream synthetic methods of 4- provided by the invention, used reaction
Device is micro passage reaction, and reaction principle is as follows：
Reaction process is ketene dimer with liquid chlorine by the advanced chlorination reaction of micro passage reaction module 1, chlorated liquid with
Reacted module 2 carries out esterification up to the chloro- 3- oxobutyric acid ethyl esters crude products of 4- to ethanol again, after crude product rectification under vacuum to obtain the final product
The chloro- 3- oxobutyric acid ethyl esters finished products of 4-.Since micro passage reaction has certain resistance, conventional feed arrangement can not be real
Existing liquid chlorine charging, in micro passage reaction, gas liquid reaction mixed effect does not have that reactive liquid solution effect is good, and gas dosing is accurate
Degree is poor, it may appear that the problems such as byproduct of reaction increases, and yield declines, reaction shape of the present invention for guarantee chlorine in microreactor
State is liquid, and special design has been carried out to its feed system, and to ensure that its pressure is enough, liquid chlorine feed system is as shown in Figure 1.
The solvent-free chloro- 3- oxobutyric acid ethyl esters continuous stream synthesis techniques of 4- comprise the following steps that：
1. opening inverted 1 valve of chlorine cylinder, and pipeline shut-off valve 3 is opened, releases liquid chlorine, import liquid chlorine booster jar 5,
After liquid level reaches 2/3,1 valve of chlorine cylinder and shut-off valve (3) are turned off, opens 2 valve of nitrogen cylinder and pipeline shut-off valve 4,
Booster jar is pressurized；
2. opening pipeline shut-off valve 6, liquid chlorine and ketene dimer 9 enter reaction module 8 at the same time by metering pump 7 and 10 respectively
Chlorination reaction is carried out, the temperature range of chlorination reaction is -55 DEG C~25 DEG C, and the reaction time is 0.1s~55s, liquid chlorine and double ethene
The reaction molar ratio of ketone is 0.8~2:1；
3. after chlorination reaction, the ethanol in ethanol storage tank 11 together enters reaction mould by metering pump 12 and chlorated liquid
Block 13, the temperature range of esterification are -20 DEG C~40 DEG C, and the reaction time is 0.1s~50s, the reaction of ethanol and ketene dimer
Molar ratio is 0.9~1.5:1；
After 4. crude product is by 14 pressure release of pressure gauge counterbalance valve, into gas-liquid separation surge tank 15, tail gas, which enters, to be absorbed
Tank 16；
5. 3- oxobutyric acid ethyl esters chloro- to crude product 4- carry out rectification under vacuum, up to the chloro- 3- oxo-butynic acids second of product 4-
Ester.
As preferred：The temperature range of chlorination reaction is -30 DEG C~15 DEG C, and the reaction time is 5s~40s, liquid chlorine and double second
The reaction molar ratio of ketenes is 1.0~1.1:1；The temperature range of esterification be -10 DEG C~25 DEG C, the reaction time for 5s~
The reaction molar ratio of 30s, ethanol and ketene dimer is 1~1.1:1.
Beneficial effects of the present invention are as follows：
The present invention, using liquid chlorine feed arrangement, is connected using ketene dimer, liquid chlorine and ethanol as raw material by micro passage reaction
The continuous synthesis chloro- 3- oxobutyric acid ethyl esters of 4-, specific effect are as follows：
1) present invention is process for cleanly preparing, and the chloro- 3- oxobutyric acid ethyl esters of 4- are synthesized using solventless method, technique green
Environmental protection, it is not necessary to which recycling design, can save production cost；
2) present invention is using the microchannel continuity method synthesis chloro- 3- oxobutyric acid ethyl esters of 4-, compared with batch process, the chloro- 3- of 4-
Oxobutyric acid ethyl ester yield and product content increase.
Brief description of the drawings
Fig. 1 is a kind of solvent-free chloro- 3- oxobutyric acid ethyl esters continuous stream synthesis system figures of 4-.
Fig. 2 is the structure chart for the reaction module being related to.
Wherein：1- chlorine cylinders, 2- nitrogen cylinders, 3- pipeline shut-off valves, 4- pipeline shut-off valves, 5- booster jars, 6- pipelines are cut
Only valve, 7- metering pumps, 8- chlorination reaction modules, 9- ketene dimer storage tanks, 10- metering pumps, 11- ethanol storage tanks, 12- metering pumps,
13- esterification modules, 14- pressure gauge counterbalance valves, 15- gas-liquid separation surge tanks, 16- touries.
Embodiment
With reference to embodiment, the present invention is further elaborated, it will be appreciated by those skilled in the art that the embodiment
It is given for example only, without forming any restrictions to the present invention.
The present invention provides a kind of solvent-free chloro- 3- oxobutyric acid ethyl esters continuous stream synthesis systems of 4-, the solvent-free 4-
Chloro- 3- oxobutyric acid ethyl esters continuous stream synthetic method is applied to the system, the solvent-free chloro- 3- oxobutyric acid ethyl esters of 4-
Continuous stream synthesis system includes chlorine cylinder 1, and the bottom of the chlorine cylinder 1 is connected by pipeline with the top of booster jar 5, institute
The upper end for stating booster jar 5 is also connected with nitrogen cylinder 2, and the top of the booster jar 5 is connected through metering pump 7 with chlorination reaction module 8,
The chlorination reaction module 8 is also connected with ketene dimer storage tank 9, the outlet connection esterification module 13 of chlorination reaction module 8,
The esterification module 13 is also connected through metering pump 12 with ethanol storage tank 11, the outlet and gas-liquid separation of esterification module 13
Surge tank 15 connects, and the gas-liquid separation surge tank 15 is connected with tourie 16.In the chlorine cylinder 1, nitrogen cylinder 2 and supercharging
Pipeline shut-off valve is set respectively on the pipeline behind tank 5；Pressure gauge is set to carry on the back on pipeline after the esterification module 13
Pressure valve 14.Embodiment 1：A kind of chloro- 3- oxobutyric acid ethyl esters continuous stream synthetic methods of solvent-free 4-：
1. opening inverted 1 valve of chlorine cylinder, and pipeline shut-off valve 3 is opened, releases liquid chlorine, import liquid chlorine booster jar 5,
After liquid level reaches 2/3,1 valve of chlorine cylinder and shut-off valve 3 are turned off, opens 2 valve of nitrogen cylinder and pipeline shut-off valve 4, it is right
Booster jar is pressurized；
2. opening pipeline shut-off valve 6, liquid chlorine and ketene dimer 9 enter reaction module 8 at the same time by metering pump 7 and 10 respectively
Chlorination reaction is carried out, the temperature of chlorination reaction is -30 DEG C, reaction time 5s, and the reaction molar ratio of liquid chlorine and ketene dimer is
1:1；
3. after chlorination reaction, the ethanol in ethanol storage tank 11 together enters reaction mould by metering pump 12 and chlorated liquid
Block 13, the temperature of esterification is -10 DEG C, reaction time 5s, and the reaction molar ratio of ethanol and ketene dimer is 1:1；
After 4. crude product is by 14 pressure release of pressure gauge counterbalance valve, into gas-liquid separation surge tank 15, tail gas, which enters, to be absorbed
Tank 16；
5. 3- oxobutyric acid ethyl esters chloro- to crude product 4- carry out rectification under vacuum, up to the chloro- 3- oxo-butynic acids second of product 4-
Ester, product yield 92%, product G C content 98.5%.
Embodiment 2：A kind of chloro- 3- oxobutyric acid ethyl esters continuous stream synthetic methods of solvent-free 4-：
1. describe same embodiment 1；
2. opening pipeline shut-off valve 6, liquid chlorine and ketene dimer 9 enter reaction module 8 at the same time by metering pump 7 and 10 respectively
Chlorination reaction is carried out, the temperature of chlorination reaction is -5 DEG C, reaction time 20s, and the reaction molar ratio of liquid chlorine and ketene dimer is
1.05:1；
3. after chlorination reaction, the ethanol in ethanol storage tank 11 together enters reaction mould by metering pump 12 and chlorated liquid
Block 13, the temperature of esterification is 5 DEG C, reaction time 15s, and the reaction molar ratio of ethanol and ketene dimer is 1.02:1；
After 4. crude product is by 14 pressure release of pressure gauge counterbalance valve, into gas-liquid separation surge tank 15, tail gas, which enters, to be absorbed
Tank 16；
5. 3- oxobutyric acid ethyl esters chloro- to crude product 4- carry out rectification under vacuum, up to the chloro- 3- oxo-butynic acids second of product 4-
Ester, product yield 91%, product G C content 98.2%.
Embodiment 3：A kind of chloro- 3- oxobutyric acid ethyl esters continuous stream synthetic methods of solvent-free 4-：
1. describe same embodiment 1；
2. opening pipeline shut-off valve 6, liquid chlorine and ketene dimer 9 enter reaction module 8 at the same time by metering pump 7 and 10 respectively
Chlorination reaction is carried out, the temperature of chlorination reaction is 15 DEG C, reaction time 40s, and the reaction molar ratio of liquid chlorine and ketene dimer is
1.1:1；
3. after chlorination reaction, the ethanol in ethanol storage tank 11 together enters reaction mould by metering pump 12 and chlorated liquid
Block 13, the temperature of esterification is 25 DEG C, reaction time 30s, and the reaction molar ratio of ethanol and ketene dimer is 1.1:1；
After 4. crude product is by 14 pressure release of pressure gauge counterbalance valve, into gas-liquid separation surge tank 15, tail gas, which enters, to be absorbed
Tank 16；
5. 3- oxobutyric acid ethyl esters chloro- to crude product 4- carry out rectification under vacuum, up to the chloro- 3- oxo-butynic acids second of product 4-
Ester, product yield 92.6%, product G C content 98.5%.
Claims (7)
- A kind of 1. chloro- 3- oxobutyric acid ethyl esters continuous stream synthetic methods of solvent-free 4-, it is characterised in that：1. opening inverted chlorine cylinder (1) valve, and pipeline shut-off valve (3) is opened, release liquid chlorine, import liquid chlorine booster jar (5), after liquid level reaches 2/3, chlorine cylinder (1) valve and shut-off valve (3) are turned off, opens nitrogen cylinder (2) valve and pipeline Shut-off valve (4), is pressurized booster jar；2. opening pipeline shut-off valve (6), liquid chlorine and ketene dimer storage tank (9) enter at the same time by metering pump (7) and (10) respectively Chlorination reaction module (8) carries out chlorination reaction, and the temperature range of chlorination reaction is -55 DEG C~25 DEG C, the reaction time for 0.1s~ The reaction molar ratio of 55s, liquid chlorine and ketene dimer is 0.8~2:1；3. after chlorination reaction, the ethanol in ethanol storage tank (11) together enters esterification instead by metering pump (12) and chlorated liquid Module (13) is answered to carry out esterification, the temperature range of esterification is -20 DEG C~40 DEG C, and the reaction time is 0.1s~50s, second The reaction molar ratio of alcohol and ketene dimer is 0.9~1.5:1；After 4. crude product is by pressure gauge counterbalance valve (14) pressure release, into gas-liquid separation surge tank (15), tail gas, which enters, to be absorbed Tank (16)；5. 3- oxobutyric acid ethyl esters chloro- to crude product 4- carry out rectification under vacuum, up to the chloro- 3- oxobutyric acid ethyl esters of product 4-.
- 2. a kind of chloro- 3- oxobutyric acid ethyl esters continuous stream synthetic methods of solvent-free 4-, its feature exist according to claim 1 In：The step 2. middle chlorination reaction temperature range be -30 DEG C~15 DEG C, the reaction time is 5s~40s.
- 3. a kind of chloro- 3- oxobutyric acid ethyl esters continuous stream synthetic methods of solvent-free 4-, its feature exist according to claim 1 In：The step 2. middle liquid chlorine and ketene dimer reaction molar ratio be 1.0~1.1:1.
- 4. a kind of chloro- 3- oxobutyric acid ethyl esters continuous stream synthetic methods of solvent-free 4-, its feature exist according to claim 1 In：The step 3. middle esterification temperature range be -10 DEG C~25 DEG C, the reaction time is 5s~30s.
- 5. a kind of chloro- 3- oxobutyric acid ethyl esters continuous stream synthetic methods of solvent-free 4-, its feature exist according to claim 1 In：The step 3. middle ethanol and ketene dimer reaction molar ratio be 1~1.1:1.
- A kind of 6. any one of chloro- 3- oxobutyric acid ethyl esters continuous stream synthesis systems of solvent-free 4-, claim 1-5 solvent-free 4- Chloro- 3- oxobutyric acid ethyl esters continuous stream synthetic method is applied to the system, it is characterised in that：The chloro- 3- oxygen of solvent-free 4- Generation-ethyl butyrate continuous stream synthesis system includes chlorine cylinder (1), and the bottom of the chlorine cylinder (1) passes through pipeline and supercharging The top connection of tank (5), the upper end of the booster jar (5) are also connected with nitrogen cylinder (2), and the top of the booster jar (5) is through meter Amount pump (7) is connected with chlorination reaction module (8), and the chlorination reaction module (8) is also connected with ketene dimer storage tank (9), chlorination The outlet connection esterification module (13) of reaction module (8), the esterification module (13) is gone back through metering pump (12) and second Alcohol storage tank (11) connects, and the outlet of esterification module (13) is connected with gas-liquid separation surge tank (15), and the gas-liquid separation is delayed Tank (15) is rushed to be connected with tourie (16).
- 7. the chloro- 3- oxobutyric acid ethyl esters continuous stream synthesis systems of solvent-free 4- according to claim 6, it is characterised in that Pipeline shut-off valve is set respectively on pipeline behind chlorine cylinder (1), nitrogen cylinder (2) and booster jar (5)；In the esterification Pressure gauge counterbalance valve (14) is set on the pipeline after module (13).
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109503381A (en) * | 2018-12-12 | 2019-03-22 | 安徽金禾实业股份有限公司 | 4- chloroacetyl acetacetic ester microchannel plate induction method and device |
| CN109529722A (en) * | 2018-12-20 | 2019-03-29 | 山东玉皇化工有限公司 | A kind of method and apparatus of low boiling material to high-pressure installation continuous feed |
| CN111233718A (en) * | 2020-03-19 | 2020-06-05 | 宁夏格瑞精细化工有限公司 | Method for continuously synthesizing perchloromethylmercaptan |
| CN112979461A (en) * | 2021-02-26 | 2021-06-18 | 复旦大学 | Full continuous flow preparation method of 3-chloro-4-oxoacetic acid amyl ester |
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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 |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109503381A (en) * | 2018-12-12 | 2019-03-22 | 安徽金禾实业股份有限公司 | 4- chloroacetyl acetacetic ester microchannel plate induction method and device |
| CN109503381B (en) * | 2018-12-12 | 2022-04-29 | 安徽金禾实业股份有限公司 | 4-chloroacetoacetic acid ethyl ester microchannel reaction method and device |
| CN109529722A (en) * | 2018-12-20 | 2019-03-29 | 山东玉皇化工有限公司 | A kind of method and apparatus of low boiling material to high-pressure installation continuous feed |
| CN111233718A (en) * | 2020-03-19 | 2020-06-05 | 宁夏格瑞精细化工有限公司 | Method for continuously synthesizing perchloromethylmercaptan |
| CN111233718B (en) * | 2020-03-19 | 2022-03-11 | 宁夏格瑞精细化工有限公司 | Method for continuously synthesizing perchloromethylmercaptan |
| CN112979461A (en) * | 2021-02-26 | 2021-06-18 | 复旦大学 | Full continuous flow preparation method of 3-chloro-4-oxoacetic acid amyl ester |
| CN112979461B (en) * | 2021-02-26 | 2022-03-18 | 复旦大学 | Full continuous flow preparation method of 3-chloro-4-oxoacetic acid amyl ester |
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