CN106748764A - The continuous synthesis system and method for a kind of 4 chloroacetyl acetacetic ester - Google Patents
The continuous synthesis system and method for a kind of 4 chloroacetyl acetacetic ester Download PDFInfo
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- CN106748764A CN106748764A CN201710152138.7A CN201710152138A CN106748764A CN 106748764 A CN106748764 A CN 106748764A CN 201710152138 A CN201710152138 A CN 201710152138A CN 106748764 A CN106748764 A CN 106748764A
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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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- 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
Abstract
The present invention relates to the continuous synthesis system and method for a kind of 4 chloroacetyl acetacetic ester, with ketene dimer and chlorine, ethanol as raw material, micro passage reaction is input into through measuring pump, 4 chloroacetyl acetacetic esters are synthesized after chlorination, esterification.4 chloroacetyl acetacetic esters of continuous synthesis of the invention, substantially reduce the reaction time, and the product content of production is high, low cost, pollute small, safe, meet industrialization production requirements.
Description
Technical field
The invention belongs to chemical technology field, and in particular to a kind of continuous synthesis system of 4- chloroacetyl acetacetic esters and side
Method.
Background technology
4- chloroacetyl acetacetic esters are colourless to light yellow transparent liquid, are to produce nitrogen Flordipine, Oxiracetam, atropic to cut down
The important intermediate of the raw materials such as spit of fland calcium, market demand is larger.Existing industrialized production is mainly is given birth to by batch tank chlorination
Produce, there is that the reaction time is long, depth of chlorination is difficult to control to, and accessory substance is more, the low problem of yield.
Patent CN201210257429.X and CN201310321570.6 disclose one kind with ketene dimer as initiation material,
Through superchlorination and esterification two steps synthesis 4- chloroacetyl acetacetic esters, its raw material is cheap and easy to get and turn into the production method of main flow,
But it also has the shortcomings that to be exactly inherently relatively low product yield, and only 75%-88% causes high expensive, and causes yield
Low the reason for is exactly that can generate a certain amount of 2- chloroacetyl acetacetic esters in course of reaction（5% or so）, and 2- chloroethene ethyl acetoacetic acid second
The boiling point of ester and the boiling point of product 4- chloroacetyl acetacetic esters very close to（About 2-3 DEG C at reduced pressure conditions）, therefore in purifying
Shi Tongchang will rectifying repeatedly, cause a large amount of decomposition of product, ultimately result in yield relatively low.
Patent WO2012146604A1 and CN105693509A report the continuous synthesis of 4- chloroacetyl acetacetic esters, with double
Ketenes and chlorine are raw material, are reacted in falling film reactor, and reaction is esterified after terminating into esterifying kettle, synthesize 4- chlorine
Ethyl acetoacetate, the technical scheme process reaction is difficult to control, and is difficult industrialization production.
The content of the invention
Goal of the invention：In order to solve the problems, such as above-mentioned technology, first purpose of the present invention provides a kind of micro- logical
The apparatus system of continuous synthesis 4- chloroacetyl acetacetic esters in road reactor；Second purpose provides one kind in micro passage reaction
In continuous synthesis 4- chloroacetyl acetacetic esters method.
Technical scheme：A kind of continuous synthesis system of 4- chloroacetyl acetacetic esters, including the first NaOH solution tank NaOH（1）, it is second molten
Flow container（2）, pump（3）, micro passage reaction（4）；The micro passage reaction（4）Upstream be provided with feed pipe（5）, downstream is provided with out
Expects pipe（6）；First NaOH solution tank NaOH（1）, the second NaOH solution tank NaOH（2）Pass through pump respectively（3）With the micro passage reaction（4）Enter
Expects pipe（5）Connection；Also include second reactor（7）, the second reactor（7）Including feed-inputing branched pipe（8）, discharge header pipe（9）, institute
State feed-inputing branched pipe（8）At least 2；Also include the 3rd NaOH solution tank NaOH（12）, the feed-inputing branched pipe（8）Respectively with the 3rd solution
Tank（12）, discharge nozzle（6）Connection, the 3rd NaOH solution tank NaOH（12）With the feed-inputing branched pipe（8）Between be provided with pump（3）；Also include receiving
Collection tank（13）, device for absorbing tail gas（14）, the collecting tank（13）Positioned at the discharge header pipe（9）Downstream；Device for absorbing tail gas
（14）Positioned at the collecting tank（13）Downstream.
Preferably, the second reactor（7）Feed-inputing branched pipe（8）, discharge header pipe（9）Inner chamber in be provided with island
（10）, the island（10）There is multiple, in heart, adjacent island（10）Between have gap, it is evenly distributed；The feed-inputing branched pipe（8）With institute
State discharge header pipe（9）Junction be provided with central island（11）, the central island（11）It is circle；The feed-inputing branched pipe（8）With it is described
Discharge header pipe（9）Junction for flexible connection.
Preferably, first NaOH solution tank NaOH（1）It is ketene dimer solvent tank；Second NaOH solution tank NaOH（2）It is chlorine solution tank；
3rd NaOH solution tank NaOH（12）It is Ethanol tank.
Preferably, the pump（3）It is measuring pump.
A kind of method of continuous synthesis system using above-mentioned 4- chloroacetyl acetacetic esters, mainly includes the following steps that：
1）Ketene dimer and chlorine are dissolved in organic solvent respectively, wiring solution-forming；Ketene dimer is with the mol ratio of organic solvent
0.05~50:1；Chlorine is 0.01 ~ 50 with the mol ratio of organic solvent:1；
2）The ketene dimer and chlorine solution that will be prepared are through pump（3）It is input to micro passage reaction（4）In, carry out chlorination reaction；
Ketene dimer solution is -50 DEG C ~ 0 DEG C with chlorine solution range of reaction temperature, and the reaction time is 0.1 ~ 50s, ketene dimer and chlorine
Gas mol ratio is 0.9 ~ 1.5:1；
3）After ketene dimer chlorination reaction terminates, second reactor is passed through with ethanol（7）Reacted, synthesized 4- chloroethene ethyl acetoacetic acids
Ethyl ester, product passes through discharge header pipe（9）Into collecting tank（13）, collecting tank（13）Connection device for absorbing tail gas（14）, crude product enters
Enter follow-up refined.
Preferably, the organic solvent is monochloro methane, dichloromethane, chloroform, carbon tetrachloride, the chloroethenes of 1,2- bis-
Alkane, 1,1- dichloroethanes, 1,1,2- trichloroethanes, in 1,1,1- trichloroethanes, n-hexane, normal heptane, p-chloro benzo trifluoride-99
One or more mixtures for configuring by a certain percentage.
Preferably, ketene dimer is preferably 0.1 ~ 0.5 with the mol ratio of organic solvent:1；Chlorine rubs with organic solvent
That ratio preferably 0.05 ~ 0.2:1.
Preferably, ketene dimer solution is -30 DEG C ~ 0 DEG C with chlorine solution reaction preferred range, the reaction time is excellent
Scope is selected for 5 ~ 30s, ketene dimer is 1.0 ~ 1.1 with chlorine mol ratio preferred scope:1.
Beneficial effect：The present invention is using micro passage reaction, second reactor, reaction generation 4- chloroethene ethyl acetoacetic acid second
Ester, in the accurate measurement control conveying reaction mass of measuring pump, is done directly chlorination and esterification, product in micro passage reaction
Later separation is directly entered, reaction selectivity is greatly improved, production cost is reduced, reaction time, specific effect is shortened
It is as follows：
1st, the present invention have mass-and heat-transfer efficiently, accurate temperature controlling control when, safety and stability, the real-time prison without enlarge-effect and reaction
The advantages of control；
2nd, the present invention carries out the synthesis of compound multi-step using micro passage reaction, it is possible to reduce the use to organic solvent,
Avoid with poisonous, dangerous reagent directly contact, the time of reaction process is reduced significantly, and effectively control polychloride, drop
Low many chlorine products and other accessory substances are generated；
3rd, the present invention reduces the circulation and stress of material amounts and waste and potential catalyst, improves the content and receipts of product
Rate, effectively reduces raw materials for production cost and energy cost, reduces the pollutant in production process；
4th, using second reactor, between feed-inputing branched pipe and discharge header pipe for flexible connection, adjustable-angle, feed-inputing branched pipe with go out
Expect to be provided with evenly distributed island, circular central island in total tube cavity, can play material diversion, be sufficiently mixed reaction, reaction is more
Plus it is fine accurate, it is to avoid the generation of by-product, be conducive to the carrying out of forward reaction.
Brief description of the drawings
Fig. 1 is structural representation of the invention；
Fig. 2 is the structural representation of second reactor of the present invention.
Specific embodiment
With reference to specific embodiment, the present invention is expanded on further.It should be understood that these embodiments are merely to illustrate the present invention
Rather than limitation the scope of the present invention.
Case study on implementation 1
As shown in Figure 1 and Figure 2, a kind of continuous synthesis system of 4- chloroacetyl acetacetic esters, including the first NaOH solution tank NaOH 1, the second solution
Tank 2, pump 3, micro passage reaction 4；The upstream of the micro passage reaction 4 is provided with feed pipe 5, and downstream is provided with discharge nozzle 6；Described
One NaOH solution tank NaOH 1, the second NaOH solution tank NaOH 2 are connected by pump 3 with the feed pipe 5 of the micro passage reaction 4 respectively；Also include that second is anti-
Device 7 is answered, the second reactor 7 includes feed-inputing branched pipe 8, discharge header pipe 9, the feed-inputing branched pipe 8 at least 2；Also include the 3rd
NaOH solution tank NaOH 12, the feed-inputing branched pipe 8 is connected with the 3rd NaOH solution tank NaOH 12, discharge nozzle 6 respectively, the 3rd NaOH solution tank NaOH 12 with it is described
Pump 3 is provided between feed-inputing branched pipe 8；Also include collecting tank 13, device for absorbing tail gas 14, the collecting tank 13 is located at the discharge header pipe
9 downstream；Device for absorbing tail gas 14 is located at the downstream of the collecting tank 13.
In the present embodiment, island 10 is provided with feed-inputing branched pipe 8, the inner chamber of discharge header pipe 9 of the second reactor 7, the island
10 have multiple, in heart, there is gap between adjacent island 10, evenly distributed；The friendship of the feed-inputing branched pipe 8 and the discharge header pipe 9
The place of connecing is provided with central island 11, and the central island 11 is circle；The feed-inputing branched pipe 8 is flexibility with the junction of the discharge header pipe 9
Connection.First NaOH solution tank NaOH 1 is ketene dimer solvent tank；Second NaOH solution tank NaOH 2 is chlorine solution tank；3rd NaOH solution tank NaOH 12 is second
Alcohol tank；The pump 3 is measuring pump.
Embodiment 2
The method of the continuous synthesis system of 4- chloroacetyl acetacetic esters, mainly includes the following steps that described in a kind of use embodiment 1：
1）Ketene dimer and chlorine are dissolved in organic solvent respectively, wiring solution-forming；Ketene dimer is with the mol ratio of organic solvent
0.05~50:1；Chlorine is 0.01 ~ 50 with the mol ratio of organic solvent:1；
2）The ketene dimer and chlorine solution of preparation are input in micro passage reaction 4 through pump 3, chlorination reaction is carried out；Double second
Ketenes solution is -50 DEG C ~ 0 DEG C with chlorine solution range of reaction temperature, and the reaction time is 0.1 ~ 50s, and ketene dimer rubs with chlorine
You are than being 0.9 ~ 1.5:1；
3）After ketene dimer chlorination reaction terminates, reacted by second reactor 7 with ethanol, synthesized 4- chloroethene ethyl acetoacetic acid second
Ester, product enters collecting tank 13 by discharge header pipe 9, and collecting tank 13 connects device for absorbing tail gas 14, and crude product enters follow-up refined.
In the present embodiment, the organic solvent is monochloro methane, dichloromethane, chloroform, carbon tetrachloride, 1,2- dichloros
Ethane, 1,1- dichloroethanes, 1,1,2- trichloroethanes, in 1,1,1- trichloroethanes, n-hexane, normal heptane, p-chloro benzo trifluoride-99
One or more mixtures for configuring by a certain percentage.
Ketene dimer is preferably 0.1 ~ 0.5 with the mol ratio of organic solvent:1；Chlorine is preferred with the mol ratio of organic solvent
It is 0.05 ~ 0.2:1.
Ketene dimer solution is -30 DEG C ~ 0 DEG C with chlorine solution reaction preferred range, and reaction time preferred scope is 5
~ 30s, ketene dimer is 1.0 ~ 1.1 with chlorine mol ratio preferred scope:1.
Case study on implementation 3
The present embodiment is using device with embodiment 1.
It is 0.2 by ketene dimer and dichloromethane mol ratio:1 is configured to solution, and chlorine is 0.05 with dichloromethane mol ratio:
1 is configured to solution；
Ketene dimer solution, the chlorine solution that will be prepared are input in continuous stream micro passage reaction by measuring pump respectively,
Ketene dimer is 1.1 with the mol ratio of chlorine:1, reaction temperature is -5 DEG C, and the reaction time is 30s；
After ketene dimer chlorination reaction terminates, ethanol is input into by measuring pump, reaction enters product collecting tank, collecting tank after terminating
Connection device for absorbing tail gas.GC analysis ethyl acetoacetate contents are 96%, 2,4- for the content of 1%, 4- chloroacetyl acetacetic esters
The content of dichloroacetyl ethyl acetate is about 0.2%, and other impurities are 2.8%.
Case study on implementation 4
The present embodiment is using device with embodiment 1.
Ketene dimer is 0.2 with 1,2- dichloroethanes mol ratio:1, it is hybridly prepared into solution, chlorine and 1,2- dichloroethanes
Mol ratio is 0.1:1 is configured to solution；
Ketene dimer solution, the chlorine solution that will be prepared are input in continuous stream micro passage reaction by measuring pump respectively,
Ketene dimer is 1 with the mol ratio of chlorine:1, reaction temperature is -10 DEG C, and the reaction time is 20s；
After ketene dimer chlorination reaction terminates, ethanol is input into by measuring pump, reaction enters product collecting tank, collecting tank after terminating
Connection device for absorbing tail gas.GC analysis ethyl acetoacetate contents are 97%, 2 for the content of 1.5%, 4- chloroacetyl acetacetic esters,
The content of 4- dichloroacetyl ethyl acetate is about 0.3%, and other impurities are 1.2%.
Case study on implementation 5
The present embodiment is using device with embodiment 1.
Ketene dimer is 0.5 with 1,2- dichloroethanes mol ratio:1, it is configured to after mixing, solution, chlorine and dichloroethanes
Mol ratio is 0.2:1, solution is configured to after mixing；
Ketene dimer solution, the chlorine solution that will be prepared are input in continuous stream micro passage reaction by measuring pump respectively,
Ketene dimer is 1 with the mol ratio of chlorine:1, reaction temperature is -20 DEG C, and the reaction time is 10s；
After ketene dimer chlorination reaction terminates, ethanol is input into by measuring pump, reaction enters product collecting tank, collecting tank after terminating
Connection device for absorbing tail gas.GC analysis ethyl acetoacetate contents are 95%, 2 for the content of 2.5%, 4- chloroacetyl acetacetic esters,
The content of 4- dichloroacetyl ethyl acetate is about 1.3%, and other impurities are 1.2%.
Claims (8)
1. a kind of continuous synthesis system of 4- chloroacetyl acetacetic esters, it is characterised in that：Including the first NaOH solution tank NaOH（1）, it is second molten
Flow container（2）, pump（3）, micro passage reaction（4）；The micro passage reaction（4）Upstream be provided with feed pipe（5）, downstream is provided with out
Expects pipe（6）；First NaOH solution tank NaOH（1）, the second NaOH solution tank NaOH（2）Pass through pump respectively（3）With the micro passage reaction（4）Enter
Expects pipe（5）Connection；Also include second reactor（7）, the second reactor（7）Including feed-inputing branched pipe（8）, discharge header pipe（9）, institute
State feed-inputing branched pipe（8）At least 2；Also include the 3rd NaOH solution tank NaOH（12）, the feed-inputing branched pipe（8）Respectively with the 3rd solution
Tank（12）, discharge nozzle（6）Connection, the 3rd NaOH solution tank NaOH（12）With the feed-inputing branched pipe（8）Between be provided with pump（3）；Also include receiving
Collection tank（13）, device for absorbing tail gas（14）, the collecting tank（13）Positioned at the discharge header pipe（9）Downstream；Device for absorbing tail gas
（14）Positioned at the collecting tank（13）Downstream.
2. the continuous synthesis system of 4- chloroacetyl acetacetic esters according to claim 1, it is characterised in that：Described second is anti-
Answer device（7）Feed-inputing branched pipe（8）, discharge header pipe（9）Inner chamber in be provided with island（10）, the island（10）There is multiple, it is adjacent in heart
Island（10）Between have gap, it is evenly distributed；The feed-inputing branched pipe（8）With the discharge header pipe（9）Junction be provided with central island
（11）, the central island（11）It is circle；The feed-inputing branched pipe（8）With the discharge header pipe（9）Junction for flexible connection.
3. the continuous synthesis system of 4- chloroacetyl acetacetic esters according to claim 1, it is characterised in that：Described first is molten
Flow container（1）It is ketene dimer solvent tank；Second NaOH solution tank NaOH（2）It is chlorine solution tank；3rd NaOH solution tank NaOH（12）It is Ethanol tank.
4. the continuous synthesis system of 4- chloroacetyl acetacetic esters according to claim 1, it is characterised in that：The pump（3）
It is measuring pump.
5. a kind of method of continuous synthesis system using 4- chloroacetyl acetacetic esters as claimed in claim 1, it is characterised in that：
Mainly include the following steps that：
1）Ketene dimer and chlorine are dissolved in organic solvent respectively, wiring solution-forming, are respectively placed in the first NaOH solution tank NaOH（1）, second
NaOH solution tank NaOH（2）；Ketene dimer is 0.05 ~ 50 with the mol ratio of organic solvent:1；The mol ratio of chlorine and organic solvent for 0.01 ~
50:1；
2）The ketene dimer and chlorine solution that will be prepared are through pump（3）It is input to micro passage reaction（4）In, carry out chlorination reaction；
Ketene dimer solution is -50 DEG C ~ 0 DEG C with chlorine solution range of reaction temperature, and the reaction time is 0.1 ~ 50s, ketene dimer and chlorine
Gas mol ratio is 0.9 ~ 1.5:1；
3）After ketene dimer chlorination reaction terminates, second reactor is passed through with ethanol（7）Reacted, synthesized 4- chloroethene ethyl acetoacetic acids
Ethyl ester, object passes through discharge header pipe（9）Into collecting tank（13）, collecting tank（13）Connection device for absorbing tail gas（14）, crude product
Refined into follow-up.
6. the method for continuously synthesizing of 4- chloroacetyl acetacetic esters according to claim 5, it is characterised in that：It is described organic molten
Agent is monochloro methane, dichloromethane, chloroform, carbon tetrachloride, 1,2- dichloroethanes, 1,1- dichloroethanes, 1,1,2- trichlorines
Ethane, what one or more in 1,1,1- trichloroethanes, n-hexane, normal heptane, p-chloro benzo trifluoride-99 were configured by a certain percentage
Mixture.
7. the method for continuously synthesizing of a kind of 4- chloroacetyl acetacetic esters according to claim 5, it is characterised in that：Double ethene
Ketone is preferably 0.1 ~ 0.5 with the mol ratio of organic solvent:1；Chlorine is preferably 0.05 ~ 0.2 with the mol ratio of organic solvent:1.
8. a kind of method for continuously synthesizing of 4- chloroacetyl acetacetic esters according to claim 5, it is characterised in that double ethene
Ketone solution is -30 DEG C ~ 0 DEG C with chlorine solution reaction preferred range, and reaction time preferred scope is 5 ~ 30s, ketene dimer
It is 1.0 ~ 1.1 with chlorine mol ratio preferred scope:1.
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Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107915631A (en) * | 2017-10-31 | 2018-04-17 | 南通醋酸化工股份有限公司 | A kind of post-processing approach of 4 chloro methyl acetoacetates of continuous synthesis |
| CN107915632A (en) * | 2017-10-31 | 2018-04-17 | 南通醋酸化工股份有限公司 | A kind of post-processing approach of continuous synthesis 4 chlorine, 3 oxobutyric |
| CN107915623A (en) * | 2017-10-31 | 2018-04-17 | 南通醋酸化工股份有限公司 | A kind of solvent-free 4 chloro methyl acetoacetate continuous stream synthetic method and system |
| CN107915622A (en) * | 2017-10-31 | 2018-04-17 | 南通醋酸化工股份有限公司 | A kind of solvent-free 4 chlorine, 3 oxobutyric continuous stream synthetic method and system |
| CN108752211A (en) * | 2018-07-03 | 2018-11-06 | 浙江禾本科技有限公司 | A method of 99% alpha-chloro methyl propionate is synthesized using micro- reaction method |
| 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 |
| CN110292894A (en) * | 2018-03-21 | 2019-10-01 | 南通醋酸化工股份有限公司 | A kind of tubular type continuous flow reaction unit and the method for preparing tert-butyl acetoacetate |
| CN112457211A (en) * | 2020-11-05 | 2021-03-09 | 丽珠集团新北江制药股份有限公司 | Method for preparing ethyl aminothiazolyloximate intermediate |
| CN112500290A (en) * | 2020-12-02 | 2021-03-16 | 江苏恒安化工有限公司 | Method for synthesizing 4-chloroacetoacetic acid methyl ester or 4-chloroacetoacetic acid ethyl ester |
| CN113087617A (en) * | 2021-03-10 | 2021-07-09 | 江苏琦衡农化科技有限公司 | Preparation method and preparation device of trichloroacetyl chloride |
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| CN107915631A (en) * | 2017-10-31 | 2018-04-17 | 南通醋酸化工股份有限公司 | A kind of post-processing approach of 4 chloro methyl acetoacetates of continuous synthesis |
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| CN107915623A (en) * | 2017-10-31 | 2018-04-17 | 南通醋酸化工股份有限公司 | A kind of solvent-free 4 chloro methyl acetoacetate continuous stream synthetic method and system |
| CN107915622A (en) * | 2017-10-31 | 2018-04-17 | 南通醋酸化工股份有限公司 | A kind of solvent-free 4 chlorine, 3 oxobutyric continuous stream synthetic method and system |
| CN107915631B (en) * | 2017-10-31 | 2020-11-13 | 南通醋酸化工股份有限公司 | Post-treatment method for continuously synthesizing 4-chloroacetoacetic acid methyl ester |
| CN107915632B (en) * | 2017-10-31 | 2020-11-13 | 南通醋酸化工股份有限公司 | Post-treatment method for continuously synthesizing 4-chloro-3-oxo-ethyl butyrate |
| CN110292894A (en) * | 2018-03-21 | 2019-10-01 | 南通醋酸化工股份有限公司 | A kind of tubular type continuous flow reaction unit and the method for preparing tert-butyl acetoacetate |
| CN108752211A (en) * | 2018-07-03 | 2018-11-06 | 浙江禾本科技有限公司 | A method of 99% alpha-chloro methyl propionate is synthesized using micro- reaction method |
| 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 |
| CN112457211A (en) * | 2020-11-05 | 2021-03-09 | 丽珠集团新北江制药股份有限公司 | Method for preparing ethyl aminothiazolyloximate intermediate |
| CN112457211B (en) * | 2020-11-05 | 2023-02-28 | 丽珠集团新北江制药股份有限公司 | Method for preparing ethyl aminothiazolyloximate intermediate |
| CN112500290A (en) * | 2020-12-02 | 2021-03-16 | 江苏恒安化工有限公司 | Method for synthesizing 4-chloroacetoacetic acid methyl ester or 4-chloroacetoacetic acid ethyl ester |
| CN113087617A (en) * | 2021-03-10 | 2021-07-09 | 江苏琦衡农化科技有限公司 | Preparation method and preparation device of trichloroacetyl chloride |
| CN114516812A (en) * | 2022-02-24 | 2022-05-20 | 复旦大学 | Full continuous flow preparation method of levocarnitine |
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Application publication date: 20170531 |