CN109776319A - A kind of production technology of trifluoroacetone acetoacetic ester - Google Patents
A kind of production technology of trifluoroacetone acetoacetic ester Download PDFInfo
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- CN109776319A CN109776319A CN201910239958.9A CN201910239958A CN109776319A CN 109776319 A CN109776319 A CN 109776319A CN 201910239958 A CN201910239958 A CN 201910239958A CN 109776319 A CN109776319 A CN 109776319A
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- acetoacetic ester
- trifluoroacetone acetoacetic
- production technology
- trifluoroacetone
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Abstract
The invention discloses a kind of production technologies of trifluoroacetone acetoacetic ester, include the following steps: for zinc powder, pyridine, diethy-aceto oxalate and catalyst to be added to in churned mechanically three-necked flask, open stirring, it vacuumizes, it is passed through bromotrifluoromethane gas at a certain temperature, it controls draft speed and keeps normal pressure, until zinc powder total overall reaction is complete in flask, continue stirring 4 hours；Then reaction solution is poured into cryosel acid and is hydrolyzed；Finished product trifluoroacetone acetoacetic ester is obtained using extraction, drying, distillation, rectifying.Material of the present invention is simple and easy to get, and production equipment is simple；Process flow is short, without complicated after-treatment device；Good reaction selectivity, high income；Product purity is high, and the content of trifluoroacetone acetoacetic ester obtained is 98.5% or more.
Description
Technical field
The invention belongs to chemical production fields, and in particular to a kind of production technology of trifluoroacetone acetoacetic ester.
Background technique
Trifluoropyruvate compound is a kind of maximum trifluoromethyl building block reagent of current needs amount, in organic fluoride
It occupies an important position in the synthesis of work.This kind of compound has two reaction centers (carbonyl and ester group), can synthesize three
The compound of the complexity such as methyl fluoride heterocyclic compounds, this kind of compound are former as the precursor in the fields such as medicine of new generation, pesticide
Material is widely used.Such as in pharmaceuticals industry, trifluoropyruvate compound can synthesize anti-inflammatory agent, anticancer and the classes such as antiviral
Drug.
There are mainly two types of the synthetic routes of trifluoropyruvate compound.One is with bromotrifluoromethane and ethanedioic acid two
Ester is raw material, at normal temperatures and pressures, with after the compound body catalyst synthetic intermediate of zinc powder-pyridine again through sour water solution be made trifluoropropyl
Keto ester, product yield are about 60%.The route reaction time is longer, and yield is low, and three wastes yield is big, and operating condition is more severe
It carves, is not suitable for being mass produced.
Another technique be using the fluoro- 2- alkoxy-trifluoropropyl acid esters of 2- and the concentrated sulfuric acid or oleum as primary raw material,
It in the presence of white carbon black, is reacted at 110~140 DEG C, obtains trifluoroacetone acid esters, yield is relatively low, is not higher than 90%；And
Content is relatively low, and only 95%, need rectifying again that can just obtain qualified products.This technique have operating condition it is mild, yield compared with
The advantages that high；But reaction selectivity is lower, and crude product purity is low, must handle through subsequent purification, lead to the disadvantages of complicated for operation.
Summary of the invention
Goal of the invention: in order to solve the deficiencies in the prior art, the present invention provides a kind of productions of trifluoroacetone acetoacetic ester
Technique.
Technical solution: a kind of production technology of trifluoroacetone acetoacetic ester includes the following steps:
(1) zinc powder, pyridine, diethy-aceto oxalate and catalyst are added to in churned mechanically three-necked flask, unlatching is stirred
It mixes, vacuumizes, be passed through bromotrifluoromethane gas at a certain temperature, control draft speed keeps normal pressure, until zinc powder in flask
Total overall reaction is complete, continues stirring 4 hours；
(2) then reaction solution is poured into cryosel acid and is hydrolyzed；
(3) finished product trifluoroacetone acetoacetic ester is obtained using extraction, drying, distillation, rectifying；Wherein, institute in extraction process
With extractant ether, methyl tertiary butyl ether(MTBE), isopropyl ether, methylene chloride, ethyl acetate；Desiccant used is nothing in drying process
Water magnesium sulfate, anhydrous sodium sulfate, silica gel, molecular sieve (5A)；Recycling pyridine, unreacted oxalic acid diethyl are obtained in distillation process
Ester and crude product trifluoroacetone acetoacetic ester；The product that 134-136 DEG C is collected in distillation process, obtains finished product trifluoroacetone acetoacetic ester.
As optimization: the molar ratio of the diethy-aceto oxalate and zinc powder is 1:0.5-1.
As optimization: the molar ratio of the diethy-aceto oxalate and zinc powder is 1:0.8.
As optimization: the diethy-aceto oxalate and pyridine mass ratio is 1:1-6.
As optimization: the diethy-aceto oxalate and pyridine mass ratio is 1:2.
As optimization: the bromotrifluoromethane gas is passed through temperature when being passed through be 0-50 DEG C.
As optimization: the bromotrifluoromethane gas is passed through temperature when being passed through be 15-20 DEG C.
As optimization: the cryosel acid is the hydrochloric acid of 20% mass fraction.
As optimization: controlled at 0-5 DEG C when the reaction solution pours into cryosel acid.
The utility model has the advantages that material of the present invention is simple and easy to get, production equipment is simple；Process flow is short, is not necessarily to complexity
After-treatment device；Good reaction selectivity, high income；Product purity is high, and the content of trifluoroacetone acetoacetic ester obtained exists
98.5% or more.
Specific embodiment
The technical scheme in the embodiments of the invention will be clearly and completely described below, so that the technology of this field
Personnel can better understand advantages and features of the invention, to make apparent boundary to protection scope of the present invention
It is fixed.Embodiment described in the invention is only a part of the embodiment of the present invention, instead of all the embodiments, based on the present invention
In embodiment, those of ordinary skill in the art's every other implementation obtained without making creative work
Example, shall fall within the protection scope of the present invention.
Specific embodiment 1
A kind of production technology of trifluoroacetone acetoacetic ester, includes the following steps:
(1) zinc powder, pyridine, diethy-aceto oxalate and catalyst are added to in churned mechanically three-necked flask, unlatching is stirred
It mixes, vacuumizes, be passed through bromotrifluoromethane gas at a certain temperature, control draft speed keeps normal pressure, until zinc powder in flask
Total overall reaction is complete, continues stirring 4 hours；The molar ratio of the diethy-aceto oxalate and zinc powder is 1:0.5；The oxalic acid diethyl
Ester and pyridine mass ratio are 1:1；The bromotrifluoromethane gas is passed through temperature when being passed through be 50 DEG C；
(2) then reaction solution is poured into cryosel acid and is hydrolyzed；The cryosel acid is the hydrochloric acid of 20% mass fraction, described
Reaction solution pour into cryosel acid in when controlled at 0 DEG C；
(3) finished product trifluoroacetone acetoacetic ester is obtained using extraction, drying, distillation, rectifying；Wherein, institute in extraction process
With extractant ether, methyl tertiary butyl ether(MTBE), isopropyl ether, methylene chloride, ethyl acetate；Desiccant used is nothing in drying process
Water magnesium sulfate, anhydrous sodium sulfate, silica gel, molecular sieve (5A)；Recycling pyridine, unreacted oxalic acid diethyl are obtained in distillation process
Ester and crude product trifluoroacetone acetoacetic ester；The product that 134 DEG C are collected in distillation process, obtains finished product trifluoroacetone acetoacetic ester.
Specific embodiment 2
A kind of production technology of trifluoroacetone acetoacetic ester, includes the following steps:
(1) zinc powder, pyridine, diethy-aceto oxalate and catalyst are added to in churned mechanically three-necked flask, unlatching is stirred
It mixes, vacuumizes, be passed through bromotrifluoromethane gas at a certain temperature, control draft speed keeps normal pressure, until zinc powder in flask
Total overall reaction is complete, continues stirring 4 hours；The molar ratio of the diethy-aceto oxalate and zinc powder is 1:1；The diethy-aceto oxalate
It is 1:6 with pyridine mass ratio；The bromotrifluoromethane gas is passed through temperature when being passed through be 15 DEG C；
(2) then reaction solution is poured into cryosel acid and is hydrolyzed；The cryosel acid is the hydrochloric acid of 20% mass fraction, described
Reaction solution pour into cryosel acid in when controlled at 5 DEG C；
(3) finished product trifluoroacetone acetoacetic ester is obtained using extraction, drying, distillation, rectifying；Wherein, institute in extraction process
With extractant ether, methyl tertiary butyl ether(MTBE), isopropyl ether, methylene chloride, ethyl acetate；Desiccant used is nothing in drying process
Water magnesium sulfate, anhydrous sodium sulfate, silica gel, molecular sieve (5A)；Recycling pyridine, unreacted oxalic acid diethyl are obtained in distillation process
Ester and crude product trifluoroacetone acetoacetic ester；The product that 136 DEG C are collected in distillation process, obtains finished product trifluoroacetone acetoacetic ester.
Specific embodiment 3
A kind of production technology of trifluoroacetone acetoacetic ester, includes the following steps:
(1) zinc powder, pyridine, diethy-aceto oxalate and catalyst are added to in churned mechanically three-necked flask, unlatching is stirred
It mixes, vacuumizes, be passed through bromotrifluoromethane gas at a certain temperature, control draft speed keeps normal pressure, until zinc powder in flask
Total overall reaction is complete, continues stirring 4 hours；The molar ratio of the diethy-aceto oxalate and zinc powder is 1:0.8；The oxalic acid diethyl
Ester and pyridine mass ratio are 1:2；The bromotrifluoromethane gas is passed through temperature when being passed through be 20 DEG C；
(2) then reaction solution is poured into cryosel acid and is hydrolyzed；The cryosel acid is the hydrochloric acid of 20% mass fraction, described
Reaction solution pour into cryosel acid in when controlled at 3 DEG C；
(3) finished product trifluoroacetone acetoacetic ester is obtained using extraction, drying, distillation, rectifying；Wherein, institute in extraction process
With extractant ether, methyl tertiary butyl ether(MTBE), isopropyl ether, methylene chloride, ethyl acetate；Desiccant used is nothing in drying process
Water magnesium sulfate, anhydrous sodium sulfate, silica gel, molecular sieve (5A)；Recycling pyridine, unreacted oxalic acid diethyl are obtained in distillation process
Ester and crude product trifluoroacetone acetoacetic ester；The product that 135 DEG C are collected in distillation process, obtains finished product trifluoroacetone acetoacetic ester.
Material of the present invention is simple and easy to get, and production equipment is simple；Process flow is short, fills without complicated post-processing
It sets；Good reaction selectivity, high income；Product purity is high, and the content of trifluoroacetone acetoacetic ester obtained is 98.5% or more.
Claims (9)
1. a kind of production technology of trifluoroacetone acetoacetic ester, characterized by the following steps:
(1) zinc powder, pyridine, diethy-aceto oxalate and catalyst are added to in churned mechanically three-necked flask, open stirring, taken out
Vacuum is passed through bromotrifluoromethane gas at a certain temperature, and control draft speed keeps normal pressure, until zinc powder is all anti-in flask
It has been answered that, continue stirring 4 hours；
(2) then reaction solution is poured into cryosel acid and is hydrolyzed；
(3) finished product trifluoroacetone acetoacetic ester is obtained using extraction, drying, distillation, rectifying；Wherein, extraction used in extraction process
Take agent ether, methyl tertiary butyl ether(MTBE), isopropyl ether, methylene chloride, ethyl acetate；Desiccant used is anhydrous sulphur in drying process
Sour magnesium, anhydrous sodium sulfate, silica gel, molecular sieve (5A)；Obtained in distillation process recycling pyridine, unreacted diethy-aceto oxalate and
Crude product trifluoroacetone acetoacetic ester；The product that 134-136 DEG C is collected in distillation process, obtains finished product trifluoroacetone acetoacetic ester.
2. the production technology of trifluoroacetone acetoacetic ester according to claim 1, it is characterised in that: the diethy-aceto oxalate
Molar ratio with zinc powder is 1:0.5-1.
3. the production technology of trifluoroacetone acetoacetic ester according to claim 2, it is characterised in that: the diethy-aceto oxalate
Molar ratio with zinc powder is 1:0.8.
4. the production technology of trifluoroacetone acetoacetic ester according to claim 1, it is characterised in that: the diethy-aceto oxalate
It is 1:1-6 with pyridine mass ratio.
5. the production technology of trifluoroacetone acetoacetic ester according to claim 4, it is characterised in that: the diethy-aceto oxalate
It is 1:2 with pyridine mass ratio.
6. the production technology of trifluoroacetone acetoacetic ester according to claim 1, it is characterised in that: the bromotrifluoromethane
It is 0-50 DEG C that temperature is passed through when gas is passed through.
7. the production technology of trifluoroacetone acetoacetic ester according to claim 1, it is characterised in that: the bromotrifluoromethane
It is 15-20 DEG C that temperature is passed through when gas is passed through.
8. the production technology of trifluoroacetone acetoacetic ester according to claim 1, it is characterised in that: the cryosel acid is
The hydrochloric acid of 20% mass fraction.
9. the production technology of trifluoroacetone acetoacetic ester according to claim 1, it is characterised in that: the reaction solution pours into
Controlled at 0-5 DEG C when in cryosel acid.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103880715A (en) * | 2012-12-19 | 2014-06-25 | 张家港市国泰华荣化工新材料有限公司 | Method for continuously preparing ethyl trifluoromethanesulfonate |
| CN107056606A (en) * | 2017-06-09 | 2017-08-18 | 浙江工业大学 | A kind of preparation method of 3 fluoropyruvate |
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2019
- 2019-03-27 CN CN201910239958.9A patent/CN109776319A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103880715A (en) * | 2012-12-19 | 2014-06-25 | 张家港市国泰华荣化工新材料有限公司 | Method for continuously preparing ethyl trifluoromethanesulfonate |
| CN107056606A (en) * | 2017-06-09 | 2017-08-18 | 浙江工业大学 | A kind of preparation method of 3 fluoropyruvate |
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