CN108017523A - A kind of method for preparing the chloro- 3,3,3- trifluoroacetones of 1- - Google Patents
A kind of method for preparing the chloro- 3,3,3- trifluoroacetones of 1- Download PDFInfo
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- CN108017523A CN108017523A CN201610945169.3A CN201610945169A CN108017523A CN 108017523 A CN108017523 A CN 108017523A CN 201610945169 A CN201610945169 A CN 201610945169A CN 108017523 A CN108017523 A CN 108017523A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/42—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by hydrolysis
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- C—CHEMISTRY; METALLURGY
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- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
- C07C45/67—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton
- C07C45/673—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by change of size of the carbon skeleton
- C07C45/676—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by change of size of the carbon skeleton by elimination of carboxyl groups
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- C07C67/00—Preparation of carboxylic acid esters
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Abstract
The invention discloses the method that one kind prepares 1 chlorine, 3,3,3 trifluoroacetone, and with 2,3 dichloro of hexafluoro, 2 butene feedstock, first the ethanol solution with sodium ethoxide reacts, then acidified and decarboxylic reaction obtains 1 chlorine, 3,3,3 trifluoroacetone.Method provided by the invention, has the advantages that raw material is easy to get, cost is low, high income, preparation process are gentle, reaction is safe.1 chlorine, 3,3,3 trifluoroacetone prepared, is suitable for synthesis medicine, pesticide intermediate and bulk pharmaceutical chemicals.
Description
Technical field
1- chloro- 3 is prepared the present invention relates to one kind, the method for 3,3- trifluoroacetones, more particularly to one kind with hexafluoro -2,
3- dichloro-2-butenes are the method that raw material prepares the chloro- 3,3,3- trifluoroacetones of 1-.
Background technology
1- chloro- 3,3,3- trifluoroacetones, referred to as " a chlorine trifluoroacetone ", and English name 1-chloro-3,3,3-
Trifluoroacetone, molecular formula C3H2ClF3O, CAS 431-37-8, molecular weight 146.5,71~72 DEG C of boiling point, density
1.45g/cm3, refractive index 1.3445, structural formula is as follows：
One chlorine trifluoroacetone contains acetonyl, cyclization can form the heterocycles such as pyrazoles, oxazole, thiazole under mild conditions
Derivative, so as to introduce trifluoromethyl group, therefore is used not only for synthesis medicine, pesticide intermediate and bulk pharmaceutical chemicals, also can
For synthesizing various fluoride-containing PMMAs, such as the synthesis three of Japan Patent JP2000336057 and JP2003160528 report
Tri- fluoro- 1,2 epoxy prapanes (TFPO) of synthesis 3,3,3-, the Japan Patent that fluorine acetone, European patent EP 866064 are reported
The fluoro- 2- aryl -2- propyl alcohol of the chloro- 1,1,1- tri- of synthesis 3- of JP11228470 reports.Wherein tri- fluoro- 1,2 epoxy prapanes of 3,3,3-
(TFPO) it is a kind of highly useful intermediate, can be used in synthesizing the precursor of trifluoromethyl ethylene carbonate, and trifluoromethyl
Ethylene carbonate is a kind of electrolyte of useful lithium battery and fuel cell, has high energy transformation ratio, pernicious gas and makes an uproar
The features such as sound discharge is low.
For the preparation method of a chlorine trifluoroacetone, the prior art has following report：
(1) nineteen fifty, document J.Am.Chem.Soc., 1950,72:3289 reports are using trifluoroacetic ethyl acetoacetate as starting
The method that raw material prepares a chlorine trifluoroacetone.Chlorine is passed through in trifluoroacetic ethyl acetoacetate, and rectifying obtains chloro trifluoroacetyl second
Acetoacetic ester, 67~69 DEG C of boiling point.Chloro trifluoroacetic ethyl acetoacetate and the reflux of 30% sulfuric acid.Reactant is done with phosphorus pentoxide
Dry, distillation obtains a chlorine trifluoroacetone.The route raw material is related to chlorine operation, has certain danger, and trifluoroacetyl second
Acetoacetic ester price is costly；
(2) nineteen fifty-five, Dow Chemical company United States Patent (USP) US2715144, which discloses to be related to, prepares a chlorine trifluoroacetone
Method.By the chloro- 2- methoxyl groups -3,3 of 1-, after a certain period of time, reactant is added for 3- trifluoro propenes and hydroiodic acid back flow reaction
In water, organic phase is separated, the chloro- 1,1,1-trifluoroacetone of 3- is can obtain after rectifying.Reaction equation is as follows：
Raw material involved by the route is not easy to obtain, and expensive, and reaction mechanism is complicated；
(3) the Japan Patent JP02040338 of nineteen ninety Japan nitre subsidiary is reported with the fluoro- 2- third of 3,3,3- tri-
The method that zinecarboxylic acid ester prepares a chlorine trifluoroacetone for raw material.Reaction equation is as follows：
3,3,3- tri- fluoro- 2- propylene formic acid esters and chlorine or bromine reaction, for temperature at 20~80 DEG C, catalyst is phosphoric
Antimony, can be prepared a chlorine trifluoroacetone and the bromo- 1,1,1-trifluoroacetone of 3-.The route raw material is related to halogen operation, dangerous
Height, and reagent price is expensive, is not easy to prepare.
The method of the one chlorine trifluoroacetone of preparation of prior art report, there are expensive raw material price and operational hazards etc. to lack
Fall into.It is therefore desirable to the preparation method of a chlorine trifluoroacetone is further improved.
The content of the invention
It is an object of the invention to provide a kind of 1- chloro- 3, the preparation method of 3,3- trifluoroacetones, there is raw material to be easy to get, into
The features such as this low, high income, preparation process are gentle, reaction is safe.
The present invention with hexafluoro -2,3- dichloro-2-butene (referred to as " R1316 ") for raw material, first and sodium ethoxide ethanol solution
Reaction, intermediate product 2- chloro- 4 is obtained after then carrying out acidification reaction with acid, 4,4- tri- fluoro- 3,3- diethoxies ethyl butyrates,
Again the chloro- 3,3,3- trifluoroacetones of 1- are obtained through decarboxylic reaction.
The reaction scheme of preparation method provided by the invention is as follows：
The present invention provides following technical solution：
One kind prepares 1- chloro- 3, the method for 3,3- trifluoroacetones, the described method includes：
(1) ethanol solution and hexafluoro -2,3- dichloro-2-butenes for first making sodium ethoxide react to obtain reaction solution；
(2) reaction solution and acid is carried out acidification reaction, obtain 2- chloro- 4,4,4- tri- fluoro- 3,3- diethoxies butyric acid second
Ester；
(3) the fluoro- 3,3- diethoxies ethyl butyrates of the chloro- 4,4,4- tri- of 2- and decarboxylating agent is made to react to obtain the chloro- 3,3,3- of 1-
Trifluoroacetone.
Preparation 1- chloro- 3 provided by the invention, the method for 3,3- trifluoroacetones, the first step first makes the ethanol solution of sodium ethoxide
Reacted with hexafluoro -2,3- dichloro-2-butene, to obtain reaction solution.In operation, preferable mode is：In 20~50 DEG C of temperature
Under, first toward the ethanol solution of addition sodium ethoxide in reactor, hexafluoro -2,3- dichloro-2-butene is added, is controlled after the completion of charging
Temperature in reactor is 60~130 DEG C, when making its reaction 1.0~8.0 small.The wherein preparation of the ethanol solution of sodium ethoxide, can
To be to be realized successively toward addition ethanol in reactor and sodium ethoxide, the ethanol solution of sodium ethoxide is configured to.
The ethanol solution of the sodium ethoxide, available concentration are generally zero to saturated concentration.The saturated concentration is second
In the ethanol solution of sodium alkoxide, sodium ethoxide is set to reach the concentration of saturation state.Preferably, the ethanol solution of the sodium ethoxide is dense
Spend for 10~35%.
Preparation 1- chloro- 3 provided by the invention, the method for 3,3- trifluoroacetones, in first step reaction, sodium ethoxide and hexafluoro-
The mol ratio of 2,3- dichloro-2-butenes meets to be smoothed out reaction.Preferably, the sodium ethoxide and hexafluoro -2,
The mol ratio of 3- dichloro-2-butenes is 3.0~6.0:1.0.It may further be preferable that the sodium ethoxide and hexafluoro -2,3- bis-
The mol ratio of chloro- 2- butylene is 3.5~5.0:1.0.
Preparation 1- chloro- 3 provided by the invention, the method for 3,3- trifluoroacetones, second step reaction carry out reaction solution and acid
Acidification reaction, obtains 2- chloro- 4,4,4- tri- fluoro- 3,3- diethoxies ethyl butyrates.In operation, preferable mode is：First make
Reaction solution and acid carry out acidification reaction, the temperature of reaction system is cooled to 20~30 DEG C, add water and organic solvent,
The fluoro- 3,3- diethoxies ethyl butyrates of the chloro- 4,4,4- tri- of intermediate 2- are obtained after separation.
The acid, be capable of providing acid ion in theory could be used for the present invention.Preferably, the acid is selected from dense sulphur
At least one of acid, concentrated hydrochloric acid, acetic acid, anhydrous formic acid and methanesulfonic acid.It may further be preferable that the acid is selected from the concentrated sulfuric acid
And/or anhydrous formic acid.
The mol ratio of the acid and sodium ethoxide, satisfaction are smoothed out reaction.Preferably, the acid and ethanol
The mol ratio of sodium is 0.3~2.0:1.0.It may further be preferable that the mol ratio of the acid and sodium ethoxide is 0.5~1.5:
1.0.The organic solvent, organic solvent commonly used in the art could be used for the present invention.Preferably, the organic solvent is selected from
At least one of ethyl acetate, dichloromethane, hexamethylene and tetrahydrofuran.It may further be preferable that the organic solvent choosing
From ethyl acetate and/or dichloromethane.
Preparation 1- chloro- 3 provided by the invention, the method for 3,3- trifluoroacetones, three-step reaction makes intermediate 2- chloro- 4,4,
The fluoro- 3,3- diethoxies ethyl butyrates of 4- tri- and decarboxylating agent react to obtain the chloro- 3,3,3- trifluoroacetones of 1-.In operation, preferably
Mode be：It is toward addition 2- chloro- 4,4,4- tri- fluoro- 3,3- diethoxies ethyl butyrates, controlling reaction temperature in reactor first
80~180 DEG C, decarboxylating agent is added, when reaction 0.5~8.0 is small.
The decarboxylating agent, in theory decarboxylating agent commonly used in the art be used equally for the present invention.Preferably, the decarboxylating agent
Selected from least one of the concentrated sulfuric acid, concentrated hydrochloric acid, acetic acid, anhydrous formic acid and methanesulfonic acid.It may further be preferable that the decarboxylating agent
Selected from the concentrated sulfuric acid and/or methanesulfonic acid.
The decarboxylating agent and 2- chloro- 4, the mol ratio of 4,4- tri- fluoro- 3,3- diethoxies ethyl butyrates, satisfaction make reaction
It is smoothed out.Preferably, the decarboxylating agent and 2- chloro- 4, mole of 4,4- tri- fluoro- 3,3- diethoxies ethyl butyrates
Match as 1.0~6.0:1.0.It may further be preferable that the decarboxylating agent and 2- chloro- 4,4,4- tri- fluoro- 3,3- diethoxies fourths
The mol ratio of acetoacetic ester is 1.2~2.0:1.0.
Preparation 1- chloro- 3 provided by the invention, the method for 3,3- trifluoroacetones, the temperature in three-step reaction per single step reaction
Reaction should be enable to be smoothed out.Preferably, the reaction temperature of step (1) is 80~120 DEG C, and acidifying is anti-in step (2)
The reaction temperature answered is 90~120 DEG C, and the reaction temperature of step (3) is 120~160 DEG C.
1- chloro- 3 prepared by the present invention, 3,3- trifluoroacetones, can further carry out distillation operation to improve 1- chloro- 3,3,
The purity of 3- trifluoroacetones.The distillation operation, can be used distillation operation means commonly used in the art.
Preparation 1- chloro- 3 provided by the invention, the method for 3,3- trifluoroacetones, compared with prior art, has following excellent
Point：It is homogeneous reaction using the ethanol solution of sodium ethoxide as reaction system, reacts more complete, yield higher；Raw material hexafluoro -2,3-
Dichloro-2-butene is easy to get, and cost of material is low；Preparation process is novel, and process safety is reliable.
Embodiment
The present invention is further described with reference to specific embodiment, but does not limit the invention to these tools
Body embodiment.One skilled in the art would recognize that present invention encompasses may include in Claims scope
All alternatives, improvement project and equivalents.
Embodiment 1
At 25 DEG C, 45mL absolute ethyl alcohols are added in the reactor, are slow added into 15.6g (0.23mol) sodium ethoxide, stir
The ethanol solution of 30% sodium ethoxide is configured to, then starts that 14g (0.06mol) R1316 is added dropwise, when dropwise addition keeps reacting liquid temperature
For 25~40 DEG C, 100 DEG C, when stirring reaction 5 is small are warming up to after being added dropwise.Reaction solution is cooled to 10~20 DEG C, nothing is added dropwise
Water beetle acid 12.5g (0.27mol), it is 20~30 DEG C to control reacting liquid temperature, after being added dropwise, is warming up to 110 DEG C, the reaction time
2 it is small when.Reaction solution is cooled to 20~30 DEG C, adds 100mL water and 50mL ethyl acetate, extraction liquid separation obtains organic phase, washes
Wash, be concentrated to give the crude product of the fluoro- 3,3- diethoxies ethyl butyrates of the chloro- 4,4,4- tri- of 2-.The chloro- tri- fluoro- 3,3- of 4,4,4- of 2-
Diethoxy ethyl butyrate crude product is warming up to 130 DEG C, and methanesulfonic acid 4.8g (0.05mol) is added dropwise, and after being added dropwise, reaction 5 is small
When.Rectifying obtains a chlorine trifluoroacetone 6.2g, yield 70.5%, purity 97.2% after distilling out reaction product.
Embodiment 2
At 25 DEG C, 115mL absolute ethyl alcohols are added in the reactor, 30.6g (0.45mol) sodium ethoxide is slow added into, stirs
The ethanol solution for being configured to 25% sodium ethoxide is mixed, then starts that 27.9g (0.12mol) R1316 is added dropwise, when dropwise addition keeps reaction solution
Temperature is 25~40 DEG C, and 110 DEG C, when stirring reaction 4 is small are warming up to after being added dropwise.Reaction solution is cooled to 10~20 DEG C, drop
Add sulfuric acid 22.5g (0.23mol), it is 20~30 DEG C to control reacting liquid temperature, after being added dropwise, is warming up to 100 DEG C, the reaction time
3 it is small when.Reaction solution is cooled to 20~30 DEG C, adds 150mL water and 70mL ethyl acetate, extraction liquid separation obtains organic phase, washes
Wash, be concentrated to give the crude product of the fluoro- 3,3- diethoxies ethyl butyrates of the chloro- 4,4,4- tri- of 2-.The chloro- tri- fluoro- 3,3- of 4,4,4- of 2-
Diethoxy ethyl butyrate crude product is warming up to 150 DEG C, and concentrated sulfuric acid 10.8g (0.11mol) is added dropwise, and after being added dropwise, reaction 6 is small
When.Rectifying obtains a chlorine trifluoroacetone 12.8g, yield 72.8%, purity 98.1% after distilling out reaction product.
Embodiment 3
At 25 DEG C, 105mL absolute ethyl alcohols are added in the reactor, 21.1g (0.31mol) sodium ethoxide is slow added into, stirs
The ethanol solution for being configured to 20% sodium ethoxide is mixed, then starts that 18.6g (0.08mol) R1316 is added dropwise, when dropwise addition keeps reaction solution
Temperature is 25~40 DEG C, and 130 DEG C, when stirring reaction 3 is small are warming up to after being added dropwise.Reaction solution is cooled to 10~20 DEG C, drop
Add anhydrous formic acid 15.2g (0.33mol), it is 20~30 DEG C to control reacting liquid temperature, after being added dropwise, is warming up to 120 DEG C, reaction
Time 2 h.Reaction solution is cooled to 20~30 DEG C, adds 100mL water and 50mL ethyl acetate, extraction liquid separation obtains organic
Phase, washs, is concentrated to give 2- chloro- 4, the crude product of 4,4- tri- fluoro- 3,3- diethoxies ethyl butyrates.The chloro- 4,4,4- tri- of 2- are fluoro-
3,3- diethoxy ethyl butyrate crude products are warming up to 140 DEG C, and concentrated sulfuric acid 6.3g (0.06mol) is added dropwise, after being added dropwise, reaction
5 it is small when.Rectifying obtains a chlorine trifluoroacetone 8.1g, yield 68.3%, purity 98.2% after distilling out reaction product.
Embodiment 4
At 25 DEG C, 300mL absolute ethyl alcohols are added in the reactor, 102.7g (1.51mol) sodium ethoxide is slow added into, stirs
The ethanol solution for being configured to 30% sodium ethoxide is mixed, then starts that 100.3g (0.43mol) R1316 is added dropwise, reaction is kept during dropwise addition
Liquid temperature degree is 30~50 DEG C, and 120 DEG C, when stirring reaction 6 is small are warming up to after being added dropwise.Reaction solution is cooled to 10~20 DEG C,
Concentrated sulfuric acid 73.9g (0.75mol) is added dropwise, it is 30~40 DEG C to control reacting liquid temperature, after being added dropwise, is warming up to 130 DEG C, reaction
When time 3 is small.Reaction solution is cooled to 20~30 DEG C, adds 300mL water and 200mL dichloromethane, extraction liquid separation obtains organic
Phase, washs, is concentrated to give 2- chloro- 4, the crude product of 4,4- tri- fluoro- 3,3- diethoxies ethyl butyrates.The chloro- 4,4,4- tri- of 2- are fluoro-
3,3- diethoxy ethyl butyrate crude products are warming up to 150 DEG C, concentrated sulfuric acid 30.4g (0.31mol) are added dropwise, after being added dropwise, instead
Answer 6 it is small when.Rectifying obtains a chlorine trifluoroacetone 46.9g, yield 74.5%, purity 97.8% after distilling out reaction product.
Embodiment 5
At 25 DEG C, 438mL absolute ethyl alcohols are added in the reactor, 116.9g (1.72mol) sodium ethoxide is slow added into, stirs
The ethanol solution for being configured to 25% sodium ethoxide is mixed, then starts that 100.1g (0.43mol) R1316 is added dropwise, reaction is kept during dropwise addition
Liquid temperature degree is 30~50 DEG C, and 110 DEG C, when stirring reaction 4 is small are warming up to after being added dropwise.Reaction solution is cooled to 10~20 DEG C,
Anhydrous formic acid 102.6g (2.23mol) is added dropwise, it is 30~40 DEG C to control reacting liquid temperature, after being added dropwise, is warming up to 120 DEG C,
When reaction time 3 is small.Reaction solution is cooled to 20~30 DEG C, adds 300mL water and 200mL dichloromethane, extraction liquid separation obtains
Organic phase, washs, is concentrated to give 2- chloro- 4, the crude product of 4,4- tri- fluoro- 3,3- diethoxies ethyl butyrates.The chloro- 4,4,4- of 2-
Three fluoro- 3,3- diethoxies ethyl butyrate crude products are warming up to 140 DEG C, and methanesulfonic acid 32.6g (0.34mol) is added dropwise, is added dropwise
Afterwards, when reaction 7 is small.Rectifying obtains a chlorine trifluoroacetone 46.1g, yield 73.2%, purity after distilling out reaction product
97.5%.
Embodiment 6
At 25 DEG C, 418mL absolute ethyl alcohols are added in the reactor, 143.5g (2.11mol) sodium ethoxide is slow added into, stirs
The ethanol solution for being configured to 30% sodium ethoxide is mixed, then starts that 137.4g (0.59mol) R1316 is added dropwise, reaction is kept during dropwise addition
Liquid temperature degree is 25~40 DEG C, and 130 DEG C, when stirring reaction 6 is small are warming up to after being added dropwise.Reaction solution is cooled to 10~20 DEG C,
Anhydrous formic acid 106.7g (2.32mol) is added dropwise, it is 30~40 DEG C to control reacting liquid temperature, after being added dropwise, is warming up to 130 DEG C,
When reaction time 4 is small.Reaction solution is cooled to 20~30 DEG C, adds 400mL water and 300mL dichloromethane, extraction liquid separation obtains
Organic phase, washs, is concentrated to give 2- chloro- 4, the crude product of 4,4- tri- fluoro- 3,3- diethoxies ethyl butyrates, rectifying obtains sterling
143g, purity 99.5%.By 2- chloro- 4,4,4- tri- fluoro- 3,3- diethoxies ethyl butyrates are warming up to 150 DEG C, and the concentrated sulfuric acid is added dropwise
46.1g (0.47mol), after being added dropwise, when reaction 8 is small.Rectifying obtains a chlorine trifluoroacetone after distilling out reaction product
53.2g, yield 61.5%, purity 98.6%.
Claims (12)
1. one kind prepares 1- chloro- 3, the method for 3,3- trifluoroacetones, it is characterised in that the described method includes：
(1) ethanol solution and hexafluoro -2,3- dichloro-2-butenes for first making sodium ethoxide react to obtain reaction solution；
(2) reaction solution and acid is carried out acidification reaction, obtain 2- chloro- 4,4,4- tri- fluoro- 3,3- diethoxies ethyl butyrates；
(3) the fluoro- 3,3- diethoxies ethyl butyrates of the chloro- 4,4,4- tri- of 2- and decarboxylating agent is made to react to obtain the chloro- 3,3,3- trifluoros of 1-
Acetone.
2. preparation 1- chloro- 3 described in accordance with the claim 1, the method for 3,3- trifluoroacetones, it is characterised in that the step (1)
In：The ethanol solution of the sodium ethoxide, its concentration are to saturated concentration more than zero；Sodium ethoxide and hexafluoro -2,3- dichloro-2-butenes
Mol ratio be 3.0~6.0:1.0.
3. preparation 1- chloro- 3 described in accordance with the claim 2, the method for 3,3- trifluoroacetones, it is characterised in that the step (1)
In：The ethanol solution of the sodium ethoxide, its concentration are 10~35%；Sodium ethoxide and hexafluoro -2,3- dichloro-2-butenes mole are matched somebody with somebody
Than for 3.5~5.0:1.0.
4. preparation 1- chloro- 3 described in accordance with the claim 1, the method for 3,3- trifluoroacetones, it is characterised in that the step (2)
In：Acid is selected from least one of the concentrated sulfuric acid, concentrated hydrochloric acid, acetic acid, anhydrous formic acid and methanesulfonic acid, the mol ratio of acid and sodium ethoxide
For 0.3~2.0:1.0.
5. according to the preparation 1- chloro- 3 described in claim 4, the method for 3,3- trifluoroacetones, it is characterised in that the step (2)
In：Acid is selected from the concentrated sulfuric acid and/or anhydrous formic acid, and sour and sodium ethoxide mol ratio is 0.5~1.5:1.0.
6. preparation 1- chloro- 3 described in accordance with the claim 1, the method for 3,3- trifluoroacetones, it is characterised in that the step (2)
In：After reaction solution and acid carry out acidification reaction, the temperature of reaction system is cooled to 20~30 DEG C, add water and organic molten
Agent, obtains 2- chloro- 4,4,4- tri- fluoro- 3,3- diethoxies ethyl butyrates after separation；The organic solvent is selected from ethyl acetate, two
At least one of chloromethanes, hexamethylene and tetrahydrofuran.
7. according to the preparation 1- chloro- 3 described in claim 6, the method for 3,3- trifluoroacetones, it is characterised in that：It is described organic molten
Agent is selected from ethyl acetate and/or dichloromethane.
8. preparation 1- chloro- 3 described in accordance with the claim 1, the method for 3,3- trifluoroacetones, it is characterised in that：In step (3)
Decarboxylating agent is selected from least one of the concentrated sulfuric acid, concentrated hydrochloric acid, acetic acid, anhydrous formic acid and methanesulfonic acid, decarboxylating agent and 2- chloro- 4,4,4-
The mol ratio of three fluoro- 3,3- diethoxies ethyl butyrates is 1.0~6.0:1.0.
9. according to the preparation 1- chloro- 3 described in claim 8, the method for 3,3- trifluoroacetones, it is characterised in that：In step (3)
Decarboxylating agent is selected from the concentrated sulfuric acid and/or methanesulfonic acid, and decarboxylating agent rubs with chloro- 4,4,4- tri- fluoro- 3,3- diethoxies ethyl butyrates of 2-
Your proportioning is 1.2~2.0:1.0.
10. preparation 1- chloro- 3 described in accordance with the claim 1, the method for 3,3- trifluoroacetones, it is characterised in that：In step (1),
At a temperature of 20~50 DEG C, the ethanol solution of sodium ethoxide is first added, adds hexafluoro -2,3- dichloro-2-butene；In step (2),
At a temperature of 10~40 DEG C, acid is added into reaction solution.
11. preparation 1- chloro- 3 described in accordance with the claim 1, the method for 3,3- trifluoroacetones, it is characterised in that：Step (1)
Reaction temperature is 60~130 DEG C, and the reaction temperature of acidification reaction is 60~130 DEG C in step (2), the reaction temperature of step (3)
For 80~180 DEG C.
12. according to the preparation 1- chloro- 3 described in claim 11, the method for 3,3- trifluoroacetones, it is characterised in that：Step (1)
Reaction temperature is 80~120 DEG C, and the reaction temperature of acidification reaction is 90~120 DEG C in step (2), the reaction temperature of step (3)
For 120~160 DEG C.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110563568A (en) * | 2018-06-05 | 2019-12-13 | 浙江蓝天环保高科技股份有限公司 | Preparation method of trifluoroacetylacetone |
| CN115894191A (en) * | 2022-11-22 | 2023-04-04 | 山东华安新材料有限公司 | Method for co-producing trifluoroacetone and difluoroacetic acid ester |
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| US2715144A (en) * | 1950-06-02 | 1955-08-09 | Dow Chemical Co | Hydrolysis of unsaturated fluorinecontaining ethers |
| JPH0240338A (en) * | 1988-07-28 | 1990-02-09 | Central Glass Co Ltd | Production of 1-halogeno-3,3,3-trifluoroacetone |
| US5739394A (en) * | 1995-12-22 | 1998-04-14 | Bayer Aktiengesellschaft | 3,3-dioxy-4,4,4-trifluorobutyric acid derivatives |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US2715144A (en) * | 1950-06-02 | 1955-08-09 | Dow Chemical Co | Hydrolysis of unsaturated fluorinecontaining ethers |
| JPH0240338A (en) * | 1988-07-28 | 1990-02-09 | Central Glass Co Ltd | Production of 1-halogeno-3,3,3-trifluoroacetone |
| US5739394A (en) * | 1995-12-22 | 1998-04-14 | Bayer Aktiengesellschaft | 3,3-dioxy-4,4,4-trifluorobutyric acid derivatives |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110563568A (en) * | 2018-06-05 | 2019-12-13 | 浙江蓝天环保高科技股份有限公司 | Preparation method of trifluoroacetylacetone |
| CN115894191A (en) * | 2022-11-22 | 2023-04-04 | 山东华安新材料有限公司 | Method for co-producing trifluoroacetone and difluoroacetic acid ester |
| CN115894191B (en) * | 2022-11-22 | 2024-01-30 | 山东华安新材料有限公司 | Method for coproducing trifluoroacetone and difluoroacetate |
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