CN108191628B - Method for preparing bis- (heptafluoroisopropyl) -ketone by oxalyl chloride fluorination - Google Patents
Method for preparing bis- (heptafluoroisopropyl) -ketone by oxalyl chloride fluorination Download PDFInfo
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- CN108191628B CN108191628B CN201810091739.6A CN201810091739A CN108191628B CN 108191628 B CN108191628 B CN 108191628B CN 201810091739 A CN201810091739 A CN 201810091739A CN 108191628 B CN108191628 B CN 108191628B
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Abstract
The invention discloses a method for preparing bis- (heptafluoroisopropyl) -ketone by oxalyl chloride fluorination. The invention designs a reaction kettle provided with an outer tank body and an inner tank body, wherein a liquefaction layer for cooling is formed in a gap between the outer tank body and the inner tank body, a fluorinating agent, a phase transfer catalyst, a polar aprotic solvent and oxalyl chloride are sequentially added into the reaction kettle, hexafluoropropylene gas is introduced, the temperature is raised to 60-200 ℃ under the stirring condition for reaction, a reaction product crude product is directly condensed in the liquefaction layer after the reaction is finished, and the solvent phase is separated out for rectification and purification. The preparation method is simple, stable and efficient, and the prepared bis- (heptafluoroisopropyl) -ketone has high yield and high purity.
Description
Technical Field
The invention belongs to the field of organic chemical industry, and particularly relates to a method for preparing bis- (heptafluoroisopropyl) -ketone by oxalyl chloride fluorination.
Background
The bis- (heptafluoroisopropyl) -ketone is an important organic chemical intermediate, is used for preparing other fluorine-containing compounds such as heptafluoroisobutyrate, heptafluoroisopropyl acyl fluoride, heptafluoropropane and the like, can also be used as an important intermediate of environment-friendly insulating gas heptafluoroisobutyronitrile, and has good application prospect.
Bis- (heptafluoroisopropyl) -ketone is not currently produced in China. The following preparation methods are mainly reported in the literature: under the condition of oil bath at 75-100 ℃, cesium fluoride is used as a fluorinating agent, and the cesium fluoride can be prepared from fluorophosphates and liquefied hexafluoropropylene in an acetonitrile solvent, wherein the yield is 39%; under the condition of 100 ℃ oil bath, cesium fluoride is used as a fluorinating agent, and the cesium fluoride can be prepared from heptafluoro isobutyl acyl fluoride and liquefied hexafluoropropylene in an acetonitrile solvent, wherein the yield is 38%; under the condition of oil bath at 75-80 ℃, potassium fluoride is used as a fluorinating agent, oxalyl chloride and liquefied hexafluoropropylene can be prepared in an acetonitrile solvent, and the yield is 20%. The prior preparation methods all need hexafluoropropylene liquefied at the temperature of-70 ℃, which causes high general energy consumption, the former two methods have expensive raw materials and low safety, the latter method has low yield and poor repeatability, and the three methods are not suitable for industrial production.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides the method for synthesizing the bis- (heptafluoroisopropyl) -ketone, which has the advantages of low energy consumption, high yield, stability, repeatability, low equipment investment, cheap raw materials, high safety and the like.
Molecular structure of bis- (heptafluoroisopropyl) -one:
the technical scheme provided by the invention is as follows:
a process for the preparation of bis- (heptafluoroisopropyl) -one by fluorination of oxalyl chloride comprising the steps of:
adding a fluorinating agent, a phase transfer catalyst, a polar aprotic solvent and oxalyl chloride into a reaction kettle together, introducing hexafluoropropylene gas, heating to 60-200 ℃ under the stirring condition for reaction, continuously stirring after the reaction is finished, cooling to room temperature, and separating the obtained solid-liquid mixture to obtain crude bis- (heptafluoroisopropyl) -ketone liquid; separating liquid of the crude bis- (heptafluoroisopropyl) -ketone product, and then rectifying and purifying to obtain bis- (heptafluoroisopropyl) -ketone;
wherein the molar ratio of the fluorinating agent to the phase transfer catalyst to the oxalyl chloride to the hexafluoropropylene is 1-12: 0.01-3: 1: 1-10.
The reaction equation for preparing the bis- (heptafluoroisopropyl) -ketone by oxalyl chloride fluorination is as follows:
the fluorinating agent is one or a mixture of more of sodium fluoride, potassium bifluoride, calcium fluoride, cesium fluoride, tetramethylammonium fluoride and tetrabutylammonium fluoride.
The phase transfer catalyst is one or a mixture of more than one of 15-crown-5, 18-crown-6, tetraphenyl phosphine bromide, tetra (diethylamino) phosphine bromide and polyethylene glycol.
The polar aprotic solvent is one or a mixture of more of dimethyl sulfoxide, dimethyl sulfone, dimethylformamide, sulfolane, dimethylacetamide, N-methyl pyrrolidone, diphenyl sulfone, acetonitrile, nitrobenzene, nitrotoluene, dichlorotoluene, benzonitrile and tetraethylene glycol dimethyl ether.
Preferably:
the fluorinating agent is placed in a muffle furnace to be activated for 1 hour at 400 ℃ before being added into the reaction kettle.
The molar ratio of the fluorinating agent to the phase transfer catalyst to the oxalyl chloride to the hexafluoropropylene is 10:1:1: 3.
The oxalyl chloride is dropwise added or injected by a funnel method: the average flow rate is 0.1-100 g/s.
The stirring speed is 200-1500 rpm, the final temperature of temperature rise is 140 ℃, and the reaction time is 7-24 h; further, the reaction temperature was raised for 1 hour and the constant temperature was maintained for 6 hours.
The method for separating the solid-liquid mixture is to utilize a reaction kettle device which is designed independently in a specific way to realize the automatic separation of liquid-phase reaction products and solids, and avoid the liquid-phase products with higher density from being mixed in a fluoridizing agent emulsion layer.
The reaction kettle comprises an outer tank body and an inner tank body, wherein a mechanical stirring device, an air inlet valve, an air outlet valve and a constant-pressure dropping funnel are arranged on the inner tank body, a cooling layer for liquefaction is formed in a gap between the outer tank body and the inner tank body, the ratio of the thickness of the cooling layer to the inner diameter of the outer tank body is 1: 25-35, a discharging port is arranged at the bottom of the outer tank body, and the temperature in the kettle is used as feedback temperature to adjust the temperature of heat conducting oil in a jacket of the reaction kettle. And after the reaction is finished, continuously stirring in the cooling process so as to liquefy the crude product obtained by the reaction in the interlayer of the reaction kettle.
The material of the tank body in the reaction kettle is quartz or polytetrafluoroethylene, the material of other parts of the reaction kettle, which are in contact with reactants, can be 316L, Hastelloy or other chlorine-resistant and acid-resistant metals, and the pressure of the reaction kettle is not less than 2.5 MPa.
The rectification purification process comprises the following three processes: (1) removing front fractions, (2) obtaining fractions at 71-72 ℃, and (3) recovering fractions with the mass fraction of more than 40%. The heating temperature of the tower kettle is controlled to be 90-110 ℃, the compensation temperature of the upper half section of the rectifying column is controlled to be 45-80 ℃, the compensation temperature of the lower half section of the rectifying column is controlled to be 60-95 ℃, and the recovery rate is more than 90%.
The method prepares the bis- (heptafluoro-isopropyl) -ketone by dissolving a solid fluorinating agent, a phase transfer catalyst and oxalyl chloride into a polar aprotic solvent and introducing hexafluoropropylene gas, wherein the reaction yield is more than 40 percent, and the final purity after separation is more than 99 percent. Other auxiliary steps such as designing a special reaction kettle device and continuously stirring after the reaction is finished so as to facilitate solid-liquid separation and optimization of the rectification process, so that a high-purity product is obtained with high yield.
The invention has the following advantages and beneficial effects:
(1) according to the invention, hexafluoropropylene is introduced into the reaction kettle in a gas form, and the yield of bis- (heptafluoroisopropyl) -ketone is greatly improved by adding the phase transfer catalyst, wherein the reaction yield is more than 40%.
(2) The existing reaction kettle can not realize the automatic separation of liquid phase reactants and solids, and the reaction kettle provided by the invention is mainly used for separating solid and liquid phases, is convenient for collecting products and reduces the post-treatment steps.
Drawings
FIG. 1 is a process flow diagram of the present invention for the preparation of bis- (heptafluoroisopropyl) -one from oxalyl chlorofluorination.
Detailed Description
The technical scheme of the invention is further explained by combining the embodiments, the following embodiments are all carried out in the reaction kettle designed by the inventor, the reaction kettle comprises an outer tank body and an inner tank body, a mechanical stirring device, an air inlet valve, an air outlet valve and a constant-pressure dropping funnel are arranged on the inner tank body, a cooling layer for liquefaction is formed in a gap between the outer tank body and the inner tank body, the ratio of the thickness of the cooling layer to the inner diameter of the outer tank body is 1: 25-35, a discharging port is arranged at the bottom of the outer tank body, and the temperature of the heat-conducting oil of a jacket of the reaction kettle is adjusted by taking the temperature in the kettle as. And after the reaction is finished, continuously stirring in the cooling process so as to liquefy the crude product obtained by the reaction in the interlayer of the reaction kettle.
Example 1
Activating potassium fluoride in a muffle furnace at 400 ℃ for 1 hour, grinding for later use, adding 17.4g of activated and ground potassium fluoride into a polytetrafluoroethylene tank body of a reaction kettle according to the molar ratio of 10:1:6 of a fluorinating agent to obtain a fluorinating agent, adding 60m L acetonitrile into the tank body, adding 3.81g of oxalyl chloride into a funnel of the reaction kettle, injecting for 38s, introducing 27g of hexafluoropropylene gas, setting the rotating speed to be 200rpm, after the gas introduction is finished, heating the reaction kettle to 140 ℃ after 1 hour, keeping the temperature for 6 hours after the reaction is finished, continuously stirring in the cooling process after the reaction is finished to liquefy a crude product obtained by the reaction in an interlayer of the reaction kettle, and rectifying the crude product after simple liquid separation treatment to obtain 0.45g of bis- (heptafluoroisopropyl) -ketone with the purity of more than 99%, wherein the yield is 4.1%.
Example 2
Activating potassium fluoride in a muffle furnace at 400 ℃ for 1 hour, grinding for later use, adding a fluorinating agent, a phase transfer catalyst, oxalyl chloride and hexafluoropropylene in a molar ratio of 10:1:1:3, adding 34.8g of activated and ground potassium fluoride and 15.84g of 18-crown-6 into a quartz tank body of a reaction kettle, measuring 120m L acetonitrile by using a measuring cylinder, adding into the tank body, further measuring 7.62g of oxalyl chloride, adding into a funnel of the reaction kettle, introducing 27g of hexafluoropropylene gas, setting the rotating speed to be 200rpm, after the gas introduction is finished, starting to heat the reaction kettle, heating to 140 ℃ after 1 hour, keeping the temperature for 6 hours at constant temperature, continuously stirring to liquefy a crude product obtained by the reaction in an interlayer of the reaction kettle in the process of cooling after the reaction is finished, and rectifying the crude product after simple liquid separation treatment to finally obtain 9.88g and 45 percent of bis- (heptafluoroisopropyl) -ketone with the purity of more than 99 percent.
Example 3
Activating potassium fluoride in a muffle furnace at 400 ℃ for 1 hour for later use, grinding, adding a fluorinating agent, a phase transfer catalyst, oxalyl chloride and hexafluoropropylene in a molar ratio of 10:1:1:3, adding 348g of activated potassium fluoride and 158.4g of 18-crown-6 into a quartz tank body of a reaction kettle, measuring 1200m of L acetonitrile by using a measuring cup, adding 76.2g of oxalyl chloride into a funnel of the reaction kettle by using a platform scale, injecting 270g of hexafluoropropylene gas for 3s, setting the rotating speed to be 300rpm, after the ventilation is finished, heating the reaction kettle to 140 ℃ after 1 hour, keeping the temperature for 6 hours, continuously stirring in the cooling process after the reaction is finished so as to liquefy a crude product obtained by the reaction in an interlayer of the reaction kettle, performing simple liquid separation treatment on the crude product, and then rectifying to obtain 94.4g of bis- (heptafluoroisopropyl) -ketone with the purity of more than 99%, wherein the yield is 43%.
Rectification procedures of examples 1 to 3: (1) removing front cut fraction: the heating temperature of the tower kettle of the first stage is controlled at 90 ℃, the compensation temperature of the upper half section of the rectifying column is controlled at 45 ℃, the compensation temperature of the lower half section of the rectifying column is controlled at 60 ℃, the total reflux is carried out for 30min, and the reflux ratio is 3:1 so as to remove the first fraction; the heating temperature of the tower kettle in the second stage is controlled at 90 ℃, the compensation temperature of the upper half section of the rectifying column is controlled at 55 ℃, the compensation temperature of the lower half section of the rectifying column is controlled at 70 ℃, the total reflux is carried out for 30min, and the reflux ratio is 3:1 so as to remove the second fraction; in the third stage, the heating temperature of the tower kettle is controlled at 90 ℃, the compensation temperature of the upper half section of the rectifying column is controlled at 60 ℃, the compensation temperature of the lower half section of the rectifying column is controlled at 75 ℃, the total reflux is carried out for 30min, and the reflux ratio is 3:1 so as to remove the third fraction; heating temperature of the tower kettle at the fourth stage is controlled at 100 ℃, compensation temperature of the upper half section of the rectifying column is controlled at 70 ℃, compensation temperature of the lower half section of the rectifying column is controlled at 85 ℃, total reflux is carried out for 30min, and reflux ratio is 3:1 so as to remove the fourth fraction; (2) obtaining a fraction at 71-72 ℃: in the fifth stage, the heating temperature of the tower kettle is controlled at 100 ℃, the compensation temperature of the upper half section of the rectifying column is controlled at 70 ℃, the compensation temperature of the lower half section of the rectifying column is controlled at 85 ℃, total reflux is carried out for 30min, and the reflux ratio is 10:1 so as to obtain fraction at 71-72 ℃; in the sixth stage, the heating temperature of the tower kettle is controlled at 100 ℃, the compensation temperature of the upper half section of the rectifying column is controlled at 75 ℃, the compensation temperature of the lower half section of the rectifying column is controlled at 90 ℃, total reflux is carried out for 30min, and the reflux ratio is 10:1 so as to obtain fraction at 71-72 ℃; in the seventh stage, the heating temperature of the tower kettle is controlled at 110 ℃, the compensation temperature of the upper half section of the rectifying column is controlled at 75 ℃, the compensation temperature of the lower half section of the rectifying column is controlled at 90 ℃, total reflux is carried out for 30min, and the reflux ratio is 10:1 so as to obtain fraction at 71-72 ℃; in the eighth stage, the heating temperature of the tower kettle is controlled at 110 ℃, the compensation temperature of the upper half section of the rectifying column is controlled at 75 ℃, the compensation temperature of the lower half section of the rectifying column is controlled at 90 ℃, total reflux is carried out for 30min, and the reflux ratio is 10:1 so as to obtain fraction at 71-72 ℃; (3) recovering fractions with the mass fraction of more than 40 percent: in the ninth stage, the heating temperature of the tower bottom is controlled at 110 ℃, the compensation temperature of the upper half section of the rectifying column is controlled at 80 ℃, the compensation temperature of the lower half section of the rectifying column is controlled at 95 ℃, total reflux is carried out for 30min, and the reflux ratio is 3:1 so as to obtain the fraction below 90 ℃ to be recycled. After gas chromatography, mass spectrum, fluorine spectrum and infrared detection, the overall purity of the final product is over 99 percent, and the recovery rate is over 90 percent.
The potassium fluoride agent described in the above embodiments may be replaced by sodium fluoride, potassium bifluoride, calcium fluoride, cesium fluoride, tetramethylammonium fluoride, tetrabutylammonium fluoride; the phase transfer catalyst 18-crown-6 can be replaced by 15-crown-5, tetraphenylphosphonium bromide, tetra (diethylamino) phosphine bromide and polyethylene glycol; the polar aprotic solvent acetonitrile can be replaced by dimethyl sulfoxide, dimethyl sulfone, dimethylformamide, sulfolane, dimethylacetamide, N-methylpyrrolidone, diphenylsulfone, nitrobenzene, nitrotoluene, dichlorotoluene, benzonitrile, and tetraglyme; the actual effect of the invention is not affected.
The technical solutions of the present invention have been described in detail with reference to the specific embodiments, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention and are made by those skilled in the art are deemed to be equivalent substitutions within the scope of the present invention.
Claims (8)
1. A process for the preparation of bis- (heptafluoroisopropyl) -one by fluorination of oxalyl chloride, comprising the steps of:
adding a fluorinating agent, a phase transfer catalyst, a polar aprotic solvent and oxalyl chloride into a reaction kettle together, introducing hexafluoropropylene gas, heating to 60-200 ℃ under the stirring condition for reaction, continuously stirring after the reaction is finished, cooling to room temperature, and separating the obtained solid-liquid mixture to obtain crude bis- (heptafluoroisopropyl) -ketone liquid; separating liquid of the crude bis- (heptafluoroisopropyl) -ketone product, and then rectifying and purifying to obtain bis- (heptafluoroisopropyl) -ketone;
wherein the molar ratio of the fluorinating agent to the phase transfer catalyst to the oxalyl chloride to the hexafluoropropylene is 1-12: 0.01-3: 1: 1-10;
the fluorinating agent is one or a mixture of more of sodium fluoride, potassium bifluoride, calcium fluoride, cesium fluoride, tetramethylammonium fluoride and tetrabutylammonium fluoride;
the phase transfer catalyst is one or a mixture of more of 15-crown-5, 18-crown-6, tetraphenyl phosphine bromide, tetra (diethylamino) phosphine bromide and polyethylene glycol;
the polar aprotic solvent is one or a mixture of more of dimethyl sulfoxide, dimethyl sulfone, dimethylformamide, sulfolane, dimethylacetamide, N-methyl pyrrolidone, diphenyl sulfone, acetonitrile, nitrobenzene, nitrotoluene, dichlorotoluene, benzonitrile and tetraethylene glycol dimethyl ether.
2. The method of claim 1, wherein: the fluorinating agent is placed in a muffle furnace to be activated for 1 hour at 400 ℃ before being added into the reaction kettle.
3. The method of claim 1, wherein: the molar ratio of the fluorinating agent to the phase transfer catalyst to the oxalyl chloride to the hexafluoropropylene is 10:1:1: 3.
4. The method of claim 1, wherein: the oxalyl chloride is added dropwise or by injection through a funnel, and the average speed is 0.1-100 g/s.
5. The method of claim 1, wherein: the stirring speed is 200-1500 rpm, the final temperature of temperature rise is 140 ℃, and the reaction time is 7-24 h.
6. The method of claim 1, wherein: the temperature rise time during the reaction is 1h, and the constant temperature time is 6 h.
7. The method of claim 1, wherein: during rectification, the heating temperature of the tower kettle is 90-110 ℃, the compensation temperature of the upper half section of the rectification column is 45-75 ℃, and the compensation temperature of the lower half section of the rectification column is 60-90 ℃.
8. The method according to any one of claims 1 to 7, wherein: the reaction kettle comprises an outer tank body and an inner tank body, wherein a mechanical stirring device, an air inlet valve, an air outlet valve and a constant-pressure dropping funnel are arranged on the inner tank body, a cooling layer for liquefaction is formed in a gap between the outer tank body and the inner tank body, the ratio of the thickness of the cooling layer to the inner diameter of the outer tank body is 1: 25-35, and a discharging hole is formed in the bottom of the outer tank body.
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| CN103360222A (en) * | 2013-07-29 | 2013-10-23 | 中国科学院上海有机化学研究所 | Preparation of 2,2,2- trifluoroethyl-1,1,2,3,3,3-hexafluoroisopropyl ether |
| CN106316809A (en) * | 2016-07-22 | 2017-01-11 | 北京天康达科技发展有限公司 | Method of preparing pentafluoroethyl isopropyl ketone |
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| CN103360222A (en) * | 2013-07-29 | 2013-10-23 | 中国科学院上海有机化学研究所 | Preparation of 2,2,2- trifluoroethyl-1,1,2,3,3,3-hexafluoroisopropyl ether |
| CN106316809A (en) * | 2016-07-22 | 2017-01-11 | 北京天康达科技发展有限公司 | Method of preparing pentafluoroethyl isopropyl ketone |
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| "Reactions of perfluoro-2,5-dimethyl-3,4-hexanedione with amines";SeiJi Shin-YA,et al.;《Bulletin of the chemical society of Japan》;197701;第50卷(第1期);329-330,第330页实验第1段，第329页结构式1 * |
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