JP2013006786A - Method for producing fluorinated alkane - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for producing a fluorinated alkane in a good yield, in fluorinating an alkyl sulfonate by an interchange reaction with an alkali metal fluoride.SOLUTION: This method can produce the target fluorinated alkane in a good yield by virtue of using a reactor equipped with a screw type agitation blades or a rotary kiln type reactor in an interchange reaction with an alkali metal fluoride, even in a reaction pattern yielding a massive amount of solid contents.

Description

  The present invention relates to a method for producing a fluorinated alkane useful as a plasma reaction gas such as etching or CVD, or a medium such as a fluorine-containing pharmaceutical intermediate or a refrigerant / heat medium, which is useful in the field of manufacturing semiconductor devices. The highly purified fluorinated alkane is particularly suitable for a plasma etching gas, a chemical vapor deposition (CVD) gas, or the like in the field of manufacturing a semiconductor device using a plasma reaction.

As a method for producing the fluorinated alkane represented by the structural formula (2), several production methods are disclosed.
In Patent Document 1, when a lower alkylsulfonyl derivative is fluorinated with an alkali or alkaline earth metal fluoride, a polyethylene glycol having a molecular weight of 400 is used as a solvent.
In Non-Patent Document 1, hexyl derivatives of methanesulfonate, benzenesulfonate, and toluenesulfonate are used as a fluorinating agent, and 1-fluorohexane is obtained in a reduced pressure system in a diethylene glycol solvent.
Also in Non-Patent Document 2, various alkyl fluorides are obtained in a reduced pressure system using p-toluenesulfonic acid ester of methane, ethane or propane as a fluorinating agent and potassium fluoride as a fluorinating agent without solvent or in diethylene glycol solvent. .
In Non-Patent Document 3, 1-bromo-2-fluoroethane is obtained with good yield by using tetrabromobutylammonium fluoride as a fluorinating agent for 2-bromoethyl trifluoromethanesulfonate.

JP-T 62-501974

Canadian Journal of Chemistry, Vol. 34, 737 (1956) Journal of American Chemical Society, Vol. 77, 4899 (1955) Journal of Organic Chemistry, Vol. 52,658 (1987)

In the Examples of Patent Document 1, methanesulfonate and p-toluenesulfonates are fluorinated with potassium fluoride in a polyethylene glycol solvent, and 1-phenyl-2-fluoroethane is obtained in a yield of 70%. The amount of potassium fluoride used is as much as 5 times equivalent to the raw material sulfonic acid ester. Thus, when there is much quantity of potassium fluoride, the fluorine ion in the waste liquid after reaction will increase very much. Fluorine ions in the waste liquid must be removed in industrial production, and the use of a large amount of potassium fluoride leads to a decrease in productivity.
In Non-Patent Document 1, alkylmethane sulfonate is fluorinated with potassium fluoride in a diethylene glycol solvent, and a fluorinated product is obtained with a maximum yield of 75%. A large amount of diethylene glycol is used. Like potassium fluoride, using a large amount of solvent leads to a decrease in productivity.

In Non-Patent Document 2, alkyl p-toluenesulfonate is fluorinated with potassium fluoride, and a fluorinated product is obtained at a maximum of 89%. However, the amount of potassium fluoride used is the alkyl p-toluene starting material. It is used in an extremely large amount of 5 times equivalent to sulfonate.
Regarding Non-Patent Document 3, a fluorinated product can be obtained in a high yield because of the use of trifluoromethanesulfonate having a high desorption ability and the use of tetrabutylammonium fluoride that easily generates a bare fluorine anion. However, trifluoromethanesulfonyl anhydride for producing trifluoromethanesulfonate, trifluoromethanesulfonylating agents such as trifluoromethanesulfonyl chloride, and tetrabutylammonium fluoride used as the fluorinating agent are both expensive. It is a drug and difficult to use industrially. In addition, tetrabutylammonium fluoride is a fluorinating agent with a large molecular weight, so the amount added to the raw material becomes very large, which requires a very large volume of reaction equipment and waste generated after the reaction. Since it becomes a large quantity, it is not industrially preferable also from these viewpoints.

When we fluorinate alkylsulfonic acid esters with a large desorption capacity as raw materials, we reduced the amount of inexpensive metal fluoride used as a fluorinating agent and realized simple waste liquid treatment, which is industrially advantageous. It was necessary to establish a new method for producing fluorinated alkanes.
However, when a reaction system using alkyl sulfonic acid ester as a raw material and potassium fluoride as a fluorinating agent was studied on an industrial production scale such that the raw material alkyl sulfonic acid ester becomes 1 kg or more, as the reaction proceeds. Due to the large amount of potassium alkylsulfonate, the contents became very viscous even when the reaction was carried out in a solvent, and sometimes sherbet-like solids were precipitated. Furthermore, in a viscous reaction system or a reaction system in which a solid is deposited, stirring with a stirring blade becomes very difficult. For this reason, when the reaction proceeds to some extent, the conversion rate of the raw material is remarkably lowered from the middle, and it is difficult to secure a sufficient yield.
From this, it was found that Patent Document 1 and Non-Patent Documents 1 to 3 are both small-scale reactions, and therefore, good yields were realized as reported in each document.
Furthermore, it was found from observation of the reaction that the sherbet-like solid tends to adhere to the inner surface of the reactor as the reaction proceeds, and then the solid tends to grow. It was confirmed that this solid did not easily collapse with a paddle, a turbine, or an anchor type stirring blade. Stirring can be facilitated by using a large amount of solvent, but the use of a large amount of solvent leads to an increase in the size of the reactor and an increase in waste, so that it can be adopted for industrial production. It will not be.
Thus, as a result of intensive studies, the inventor used a reactor equipped with a screw-type stirring blade or a rotary kiln reactor to reduce the amount of metal fluoride used, and achieve a high yield of the target fluorinated alkane. Has been found to be able to be produced, and the present invention has been completed.

  Thus, according to the present invention, when an alkyl sulfonate represented by the following structural formula (1) is fluorinated with an alkali metal fluoride in a solvent, the alkali metal fluoride is 1. There is provided a method for producing a fluorinated alkane represented by the structural formula (2), wherein the fluorination is performed in a reactor having 5 to 3.5 equivalents and equipped with a screw type stirring blade or a rotary kiln reactor. Provided.

(However, R ¹ represents a linear or branched alkyl group having 3 to 6 carbon atoms, and R ² represents an alkyl group having 1 to 7 carbon atoms or an aromatic group that may have a methyl group as a substituent. .)

(However, R ¹ represents a linear or branched alkyl group having 3 to 6 carbon atoms.)
The alkali metal fluoride is preferably potassium fluoride or cesium fluoride.
Moreover, it is preferable that the usage-amount of the said solvent is 3-7 weight part with respect to 1 weight part of alkylsulfonic acid ester which is a raw material.
In the alkylsulfonic acid ester represented by the structural formula (1) and the fluorinated alkane represented by the structural formula (2), R ¹ preferably has 4 or 5 carbon atoms.

It is a figure which shows embodiment of the reactor provided with the screw type stirring blade which concerns on this invention. It is a figure which shows embodiment of the rotary kiln threshold reactor which concerns on this invention.

As the raw material used in the present invention, an alkylsulfonic acid ester represented by the structural formula (1) is used. In the structural formula (1), R ² is particularly preferably a methyl group or a p-methylphenyl group.
Examples of the alkyl sulfonate ester represented by the structural formula (1) include 1-propyl methane sulfonate, isopropyl methane sulfonate, 1-butyl methane sulfonate, isobutyl methane sulfonate, 2-butyl methane sulfonate, 1-pentyl methane sulfonate, and 2-pentyl. Methanesulfonate, such as methanesulfonate, 3-pentylmethanesulfonate, 1- (2-methylbutyl) methanesulfonate, 3-methyl-1-butylmethanesulfonate, 1-hexylmethanesulfonate, 2-hexylmethanesulfonate, 3-hexylmethanesulfonate 1-propyl ethane sulfonate, isopropyl ethane sulfonate, 1-butyl ethane sulfonate, isobutyl ethane sulfonate, 2-butyl ethane sulfonate 1-pentylethanesulfonate, 2-pentylethanesulfonate, 3-pentylethanesulfonate, 1- (2-methylbutyl) ethanesulfonate, 3-methyl-1-butylethanesulfonate, 1-hexylethanesulfonate, 2-hexylethanesulfonate Ethanesulfonates such as 3-hexylethanesulfonate; 1-propylbenzenesulfonate, isopropylbenzenesulfonate, 1-butylbenzenesulfonate, isobutylbenzenesulfonate, 2-butylbenzenesulfonate, 1-pentylbenzenesulfonate, 2-pentylbenzenesulfonate 3-pentylbenzenesulfonate, 1- (2-methylbutyl) benzenesulfonate, 3-methyl-1-butylbenzenesulfonate, Benzene sulfonates such as hexyl benzene sulfonate, 2-hexyl benzene sulfonate, 3-hexyl benzene sulfonate; 1-propyl p-toluene sulfonate, isopropyl p-toluene sulfonate, 1-butyl p-toluene sulfonate, isobutyl p-toluene sulfonate, 2-butyl p-toluenesulfonate, 1-pentyl p-toluenesulfonate, 2-pentyl p-toluenesulfonate, 3-pentyl p-toluenesulfonate, 1- (2-methylbutyl) p-toluenesulfonate, 3-methyl-1- P-Toluenesulfonates such as butyl p-toluenesulfonate, 1-hexyl p-toluenesulfonate, 2-hexyl p-toluenesulfonate, 3-hexyl p-toluenesulfonate And the like.
Among these, 1-propyl methane sulfonate, isopropyl methane sulfonate, 1-butyl methane sulfonate, isobutyl methane sulfonate, 2-butyl methane sulfonate, 1-pentyl methane sulfonate, 2-pentyl methane sulfonate, 3-pentyl methane sulfonate, 1- Methanesulfonates such as (2-methylbutyl) methanesulfonate, 3-methyl-1-butylmethanesulfonate, 1-hexylmethanesulfonate, 2-hexylmethanesulfonate, 3-hexylmethanesulfonate; and 1-propyl p-toluenesulfonate , Isopropyl p-toluenesulfonate, 1-butyl p-toluenesulfonate, isobutyl p-toluenesulfonate, 2-butyl p-toluenesulfonate, 1 Pentyl p-toluenesulfonate, 2-pentyl p-toluenesulfonate, 3-pentyl p-toluenesulfonate, 1- (2-methylbutyl) p-toluenesulfonate, 3-methyl-1-butyl p-toluenesulfonate, 1-hexyl p -P-toluenesulfonates such as toluene sulfonate, 2-hexyl p-toluenesulfonate, 3-hexyl p-toluenesulfonate;

In the present invention, potassium fluoride, rubidium fluoride, and cesium fluoride can be used as the alkali metal fluoride. Among these, potassium fluoride and cesium fluoride are preferable, and special potassium fluoride is preferable. These alkali metal fluorides can be used in a granular form, but it is preferable to use a spray-dried or freeze-dried one having a smaller particle size from the viewpoint of improving the reactivity.
The addition amount of the alkali metal fluoride is 1.5 to 3.5 equivalents, preferably 1.5 to 3 equivalents, and more preferably 1.5 to 2.5 equivalents with respect to the alkylsulfonic acid ester as the raw material. When the addition amount of the alkali metal fluoride is too small, the conversion rate of the reaction is lowered, and when the addition amount is too large, the concentration of the solid content with respect to the solvent becomes large and stirring becomes difficult.

As the reaction solvent, alcohols are preferred. In particular, polyhydric alcohols are preferable. For example, ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol and the like are desirable from the viewpoint of dissolving the alkali metal fluoride well. Among these, propylene glycol and diethylene glycol can be used more preferably.
The amount of these reaction solvents used is desirably in the range of 3 to 7 by weight ratio with respect to the alkylsulfonic acid ester as the raw material. If the amount of the reaction solvent used is small, poor stirring due to the precipitation of a large amount of solids tends to occur during the reaction, and if the amount used is large, the treatment after the reaction is troublesome.

As reaction temperature, 50-120 degreeC is preferable and 60-110 degreeC is more preferable. When the reaction temperature is low, the raw material conversion rate becomes low and the reaction time becomes very long.
On the other hand, if the reaction temperature is too high, the reaction proceeds all at once, causing solids to precipitate at a stretch, damaging the stirrer and making reaction control difficult.
As a method for adding the alkylsulfonic acid ester as a raw material, a method in which the alkylsulfonic acid ester is added dropwise after setting the mixture of the alkali metal fluoride and the reaction solvent to an arbitrary reaction temperature is preferable.
The dropping rate is preferably 200 to 2000 mol / m ³ / hr per unit volume of the reaction vessel and unit time. If the dropping speed is too fast, the reaction proceeds rapidly, making it difficult to control the reaction, and if the dropping speed is too slow, the reaction time becomes very long and the production efficiency deteriorates.

As a form of the reactor used in the present invention, a reactor equipped with a screw type stirrer or a rotary kiln type reactor can be suitably used.
A reactor equipped with a screw-type stirring blade is a reactor equipped with a screw-type stirring blade in a reaction vessel as shown in FIG. 1, and a reaction mixture containing a solid content is continuously fed from the bottom to the top. Because it can be flowed, the contents due to stagnation of local solid matter that occurs when a large-scale reaction is performed using a reactor equipped with a paddle type or anchor type stirring blade that can be used even on a small scale The non-uniform stirring can be reduced. In addition, it is possible to suppress a significant decrease in nucleophilicity caused by coating the surface of the metal fluoride as a fluorine source with potassium alkyl sulfonate, cesium or the like.
As a method for recovering the product from the reaction system, although depending on the boiling point and reaction temperature of the product, a method of extracting the reaction system outside the reaction system and collecting it in a trap cooled with a refrigerant or the like is usually applicable. The product having a high boiling point is preferably collected in a trap cooled with a refrigerant or the like under reduced pressure after the reaction is stopped.

In the case of a rotary kiln type reactor, an apparatus as shown in FIG. 2 can be used. An alkali metal fluoride and a reaction solvent are charged into a rotating cylindrical reactor, and the cylinder itself is rotated by a suitable driving means. While rotating, the entire cylinder is heated to a predetermined temperature, and the alkylsulfonic acid ester as a raw material is dropped from a raw material inlet at the top of the cylinder via a liquid feed pump or the like. In order to efficiently stir the contents inside the cylinder, it is desirable to install a baffle plate or the like.
About the method for recovering the product from the reaction system, as with the reaction using a screw-type stirring blade, although it depends on the boiling point and reaction temperature of the product, it is usually extracted from the reaction system while reacting and cooled with a refrigerant or the like. Collected in the trap. The product having a high boiling point is preferably collected in a trap cooled with a refrigerant or the like under reduced pressure after the reaction is stopped. The crude product collected in the trap can be purified by an operation such as distillation, and further purified.

  After the completion of the reaction, the contents in the reactor were slowly charged with water in both the screw-type stirred reactor and the rotary kiln-type reactor, and the stirring was continued. Dissolve. The solution-like contents are discharged from the bottom outlet.

  EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited the range by the following Examples. Unless otherwise specified, “parts” and “%” represent “parts by weight” and “% by weight”, respectively.

The analysis conditions adopted below are as follows.
・ Gas chromatography analysis (GC analysis)
Apparatus: GC-2010 (manufactured by Shimadzu Corporation)
Column: TC-1 manufactured by GL Sciences Inc., length 60 m, inner diameter 0.25 mm, film thickness 1.0 μm
Column temperature: After holding at 40 ° C. for 10 minutes, the temperature was raised at 20 ° C./minute and held at 240 ° C. for 10 minutes.
Injection temperature: 200 ° C
Carrier gas: Nitrogen gas Split ratio: 100/1
Detector: FID
・¹ H and ¹⁹ F-NMR measurement apparatus: JNM-ECA-500 (manufactured by JEOL Ltd.)

[Production Example 1] Synthesis of 1-butyl-methanesulfonate (molecular weight 152.21) In a glass reactor equipped with a stirring blade and a dropping funnel, 148 parts of 1-butanol, 260 parts of methanesulfonyl chloride, and 900 parts of dry tetrahydrofuran were added. Charged and cooled with ice water.
From the dropping funnel, 250 parts of triethylamine was added dropwise over 3 hours. After completion of the addition, stirring was continued for 1 hour and further stirred at room temperature for 6 hours. Triethylamine hydrochloride generated by the reaction was removed by filtration under reduced pressure, and the filtrate was concentrated by an evaporator. Diisopropylamine was added to the residue, washed with 5% hydrochloric acid, saturated aqueous sodium hydrogen carbonate and saturated brine, and dried over magnesium sulfate. Again, the solvent was distilled off with a rotary evaporator, and the residue was pumped up to obtain 270 parts of 1-butyl-methanesulfonate (yield 89%).

[Production Example 2] Synthesis of 1-butyl-p-toluenesulfonate (molecular weight 228.31) In a glass reactor equipped with a stirring blade and a dropping funnel, 74 parts of 1-butanol, 187 parts of p-toluenesulfonyl chloride, N , 3 parts of N-dimethylaminopyridine and 550 parts of dry tetrahydrofuran were charged and cooled with ice water.
From the dropping funnel, 82 parts of pyridine was added dropwise over 3 hours. After completion of the addition, stirring was continued for 1 hour and further stirred at room temperature for 5 hours. The reaction solution was concentrated with an evaporator, and diisopropylamine was added to the residue. The extract was washed with 5% hydrochloric acid, saturated aqueous sodium hydrogen carbonate, and saturated brine, and then dried over magnesium sulfate. Again, the solvent was distilled off with a rotary evaporator, and the residue was pumped up to obtain 184 parts of 1-butyl-p-toluenesulfonate (yield 81%).

[Production Example 3] Synthesis of 2-pentyl-methanesulfonate (molecular weight 166.24) In a glass reactor equipped with a stirring blade and a dropping funnel, 176 parts of 2-pentanol, 260 parts of methanesulfonyl chloride, 900 parts of dry tetrahydrofuran And cooled with ice water.
From the dropping funnel, 250 parts of triethylamine was added dropwise over 3 hours. After completion of the addition, stirring was continued for 1 hour and further stirred at room temperature for 5 hours. Triethylamine hydrochloride generated by the reaction was removed by filtration under reduced pressure, and the filtrate was concentrated by an evaporator. Diisopropylamine was added to the residue, washed with 5% hydrochloric acid, saturated aqueous sodium hydrogen carbonate and saturated brine, and dried over magnesium sulfate. Again, the solvent was distilled off with a rotary evaporator, and the residue was pumped up to obtain 278 parts of 2-pentyl-methanesulfonate (yield 84%).

[Example 1]
In a stainless steel reactor equipped with a screw type stirring blade, a raw material feed pump, and a heater, 1200 g (20.7 mol) of spray-dried potassium fluoride and 5000 g of propylene glycol were charged. The reactor was heated to 95 ° C. via a heater and left for 30 minutes with stirring. Thereafter, 1522 g of 1-butyl-methanesulfonate synthesized in Production Example 1 was added dropwise via a liquid feed pump over 3 hours.
While stirring was continued, the product was continuously extracted from the extraction port at the top of the stainless steel reactor and collected in a trap immersed in a dry ice / ethanol bath. Three hours after the completion of the raw material dropping, the organic matter recovered in the trap was analyzed by gas chromatography. As a result, 652 g (yield 85%) of 1-fluorobutane was contained.
<Spectra data of 1-fluorobutane>
¹ H-NMR (CDCl ₃ , TMS) δ 0.95 ppm (t, 3H), 1.43 (m, 2H), 1.70 (m, 2H), 4.45 (dt, 2H)
¹⁹ F-NMR (CDCl ₃ , CFCl ₃ ) δ-219 ppm (m, F)

[Example 2]
In Example 1, the reaction was performed in the same manner as in Example 1 except that 1522 g of 1-butyl-methanesulfonate was changed to 2283 g of 1-butyl-p-toluenesulfonate and 8000 g of propylene glycol. Four hours after the completion of the raw material dropping, the organic matter recovered in the trap was analyzed by gas chromatography. As a result, 610 g (yield 80%) of 1-fluorobutane was contained.

[Example 3]
12,000 g (207 mol) of spray-dried potassium fluoride and 50000 g of propylene glycol were charged into a stainless steel reactor equipped with a screw type stirring blade, a raw material feed pump, and a heater. The reactor was heated to 60 ° C. via a heater and left for 1.5 hours with stirring. Then, 16600 g of 2-pentyl-methanesulfonate synthesized in Production Example 3 was added dropwise via a liquid feed pump over 4 hours.
While stirring was continued, the product was continuously extracted from the extraction port at the top of the stainless steel reactor and collected in a trap immersed in a dry ice / ethanol bath. Six hours after the completion of the raw material dropping, the organic matter collected in the trap was analyzed by gas chromatography. As a result, 5540 g (61% yield) of 2-fluoropentane and 1710 g of a mixture of 1-pentene and 2-pentene ( 24%).
<Spectra data of 2-fluoropentane>
¹ H-NMR (CDCl ₃ , TMS) δ 0.96 ppm (t, 3H), 1.26 (d, 2H), 1.35 (m, 2H), 1.56 (m, 2H), 4.54- 4.78 (m, 2H)
¹⁹ F-NMR (CDCl ₃ , CFCl ₃ ) δ-173 ppm (m, F)

[Example 4]
In Example 1, the reaction was carried out except that 1522 g of 1-butyl-methanesulfonate was changed to 2143 g of isopropyl-p-toluenesulfonate (manufactured by Tokyo Chemical Industry Co., Ltd., molecular weight 214.28) and 7000 g of propylene glycol. The reaction was carried out in the same manner as in 1. Six hours after the completion of the raw material dropping, the organic matter collected in the trap was analyzed by gas chromatography. As a result, 496 g (yield 79%) of 2-fluoropropane and 53 g (12%) of propene were contained.
<Spectra data of 2-fluoropropane>
¹ H-NMR (CDCl ₃ , TMS) δ 1.14 ppm (d, 3H × 2), 4.47 (m, H)
¹⁹ F-NMR (CDCl ₃ , CFCl ₃ ) δ-165 ppm (m, F)

[Example 5]
In a stainless steel rotary kiln type reactor having an inner diameter of 160 mm and a length of 570 mm, 1200 g (20.7 mol) of spray-dried potassium fluoride and 5000 g of propylene glycol were charged.
The reactor was heated to 95 ° C. via a heater and left for 30 minutes while rotating the reactor at 120 rpm. Thereafter, 1520 g of 1-butyl-methanesulfonate synthesized in Production Example 1 was fed through a feeding pump over 3 hours. After completion of the raw material dropping, a trap line immersed in a dry ice / ethanol bath was connected to the raw material dropping port, and the product was collected. Five hours after the completion of the raw material dropping, the organic matter recovered in the trap was analyzed by gas chromatography. As a result, 590 g (yield 78%) of 1-fluorobutane was contained.

[Comparative Example 1]
In a glass reactor equipped with an anchor type stirring blade and a liquid feed pump, 1200 g of spray-dried potassium fluoride and 5000 g of propylene glycol were charged. The reactor was heated to 95 ° C. in an oil bath and left for 30 minutes with stirring. Thereafter, 1522 g of 1-butyl-methanesulfonate synthesized in Production Example 1 was dropped from the dropping funnel over 3 hours.
While stirring was continued, the product was continuously removed from the outlet at the top of the glass reactor and collected in a trap immersed in a dry ice / ethanol bath. About 1.5 hours after the completion of the raw material dropping, precipitation of solid content on the sherbet was observed on the inner surface of the glass reactor, and stirring of the anchor type stirring blade became impossible. When the organic substance collected in the trap was analyzed by gas chromatography, it contained only 343 g (yield 45%) of 1-fluorobutane.

[Comparative Example 2]
In Comparative Example 1, the reaction was carried out in the same manner as in Comparative Example 1 except that the stirring blade was changed from the anchor type to the paddle type. About 1.2 hours after the completion of the raw material dropping, solid matter on the sherbet was observed on the inner surface of the glass reactor, and the solid matter was also deposited on the upper surface of the paddle type stirring blade. When the organic substance collected in the trap was analyzed by gas chromatography, it contained only 254 g of 1-fluorobutane (yield 33%).

  From the above, even in a fluorination reaction in which a large amount of solid content is generated by changing to a reactor equipped with a screw type stirring blade or a rotary kiln type reactor, a large scale (1 kg to 1000 kg) is obtained. It can be seen that a fluorinated alkane can be produced at a degree.

DESCRIPTION OF SYMBOLS 1 Stirring motor 2 Raw material dropping port 3 Product recovery port 4 Screw type stirring blade 5 Heater 6 Discharge port 7 Raw material feed port / product recovery port 8 Rotary joint 9 Discharge port

Claims (4)

When the alkylsulfonic acid ester represented by the following structural formula (1) is fluorinated with an alkali metal fluoride in a solvent, the alkali metal fluoride is 1.5 to 3.5 equivalents relative to the alkylsulfonic acid ester. A method for producing a fluorinated alkane represented by the structural formula (2), wherein fluorination is carried out in a reactor equipped with a screw type stirring blade or a rotary kiln reactor.

(However, R ¹ represents a linear or branched alkyl group having 3 to 6 carbon atoms, and R ² represents an alkyl group having 1 to 7 carbon atoms or an aromatic group that may have a methyl group as a substituent. .)

(However, R ¹ represents a linear or branched alkyl group having 3 to 6 carbon atoms.) 2. The method according to claim 1, wherein the alkali metal fluoride is potassium fluoride or cesium fluoride. The production method according to claim 1 or 2, wherein the solvent is used in an amount of 3 to 7 parts by weight with respect to 1 part by weight of the alkyl sulfonate ester as a raw material. 4. The alkyl sulfonate ester represented by the structural formula (1) and the fluorinated alkane represented by the structural formula (2), wherein R ¹ has 4 or 5 carbon atoms. The manufacturing method of crab.

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