JPH0699359B2 - Method for producing perfluoromalonyl fluoride - Google Patents

Description

TECHNICAL FIELD The present invention relates to a method for producing perfluoromalonyl fluoride which can be suitably used as a raw material for producing various fluorine-containing compounds.

[Problems to be Solved by Prior Art and Invention]

Conventionally, a method for producing perfluoromalonyl fluoride used as a raw material for producing an ion exchange resin is, for example, CH ₃ O.
Method of reacting CF ₂ CF ₂ COF with SO ₃ (JP-A-53-82713) or method of reacting CH ₃ OCF ₂ CF ₂ COF with SbF ₅ (JP-A-57-98226) However, CH ₃ OCF ₂ CF ₂ COF used as a raw material in such a method requires multiple reaction steps in the synthesis and has a low yield. This method is not economically advantageous.

[Means for solving problems]

In view of the above problems, the present inventors have sought a compound that can be preferably used as a raw material for producing perfluoromalonyl fluoride. As a result, 1,2-epoxypentafluoropropane-3-fluorosulfate (hereinafter, abbreviated as EPPS), which is relatively easy to synthesize, has a high yield, and can be preferably used as a raw material for producing perfluoromalonyl fluoride. Have already proposed (Japanese Patent Application No. 62-309349). Then, they have found that perfluoromalonyl fluoride can be easily produced using the above EPPS as a raw material, and completed the present invention.

That is, the present invention is a method for producing perfluoromalonyl fluoride, which comprises contacting 1,2-epoxypentafluoropropane-3-fluorosulfate with a fluorine ion generating compound.

EPPS used as a raw material in the present invention is a novel compound and has the following structural formula: Is a compound represented by.

EPPS can be confirmed by the following means.

a) Measure the infrared absorption spectrum (hereinafter abbreviated as IR) to 1545 cm ^-1 And the characteristic absorption derived from the —OSO ₂ F group at 1495 cm ⁻¹ can be observed.

b) ¹⁹ F- NMR spectrum (hereinafter, abbreviated as ¹⁹ F-NMR.) it is possible to know the binding mode of the fluorine atoms present in EPPS by measuring.

c) Measurement of mass spectrum (hereinafter abbreviated as MS)
The observed peaks (generally the ion mass m is
Value expressed by m / e divided by the charge number e of
By calculating the composition formula,
Know the molecular weight and the bonding mode of each atomic group in the molecule.
You can That is,(M / e = 147) SO₂Characteristic derived from F (m / e = 83)
Strong peaks can be observed.

The method for producing EPPS is not particularly limited and may be any method, but for example, it can be suitably produced by the following method. Perfluoroallyl fluorosulfate [CH ₂ = CFCF ₂ OSO ₂ F] (hereinafter FAS
Is abbreviated. ) Is oxidized to obtain EPPS. A known oxidizing agent is usually used for the oxidation of FAS.

As the above-mentioned oxidizing agent, for example, oxygen, hypohalite, organic hydroperoxide, hydrogen peroxide, etc. can be preferably used.

When oxygen is used as the oxidizing agent, the molar ratio of oxygen to FAS is usually selected from the range of 1: 3 to 10: 1, preferably 1: 2 to 3: 1. The reaction can be carried out in the presence or absence of a solvent. When a solvent is used, halogenated solvents, for example, perfluorodimethylcyclobutane, fluorotrichloromethane, 1,1,2-trichloro-1,2,2-trifluoroethane, halogenated hydrocarbons such as carbon tetrachloride, etc. Perfluoropolyethers such as Krytox (trade name: manufactured by DuPont), fomblin oil (trade name: manufactured by Asahi Glass Co., Ltd.), and polytrifluoro-ethylene chloride (manufactured by Daikin Industries, Ltd.) can be used. The reaction temperature is usually selected in the range of 30 to 200 ° C, preferably 70 to 150 ° C. Reaction time is 10
It is selected from the range of minutes to 1 day, preferably 1 to 10 hours.
Further, it is preferable to carry out stirring during the reaction.

Next, the hypohalite used as an oxidizing agent is represented by the following formula M (OX) n [wherein M is an alkali metal or an alkaline earth metal, X is chlorine, bromine or iodine, and n is
Is 1 or 2. ] It is a compound shown by these. Among the hypohalites that can be preferably used, in the above formula, M is sodium or potassium, X is chlorine or bromine, and chlorine is particularly preferable from the viewpoint of reactivity and stability. The molar ratio of hypohalite to FAS is preferably in the range of 1: 1 to 10: 1. The reaction is generally preferably carried out in the presence of an inert solvent, using a quaternary ammonium salt in the range of 0.1 to 10% by weight based on the hypohalite. The above-mentioned halogen-based solvent can be used as the inert solvent. Examples of the quaternary ammonium salt used as the phase transfer catalyst include tetramethylammonium chloride, tetraethylammonium bromide, trimethylbenzylammonium chloride,
Triethylbenzylammonium chloride, tetrabutylammonium bromide, tetrabutylammonium hydrogensulfate, trioctylmethylammonium chloride, laurylmethylammonium chloride, benzylcetyldimethylammonium chloride and the like can be used alone or in combination of two or more kinds. The reaction temperature is usually -30 to 40 ° C, preferably -20 to 10 ° C.
Selected from the range. The reaction time is usually selected from the range of 5 minutes to 10 hours, preferably 10 minutes to 2 hours. Further, it is preferable to carry out stirring during the reaction.

When an organic hydroperoxide is used as the oxidizing agent, a compound that has been conventionally used for the epoxidation reaction of an olefin can be used as the organic hydroperoxide. Examples thereof include tertiary butyl hydroperoxide, cumene hydroperoxide, diisopropylbenzene hydroperoxide, ethylbenzene hydroperoxide, and the like, and tertiary butyl hydroperoxide and cumene hydroperoxide are particularly preferable. The molar ratio of organic hydroperoxide to FAS is preferably 1: 3 to 5: 1. In the reaction, using a molybdenum compound such as molybdenum arbonyl or a tungsten compound such as tungsten carbonyl, which has been adopted in the conventional epoxidation with organic hydroperoxide, as a catalyst increases the reaction rate and shortens the reaction time. It is suitable for proceeding the reaction.
These catalysts are generally 0.005 to 0.1 mol% based on FAS.
Preference is given to using. Further, it is preferable to carry out the reaction in the presence of the above-mentioned inert solvent. The reaction temperature is usually selected in the range of 30 to 200 ° C, preferably 70 to 150 ° C. The reaction time is generally 1 to 50 hours, preferably 3 to 15 hours.

When hydrogen peroxide is used as the oxidizing agent, it is preferable to use the above-mentioned halogen-based solvent as the diluting solvent.
The reaction is preferably carried out on the alkaline side by adding sodium hydroxide or potassium hydroxide. A phase transfer catalyst composed of a quaternary ammonium salt can also be used.

The reaction temperature is −40 ° C. to 50 ° C., and the reaction time is preferably 1 hour to 1 day. The molar ratio of hydrogen peroxide to FAS which is an oxidant is 1: 3 to 10: 1, preferably 1: 2 to 3: 1.

FAS, which is the raw material of EPPS, can
Of American Chemical Society (J.Ame
r.Chem.Soc.) 103 , 5598, (1981).

-CF ₂ OSO ₂ F groups which the above EPPS has is extremely reactive high group, a -COF group readily degraded by fluoride ion generating compounds such as KF. On the other hand, EPPS has Is decomposed into a —CF ₂ COF group by the above-mentioned fluorine ion generating compound. Therefore, perfluoromalonyl fluoride (FCOCF ₂ COF) can be produced in one step by contacting EPPS with a fluorine ion generating compound.

Examples of the above-mentioned fluorine ion generating compound include inorganic fluorides such as sodium fluoride, potassium fluoride, cesium fluoride, rubidium fluoride, lithium fluoride, silver fluoride, and antimony pentafluoride; tetramethylammonium fluoride, tetraethyl Tetraalkylammonium fluoride and the like such as ammonium fluoride and tetrabutylammonium fluoride are used. Above all, potassium fluoride or cesium fluoride having a particle size of 0.1 to 100 μm is preferably used. The amount of the fluorine ion generating compound used is 0.1 to 10 mol, preferably 0.5 to 4 mol, per 1 mol of EPPS.

The reaction conditions of EPPS and a fluorine ion-generating compound are generally from 0 to 3 atm, preferably under normal pressure, at -30 ° C to 40 ° C.
A reaction time of 1 second to 2 days at a temperature of 0 ° C. is adopted.

In contacting EPPS with the fluorine ion generating compound, it is preferable to use an aprotic solvent as a reaction medium.
Examples of the aprotic solvent include diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, acetonitrile, adiponitrile, propionitrile, tetrahydrofuran, dioxane, benzonitrile, nitroethane, tetramethylene sulfone and the like. . These aprotic solvents for EPPS
It is preferable to use 0.1 to 10 times (weight). Also, EPPS
Is diluted with an inert gas such as nitrogen gas to 1 to 20 times, and an inorganic fluoride such as sodium fluoride, potassium fluoride or cesium fluoride is reacted at a reaction temperature of 50 to 450 ° C. and a contact time of 0.1.
Perfluoromalonyl fluoride can also be obtained by contacting under the condition of -10 minutes.

When the EPPS is brought into contact with the fluoride ion-generating compound using the above reaction medium, perfluoromalonyl fluoride can be isolated by the following method. That is, perfluoromalonyl fluoride can be distilled and isolated by contacting EPPS with a fluorine ion generating compound and then heating to a temperature of 0 to 200 ° C., preferably 30 to 100 ° C. . 0.1-200 when heating above
Distillation of perfluoromalonyl fluoride can be carried out more effectively by reducing the pressure to mmHg.

[Effect]

As described above, according to the present invention, EP as a raw material
Perfluoromalonyl fluoride can be easily produced in high yield by using PS. Therefore, the present invention is an advantageous method for synthesizing various fluorine compounds including ion exchange resins.

〔Example〕

In order to describe the present invention more specifically, examples and production examples will be described below, but the present invention is not limited to these examples and production examples.

Production Example-1 Perfluoroallyl fluorosulfate CF ₂ was added to a 100 ml ml autoclave equipped with a stirrer combined with an oxygen cylinder.
= CFCF ₂ OSO ₂ F 30.0g and 1,1,2-trichloro-1,2,2-trifluoroethane 50.0g were charged, and after heating to 90 ° C, the partial pressure of oxygen gas became 5kg / cm ² . Pressed in the quantity. Since the reaction started immediately and oxygen gas was consumed and the pressure dropped, oxygen gas was successively injected so that the partial pressure of oxygen gas was kept at 5 kg / cm ² . After 5 hours, when the consumption of oxygen gas stopped, the autoclave was cooled to 20 ° C. Oxygen gas consumption
It was 1.95 (calculated from the difference in internal pressure of the oxygen cylinder before and after the reaction). After cooling, 76.0 g of reaction product was taken out. When the product was isolated by distillation, the boiling point was 60 ° C.
11.6 g of a fraction was obtained. The structures of the compounds of the fraction are shown below. By IR, ¹⁹ F-NMR, MS, Was confirmed.

a) IR b) ¹⁹ F-NMR (trichlorofluoromethane standard; expressed in ppm with the high magnetic field side as positive) Chemical shift (a) 107.8ppm, 110.8ppm (b) 152.5ppm (c) 78.6ppm (d) -47.8ppm c) MS Production Example-2 The reaction was performed in the same manner as in Example-1 without using 1,1,2-trichloro-1,2,2-trifluoroethane used in Example-1. Oxygen consumed 2.02. 29.5 g of the reaction product was taken out. When the product was isolated by distillation, the boiling point was 60 ° C.
A fraction of 16.4 g was obtained. The fraction was analyzed by IR, ¹⁹ F-NMR and MS. Was confirmed.

Production Example-3 Sodium hypochlorite solution (effective chlorine 10%) in a three-necked flask equipped with a stirrer, a dropping funnel, and a thermometer.
I put 500 ml. The reactor was cooled to −15 ° C., 30.0 g of perfluoroallyl fluorosulfate diluted with 100 ml of Daifloyl # 1 (trade name: manufactured by Daikin Industries) was added dropwise over 30 minutes while gently stirring, and 2.0 ml of trioctyl ammonium chloride was added. Was added. After the addition was completed, the mixture was vigorously stirred and reacted for 1 hour. The reaction solution was transferred to a separatory funnel, and the difloyl layer was separated, and then depressurized at room temperature to collect 23.8 g of a reaction product. Then, distillation was performed to obtain 5.1 g of a fraction having a boiling point of 60 ° C. The fraction was analyzed by IR, ¹⁹ F-NMR and MS. Was confirmed.

Production Example-4 In a 100 ml glass autoclave equipped with a stirrer, perfluoroallyl fluorosulfate (CF ₂ = CFCF ₂ OS
O ₂ F) 10.0 g, 1,1,2-trichloro-1,2,2-trifluoroethane 60.0 g, tertiary butyl hydroperoxide 20.
0 g and 0.7 g of molybdenum carbonyl [Mo (CO) ₆ ] were charged and the temperature was raised to 70 ° C. After reacting for 16 hours as it is,
Cooled to room temperature. After cooling, 76.5 g of reaction product was taken out. Isolate the product by distillation and distillate with a boiling point of 60 ° C 2.
I got 4g. The fraction was analyzed by IR, ¹⁹ F-NMR and MS. Was confirmed.

Example-1 0.8 g of anhydrous KF and 10 ml of dry tetraglyme were placed in a 100 ml three-necked flask equipped with a stirrer, a dropping funnel and a reflux condenser at -10 ° C connected to a trap cooled with a dry ice-methanol bath. Cool the reactor to 0 ° C.,
EPPS 15.0 g was added dropwise in 30 minutes.

After 2 hours, the temperature of the reactor was raised to room temperature, the cooling water of the reflux condenser was set to 0 ° C., and the reaction was carried out for 16 hours. 50 after reaction
The pressure was reduced at 0 ° C. to obtain 6.6 g of a reaction product in a trap cooled in a dry ice-methanol bath. The product was perfluoromalonyl fluoride by IR, ¹⁹ F-NMR and MS.

Example-2 6 g of dried potassium fluoride (Spray Dried KF manufactured by Morita Chemical Co., Ltd.) and 30 g of sulfolane were placed in the same 100 ml three-necked flask as used in Example-1, and 10 g of EPPS was added dropwise over 30 minutes. Sulfuryl floyd was formed in the dry ice-methanol trap. After leaving for 2 hours,
The reaction solution was gradually heated from room temperature to 70 ° C. under a reduced pressure of 50 mmHg and kept for 2 hours. After that, when sulfuryl fluoride was removed from each trap, 5 g of a liquid product was obtained. The product was perfluoromalonyl fluoride by IR, ¹⁹ F-NMR.

Example-3 Perfluoromalonyl fluoride was synthesized using the same reaction apparatus as in Example-1. Dried cesium fluoride, 6 g and 40 g of tetraethylene glycol methyl ether were added, and 10 g of EPPS was added dropwise at a temperature of 0 ° C. over 1 hour and left to react for 16 hours. Then, the temperature of the reaction solution was gradually raised under a reduced pressure of 50 to 10 mmHg, and heated at 80 ° C. for 3 hours. After removing the sulfuryl fluoride and the raw material from each trap, 3.5 g of perfluoromalonyl fluoride was obtained.

Example-4 A glass tube having a diameter of 2 cm and a length of 50 cm was filled with 50 g of potassium fluoride, glass beads were packed on the upper portion thereof, and then the glass tube was placed in a constant temperature bath at 250 ° C. Next, use EPPS 15g with Microfizer 5
The mixture was put into a reaction tube at a rate of g / hour and simultaneously reacted with nitrogen gas as a diluent gas at a rate of 40 cc / minute for 4 hours. The reaction product was collected in a trap of dry ice / methanol. The crude product was subjected to simple distillation at a low temperature to obtain 4.4 g of perfluoromalonyl fluoride.

Example-5 Using the same reaction apparatus as in Example-1, 5 g of EPPS was added dropwise to 5 g of tetrabutylammonium fluoride and 10 g of tetraethylene glycol dimethyl ether at 0 ° C over 30 minutes, and the reaction was continued for 4 hours. Then, the temperature of the reaction solution was gradually raised under a reduced pressure of 50 mmHg and heated at 70 ° C. for 2 hours to collect perfluoromalonyl fluoride in the trap. As a result, 1.5 g of perfluoromalonyl fluoride was obtained.

[Brief description of drawings]

FIG. 1 shows 1,2-used as a raw material in the present invention.
1 is a chart of ¹⁹ F-nuclear magnetic resonance spectrum of epoxypentafluoropropane-3-fluorosulfate.

Claims (1)

[Claims] 1. A 1,2-epoxypentafluoropropane-
A method for producing perfluoromalonyl fluoride, which comprises contacting 3-fluorosulfate with a fluorine ion-generating compound.