JP2000351751A - Fluorine-containing ester and production of perfluoropropionyl halide using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for producing a fluorine-containing ester and CF3CF2COF by using CF3CF2CH2OH as a raw material. SOLUTION: This method for producing CF3CF2COF comprises reacting CF3CF2CH2OH with any one kind of CF3CF2COOH, CF3CF2COF, CF3CF2COCl and CF3CF2CCl2OC (=O) CF2CF3, producing CF3CF2CH2OC(=O)CF2CF3, then chlorinating the produced CF3CF2CH2OC(=O)CF2CF3 and reacting the resultant CF3CF2CCl2OC(=O)CF2CF3 with a fluorinating agent.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a novel fluorinated ester which is important as a precursor for organic synthesis and a method for producing a perfluoropropionic halide using the same.

[0002]

2. Description of the Related Art 2,2,3,3,3-pentafluoropropionic acid fluoride (perfluoropropionic acid fluoride; CF ₃ CF ₂ COF; hereinafter also referred to as PF)
It is a compound necessary for producing perfluoro (propyl vinyl ether) which is important as a raw material monomer for producing a fluororesin or a fluororubber.

Conventionally, as a technique for producing PF, hexafluoropropene oxide (hereinafter referred to as HFPO) has been used.
Isomerization is also used industrially, and is carried out in the presence of a catalyst comprising a tertiary amine (GB Patent 1,
No. 019,788) and a method (JP-A-58-38231) in the presence of an alkali metal fluoride catalyst.
HFPO is produced by oxidizing hexafluoropropene.

As another manufacturing method, CF ₃ CF ₂ CHC
A method of oxidizing IF (WO96 / 29298) has been reported, but 2,2,3,3,3-pentafluoropropanol (CF ₃ CF ₂ CH ₂ OH; hereinafter also referred to as 5FP) is used as a raw material. There is no report on a method for producing PF with high yield in a high yield.

Also, 2,2,3,3,3-pentafluoropropionic chloride (perfluoropropionic chloride; CF ₃ CF ₂ COCl; hereinafter also referred to as PCl)
Are useful compounds used as various catalysts, intermediates for agrochemicals and the like. Conventionally, as a technique for producing PCl, for example, a method of oxidizing 1,1,1,2,2-pentafluorodichloropropane with oxygen in the presence or absence of chlorine under light irradiation (Japanese Patent Laid-Open No. 118197). Also, as a production method using alcohol as a raw material,
Directly or in the presence of a catalyst, aldehyde and RfC (= O)
There is a method (WO98 / 29377) for production via OCHClRf (wherein Rf is a polyfluoroalkyl group), but a production method via RfC ((O) OCH ₂ Rf has been reported so far. It has not been.

[0006]

SUMMARY OF THE INVENTION An object of the present invention is to provide a CF
An object of the present invention is to provide a method for producing a novel fluorinated ester, PF and PCl in high yield using ₃ CF ₂ CH ₂ OH as a raw material.

[0007]

Means for Solving the Problems The present inventors have conducted intensive studies to achieve this object, and as a result, 2, 2, 3, 3,
3-pentafluoropropanol [CF ₃ CF ₂ CH ₂ O
H; 5FP] as a raw material, and using perfluoropropionic acid-2,2,3,3,3-pentafluoropropyl [CF ₃ CF ₂ CH ₂ OC (＝ O) CF ₂ CF ₃ ; compound (I)]
Is prepared, and this is photochlorinated to give 1-chloro-2,2,3,3,3-pentafluoropropyl perfluoropropionate [CF ₃ CF ₂ CHClOC (＝ O) C
F ₂ CF ₃ ; Compound (II)], and 1,1-dichloro-2,2,3,3,3-pentafluoropropyl perfluoropropionate [CF ₃ CF ₂ CCl ₂ OC (＝ O)
CF ₂ CF ₃ ; Compound (III)], which is reacted with a fluorinating agent such as an alkali metal fluoride to give 2,2,3,3,3-pentafluoropropionic acid fluoride in good yield It has been found that [perfluoropropionic acid fluoride; CF ₃ CF ₂ COF; PF] can be produced.

Further, by thermally decomposing compound (III), 2,2,3,3,3-pentafluoropropionic acid chloride [perfluoropropionic acid chloride; CF ₃
CF ₂ COCl; PCl] can be produced in good yield.

That is, the present invention provides a method for producing a novel fluorine-containing ester and a perfluoropropionic acid halide as described below. Item 1. Formula CF ₃ CF ₂ CXYOC (＝ O) CF ₂ CF ₃ wherein X represents a chlorine atom or a hydrogen atom, and Y represents a chlorine atom or a hydrogen atom. ] The fluorine-containing ester represented by these. Item 2. Under light irradiation, a compound represented by the formula RfCH ₂ OH [wherein Rf represents an alkyl group containing at least one fluorine atom. RfCH ₂ OC (＝ O) Rf, wherein Rf is as defined above. ] The manufacturing method of the fluorine-containing ester represented by these. Item 3. Under light irradiation, which comprises reacting the CF ₃ CF ₂ CH ₂ OH and chlorine _{CF 3 CF 2 CH 2 OC (} = O)
A method for producing CF ₂ CF ₃ . Item 4. CF ₃ CF ₂ CH ₂ OH and CF ₃ CF ₂ COO
H, CF ₃ CF ₂ COF, CF ₃ CF ₂ COCl and CF ₃
Reacting with any one of CF ₂ CCl ₂ OC (＝ O) CF ₂ CF ₃ , wherein CF ₃ CF ₂ CH ₂ OC (=
O) A method for producing CF ₂ CF ₃ . Item 5. Under light irradiation, CF ₃ CF ₂ CH ₂ OC (= O) CF ₂
CF ₃ CF _2, characterized in that the reaction of CF ₃ and chlorine
CHClOC (= O) CF ₂ CF ₃ and / or CF ₃ CF ₂ C
A method for producing Cl ₂ OC (＝ O) CF ₂ CF ₃ . Item 6. Wherein RfCCl ₂ OC (= O) Rf [wherein, Rf represents an alkyl group containing at least one fluorine atom. ]
Wherein the fluorinated ester represented by the formula is reacted with a fluorinating agent, wherein Rf is the same as defined above. ] The method for producing an acid fluoride represented by the formula: Item 7. _{CF 3 CF 2 CCl 2 OC (} = O) and wherein the reacting CF ₂ CF ₃ and the fluorinating agent CF ₃ CF ₂ CO
Method for producing F. Item 8. Item 8. The method according to Item 6 or 7, wherein the fluorinating agent is an alkali metal fluoride. Item 9. A method for producing CF ₃ CF ₂ COCl, comprising decomposing CF ₃ CF ₂ CCl ₂ OC (＝ O) CF ₂ CF ₃ in the presence or absence of a catalyst. Item 10. CF ₃ CF ₂ CH ₂ OH and CF ₃ CF ₂ COO
H, CF ₃ CF ₂ COF, CF ₃ CF ₂ COCl and CF ₃
By reacting with any one of CF ₂ CCl ₂ OC (＝ O) CF ₂ CF ₃ to produce CF ₃ CF ₂ CH ₂ OC (＝ O) CF ₂ CF ₃ , which is chlorinated CF ₃ C obtained
A method for producing CF ₃ CF ₂ COF, comprising reacting F ₂ CCl ₂ OC (＝ O) CF ₂ CF ₃ with a fluorinating agent.

The fluorinated ester of the above item 1 is a novel compound not described in any literature.

[0011]

DETAILED DESCRIPTION OF THE INVENTION [CF ₃ CF ₂ CH ₂ OC (O) C
Production of F ₂ CF ₃ ] CF ₃ CF ₂ CH ₂ OC (＝ O) CF ₂ CF
₃ (Compound (I)) can be produced by CF ₃ CF ₂ CH ₂ OH
(5FP) may be chlorinated under light irradiation or 5FP.
May be reacted with perfluoropropionic acid, a derivative thereof, or compound (III).

In the production of compound (I) by photochlorination of 5FP, the reaction is preferably carried out at a low temperature of 0 to 20 ° C. in order to avoid the formation of by-products due to the cleavage of the carbon-carbon bond. As the light source used at this time, any light source can be used as long as the light source includes light having a wavelength (300 to 500 nm) at which chlorine is cleaved. Specific examples of the light source include an indium lamp and a high-pressure mercury lamp. In the case of high-pressure mercury lamps, light of short wavelength (300 nm or less) is blocked by a filter or the like,
Breakage of the CF bond can be prevented, and the amount of fluoride ions generated can be reduced.

The reaction pressure is not particularly limited.
In order to increase the amount of chlorine dissolved in the reaction solution, it is more preferable to carry out the reaction under atmospheric pressure to pressurized conditions.

The reaction proceeds easily by supplying chlorine to 5 FP by means of bubbling or the like under light irradiation, and continuously extracting hydrochloric acid generated by the reaction to the outside of the system. The optimal flow rate of chlorine is determined by the reaction pressure, the shape of the apparatus, and the like, but is not particularly limited since the reaction proceeds if chlorine coexists in the reaction solution.

A reaction solvent is not particularly required, but a solvent which does not essentially react with chlorine, for example, an inert solvent containing no H in a molecule such as CCIF ₂ CCl ₂ F or perfluorohexane may be used.

As a method for producing the compound (I) from 5FP and perfluoropropionic acid, a method involving azeotropic distillation with an organic solvent, a commonly used dehydrating agent such as phosphorus pentoxide, concentrated sulfuric acid, etc. Among them, there is a method of performing dehydration condensation using at least one of them.

The amount of perfluoropropionic acid used is 5
It is preferably 0.1 to 10 mol, particularly preferably 0.8 to 1.2 mol, per 1 mol of FP. The amount of the dehydrating agent used is preferably 0.5 to 3 equivalents, and particularly preferably 0.8 to 1.2 equivalents, per 1 mol of 5FP. The reaction temperature is preferably from 10 to 90 ° C, particularly preferably from 50 to 85 ° C. The reaction time is
It is preferably 0.5 to 20 hours, particularly preferably 1 hour.
~ 8 hours.

In the case of producing compound (I) from 5FP and perfluoropropionic acid fluoride (PF), the reaction is fast and only by introducing PF into 5FP, compound (I) can be obtained under the conditions of normal temperature and normal pressure. Can be manufactured.

The amount of PF used is based on 1 mol of 5FP.
It is preferably 0.1 to 10 mol, particularly preferably 0.8 to 1.2 mol.

It should be noted that the temperature is 50 to 100 ° C, preferably 70 to 100 ° C.
By heating to 90 ° C., the reaction can be performed more quickly. Further, by removing hydrofluoric acid generated in the system in the presence of a tertiary amine such as diethylaniline or triethylamine, the reaction can be carried out more quickly.

A reaction solvent is not particularly required, but a solvent which does not essentially react with PF and hydrofluoric acid formed, such as perfluorohexane and CCl ₂ FCF ₂ Cl, may be used.

Perfluoropropionic chloride (PC
l) or CF ₃ CF ₂ CCl ₂ OC (＝ O) CF ₂ CF
_{3 When} producing compound (I) from (compound (III)) and 5FP, dimethylformamide is added to 5FP in an amount of 0.01%.
The addition of from 10 to 10% by weight, more preferably from 0.1 to 5% by weight, can promote the progress of the reaction.

The amount of PCl used is preferably 0.1 to 10 mol, particularly preferably 0.3 to 1.2 mol, per 1 mol of 5FP. The amount of compound (III) to be used is preferably 0.1 to 10 mol, particularly preferably 0.4 to 0.6 mol, per 1 mol of 5FP. Although the reaction proceeds at room temperature, it is preferable to perform the reaction at 50 to 80 ° C. because the reaction rate is increased.

The reaction solvent is not particularly required, but is essentially a PCl such as perfluorohexane, CCl ₂ FCF ₂ Cl or the like.
A solvent that does not react with the generated hydrofluoric acid may be used.

[CF ₃ CF ₂ CH ₂ OC (＝ O) CF ₂ CF ₃
Chlorination of the _{chlorinated] CF 3 CF 2 CH 2 OC} (= O) CF 2 CF 3 ( Compound (I)) is carried out by photoreaction. Regarding the chlorination of such esters, chlorination of trifluoroethyl ester (Japanese Patent Publication No. 2-14340) and chlorination of α, α-dichloroperfluoroalkyl ester (Journal of Organic Chemistry, Vol. 26, 5091
P.) Are known. The reaction temperature is preferably from 50 to 150 ° C, and the reaction can be carried out while refluxing the ester at its boiling point. As the light source used for the reaction, the same light source as used in the photochlorination of 5FP described above can be used. Compound
The chlorination of (I) can be performed by introducing chlorine gas under light irradiation.

The reaction pressure is not particularly limited.
In order to increase the amount of chlorine dissolved in the reaction solution, it is more preferable to carry out the reaction under atmospheric pressure to pressurized conditions.

The reaction proceeds easily by supplying chlorine to the compound (I) by means of bubbling or the like under light irradiation, and continuously extracting hydrochloric acid generated by the reaction to the outside of the system. The optimal flow rate of chlorine is determined by the reaction pressure, the shape of the apparatus, and the like, but is not particularly limited since the reaction proceeds if chlorine coexists in the reaction solution.

A reaction solvent is not particularly required, but a solvent which does not essentially react with chlorine, such as perfluorohexane and CCIF ₂ CCl ₂ F, may be used.

In the chlorination reaction, compound (I) is converted to CF ₃ C
This is a sequential reaction in which CF ₃ CF ₂ CCl ₂ OC (＝ O) CF ₂ CF ₃ (compound (III)) is synthesized via F ₂ CHClOC (＝ O) CF ₂ CF ₃ (compound (II)). . Therefore, the compounds (I) to (III) obtained by adjusting the reaction time
Compound (II) can be obtained from the mixture of the above by using a commonly used isolation method such as rectification. On the other hand, the reaction molar ratio of compound (I) and chlorine gas (compound (I): C consumed in the reaction)
l ₂ ) is adjusted to 1: 1.9 to 1: 2.0 to give compound (III) with a conversion of 100% and a selectivity of 95% or more.
Can be synthesized.

In the above-mentioned photochlorination of 5FP,
5FP is chlorinated to produce Compound (I), and then chlorination is carried out to obtain Compound (II) and Compound (I).
(III) can also be produced.

[Production of CF ₃ CF ₂ COCl] Compound (II)
I) is easily decomposed by heating to produce perfluoropropionyl chloride (CF ₃ CF ₂ COCl; PCl). The reaction temperature for the decomposition is preferably between 50 and 300
° C, particularly preferably 100 to 200 ° C.

The decomposition rate can be increased by adding a tertiary amide such as dimethylformamide, a tertiary amine such as diethylaniline, or a quaternary ammonium salt such as tetramethylammonium chloride as a catalyst. , 0 to 100 ° C. The amount of the catalyst added, relative to compound (III),
It is preferably from 0.01 to 20% by weight, more preferably from 0.1 to 3% by weight.

[Production of CF ₃ CF ₂ COF] Compound (III)
Fluorination produces perfluoropropionic acid fluoride (CF ₃ CF ₂ COF; PF).

As the fluorinating agent used for the fluorination of the compound (III), a tertiary amine hydrochloride or an alkali metal fluoride can be used. The reaction rate of fluorination when using an alkali metal fluoride is CsF >> KF >>
>NaF> LiF, and it is preferable to use CsF or KF as the fluorinating agent.

The reaction is carried out in a gas or liquid phase. When the reaction is performed in the gas phase, the reaction is performed by flowing the compound (III) into a reaction tube containing a solid fluorinating agent. The reaction temperature is preferably 100 to 500 ° C., particularly preferably 250 to 500 ° C.
３５０350 ° C. The contact time (W / Fo) is preferably 10 to 1000 g · sec / cc, more preferably 5 to 1000 g · sec / cc.
0 to 500 g · sec / cc. Here, W is the weight (unit: g) of the fluorinating agent, and Fo is the compound (III)
(Unit: cc / sec).

When the reaction is carried out in a liquid phase, the amount of the fluorinating agent to be used is preferably 1 to 20 mol, particularly preferably 2 to 5 mol, per 1 mol of compound (III). The reaction temperature is preferably from 50 to 200 ° C, particularly preferably from 80 to 120 ° C. The reaction time is preferably 1 to 50 hours, particularly preferably 2 to 15 hours. The reaction pressure is preferably from 0 to 10 MPaG, and from 0 to 2 MPa.
MPaG is particularly preferred.

In the reaction, CFCl ₂ CF ₂ Cl, CFCl
₂ CF ₂ CFClCF ₂ Cl, can be used a solvent inert with respect to PF such as perfluorohexane.

From the above findings, it is considered preferable to employ any one of the following methods A and B as a method for producing PF from 5FP in good yield. [Method A] 1. a step of synthesizing CF ₃ CF ₂ CH ₂ OC (＝ O) CF ₂ CF ₃ by photochlorinating CF ₃ CF ₂ CH ₂ OH; By photochlorinating CF ₃ CF ₂ CH ₂ OC (ＯO) CF ₂ CF ₃ , CF ₃ CF ₂ CCl ₂ OC (＝ O) CF ₂
2. synthesizing CF ₃ , and A step of synthesizing CF ₃ CF ₂ COF by fluorinating CF ₃ CF ₂ CCl ₂ OC (＝ O) CF ₂ CF ₃ . [Method B] CF ₃ CF ₂ CH ₂ OH and CF ₃ CF ₂ CCl ₂ OC
1. a step of reacting (＝ O) CF ₂ CF ₃ or CF ₃ CF ₂ COCl to synthesize CF ₃ CF ₂ CH ₂ OC (＝ O) CF ₂ CF ₃ ; By photochlorinating CF ₃ CF ₂ CH ₂ OC (ＯO) CF ₂ CF ₃ , CF ₃ CF ₂ CCl ₂ OC (＝ O) CF ₂
2. synthesizing CF ₃ , and 2. CF ₃ CF ₂ CCl ₂ OC (=
O) half of CF ₂ CF ₃ A step of synthesizing CF ₃ CF ₂ COF by fluorinating the remaining amount.

As a method for producing PCl from 5FP in good yield, it is considered preferable to employ any one of the following methods C and D. [Method C] 1. a step of synthesizing CF ₃ CF ₂ CH ₂ OC (＝ O) CF ₂ CF ₃ by photochlorinating CF ₃ CF ₂ CH ₂ OH; By photochlorinating CF ₃ CF ₂ CH ₂ OC (ＯO) CF ₂ CF ₃ , CF ₃ CF ₂ CCl ₂ OC (＝ O) CF ₂
2. synthesizing CF ₃ , and A step of synthesizing CF ₃ CF ₂ COCl by thermally decomposing CF ₃ CF ₂ CCl ₂ OC (ＣＦO) CF ₂ CF ₃ . [Method D] 1. CF ₃ CF ₂ CH ₂ OH and CF ₃ CF ₂ CC
1. a step of reacting l ₂ OC ((O) CF ₂ CF ₃ or CF ₃ CF ₂ COCl to synthesize CF ₃ CF ₂ CH ₂ OC ((O) CF ₂ CF ₃ ; By photochlorinating CF ₃ CF ₂ CH ₂ OC (ＯO) CF ₂ CF ₃ , CF ₃ CF ₂ CCl ₂ OC (＝ O) CF ₂
2. synthesizing C ₃ , and 2. CF ₃ CF ₂ CCl ₂ OC (=
O) half of CF ₂ CF ₃ A step of synthesizing CF ₃ CF ₂ COCl by thermally decomposing the remaining amount.

In order to isolate and purify the novel fluorinated ester, PF and PCl obtained as described above, ordinary methods such as a recrystallization method, a column purification method and a distillation method can be used.

[0041]

The present invention will be described more specifically with reference to the following examples.

Example 1 5FP (100 g, 0.67 mol) was added to 6.5 to 12.8.
℃, while irradiating light with a high pressure mercury lamp as the light source,
Chlorine gas was flowed at a flow rate of 100 ml / min for 6 hours. A mixture of 61.5% by weight of compound (I), 30.3% by weight of compound (II) and 8.0% by weight of compound (III) was obtained. The amount of the reaction solution collected was 94.6 g, and the total yield of the three esters was 89.4%.

The analysis results of compound (I), compound (II) and compound (III) are shown below. F-NMR (internal standard: CFCl ₃ , 282 MHz) a 84.4 ppm, [m, 3F, CF ₃ ] d 83.4 ppm, [m, 3F, CF ₃ ] c 121.5 ppm, [m, 2F, -CF ₂ C (=
O)] b 123.9 ppm, [t, J = 12.1 Hz, 2
_{F, -CF 2 CH 2] H} -NMR ( internal standard: TMS, 300MHz) 4.83ppm [t , J = 12.1Hz, 2H, -CF
₂ CH ₂ O] IR spectrum (liquid film method) 1801.8 cm ⁻¹ (COO) 2983 cm ⁻¹ , 3034 cm ⁻¹ (CH ₂ O) F-NMR (internal standard: CFCl ₃ , 282 MHz) a 83.1 ppm, [m, 3F, CF ₃ ] d 81.4 ppm, [m, 3F, CF ₃ ] c 121.7 ppm, [m, 2F, -CF ₂ C (=
O)] b 126.9 ppm, [dd, J = 279.1 Hz,
10.7 Hz, 2F × 0.5, —CF ₂ CHCl] 121.2 ppm, [dd, J = 279.1 Hz, 5.
0 Hz, 2F × 0.5, —CF ₂ CFCl] (The optical isomer is present at a ratio of 1: 1.) H-NMR (internal standard: TMS, 300 MHz) 6.86 ppm [dd, J = 10.7 Hz, 5.0H
z, 2H, -CF ₂ CH ₂ O] IR spectrum (liquid film method) 1813.6 cm ^-1 (COO) 3002.4 cm ^-1 (CHClO) F-NMR (internal standard: CFCl ₃ , 282 MHz) a 77.0 ppm, [m, 3F, CF ₃ ] d 83.1 ppm, [m, 3F, CF ₃ ] c 118.9 ppm, [m, 2F, -CF ₂ C (=
O)] b 122.0ppm, [m , 2F, -CF 2 CCl 2] IR spectrum (Ekimakuho) 1828.2cm ^-1 (COO).

Example 2 At room temperature (25 ° C.), a mixture of 5FP (300 g, 2.0 mol) and diethylaniline (320 g, 2.1 mol) was placed in a reaction vessel, and PF was added at room temperature and normal pressure. 1
Bubbling was performed at a flow rate of 00 ml / min for 8 hours. By subjecting the obtained mixture to simple distillation, 520 g (yield: 87.8%) of Compound (I) having a purity of 99% could be obtained.

Example 3 5FP (20 g, 0.13 mol) was placed in a flask equipped with a dry ice / methanol condenser, and PCl (10 g, 0.055 mol) was introduced with stirring.
When the reaction was carried out at 40 ° C. for 2.5 hours, it was confirmed that the compound (I) was produced at a conversion rate of PCl of 29%.
Further, 0.2 g of dimethylformamide was added to this solution, and the mixture was heated to 73 ° C., so that the conversion of PCl became 100%. 84%).

Example 4 5FP (33.0 g, 0.22 mol) and compound (III)
(36.5 g, 0.1 mol) in dry ice /
Place in a reaction vessel equipped with a methanol trap,
After addition of 5 g of dimethylformamide, 60-78
The reaction was performed for 1.8 hours under a temperature condition of ° C. After reaction 6
2.73 g of liquid was recovered. As a result of analyzing this solution, 5
It was a mixture of 7.1% by weight of FP and 92.5% by weight of compound (I), and the reaction yield was 98%.

Example 5 Compound (I) (180 g, 0.61 mol) was placed in a Pyrex glass photoreactor and heated to 80 ° C. 100
While irradiating with a W high-pressure mercury lamp, chlorine gas was introduced at 80 ml / min for 10 hours. After completion of the reaction, 189 g of compound (III) was obtained from the liquid in the container. With 100% conversion,
The reaction yield was 85%.

Example 6 Compound (III) was placed in a reaction vessel equipped with a condenser and a collection tube cooled with dry ice / methanol at the outlet.
(79.2 g, 0.22 mol) and dimethylformamide (0.5 g) were added, and the mixture was stirred at 12 ° C for 4 hours. After the completion of the reaction, 77.0 g of a liquid was collected in the collecting tube, which was analyzed to be all PCl. Selectivity 100%
And the yield was 97.7%.

Example 7 Compound (III) (30 g, 0.082 mol), KF (1
4.3 g, 0.25 mol) and the solvent CFCl ₂ CF ₂ C
1 (23.5 g) in a reaction vessel
A time reaction was performed. At the end of the reaction, the reaction pressure is 1.6MP
a. The contents of the reaction vessel were trapped with liquid oxygen to obtain 23.8 g of PF. The yield was 87.2%.

[0050]

According to the present invention, a novel fluorine-containing ester, PF and PC can be prepared by using CF ₃ CF ₂ CH ₂ OH as a raw material.
1 is provided in a high yield.

Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat II (Reference) C07C 67/14 C07C 67/14 67/287 67/287 67/40 67/40 69/63 69/63 (72) Invention Person Shoji Takagi 1-1, Nishiichitsuya, Settsu-shi, Osaka Daikin Industries, Ltd. Yodogawa Works (72) Inventor Yukio Homoto 1-1, Nishiichitsuya, Settsu-shi, Osaka Daikin Industries, Ltd. Yodogawa Works (72) Inventor Hirokazu Aoyama 1-1, Nishiichitsuya, Settsu-shi, Osaka Daikin Industries, Ltd. Yodogawa Works (72) Inventor Satoshi Koyama 1-1-1, Nishiichitsuya, Settsu-shi, Osaka Daikin Industries, Ltd. F-term in Yodogawa Works 4H006 AA01 AA02 AB84 AC30 AC47 AC48 BA51 BA95 BE53 BE61 BM10 BM71 BM72 KA03 KA06 KA35

Claims (10)

[Claims] 1. The formula CF ₃ CF ₂ CXYOC (＝ O) CF ₂
CF ₃ [wherein, X represents a chlorine atom or a hydrogen atom, and Y represents a chlorine atom or a hydrogen atom. ] The fluorine-containing ester represented by these. 2. A compound of the formula RfCH ₂ OH under the irradiation of light
Rf represents an alkyl group containing at least one fluorine atom. RfCH ₂ OC (＝ O) Rf, wherein Rf is as defined above. ] The manufacturing method of the fluorine-containing ester represented by these. _3. A CF ₃ CF ₂ CH ₂ OC comprising reacting CF ₃ CF ₂ CH ₂ OH with chlorine under light irradiation.
A method for producing (方法 O) CF ₂ CF ₃ . 4. CF ₃ CF ₂ CH ₂ OH and CF ₃ CF ₂ C
OOH, CF ₃ CF ₂ COF, CF ₃ CF ₂ COCl and C
CF ₃ CF ₂ CH ₂ OC characterized by reacting with any one of F ₃ CF ₂ CCl ₂ OC (ＯO) CF ₂ CF ₃
A method for producing (方法 O) CF ₂ CF ₃ . 5. Under light irradiation, CF ₃ CF ₂ CH ₂ OC (=
O) C characterized by reacting CF ₂ CF ₃ with chlorine
F ₃ CF ₂ CHClOC (＝ O) CF ₂ CF ₃ and / or CF
_{3 CF 2 CCl 2 OC (=} O) method for producing CF ₂ CF _3. 6. The formula RfCCl ₂ OC (＝ O) Rf wherein
Rf represents an alkyl group containing at least one fluorine atom. A fluorinated ester represented by the following formula: RfCOF wherein Rf is the same as defined above. ] The method for producing an acid fluoride represented by the formula: 7. CF ₃ CF ₂ CCl ₂ OC (＝ O) CF ₂ CF
CF ₃ CF characterized by reacting ₃ with a fluorinating agent
₂ COF production method. 8. The method according to claim 6, wherein the fluorinating agent is an alkali metal fluoride. 9. CF ₃ CF ₂ CCl ₂ OC (＝ O) CF ₂ CF
_{3. A} process for producing CF ₃ CF ₂ COCl, wherein ₃ is decomposed in the presence or absence of a catalyst. 10. CF_ThreeCF_TwoCH_TwoOH and CF_ThreeCF_Two
COOH, CF_ThreeCF _TwoCOF, CF_ThreeCF_TwoCOCl and
CF_ThreeCF_TwoCCl_TwoOC (= O) CF_TwoCF_ThreeAny one of
Reacting with the seeds to produce CF_ThreeCF_TwoCH_TwoOC (= O) CF_TwoC
F_ThreeWhich is obtained by chlorinating this
F_ThreeCF_TwoCCl_TwoOC (= O) CF_TwoCF_ThreeWith a fluorinating agent
Reacting a CF_ThreeCF_TwoHow to make COF
Law.