JP2887310B2 - New fluorine compounds - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a fluorine-containing ether compound and a method for producing the same.

[0002]

2. Description of the Related Art Conventionally, refrigerants, detergents, expanding agents for polyolefins and polyurethanes, aerosol propellants, heat transfer media, gaseous dielectrics, fire extinguishers, power circulating working fluids, polymerization reaction media, particle removers, carriers As the carrier, buffing abrasive and displacement drying agent, chlorofluorocarbon (CF
C) and hydrochlorofluorocarbons (HCFCs) are widely used. However, such CFCs
And HCFCs are likely to destroy the stratospheric ozone layer when released into the atmosphere, and have been shown to have serious adverse effects on global ecosystems, including humans, and are now replacing CFCs and HCFCs The development of materials is being actively pursued.

As an alternative to CFC and HCFC, fluorinated ethers can be considered. Conventionally, methods for producing fluorinated ethers can be broadly classified into a method of fluorinating an ether compound and a method of reacting a compound containing a fluorine atom by various methods to form an ether compound. The former includes (1) direct fluorination of ether compounds with fluorine gas (A. Sekiya et al., Che.
m. Lett. R., 1990, 609;
J. Lagow et al. , J. et al. Org. Ch
em. , 1988, 53, 78), (2) Indirect fluorination using a metal fluoride or the like of an ether compound (M.
Bradwood et al. , J. et al. Fluor
ine Chem. , 1975, 5,521), (3)
Electrolytic fluorination of ether compounds (T. Abe et
al. , J. et al. Fluorine Chem. , 19
80, 15, 353). On the other hand, the latter
(4) Addition reaction of alcohol to fluorinated olefin (RD Chambers et al., A
dv. Fluorine Chem. 1965,
4, 50), (5) Reaction of alcohols with alkyl halides (JA Young et al.,
J. Am. Chem. Soc. , 1950, 7
2, 1860), (6) Reaction of fluorinated alcohol with sulfonic acid ester (UK Patent Specification No. 81449)
No. 3), (7) Reaction of acid fluoride with sulfonic acid ester (German Patent Specification No. 1294949), (8)
There is a reaction of fluorophosgene with a sulfonic acid ester (JP-A-7-179886).

[0004]

DISCLOSURE OF THE INVENTION The present invention relates to a fluorine-containing material which is used as a raw material for obtaining a fluorine-containing ether compound which has no problem of depletion of the ozone layer and is advantageously used as a substitute for chlorofluorocarbon or hydrochlorofluorocarbon. An object of the present invention is to provide an ether compound and a method for producing the same.

[0005]

Means for Solving the Problems The present inventors have made intensive studies to solve the above-mentioned problems, and as a result, have completed the present invention. That is, according to the present invention, the following general formula (1)

Embedded image (Wherein, R ¹ , R ² , R ³ and R ⁴ represent hydrogen, halogen or an alkyl group optionally containing halogen;
Represents a halogen other than fluorine). Further, according to the present invention, the following general formula (1)

Embedded image (Wherein, R ¹ , R ² , R ³ and R ⁴ represent hydrogen, halogen or an alkyl group optionally containing halogen;
Represents a halogen other than fluorine) in the method for producing a fluorinated ether compound represented by the following general formula (2):

Embedded image (Wherein, X has the same meaning as described above)
A halogeno-1-trifluoromethoxytetrafluoroethane is represented by the following general formula (3)

Embedded image (Wherein R ¹ , R ² , R ³ and R ⁴ have the same meaning as described above).

[0006]

BEST MODE FOR CARRYING OUT THE INVENTION In the 1-halogeno-1-trifluoromethoxytetrafluoroethane represented by the general formula (2) used as a starting material in the present invention, X represents a halogen other than fluorine. Examples include iodine, bromine and chlorine, and preferably iodine. As a specific example of this, for example, 1-iodo-
1-trifluoromethoxytetrafluoroethane, 1-
Bromo-1-trifluoromethoxytetrafluoroethane, 1-chloro-1-trifluoromethoxytetrafluoroethane and the like can be mentioned.

In the present invention, among the olefinic compounds which may be used as the other starting material and which may contain a halogen represented by the general formula (3), R ¹ , R ² , R
³ and R ⁴ represent hydrogen, halogen or an alkyl group optionally containing halogen. In this case, the alkyl group has 1 to 8, preferably 1 to 6, more preferably 1 to carbon atoms.
4. In this case, the halogen is chlorine,
Bromine, iodine and fluorine.

The olefinic compound represented by the general formula (3) includes olefins and halogenated olefins. Illustrative examples of olefins include, for example, ethylene, propylene, 1-butene, 2-butene, isobutene, 1-pentene, 2-pentene, 3-pentene, isopentene, 1-hexene, 2-hexene, 3-hexene, 1,3-butadiene and the like can be mentioned. On the other hand, specific examples of halogenated olefins include, for example, fluoroethylene, chloroethylene, bromoethylene, iodoethylene, 1,1-difluoroethylene, 1,2-difluoroethylene, 1,1-dichloroethylene, 2-dichloroethylene, 1,1-dibromoethylene, 1,2-dibromoethylene, trifluoroethylene, trichloroethylene,
Tribromoethylene, chlorotrifluoroethylene, hexafluoropropene, 3,3,3-trifluoropropene,
Tetrafluoroethylene, 3-fluoro-1-propene, 1
-Bromo-2-chloro-1,1,2-trifluoro-3-
Butene, 2-bromo-1,1-difluoroethylene, 3-
Bromo-1,1,2-trifluoro-1,3-butadiene, 4-bromo-1,1,2-trifluoro-1-butene, 2-chloro-1,1-difluoroethylene, 1-chloro-1- Fluoroethylene, 1-chloro-2-fluoroethylene, 2-chloro-1,1,1,4,4,4-hexafluoro-2-butene, 1,1-dibromodifluoroethylene, 1,2-dichlorodi Fluoroethylene, 1,1-dichlorodifluoroethylene, 3,3,4,4,5,5,5-
Heptafluoro-1-pentene, iodotrifluoroethylene, 3,3,4,4,4-pentafluorobutene,
1,1,1,3,3-pentafluoropropene, 3,3
4,4,5,5,6,6,6-Nonafluoro-1-hexene, 1,1,2-trichloro-3,3,3-trifluoropropene and the like.

In the present invention, the compound of the general formula (2) is reacted with the compound of the general formula (3) to obtain a fluorinated ether compound represented by the general formula (1).
The reaction in this case is represented by the following equation.

Embedded image

The above-mentioned reaction is carried out without a solvent or in an organic solvent. However, it is preferable to carry out the reaction without a solvent since the separation operation after the reaction becomes easy. This reaction can easily proceed in the presence of a metal catalyst. Examples of the metal catalyst include zinc, copper and the like, but it is needless to say that the metal catalyst is not limited thereto. The charging ratio of 1-halogeno-1-trifluoromethoxytetrafluoroethane and the olefinic compound is not particularly limited, and the charging can be performed at an arbitrary ratio. The pressure in this reaction is not particularly limited, and the reaction proceeds at any pressure from reduced pressure to increased pressure. When the reaction is performed under pressure, the pressure is not particularly limited, but is preferably 50 kg / cm ² G or less from the viewpoint of operability and the like. The reaction temperature varies depending on the reaction time, reaction pressure, amount of catalyst and the like, but is usually 0 to 200 ° C., preferably 2 to 200 ° C.
It is selected from the range of 0 to 100 ° C.

The general formula (1) obtained by the above reaction
In the fluorine-containing ether compound represented by the formula, various derivatives can be obtained by utilizing the reactivity of the halogen X bonded thereto. Examples of such derivatives are as follows.

(1) Derivative in which X is Substituted with Hydrogen This derivative can be obtained by hydrogenating a fluorinated ether compound and substituting X with hydrogen. (2) Derivative in which X is substituted with another type of halogen This derivative can be obtained by subjecting a fluorine-containing ether compound to a halogen substitution reaction with a metal halide and substituting X with another type of halogen. For example, X can be replaced with fluorine by reacting with metal fluoride. (3) Derivative in which X is substituted with an aliphatic hydrocarbon group This derivative can be obtained by reacting a fluorinated ether compound with a Grignard reagent and substituting X with an aliphatic hydrocarbon group. Examples of the aliphatic hydrocarbon group in this case include an alkyl group, an alkenyl group, and an alkynyl group having 1 to 8, preferably 1 to 6 carbon atoms.

Further, the fluorine-containing ether represented by the general formula (1) can introduce a double bond by dehydrohalogenating X together with hydrogen bonding to an adjacent carbon. This dehydrohalogenation reaction can be preferably performed in the presence of an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide.

[0014]

Next, the present invention will be described in more detail with reference to examples.

Example 1 1.9 g of copper powder and 62.9 g of 1-iodo-1-trifluoromethoxytetrafluoroethane were charged into a glass reactor equipped with a stirrer, thermometer, water-cooled refluxer and dropping funnel. The mixture was heated with stirring, and 1-hexene was added dropwise. The dropping rate was adjusted so that the reaction temperature was 45 to 60 ° C. After finally dropping 17.0 g, the mixture was reacted at 70 ° C. for 2 hours. The reaction mixture was filtered to give a clear, colorless liquid.
0 g was obtained. When this liquid was analyzed by gas chromatography, the purity was 91.3%. ¹ H-NMR, ¹⁹
From F-NMR, it was found that this liquid was 4-iodo-2-trifluoromethoxy-1,1,1,2-tetrafluorooctane represented by the following formula. ¹ H-NM
The R, ¹⁹ F-NMR spectrum data is shown below.
In the measurement of ¹ H-NMR and ¹⁹ F-NMR, deuterated chloroform was used as a solvent, and tetramethylsilane and trichlorofluoromethane were used as standard substances.

Embedded image In the above, a represents F of CF ₃ , b represents F of CF, c represents F of OCF ₃ , d, e, f, g, h and i each represent H bonded to each carbon atom. Show.

¹ H-NMR (CDCl 3): δ
3. 7-3.0 ppm (2H, multiplet; d);
3 ppm (1H, multiplet; e), 1.8 ppm
(2H, multiplet; f), 1.5 ppm (2
H, multiplet; g), 1.4 ppm (2H, multiplet; h), 0.9 ppm (3H, multiplet;
i) ¹⁹ F-NMR (CDCl 3): δ-83.3 pp
m (3F, multiplet; a), -132.1 ppm
(1F, multiplet; b), -53.6 ppm (3
F, multiplet; c)

Reference Example 1 Tributyltin hydride (70.8) was placed in a glass reactor equipped with a stirrer, a thermometer, a distillation column equipped with a water-cooled refluxer, and a dropping funnel.
g, 2,2'-azobisisobutyronitrile 0.08 g
Was heated with stirring, and 4-iodo-2-trifluoromethoxy-1,1,1,2-tetrafluorooctane was added dropwise. The dropping speed is such that the reaction temperature is 50-70.
℃. After finally dropping 70.0 g, the mixture was distilled as it was to obtain 16.5 g of a colorless and transparent liquid. When this liquid was analyzed by gas chromatography,
The purity was 87.2%. ¹ H-NMR, ¹⁹ F-NM
From R, this liquid was found to be 2-trifluoromethoxy-1,1,1,2-tetrafluorooctane represented by the following formula. ^{The 1} H-NMR and ¹⁹ F-NMR spectrum data are shown below. In addition, ¹ H-NMR and
^For the measurement of ¹⁹ F-NMR, chloroform was used as a solvent, and tetramethylsilane and trichlorofluoromethane were used as standard substances.

Embedded image

¹ H-NMR (CDCl 3): δ
1 ppm (2H, multiplet; d), 1.5 ppm
(2H, multiplet; e), 1.3 ppm (6
H, multiplet; f, g, h), 0.9 ppm (3
H, multiplet; i) ¹⁹ F-NMR (CDCl 3): δ-83.4 pp
m (3F, singlet; a), -129.0 ppm
(1F, multiplet; b), −53.8 ppm (3
F, multiplet; c)

Example 2 3.2 g of copper powder was placed in a 200 ml stainless steel reactor equipped with a stirrer, a pressure gauge, a thermometer, a gas inlet tube and a gas outlet tube.
78.0 g of 1-iodo-1-trifluoromethoxytetrafluoroethane was charged, cooled with liquid nitrogen, and evacuated. The mixture was heated with stirring, and reacted at 45 to 65 ° C. while gradually adding ethylene so that the reaction pressure did not exceed 7 kg / cm ² . After the pressure drop was no longer observed, the temperature was kept at 50 ° C. for another 2 hours. After purging excess ethylene, 83.1 g of a colorless and transparent liquid was obtained. When this liquid was analyzed by gas chromatography, the purity was 99.6%. ¹ H-NMR, ¹⁹ F-
From NMR, this liquid was 4-iodo-2 represented by the following formula.
-Trifluoromethoxy-1,1,1,2-tetrafluorobutane. ¹ H-NMR, ¹⁹
The F-NMR spectrum data is shown below. In ^addition, 1 H-
For measurement of NMR and ¹⁹ F-NMR, chloroform was used as a solvent, and tetramethylsilane and trichlorofluoromethane were used as standard substances, respectively.

Embedded image

¹ H-NMR (CDCl 3): δ
7 ppm (2H, multiplet; d), 3.2 ppm
(2H, multiplet; e) ¹⁹ F-NMR (CDCl3): δ-83.2 pp
m (3F, singlet; a), -131.1 ppm (1
F, multiplet; b), -53.9 ppm (3F, multiplet; c)

Example 3 Zinc powder 3.3 was placed in a 200 ml stainless steel reactor equipped with a stirrer, a pressure gauge, a thermometer, a gas inlet tube and a gas outlet tube.
g, 78.2 g of 1-iodo-1-trifluoromethoxytetrafluoroethane, cooled with liquid nitrogen,
A vacuum was applied. This was heated with stirring, and reacted at 60 to 100 ° C. while gradually adding ethylene so that the reaction pressure did not exceed 7 kg / cm ² . After purging excess ethylene, 81.7 g of a colorless and transparent liquid was obtained. When this liquid was analyzed by gas chromatography,
The purity was 98.4%. ¹ H-NMR, ¹⁹ F-NM
From R, this liquid was found to be 4-iodo-2-trifluoromethoxy-1,1,1,2-tetrafluorobutane.

Reference Example 2 Tributyltin hydride 13 was added to a glass reactor equipped with a stirrer, a thermometer, a distillation column equipped with a water-cooled reflux device, and a dropping funnel.
1.1 g, 2,2'-azobisisobutyronitrile 0.1 g
05 g, and warmed with stirring.
-Trifluoromethoxy-1,1,1,2-tetrafluorobutane was added dropwise. The dropping speed is such that the reaction temperature is 50 to
The temperature was adjusted to 70 ° C. Finally, 99.6 g of liquid was dropped and distilled as it was to obtain 51.0 g of a colorless and transparent liquid.
I got When this liquid was analyzed by gas chromatography, the purity was 98.6%. ¹ H-NMR, ¹⁹ F-
From NMR, it was found that this liquid was 2-trifluoromethoxy-1,1,1,2-tetrafluorobutane represented by the following formula. ¹ H-NMR, ¹⁹ F-NM
The R spectrum data is shown below. In the measurement of ¹ H-NMR and ¹⁹ F-NMR, deuterated chloroform was used as a solvent, and tetramethylsilane and trichlorofluoromethane were used as standard substances.

Embedded image

¹ H-NMR (CDCl 3): δ
2ppm (2H, Double line 14Hz, Quad line
7.6 Hz; d), 1.1 ppm (2H, triplet; e) ¹⁹ F-NMR (CDCl 3): δ-83.3 pp
m (3F, singlet; a), -130.5 ppm (1
F, triple line 14Hz, quad line 12Hz;
b), -53.9 ppm (3F, double line 12H
z; c)

[0024]

As described above, the fluorine-containing ether compound of the present invention contains no chlorine atom by using it as a reaction raw material.
There are no concerns about ozone depletion, and there is little or no effect on the global environment when released into the atmosphere. Can be obtained.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁶ Identification code FI C11D 7/28 C11D 7/28 7/50 7/50 C10N 40:08 (72) Inventor Naoto Takada 2-chome Hongo, Bunkyo-ku, Tokyo 40-17 17th Hongo Wakai Building 6th Floor Hongo Wakai Building 6F Hongo Wakai Building 2-40-17 Hongo, Bunkyo-ku, Tokyo Inventor Etsuo Fujimoto Inside the New Refrigerants Project Office (72) Inventor: Akira Sekiya 1-1-1 Higashi, Tsukuba, Ibaraki Pref. 263674 (JP, A) JP-A-58-43934 (JP, A) Phys. Chem. Neu Fold, Vol. 158, no. 1 (1988) p. 15-p. 23 (58) Field surveyed (Int.Cl. ⁶ , DB name) C07C 43/12 CA (STN) CAOLD (STN) REGISTRY (STN)

Claims (3)

(57) [Claims] [Claim 1] The following general formula (1) (Wherein, R ¹ , R ² , R ³ and R ⁴ represent hydrogen, halogen or an alkyl group optionally containing halogen;
Represents a halogen other than fluorine). 2. The following general formula (1): (Wherein, R ¹ , R ² , R ³ and R ⁴ represent hydrogen, halogen or an alkyl group optionally containing halogen;
Represents a halogen other than fluorine) in the method for producing a fluorine-containing ether compound represented by the following general formula (2): (Wherein, X has the same meaning as described above)
Halogeno-1-trifluoromethoxytetrafluoroethane is converted to a compound represented by the following general formula (3): (Wherein R ¹ , R ² , R ³ and R ⁴ have the same meanings as described above). 3. The method of claim 2 wherein X is iodine.