JP2972912B2 - New fluorinated vinyl ether - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel fluorine compound, and more particularly to a refrigerant, a cleaning agent, an expanding agent for polyolefin and polyurethane, an aerosol propellant, a heat transfer medium, a gaseous dielectric, and an etching gas. The present invention relates to a novel fluorine compound useful as a fire extinguisher, a power circulating working fluid, a polymerization reaction medium, a particle remover, a carrier carrier, a buffing abrasive, a displacement drying agent, a polymer raw material and a copolymer raw material.

[0002]

2. Description of the Related Art Conventionally, refrigerants, detergents, expanders 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 best known. CFCs and HCFCs have been widely used in various industrial fields because of their low toxicity, nonflammability, and chemical and thermal stability. But,
Since such a chlorofluorocarbon-containing hydrocarbon has a chlorine atom, it has been pointed out that a serious disadvantage of destroying the ozone layer in the stratosphere has been pointed out, and it has been internationally decided to stop the production and use thereof. Under such circumstances, there has been a demand for the development of a method for reducing the amount of chlorofluorocarbon and chlorine-containing fluorocarbons used. On the other hand, fluorine-containing ethers can be considered as alternative compounds to CFC and HCFC.
Conventionally, methods for producing a fluorinated ether 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 following method is shown as the former method of fluorinating an ether compound. (1) Direct fluorination of ether compounds with fluorine gas (A. Sekiya et al., Chem. Lett., 1990, 609; or RJ Lagow et al., J. Org. Chem., 1988, 53, 7)
8), (2) Indirect fluorination using a metal fluoride or the like of an ether compound (M. Bradwood et al., J. Flulorine Chem., 197)
5, 5, 521), (3) Electrofluorination of ether compounds (T. Abe et al.,
J. Fluorine Chem., 1980, 15, 353) and the like. On the other hand, the latter method for converting a fluorine-containing compound into an ether compound is as follows. (4) Addition reaction of alcohol to fluorinated olefin
(RD Chambers et al., Adv.Fluorine Chem. 1965,
4, 50), (5) Reaction of alcohol with alkyl halide (J.
A. Young et al., J. Am. Chem. Soc., 1950, 72, 186
0), (6) Reaction of a fluorinated alcohol with a sulfonic acid ester (UK Patent Specification No. 814493), (7) Reaction of an acid fluoride with a sulfonic acid ester (German Patent Specification No. 1294949), ( 8) Reaction of fluorophosgene with sulfonic acid ester
(JP-A-7-179386) and the like. The fluorine-containing vinyl ether of the present invention is a novel compound that has not been synthesized by any of these methods.

[0003]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a novel compound which does not impair the excellent properties of CFCs and HCFCs containing chlorine and does not cause the ozone layer to be destroyed.

[0004]

According to the present invention, 2-trifluoromethoxy-1,1,1 represented by the following formula (1) CF ₃ CF (OCF ₃ ) CHＣＨCH ₂ (1) , 2
-Tetrafluoro-3-butene is provided. Further, according to the present invention, 2-trifluoromethoxy-1,1,1,1 represented by the following formula (2) CF ₃ CF (OCF ₃ ) CH ＝ CF ₂ (2)
2,4,4-Hexafluoro-3-butene is provided.

[0005]

BEST MODE FOR CARRYING OUT THE INVENTION The compound of the above formula (1) of the present invention is represented by the following formula (3): CF ₃ CF (OCF ₃ ) CH ₂ CH ₂ I (3) Fluoromethoxy-
It can be obtained by subjecting 1,1,1,2-tetrafluorobutane to a dehydroiodination reaction. in this case,
The reaction temperature is 0 to 150 ° C, preferably 30 to 100 ° C.
° C and the reaction pressure is usually normal pressure. Also,
This reaction is preferably carried out in the presence of a phase transfer catalyst such as alkali hydroxide and n-hexadecyltrimethylammonium chloride.

[0006] The compound of formula (2) of the present invention has the following formula _{(4) CF 3 CF (OCF} 3) represented by CH ₂ CF ₂ I (4) 4-iodo-2-trifluoromethoxy -
It can be obtained by subjecting 1,1,1,2,4,4-hexafluorobutane to a dehydroiodination reaction. In this case, the reaction temperature is 0 to 150 ° C, preferably 30 ° C.
To 100 ° C., and the reaction pressure is usually normal pressure. This reaction is preferably carried out in the presence of a phase transfer catalyst such as alkali hydroxide and n-hexadecyltrimethylammonium chloride.

The compounds of the formulas (1) and (2) of the present invention are both liquid at ordinary temperature, the compound of the formula (1) has a boiling point of about 36 ° C., and the compound of the formula (2) The boiling point of the compound is about 34 ° C. All of these compounds are advantageously used as alternatives to conventional CFCs and HCFCs. The fluorine compound of the present invention is a refrigerant, a detergent, an expanding agent for polyolefin and polyurethane, an aerosol propellant, a heat transfer medium, a gaseous dielectric, an etching gas, a fire extinguisher, a power circulating working fluid, a polymerization reaction medium, and a particle remover. It is advantageously used as a carrier carrier, buffing abrasive, displacement desiccant, polymer raw material and copolymer raw material.

[0008]

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

Example 1 (1) Synthesis of CF ₃ CF (OCF ₃ ) CH ₂ CH ₂ I Copper powder was placed in a 200 ml stainless steel reactor equipped with a stirrer, pressure gauge, thermometer, gas inlet tube and gas outlet tube. 3.2 g, 1
78.0 g of -iodo-1-trifluoromethoxytetrafluoroethane was charged, cooled with liquid nitrogen, and evacuated. This was heated while stirring, and the reaction pressure was 7
The reaction was carried out at 45 to 65 ° C. while gradually adding ethylene so as not to exceed 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-NMR
From this, it was found that this liquid was 4-iodo-2-trifluoromethoxy-1,1,1,2-tetrafluorobutane. ^{The 1} H-NMR and ¹⁹ F-NMR spectrum data are shown below. In addition, ¹ H-NMR and ¹⁹ F-NMR
In the measurement of, heavy chloroform was used as a solvent, and tetramethylsilane and trichlorofluoromethane were used as standard substances, respectively. ¹ H-NMR (CDCl ₃ ); δ 2.7 ppm (2H,
Multiplet; d), 3.2 ppm (2H, multiplet; e) ¹⁹ F-NMR (CDCl ₃ ); δ-83.2 ppm (3
F, singlet; a), -131.1 ppm (1F, multiplet; b), -53.9 ppm (3F, multiplet; c)

(2) CF ₃ CF (OCF ₃ ) CH = CH ₂
30 g of sodium hydroxide and 1.6 g of n-hexadecyltrimethylammonium chloride were charged into a glass reactor equipped with a stirrer, thermometer, distillation tower and dropping funnel, and heated while stirring to obtain the above. 4-Iodo-2-trifluoromethoxy-1,1,1,2-tetrafluorobutane was added dropwise. The dropping speed is such that the reaction temperature is 60-70.
℃. After finally dropping 170.2 g, the mixture was heated to 90 ° C. and reacted for 2 hours, and then a fraction at 34 to 83 ° C. was extracted from the upper part of the distillation column. This is again subjected to precision distillation to obtain a colorless and transparent liquid 1 having a boiling point of 35 to 38 ° C.
3.4 g were obtained. When this liquid was analyzed by gas chromatography, the purity was 96.4%. ¹ H-NMR,
^{From 19} F-NMR, this liquid was found to be 2-trifluoromethoxy-1,1,1,2-tetrafluoro-3-butene. ^{The 1} H-NMR and ¹⁹ F-NMR spectrum data are shown below. 1 and 2 show the spectrum charts. In addition, ¹ H-NMR and ¹⁹ F-NMR
In the measurement of, heavy chloroform was used as a solvent, and tetramethylsilane and trichlorofluoromethane were used as standard substances, respectively. _{^{1 H-NMR (CDCl 3)}} ; δ5.9ppm (1 H, multiplet; d), 6.0ppm (2H, ^{multiplet; e) 19 F-NMR (} CDCl 3); δ-85.2ppm (3
F, double line 3 Hz; a), -133.1 ppm (1F,
Multiplet; b), -53.9 ppm (3F, doublet 7H
z; c)

Example 3 (1) Synthesis of CF ₃ CF (OCF ₃ ) CH ₂ CF ₂ I Copper powder was placed in a 200 ml stainless steel reactor equipped with a stirrer, pressure gauge, thermometer, gas inlet tube, and gas outlet tube. 1.9g
(0.03 mol), 98.6 g of 1-iodo-1-trifluoromethoxytetrafluoroethane (0.316 mol
l) was charged, cooled with liquid nitrogen, and evacuated. This was heated with stirring, and when the temperature reached about 90 ° C., 20.1 g (0.31) of 1,1-difluoroethylene previously filled in a 50 ml stainless steel cylinder was used.
4 mol) at a supply pressure of 5 kg / cm ² G.
C. for 21 hours, the pressure was 0.2 kg / cm ² G
Has dropped. This was evacuated while trapping it in an acetone cooling bath cooled with dry ice to obtain 119.7 g of a colorless and transparent liquid. When this liquid was analyzed by GC,
The purity was 65.6%. This was distilled to a purity of 99%, and ¹ H-NMR and ¹⁹ F-NMR were measured. As a result, the liquid was found to be 4-iodo-2-trifluoromethoxy-1,
It was confirmed to be 1,1,2,4,4-hexafluorobutane. ^{The 1} H-NMR and ¹⁹ F-NMR spectrum data are 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. ¹ H-NMR (CDCl ₃ ); δ 3.4 ppm (2H, multiplet; d) ¹⁹ F-NMR (CDCl ₃ ); δ-83.9 ppm (3
F, singlet; a), 131.3 ppm (1F, multiplet;
b), -53.9 ppm (3F, singlet; c), -3
9.5 ppm (2F, AB pattern 175 Hz; e)

(2) CF ₃ CF (OCF ₃ ) CH = CF ₂
8.0 g of sodium hydroxide and 0.34 g of n-hexadecyltrimethylammonium chloride were charged into a glass reactor equipped with a stirrer, thermometer, distillation tower and dropping funnel, and heated to 50 ° C. while stirring. 4 obtained by the method of Example 3
-Iodo-2-trifluoromethoxy-1,1,1,
2,4,4-hexafluorobutane was added dropwise. After finally dropping 38.2 g, the temperature was raised to 80 ° C., and the mixture was reacted for 2 hours.
0.2 g was extracted. When this liquid was analyzed by gas chromatography, the purity was 98.5%. ¹ H-NM
From R, ¹⁹ F-NMR, this liquid was 2-trifluoromethoxy-1,1,1,2,4,4-hexafluoro-3
-Butene was found. ¹ H-NMR, ¹⁹ F-
The NMR spectrum data is shown below. In addition, ¹ H-NM
For measurement of R and ¹⁹ F-NMR, deuterated chloroform was used as a solvent, and tetramethylsilane and trichlorofluoromethane were used as standard substances. ¹ H-NMR (CDCl ₃ ); δ 4.7 ppm ( ¹ H, doublet 18 Hz, doublet 17 Hz, multiplet; d) ¹⁹ F-NMR (CDCl ₃ ); δ-86.2 ppm (3
F, double line 4 Hz, double line 3 Hz; a), -126.8
ppm (1F, multiplet; b), -54.9 ppm (3
F, double line 8Hz, double line 4Hz, double line 3Hz;
c), -69.9 ppm (1F, multiplet; e), -7
0.2 ppm (1F, multiplet; f)

[0012]

Since the compounds of the present invention do not contain chlorine atoms, there is no concern about destruction of the ozone layer, and even if they are released into the atmosphere, they have little or no effect on the global environment. Therefore, it is advantageously used as a substitute for CFC and HCFC.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁶ Identification code FI C09K 5/04 C09K 5/04 C10M 105/54 C10M 105/54 C11D 7/50 ZAB C11D 7/50 ZAB C10N 40:08 (72 Inventor Naoto Takada 6F, Hongo Wakai Building, 2-40-17 Hongo, Bunkyo-ku, Tokyo New Refrigerant Project Room (72) Inventor Etsuo Fujimoto 2-40- Hongo, Bunkyo-ku, Tokyo 17 Hongo Wakai Building 6th Floor New Refrigerants Project Room (72) Inventor Akira Sekiya 1-1-1 Higashi, Tsukuba, Ibaraki Pref. ) investigated the field (Int.Cl. ^6, DB name) C07C 43/17 CA (STN) CAOLD (STN) CAPL S (STN) REGISTRY (STN)

Claims (2)

(57) [Claims] 1. 2-trifluoromethoxy-1,1,1,2 represented by the following formula (1) CF ₃ CF (OCF ₃ ) CH ＝ CH ₂ (1)
-Tetrafluoro-3-butene. 2. 2-trifluoromethoxy-1,1,1,1 represented by the following formula (2) CF ₃ CF (OCF ₃ ) CH ＝ CF ₂ (2)
2,4,4-hexafluoro-3-butene.