JPS6115860B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention has the general formula (n is an integer from 0 to 50; Z is fluorine, hydroxyl group, alkoxy group, -OM group; M is an alkali metal; X and Y are fluorine, trifluoromethyl group; the same applies hereinafter) Concerning methods for producing compounds. Regarding fluorocarbons containing perfluorovinyloxy groups, Japanese Patent Publication No. 39-21228, Japanese Patent Publication No. 38
−1617, JP 52-10851, JP 52-33623
It is described in the specifications of JP-A-51-136686, JP-B-42-1664, British Patent No. 1145445, British Patent No. 1094500, etc. The production method described in the above specification relates to a method in which a perfluorovinyloxy group is created at the terminal by a thermal decomposition method. The present invention, unlike the above-mentioned known examples, relates to a fluorocarbon containing a perfluoroallyloxy group, that is, a CF ₂ =CFCF ₂ O- group at the end. For example, as a typical example, CF ₂ = CFCF ₂ O− (CF (CF ₃ ) CF ₂ O) _o CF (CF ₃ ) COOCH ₃ CFCl = CFCF ₂ O− (CF (CF ₃ ) CF ₂ O) _o CF (CF ₃ ) COOH CF ₂ = CFCF ₂ O− (CF ₂ CF ₂ O) _o CF ₂ COF CF ₂ = CFCF ₂ O− (CF ₂ CF ₂ O) _o CF ₂ COOCH ₃ , etc. Conventionally, it has been impossible to synthesize a fluoro compound having a terminal group of CF ₂ =CFCF ₂ O- due to the lack of a raw material compound, but the present inventors have
We succeeded in synthesizing this raw material and achieved the method of the present invention for producing a new fluorine-containing unsaturated ether. Conventionally, in order to obtain CF ₂ =CFO- group, raw materials are thermally decomposed at high temperatures of 150 to 500°C, and the yield is as low as 30%, and toxic carbonyl fluoride is released during the reaction. There are disadvantages such as the occurrence of
Industrially, various restrictions arise in its implementation. In order to improve these drawbacks, the present inventors have conducted intensive research and found that a high yield of 70% or more can be achieved easily under mild reaction conditions by dechlorination reaction of compound (1) represented by the following general formula. A method for producing a new fluorine-containing unsaturated ether has been discovered. The present invention is based on the general formula It is characterized in that the compound represented by is obtained by a dechlorination reaction. For example CF ₂ ClCFClCF ₂ OCF(CF ₃ ) COOCH ₃
The dechlorination reaction of CF ₂ = CFCF ₂ OCF
Produce (CF ₃ ) COOCH ₃ . Examples of perfluoroolefin epoxides include tetrafluoroethylene oxide, hexafluoropropylene oxide, and octafluoroisobutylene oxide. In the dechlorination reaction, CF ₂ ClCFCl− in the general formula (1)
The target is chlorine bound to the group. In this case, it is preferable to use, for example, zinc, iron, magnesium, etc. as a dechlorination agent, or to add a trace amount of a reaction accelerator such as iodine. Zinc can also be used after being activated with acetic acid, hydrogen, or the like.
Although the reaction proceeds without using a solvent, it is better to use a solvent. Examples of the solvent include diethylene glycol dimethyl ether, diethylene glycol dibutyl ether, methanol, and ethanol, and a mixture of these may be used. The higher the reaction temperature, the easier it will be to proceed, but if it is too high, side reactions will occur, so the reaction temperature is usually between 0°C and 200°C.
°C, preferably from 50 °C to 120 °C. The reaction proceeds under reduced pressure, normal pressure, or increased pressure. The amount of the dechlorinating agent used is 1 mol or more per 1 mol of compound (1) as a raw material. Preferably, it is appropriate to use 1 to 3 times the mole amount. If zinc chloride is produced as a by-product in this reaction, it will alter the quality of the product, so after the reaction is complete,
It is preferable to separate the reaction solution and solid components by filtration, distillation, or the like. Further, in order to accelerate the reaction, it is more preferable to take out the product continuously. The compound of the present invention thus obtained can be polymerized to form functional polymers such as ion exchange membranes.
It is suitable for use as a surfactant, fiber treatment agent, metal cleaning agent, solvent, surface treatment agent, etc., and can be used in a wide range of other applications. The present invention will be further explained below with reference to Examples.
The present invention is not limited to these examples. Incidentally, in this example, steps a to c were performed in order to confirm the product during the process, but normally, there is no problem in carrying out each of these steps continuously. Example 1 The desired product was obtained by performing the following steps a to c. a: Synthesis of raw materials 200 ml with stirring blade, vent pipe, blowing pipe, 50 g of 2,3-dichlorotrifluoropropionyl fluoride, 1 dry cesium fluoride in a steel autoclave
After charging 50 g of dry diethylene glycol dimethyl ether and sealing the autoclave, the autoclave was cooled to -50°C with dry ice-methanol. After removing the gas from the autoclave using a vacuum pump, 50 g of hexafluoropropylene oxide was charged. After raising the reaction temperature to 80°C, the mixture was stirred vigorously and reacted for 5 hours. After cooling the autoclave to room temperature and releasing unreacted hexafluoropropylene oxide as a gas, the reaction solution was removed from the autoclave and subjected to fractional distillation.
12.5 g of CF ₂ ClCFClCF ₂ OCF (CF ₃ )COF was obtained. 10g of methanol CF ₂ ClCFClCF ₂ OCF
(CF ₃ ) was gradually added to 12.5 g of COF, and by fractional distillation, CF ₂ ClCFClCF ₂ OCF (CF ₃ )
11 g of COOCH ₃ was obtained. CF ₂ ClCFClCF ₂ OCF
NMR data of (CF ₃ )COOCH ₃ is shown in Table 1. Table 1 NMR data δ (chemical shift from TMS) δ=123.23PPm (C ₍₁₎ ) δ=103.09 〃 (C ₍₂₎ ) δ=117.63PPm (C ₍₃ ⁾ ) δ=117.77 〃 (C ₍₄₎ ⁾ ) δ＝100.19 〃 (C ₍₅₎ ) δ＝158.75 〃 (CO) δ＝ 53.31 〃 (CH ₃ ) J＝(Coupling constant) Jc ₍₁₎ F ₍₁₎ ＝Jc ₍₁₎ F ₍₂₎ ＝301.43cps. Jc ₍₁₎ F ₍₃₎ ＝33.77cps. Jc ₍₂₎ F ₍₃₎ ＝133.83cps. Jc ₍₂₎ F ₍₁₎ ＝Jc ₍₂₎ F ₍₂₎ ＝Jc ₍₂₎ F ₍₄₎ = Jc ₍₂₎ F ₍₅₎ = 33.89 Jc ₍₃₎ F ₍₄₎ = Jc ₍₃₎ F ₍₅₎ = 285.32cps. Jc ₍₃₎ F ₍₃₎ = 29.43cps. Jc _{( 4)} F ₍₇₎ = Jc ₍₄₎ F ₍₈₎ = Jc ₍₄₎ F ₍₉₎ = 428.74cps. Jc ₍₄₎ F ₍₆₎ = 30.96cps. Jc ₍₅₎ F ₍₆₎ = 131.60 cps. Jc ₍₅₎ F ₍₇₎ = Jc ₍₅₎ F ₍₈₎ = Jc ₍₅₎ F ₍₉₎ = 38.25 cps. Jc ₍₆₎ F ₍₆₎ = 32.24 cps. Gas-mass spectrum (electron From analysis using impact type ion source and chemical ionization type ion source)
m/e of CF ₂ ClCFClCF ₂ OCF (CF ₃ ) COOCH ₃
found the following values: m/e;

[Formula] 85.87 (CF ₂ Cl−) ⁺ , 151, 153, 155 (CF ₂ Cl
−CFCl−) ⁺ , 201, 203, 205(CF ₂ Cl−
CFCl−CF ₂ −) ⁺ ,

[Formula] 341(L-Cl) ⁺ , 69(CF ₃ ) ⁺ , where L is the molecular weight Based on the analysis results above, this product is
It was found to be CF ₂ ClCFClCF ₂ OCF (CF ₃ ) COOCH ₃ . b; Synthesis of activated zinc 5 g of zinc, 10 ml of acetic acid, and 0.1 g of copper acetate were added to a 100 ml Erlenmeyer flask, heated at 80° C. for 5 minutes, and then filtered by suction. The solid matter was washed with 20 ml of ethylene glycol dimethyl ether. c; Dechlorination reaction step The zinc obtained in b and 50 ml of diethylene glycol dimethyl ether were charged into a round bottom flask (made of glass, capacity 100 ml) equipped with a stirring device, a dropping funnel, and a suction port, and then heated to 80°C. The distillate was cooled and collected at -50° C. while 10 g of CF ₂ ClCFClCF ₂ OCF (CF ₃ ) COOCH ₃ was gradually added dropwise. The collected distillate was analyzed by gas chromatography and found to be CF ₂ = CFCF ₂ OCF (CF ₃ ) COOCH ₃ 6.9
g (calculated based on area ratio) was obtained. The following m/e values were detected from gas-mass spectrum analysis (using an electron impact ion source and a chemical ionization ion source) of this product. m/e;

[Formula] 131 (CF ₂ = CF - CF ₂ -) ⁺ ,

[Formula] 306 (molecular ion (L) ⁺ ), others 69 (-
CF ₃ ) ⁺ From the above analysis results, this product is
It was found to be CF ₂ ClCFClCF ₂ OCF (CF ₃ ) COOCH ₃ . Example 2 The desired product was obtained by performing the following steps a to b. a; Synthesis of raw materials When the reaction temperature is 30°C and the reaction time is 30 hours, after reacting 2,3-dichlorodifluoropropionyl fluoride and hexafluoropropylene oxide according to Example 1, unreacted hexafluoropropylene The oxide was expelled and the reaction solution was filtered. Then 50 g of methanol was added to remove CF ₂ ClCFClCF ₂ OCF (CF ₃ ) by fractional distillation.
COOCH ₃ 6.2g CF ₂ ClCFClCF ₂ OCF (CF ₃ )
1.3 g of CF ₂ OCF (CF ₃ ) COOCH ₃ was obtained. The elemental analysis values for each product are shown below. CF ₂ ClCFClCF ₂ OCF (CF ₃ ) COOCH ₃ Actual measurement % C 22.54 H 0.97 Cl 19.01 F 45.62 CF ₂ ClCFClCF ₂ OCF (CF ₃ ) CF ₂ OCF (CF ₃ )
COOCH ₃ Actual value % C 22.82 H 0.64 Cl 12.96 F 52.31 All of these products showed absorption in the infrared absorption spectrum around 2960 cm ^-1 indicating methyl group content and absorption around 1780 cm ^-1 indicating carbonyl ester. From these data, it was confirmed that it was the above compound. b; Dechlorination step 1 g of zinc treated according to b of Example 1 and 5 ml of diethylene glycol were placed in a round bottom flask equipped with a stirrer, a thermometer, a reflux tower, and a dropping funnel, heated to 90°C, and heated to CF while stirring. ₂ ClCFClCF ₂ OCF
(CF ₃ )CF ₂ OCF (CF ₃ )COOCH ₃ 1g is added dropwise. After heating at 90°C for 30 minutes, the reaction solution was analyzed using gas chromatography, and CF ₂ = CFCF ₂ OCF (CF ₃ ) CF ₂ OCF
0.6 g (CF ₃ )COOCH ₃ (calculated by area ratio) was obtained.
CF ₂ ClCFClCF ₂ OCF (CF ₃ ) CF ₂ OCF (CF ₃ )
Traces of COOCH ₃ were detected. Obtained CF ₂ =
CFCF ₂ OCF (CF ₃ ) CF ₂ OCF (CF ₃ ) COOCH ₃
gas-mass spectrum (electron impact ion source,
and chemical ion (using chemical ion source) analysis,
The following values of m/e were detected. m/e; 131 (CF ₂ = CF−CF ₂ −) ⁺ ,

【formula】

[Formula] 69 (−CF ₃ ) ⁺ 225 247 ( _CF2 = CF- _CF2 -O-CF( _CF3 )-) ⁺ From these analytical data, it was confirmed that it was the above compound.

Claims (1)

[Claims] 1. General formula (X and Y are fluorine or trifluoromethyl group. Z is fluorine, hydroxyl group, alkoxy group, or OM group. M is an alkali metal. n is 0 to
By performing a dechlorination reaction on the compound represented by the formula (an integer of 50), the general formula (X, Y, Z and n are the same as above) A method for producing a fluorine-containing unsaturated ether. 2. The method according to claim 1, wherein X is a trifluoromethyl group and Y is fluorine. 3. The manufacturing method according to claim 1 or 2, wherein zinc is used in the dechlorination reaction. 4. The production method according to claim 1, 2 or 3, wherein the reaction is carried out in a diethylene glycol dimethyl ether solvent.