JPS6232183B2 - - Google Patents

Description

[Detailed Description of the Invention] The present invention relates to the general formula (G is a hydrocarbon group having 1 or 2 carbon atoms; x is 0 or 1; Z is an alkoxy group).

The present invention performs a telomerization reaction between a fluorine-containing olefin and an alcohol, and then performs an oxidation reaction of the alcohol obtained in the telomerization reaction, and then performs a dehydrochlorination reaction, an esterification reaction, or an esterification reaction. The present invention relates to a method for producing a novel diene-based fluorine-containing compound, which comprises performing a dehydrochlorination reaction and then a dechlorination reaction.

That is, by combining these reactions,
This led to the invention of a completely new carboxylic acid derivative with two double bonds in the molecule.

First, the telomerization reaction in the present invention is carried out using 1,2-
This is a reaction between dichloro-1,2-difluoroethylene and alcohol.

The alcohol is at least one selected from methanol, ethanol, 1-propanol, and 2-propanol.

Among the products obtained by the telomerization reaction, the general formula H(C ₂ F ₂ CI ₂ ) ₂ -Y-OH (Y has 1 to 3 carbon atoms)
Compounds represented by (hydrocarbon group) are used in the present invention. The reaction between olefin and alcohol described above may be carried out by adding an initiator or by irradiating with ultraviolet rays or radiation.

The initiator may be an organic peroxide such as an acyl peroxide such as benzoyl peroxide or acetyl peroxide, an alkyl peroxide such as di-tert-butyl peroxide,
Inorganic peroxides and salts of peroxides, such as tert-butyloctyl peroxide; organometallic compounds, such as hydrogen peroxide, sodium peroxide, potassium peroxide, ammonium persulfate; azo compounds, such as azobisisobutyronitrile; , for example, tetraalkyl lead, tetraphenyltin, etc., hydrazine, amine oxide, oxygen oxide, oxygen, ozone, etc. Radiation such as ultraviolet rays or radiation such as CO ⁶⁰ or γ rays can also be used instead of the initiator.

The amount of alcohol per mole of olefin is
The amount is from 0.01 to 100 mol, preferably from 1 to 10 mol.

The reaction temperature is from -50°C to 200°C, preferably from 0°C to 100°C.

When using an initiator, the amount of initiator per mol of alcohol is 1 x 10 ^-5 to 1 x 10 ^-1 mol,
Preferably, it is 1×10 ⁻² to 1×10 ⁻² mol. Next, the desired product telomer alcohol obtained in the telomerization reaction is oxidized with an oxidizing agent to form the corresponding carboxylic acid.

Oxidizing agents are, for example, alkali metal and alkaline earth metal permanganates, such as potassium permanganate, barium permanganate, potassium dichromate, oleum, concentrated sulfuric acid, nitric acid, etc., or mixtures thereof. It is also possible to use

The reaction temperature is 30°C to 200°C, preferably 50°C to 120°C.

The amount of the oxidizing agent to be used is an equivalent or more, preferably 1 to 3 times the mole relative to the above-mentioned telomel alcohol. Examples of solvents include water, saturated carboxylic acids such as acetic acid, propionic acid, harsh acids, etc., and mixtures thereof can also be used.

Examples of dehydrochlorination agents include sodium hydroxide, potassium hydroxide, calcium carbonate, metal salts of fatty acids such as sodium formate and potassium acetate, and alcoholates such as sodium ethylate.

In this case as well, the reaction can occur without using a solvent, but it is preferable to use one.

Examples include water, alcohols such as methanol, ethanol, isopropyl alcohol, ethers such as ethyl ether, diethylene glycol dibutyl ether, organic acids, and the like.

It is also possible to use mixtures thereof.

The dehydrochlorination agent may be used in an amount of 0.5 mol or more, preferably 0.5 mol to 4 mol, per 1 mol of the carboxylic acid derivative.

The amount of solvent is based on 1 part by weight of dehydrochlorination agent.
The amount is from 0.01 to 50 parts by weight, preferably from 0.1 to 5 parts by weight.

The reaction temperature is 0°C to 200°C, preferably 30°C to 150°C. The reaction is carried out under reduced pressure, normal pressure,
Reacts under pressure.

As the dechlorination agent used in the subsequent dechlorination reaction, for example, zinc, iron, or magnesium may be added, or a trace amount of a reaction accelerator such as iodine may be added.

Furthermore, when zinc is used, it can be activated with acetic acid, hydrogen, etc. before use.

Although the reaction proceeds even without the use of a solvent, it is preferable to use a solvent.

Examples of the solvent include ethers and alcohols, such as diethylene glycol dimethyl ether, diethylene glycol dibutyl ether, methanol, and ethanol.

The higher the reaction temperature, the easier it will be to proceed, but if it is too high, side reactions will occur, so the temperature is usually between 0°C and 200°C.
C., preferably 50.degree. C. to 120.degree. The reaction proceeds under reduced pressure, normal pressure, or increased pressure.

The amount of the dechlorinating agent is 0.5 mol or more, preferably 0.5 to 4 mol, per 1 mol of the raw material.

Since zinc chloride alters the quality of the product, it is preferable to separate the reaction liquid and solid content by filtration, distillation, etc. after the reaction is completed.

Further, in order to promote the reaction, it is more preferable to take out the product continuously.

The compound of the present invention thus obtained is suitable for use as functional polymers such as ion exchange membranes, surfactants, fiber treatment agents, emulsifiers, metal purification agents, solvents, surface treatment agents, etc. It can be used in a wide range of other applications.

Example 1 The desired product was obtained by performing the following steps A to D.

A Method for producing fluorine-based alcohol: 300 methanol in a 500 ml Pyrex container.
ml and 266 g of 1,2-dichloro-1,2-difluoroethylene were placed in the flask and the flask was sealed. This container was irradiated with γ-rays at 0.6 × 10 ⁵ r/hr using Co ⁶⁰ radiation, and 40
The reaction was carried out at ℃ for 700 hours.

The reaction solution was distilled to H(C ₂ Cl ₂ F ₂ ) CH ₂ OH 37
5 g of H(C ₂ Cl ₂ F ₂ ) ₂ CH ₂ OH were obtained.

The infrared absorption spectrum of H(C ₂ Cl ₂ F ₂ ) ₂ CH ₂ OH showed absorption in the vicinity of 2.7 to 2.8 μ, which indicates absorption of the —OH group.

The structure of H(C ₂ Cl ₂ F ₂ ) ₂ CH ₂ OH was confirmed by infrared absorption spectrum and the results of elemental analysis described below.

Elemental analysis results Actual value Theoretical value % C 20.10 20.16 H 1.51 1.36 Cl 47.40 47.60 F 25.04 25.51 B Oxidation process Potassium dichromate in reflux tower, thermometer, dropping funnel, and flask with stirrer (capacity 200 ml)
After adding 36g of water, 100ml of water, and 30g of concentrated sulfuric acid, the mixture was heated to 85°C with stirring. H using a dropping funnel
30 g of (C ₂ Cl ₂ F ₂ ) ₂ CH ₂ OH was added dropwise. 4 hours later
After the reaction at 85°C, the mixture was returned to room temperature and filtered.

The filtrate was extracted with 50 ml of ethyl ether. The ethyl ether solution was made weakly basic with a 1N aqueous potassium hydroxide solution, and then the aqueous solution was separated.

C Dehydrochlorination, esterification process Potassium hydroxide 10 in a flask (capacity 100 ml) equipped with a reflux tower, thermometer, dropping funnel and stirring device
g and 20 g of water were added and heated to 70° C. with stirring.

After dropping the aqueous solution obtained in B into the flask,
The reaction was carried out at 70°C for 4 hours. After the reaction solution was cooled to room temperature, diluted hydrochloric acid was added for extraction. After washing the ethyl ether solution three times with 10 ml of water, the ethyl ether was removed under reduced pressure to obtain 4.2 g of nonvolatile matter. Reflux tower, flask with dropping funnel (capacity 100ml)
After adding 4.2 g of the nonvolatile matter obtained in step 1 and 0.05 g of concentrated sulfuric acid, the temperature was gradually raised while adding 20 ml of methanol dropwise, and the mixture was boiled and reacted for 2 hours.

D Chlorine escape process Add 1 g of zinc and 5 ml of methanol to a reflux tower, stirrer, thermometer, and flask with a dropping funnel.
The temperature was raised to 50°C while stirring. The reaction solution obtained in D was added dropwise. After reacting for 2 hours at 50°C, the flask was absorbed at 80-120 mmHg and the distillate was heated to -50°C.
It was collected in

Analysis of the collected reaction solution by gas chromatography area ratio revealed that 5-chloro-2,3,
Methyl 4,5-hexafluoro-2,4-pentadienoate (ClFC=CF-CF=CFCOOCH ₃ )
0.7g was obtained. Fraction cut of this component was performed using gas chromatography, and infrared absorption spectrum and elemental analysis were performed.

In the infrared absorption spectrum, there is an absorption of carbonyl group around 5.7μ, and the absorption near the shoulder of this absorption is
There was an absorption of C=C bond around 5.6μ.

Elemental analysis results Actual value % Theoretical value % C 33.01 32.97 H 1.34 1.39 F 34.71 34.78 Cl 16.69 16.22 The structure of the product was confirmed based on these analysis results.

Claims (1)

[Claims] 1 General formula H(C ₂ F ₂ CI ₂ ) ₂ obtained by telomerization reaction of 1,2-dichloro-1,2-difluoroethylene and a saturated alcohol having 1 to 3 carbon atoms. A compound represented by Y-OH (Y is a hydrocarbon group having 1 to 3 carbon atoms) is oxidized with an oxidizing agent, followed by a dehydrochlorination reaction, and then an esterification reaction, or an esterification reaction followed by a dehydrochlorination reaction. , a general formula characterized by further performing a dechlorination reaction (G is a hydrocarbon group having 1 or 2 carbon atoms. x is 0 or 1. Z is an alkoxy group.) A method for producing a diene-based fluorine-containing compound. 2. The manufacturing method according to claim 1, wherein the saturated alcohol is methanol.