JPH0588700B2 - - Google Patents

Description

[Detailed description of the invention]

INDUSTRIAL APPLICATION FIELD The present invention relates to a novel fluorine-containing amine having a relatively long fluorocarbon chain and a method for producing the same. Conventional techniques and problems to be solved by the invention In general, compounds with fluorocarbon chains have specific physical and chemical properties, so they are used in fluorine-containing polymers, surfactants, fine chemicals such as pharmaceuticals, agricultural chemicals, etc. It has long been attracting attention in various fields. In particular, compounds with perfluoroalkenyl groups can be synthesized from fluoroolefins such as tetrafluoroethylene and hexafluoropropene by a relatively simple method, and many derivatives have been reported. Many of them are chemically unstable, such as being unstable due to atoms or reacting with fluoroolefins, so stable fluorine-containing amines are required. The present invention has been made in response to such demands. Means for Solving the Problems That is, the present invention solves the problem using the general formula ():

The present invention relates to a fluorine-containing amine represented by the formula: (wherein Rf represents a perfluoroalkenyl group having 3 to 12 carbon atoms) and a method for producing the fluorine-containing amine. Examples of Rf include a perfluorohexenyl group or a perfluorononenyl group derived from a hexafluoropropene dimer or trimer. Fluorine-containing amines represented by the general formula () are:

[Formula] (wherein Rf has the same meaning as above) It is produced in good yield by solvolysis of p-perfluoroalkenylacetanilide. It is obtained by reacting an oligomer (for example, a dimer or trimer of hexafluoropropene) in a non-aqueous polar solvent in the presence of a basic catalyst at about 0 to 25°C. Non-aqueous polar solvents include acetonitrile, N,N
-dimethylformamide, tetrahydrofuran,
Examples include diglyme, tetrahydropyran, dimethyl carbitol, dimethyl ether and the like, with acetonitrile or N,N-dimethylformamide being particularly preferred. Examples of the basic catalyst include trimethylamine, triethylamine, sodium carbonate, potassium carbonate, etc., and triethylamine is particularly preferred. The amount of the basic catalyst used is, for example, 1 to 2 equivalents relative to the hexafluoropropene oligomer (usually approximately equivalent). The solvolysis of p-perfluoroalkenyloxyacetonitrile represented by the general formula () is as follows:
Carry out in a polar solvent in the presence of an acid. Examples of polar solvents include water, methanol, ethanol, propanol, isopropanol, butanol, isobutanol, ethylene glycol, diethylene glycol, mixed solvents of two or more of these, and water-methanol or water-ethanol mixed solvents are particularly preferred. . Examples of acids include hydrochloric acid, sulfuric acid, hydrobromic acid, hydriodic acid, perchloric acid, etc., with hydrochloric acid or sulfuric acid being particularly preferred. The reaction temperature for solvolysis is from room temperature to the boiling point of the solvent, preferably from about 50°C to the boiling point of the solvent. By subjecting the amine acid salt produced by this solvolysis to an alkali treatment, a fluorine-containing amine represented by the above general formula () can be obtained.
Examples of the alkali include sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, etc., and an aqueous solution of sodium carbonate or potassium carbonate is preferred. Note that another method for producing p-perfluoroalkenyloxyaniline represented by the general formula () is a method of reducing a nitro compound obtained by nitrating perfluoroalkenyloxybenzene. However, as explained in connection with the examples below, while the nitro compounds are easily prepared, the reduction reaction is performed using activated carbon, which has extremely high catalytic activity to produce high purity amino compounds in high yields. -It was found that the reaction was difficult to proceed even when an iron chloride () catalyst (see Journal of the Chemical Society of Japan, 1975, No. 7, pages 1223 to 1227) was used. Hereinafter, the present invention will be explained with reference to Examples. Examples Example 1 (1) Synthesis of p-perfluorohexenyloxyacetanilide: Into 100 ml of N,N-dimethylformamide in a three-necked flask (500 ml) equipped with a dropping funnel, thermometer, stirrer and reflux condenser. p-oxyanilide
15.1g (0.10mol) and triethylamine 10.1
g (0.10 mol) was dissolved, and 30.0 g (0.10 mol) of hexafluoropropene dimer was gradually added dropwise into the solution while stirring while cooling with an ice-water mixture. After the dropwise addition was completed, stirring was further continued. . The reaction mixture was neutralized with dilute hydrochloric acid, the solid product was extracted with ethyl acetate, thoroughly washed with water, the oil was separated, and this was dried with magnesium sulfate. The solid obtained by subjecting the filtrate to evaporation using an evaporator was recrystallized from methanol (yield: 37.9 g: yield: 88%). The physical properties of the obtained product are shown in Table 1 below. (2) Synthesis of p-perfluorohexenyloxyaniline: Methanol in a three-necked flask (500 ml) equipped with a dropping funnel, thermometer, stirrer and reflux condenser.
21.6 g of p-perfluorohexenyloxyacetanilide prepared as above in 100 ml
(0.05 mol) and while refluxing the solution using an oil bath, 30 ml of hydrochloric acid was added into the solution.
It was dripped gradually over time. After the dropwise addition was completed, heating and stirring was continued for another 5 hours, and the reaction mixture was cooled to room temperature, transferred to a beaker (2), and then poured with water.
Pour 500ml into a beaker, add 10% K ₂ CO ₃ aqueous solution until the pH of the system becomes 9 to 10, extract the liberated product using carbon tetrachloride, and wash thoroughly with water. . The separated organic layer was dried using magnesium sulfate and then subjected to evaporation using an evaporator, and the yellow solid residue was recrystallized from n-heptane to obtain the title compound (yield:
18.0g; yield 92%). The physical properties of this compound are shown in Table 1 below. Example 2 (1) p-perfluorononenyloxyacetanilide was synthesized according to the procedure of Example 1 (1) except that hexapropene trimer was used instead of hexapropene dimer (yield 72%). (2) p-Perfluorononenyloxyaniline was synthesized according to the procedure of Example 1 (2) except that p-perfluorononenyloxyacetanilide was used instead of p-perfluorohexenyloxyacetanilide ( yield 98%). Comparative Example 1 (1) Synthesis of p-perfluorohexenyloxynitrobenzene: 23.9 g of concentrated nitric acid was placed in a three-necked flask (500 ml) equipped with a dropping funnel, thermometer, stirrer, and reflux condenser.
was added, 30.9 g of concentrated sulfuric acid was gradually added while stirring while cooling, and 50.0 g (0.134 mol) of perfluorohexenyloxybenzene was added dropwise over about 1 hour.
After the addition was completed, the temperature of the system was raised to 70°C and nitration was carried out for about 4 hours. The reaction mixture cooled to room temperature was placed in ice water, the precipitated solid was collected by filtration, thoroughly washed with water, dissolved in carbon tetrachloride, dried using magnesium sulfate, and then the evaporator was removed. The solid residue was recrystallized from n-hexane to obtain 41 g of the title compound as pale yellow crystals (yield 70%). The physical properties of this compound are shown in Table 1 below. (2) Synthesis of p-perfluorohexenyloxyaniline: P prepared as above was added to 130 ml of methanol in a three-necked flask (1000 ml) equipped with a dropping funnel, thermometer, stirrer and reflux condenser. -Perfluorohexenyloxynitrobenzene 40.3
g (0.10 mol), activated carbon 5.0 g and FeCl ₃ .
After adding 100 mg of 6H ₂ O and heating and stirring for 20 minutes, a mixed solution of 8.0 g (0.16 mol) of N ₂ H ₄ .H ₂ O and methanol was added dropwise over about 1 hour while stirring under reflux. After the dropwise addition was completed, reflux stirring was continued for another 36 hours, during which time the disappearance of the nitro compound and the production of amine were monitored by GLC analysis, but no production of the title compound was observed. The above procedure was repeated four times with similar results. Comparative Example 2 (1) Synthesis of p-perfluoronenyloxynitrobenzene: The described compound was prepared according to the procedure of Comparative Example 1 (1) except that perfluorononenyloxybenzene was used instead of perfluorohexenyloxybenzene. was prepared (yield 57%). (2) Synthesis of p-perfluorononenyloxyaniline: The procedure of Comparative Example 1(2) was repeated except that p-perfluoronenyloxynitrobenzene was used instead of p-perfluoronenyloxynitrobenzene. In this case, GLC analysis showed approximately 30% amine formation, but the reaction did not proceed any further. In addition, in Table 1, C ₆ F ₁₁ − and C ₉ F ₁₇ −
represents a group represented by the following structural formula.

【formula】

【formula】

[Table] Effects of the Invention According to the present invention, a stable amine having a relatively long fluorocarbon chain can be obtained in good yield. The fluorine-containing amine can be used not only as a surface smoothness improver for various plastic products or as a raw material for these products, but also as a new material that is expected to be used as a raw material for many fluorine-based compounds, including pharmaceuticals. It is a compound.

Claims (1)

[Scope of Claims] 1. A fluorine-containing amine represented by the general formula (): [Formula] (wherein Rf represents a perfluoroalkenyl group having 3 to 12 carbon atoms). 2. The fluorine-containing amine according to item 1, wherein Rf represents a perfluorohexenyl group or a perfluorononenyl group. 3 General formula (): [Formula] (wherein, Rf represents a perfluoroalkenyl group having 3 to 12 carbon atoms) is added to p-perfluoroalkenyloxy-acetanilide in a polar solvent with an acid. A method for producing a fluorine-containing amine represented by the general formula (): [Formula] (wherein Rf has the same meaning as above), characterized by solvent decomposition. 4. The method according to item 3, wherein Rf represents a perfluorohexenyl group or a perfluorononenyl group. 5. The method according to item 3, wherein the polar solvent is a water-alcohol mixed solvent. 6. The method according to item 3, wherein the acid is hydrochloric acid or sulfuric acid. 7. The method according to item 3, wherein the temperature of the solvolysis reaction is 50°C to the boiling point of the solvent.