JPH0415211B2 - - Google Patents

Description

Detailed Description of the Invention The present invention relates to the general formula R-Rf...() (wherein, Rf is a perfluoroalkyl group having 1 to 20 carbon atoms, and R is a substituted or unsubstituted alkyl group, aryl , allyl group, or ethynyl group). Among the perfluoroalkyl compounds represented by the general formula () obtained by the present invention, for example, 3-(perfluoroalkyl)-1-propene is useful as an intermediate for the synthesis of useful products [J.
See Organometal.Chem., 39 , 395 (1972)]. That is, by oxidation, it can be led to perfluoroalkyl acetic acid, which is useful as a surfactant, water/oil repellent, etc., or as an intermediate thereof [J.
Organometal.Chem., 39 , 395 (1972), West German Patent No. 1916669, 2742685, 2742686]. Conventionally, the method for producing 3-(perfluoroalkyl)-1-propene involves heating iodoperfluoroalkane in a dimethyl sulfoxide solvent in the presence of activated copper powder to produce a perfluoroalkyl copper salt, which then reacts with allyl bromide. There is a known method to obtain it [J.Organometal.Chem., 39 ,
395 (1972)]. Of these, 1-trifluoromethyl-2-propene can be obtained by reacting allyl chloride or allene with iodotrifluoromethane in a Pyrex container under ultraviolet irradiation, and then treating with excess zinc or zinc and magnesium. (See J.Chem.Soc., 1954 , 1634). However, the conventional method cannot be called an industrial method because it requires a large amount of metal and a long period of light irradiation. As conventional methods for producing perfluoroalkyl compounds, the following methods, including those described above, are known. (1) In the presence of iodine or bromine compound and copper powder,
Method of reaction with iodoperfluoroalkane [Tetrahedron, 25, 5921 (1969), Chem.
Commun., 1967 , 1259, J.Organometal.Chem.,
39, 395 (1972), Tetrahedron Lett., 1979 ,
4071]. (2) A method in which a vinyl compound or an ethynyl compound is reacted with an iodoperfluoroalkane under radical-generating conditions, and then dehydriodized by alkali treatment [see US Pat. No. 3,285,975]. (3) A method of reacting an aromatic compound and an iodoperfluoroalkane under heating or light irradiation [Collect.
Czech.Commun., 32 , 183 (1967)]. (4) Method of reacting perfluoroacyl halide and aromatic compound in the presence of nickel carbonyl [J.
Amem.Chem.Soc., 82 , 5111 (1960)], etc. are known. However, in method (1), when a bromine compound is used as one of the raw material compounds, the yield is low. Therefore, expensive iodine compounds must be used and a large amount of copper is consumed. Method (2) is a two-step reaction, and if there is a functional group that easily reacts with radical species in the same molecule, the selectivity is poor, and if the compound is easily polymerized, polymerization reactions occur simultaneously under the reaction conditions. Therefore, it has the disadvantage that it is difficult to control the reaction. Furthermore, in the case of photoreaction, a long reaction time is required, and there is also the problem of the lifespan of the light source. In method (3), the reaction yield is low both under heating and under light irradiation. Method (4) requires the use of highly toxic nickel carbonyl. From the above, all of the conventional methods (1) to (4) have problems as industrial methods. As a result of intensive studies aimed at overcoming the conventional drawbacks, the present inventors have discovered a method for producing perfluoroalkyl compounds in good yield from readily available carbanion compounds, and have completed the present invention. That is, the present invention, in which a perfluoroalkyl group is directly introduced into a carbanion (carbon anion) as a form of a carbon-carbon bond reaction, is an invention using a completely new reaction form. The present invention is based on the general formula (In the formula, Rf is a perfluoroalkyl group having 1 to 20 carbon atoms, Ar is a phenyl group or a phenyl group substituted with a lower alkyl group, and X is -
A group represented by OSO ₂ Y or a halogen atom.
However, Y is a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a halogen atom,
It is an OM' group, an alkoxy group, a phenoxy group, or a perhaloalkyl group, and M' is a hydrogen atom, an alkali metal atom, an ammonium residue, a pyridinium residue, or a group represented by the formula. ) and a perfluoroalkylaryl iodonium compound represented by the general formula R M ... () (R is a substituted or unsubstituted alkyl group, aryl group, vinyl group or ethynyl group, M is a counter ion of a carbanion, , alkali metal atom,
It contains an alkaline earth metal atom, a metal atom of group Ib of the periodic table, or a metal atom of group b of the periodic table. ) A perfluoroalkyl compound represented by the general formula () is obtained by reacting with a carbanion compound represented by the formula (). The perfluoroalkylaryl iodonium compound represented by the general formula (), which is a raw material of the present invention, is a di(trifluoroacetoxy)iodo perfluoroalkane or difluoroiodo obtained by oxidizing or fluorinating an industrially available iodized perfluoroalkane. Perfluoroalkane [Zh.Org.Khim. 6 , 329 (1970), J.Fluorine
Chem., 8 , 177 (1976) and J.Amer.Chem.Soc.
91, 3054 (1969)] with substituted or unsubstituted benzene in the presence of an acid, a method of reacting with substituted or unsubstituted benzene and then treating with an alkali metal halide salt, or perfluoroalkyl-p - Can be obtained by a method of reacting tolyliodonium chloride and silver salt [Zh.
Org.Khim. 7 , 1473 (1971), Zh.Org.Khim., 16 ,
232 (1980) and JP-A-55-162763]. In addition, in the perfluoroalkylaryl iodonium compound represented by the general formula (), when X is -OSO ₂ Y and Y is an alkali metal atom, ammonium residue, or pyridinium residue, the perfluoroalkylaryl iodonium compound represented by the general formula () Obtained by treating the compound (X=OSO ₂ Y, Y=OH) with the corresponding base. The perfluoroalkylaryl iodonium compound represented by the general formula () is n-
Heneicosafluorodecyl phenyl iodonium trifluoromethanesulfonate, 7-trifluoromethyl-hexadecafluorooctyl phenyl iodonium trifluoromethanesulfonate, n-heptadecafluorooctyl phenyl iodonium trifluoromethanesulfonate, n
-Pentadecafluoroheptyl phenyl iodonium trifluoromethanesulfonate, n-tridecafluorohexylphenyl iodonium trifluoromethanesulfonate, i-heptafluoropropylphenyl iodonium trifluoromethanesulfonate, n-heptafluoropropylphenyl iodonium trifluoromethanesulfonate, pentafluoroheptyl phenyl iodonium trifluoromethanesulfonate Fluoroethyl phenyl iodonium trifluoromethanesulfonate, trifluoromethyl phenyl iodonium trifluoromethanesulfonate, pentafluoroethyl phenyl iodonium chloride, n-heptafluoropropyl-p-tolyliodonium chloride, n-
heptadecafluorooctyl tolyliodonium chloride, n-heptadecafluorooctyl phenyl iodonium methanesulfonate, n-heptadecafluorooctyl phenyl iodonium trichloromethane sulfonate, n-heptafluoropropyl-p-tolyliodonium methanesulfonate, n-heptadeca Fluorooctyltolyliodonium methanesulfonate, n-heptafluoropropyl-p-tolyliodonium benzenesulfonate, mono(pentafluoroethyl phenyl iodonium) sulfate, mono(n
-heptafluoropropylphenyl iodonium) sulfate, mono(i-heptafluoropropylphenyl iodonium) sulfate, mono(n-tridecafluorohexyl phenyliodonium) sulfate, mono(n-heptadecafluorooctyl phenyliodonium) sulfate , mono(n-heneicosafluorodecylphenyl iodonium) sulfate, bis(n
-heptafluoropropylphenyl iodonium) sulfate, n-heptafluoropropylphenyl iodonium fluorosulfonate, n
-heptadecafluorooctyl phenyl iodonium chlorosulfonate, n-heptafluoropropylphenyl iodonium methyl sulfate, n-heptadecafluorooctyl phenyl iodonium pyridinium sulfate, n-heptafluoropropylphenyl iodonium sodium sulfate phate, n-heptafluoropropylphenyl iodonium potassium sulfate, and the like. Further, the carbanion compound represented by the general formula () can be obtained by a method known in organic synthetic chemistry. For example, (1) a method in which a base acts on RH, (2) a method in which a metal atom or an organometallic compound acts on RX (X is a halogen), (3) a method using a metal exchange reaction [Chemistry Special Edition No. 117" New organic synthesis reactions that take advantage of the properties of metals,
Compt.Rend., 130 , 1322 (1900), Ber., 20 ,
1210 (1887), Org.Reactions, 6 , 339 (1951), J.
Amer.Chem.Soc., 89 , 3911 (1967), Reagents
for organic synthesis, Vol. 1, 1285], and examples of carbanions include butyl lithium, butyl magnesium bromide, butyl copper salt,
dibutyl copper salt, octylmagnesium chloride,
Benzylmagnesium chloride, 2-phenylethylmagnesium bromide, allylmagnesium chloride, cyclopentadienyl sodium, 2
-Methyl-2-propenylmagnesium chloride, 3-phenyl-2-propenylmagnesium chloride, 2,4-pentadienylmagnesium chloride, 1-lithio-1-phenylthio-2-
Propene, t-butylacetate lithium salt, 2-lithio-1,3-dithiacyclohexane, t-butoxycarbonylmethylzinc bromide, 1-sodium-4-lithio-3-oxo-butyric acid methyl ester, diethyl malonate sodium salt , nitromethane sodium salt, nitroethane sodium salt, 2
- nitropropane sodium salt, 2-nitropropane lithium salt, bis(2-nitropropane) calcium salt, 2-nitropropane potassium salt, methyl cyanoacetate sodium salt, phenylthiomethyllithium salt, phenylsulfonylmethyl sodium salt, Phenylmethanesulfonylmethyl sodium salt, ethenyllithium, 2-ethoxyethenyllithium, ethenylmagnesium bromide, β
-lithiostyrene, 1-propenylmagnesium bromide, phenylmagnesium bromide, phenylmagnesium iodide, phenyllithium,
Methoxyphenyllithium, tolylmagnesium bromide, chlorophenyllithium, lithioacetylide, sodium acetylide, lithiophenylacetylide, phenylethynylmagnesium chloride, sodium phenylacetylide, lithio-
Examples include p-tolylacetylide, silver acetylide, mercury acetylide, lithio-hexylacetylide, calcium carbide, dimethylmercury, and dimethylcadmium. In carrying out the reaction, it is preferable to use a solvent, such as an ether such as diethyl ether, tetrahydrofuran (THF), dioxane, benzene,
Hydrocarbon solvents such as toluene, hexane, cyclohexane, octane, and decalin can be used. Further, when X in the above general formula () is a halogen, the yield is improved if the reaction is carried out in the presence of a radical inhibitor such as nitrobenzene, dinitrobenzene, p-quinone or the like. The reaction temperature is -130°C to 100°C, but preferably -120°C to 60°C for the reaction to proceed efficiently. Hereinafter, the present invention will be explained in more detail with reference to Examples. Example 1 n-heptadecafluorooctyl phenyl iodonium trifluoromethanesulfonate 0.5 g
(0.65 mmol) and 2.5 ml of dry THF with stirring at -78°C under an argon atmosphere.
(1.3 mmol) was added dropwise over about 2 minutes. -78℃
After stirring for 35 minutes, the mixture was returned to room temperature. After the reaction was completed by adding aqueous ammonium chloride, extraction with ether was performed, washed with water, and dried over anhydrous magnesium sulfate. The yield of the product was 65% as calculated by gas chromatography using the internal standard method. The oily substance that remained after distilling off the ether was separated and purified by silica gel column chromatography to obtain 0.16 g of 1-
(n-heptadecafluorooctyl)octane was obtained as an oil. Isolated yield 47%. The physical property values are shown in Table 2. Examples 2 to 22 Reactions were carried out in the same manner as in Example 1 under the conditions shown in Table 1. The results are shown in Table 1. The physical properties of the obtained substance are shown in Table 2. [Table] [Table] [Table]

Claims (1)

[Claims] 1. General formula A method for producing a perfluoroalkyl compound represented by the general formula R-Rf, which is characterized by reacting a perfluoroalkylaryl iodonium compound represented by the following with a carbanion compound represented by the general formula RM (wherein Rf is carbon It is a perfluoroalkyl group having 1 to 20 atoms, Ar is a phenyl group or a phenyl group substituted with a lower alkyl group, and X is -
A group represented by OSO ₂ Y or a halogen atom. However, Y is a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a halogen atom, an OM' group, an alkoxy group, a phenoxy group, or a perhaloalkyl group, and M' is a hydrogen atom,
It is an alkali metal atom, an ammonium residue, a pyridinium residue, or a group represented by the formula. R is a substituted or unsubstituted alkyl group, aryl group,
It is an allyl group or an ethynyl group, and M is a counter ion of a carbanion and contains an alkali metal atom, an alkaline earth metal atom, a metal atom of Group Ib of the periodic table, or a metal atom of Group B of the periodic table. ).