JP2995793B2 - Method for producing fluorine-containing aromatic amine compound, fluorine-containing aromatic urethane compound and method for producing the same - Google Patents

Description

The present invention relates to a fluorine-containing surfactant, a fluorine-containing polymer,
The present invention relates to a method for producing a fluorinated aromatic amine compound useful as a raw material or a modifier for pharmaceuticals, agricultural chemicals and the like, a fluorinated aromatic urethane compound which is an intermediate for the production thereof, and a method for producing the same.

[Conventional technology]

Fluorine-containing aromatic compounds having both a reactive functional group and a perfluoroalkenyl group are attracting attention as raw materials or modifiers for fluorine-containing surfactants, fluorine-containing polymers, pharmaceuticals, agricultural chemicals, and the like. Aromatic aromatic compounds are provided.

Conventionally, an example of a fluorine-containing aromatic compound having both a reactive functional group and a perfluoroalkenyl group is disclosed in
No. 121243, formula The benzoic acid derivative represented by is shown.

In addition, JP-A-63-233940 discloses the formula The phenol derivative represented by is shown.

Further, JP-A-1-299243 discloses a formula The phenethyl alcohol derivative represented by is shown.

Further, the formula is disclosed in JP-A-62-178551. (Wherein, Rf represents a perfluoroalkenyl group).

[Problems to be solved by the invention]

The compound disclosed in JP-A-50-121243 is a fluorine-containing benzoic acid derivative having a carboxyl group.
Further, the compound shown in JP-A-63-233940 is a fluorine phenol derivative having a hydroxy group, and the compound shown in JP-A-1-299243 is
It is a fluorine-containing phenethyl alcohol derivative having a hydroxyethyl group.

The compound disclosed in Japanese Patent Application Laid-Open No. 62-178551 is a fluorine-containing amine compound represented by the above-mentioned formula. Need.

Therefore, the present invention provides a method capable of producing an aromatic amine compound having both an amine group and a perfluoroalkenyloxy group under mild conditions, a fluorine-containing aromatic urethane compound as an intermediate for the method, and a method for producing the same. With the goal.

[Means for solving the problem]

The fluorinated aromatic amine compound produced in the present invention,
General formula (I) [In the formula, Rf is, -C _n F _2n-1 (where n is 6 to 12
Which contains one double bond and may be appropriately branched, and the hydrogen of the aromatic ring is substituted with a lower alkyl group, a lower alkoxy group, fluorine, chlorine or bromine. And the amine group is bonded to the aromatic ring at the ortho, meta or para position with respect to the ether bond].

Examples of the compound represented by the general formula (I) include 4- (perfluorononenyloxy) aniline, 4- (perfluorononenyloxy) -2-methylaniline, and 4- (perfluorononenyloxy) -2. -Methoxyaniline, 4
-(Perfluorononenyloxy) -2,3,5,6-tetrafluoroaniline, 4- (porfluorononenyloxy) -2-chloroaniline, 4- (perfluorononenyloxy) -2-bromoaniline 3- (perfluorononenyloxy) aniline, 3- (perfluorononenyloxy) -5-methylaniline, 3- (perfluorononenyloxy) -5-methoxyaniline, 3- (perfluorononenyloxy) ) -2,4,5,6-Tetrafluoroaniline, 3- (perfluorononenyloxy) -5
Chloroaniline, 3- (perfluorononenyloxy)
-5-bromoaniline, 2- (perfluorononenyloxy) aniline, 2- (perfluorononenyloxy)
-5-methylaniline, 2- (perfluorononenyloxy) -5-methoxyaniline, 2- (perfluorononenyloxy) -3,4,5,6-tetrafluoroaniline,
2- (perfluorononenyloxy) -5-chloroaniline, 2- (perfluorononenyloxy) -5-bromoaniline, 4- (perfluorohexenyloxy) aniline, 4- (perfluorohexenyloxy) -2 −
Methylaniline, 4- (perfluorohexenyloxy) -2-methoxyaniline, 4- (perfluorohexenyloxy) -2,3,5,6-tetrafluoroaniline,
4- (perfluorohexenyloxy) -2-chloroaniline, 4- (perfluorohexenyloxy) -2-
Bromoaniline, 3- (perfluorohexenyloxy) aniline, 3- (perfluorohexenyloxy)
-5-methylaniline, 3- (perfluorohexenyloxy) -5-methoxyaniline, 3- (perfluorohexenyloxy) -2,4,5,6-tetrafluoroaniline, 3- (perfluorohexenyloxy)- 5-chloroaniline, 3- (perfluorohexenyloxy)-
5-bromoaniline, 2- (perfluorohexenyloxy) aniline, 2- (perfluorohexenyloxy) -5-methylaniline, 2- (perfluorohexenyloxy) -5-methoxyaniline, 2- (perfluorohexenyloxy) ) -3,4,5,6-Tetrafluoroaniline, 2- (perfluorohexenyloxy) -5
Chloroaniline, 2- (perfluorohexenyloxy) -5-bromoaniline and the like.

In these compounds, the perfluoro root sulfonyl group are those Rf in the general formula (I) is -C ₉ F _17, Rf in the general formula (I) is a perfluoro-hexenyl group is -C ₆ F ₁₁ And the same applies to the following.

In the compounds exemplified above, instead of the perfluorononenyl group or the perfluorohexenyl group, a group -C
Compounds having ₁₀ F ₁₃ , a group —C ₁₂ F _{23 and the} like can be similarly exemplified.

The novel fluorine-containing aromatic urethane compound of the present invention has the general formula (II) [Wherein, Rf is the same as general formula (I);
¹ represents an alkyl group which may have a substituent or an aryl group which may have a substituent, wherein hydrogen of the aromatic ring is a lower alkyl group, a lower alkoxy group, fluorine, chlorine or bromine; And the urethane group is bonded to the aromatic ring at the ortho, meta, or para position with respect to the ether bond].

As the urethane compound represented by the general formula (II), 1
-(N- (methyloxycarbonyl) amino) -4-
(Perfluorononenyloxy) benzene, 1- (N-
(Ethyloxycarbonyl) amino) -4- (perfluorononenyloxy) benzene, 1- (N- (propyloxycarbonyl) amino) -4- (perfluorononenyloxy) benzene, 1- (N- (i -Propyloxycarbonyl) amino) -4- (perfluorononenyloxy) benzene, 1- (N- (butyloxycarbonyl) amino) -4- (perfluorononenyloxy) benzene, 1- (N- (i -Butyloxycarbonyl) amino) -4- (perfluorononenyloxy) benzene, 1- (N- (t-butyloxycarbonyl) amino) -4- (perfluorononenyloxy) benzene,
1- (N- (pentyloxycarbonyl) amino) -4
-(Perfluorononenyloxy) benzene, 1- (N
-(Hexyloxycarbonyl) amino) -4- (perfluorononenyloxy) benzene, 1- (N- (heptyloxycarbonyl) amino) -4- (perfluorononenyloxy) benzene, 1- (N- ( Octyloxycarbonyl) amino) -4- (perfluorononenyloxy) benzene, 1- (N- (benzyloxycarbonyl) amino) -4- (perfluorononenyloxy)
Benzene, 1- (N-phenyloxycarbonyl) amino) -4- (perfluorononenyloxy) benzene,
1- (N- (methyloxycarbonyl) amino) -3-
(Perfluorononenyloxy) benzene, 1- (N-
(Ethyloxycarbonyl) amino) -3- (perfluorononenyloxy) benzene, 1- (N- (propyloxycarbonyl) amino) -3- (perfluorononenyloxy) benzene, 1- (N- (i -Propyloxycarbonyl) amino) -3- (perfluorononenyloxy) benzene, 1- (N- (butyloxycarbonyl) amino) -3- (perfluorononenyloxy) benzene, 1- (N- (i -Butyloxycarbonyl) amino) -3- (perfluorononenyloxy) benzene, 1- (N- (t-butyloxycarbonyl) amino) -3- (perfluorononenyloxy) benzene,
1- (N- (pentyloxycarbonyl) amino) -3
-(Perfluorononenyloxy) benzene, 1- (N
-(Hexyloxycarbonyl) amino) -3- (perfluorononenyloxy) benzene, 1- (N- (heptyloxycarbonyl) amino) -3- (perfluorononenyloxy) benzene, 1- (N-octyl) (Oxycarbonyl) amino) -3- (perfluorononenyloxy) benzene, 1- (N- (benzyloxycarbonyl) amino) -3- (perfluorononenyloxy) benzene, 1- (N- (phenyloxy) Carbonyl) amino) -3- (perfluorononenyloxy) benzene,
1- (N- (methyloxycarbonyl) amino) -2-
(Perfluorononenyloxy) benzene, 1- (N-
(Ethyloxycarbonyl) amino) -2- (perfluorononenyloxy) benzene, 1- (N-propyloxycarbonyl) amino) -2- (perfluorononenyloxy) benzene, 1- (N- (i- Propyloxycarbonyl) amino) -2- (perfluorononenyloxy) benzene, 1- (N- (butyloxycarbonyl) amino) -2- (perfluorononenyloxy) benzene, 1- (N- (i- Butyloxycarbonyl) amino) -2- (perfluorononenyloxy) benzene, 1- (N- (t-butyloxycarbonyl) amino) -2- (perfluorononenyloxy) benzene,
1- (N- (pentyloxycarbonyl) amino) -2
-(Perfluorononenyloxy) benzene, 1- (N
-(Hexyloxycarbonyl) amino) -2- (perfluorononenyloxy) benzene, 1- (N- (heptyloxycarbonyl) amino) -2- (perfluorononenyloxy) benzene, 1- (N-octyl) (Oxycarbonyl) amino) -2- (perfluorononenyloxy) benzene, 1- (N- (benzyloxycarbonyl) amino) -2- (perfluorononenyloxy) benzene, 1- (N- (phenyloxy) Carbonyl) amino) -2- (perfluorononenyloxy) benzene,
1- (N- (methyloxycarbonyl) amino) -4-
(Perfluorohexenyloxy) benzene, 1- (N
-(Ethyloxycarbonyl) amino) -4- (perfluorohexenyloxy) benzene, 1- (N- (propyloxycarbonyl) amino) -4- (perfluorohexenyloxy) benzene, 1- (N- (i- Propyloxycarbonyl) amino) -4- (perfluorohexenyloxy) benzene, 1- (N- (butyloxycarbonyl) amino) -4- (perfluorohexenyloxy) benzene, 1- (N- (i-butyloxy) Carbonyl) amino) -4- (perfluorohexenyloxy) benzene, 1- (N- (t-butyloxycarbonyl) amino) -4- (perfluorohexenyloxy)
Benzene, 1- (N- (pentyloxycarbonyl) amino) -4- (perfluorohexenyloxy) benzene, 1- (N- (hexyloxycarbonyl) amino)
-4- (perfluorohexenyloxy) benzene, 1
-(N- (heptyloxycarbonyl) amino) -4-
(Perfluorohexenyloxy) benzene, 1- (N
-(Octyloxycarbonyl) amino) -4- (perfluorohexenyloxy) benzene, 1- (N- (benzyloxycarbonyl) amino) -4- (perfluorohexenyloxy) benzene), 1- (N- (f (Enyloxycarbonyl) amino) -4- (perfluorohexenyloxy) benzene, 1- (N- (methyloxycarbonyl) amino) -3- (perfluorohexenyloxy) benzene, 1- (N- (ethyloxycarbonyl) benzene Amino) -3- (perfluorohexenyloxy)
Benzene, 1- (N- (propyloxycarbonyl) amino) -3- (perfluorohexenyloxy) benzene, 1- (N- (i-propyloxycarbonyl) amino) -3- (perfluorohexenyloxy) benzene, 1- (N- (butyloxycarbonyl) amino)-
3- (perfluorohexenyloxy) benzene, 1-
(N- (i-butyloxycarbonyl) amino) -3-
(Perfluorohexenyloxy) benzene, 1- (N
-(T-butyloxycarbonyl) amino) -3- (perfluorohexenyloxy) benzene, 1- (N-
(Pentyloxycarbonyl) amino) -3- (perfluorohexenyloxy) benzene, 1- (N- (pentyloxycarbonyl) amino) -3- (perfluorohexenyloxy) benzene, 1- (N- (hexyloxycarbonyl) ) Amino) -3- (Perfluorohexenyloxy) benzene, 1- (N- (heptyloxycarbonyl) amino) -4- (perfluorohexenyloxy) benzene, 1- (N- (octyloxycarbonyl) amino)- 3- (perfluorohexenyloxy)
Benzene, 1- (N- (benzyloxycarbonyl) amino) -3- (perfluorohexenyloxy) benzene, 1- (N- (phenyloxycarbonyl) amino)
-3- (perfluorohexenyloxy) benzene, 1
-(N- (methyloxycarbonyl) amino) -2-
(Perfluorohexenyloxy) benzene, 1- (N
-(Ethyloxycarbonyl) amino) -2- (perfluorohexenyloxy) benzene, 1- (N- (propyloxycarbonyl) amino) -2- (perfluorohexenyloxy) benzene, 1- (N- (i- Propyloxycarbonyl) amino) -2- (perfluorohexenyloxy) benzene, 1- (N- (butyloxycarbonyl) amino) -2- (perfluorohexenyloxy) benzene, 1- (N- (i-butyloxy) Carbonyl) amino) -2- (perfluorohexenyloxy) benzene, 1- (N- (t-butyloxycarbonyl) amino) -2- (perfluorohexenyloxy)
Benzene, 1- (N- (pentyloxycarbonyl) amino) -2- (perfluorohexenyloxy) benzene, 1- (N- (hexyloxycarbonyl) amino)
-2- (perfluorohexenyloxy) benzene, 1
-(N- (heptyloxycarbonyl) amino) -2-
(Perfluorohexenyloxy) benzene, 1- (N
-(Octyloxycarbonyl) amino) -2- (perfluorohexenyloxy) benzene, 1- (N- (benzyloxycarbonyl) amino) -2- (perfluorohexenyloxy) benzene, 1- (N- (phenyl) (Oxycarbonyl) amino) -2- (perfluorohexenyloxy) benzene. In the compound thus exemplified, instead of the perfluorononenyl group or the perfluorohexenyl group, a group -C ₁₀ F ₁₉ , a group -C ₁₂ F
Compounds having ₂₃ or the like can be similarly exemplified. The aromatic amine compound represented by the general formula (I) can be produced by subjecting the fluorine-containing aromatic urethane compound represented by the general formula (II) to a deprotection reaction of a urethane-type protecting group. Here, the urethane-type protecting group specifically means —COOR ¹ in the general formula (II).

The above deprotection reaction can be performed, for example, by the following method.

A solution of the above-mentioned fluorine-containing aromatic urethane compound in an organic solvent such as ethyl acetate, dimethylformamide, dimethylacetamide, benzene, xylene, acetone, tetrahydrofuran or the like is subjected to hydrogen gas at 0 to 100 ° C in the presence of a catalyst such as palladium carbon. (Particularly preferably around room temperature)
(The time for passing hydrogen gas may be determined as appropriate, but usually 1 to 10 hours is sufficient), dissolving the fluorine-containing aromatic urethane compound in the organic solvent as described above,
A method of reacting by adding a hydrogen acid such as HF, HBr, HCl, or H ₂ SO ₄ (hydrogen acid is preferably reacted in an equivalent amount or more with respect to the fluorine-containing aromatic urethane compound. When HF is used, The reaction is preferably carried out at room temperature or lower, particularly at 0 ° C. or lower, and in the case of other hydrogen acids, it is preferable to carry out the reaction at 0 to 100 ° C., particularly at around room temperature. 0.1 to 1 hour when used, and 1 to 10 hours when other hydrogen acids are used) is sufficient, and the above-mentioned fluorine-containing aromatic urethane compound is converted into sodium hydrogen carbonate, potassium hydrogen carbonate, sodium hydroxide, potassium hydroxide. (It is preferable that water is used in an equivalent amount or more with respect to the fluorine-containing aromatic urethane compound, and the reaction is carried out with water, Methanol, ethanol Alcohol or cresol, etc. as a solvent)
and so on.

The aromatic diamine compound represented by the general formula (I) thus obtained can be purified by recrystallization from ether or the like.

The aromatic urethane compound represented by the general formula (II) is represented by the general formula (III) Wherein Rf is the same as in the general formula (I), hydrogen of the aromatic ring may be substituted with a lower alkyl group, a lower alkoxy group, fluorine, chlorine or bromine, and a carboxyl group is A fluorine-containing aromatic carboxylic acid compound represented by the general formula (IV): which is bonded to the aromatic ring at the ortho, meta or para position with respect to the ether bond. (Wherein, R ² represents a lower alkyl group or an aryl group) and a general formula (V) R ¹ OH (V) wherein R ¹ is a group represented by the general formula (II The same as in [1])) in a solvent or without a solvent in the presence of a base.

Examples of the carboxylic acid compound represented by the general formula (III) include 4- (perfluorononenyloxy) benzoic acid,
-(Perfluorononenyloxy) benzoic acid, 2- (perfluorononenyloxy) benzoic acid, 4- (perfluorononenyloxy) -2-methylbenzoic acid, 4- (perfluorononenyloxy) -2 -Methoxybenzoic acid,
4- (perfluorononenyloxy) -2,3,5,6-tetrafluorobenzoic acid, 4- (perfluorononenyloxy) -2-chlorobenzoic acid, 4- (perfluorononenyloxy) -2 -Bromobenzoic acid, 3- (perfluorononenyloxy) -5-methylbenzoic acid, 3- (perfluorononenyloxy) -5-methoxybenzoic acid, 3-
(Perfluorononenyloxy) -2,4,5,6-tetrafluorobenzoic acid, 3- (perfluorononenyloxy)
-5-chlorobenzoic acid, 3- (perfluorononenyloxy) -5-bromobenzoic acid, 3- (perfluorohexenyloxy) -5-methylbenzoic acid, 3- (perfluorohexenyloxy) -5-methoxy Benzoic acid, 3-
(Perfluorohexenyloxy) -2,4,5,6-tetrafluorobenzoic acid, 3- (perfluorohexenyloxy) -5-chlorobenzoic acid, 3- (perfluorohexenyloxy) -5-bromobenzoic acid, 2- (perfluorohexenyloxy) -5-methylbenzoic acid, 2- (perfluorohexenyloxy) -5-methoxybenzoic acid, 2- (perfluorohexenyloxy) -3,4,5,6
-Tetrafluorobenzoic acid, 2- (perfluorohexenyloxy) -5-chlorobenzoic acid, 2- (perfluorohexenyloxy) -5-bromobenzoic acid, 2- (perfluorononenyloxy) -5-methylbenzoic acid Acid, 2
-(Perfluorononenyloxy) -5-methoxybenzoic acid, 2- (perfluorononenyloxy) -3,4,5,6
-Tetrafluorobenzoic acid, 2- (perfluorononenyloxy) -5-chlorobenzoic acid, 2- (perfluorononenyloxy) -5-bromobenzoic acid, 4- (perfluorohexenyloxy) benzoic acid, 3 -(Perfluorohexenyloxy) benzoic acid, 2- (perfluorohexenyloxy) benzoic acid, 4- (perfluorohexenyloxy) -2-methylbenzoic acid, 4- (perfluorohexenyloxy) -2-methoxybenzoic acid , 4-
(Perfluorohexenyloxy) -2,3,5,6-tetrafluorobenzoic acid, 4- (perfluorohexenyloxy) -2-chlorobenzoic acid, 4- (perfluorohexenyloxy) -2-bromobenzoic acid.

The 4- (perfluorononenyloxy) benzoic acid and 4- (perfluorohexenyloxy) benzoic acid are
For example, as described in JP-A-50-121243,
Reaction of a trimer or dimer of hexahydropropene with a parahydroxybenzoic acid ester such as phenyl parahydroxybenzoate or benzyl parahydroxybenzoate in an organic polar solvent at or below room temperature in the presence of a proton acceptor After the reaction, the reaction product is isolated, and the reaction product is obtained by hydrolyzing in the presence of a basic catalyst such as sodium hydroxide or potassium hydroxide, and further appropriately treating with an acid such as hydrochloric acid. Can be. Other carboxylic acid compounds among the carboxylic acids represented by the general formula (III) can also be obtained by using corresponding hydroxybenzoic acid ester compounds and oligomers of fluoroalkenes such as oligomers of hexahydropropene and oligomers of tetrafluoroethylene. It can be manufactured similarly.

Examples of the perfluorononenyl group include compounds represented by the formula (A) And a perfluorohexenyl group is, for example, a compound represented by the formula (B) There is a group.

Examples of the azide compound represented by the general formula (IV) include diphenyl phosphoryl azide, diethyl phosphoryl azide,
Di-p-nitrophenyl phosphoryl azide, dimorpholyl phosphoryl azide and the like.

Examples of the alcohol represented by the general formula (V) include methanol, ethanol, propanol, i-propanol, butanol, i-butanol, t-butanol, pentanol, hexanol, heptanol, octanol, benzyl alcohol, and phenol.

The synthesis reaction for obtaining a fluorine-containing aromatic urethane compound represented by the general formula (II) is described in Takayuki Shioiri, Shunichi Yamada, Journal of the Society of Synthetic Organic Chemistry, Vol. 31, No. 8, pp. 666-674 (1973). A new Curtius reaction, as shown, can be applied. That is, by reacting a carboxylic acid compound represented by the general formula (III) with an azide compound represented by the general formula (IV) and an alcohol represented by the general formula (V) in the presence of a base, A fluorine-containing aromatic urethane compound can be obtained. As the base, trimethylamine,
It is preferable to use a tertiary amine such as triethylamine and pyridine. The above reaction is performed in an organic solvent or using an alcohol represented by the general formula (V) as a solvent. As the organic solvent, it is preferable to use benzene, toluene, tetrahydrofuran, dioxane, diethyl ether and the like. These solvents may be used as a mixture of two or more as long as they are compatible with each other.

In the above reaction, the carboxylic acid compound represented by the general formula (III) and the azide compound represented by the general formula (IV) react in the middle, and the carboxylic acid azide and the carboxylic acid azide undergo a thermal rearrangement reaction to produce an isocyanate compound. Is produced, but the reaction can be carried out with or without isolation of these intermediates. The conditions for the above reaction differ depending on the reagent used and are not particularly limited, but the following conditions are preferred.

First, the carboxylic acid compound represented by the general formula (III), the azide compound represented by the general formula (IV), the tertiary amine, and the alcohol represented by the general formula (V) are reacted at a time to give an apparent reaction. When the intended fluorine-containing aromatic urethane compound is obtained in the above one step, the reaction temperature is -80 to 250 ° C.
And particularly preferably room temperature to 150 ° C. The azide compound, the tertiary amine and the alcohol, respectively, 0.5 to 5.0 molar equivalents relative to the carboxylic acid compound,
It is preferable to use 0.5 to 3.0 molar equivalents and 0.5 molar equivalents to a large excess.

Second, the carboxylic acid azide can be isolated once. In this case, first, the carboxylic acid and the azide compound are reacted in the presence of the tertiary amine, and the resulting carboxylic acid azide is isolated. I do. At this time, the reaction temperature is-
80 to 100 ° C. is preferable, and the azide compound and the tertiary amine are each 0.5% to the carboxylic acid compound.
It is preferred to use 〜5.0 molar equivalents and 0.5-3.0 molar equivalents. Next, the isolated carboxylic acid azide is reacted in an alcohol in an amount of 0.5 molar equivalent to a large excess thereof to obtain a desired fluorine-containing aromatic urethane compound. The reaction temperature at this time is preferably -80-250 ° C.

Third, an isocyanate compound can be isolated once. In this case, first, a carboxylic acid compound is reacted with an azide compound represented by the general formula (IV) in the presence of a tertiary amine to obtain an isocyanate compound. Is isolated. At this time, the azide compound 0.5 relative to the carboxylic acid compound
It is preferable to use 0.5 to 3.0 molar equivalents and 0.5 to 3.0 molar equivalents of the above tertiary amine, and the reaction temperature is preferably -80 to 250 ° C. The resulting isocyanate was then added to it at 0.
By reacting in 5 molar equivalents to a large excess of alcohol, a fluorine-containing aromatic urethane compound can be obtained. At this time, the reaction temperature is preferably from -80 to 250C.

The first to third methods are appropriately selected in consideration of the yield and the like.

The fluorine-containing aromatic urethane compound thus obtained can be purified by recrystallization from hexane or the like.

〔Example〕

Next, examples of the present invention will be described. The 4- (perfluorononenyloxy) benzoic acid used below has the formula Is a compound of

Example 1 1.14 g of 4- (perfluorononenyloxy) benzoic acid
(2.0 mmol), 0.65 g of diphenylphosphoryl azide (2.4 m
mol) and 0.24 g (2.4 mmol) of triethylamine were reacted in dioxane at 60 ° C. for 1 hour and then at reflux temperature for 2 hours, and then 0.22 g (4.8 mmol) of ethanol was added and reacted at 70 ° C. for 9 hours. After completion of the reaction, the solvent was distilled off, and the residue was recrystallized from hexane to obtain the desired product, 1- (N-ethyloxycarbonyl) amine) -4-perfluorononenyloxybenzene, at a yield of 39%. Physical properties and elemental analysis results of the compound are as follows.

(1) Melting point 75-80 ° C (2) ¹ H-NMR spectrum (solvent acetone-d ₆ , TMS standard); 8.63 ppm (2H, NH, s), 7.66 ppm (2H, Aromatic, d), 7.12 pp
m (2H, Aromatic, d) , 3.24ppm (4H, CH 2, q), 1.13ppm (3
H, CH ₃ , t) [Figures in parentheses indicate the integrated intensity ratio of hydrogen, the group and peak type that are the basis of absorption, s is a singlet, d is a doublet,
t indicates a triplet, and q indicates a quadruple. The same applies to the following. ] (3) ¹⁹ F-NMR spectrum (solvent acetone -d _6, trifluorotoluene _{standard); 11.30ppm (3F, CF 3} , d), - 3.77ppm (6F, CF 3, s), - 4.9
_{2ppm (6F, CF 3, d} ), - 99.26ppm, (1F, CF, quart.) - 10
1.58 ppm (1F, CF, quint.) [Figures in parentheses indicate the integrated intensity ratio of fluorine, the group of the group and the peak that are the basis of absorption, s is a singlet, d is a doublet,
quart. indicates a quintet, and quint. indicates a quintet. The same applies to the following. (4) IR absorption spectrum; 3322 cm ^-1 (N-H, urethane),
1700 cm ^-1 (C = O, urethane), 1550 cm ^-1 (NH, urethane), 1245 cm ^-1 (CF) (5) Elemental analysis value (%) From the above, generation of the target substance was confirmed. Its structural formula is as follows:

Example 2 1.14 g of 4- (perfluorononenyloxy) benzoic acid
(2.0 mmol), 0.66 g of diphenyl phosphoryl azide (2.4 m
mol) and 0.24 g (2.4 mmol) of triethylamine in dioxane at 60 ° C. for 1 hour and at reflux temperature for 2 hours.
0.36 g (4.8 mmol) of t-butanol was added and reacted at 70 ° C. for 12 hours. After completion of the reaction, the solvent was distilled off, and the residue was recrystallized from hexane to obtain 1- (Nt-butyloxycarbonyl) amino) -4-perfluorononenyloxybenzene as a target substance in a yield of 49%. Was.

Example 3 1.14 g of 4- (perfluorononenyloxy) benzoic acid
(2.0 mmol), 0.66 g of diphenyl phosphoryl azide (2.4 m
mol) and 0.24 g (2.4 mmol) of triethylamine were reacted in 10 mL of t-butanol at a reflux temperature for 20 hours. After completion of the reaction, t-butanol was distilled off, and the residue was recrystallized from hexane to give 1- (Nt-butyloxycarbonyl) amino) -4-perfluorononenyloxybenzene as a target substance in a yield of 59%. I got it.

 The physical properties and elemental analysis results of this compound are shown below.

(1) Melting point 88-92 ° C. (2) ¹ H-NMR spectrum (solvent acetone-d ₆ , TMS standard); 8.62 ppm (2H, NH, s), 7.68 ppm (2H, Aromatic, d), 7.09 pp
m (2H, Aromatic, d), 1.49 ppm (9H, t-Bu, t) (3) ¹³ F-NMR spectrum (solvent acetone-d ₆ , trifluorotoluene standard); 11.42 ppm (3F, CF ₃ , d ), - 3.70ppm (6F, CF 3, s), - 4.8
_{4ppm (6F, CF 3, d} ), - 99.50ppm, (1F, CF, quart.) - 10
1.60 ppm (1F, CF, quint.) (4) IR absorption spectrum; 3330 cm ^-1 (NH, urethane),
The spectrum is shown in FIG. 1 at 1696 cm ^-1 (C = O, urethane), 1500 cm ^-1 (NH, urethane), and 1244 cm ^-1 (CF).

(5) Elemental analysis value (%) From the above, generation of the target substance was confirmed. The production formula is as follows.

Example 4 1.14 g of 4- (perfluorononenyloxy) benzoic acid
(2.0 mmol), 0.66 g of diphenyl phosphoryl azide (2.4 m
mol) and 0.24 g (2.4 mmol) of triethylamine in dioxane at 60 ° C. for 1 hour, and then at reflux temperature for 2 hours.
The reaction was performed at 9 ° C. for 9 hours. After completion of the reaction, the solvent was distilled off, and the residue was recrystallized from hexane to obtain 1- (N-benzyloxycarbonyl) amino) -4-perfluorononenyloxybenzene as a target substance at a yield of 45%.

 The structural formula of this compound is as follows.

Example 5 To 0.200 g (0.313 mmol) of 1- (N- (t-butyloxycarbonyl) amino) -4-perfluorononenyloxybenzene obtained in Example 3 was added 2.35 mL of 4N sodium hydrogen carbonate / methanol. And stirred at room temperature for 4 hours. Next, methanol was distilled off and extracted with ether.
After washing the ether solution with water, the ether was distilled off to obtain the desired product, 4- (perfluorononenyloxy) aniline. The yield was 45%, and the target product was a viscous oily liquid.

The analytical data of the obtained 4- (perfluorononenyloxy) aniline are shown below.

(1) ¹ H-NMR spectrum (solvent acetone-d ₆ , TMS standard); 6.80 to 6.70 ppm (4H, Aromatic, m) 4.82 ppm (2H, NH ₂ , s) The spectrum is shown in FIG.

(2) ¹⁹ F-NMR spectrum (solvent acetone -d _6, trifluorotoluene _{standard); 11.19ppm (3F, CF 3} , d), - 3.86ppm (6F, CF 3, s), - 5.0
_{1ppm (6F, CF 3, d} ), - 99.35ppm, (1F, CF, quart.) - 10
1.77 ppm (1F, CF, quint.) (3) IR absorption spectrum; 1628 cm ^-1 (NH, amine), 15
The 10cm ^-1 (Aromatic) and 1240cm ^-1 (CF) spectra are shown in FIG.

(4) Elemental analysis value (%) From the above, it was confirmed that the compound was the target compound. The structural formula of this compound is as follows.

Example 6 To 0.200 g (0.313 mmol) of 1- (N- (t-butyloxycarbonyl) amino) -4-perfluorononenyloxybenzene obtained in Example 3 was added 3N hydrochloric acid / ethyl acetate 3.0.
mL was added and stirred at room temperature for 4 hours. After an aqueous sodium hydroxide solution was added until the solution became basic, the oil layer was extracted with ethanol. The ether was distilled off to obtain the desired product, 4- (perfluorononenyloxy) aniline.
The yield was 55%, and the target product was a viscous oily liquid.

Example 7 0.202 g (0.300 mmol) of 1- (N- (benzyloxycarbonyl) amino) -4-perfluorononenyloxybenzene obtained in Example 4 was added to dimethylformamide 5.0
The solution was dissolved in mL, and 0.03 g of 5% palladium on carbon was added and stirred. Here, hydrogen gas was passed for 6 hours for reduction. The palladium carbon was removed by filtration, extracted with ether, washed with water, and the ether was distilled off to obtain the desired compound, 4-
(Perfluorononenyloxy) aniline was obtained. The yield was 50%, and the target product was a viscous oily liquid.

〔The invention's effect〕

The fluorine-containing aromatic urethane compound obtained in claim 1 is novel, and is useful as an intermediate for producing a fluorine-containing aromatic amine compound of the general formula (I).

According to the production method of claim 2, the fluorine-containing aromatic urethane compound of claim 1 can be produced.

According to the production method of the third aspect, the fluorinated aromatic amine compound of the general formula (1) can be produced.

[Brief description of the drawings]

FIG. 1 is an IR absorption spectrum of 1- (Nt-butyloxycarbonyl) amino-4-perfluorononenyloxybenzene obtained in Example 3, and FIG. (Perfluorononenyloxy) aniline
¹ H-NMR spectrum, FIG. 3 shows an IR absorption spectrum of the chemical substance.

Claims (3)

(57) [Claims] 1. A compound of the general formula (II) [However, Rf in the formula, -C _n F _2n-1 (where n is an integer of 6-12) indicates which comprises one double bond, may also be appropriately branched, R ¹ represents an alkyl group or an aryl group which may be substituted with a phenyl group, and the hydrogen of the aromatic ring may be substituted with a lower alkyl group, a lower alkoxy group, fluorine, chlorine or bromine; The group is ortho-position, meta-position,
Or bonded to the para-position]]. 2. A compound of the general formula (III) [However, Rf in the formula, -C _n F _2n-1 (where n is an integer of 6-12) indicates which comprises one double bond, may also be appropriately branched, The hydrogen of the aromatic ring may be substituted with a lower alkyl group, a lower alkoxy group, fluorine, chlorine or bromine, and the carboxyl group is bonded to the aromatic ring at the ortho, meta or para position with respect to the ether bond. And a fluorine-containing aromatic carboxylic acid compound represented by the general formula (IV) (Wherein, R ² represents a lower alkyl group or an aryl group) and a general formula (V) R ¹ OH (V) (where R ¹ is a phenyl group A fluorine-containing aromatic compound according to claim 1, which is reacted with an alcohol represented by an alkyl group or an aryl group which may be substituted in a solvent or in the absence of a solvent in the presence of a base. For producing an aromatic urethane compound. 3. A compound of the general formula (I) wherein the urethane-type protecting group is deprotected from the fluorine-containing aromatic urethane compound according to claim 1. [However, Rf in the formula, -C _n F _2n-1 (where n is an integer of 6-12) indicates which comprises one double bond, may also be appropriately branched, The hydrogen of the aromatic ring may be substituted with a lower alkyl group, a lower alkoxy group, fluorine, chlorine or bromine, and the amino group is bonded to the aromatic ring at the ortho, meta or para position with respect to the ether bond. The method for producing a fluorine-containing aromatic amine compound according to the above.