JP2003055322A - Halogen-containing aromatic diamine compound - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a new halogen-containing aromatic compound. SOLUTION: This halogen-containing aromatic compound is represented by formula (1) wherein, X is formula (2) [Z is independently a halogen atom; p is an integer of 0-5; q is an integer of 0-5; with the proviso that p+q is 5]; Y is independently a halogen; m is an integer of 0-3; n is an integer of 1-4; with the proviso that m+n is 4}.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a novel halogen-containing aromatic compound.

The halogen-containing aromatic compound of the present invention is an important intermediate in the synthesis of dyes, pharmaceuticals, agricultural chemicals and polymer compounds, and is a resin having excellent heat resistance, water repellency, chemical resistance and low dielectric property. It is useful as a raw material.

[0003]

2. Description of the Related Art Halogenated m-phenylenediamine compounds such as tetrafluoro-m-phenylenediamine are important intermediates in the synthesis of dyes, pharmaceuticals, agricultural chemicals and polymer compounds, and have excellent heat resistance and water repellency. , Useful as a raw material for a resin having chemical resistance and low dielectric property, and further, for example, a solar cell, an electroluminescent element,
It is preferably used as a charge transfer material (particularly, a hole transfer material) in electrophotographic photoreceptors and the like.

Therefore, various m-phenylenediamine derivatives according to various uses and methods for producing the same are described below.
Currently, research and development are actively conducted.

[0005]

Therefore, an object of the present invention is to provide a novel halogen-containing aromatic compound.

Another object of the present invention is to provide a halogen-containing aromatic compound which is useful as a raw material for a resin having excellent heat resistance, water repellency, chemical resistance and low dielectric property.

[0007]

Various objects of the present invention are as follows.
It is achieved by (a) to (d).

(A) The following formula (1):

[0009]

[Chemical 4]

However, X is the following formula (2):

[0011]

[Chemical 5]

However, each Z independently represents a halogen atom; p is an integer of 0 to 5; and q is 0.
Is an integer of 5 to 5; and p + q is 5; Y is each independently a halogen atom; m is an integer of 0 to 3; Is an integer of 4; and m + n is 4, a halogen-containing aromatic compound.

(A) In the above formula (1), Y represents a fluorine atom, and the halogen-containing aromatic compound described in (a) above.

(C) In the above formula (2), Z represents a fluorine atom, and the halogen-containing aromatic compound described in (A) or (A) above.

(D) The halogen-containing aromatic compound is
Formula (3) below:

[0016]

[Chemical 6]

However, m is an integer of 0 to 3; n
Is an integer of 1 to 4; and m + n is 4, a halogen-containing aromatic compound.

[0018]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in detail below.

The present invention provides a halogen-containing aromatic compound represented by the above formula (1).

In the above formula (1), Y represents a halogen atom, that is, a fluorine atom, a chlorine atom, a bromine atom or an iodine atom, preferably a fluorine atom or a chlorine atom, and particularly preferably a fluorine atom. When a plurality of Y's are present, they may be the same or different.

In the above formula (1), n is m-
It represents the number of bonds of X to phenylenediamine, is an integer of 1 to 4, preferably an integer of 1 to 3, and is particularly preferably 1 in consideration of heat resistance. The bonding position of X to m-phenylenediamine varies depending on the number and type of bonds of X and desired characteristics of the halogen-containing aromatic compound. For example, when n is 1, X is m-phenylene. Considering the reactivity of the diamine, it is desirable to bond to the 4-position or 2-position of m-phenylenediamine, particularly preferably 4-position, and when n is 2, X is 4 of m-phenylenediamine. , 6-position, 2,4-position, particularly preferably 4,6-position. When n is 3, the 2,4,6 positions are preferred.

In the above formula (1), m represents the number of bonds of Y to m-phenylenediamine, and is an integer of 0 to 3,
It is preferably 2 or 3, and considering the heat resistance, it is particularly preferably 3. In the above formula (1),
The sum of n and m is always 4 (n + m = 4).

Further, in the above formula (1), X is a group represented by the above formula (2), that is, X is a trifluoromethyl group (-CF ₃ ) or a halogen atom at all residues of the phenoxy group. It is a bonded group. In the above formula (2), Z represents a halogen atom, that is, a fluorine atom, a chlorine atom, a bromine atom or an iodine atom, preferably a fluorine atom and a chlorine atom, and particularly preferably a fluorine atom. When a plurality of Z's are present, they may be the same or different.

In the above formula (2), p represents the number of bonds of the trifluoromethyl group (--CF ₃ ) to the phenoxy group and is an integer of 0-5, preferably an integer of 1-3. Particularly preferably, it is 1. The bonding position of the trifluoromethyl group (—CF ₃ ) to the phenoxy group when p is 1, which is a particularly preferred embodiment, differs depending on the desired characteristics of the halogen-containing aromatic compound, and is o-, m- or It may be either p-position, but is preferably p-position.

In the above formula (2), q represents the number of bonds of Z to the phenoxy group and is an integer of 0-5, preferably an integer of 2-4, particularly preferably 4.
In addition, in the above formula (2), the sum of p and q is always 5 (p + q = 5).

As mentioned above, X is p of the phenoxy group.
A group in which a trifluoromethyl group (—CF ₃ ) is bonded to the − position and a fluorine atom is bonded to the remaining 4 positions is particularly preferable.

Therefore, a preferable example of the halogen-containing aromatic compound of the present invention is the following formula (4):

[0028]

[Chemical 7]

However, X is the following formula (5):

[0030]

[Chemical 8]

M is an integer of 0 to 3; n is an integer of 1 to 4; and m + n is 4
And more preferably a compound represented by the following formula (3):

[0032]

[Chemical 9]

A compound represented by the formula:

[0034]

[Chemical 10]

Examples include compounds represented by: In the above formula (3), m and n have the same definitions as in the above formula (1).

Of the above preferred examples of halogen-containing aromatic compounds, 2,5,6-trifluoro-4- (2,3,5,5)
6-Tetrafluoro-4-trifluoromethylphenoxy) benzenediamine is particularly preferred as the halogen-containing aromatic compound of the present invention.

The halogen-containing aromatic compound of the present invention may be produced by a known method such as the method described in JP-A No. 11-147,955 and is not particularly limited. Hereinafter, one embodiment of a method for producing a halogen-containing aromatic compound represented by the above formula (4), which is a preferred compound of the present invention, will be described. Note that other halogen-containing aromatic compounds of the present invention can also be produced in the same manner as in the method described in the following embodiments, and, for example, in the following embodiments, they can be produced at desired positions in place of tetrafluoroisophthalonitrile. To use a compound substituted with other halogen atom, and to use a compound substituted with a desired halogen atom and a trifluoromethyl group at a desired position in place of the tetrafluoro (trifluoromethyl) phenol derivative Can be similarly synthesized.

That is, according to one embodiment, (1) tetrafluoroisophthalonitrile is added in the presence of a base in an organic solvent according to the following formula:

[0039]

[Chemical 11]

By reacting with a tetrafluoro (trifluoromethyl) phenol derivative represented by the following formula:

[0041]

[Chemical 12]

By synthesizing an isophthalonitrile derivative represented by: (2) by hydrolyzing the isophthalonitrile derivative, the following formula:

[0043]

[Chemical 13]

Producing an isophthalic acid derivative of
Further, (3) the isophthalic acid derivative is reacted with an azide compound in the presence of a Lewis base in a solvent to obtain an acid azide, and the acid azide is subjected to thermal rearrangement and hydrolysis to give the following formula:

[0045]

[Chemical 14]

A desired halogen-containing aromatic compound represented by: is produced. In the above embodiment, "isophthalonitrile derivatives", an amino group (-NH ₂₎ is both a cyano group-containing halogenated aromatic compound of the present invention (-
Refers to a compound substituted with CN), also, the "isophthalic acid derivatives", amino group of halogen-containing aromatic compound (-NH ₂₎ is a carboxyl group (-C both of the present invention
OOH) is substituted.

In the step (1), the tetrafluoro (trifluoromethyl) phenol derivative is appropriately selected according to the structure of the desired halogen-containing aromatic compound. That is, 2-hydroxy-3,4,5,6
-Tetrafluorobenzotrifluoride, 3-hydroxy-2,4,5,6-tetrafluorobenzotrifluoride, and 4-hydroxy-2,3,5,6-tetrafluorobenzotrifluoride are tetrafluoro (trifluoromethyl) ) Phenol derivatives, of which 4-hydroxy-2,3,5,6-
Tetrafluorobenzotrifluoride is particularly preferably used.

In the step (1), the charged amount of tetrafluoroisophthalonitrile is the number of moles of tetrafluoro (trifluoromethyl) phenol derivative added to tetrafluoroisophthalonitrile [that is, n in the above formula (1)]. Number], and is not particularly limited as long as it is an amount capable of efficiently reacting with a tetrafluoro (trifluoromethyl) phenol derivative, but considering the reaction efficiency and reaction selectivity, It is preferably present in excess. For example, when the number of moles of tetrafluoro (trifluoromethyl) phenol derivative added to tetrafluoroisophthalonitrile is 1, that is, when n in the above formula (1) is 1, tetrafluoroisophthalonitrile The amount charged is 1 to 4 with respect to 1 mol of the tetrafluoro (trifluoromethyl) phenol derivative.
It is preferably 0 mol, more preferably 1 to 20 mol. When n in the above formula (1) is 1, the tetrafluoro (trifluoromethyl) phenol derivative is at the 4-position or 2-position of tetrafluoroisophthalonitrile due to its three-dimensional structure (reactivity). Selectively combine. In addition, for example, when the number of moles of the tetrafluoro (trifluoromethyl) phenol derivative added to tetrafluoroisophthalonitrile is 2, that is, when n in the formula (1) is 2, tetrafluoroisophthalo The amount of nitrile charged is preferably 0.5 to 20 mol, and more preferably 0.5 to 10 mol, based on 1 mol of the tetrafluoro (trifluoromethyl) phenol derivative. When n in the above formula (1) is 2, the tetrafluoro (trifluoromethyl) phenol derivative is at the 4,6 position of tetrafluoroisophthalonitrile due to its three-dimensional structure (reactivity). It selectively binds to the 2,4 position. Furthermore, for example, when the number of moles of the tetrafluoro (trifluoromethyl) phenol derivative added to tetrafluoroisophthalonitrile is 3, that is, when n in the above formula (1) is 3, tetrafluoroisophthalo The amount of the nitrile charged was 0.1% with respect to 1 mol of the tetrafluoro (trifluoromethyl) phenol derivative.
It is preferably 1 to 10 mol, more preferably 0.1 to 5 mol. In addition, when n in the above formula (1) is 3, the tetrafluoro (trifluoromethyl) phenol derivative is converted into the 2,4,6-position of tetrafluoroisophthalonitrile due to its three-dimensional structure (reactivity). Selectively bind to. At this time, if the charged amount of tetrafluoroisophthalonitrile is less than the lower limit, it cannot sufficiently react with the tetrafluoro (trifluoromethyl) phenol derivative,
The yield of the target isophthalonitrile derivative may decrease, and the reaction selectivity may decrease. On the contrary, even if the charged amount of tetrafluoroisophthalonitrile exceeds the upper limit, it is not economical because the effect commensurate with the addition is not obtained, and excess tetrafluoroisophthalonitrile remains and the recovery cost increases. It may end up.

Examples of the base used in the above step (1) include alkali metal salts such as potassium fluoride, sodium fluoride, lithium fluoride, potassium chloride, sodium chloride and lithium chloride; alkali salts such as calcium chloride and magnesium chloride. Earth metal salts; sodium hydrogen carbonate,
Alkali metal carbonates such as lithium hydrogen carbonate, potassium hydrogen carbonate, sodium carbonate, lithium carbonate and potassium carbonate; alkaline earth metal carbonates such as calcium carbonate and magnesium carbonate; trimethylamine, triethylamine, tripropylamine, tributylamine, Examples thereof include tertiary amines such as tricyclohexylamine, tribenzylamine, triphenylamine and pyridine. Of these, potassium fluoride, sodium carbonate,
Preference is given to potassium carbonate, triethylamine, tripropylamine and pyridine. The addition amount of the base is not particularly limited as long as it can efficiently proceed the reaction with the tetrafluoroisophthalonitrile and the tetrafluoro (trifluoromethyl) phenol derivative, but is not limited to the tetrafluoro (trifluoromethyl) phenol derivative. , Usually 0.5 to 20 mol%, preferably 1 to 10 mol%.

In the above step (1), as the organic solvent, nitriles such as acetonitrile and benzonitrile; acetone, methyl isobutyl ketone (MIB
K), ketones such as methyl ethyl ketone (MEK) and cyclohexanone; halogenated hydrocarbons such as chloroform, methylene chloride, carbon tetrachloride, chloroethane, dichloroethane, trichloroethane and tetrachloroethane; aromatic hydrocarbons such as benzene, toluene and xylene Hydrocarbons such as pentane, hexane, cyclohexane and heptane; diethyl ether, isopropyl ether, tetrahydrofuran (THF), dioxane,
Diphenyl ether, benzyl ether and tert-
Ethers such as butyl ether; esters such as methyl formate, ethyl formate, methyl acetate, ethyl acetate, propyl acetate and isopropyl acetate; and N-methylpyrrolidinone (NMP), dimethylformamide (DMF),
Examples thereof include dimethyl sulfoxide (DMSO) and dimethylacetamide. Among these, acetonitrile, methyl isobutyl ketone (MIBK), N-methylpyrrolidinone (NMP), dimethylformamide (DM
F) and dimethylsulfoxide (DMSO) are preferred. The amount of the organic solvent is not particularly limited as long as the reaction of the step (1) can efficiently proceed, but for example, tetrafluoroisophthalonitrile is contained in the organic solvent at 1 to 80% by mass, preferably 5%. -50% by weight.

Next, step (2) in one embodiment of the method for producing the halogen-containing aromatic compound will be described below.

In the step (2), the isophthalonitrile derivative synthesized in the step (1) is hydrolyzed,
The desired isophthalic acid derivative is synthesized by converting the two cyano groups of the isophthalonitrile derivative into carboxyl groups.

In the above step (2), the hydrolysis of the isophthalonitrile derivative is carried out in the presence of an acid and / or an alkali, preferably in the presence of an acid. Acids used at that time include concentrated sulfuric acid, trichloroacetic acid, sulfuric acid,
Pyrophosphoric acid, triphosphoric acid, polyphosphoric acid such as trimetaphosphoric acid and tetrametaphosphoric acid, trifluoroacetic acid, trifluoroacetic anhydride, hydrochloric acid, fuming sulfuric acid, concentrated hydrochloric acid, hydrobromic acid,
Propionic acid, formic acid, nitric acid and acetic acid; and mixtures thereof, for example, trifluoroacetic acid-trifluoroacetic anhydride (mixing ratio is 1: 9 to 9: 1 by mass ratio, preferably 3: 7 to 7: 3). ) And a mixed solution of trichloroacetic acid and sulfuric acid (mixing ratio is 1: 9 to 9: 1 by mass ratio, preferably 3: 7 to 7: 3) and the like. The above acids may be used alone or in the form of a mixture of two or more kinds. Further, these acids may be used as they are or may be used in the form of an aqueous solution, and the concentration in the latter case is not particularly limited as long as it is a concentration at which the isophthalonitrile derivative can be sufficiently hydrolyzed. The amount is, for example, 40 to 85% by mass, preferably 50 to 80% by mass, although it varies depending on the kind of the acid. Of these, sulfuric acid,
Particularly, a 50 to 80 mass% sulfuric acid aqueous solution is preferably used as the acid. Among these, at least one selected from the group consisting of polyphosphoric acid, trifluoroacetic acid-trifluoroacetic anhydride, trichloroacetic acid, propionic acid, hydrochloric acid, concentrated hydrochloric acid and sulfuric acid, particularly sulfuric acid, propionic acid, concentrated hydrochloric acid and polyphosphoric acid, and These aqueous solutions are preferably used as the acid. Further, as the alkali used in the hydrolysis, sodium hydroxide, lithium hydroxide, potassium hydroxide, rubidium hydroxide, cesium hydroxide, beryllium hydroxide, magnesium hydroxide, calcium hydroxide, strontium hydroxide and water. Examples thereof include barium oxide, and of these, sodium hydroxide, potassium hydroxide, calcium hydroxide and barium hydroxide are preferably used as the alkali. Similarly, the alkali may be used alone or in the form of a mixture of two or more kinds. Furthermore, the amount of the acid and / or alkali used is not particularly limited as long as the isophthalonitrile derivative is sufficiently hydrolyzed, but the concentration of the isophthalonitrile derivative with respect to the acid and / or alkali is usually 1 to 80 mass. %, Preferably 5 to 50% by mass.

The hydrolysis condition in the above step (2) is not particularly limited as long as it can sufficiently hydrolyze the isophthalonitrile derivative, but the hydrolysis temperature is usually from -20 to 200 ° C, preferably from 0 to 200 ° C. It is 150 ° C., and the hydrolysis time is usually 0.1 to 40 hours, preferably 0.1 to 20 hours. The hydrolysis may be carried out under pressure, at atmospheric pressure or under reduced pressure, but preferably under atmospheric pressure.

The isophthalic acid derivative thus obtained is highly purified by a known method such as column chromatography using silica gel or alumina, distillation, preferably solid distillation, recrystallization, reprecipitation and sublimation. It can be manufactured with purity.

Further, step (3) in one embodiment of the method for producing a halogen-containing aromatic compound will be described below.

In the above step (3), the isophthalic acid derivative obtained in the above step (2) is reacted with an azide compound in the presence of a Lewis base in a solvent to react with the carboxyl group (--COOH) of the isophthalic acid derivative. ) Is -CON ₃
A desired halogen-containing aromatic compound is obtained by obtaining an acid azide converted into a group and subjecting this acid azide to thermal rearrangement and hydrolysis.

The azide compound used in this case is -N ₃
It is not particularly limited as long as it has a group and can efficiently convert the carboxyl group of the isophthalic acid derivative into a -CON ₃ group, but specifically, the following formula:

[0059]

[Chemical 15]

Compounds represented by are preferred. In the above formula
And R¹And R²Each independently has 1 carbon atom
~ 5 alkyl groups, for example methyl, ethyl, propyl
Ru, isopropyl, n-butyl, pentyl, neo pliers
Le, sec-butyl and tert-butyl; carbon atom number
3-8 cycloalkyl groups, for example cyclopropyl,
Cyclobutyl, cyclopentyl, cyclohexyl, shik
Roheptyl and cyclooctyl; benzyl group; or
It represents a phenyl group which may have a substituent. Also, R ¹Over
And R²Is a phenyl group which may have a substituent
The substituent that can be used is not particularly limited, but
Specifically, an alkyl group having 1 to 5 carbon atoms, for example, a methyl group
Ru, ethyl, propyl, isopropyl, n-butyl, pe
Ethyl, neopentyl, sec-butyl and tert-
Butyl; an alkoxy group having 1 to 5 carbon atoms, for example,
Toxy, ethoxy, propoxy, isopropoxy, n-
Butoxy, pentoxy, neopentoxy, sec-but
Xy and tert-butoxy; acetyl group, chloroacetate
Cyl group, trichloroacetyl group, trifluoroacetyl
Group, carboxyl group, amino group, halogen atom, for example
For example, fluorine, chlorine, bromine and iodine, nitrile groups, sulfur
Honyl, nitro, and ester groups such as
Examples include chill ester and ethyl ester. This
At the time of R¹And R²Are the same or different
May be Furthermore, the above R¹And R²Out of
Ru, ethyl, propyl, tert-butyl, benzyl and
And phenyl are preferred, especially R¹And R²Is phenyl
Diphenylphosphoric acid azide (hereinafter simply referred to as “DPPA”)
Is also omitted) is particularly preferable.

The addition amount of the azide compound is not particularly limited as long as it allows the reaction with the isophthalic acid derivative to proceed favorably, and depends on the type and amount of the isophthalic acid derivative, Lewis base, solvent and the like used. different. Specifically, the addition amount of the azide compound is usually 2 to 50 mol, preferably 2 to 1 mol of the isophthalic acid derivative.
10 to 10 mol.

In the above step (3), the isophthalic acid derivative is reacted with the azide compound in a solvent in the presence of a Lewis base. The Lewis base used in this case is sodium hydroxide, lithium hydroxide, Alkali metal hydroxides such as potassium hydroxide, rubidium hydroxide and cesium hydroxide; alkaline earth metal hydroxides such as beryllium hydroxide, magnesium hydroxide, calcium hydroxide, strontium hydroxide and barium hydroxide; methylamine , Ethylamine, propylamine, n-butylamine, sec
-Primary amines such as butylamine, tert-butylamine, cyclohexylamine, benzylamine and phenylamine; dimethylamine, diethylamine, dipropylamine, dibutylamine, diisobutylamine, di-sec-butylamine, di-tert-butylamine, dicyclohexyl. Secondary amines such as amines, dibenzylamine and diphenylamine; trimethylamine,
Tertiary amines such as triethylamine, tripropylamine, tributylamine, tricyclohexylamine, tribenzylamine and triphenylamine; pyridine;
Sodium hydrogen carbonate, lithium hydrogen carbonate, potassium hydrogen carbonate, rubidium hydrogen carbonate and cesium hydrogen carbonate, sodium carbonate, lithium carbonate, potassium carbonate, rubidium carbonate, cesium carbonate, beryllium carbonate, magnesium carbonate, calcium carbonate, strontium carbonate, barium carbonate, etc. Alkali metal and alkaline earth metal carbonates thereof; and alkali metal salts and alkaline earth metal salts such as potassium fluoride, potassium chloride, sodium fluoride, sodium chloride, calcium chloride and magnesium chloride. Of these, triethylamine, trimethylamine, pyridine, sodium hydrogencarbonate, potassium hydrogencarbonate, potassium fluoride and sodium fluoride, particularly triethylamine, trimethylamine and pyridine are preferably used.

The amount of the Lewis base present is not particularly limited as long as it is a sufficient amount to catalyze the reaction of the isophthalic acid derivative with the azide compound, but is usually 2 to 50 mol per 1 mol of the isophthalic acid derivative. , Preferably 2-10
It is a mole. At this time, if the amount of the Lewis base present is less than 2 mol, the reaction of the isophthalic acid derivative does not proceed well, and the yield may decrease. On the other hand, when the amount of the Lewis base present exceeds 50 mols, the effect commensurate with the addition cannot be obtained, and conversely, it takes time and labor to remove the excess Lewis base, which ultimately leads to an increase in cost. It may be connected.

Solvents that can be used in the above step (3) include methanol, ethanol, absolute ethanol, isopropanol, benzyl alcohol, phenol and n.
-Alcohols such as butanol, sec-butanol and tert-butanol; halogenated hydrocarbons such as chloroform, methylene chloride, carbon tetrachloride, chloroethane, dichloroethane, trichloroethane and tetrachloroethane; carbonization such as pentane, hexane, cyclohexane and heptane Hydrogens; aromatic hydrocarbons such as benzene, toluene and xylene; and diethyl ether,
Isopropyl ether, tetrahydrofuran (TH
F), ethers such as dioxane, diphenyl ether, benzyl ether and tert-butyl ether. Of these, chloroform, benzene and toluene are preferably used. The amount of the solvent used is also not particularly limited as long as the reaction of the isophthalic acid derivative with the azide compound proceeds well, but the concentration of the isophthalic acid derivative in the solvent is usually
1-80 (w / v)%, preferably 5-50 (w / v)
The amount is such that it becomes%.

In step (3) above, the reaction conditions for the reaction of the isophthalic acid derivative and the azide compound are not particularly limited as long as these reactions can proceed sufficiently, but the reaction temperature is usually from -20 to 200. ℃, preferably 20 ~
It is 150 ° C., and the reaction time is usually 0.1 to 40 hours, preferably 0.1 to 20 hours. The above-mentioned reaction may be carried out under pressure, under normal pressure or under reduced pressure, but it is preferably carried out under normal pressure in consideration of ease of handling and equipment.

Furthermore, the acid azide thus obtained is subjected to thermal rearrangement and hydrolysis. More specifically, the acid azide is refluxed if necessary in the first solvent,
At a reaction temperature of 20 to 200 ° C., preferably 20 to 150 ° C. for 0.1 to 40 hours, preferably 0.1 to 20 hours,
After thermal rearrangement to obtain an isocyanate ester in which the —CON ₃ group of the acid azide is converted into an —NCO group, the isocyanate ester that is the thermal rearrangement product is further refluxed, if necessary, with a second solvent. Among them, isocyanate 10
Usually, the reaction is carried out at a reaction temperature of −50 to 200 ° C., preferably −20 to 150 ° C., with an acid or alkali in an amount of 1 to 10000 parts by weight, preferably 5 to 1000 parts by weight, based on 0. 1 to 40 hours, preferably 0.1 to 2
The desired halogen-containing aromatic compound is obtained by hydrolysis for 0 hours.

The first solvent used here includes esters such as methyl formate, ethyl formate, methyl acetate, ethyl acetate and propyl acetate; acetone, methyl isobutyl ketone (MIBK), cyclohexanone and methyl ethyl ketone (MEK), etc. Ketones; halogenated hydrocarbons such as chloroform, methylene chloride, carbon tetrachloride, chloroethane, dichloroethane, trichloroethane and tetrachloroethane; hydrocarbons such as pentane, hexane, cyclohexane and heptane; aromatics such as benzene, toluene and xylene Group hydrocarbons; and ethers such as diethyl ether, isopropyl ether, tetrahydrofuran (THF), dioxane, diphenyl ether, benzyl ether and tert-butyl ether. Of these, chloroform, benzene and toluene are preferably used.

As the second solvent, methanol,
Ethanol, absolute ethanol, isopropanol, benzyl alcohol, phenol, n-butanol, sec
Alcohols such as butanol and tert-butanol; esters such as methyl formate, ethyl formate, methyl acetate, ethyl acetate and propyl acetate; ketones such as acetone, methyl isobutyl ketone (MIBK), cyclohexanone and methyl ethyl ketone (MEK); Halogenated hydrocarbons such as chloroform, methylene chloride, carbon tetrachloride, chloroethane, dichloroethane, trichloroethane and tetrachloroethane; hydrocarbons such as pentane, hexane, cyclohexane and heptane; aromatic hydrocarbons such as benzene, toluene and xylene. And ethers such as diethyl ether, isopropyl ether, tetrahydrofuran (THF), dioxane, diphenyl ether, benzyl ether and tert-butyl ether. It is. Of these, methanol,
Ethanol, chloroform, benzene, toluene and ethyl acetate are preferably used.

The hydrolysis at this time is carried out in the presence of acid and / or alkali, preferably in the presence of acid.
As the acid used in the hydrolysis, concentrated sulfuric acid,
Trichloroacetic acid, sulfuric acid, pyrophosphoric acid, triphosphoric acid, polyphosphoric acid such as trimetaphosphoric acid and tetrametaphosphoric acid, trifluoroacetic acid, trifluoroacetic anhydride, hydrochloric acid, fuming sulfuric acid, concentrated hydrochloric acid, hydrobromic acid, propionic acid, formic acid, nitric acid And acetic acid; and a mixture thereof, for example, trifluoroacetic acid-trifluoroacetic anhydride (the mixing ratio is a mass ratio,
1: 9 to 9: 1, preferably 3: 7 to 7: 3) and a mixed solution of trichloroacetic acid and sulfuric acid (mixing ratio is mass ratio,
1: 9 to 9: 1, preferably 3: 7 to 7: 3). The above acids may be used alone or in the form of a mixture of two or more kinds. Of these, at least one selected from the group consisting of concentrated hydrochloric acid, hydrochloric acid, acetic acid, concentrated sulfuric acid, sulfuric acid, hydrobromic acid and propionic acid, particularly concentrated hydrochloric acid, hydrochloric acid and sulfuric acid is preferably used as the acid. Further, as the alkali used in the hydrolysis, sodium hydroxide, lithium hydroxide, potassium hydroxide, rubidium hydroxide, cesium hydroxide, beryllium hydroxide, magnesium hydroxide, calcium hydroxide, strontium hydroxide and water. Barium oxide and the like,
Of these, sodium hydroxide, potassium hydroxide, lithium hydroxide and calcium hydroxide are preferably used as the alkali. Similarly, the alkali may be used alone or in the form of a mixture of two or more kinds.

In the above hydrolysis, when the acid hydrolyzate exists in the form of a hydrochloride, a step of neutralizing the hydrolyzate with an alkali may be provided. The definition of the alkali that can be used in this case is the same as that of the alkali described in the above hydrolysis section.

The amount of acid azide present in the thermal rearrangement is not particularly limited, and as described above, the acid azide obtained by the reaction between the isophthalic acid derivative and the azide compound may be used as it is. The amount of acid azide in the solvent is usually 1 to 80 (w / v)%, preferably 5 to 50 (w / v)%. Also, the concentration of the isocyanate in the second solvent is also
The isocyanate ester obtained by thermal rearrangement of acid azide may be used as it is, but the concentration of the isocyanate ester in the second solvent is usually 1 to 80 (w / v).
%, Preferably 5 to 50 (w / v)%. Further, the thermal rearrangement reaction and the hydrolysis may be carried out under any of pressure, normal pressure or reduced pressure, but in view of easiness of handling and equipment, it is preferably carried out under normal pressure. .

Alternatively, instead of the step (3), the isophthalic acid derivative obtained in the step (2) is reacted with an azide compound in the presence of a Lewis base in a solvent, so that the carboxyl group of the isophthalic acid derivative is changed. After obtaining an acid azide converted to a —CON ₃ group, the acid azide is thermally rearranged to obtain an isocyanic acid ester in which the —CON ₃ group of the acid azide is converted to a —NCO group. The barrel isocyanate is further refluxed if necessary in a steam bath with an alcohol at a reaction temperature of −20 to 200 ° C., preferably 20 to 150 ° C. for 0.1 to 40 hours, preferably 0. After reacting for 1 to 20 hours to obtain urethanes, the urethanes as reaction products are further refluxed if necessary, in a third solvent, to give urethanes 10
Usually, the reaction is carried out at a reaction temperature of −50 to 200 ° C., preferably −20 to 150 ° C., with an acid or alkali in an amount of 1 to 10000 parts by weight, preferably 5 to 1000 parts by weight, based on 0. 1 to 40 hours, preferably 0.1 to 2
The desired halogen-containing aromatic compound may be obtained by hydrolysis for 0 hours [step (3 ′)].

In the above step (3 '), the step of producing an acid azide and the thermal rearrangement step of an acid azide are the same as the step in the above step (3) unless otherwise specified.

In the step (3 ′), the alcohol to be reacted with the isocyanic acid ester is not particularly limited, but examples thereof include methanol, ethanol, absolute ethanol, isopropanol, benzyl alcohol, phenol, n-butanol, sec-butanol and te
Examples include rt-butanol and the like. The solvent used in the reaction between the isophthalic acid derivative and the azide compound, the first solvent used in the thermal rearrangement reaction of the acid azide, and the alcohol used in the urethanization reaction with the thermal rearrangement product are the same. In this case, since the reaction from the isophthalic acid derivative and the azide compound to the urethanization can be performed in the same solvent without changing the solvent, the solvent used in the reaction between the isophthalic acid derivative and the azide compound; The first solvent used in the thermal rearrangement reaction of azide is preferably the same as the alcohol used in the urethanization reaction with the thermal rearrangement. At this time, if necessary, a solvent may be added. The amount of the alcohol used for the reaction with the isocyanate ester is not particularly limited as long as the reaction with the isocyanate ester proceeds satisfactorily, but is usually 1 mol per 1 mol of the isocyanate ester. ~
It is 100 mol, preferably 2 to 50 mol. In the present invention, when alcohol is also used as a solvent as described above, the upper limit of the above range is not set, that is, the amount of alcohol used when alcohol is also used as a solvent for each reaction is: It is usually 1 mol or more, preferably 2 mol or more, relative to 1 mol of the isocyanate ester.

In the reaction between the above-mentioned isocyanate and alcohol, the alcohol as the reaction reagent is in a liquid state,
It is preferable to carry out the above reaction without further adding a solvent in consideration of easiness of purification of the product, which does not necessarily require addition of a solvent. However, depending on the type and amount of the isocyanate ester or alcohol used in the reaction and the reaction conditions, it may be appropriate to further add another solvent to carry out the reaction. Is water; esters such as methyl formate, ethyl formate, methyl acetate, ethyl acetate and propyl acetate; acetone, methyl isobutyl ketone (MI
BK), cyclohexane and methyl ethyl ketone (ME
K) and other ketones; halogenated hydrocarbons such as chloroform, methylene chloride, carbon tetrachloride, chloroethane, dichloroethane, trichloroethane and tetrachloroethane; hydrocarbons such as pentane, hexane, cyclohexane and heptane; benzene, toluene and xylene. Aromatic hydrocarbons such as; and diethyl ether, isopropyl ether, tetrahydrofuran (THF), dioxane, diphenyl ether, benzyl ether and t.
Examples thereof include ethers such as ert-butyl ether.

The third solvent used in the hydrolysis step is water; methanol, ethanol, anhydrous ethanol, isopropanol, benzyl alcohol, phenol, n-butanol, sec-butanol and t.
alcohols such as ert-butanol; esters such as methyl formate, ethyl formate, methyl acetate, ethyl acetate and propyl acetate; acetone, methyl isobutyl ketone (M
IBK), cyclohexane and methyl ethyl ketone (M
EK) and other ketones; halogenated hydrocarbons such as chloroform, methylene chloride, carbon tetrachloride, chloroethane, dichloroethane, trichloroethane and tetrachloroethane; hydrocarbons such as pentane, hexane, cyclohexane and heptane; benzene, toluene and xylene. Aromatic hydrocarbons such as; and diethyl ether, isopropyl ether, tetrahydrofuran (THF), dioxane, diphenyl ether, benzyl ether and t.
Examples thereof include ethers such as ert-butyl ether. Of these, methanol, ethanol, chloroform, benzene, toluene and ethyl acetate are preferably used. The acid used in the hydrolysis, concentrated sulfuric acid, trichloroacetic acid, sulfuric acid, pyrophosphoric acid, triphosphoric acid, polyphosphoric acid such as trimetaphosphoric acid and tetrametaphosphoric acid, trifluoroacetic acid, trifluoroacetic anhydride, hydrochloric acid, fuming Sulfuric acid, concentrated hydrochloric acid, hydrobromic acid, propionic acid, formic acid, nitric acid and acetic acid; and mixtures thereof, for example
Trifluoroacetic acid-trifluoroacetic anhydride (mixing ratio is
Mass ratio is 1: 9 to 9: 1, preferably 3: 7 to 7 :.
3) and a mixed solution of trichloroacetic acid and sulfuric acid (mixing ratio is
Mass ratio is 1: 9 to 9: 1, preferably 3: 7 to 7 :.
3) etc. are mentioned. The above acids may be used alone or in the form of a mixture of two or more kinds.
Of these, at least one selected from the group consisting of concentrated hydrochloric acid, hydrochloric acid, acetic acid, concentrated sulfuric acid, sulfuric acid, hydrobromic acid and propionic acid, particularly concentrated hydrochloric acid, hydrochloric acid and sulfuric acid is preferably used as the acid. Further, as the alkali used in the hydrolysis, sodium hydroxide, lithium hydroxide, potassium hydroxide, rubidium hydroxide, cesium hydroxide, beryllium hydroxide, magnesium hydroxide, calcium hydroxide, strontium hydroxide and water. Examples thereof include barium oxide, and of these, sodium hydroxide, lithium hydroxide, potassium hydroxide and calcium hydroxide are preferably used as the alkali. Similarly, the alkali may be used alone or in the form of a mixture of two or more kinds.

At this time, when the acid hydrolyzate exists in the form of a hydrochloride, a step of neutralizing the hydrolyzate with an alkali may be provided. The definition of the alkali that can be used in this case is the same as that described above.

The amount of the isocyanate ester present in the reaction with the alcohol is not particularly limited, and as described above, the isocyanate ester may be used as it is, but the alcohol and other additives added as necessary may be used. The concentration of the isocyanate ester in the solvent is usually 1 to 8
The amount is 0 (w / v)%, preferably 5 to 50 (w / v)%. Further, the concentration of the urethanes in the third solvent may also be the urethanes obtained by the reaction of the isocyanic acid ester and the alcohol, but the concentration of the urethanes in the third solvent is usually 1 to 80 (w / v)%, preferably 5 to 50 (w /
v) The amount is%. Further, in the above aspect, the thermal rearrangement reaction and the hydrolysis may be carried out under any of pressure, normal pressure or reduced pressure, but in view of easiness of handling and equipment, it is preferable that the reaction is carried out normally. It is carried out under pressure.

The halogen-containing aromatic compound thus obtained is purified by a known method such as column chromatography using silica gel or alumina, distillation, preferably solid distillation, recrystallization, reprecipitation and sublimation. , Can be manufactured with higher purity.

[0080]

EXAMPLES The present invention will be specifically described below with reference to examples.

Example 1 In a 5 liter 4-necked flask, 596.3 g (2.98 mol) of tetrafluoroisophthalonitrile, 25.97 g (0.45 mol) of potassium fluoride, and methyl isobutyl ketone (MIBK) were added. ) 1.8 liters were charged. While stirring this mixed solution at 45 ° C., 34.91 g (0.15 mol) of 4-hydroxy-2,3,5,6-tetrafluorobenzotrifluoride was dissolved in M.
IBK (600 ml) was added dropwise over 2 hours. After the dropping was completed, this mixed solution was stirred at 65 ° C. for 3 hours. next,
The reaction solution was cooled to 25 ° C., washed with ion-exchanged water, and the solvent (MIBK) was distilled off with an evaporator. Further, by removing excess tetrafluoroisophthalonitrile by distillation, white 2,5,6
-Trifluoro-4- (2,3,5,6-tetrafluoro-4-trifluoromethylphenoxy) isophthalonitrile 32.68 g (78.90 mmol) was obtained (yield: 53.0%, purity. : 98.9%).

Example 2 2,5,6-trifluoro-4- (2,3,5,6-tetrafluoro-4-tri) obtained in Example 1 was placed in a 1-liter 4-neck reaction vessel. 40.0 g (96.58 mmol) of fluoromethylphenoxy) isophthalonitrile and 280 ml of propionic acid were charged. While stirring this mixed solution at 105 ° C., a 70 mass% sulfuric acid aqueous solution 12
0 ml was added dropwise over 1 hour and then refluxed for 26 hours. Next, after cooling this reaction solution to room temperature, the reaction solution was poured into 2 liters of water. The precipitated crystals were separated by filtration, and the filtrate was washed with water. Then, 30 ml of this filter
After dissolving it in acetone, pour it into 370 ml of water,
The precipitated crystals were filtered. The obtained crystals are heated at 100 ° C for 5
35.29 g of 2,5,6-trifluoro-4- (2,3,5,6-tetrafluoro-4-trifluoromethylphenoxy) isophthalic acid by drying for an hour
(78.05 mmol) was obtained as a white solid (crude yield: 80.8%, purity: 99.1%).

Example 3 2,5,6-trifluoro-4- (2,3,5,6-tetrafluoro-4-trifluoro) obtained in Example 2 was placed in a 10 ml two-neck reaction vessel. 0.50 g (1.1 mmol) of methylphenoxy) isophthalic acid, 0.34 ml (2.5 mmol) of triethylamine and 5 ml of tert-butanol were charged. While stirring this mixed solution at 90 ° C., 0.54 ml of diphenylphosphoric acid azide
(2.5 mmol) was added dropwise over 20 minutes and then refluxed for 3 hours. After refluxing for a predetermined time, the reaction solution is heated to 50 m.
The mixture was transferred to a l-volume eggplant flask and concentrated by an evaporator to remove the solvent. Further, 5 ml of ethyl acetate and 5 ml of hydrochloric acid were added to the eggplant flask, and the mixture was stirred at room temperature for 19 hours. After stirring, 5 ml of chloroform was further added, and the mixture was stirred for 1 hour, then, the aqueous layer and the organic layer were separated. The aqueous layer was adjusted to pH 8-9 with sodium hydrogen carbonate, extracted with ethyl acetate, washed with ion-exchanged water, dried over magnesium sulfate, and concentrated with an evaporator to obtain a brown solid. It was Furthermore, by purifying this solid by silica gel column chromatography, 2,5,6-trifluoro-4- (2,2
0.05 g (0.13 mmol) of 3,5,6-tetrafluoro-4-trifluoromethylphenoxy) benzenediamine was obtained as a white solid (crude yield: 11.5%,
Purity: 90.6%).

2,5,6-trifluoro-4- (2,3,5,6-tetrafluoro-4) thus obtained
A mass spectrum of -trifluoromethylphenoxy) benzenediamine was measured and found to be M ⁺ = 39.
It was 4. Moreover, when the reaction product was analyzed by ¹⁹ F-NMR spectrum, the results shown in FIG. 1 were obtained.

[0085]

As described above, the present invention provides a novel halogen-containing aromatic compound represented by the above formula (1). This halogen-containing aromatic compound is an important intermediate in the synthesis of dyes, pharmaceuticals, agricultural chemicals and polymer compounds, and is used as a raw material for resins with excellent heat resistance, water repellency, chemical resistance and low dielectric properties. Can be expected.

[Brief description of drawings]

FIG. 1 shows ¹⁹ F of 2,5,6-trifluoro-4- (2,3,5,6-tetrafluoro-4-trifluoromethylphenoxy) benzenediamine obtained in Example 3.
-A graph showing a chart of an NMR spectrum.

   ─────────────────────────────────────────────────── ─── Continued front page    (72) Inventor Yasunori Okumura             12-25 Kannondai, Tsukuba City, Ibaraki Prefecture             Nippon Shokubai Co., Ltd. F-term (reference) 4H006 AA01 AB46 AB84 BJ50 BM10                       BM30 BM71 BP60 BU46

Claims (2)

[Claims] 1. The following formula (1): However, X is the following formula (2): Provided that each Z independently represents a halogen atom; p is an integer of 0 to 5; q is an integer of 0 to 5; and p + q is 5. ;
Y's each independently represent a halogen atom; m
Is an integer of 0 to 3; n is an integer of 1 to 4;
And m + n is 4, a halogen-containing aromatic compound represented by. 2. The halogen-containing aromatic compound has the following formula (3): However, m is an integer of 0-3; n is an integer of 1-4; and m + n is 4, The halogen-containing aromatic compound according to claim 1.