JP2002332264A - Halogenated meta-phenylenediamine compound - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a new halogenated m-phenylenediamine compound. SOLUTION: The halogenated m-phenylenediamine compound is expressed by formula (1) (X is chlorine or bromine atom; (m) is an integer of 1-3; (n) is an integer of 1-3; and (m)+(n) is 4).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a novel halogenated m-phenylenediamine compound.

The halogenated m-phenylenediamine compound of the present invention is an important intermediate in the synthesis of dyes, drugs, agricultural chemicals, and high molecular compounds, and has excellent heat resistance, water repellency, chemical resistance and low dielectric properties. It is useful as a raw material for a resin.

[0003]

2. Description of the Related Art Halogenated m-phenylenediamine compounds such as tetrafluoro-m-phenylenediamine are important intermediates in the synthesis of dyes, drugs, agricultural chemicals, and high molecular compounds, and have excellent heat resistance and water repellency. , Is useful as a raw material of a resin having chemical resistance and low dielectric properties, and further includes, for example,
It is suitably used as a charge transport agent (particularly, a hole transport agent) in an electrophotographic photoreceptor or the like.

For this reason, various m-phenylenediamine derivatives corresponding to various uses and methods for producing the same have been proposed.
Currently, research and development are being actively conducted.

[0005]

Accordingly, an object of the present invention is to provide a novel halogenated m-phenylenediamine compound.

[0006]

The object of the present invention is to provide the following formula (1):

[0007]

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X is a chlorine atom or a bromine atom; m is an integer of 1 to 3; n is an integer of 1 to 3; and m + n is 4, a halogenated m-phenylene represented by the following formula: Achieved by diamine compounds.

In the present invention, the halogenated m-phenylenediamine compound is represented by the following formula:

[0010]

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The present invention relates to a halogenated m-phenylenediamine compound represented by any one of the above.

[0012]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail.

The present invention provides the following formula (1):

[0014]

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The present invention provides a halogenated m-phenylenediamine compound represented by the formula:

In the above formula (1), X represents a chlorine atom or a bromine atom, and there are a plurality of Xs (ie, n
Is 2 or 3), X may be the same or different, respectively. n represents the number of bonds of X to the benzene ring, and is an integer of 1 to 3, preferably 1 or 2, and particularly preferably 1. The bonding position of X to the benzene ring varies depending on the number and type of bonding of X and the desired properties of the fluorine compound.
When X is 1, X is 4 or 5 of the benzene ring;
And n is 2 when n is 2.
X is preferably bonded to the 4, 6-position of the benzene ring.

In the above formula (1), m represents the number of fluorine atoms bonded to the benzene ring, and is an integer of 1 to 3, preferably 2 or 3, and particularly preferably 3.
In the formula (1), the sum of n and m is always 4 (n + m = 4), that is, the halogenated m-phenylenediamine compound represented by the formula (1) has a carbon-hydrogen bond. There is no compound.

Accordingly, preferred examples of the halogenated m-phenylenediamine compound of the present invention include those represented by the following formula.

[0019]

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Among the above preferred examples of the halogenated m-phenylenediamine compound, 4-bromo-2,5,6
-Trifluoro-m-phenylenediamine, 4-chloro-2,5,6-trifluoro-m-phenylenediamine, 5-chloro-2,4,6-trifluoro-m-phenylenediamine, and 5-bromo- 2,4,6-trifluoro-m-phenylenediamine is particularly preferred.

The halogenated m-phenylenediamine compound of the present invention is not particularly limited as long as it is produced by a known method. One embodiment of the production method is described below.

That is, according to one embodiment, (1) producing halogenated trifluoroisophthalonitrile;
(2) further producing halogenated trifluoroisophthalic acid from the halogenated trifluoroisophthalonitrile; (3) reacting the halogenated trifluoroisophthalic acid with an azide compound in a solvent in the presence of a Lewis base. Thus, an acid azide is obtained, and the target halogenated m-phenylenediamine compound is produced by subjecting the acid azide to thermal rearrangement and hydrolysis. In addition,
In the present specification, “halogenated trifluoroisophthalonitrile” means a compound in which both the amino group (—NH ₂ ) of the halogenated m-phenylenediamine compound of the present invention is substituted with a cyano group (—CN). In addition, “halogenated trifluoroisophthalic acid” refers to the amino group (—N) of the halogenated m-phenylenediamine compound of the present invention.
H ₂ ) means a compound in which both are substituted by a carboxyl group (—COOH).

First, the step (1) in one embodiment of the method for producing the halogenated m-phenylenediamine compound will be described below.

That is, the halogenated trifluoroisophthalonitrile can be produced by a known method such as the method described in JP-B-63-5023.

Here, the first embodiment relating to the method for producing the halogenated trifluoroisophthalonitrile of the present invention will be described below. That is, according to the first embodiment, tetrafluoroisophthalonitrile is reacted with a brominating agent or a chlorinating agent (hereinafter, also collectively referred to as a “halogenating agent”) to convert fluorine in a benzene ring, respectively. Replace with bromine or chlorine. According to the above embodiment, the fluorine at the 4-position of tetrafluoroisophthalonitrile is specifically substituted with bromine or chlorine to obtain the desired 4-bromo-2,
5,6-trifluoroisophthalonitrile or 4-chloro-2,5,6-trifluoroisophthalonitrile is obtained in high yield.

In the first embodiment, the brominating agent is not particularly limited, and a known brominating agent can be used. Specific examples include sodium bromide, potassium bromide and lithium bromide. Of these, sodium bromide and potassium bromide are preferably used in consideration of their ease of handling and practical availability in commercial use and their bromination efficiency.

In the first embodiment, the chlorinating agent is not particularly limited, and a known chlorinating agent can be used. Specific examples include sodium chloride, potassium chloride, and lithium chloride. Of these, taking into account that they are easy to handle and practically commercially available,
Sodium chloride and potassium chloride are preferably used.

In the first embodiment, the amount of the halogenating agent used is not particularly limited as long as the fluorine at the 4-position of tetrafluoroisophthalonitrile can be specifically substituted with bromine or chlorine. Specifically, it is equimolar to tetrafluoroisophthalonitrile. Specifically, the amount of the halogenating agent to be used is 1 to 5 mol, more preferably 1 to 2 mol, per 1 mol of tetrafluoroisophthalonitrile.
Is a mole. At this time, if the use amount of the halogenating agent exceeds 5 mol, fluorine other than the 4-position of tetrafluoroisophthalonitrile may be replaced with bromine or chlorine,
This is because the remaining halogenating agent needs to be treated and is not economical. Conversely, if the amount of the halogenating agent is less than 1 mol, the fluorine at the 4-position of tetrafluoroisophthalonitrile cannot be sufficiently substituted with bromine or chlorine, and a large amount of unreacted tetrafluoroisophthalonitrile remains. Because it will.

In the first embodiment, the bromination or chlorination reaction of tetrafluoroisophthalonitrile may be carried out in a solvent without a solvent, but is preferably carried out in a solvent. The solvent that can be used at this time is not particularly limited as long as it does not inhibit the bromination or chlorination reaction of tetrafluoroisophthalonitrile and is inactive with respect to tetrafluoroisophthalonitrile, a brominating agent and a chlorinating agent. It is not something to be done. Specifically, nitriles such as acetonitrile and benzonitrile; ketones such as acetone, methyl isobutyl ketone (MIBK), methyl ethyl ketone (MEK) and cyclohexanone; chloroform, methylene chloride, carbon tetrachloride, chloroethane, dichloroethane, trichloroethane and tetrachloroethane Halogenated hydrocarbons such as chloroethane; aromatic hydrocarbons such as benzene, toluene and xylene; pentane;
Hydrocarbons such as hexane, cyclohexane and heptane; ethers such as diethyl ether, isopropyl ether, tetrahydrofuran (THF), dioxane, diphenyl ether, benzyl ether and tert-butyl ether; methyl formate, ethyl formate, methyl acetate, ethyl acetate, acetic acid Esters such as propyl and isopropyl acetate; and N-methylpyrrolidinone (NM
P), dimethylformamide (DMF), dimethylsulfoxide (DMSO), dimethylacetamide, sulfolane (TMSO ₂ ) and dimethylsulfolane (DMS
O ₂ ). Of these, acetonitrile, methyl isobutyl ketone (MIBK), N-methylpyrrolidinone (NMP), dimethylformamide (DM
F) and dimethylsulfoxide (DMSO) are preferred. In the present invention, when the solvent is used, the amount of the solvent used is such that the concentration of tetrafluoroisophthalonitrile in the solvent is 2 to 80 (w / v)%, preferably 5 to 5%.
The amount is such that it becomes 0 (w / v)%. In the present invention, for the purpose of improving the reaction rate and further suppressing side reactions, it is preferable to carry out a bromine or chlorine substitution reaction under anhydrous conditions. Therefore, dimethyl sulfoxide, sulfolane, dimethylformamide, N- Methyl-
When a highly hygroscopic solvent such as 2-pyrrolidone and dimethylsulfolane is used, it is preferable to remove water by adding benzene or toluene before the bromine or chlorine substitution reaction.

The reaction conditions of the tetrafluoroisophthalonitrile with the halogenating agent are not particularly limited as long as the halogen substitution reaction of the tetrafluoroisophthalonitrile proceeds sufficiently. 3
The temperature is 00 ° C, preferably 50 to 250 ° C, and the reaction time is usually 0.5 to 20 hours. In addition, the reaction may be performed under any of the pressures, normal pressures and reduced pressures, but is preferably performed under normal pressures.

Alternatively, halogenated trifluoroisophthalonitrile can be obtained by fluorinating tetrachloroisophthalonitrile or tetrabromoisophthalonitrile (hereinafter collectively referred to as "halogenated isophthalonitrile") with a fluorinating agent. (Second embodiment). According to the above embodiment, depending on the degree of nucleophilic substitution reactivity, the 2,4,6
Is specifically fluorinated to give the desired 5-chloro-2,4,6-trifluoroisophthalonitrile or 5-bromo-2,4,6-trifluoroisophthalonitrile Obtained in yield.

In the second embodiment, the fluorinating agent is not particularly limited, and a known fluorinating agent can be used.
Specific examples include potassium fluoride, cesium fluoride, sodium fluoride, barium fluoride, calcium fluoride, antimony fluoride, and the like. Of these, considering the ease of handling and availability, etc. Potassium is preferably used.

In the second embodiment, the amount of the fluorinating agent used is not particularly limited as long as it can specifically fluorinate the chlorine or bromine at the 2,4,6-position of the halogenated isophthalonitrile. Stoichiometrically, it is 3 moles per mole of the isophthalonitrile halide. Specifically, the amount of the fluorinating agent to be used is preferably 3 to 20 mol, more preferably 3 to 10 mol, per 1 mol of the halogenated isophthalonitrile. At this time, if the amount of the fluorinating agent exceeds 20 moles, the halogenated isophthalonitrile may be fluorinated up to the 5-position, and it is necessary to treat the remaining fluorinating agent, which is not economical. is there. Conversely, if the amount of the fluorinating agent is less than 3 mol,
The chlorine or bromine at the 2,4,6-position of the halogenated isophthalonitrile cannot be sufficiently fluorinated, and the desired 5-chloro-2,4,6-trifluoroisophthalonitrile or 5-bromo-2,4,4 This is because the yield of 6-trifluoroisophthalonitrile decreases.

In the second embodiment, the fluorination reaction of the halogenated isophthalonitrile may be carried out in a solvent without a solvent, but is preferably carried out in a solvent. The solvent that can be used at this time is not particularly limited as long as it does not inhibit the fluorination reaction of the halogenated isophthalonitrile and is inactive with respect to tetrachloroisophthalonitrile, tetrabromoisophthalonitrile, and the fluorinating agent. It is not something to be done. Specifically, benzonitrile, dimethyl sulfoxide (DMSO), sulfolane (TMSO ₂ ), dimethylformamide (DMF), N
- methyl-2-pyrrolidone (NMP) and dimethyl sulfolane (DMSO _2), acetonitrile, acetone, methyl ethyl ketone (MEK), and the like methyl isobutyl ketone (MIBK). Of these, benzonitrile and acetonitrile are preferably used. In the present invention, when the solvent is used, the amount of the solvent used is such that the concentration of the halogenated isophthalonitrile in the solvent is 1 to 80 (w / v)%, preferably 5 to 50%.
(W / v)%. In the present invention, for the purpose of improving the reaction rate and further suppressing side reactions, it is preferable to carry out the fluorine substitution reaction under anhydrous conditions. Therefore, dimethyl sulfoxide, sulfolane, dimethylformamide, N-methyl- When a highly hygroscopic solvent such as 2-pyrrolidone and dimethylsulfolane is used, it is preferable to remove water by adding benzene or toluene before the fluorine substitution reaction.

The reaction conditions between the halogenated isophthalonitrile and the fluorinating agent are not particularly limited as long as the fluorination reaction of the halogenated isophthalonitrile proceeds sufficiently. 400 ° C., preferably 100 to 300 ° C., and the reaction time is usually
0.5 to 20 hours. In addition, the reaction may be carried out under any pressure under pressure, normal pressure or reduced pressure,
It is preferably carried out under normal pressure or under pressure. In the latter case, the fluorination reaction of the halogenated isophthalonitrile is performed at 30 to 1000 KPa, more preferably 100 to 8 kPa.
It is preferably performed under a pressure of 00 KPa.

Further, in the second embodiment, the fluorination reaction may be carried out in the presence of a phase transfer catalyst for the purpose of increasing the fluorination reaction rate and shortening the reaction time. The phase transfer catalyst that can be used at this time is not particularly limited, and a known phase transfer catalyst can be used. Specifically, a crown compound such as dibenzo-18-crown-6-ether and polyethylene glycol (molecular weight:
300 to 600). The amount of the phase transfer catalyst to be added is 0.1 to 10 mol based on 1 mol of the halogenated isophthalonitrile.

The thus obtained halogenated trifluoroisophthalonitrile is purified by a known method such as column chromatography using silica gel or alumina, distillation, preferably solid distillation, recrystallization, reprecipitation and sublimation. Thereby, it can be manufactured with high purity.

Next, the step (2) in one embodiment of the method for producing the halogenated m-phenylenediamine compound will be described below.

That is, the halogenated trifluoroisophthalic acid of the present invention is not particularly limited as long as it is produced by a known method. Specific examples include a method of converting the cyano group to a carboxyl group by hydrolyzing the trifluoroisophthalonitrile halide obtained as described above. Alternatively, the alkyl group is oxidized after halogenating m-xylene, m-dialkylbenzene, and those obtained by substituting hydrogen of these alkyl groups with another atom or atomic group, regardless of the above step (1). Thereby, halogenated trifluoroisophthalic acid may be produced. Of these, a method of hydrolyzing halogenated trifluoroisophthalonitrile is preferably used, and this method will be described in detail below.

The hydrolysis of the trifluoroisophthalonitrile halide is carried out in the presence of an acid and / or an alkali. Acids used in this case include concentrated sulfuric acid, trichloroacetic acid, sulfuric acid, pyrophosphoric acid, polyphosphoric acid such as triphosphoric acid, 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: 1, by mass ratio.
9 to 9: 1, preferably 3: 7 to 7: 3) and a mixed solution of trichloroacetic acid and sulfuric acid (mixing ratio is 1: 9 by mass ratio).
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. These acids may be used as they are or in the form of an aqueous solution, and the concentration in the latter case is not particularly limited as long as it can sufficiently hydrolyze the trifluoroisophthalonitrile halide. Although it depends on the reaction temperature and the type of acid, it is, for example, 40 to 85% by mass. Of these, sulfuric acid, particularly a 50 to 80% by mass aqueous sulfuric acid solution, is preferably used as the acid. Among these, polyphosphoric acid, trifluoroacetic acid-trifluoroacetic anhydride, trichloroacetic acid, propionic acid, hydrochloric acid, at least one selected from the group consisting of concentrated hydrochloric acid and sulfuric acid, particularly sulfuric acid, propionic acid,
Concentrated hydrochloric acid and polyphosphoric acid are preferably used as acids.
Further, as the alkali used in the hydrolysis, sodium hydroxide, lithium hydroxide, potassium hydroxide, rubidium hydroxide, cesium hydroxide, beryllium hydroxide,
Examples thereof include magnesium hydroxide, calcium hydroxide, strontium hydroxide, and barium hydroxide. Of these, sodium hydroxide, potassium hydroxide, calcium hydroxide, and barium hydroxide are preferably used as the alkali. Similarly, the above alkalis may be used alone or in the form of a mixture of two or more. Further, the amount of acid and / or alkali used is
The amount of the trifluoroisophthalonitrile halide is not particularly limited as long as it can be sufficiently hydrolyzed. Usually, the concentration of the trifluoroisophthalonitrile with respect to the acid and / or alkali is 1 to 80% by mass, preferably 5% by mass. The amount is such that it becomes 〜50% by mass.

The conditions for the above hydrolysis are not particularly limited as long as the conditions are such that the halogenated trifluoroisophthalonitrile can be sufficiently hydrolyzed.
The temperature is 20 to 200 ° C, preferably 0 to 150 ° C, and the hydrolysis time is usually 0.1 to 40 hours, preferably 0.1 to 40 hours.
1 to 20 hours. In addition, the hydrolysis may be performed under any pressure of pressure, normal pressure or reduced pressure,
Preferably, it is performed under normal pressure.

The thus obtained halogenated trifluoroisophthalic acid can be purified by a known method such as column chromatography using silica gel or alumina, distillation, preferably solid distillation, recrystallization, reprecipitation and sublimation. Can be produced with high purity.

Further, the step (3) in one embodiment of the method for producing the halogenated m-phenylenediamine compound will be described below.

In the step (3), the halogenated trifluoroisophthalic acid obtained in the step (2) is
By reacting with an azide compound in a solvent in the presence of a Lewis base, an acid azide in which the carboxyl group of halogenated trifluoroisophthalic acid is converted to a -CON ₃ group is obtained, and the acid azide undergoes thermal rearrangement and hydrolysis. Thereby, the objective halogenated m-phenylenediamine compound is obtained.

The azide compound used at this time is -N ₃
The compound is not particularly limited as long as it has a group and can efficiently convert the carboxyl group of the halogenated trifluoroisophthalic acid into a -CON ₃ group.

[0046]

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The compounds represented by the following are preferred. In the above formula
And R¹And R^TwoAre each independently 1 carbon atom
Alkyl groups such as methyl, ethyl, propyl
, Isopropyl, n-butyl, pentyl, neo pliers
, Sec-butyl and tert-butyl; number of carbon atoms
3-8 cycloalkyl groups, for example cyclopropyl,
Cyclobutyl, cyclopentyl, cyclohexyl, cyclo
Roheptyl and cyclooctyl; benzyl group; or
Represents a phenyl group which may have a substituent. Also, R ¹Passing
And R^TwoRepresents a phenyl group which may have a substituent
The substituent that can be used is not particularly limited, but specific
Typically, an alkyl group having 1 to 5 carbon atoms, for example, methyl
, Ethyl, propyl, isopropyl, n-butyl,
N-tyl, 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
Tyl group, trichloroacetyl group, trifluoroacetyl
Group, carboxyl group, amino group, halogen atom, for example
If fluorine, chlorine, bromine and iodine, nitrile group, sulf
Phonyl, nitro, and ester groups such as
Examples include chill esters and ethyl esters. This
In the case of R¹And R^TwoAre the same or different
It may be. Further, the above R¹And R^TwoAmong them
, Ethyl, propyl, tert-butyl, benzyl and
And phenyl, especially R¹And R^TwoIs phenyl
Diphenylphosphate azide (hereinafter simply referred to as “DPPA”)
Is also particularly preferred.

The amount of the azide compound to be added is not particularly limited as long as the reaction with the halogenated trifluoroisophthalic acid proceeds well, and the halogenated trifluoroisophthalic acid, Lewis base and solvent used are not limited. Etc., depending on the type and amount. The amount of the azide compound to be added is generally 2 to 50 mol, preferably 2 to 10 mol, per 1 mol of the halogenated trifluoroisophthalic acid.

In the above step (3), it is essential that a halogenated trifluoroisophthalic acid is reacted with an azide compound in a solvent in the presence of a Lewis base. Alkali metals such as sodium hydroxide, lithium hydroxide, potassium hydroxide, rubidium hydroxide and cesium hydroxide; hydroxides such as beryllium hydroxide, magnesium hydroxide, calcium hydroxide, strontium hydroxide and barium hydroxide Alkaline earth metals; methylamine, ethylamine, propylamine, n-butylamine, sec-butylamine, t
primary amines such as tert-butylamine, cyclohexylamine, benzylamine and phenylamine; dimethylamine, diethylamine, dipropylamine, dibutylamine, diisobutylamine, di-sec-butylamine, di-tert-butylamine, dicyclohexylamine, Secondary amines such as benzylamine and diphenylamine; tertiary amines such as trimethylamine, triethylamine, tripropylamine, tributylamine, tricyclohexylamine, tribenzylamine and triphenylamine; pyridine;
Lithium bicarbonate, potassium bicarbonate, rubidium bicarbonate and cesium bicarbonate, sodium carbonate, lithium carbonate, potassium carbonate, rubidium carbonate, cesium carbonate,
Beryllium carbonate, magnesium carbonate, calcium carbonate,
Carbonates of alkali metals and alkaline earth metals such as strontium carbonate and barium carbonate; and alkali metal salts and alkaline earth metal salts such as potassium fluoride, potassium chloride, sodium fluoride, sodium chloride, calcium chloride and magnesium chloride Is mentioned. Of these, triethylamine, trimethylamine, pyridine, sodium bicarbonate, potassium bicarbonate, potassium fluoride and sodium fluoride, especially triethylamine,
Trimethylamine and pyridine are preferably used.

The amount of the Lewis base is not particularly limited as long as it can catalyze the reaction of the halogenated trifluoroisophthalic acid well. It is 50 mol, preferably 2 to 10 mol. At this time, if the amount of the Lewis base is less than 2 mol, the reaction of the halogenated trifluoroisophthalic acid does not proceed favorably, and the yield decreases, which is not preferable. On the other hand, when the amount of the Lewis base is 50
If the amount exceeds mol, the effect corresponding to the addition cannot be obtained, and on the contrary, it takes time and effort to remove the excess Lewis base,
Ultimately, this leads to an increase in cost, which is also undesirable.

Solvents that can be used in the above step (3) include methanol, ethanol, anhydrous ethanol, isopropanol, benzyl alcohol, phenol, 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. Among these, alcohols are preferable because urethane which is easily hydrolyzed to amines is obtained at a stretch, and in consideration of the fact that amines can be easily obtained under mild conditions such as cold acid or catalytic reduction, ter
t-Butanol, benzyl alcohol and ethanol are preferably used. Further, the amount of the solvent used is not particularly limited as long as the reaction of the halogenated trifluoroisophthalic acid proceeds well, but the concentration of the halogenated trifluoroisophthalic acid in the solvent is usually
1 to 80 (w / v)%, preferably 5 to 50 (w / v)
%.

In the above step (3), the reaction conditions of the reaction between the halogenated trifluoroisophthalic acid and the azide compound are not particularly limited as long as these reactions proceed sufficiently, but the reaction temperature is usually- 20-200 ° C,
Preferably it is 20 to 150 ° C., and the reaction time is usually
It is 0.1 to 40 hours, preferably 0.1 to 20 hours. In addition, the above reaction may be performed under any pressure of pressure, normal pressure or reduced pressure, but is preferably performed under normal pressure in consideration of ease of handling and equipment.

Further, the acid azide thus obtained is subjected to thermal rearrangement and hydrolysis. More specifically, the acid azide is reacted with reflux, if necessary, in a 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 performing thermal rearrangement to obtain an isocyanate in which the -CON ₃ group of the acid azide has been converted to an -NCO group, the isocyanate, which is a thermal rearrangement product, is further refluxed, if necessary, with the second solvent. In the isocyanate 10
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 usually 1 to 10000 parts by weight, preferably 5 to 1000 parts by weight, based on parts by weight. 1 to 40 hours, preferably 0.1 to 2 hours
By hydrolyzing for 0 hour, a desired halogenated m-phenylenediamine compound is obtained.

Examples of the first solvent used herein include 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). Ketones; halogenated hydrocarbons such as chloroform, methylene chloride, carbon tetrachloride, chloroethane, dichloroethane, trichloroethane and tetrachloroethane; hydrocarbons such as pentane, hexane, cyclohexane and heptane; aromas 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, anhydrous 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 acids used in the above hydrolysis include concentrated sulfuric acid, trichloroacetic acid, sulfuric acid, polyphosphoric acid such as pyrophosphoric acid, triphosphoric acid, trimetaphosphoric acid and tetrametaphosphoric acid, trifluoroacetic acid, trifluoroacetic anhydride, hydrochloric acid, and the like. 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 mixture 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.
Among them, 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 are preferably used as the acid. Examples of the alkali used in the hydrolysis include 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 can be mentioned. Of these, sodium hydroxide, potassium hydroxide, lithium hydroxide and calcium hydroxide are preferably used as alkali. Similarly, the above alkalis may be used alone or in the form of a mixture of two or more.

In the above-mentioned hydrolysis, when a hydrolyzate of an acid is present 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 at this time is the same as the alkali described in the section on hydrolysis above. The amount of the acid azide is not particularly limited, and as described above, the acid azide obtained by the reaction between the halogenated trifluoroisophthalic acid and the azide compound may be used as it is, but in the first solvent The concentration of the acid azide is usually from 1 to 80 (w /
v)%, preferably 5 to 50 (w / v)%. Further, the concentration of the isocyanate in the second solvent may also be the isocyanate obtained by thermal rearrangement of the acid azide, but the concentration of the isocyanate 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 performed under any of pressure, under normal pressure or under reduced pressure, but is preferably performed under normal pressure in consideration of ease of handling and equipment. .

Alternatively, instead of the step (3), the halogenated trifluoroisophthalic acid obtained in the step (2) is reacted with an azide compound in a solvent in the presence of a Lewis base to give a halogenated trifluoroisophthalic acid. After obtaining the acid azide in which the carboxyl group of isophthalic acid has been converted to a -CON ₃ group, the acid azide is optionally refluxed with an alcohol in a steam bath at -20 to 200 ° C, preferably at −20 to 200 ° C. After reacting at a reaction temperature of 20 to 150 ° C. for 0.1 to 40 hours, preferably 0.1 to 20 hours to obtain urethanes, urethanes as reaction products are further refluxed if necessary. Urethanes 10 in a third solvent
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 usually 1 to 10000 parts by weight, preferably 5 to 1000 parts by weight, based on parts by weight. 1 to 40 hours, preferably 0.1 to 2 hours
The desired m-phenylenediamine halide may be obtained by hydrolysis for 0 hour.

The alcohol to be reacted with the acid azide in the above step is not particularly restricted but includes, for example, methanol, ethanol, anhydrous ethanol, isopropanol, benzyl alcohol, phenol, n-butanol, sec-butanol and tert-butanol. No.

In the reaction between the above-mentioned acid azide and alcohol, the alcohol as a reaction reagent is in a liquid state, so that it is not always necessary to add a solvent, and a solvent is further added in consideration of easy purification of the product. It is preferable to carry out the above-mentioned reaction without using. However, depending on the type and amount of the acid azide or alcohol used in the reaction, the reaction conditions, and the like, it may be appropriate to conduct the reaction by further adding another solvent. Esters such as methyl formate, ethyl formate, methyl acetate, ethyl acetate and propyl acetate; ketones such as acetone, methyl isobutyl ketone (MIBK), cyclohexane and methyl ethyl ketone (MEK); chloroform, methylene chloride, carbon tetrachloride Halogenated hydrocarbons such as chloroethane, dichloroethane, trichloroethane and tetrachloroethane; hydrocarbons such as pentane, hexane, cyclohexane and heptane; benzene,
Aromatic hydrocarbons such as toluene and xylene; and ethers such as diethyl ether, isopropyl ether, tetrahydrofuran (THF), dioxane, diphenyl ether, benzyl ether and tert-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-butanol.
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
Ketones such as EK); 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 And aromatic hydrocarbons such as diethyl ether, isopropyl ether, tetrahydrofuran (THF), dioxane, diphenyl ether, benzyl ether and t
ethers such as tert-butyl ether; Of these, methanol, ethanol, chloroform, benzene, toluene and ethyl acetate are preferably used. Examples of the acid used in the hydrolysis include concentrated sulfuric acid, trichloroacetic acid, sulfuric acid, polyphosphoric acid such as pyrophosphoric acid, triphosphoric acid, trimetaphosphoric acid and tetrametaphosphoric acid, trifluoroacetic acid, trifluoroacetic anhydride, hydrochloric acid, and 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 mixture 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.
Among them, 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 are preferably used as the acid. The alkali used in the hydrolysis includes 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 can be mentioned. Of these, sodium hydroxide, lithium hydroxide, potassium hydroxide and calcium hydroxide are preferably used as alkali. Similarly, the above alkalis may be used alone or in the form of a mixture of two or more.

At this time, when the hydrolyzate of the acid 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 at this time is the same as the above. The amount of the acid azide is not particularly limited, and as described above, the acid azide may be used as it is.However, the concentration of the acid azide in the alcohol and the other solvent added as necessary is usually 1 to 80 (w / v)%, preferably 5 to 50
(W / v)%. In addition, the concentration of urethanes in the third solvent may also be the urethanes obtained by thermal rearrangement of acid azide,
The concentration of the urethane in the third solvent is usually 1 to 8
The amount is 0 (w / v)%, preferably 5 to 50 (w / v)%. Furthermore, in the above embodiment, the thermal rearrangement reaction and the hydrolysis may be performed under any of pressure, under normal pressure or under reduced pressure, but in consideration of ease of handling and equipment, preferably It is performed under pressure.

The thus obtained halogenated m-phenylenediamine compound is purified by a known method such as column chromatography using silica gel or alumina or the like, distillation, preferably solid distillation, recrystallization, reprecipitation and sublimation. Thereby, it can be produced with higher purity.

[0064]

The present invention will now be described more specifically with reference to examples.

Synthesis Example 1 200 g (1.00 mol) of tetrafluoroisophthalonitrile, 1 liter of N-dimethylformamide (DMF), 102.7 g (1.00 mol) of sodium bromide (NaBr) were placed in a 3 liter reaction vessel. Was added. The mixture was heated at 120 ° C. for 1 hour. next,
Add 3 liters of water to a 5 liter beaker,
The reaction solution obtained above was poured. Further, the formed precipitate was subjected to suction filtration, washed with water and hexane, and dried under vacuum to obtain 198.2 g of a white solid. The obtained solid was purified by solid distillation, and 4-bromo-
2,5,6-trifluoroisophthalonitrile 142.
8 g (0.55 mol) was obtained as a white solid (yield 5
5%).

The thus obtained 4-bromo-2,
The mass spectrum of 5,6-trifluoroisophthalonitrile was measured and found to be M ⁺ = 260. When the reaction product was analyzed by ¹⁹ F-NMR spectrum, the result shown in FIG. 1 was obtained.

Synthesis Example 2 In a 500 ml stainless steel autoclave container,
200.0 g of benzonitrile, 80.0 g (0.301 mol) of tetrachloroisophthalonitrile, and 83.9 g (1.445 mol) of ultrafine dry potassium fluoride were charged, and the air in the container was replaced with nitrogen gas. . Next, this mixture was heated and stirred at 220 ° C. for 18 hours. After reacting for a predetermined time, the reaction product was cooled to room temperature, and suspended potassium chloride and unreacted potassium fluoride were removed by filtration. Further, benzonitrile was distilled off from the filtered benzonitrile solution by distillation under reduced pressure to obtain 5-benzonitrile.
42.8 g (0.198 mol) of chloro-2,4,6-trifluoroisophthalonitrile were obtained as a white solid (yield: 65.8%).

Synthesis Example 3 250 g (1.15 mol) of 5-chloro-2,4,6-trifluoroisophthalonitrile obtained in the same manner as described in Synthesis Example 2 was placed in a 5-liter reaction vessel. 2500 ml of a 62% sulfuric acid aqueous solution was added, stirred, and refluxed for 3 hours. After cooling the solution to 25 ° C., the precipitated crystals were separated by filtration, and the crystals were separated by isopropyl ether (IPE).
After dissolving in 500 ml, a saturated aqueous NaCl solution 500
Washed with ml. Next, the crystals were dried over magnesium sulfate, and the solvent (IPE) was removed with an evaporator to remove 280.3 g (1.10 mol) of 5-chloro-2,4,6-trifluoroisophthalic acid as a white solid. (95.4% yield).

Synthesis Example 4 In a 200 ml four-necked flask, 20.03 g of 4-bromo-2,5,6-trifluoroisophthalonitrile obtained in the same manner as described in Synthesis Example 1 (76. 74
mmol), 40 ml of a 62% aqueous sulfuric acid solution, and 40 ml of propionic acid, and the mixture was refluxed at 130 ° C. for 18 hours.
After the solution was cooled to room temperature, the precipitated crystals were filtered off with suction and washed with a small amount of water. Next, this crystal was subjected to IPE2
It was dissolved in 00 ml and washed with 100 ml of water and 100 ml of a saturated aqueous solution of NaCl. Further, the crystals are dried over magnesium sulfate, and then the solvent (IPE) is evaporated by an evaporator.
To remove 17.2 g (57.53 mm
ol) of 4-bromo-2,5,6-trifluoroisophthalic acid as a white solid (yield 75.0%).

The thus obtained 4-bromo-2,
The mass spectrum of 5,6-trifluoroisophthalic acid was measured and found to be M ⁺ = 298. Further, when the reaction product was analyzed by ¹⁹ F-NMR spectrum, the result shown in FIG. 2 was obtained.

Example 1 The 5-chloro-2,4,6-trifluoroisophthalic acid 280 obtained in Synthesis Example 3 was placed in a 5-liter reactor.
3 g (1.10 mol), tert-butanol 81
5.1 g and triethylamine 266.7 g (2.6
4 mol) and heated to 80 ° C. with stirring.
726.9 g of diphenylphosphate azide was added to this mixture.
(2.64 mol) was added dropwise over 2 hours with stirring. After completion of the dropwise addition, the mixture was further heated to 100 ° C. for 1 hour, cooled to 25 ° C., and then the solvent (tert-butanol) was removed with an evaporator to obtain a brown viscous liquid.

Next, the brown viscous liquid obtained above and 915 ml of ethyl acetate were placed in another 5 liter reactor.
Was added, and 1200 ml of concentrated hydrochloric acid was added dropwise while stirring at room temperature, followed by stirring for 18 hours. This reaction solution is mixed with water 1500
It was diluted with ml and washed with chloroform. Further, the washed reaction solution is neutralized with a 5N NaOH aqueous solution,
Upon cooling to ° C., a precipitate formed. The precipitate was filtered by suction, dissolved in 500 ml of toluene, and the toluene solution was washed with a saturated aqueous solution of NaCl and dried over magnesium sulfate. After removing the solvent (ethyl acetate) with an evaporator, the obtained solid was vacuum-dried at room temperature for 3 hours. After distilling the solid thus obtained, it was recrystallized with a mixed solution of tolue-hexane (2: 3 (volume ratio)) to give 5-chloro-2,4,6-trifluorom-phenylenediamine. 117.6 g (0.
60 mol) as a white solid (yield 54.2).
%).

The thus obtained 5-chloro-2,
The mass spectrum of 4,6-trifluoro m-phenylenediamine was measured, and it was M ⁺ = 196. Further, the reaction product was analyzed by ¹⁹ F-NMR spectrum, the result shown in FIG. 3 were obtained.

Example 2 A 4-liter reaction vessel obtained in Synthesis Example 4 was placed in a 1-liter reaction vessel.
Lomo-2,5,6-trifluoroisophthalic acid 16.9
g (56.52 mmol), tert-butanol 26
0.8 g, triethylamine 11.6 g (114.64
mmol) and 31.4 g of diphenylphosphate azide
(114.04 mmol) at 100 ° C. for 17 hours
While heating. The reaction solution is concentrated using an evaporator.
To remove the solvent and dissolve in 350 ml of chloroform.
Was. The solution is then combined with saturated NaHCO _Three150m solution
l, 1% HCl 150ml and water 150ml
Wash twice and dry over magnesium sulfate.
By removing the solvent with a porator, a brown viscous liquid
I got a body.

The brown viscous liquid thus obtained and 140 ml of ethyl acetate were placed in a 300 ml reaction vessel.
And 23 ml of concentrated hydrochloric acid, and the mixture was stirred at 40 ° C. for 3 hours. After stirring for a predetermined time, place in a 500 ml beaker,
After adding 250 ml of this reaction solution and water and stirring for 30 minutes,
Upon standing, it separated into two layers. Further, in a 500 ml beaker, an oil layer (about 130 m
l) and 200 ml of a 5N aqueous NaOH solution were added,
After stirring for minutes, a white precipitate formed. The white precipitate was collected by suction filtration and washed with water to obtain 9.35 g of a light brown solid. This solid was recrystallized from a mixed solution of toluene-hexane (1: 1 (volume ratio)) to give 7.14 g (29.62 mmol) of 4-bromo-hexane.
2,5,6-trifluoro m-phenylenediamine was obtained as a white solid (yield 52.1%).

The thus obtained 4-bromo-2,
The mass spectrum of 5,6-trifluoro m-phenylenediamine was measured and found to be M ⁺ = 240. When the reaction product was analyzed by ¹⁹ F-NMR spectrum, the result shown in FIG. 4 was obtained.

[0077]

As described above, the present invention provides a novel halogenated m-phenylenediamine compound represented by the above formula (1). Therefore, this halogenated m-phenylenediamine compound is an important intermediate in the synthesis of dyes, drugs, pesticides, and high molecular compounds,
It can be expected to be used as a raw material for resins having excellent heat resistance, water repellency, chemical resistance and low dielectric properties.

[Brief description of the drawings]

FIG. 1 shows 4-bromo-2,5, obtained in Synthesis Example 1.
It is a graph which shows the chart of the < ¹⁹ > F-NMR spectrum of 6-trifluoroisophthalonitrile.

FIG. 2 shows 4-bromo-2,5 obtained in Synthesis Example 4.
It is a graph which shows the chart of the < ¹⁹ > F-NMR spectrum of 6-trifluoroisophthalic acid.

FIG. 3 shows the 5-chloro-2,4,4 obtained in Example 1.
¹⁹ F-NM of 6-trifluoro m-phenylenediamine
It is a graph which shows the chart of R spectrum.

4 shows 4-bromo-2,5 obtained in Example 2. FIG.
¹⁹ F-NM of 6-trifluoro m-phenylenediamine
It is a graph which shows the chart of R spectrum.

Claims (2)

[Claims] 1. The following formula (1): Wherein X represents a chlorine atom or a bromine atom;
N is an integer from 1 to 3; and m is an integer from 1 to 3;
+ N is 4. A halogenated m-phenylenediamine compound represented by the formula: 2. The halogenated m-phenylenediamine compound has the following formula: The halogenated m according to claim 1, which is represented by any of the following:
-Phenylenediamine compounds.