JPH1059921A - New production process for phthalonitrile compound and phthalocyanine compound - Google Patents

Abstract

PROBLEM TO BE SOLVED: To produce the subject compounds of high purity simply and economically through a new process in no need of the distillation separation step by completely remove impurities, for example, basic substance or the like from the reaction mixture after the completion of the nucleophilic substitution reaction. SOLUTION: A compound of formula I [X is F, Cl or a base; R<1> is H, a halogen, -NHR<2> (R<2> is an alkyl); n is 1-4] and a compound of the formula: R<3> -H [R<3> is -NHR<4> (R<4> is an alkyl or an aryl)] are subjected to a nucleophilic substitution reaction using benzonitrile as a solvent in a basic atmosphere. After completion of the reaction, the reaction mixture is washed with water whereby a phthalonitrile compound of high purity, represented by formula II is prepared in high yield. The amount of the base is 0.5-20 moles per mole (part) of the compound of formula I and the reaction is carried out at a temperature of >=-5 deg.C. Then, the reaction mixture is combined with a metal or metal oxide in an amount of 0.25-2.5 moles per mole of the compound of formula II and they are allowed to react with each other at 100-300 deg.C to form a phthalocyanine compound of formula III (M is a metal).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a novel method for producing a phthalonitrile compound and a phthalocyanine compound. These compounds are useful as near-infrared absorbing materials and the like that have absorption in the near-infrared region and have high solubility in solvents, and intermediate materials thereof.

[0002]

2. Description of the Related Art Conventionally, a phthalonitrile compound such as 3,4,5,6-tetrafluorophthalonitrile is reacted with a nucleophilic substituent in an organic solvent in the presence of a basic substance to obtain a phthalonitrile compound. A method for introducing a nucleophilic substituent into a compound is known (Japanese Patent Application Laid-Open Nos.
-16615).

In such a nucleophilic substitution reaction, the reaction product liquid after the reaction contains a basic substance and a salt thereof generated by hydrogen halide by-produced with the basic substance as impurities. Therefore, in order to separate and purify the target substance from the reaction product solution, depending on the type of the basic substance used, the basic substance and its salt are filtered and then the filtrate is evaporated to dryness,
After distilling off the solvent from the reaction product, it is necessary to dissolve the product again in a water-incompatible solvent and wash it with water.

[0004] However, in the former, in a solvent such as acetonitrile which is usually used, a basic substance and a salt thereof are partially dissolved in the solvent, so that these remain in the target substance,
Purification was necessary again for some applications. In the latter case, the solvent must be separated by distillation, and the process is extremely complicated.

On the other hand, there is known a method for producing a metal phthalocyanine compound by reacting a phthalonitrile compound with a metal salt or the like in an organic solvent (Japanese Patent Application Laid-Open No. 1-45474).
etc).

However, in the case of continuously producing a metal phthalocyanine compound using the phthalonitrile compound obtained by the nucleophilic substitution reaction, the reaction solvent is different. Had to be isolated, and a complicated process was required.

[0007]

SUMMARY OF THE INVENTION The present invention has been made in view of the above-mentioned problems of the prior art, and has as its object to convert a reaction product solution after a nucleophilic substitution reaction into a basic substance and An object of the present invention is to provide a method for producing a high-purity phthalonitrile compound in a high yield, which can completely remove impurities such as salts thereof.

Another object of the present invention is to provide a method for producing a phthalonitrile compound simply and economically without requiring a step of distilling and separating a solvent.

Still another object of the present invention is to provide a method for simply and economically producing a phthalocyanine compound without requiring a step of isolating the phthalonitrile compound after the completion of the nucleophilic substitution reaction.

[0010]

The above objects can be attained by the following method for producing a phthalonitrile compound and a phthalocyanine compound of the present invention.

That is, the present invention provides a compound represented by the general formula (I)

[0012]

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(In the formula, X represents a fluorine atom or a chlorine atom, R ¹ is the same or different and represents a hydrogen atom, a halogen atom, a —NHR ² group, a —OR ² group or a —SR ² group, and R ² is A compound (hereinafter, referred to as “compound (I)”) represented by an alkyl group or an aryl group which may have a substituent, and n represents an integer of 1 to 4;
I)

[0014]

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(Wherein, R ³ represents a —NHR ⁴ group, —OR ⁴ group or —SR ⁴ group, and R ⁴ represents an alkyl group or an aryl group which may have a substituent). Reacting with a compound (hereinafter, referred to as “compound (II)”) to obtain a compound represented by the general formula (III):

[0016]

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(Wherein X, R ¹ , R ³ and n are as defined above, and m represents an integer of 1 ≦ m ≦ n) (hereinafter referred to as “compound (III)”).
Wherein benzonitrile is used as a solvent, and water is added to the reaction product after the reaction, followed by washing, to produce a phthalonitrile compound.

In the present invention, a metal, a metal halide, a metal oxide or a metal salt of an organic acid is added to the reaction product solution obtained above and reacted with the phthalonitrile compound. IV)

[0019]

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(Wherein X, R ¹ , R ³ , n and m are as defined above, and M represents a metal, a metal halide or a metal oxide). IV))).

[0021]

BEST MODE FOR CARRYING OUT THE INVENTION The process for producing a phthalonitrile compound according to the present invention comprises reacting compound (I) with compound (II) in benzonitrile to obtain compound (III).

In the compound (I), R ¹ is —NHR ²
Groups, the case of -OR ² group or -SR ² group, the alkyl group of R ^2, a methyl group, an ethyl group, a propyl group, an isopropyl group, a cyclopropyl group, butyl group, isobutyl group, sec- butyl group, tert -Butyl group, cyclobutyl group, pentyl group, 1-methylbutyl group, 2-methylbutyl group, isopentyl group, tert-pentyl group,
1,2-dimethylpropyl group, neopentyl group, 1-ethylpropyl group, cyclopentyl group, hexyl group, 1-
Methylpentyl group, 2-methylpentyl group, 3-methylpentyl group, isohexyl group, 1-ethylbutyl group, 2
-Ethylbutyl group, 1,1-dimethylbutyl group, 1,2
-Dimethylbutyl group, 3-dimethylbutyl group, 2,2-
Dimethylbutyl group, 2,3-dimethylbutyl group, 3,3
-Dimethylbutyl group, 1-methyl-1-ethylpropyl group, 1-ethyl-2-methylpropyl group, 1,1,2-
Examples thereof include a linear, branched, or cyclic alkyl group having 1 to 20 carbon atoms such as a trimethylpropyl group, a 1,2,2-trimethylpropyl group, a cyclohexyl group, and a methylcyclohexyl group. Among these, a linear or branched alkyl group having 1 to 8 carbon atoms is preferable. Examples of the aryl group for R ² include a phenyl group, a naphthyl group, and a biphenyl group. Further, the alkyl group or the aryl group of R ² may have a substituent.
Methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, sec-butyl group, tert-
An alkyl group having 1 to 4 carbon atoms such as a butyl group; a phenyl group;
Aryl groups such as naphthyl groups; alkoxy groups such as methoxy groups and ethoxy groups; aryloxy groups such as phenoxy groups;
An alkoxycarbonyl group such as a methoxycarbonyl group and an ethoxycarbonyl group; an aryloxycarbonyl group such as a phenoxycarbonyl group; a heterocyclic group; a halogen atom such as a fluorine atom and a chlorine atom; a halogenated lower alkyl group such as trifluoromethyl and the like. Can be These substituents may further have the same substituent.

Specific examples of R ¹ include a hydrogen atom; a halogen atom such as a fluorine atom and a chlorine atom; methylamino, ethylamino, propylamino, isopropylamino, butylamino, isobutylamino, sec- Alkylamino groups such as butylamino group and tert-butylamino group; anilino group; o-toluidino group, m-toluidino group, p-toluidino group, 2,4-xylidino group,
2,6-xyridino group, o-ethylanilino group, o-butylanilino group, o- (tert-butyl) anilino group, o-chloroanilino group, p-chloroanilino group,
Substituted anilino groups such as 2,4-dichloroanilino group, 2,6-dichloroanilino group, o-fluoroanilino group, p-fluoroanilino group, 2,3,5,6-tetrafluoroanilino group A methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a butoxy group, an isobutoxy group,
alkoxy groups such as sec-butoxy group and tert-butoxy group; phenoxy group; o-methylphenoxy group, m-
Methylphenoxy group, p-methylphenoxy group, 2,4
-Dimethylphenoxy group, 2,6-dimethylphenoxy group, o-ethylphenoxy group, o-butylphenoxy group, o- (tert-butyl) phenoxy group, o-chlorophenoxy group, p-chlorophenoxy group, 2,4 -Dichlorophenoxy group, 2,6-dichlorophenoxy group,
substituted phenoxy groups such as o-fluorophenoxy group, p-fluorophenoxy group, 2,3,5,6-tetrafluorophenoxy group; alkylthio groups such as methylthio group, ethylthio group, butylthio group and tert-butylthio group; phenylthio group O-tolylthio, m-tolylthio, p-tolylthio, 2,3-xylylthio, 2,4
-Xylylthio, 2,6-xylylthio, o-ethylphenylthio, o-butylphenylthio, o- (te
(rt-butyl) phenylthio group, o-chlorophenylthio group, p-chlorophenylthio group, and substituted phenylthio groups such as 2,3,5,6-tetrafluorophenylthio group. When there are a plurality of R ¹ , each R ^1
1 may be the same or different groups selected from the above group.

Specific examples of compound (I) include tetrafluorophthalonitrile, 3,4,5-trifluorophthalonitrile, 3,4,6-trifluorophthalonitrile, 3,4-difluorophthalonitrile, 3,5-
Difluorophthalonitrile, 3,6-difluorophthalonitrile, 4,5-difluorophthalonitrile, 3-fluorophthalonitrile, 4-fluorophthalonitrile,
Tetrachlorophthalonitrile, 3,4,5-trichlorophthalonitrile, 3,4,6-trichlorophthalonitrile, 3,4-dichlorophthalonitrile, 3,5-dichlorophthalonitrile, 3,6-dichlorophthalonitrile,
4,5-dichlorophthalonitrile, 3-chlorophthalonitrile, 4-chlorophthalonitrile, 3-chloro-4,
5,6-trifluorophthalonitrile, 3,4-dichloro-5,6-difluorophthalonitrile, 3,4,5-
Trichloro-6-fluorophthalonitrile, 3-chloro-4,5-difluorophthalonitrile, 3,4-dichloro-5-fluorophthalonitrile, 3-chloro-4-fluorophthalonitrile, 3,4,6-trifluoro -5
-Methylaminophthalonitrile, 4-ethylamino-
3,5,6-trifluorophthalonitrile, 4-butylamino-3,5,6-trifluorophthalonitrile, 4
-Anilino-3,5,6-trifluorophthalonitrile, 3,4,6-trifluoro-5- (o-toluidino) phthalonitrile, 3,4,6-trifluoro-5-
(P-toluidino) phthalonitrile, 3,4,6-trifluoro-5- (2,4-xylidino) phthalonitrile, 3,4,6-trifluoro-5- (2,6-xylidino) phthalonitrile, 5- (o-chloroanilino)-
3,4,6-trifluorophthalonitrile, 5- (p-
Chloroanilino) -3,4,6-trifluorophthalonitrile, 5- (2,4-chloroanilino) -3,4,6
-Trifluorophthalonitrile, 5- (2,6-chloroanilino) -3,4,6-trifluorophthalonitrile, 3,4,6-trifluoro-5- (o-fluoroanilino) phthalonitrile, 3, 4,6-trifluoro-
5- (p-fluoroanilino) phthalonitrile, 3,
4,6-trifluoro-5- (2,3,5,6-tetrafluoroanilino) phthalonitrile, 3,4,6-trifluoro-5-methoxyphthalonitrile, 4-ethoxy-3,5,6 -Trifluorophthalonitrile, 4-butoxy-3,5,6-trifluorophthalonitrile, 3,
5,6-trifluoro-4-phenoxyphthalonitrile, 3,4,6-trifluoro-5- (o-methylphenoxy) phthalonitrile, 3,4,6-trifluoro-
5- (p-methylphenoxy) phthalonitrile, 5-
(2,4-dimethylphenoxy) -3,4,6-trifluorophthalonitrile, 5- (2,6-dimethylphenoxy) -3,4,6-trifluorophthalonitrile, 5
-(O-chlorophenoxy) -3,4,6-trifluorophthalonitrile, 5- (p-chlorophenoxy)-
3,4,6-trifluorophthalonitrile, 5- (2,
4-chlorophenoxy) -3,4,6-trifluorophthalonitrile, 5- (2,6-chlorophenoxy)-
3,4,6-trifluorophthalonitrile, 3,4,6
-Trifluoro-5- (o-fluorophenoxy) phthalonitrile, 3,4,6-trifluoro-5- (p-fluorophenoxy) phthalonitrile, 3,4,6-trifluoro-5- (2,3 , 5,6-tetrafluorophenoxy) phthalonitrile, 3,6-difluoro-4,5
-Bismethylthiophthalonitrile, 3,6-difluoro-4,5-bisethylthiophthalonitrile, 3,6-difluoro-4,5-bisbutylthiophthalonitrile,
3,6-difluoro-4,5-bis (tert-butylthio) phthalonitrile, 3,6-difluoro-4,5-
Bisphenylthiophthalonitrile, 4,5-bisethylphenylthio-3,6-difluorophthalonitrile,
3,6-difluoro-4,5-bispropylphenylthiophthalonitrile, 4,5-bisbutylphenylthio-
3,6-difluorophthalonitrile, 3,6-difluoro-4,5-bis (tert-butylphenylthio) phthalonitrile, 3,6-difluoro-4,5-bis (o
-Tolylthio) phthalonitrile, 3,6-difluoro-
4,5-bis (p-tolylthio) phthalonitrile, 3,
6-difluoro-4,5-bis (m-tolylthio) phthalonitrile, 3,6-difluoro-4,5-bis (2,
4-xylylthio) phthalonitrile, 3,6-difluoro-4,5-bis (2,3-xylylthio) phthalonitrile, 3,6-difluoro-4,5-bis (2,6-xylylthio) phthalonitrile, 4 , 5-Bis (o-chlorophenylthio) -3,6-difluorophthalonitrile, 4,5-bis (p-chlorophenylthio) -3,6
-Difluorophthalonitrile, 4,5-bis (2,4-
Dichlorophenylthio) -3,6-difluorophthalonitrile, 4,5-bis (2,6-dichlorophenylthio) -3,6-difluorophthalonitrile, 3,6-difluoro-4,5-bis (o-fluorophenyl Thio)
Phthalonitrile, 3,6-difluoro-4,5-bis (p-fluorophenylthio) phthalonitrile, 3,6
-Difluoro-4,5-bis (2,3,5,6-tetrafluorophenylthio) phthalonitrile and the like. Among these, tetrafluorophthalonitrile,
3,4,6-trifluorophthalonitrile, tetrachlorophthalonitrile, 3,4,6-trichlorophthalonitrile and the like are particularly preferred.

In the compound (II), specific examples of R ⁴ include the same as those described above for R ² .

Specific examples of compound (II) include primary alkylamines such as methylamine, ethylamine, propylamine, isopropylamine, butylamine, isobutylamine, sec-butylamine and tert-butylamine; aniline; o-toluidine; m-toluidine,
p-toluidine, 2,4-xylidine, 2,6-xylidine, o-ethylaniline, o-butylaniline, o-
(Tert-butyl) aniline, o-chloroaniline,
p-chloroaniline, 2,4-dichloroaniline, 2,
Substituted anilines such as 6-dichloroaniline, o-fluoroaniline, p-fluoroaniline, 2,3,5,6-tetrafluoroaniline; methyl alcohol, ethyl alcohol, propyl alcohol, isopropyl alcohol, butyl alcohol, isobutyl alcohol, sec
Alcohols such as -butyl alcohol and tert-butyl alcohol; phenol; o-methylphenol, m-
Methylphenol, p-methylphenol, 2,4-dimethylphenol, 2,6-dimethylphenol, o-
Ethylphenol, o-butylphenol, o- (te
rt-butyl) phenol, o-chlorophenol, p
-Chlorophenol, 2,4-dichlorophenol,
Substituted phenols such as 2,6-dichlorophenol, o-fluorophenol, p-fluorophenol, 2,3,5,6-tetrafluorophenol, methylsalicylic acid, o-phenoxyphenol, p-methoxyphenol; methanethiol, ethane Thiols such as thiol, butanethiol, tert-butanethiol and the like; benzenethiol; o-toluenethiol, m-toluenethiol, p-toluenethiol, 2,3-xylenethiol, 2,4-xylenetol, 2,5-xylene Substituted benzenes such as thiol, o-ethylbenzenethiol, o-butylbenzenethiol, o- (tert-butyl) benzenethiol, o-chlorobenzenethiol, p-chlorobenzenethiol, 2,3,5,6-tetrafluorobenzenethiol Thiol, and the like.

In the process for producing phthalonitrile of the present invention, the compound (III) is obtained by subjecting the compound (I) to a nucleophilic substitution reaction with the compound (I) using benzonitrile as a solvent. .

Since such a nucleophilic substitution reaction proceeds in a basic atmosphere, when an alcohol, phenol, thiol or phenylthiol is used as the compound (II), it is necessary to add a basic substance in addition to these. . Examples of such basic substances include fluorides of alkali metals such as sodium fluoride and potassium fluoride; hydroxides of alkali metals such as sodium hydroxide and potassium hydroxide; alkalis such as sodium hydrogen carbonate and potassium hydrogen carbonate. Metal bicarbonates; alkali metal carbonates such as sodium carbonate and potassium carbonate; alkaline earth metal fluorides such as calcium fluoride and barium fluoride; calcium hydroxide;
Hydroxides of alkaline earth metals such as barium hydroxide; carbonates of alkaline earth metals such as calcium carbonate and barium carbonate; primary amines such as aniline and butylamine; secondary amines such as dibutylamine and ethylphenylamine Amines; tertiary amines such as trimethylamine and triethylamine; Of these, alkali metal fluorides are preferred, and potassium fluoride is particularly preferred. on the other hand,
When an alkylamine or aniline is used as the compound (II), it is not necessary to add the above-mentioned basic substance because it is basic, but the reaction can be performed by adding it.

The total amount of compound (I) and compound (II) in benzonitrile is 5 to 45% by weight, preferably 10 to 3% by weight.
5% by weight is good. If the total amount of both is less than 5% by weight, the productivity is remarkably reduced, and if it exceeds 45% by weight, the raw material and the product are precipitated, which undesirably causes a problem in workability. The amount of the basic substance to be added is 0.5 to 20 parts by mol, preferably 1 to 10 parts by mol, per 1 part by mol of compound (II). If the amount of the basic substance is less than 0.5 mol part, the reaction rate is decreased, and if it exceeds 20 mol part, a large amount of the basic substance needs to be treated after completion of the reaction, which is not preferable. The reaction temperature is -5C or more, preferably -5 to 200.
° C, particularly preferably 10 to 150 ° C. If the reaction temperature is lower than −5 ° C., the reaction rate is low and productivity is undesirably reduced.

In the method for producing a phthalonitrile compound according to the present invention, the reaction solution containing the compound (III) obtained by subjecting the compound (II) to nucleophilic substitution with the compound (I) may be the same or the same. Further nucleophilic substitution reactions can be carried out using different compounds (II).

In the present invention, a salt formed by hydrogen halide such as hydrogen fluoride or hydrogen chloride by-produced in the nucleophilic substitution reaction and a basic substance or the like in the reaction solution is formed. It is necessary to have a step of removing basic substances and the like and salts thereof. In the method for producing a phthalonitrile compound of the present invention, since benzonitrile, which is incompatible with water, is used as a solvent, water is added to the reaction product after the reaction is completed, and the reaction product is washed with water as it is. Can be removed by washing without distilling off the compound, and a high-purity phthalonitrile compound can be obtained in a high yield.

Specific examples of the compound (III) thus obtained include 3,4,6-trifluoro-5-methylaminophthalonitrile, 4-ethylamino-3,5
6-trifluorophthalonitrile, 4-butylamino-
3,5,6-trifluorophthalonitrile, 4-anilino-3,5,6-trifluorophthalonitrile, 3,
4,6-trifluoro-5- (o-toluidino) phthalonitrile, 3,4,6-trifluoro-5- (p-toluidino) phthalonitrile, 3,4,6-trifluoro-
5- (2,4-xylidino) phthalonitrile, 3,4
6-trifluoro-5- (2,6-xylidino) phthalonitrile, 5- (o-chloroanilino) -3,4,6-
Trifluorophthalonitrile, 5- (p-chloroanilino) -3,4,6-trifluorophthalonitrile, 5-
(2,4-chloroanilino) -3,4,6-trifluorophthalonitrile, 5- (2,6-chloroanilino)-
3,4,6-trifluorophthalonitrile, 3,4,6
-Trifluoro-5- (o-fluoroanilino) phthalonitrile, 3,4,6-trifluoro-5- (p-fluoroanilino) phthalonitrile, 3,4,6-trifluoro-5- (2 , 3,5,6-tetrafluoroanilino) phthalonitrile, 3,4,6-trifluoro-5-
Methoxyphthalonitrile, 4-ethoxy-3,5,6-
Trifluorophthalonitrile, 4-butoxy-3,5,
6-trifluorophthalonitrile, 3,5,6-trifluoro-4-phenoxyphthalonitrile, 3,4,6-
Trifluoro-5- (o-methylphenoxy) phthalonitrile, 3,4,6-trifluoro-5- (p-methylphenoxy) phthalonitrile, 5- (2,4-dimethylphenoxy) -3,4,6 -Trifluorophthalonitrile, 5- (2,6-dimethylphenoxy) -3,4,6
-Trifluorophthalonitrile, 5- (o-chlorophenoxy) -3,4,6-trifluorophthalonitrile,
5- (p-chlorophenoxy) -3,4,6-trifluorophthalonitrile, 5- (2,4-chlorophenoxy) -3,4,6-trifluorophthalonitrile, 5-
(2,6-chlorophenoxy) -3,4,6-trifluorophthalonitrile, 3,4,6-trifluoro-5-
(O-fluorophenoxy) phthalonitrile, 3,4
6-trifluoro-5- (p-fluorophenoxy) phthalonitrile, 3,4,6-trifluoro-5- (2
3,5,6-tetrafluorophenoxy) phthalonitrile, 3,6-difluoro-4,5-bismethylthiophthalonitrile, 3,6-difluoro-4,5-bisethylthiophthalonitrile, 3,6-difluoro- 4,5-bisbutylthiophthalonitrile, 3,6-difluoro-
4,5-bis (tert-butylthio) phthalonitrile, 3,6-difluoro-4,5-bisphenylthiophthalonitrile, 4,5-bisethylphenylthio-3,
6-difluorophthalonitrile, 3,6-difluoro-
4,5-bispropylphenylthiophthalonitrile,
4,5-bisbutylphenylthio-3,6-difluorophthalonitrile, 3,6-difluoro-4,5-bis (tert-butylphenylthio) phthalonitrile,
3,6-difluoro-4,5-bis (o-tolylthio)
Phthalonitrile, 3,6-difluoro-4,5-bis (p-tolylthio) phthalonitrile, 3,6-difluoro-4,5-bis (m-tolylthio) phthalonitrile,
3,6-difluoro-4,5-bis (2,4-xylylthio) phthalonitrile, 3,6-difluoro-4,5-
Bis (2,3-xylylthio) phthalonitrile, 3,6
-Difluoro-4,5-bis (2,6-xylylthio)
Phthalonitrile, 4,5-bis (o-chlorophenylthio) -3,6-difluorophthalonitrile, 4,5-bis (p-chlorophenylthio) -3,6-difluorophthalonitrile, 4,5-bis (2 , 4-Dichlorophenylthio) -3,6-difluorophthalonitrile, 4,5
-Bis (2,6-dichlorophenylthio) -3,6-difluorophthalonitrile, 3,6-difluoro-4,5
-Bis (o-fluorophenylthio) phthalonitrile,
3,6-difluoro-4,5-bis (p-fluorophenylthio) phthalonitrile, 3,6-difluoro-4,
5-bis (2,3,5,6-tetrafluorophenylthio) phthalonitrile, 4-anilino-5-phenylthio-3,6-difluorophthalonitrile, 4-anilino-
5-butoxy-3,6-difluorophthalonitrile, 4
-Butylthio-5-phenoxy-3,6-difluorophthalonitrile, 4-butoxy-5-phenoxy-3,6
-Difluorophthalonitrile, 4-anilino-5- (o
-Toluidino) -3,6-difluorophthalonitrile,
3-fluoro-4,5,6-triphenoxyphthalonitrile, 3,4,5,6-tetraphenylthiophthalonitrile, 4-phenylthio-3,5,6-trifluorophthalonitrile, 4- (2-ethoxy Carbonyl-6-methyl) phenoxy-3,5,6-trifluorophthalonitrile, 4- (2-phenyl) phenoxy-3,5,6
-Trifluorophthalonitrile and the like.

Next, the method for producing the phthalocyanine compound of the present invention will be described. The reaction product solution obtained in the above step is used as it is, and a metal, a metal halide,
Compound (III) by adding metal oxide or metal salt of organic acid
To give compound (IV). That is, both the nucleophilic substitution reaction of the phthalonitrile compound in the preceding step and the synthesis reaction of phthalocyanine in the subsequent step are performed in benzonitrile and the same solvent is used, so that the compound (III) produced after the completion of the preceding step is simply obtained. Without separation, the reaction product liquid of the preceding step can be used as it is for the subsequent step.

Metals to be added include iron, cobalt, nickel, copper, zinc and the like, and metal halides include aluminum chloride, copper (I) chloride, copper (II) chloride, zinc chloride, and the like.
Gallium chloride, germanium chloride (II), indium chloride, tin (II) chloride, iron (II) chloride, vanadium (III) chloride, titanium (IV) chloride, cobalt chloride (I
I), cobalt (III) chloride, nickel (II) chloride, aluminum iodide, copper (I) iodide, zinc iodide, gallium iodide, indium iodide, copper (I) bromide, copper (II) bromide ), Zinc bromide, indium bromide, copper (II) fluoride,
Examples of metal oxides include zinc fluoride, indium fluoride, and the like; metal oxides such as vanadium pentoxide; and organic acid metal salts include zinc acetate, copper acetate, copper stearate, and zinc stearate.

The amount of the metal, metal halide, metal oxide or organic acid salt metal to be added is 0.25 to 2.5 parts by mol, preferably 0.1 to 2.5 parts by mol, per 1 part by mol of compound (III).
25 to 1 mol part is good. The reaction temperature is 100 to 300
C, preferably 140 to 200C. Reaction temperature is 1
If the temperature is lower than 00 ° C., the reaction rate is low.

The target compound (IV) can be obtained by evaporating the reaction product liquid after the reaction to dryness. When an insoluble component is generated in the reaction product solution, the solution is filtered and evaporated to dryness.

The compound (IV) thus obtained includes 3,5,6-dodecafluoro-4-tetrakis (anilino) dichlorotin phthalocyanine and 3,6-octafluoro-4,5-octakis (phenylthio) Vanadyl phthalocyanine, 3,5,6-dodecafluoro-
4-tetrabutoxyzinc phthalocyanine, 3,4,6-
Dodecafluoro-5-tetrakis (p-methylphenoxy) copper phthalocyanine, 3,6-octafluoro-4,
5-octakis (2,4-xylylthio) nickel phthalocyanine, 3,4,6-dodecafluoro-5-tetrakis (2,3,5,6-tetrafluorophenoxy) iron phthalocyanine, 3,4,6-dodecafluoro- 5-tetrakis (2,6-chloroanilino) chloroindium phthalocyanine and the like.

[0038]

EXAMPLES Next, the method for producing the phthalonitrile compound and the phthalocyanine compound of the present invention will be described in more detail with reference to examples, but the present invention is not limited thereto.

Example 1 500 g (2.50 mol) of tetrafluorophthalonitrile and 3500 ml of benzonitrile were added to a four-necked flask equipped with a stirrer, a cooling reflux tube, a thermometer and a dropping device, and aniline 683 was added thereto. .12 g was added dropwise over 2 hours while maintaining the temperature at 20 ° C., and the reaction was further performed for 93 hours. After completion of the reaction, add water 2
The reaction solution was washed and separated twice with 000 ml twice, twice with a 2N aqueous hydrochloric acid solution 1000 ml and three times with water 1000 ml. When the obtained reaction solution was analyzed by liquid chromatography, 4-anilino- with a purity of 99.0% was obtained.
3,5,6-tetrafluorophthalonitrile was produced.

Example 2 In a three-necked flask equipped with a stirrer, a cooling reflux tube and a thermometer, 4200 g (2.50 mol) of the reaction solution obtained in Example 1 and 142.2 g (0 .75 mol) and reacted at the reflux temperature of benzonitrile for 4 hours. After cooling to room temperature, the precipitate was filtered and evaporated to dryness under reduced pressure to give dichloro (1,3,4,8,10,11,17,18,22,22).
780.05 g of tin of 24,25-dodecafluoro-2,9,16,23-tetrakis (anilino) -29H, 31H-phthalocyaninato (2-)-N29, N30, N31, N32) was obtained.

[0041]

According to the method of the present invention for producing a phthalonitrile compound, impurities such as basic substances and salts thereof can be completely removed from the reaction product solution after the completion of the nucleophilic substitution reaction. The phthalonitrile compound can be produced in high yield.

Further, according to the method for producing a phthalonitrile compound of the present invention, a phthalonitrile compound can be produced simply and economically without a step of distilling and separating a solvent.

According to the method for producing a phthalocyanine compound of the present invention, a phthalocyanine compound can be simply and economically produced without requiring a step of isolating the phthalonitrile compound after the completion of the nucleophilic substitution reaction.

The phthalocyanine compound obtained according to the present invention is very useful as a near-infrared absorbing material having absorption in the near infrared region and having high solubility in a solvent, and the phthalonitrile compound obtained according to the present invention is extremely useful as an intermediate thereof. It is. The phthalocyanine compound obtained in the present invention is 600
Optical storage medium using a semiconductor laser, because it has excellent absorption and absorption in the near infrared region of up to 1000 nm, and also has excellent light resistance originally possessed by phthalocyanine;
Near-infrared absorbing dyes for writing or reading in liquid crystal display devices, optical character readers, etc., near-infrared light sensitizers, heat-sensitive transfer, light-heat exchangers such as heat-sensitive paper / heat-sensitive stencils, near-infrared absorbing filters, Excellent effect when used as an anti-fatigue agent, a photoconductive material, etc., as well as a photosensitive dye for tumor treatment that absorbs light in the long wavelength region with good tissue permeability, and as a heat ray shielding agent for automobiles or building materials Things. Further, the phthalocyanine compound obtained in the present invention can be used as a visible absorbing material having visible absorption, for example, a color separation filter used for an image pickup tube, a liquid crystal display element, a color CRT selective absorption filter, a color toner, an ink jet ink, a falsified forgery It is particularly useful when used for prevention barcode inks, near infrared absorbing inks, and the like.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁶ Identification number Agency reference number FI Technical indication location C09B 47/20 C09B 47/20 47/22 47/22

Claims (2)

[Claims] 1. A compound of the general formula (I) (Wherein, X represents a fluorine atom or a chlorine atom, and R ¹ is the same or different and is a hydrogen atom, a halogen atom, -NHR
² group, represents an -OR ² group, or -SR ² group, R ² represents an alkyl group or an aryl group which may have a substituent,
n represents an integer of 1 to 4. ) And a compound of the general formula (II) (Wherein, R ³ is a —NHR ⁴ group, a —OR ⁴ group, or a —SR
Represents ⁴ groups, and R ⁴ represents an alkyl group or an aryl group which may have a substituent. ) To react with a compound represented by the general formula (III): Wherein X, R ¹ , R ³ and n are as defined above, and m represents an integer of 1 ≦ m ≦ n, wherein benzonitrile is used as a solvent in the method for producing a phthalonitrile compound. A method for producing a phthalonitrile compound, wherein water is added to a reaction product solution after the completion of the reaction to wash the solution. 2. The reaction product liquid obtained in claim 1, wherein a metal,
A general formula (IV) wherein a metal halide, a metal oxide or a metal salt of an organic acid is added and reacted with the phthalonitrile compound. (Wherein X, R ¹ , R ³ , n and m are as defined above, and M represents a metal, a metal halide or a metal oxide).