JP2000095746A - Production of substituent-containing phthalonitrile or phthalocyanine compound - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for producing a substituent-containing phthalonitrile or phthalocyanine compound by subjecting a halogen-containing phthalonitrile or a halogen-containing phthalocyanine and a nucleophilic compound such as an amino compound to a nucleophilic substitution reaction, capable of rapidly filtering the deposits of the objective product, namely shortening the filtration time of the deposits, to efficiently produce the substituent- containing phthalonitrile or phthalocyanine compound. SOLUTION: This method for producing the substituent-containing phthalonitrile or phthalocyanine compound comprises filtering off solid contents from the reaction product, concentrating the filtrate, and subsequently charging the concentrated solution into water and/or an organic solvent or charging water and/or an organic solvent into the concentrated solution to deposit the substituent-containing phthalonitrile or phthalocyanine compound.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a method for producing a phthalonitrile or phthalocyanine compound having a substituent, and more particularly to a phthalonitrile having a halogen atom (for example, a fluorine atom) or a halogen atom (for example, a fluorine atom) on a benzene nucleus. The present invention relates to a method for efficiently producing a corresponding substituent-containing phthalonitrile or phthalocyanine compound by subjecting a phthalocyanine compound to a nucleophilic compound such as an amino compound, a phenol compound or a thiol compound.

[0002]

2. Description of the Related Art A soluble phthalocyanine compound having an amino group is useful as a near-infrared absorbing dye or the like, and the soluble phthalocyanine compound is obtained by subjecting a fluorine-containing phthalocyanine compound and an amino compound to a nucleophilic substitution reaction. Is known (JP-A-5-345861).

[0003] However, the method described in Japanese Patent Application Laid-Open No. 5-345861 traps hydrogen fluoride (hydrofluoric acid) by-produced in a nucleophilic substitution reaction with an amino compound, which may cause a problem of corrosion of the reactor. There is.

[0004] In order to solve the problem of corrosion of the above reaction apparatus, the applicant of the present invention carried out the above nucleophilic substitution reaction in the presence of an alkaline earth metal compound, and converted the by-produced hydrogen fluoride into alkaline earth metal. He knew that this could be solved by trapping with a metal compound, and filed a patent application earlier (Japanese Patent Application No. 10-1).
03023).

[0005]

SUMMARY OF THE INVENTION The above-mentioned Japanese Patent Application No. 10-10 / 1998.
No. 3023 describes a method in which hydrogen fluoride produced as a by-product is reacted with an alkaline earth metal compound to generate a fluoride insoluble in a reaction solvent, and the fluoride is separated and removed by an operation such as filtration. Things. As a result, the problem of corrosion of the reaction apparatus can be solved, and effects such as simplification of the purification step and improvement of the reaction rate can be obtained.

[0006] However, if the particles of the alkaline earth metal compound used are small, the alkaline earth metal compound may be formed by trapping hydrogen fluoride to form fluoride or possibly remaining unreacted alkaline earth metal compound. Solid (the form is not clear, but in the present invention,
This is referred to as “solid matter” for convenience), which requires a long time for the filtration operation (solid matter filtration time), and there is a problem that productivity is reduced. In addition, since a solid fluorate is also produced when an alkaline earth metal compound is not used, in the present invention, this solid fluorate is also referred to as a solid. Therefore, when no alkaline earth metal is used, the solid means the above solid fluorate.

[0007] In addition, when the target product is separated from the filtrate after separating the solid matter and separated by filtration, if the required time (filtration time) can be reduced, the productivity is improved. Needless to say, this is industrially advantageous.

Thus, the present invention relates to shortening the above-mentioned precipitate filtration time, that is, to improving the efficiency of the precipitate filtration operation. More specifically, the present invention relates to a nucleophilic compound such as a halogen-containing phthalonitrile or a halogen-containing phthalocyanine and an amino compound. And, if necessary, in the presence of an alkaline earth metal compound, to produce a corresponding substituent-containing phthalonitrile or phthalocyanine compound by performing a nucleophilic substitution reaction. It is an object of the present invention to provide a method for producing a phthalonitrile or phthalocyanine compound containing a substituent.

[0009]

According to the study of the present inventors, a solid substance is separated from a reaction mixture by filtration, the obtained filtrate is concentrated, and the concentrated liquid is poured into water and / or an organic solvent. Alternatively, it was found that the time required for filtration of the filtrate can be shortened by adding water and / or an organic solvent to the concentrate to precipitate the target product. The present invention has been completed based on such findings.

That is, the present invention provides a method for obtaining a phthalonitrile having at least one halogen atom or a phthalocyanine compound having at least one halogen atom on a benzene nucleus of a phthalocyanine skeleton and a nucleophilic compound in a reaction solvent. When producing a corresponding substituent-containing phthalonitrile or a substituent-containing phthalocyanine compound by performing a nuclear substitution reaction, the reaction mixture is filtered to separate and remove a solid, and then the filtrate is concentrated. A substituent-containing phthalonitrile or a substituent-containing phthalocyanine compound, which is charged into water and / or an organic solvent, or water and / or an organic solvent is charged into the concentrated solution, whereby a substituent-containing phthalonitrile or a substituent-containing phthalocyanine compound is deposited. This is a method for producing phthalonitrile or a phthalocyanine compound having a substituent.

[0011]

BEST MODE FOR CARRYING OUT THE INVENTION One of the starting materials of the present invention is
Phthalonitrile having at least one halogen atom has the general formula (1):

[0012]

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(Wherein X is a halogen atom, R is a hydrogen atom, a linear or branched alkyl group having 1 to 8 carbon atoms, an alkoxyl group having 1 to 8 carbon atoms, a hydroxyl group, a nitro group, a cyano group, Amino group, carboxyl group, acetyl group, alkyl (linear or branched alkyl group having 1 to 4 carbon atoms; the same applies hereinafter) ester group, aryl (benzene group or naphthalene ring aryl group; the same applies hereinafter) ester, thiol group , An alkylthioester, an arylthioester group, an arylthio group, or an aryloxy group, and m is an integer of 1 to 4). All of these substituents (including the halogen atom of X) need not be the same, and may be substituted by different substituents. As the halogen atom for X, a fluorine atom and a chlorine atom are preferable, and a fluorine atom is particularly preferably used. Accordingly, among the halogen-containing phthalonitriles represented by the general formula (1), a fluorine-containing phthalonitrile in which at least one of m Xs is a fluorine atom is preferably used. Therefore, the following description is given by taking fluorinated phthalonitrile as an example.
The position of the fluorine atom is not particularly limited.

Representative examples of the above-mentioned fluorine-containing phthalonitrile are as follows.

Tetrafluorophthalonitrile 4,5-difluorophthalonitrile 4-fluorophthalonitrile 5-fluorophthalonitrile 3-chloro-4,5,6-trifluorophthalonitrile 4-chloro-3, 5,6-trifluorophthalonitrile 3-amino-4,5,6-trifluorophthalonitrile 4-amino-3,5,6-trifluorophthalonitrile 3-hydroxy-4,5,6-tri Fluorophthalonitrile 4-hydroxy-3,5,6-trifluorophthalonitrile 3-methoxy-4,5,6-trifluorophthalonitrile 4-methoxy-3,5,6-trifluorophthalonitrile 3 , 4-Diamino-5,6-difluorophthalonitrile4,5-diamino-3,6-difluorophthalonitrile Tolyl 3,6-diamino-4,5-difluorophthalonitrile 3,4-dihydroxy-5,6-difluorophthalonitrile 4,5-dihydroxy-3,6-difluorophthalonitrile 3,6-dihydroxy- 4,5-difluorophthalonitrile, 3,4-dimethoxy-5,6-difluorophthalonitrile, 4,5-dimethoxy-3,6-difluorophthalonitrile, 3,6-dimethoxy-4,5-difluorophthalonitrile 3,6-difluoro-4,5-bisphenylthiophthalonitrile • 4,5,6-trifluoro-4-phenoxyphthalonitrile Of these, tetrafluorophthalonitrile is preferably used.

The phthalocyanine compound having at least one halogen atom on the benzene nucleus of the phthalocyanine skeleton, which is another starting material of the present invention, is represented by the general formula (2):

[0017]

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(Wherein X is a halogen atom, R is a hydrogen atom, a linear or branched alkyl group having 1 to 8 carbon atoms, an alkoxyl group having 1 to 8 carbon atoms, a hydroxyl group, a nitro group, a cyano group, Amino group, carboxyl group, acetyl group, alkyl (linear or branched alkyl group having 1 to 4 carbon atoms; the same applies hereinafter) ester group, aryl (benzene group or naphthalene ring aryl group; the same applies hereinafter) ester, thiol group , An alkylthioester, an arylthioester group, an arylthio group, or an aryloxy group, M represents a metal-free, metal, metal oxide or metal halide, and m is an integer of 1 to 16). Halogen phthalocyanine.

Here, “metal-free” means that there are two hydrogen atoms. Representative examples of the above metals include iron, magnesium, nickel, cobalt, copper, palladium, zinc, and the like. Representative examples of the metal oxide include titanyl (TiO) and vanadyl (VO). In addition, typical examples of the metal halide include aluminum chloride, aluminum iodide, indium chloride, germanium chloride, tin chloride, and silicon chloride.

The above substituents (including the halogen atom of X)
Need not all be the same, and may be substituted by different substituents. As the halogen atom for X, a fluorine atom and a chlorine atom are preferable, and a fluorine atom is particularly preferably used. Accordingly, among the halogen-containing phthalocyanine compounds represented by the general formula (2), a fluorine-containing phthalocyanine compound in which at least one of m Xs is a fluorine atom is preferable. Therefore, the following description is given by taking a fluorine-containing phthalocyanine compound as an example. The position of the fluorine atom is not particularly limited.

Representative examples of the above-mentioned fluorine-containing phthalocyanine compound are as follows.

Hexadecafluorophthalocyanine hexadecafluorovanadyl phthalocyanine hexadecafluorochloroaluminum phthalocyanine hexadecafluorocobalt phthalocyanine hexadecafluorocopper phthalocyanine hexadecafluoroiron phthalocyanine hexadecafluorolead phthalocyanine hexadecafluorozinc Phthalocyanine ・ Hexadecafluoromagnesium phthalocyanine ・ Hexadecafluorosilicon dichloride phthalocyanine ・ Hexadecafluorosilver phthalocyanine ・ Hexadecafluorosodium phthalocyanine ・ Hexadecafluorooxytin phthalocyanine Cyanine-Octafluorochloroaluminum phthalocyanine-Octafluorocobalt phthalocyanine-Octafluorocopper phthalocyanine-Octafluoroiron phthalocyanine-Octafluorolead phthalocyanine-Octafluorozinc phthalocyanine-Octafluoromagnesium phthalocyanine-Octafluorosilicon dichloride phthalocyanine-Octafluorosilver phthalocyanine-Octa Fluorosodium phthalocyanine, octafluorooxytin phthalocyanine, octafluorodichloride tin phthalocyanine, tetrafluorophthalocyanine, tetrafluorovanadyl phthalocyanine, tetrafluorochloroaluminum phthalocyanine, tetrafluorocobalt phthalocyanine, tetrafluorocopper phthalocyanine・ Tetrafluoroiron phthalocyanine ・ tetrafluorolead phthalocyanine ・ tetrafluorozinc phthalocyanine ・ tetrafluoromagnesium phthalocyanine ・ tetrafluorosilicon dichloride phthalocyanine ・ tetrafluorosilver phthalocyanine ・ tetrafluorosodium phthalocyanine ・ tetrafluorooxytin phthalocyanine ・ tetrafluorodichloride tin phthalocyanine Among them, hexadecafluorovanadyl phthalocyanine, octafluorovanadyl phthalocyanine, tetrafluorovanadyl phthalocyanine, hexadecafluorooxytin phthalocyanine, hexadecafluorodichloride tin phthalocyanine, octafluorooxytin phthalocyanine, octafluorodichloride tin phthalocyanine, tetraflu Oroxytin phthalocyanine and tetrafluorodichloride tin phthalocyanine are preferably used.

As the nucleophilic compound for reacting with the above fluorinated phthalonitrile or fluorinated phthalocyanine to obtain the corresponding substituted phthalonitrile or substituted phthalocyanine compound, any electron donor can be used. But typical examples are:
Examples include amino compounds, phenol compounds and thiol compounds.

The amino compound is represented by the general formula (3):

[0025]

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(Wherein R and R ′ are each independently a hydrogen atom, an alkyl group, an aryl group, an arylcarbonyl group, an aralkyl group, or a heterocyclic group).

The aryl group may have a substituent, and typical examples thereof include a phenyl group, a tolyl group, a xylyl group, a mesityl group, a cumenyl group, a biphenylyl group,
Examples include a naphthyl group, an anthryl group, and a phenanthryl group.

The aralkyl group may have a substituent, and typical examples thereof include a benzyl group, a phenethyl group and an α-methylbenzyl group. Among them, a benzyl group is preferred.

The heterocyclic group may have a substituent, and typical examples thereof include 2-furyl, 3-furyl, furfuryl, 2-thienyl, 3-thienyl, and 2-furyl. -Thenyl group, 3-thenyl group, 2-thenoyl group, 3
-Thenoyl group, 2-pyridyl group, 3-pyridyl group, 4-
Pyridyl group, 2-quinolyl group, 4-quinolyl group, 8-quinolyl group, 1-isoquinoyl group, piperidino group, morpholino group, 2-piperidyl group, 3-piperidyl group, 4-piperidyl group, 2-morpholinyl group, 3 -Morpholinyl group, indolyl group, isoindolyl group, 1H-indolyl group, indolinyl group, 1-pyrrolyl group, 2-pyrrolyl group, 3-pyrrolyl group, 2H-pyrroli-3-yl, 3H-
Examples thereof include pyrrol-2-yl, 2-oxazolyl group, 4-oxazolyl group, 5-oxazolyl group, and oxazinyl group.

Examples of the substituent which may be present on the above-mentioned aryl group, aralkyl group and heterocyclic group include, for example, halogen atom, hydroxyl group, acyl group, alkyl group, alkoxy group, halogenated alkyl group, halogenated alkoxy group. , Nitro group, amino group, alkylamino group, alkylcarbonylamino group, aryl group, arylamino group, arylcarbonylamino group, carbonyl group, alkoxycarbonyl group, alkylaminocarbonyl group, alkoxysulfonyl group, alkylthio group, carbamoyl group , An alkylaminoalkyloxycarbonyl group, a dialkylaminoalkyloxycarbonyl group, an alkoxycarbonylalkyloxycarbonyl group, an alkylaminocarbonylalkyloxycarbonyl group, an alkoxysulfonyl Le Kill oxycarbonyl group, an alkylsulfonyloxy group, an aryloxycarbonyl group, and aryloxy alkyl ether group can be exemplified, but the invention is not limited thereto. These substituents are an aryl group or an aralkyl group (benzene nucleus)
1 to 5 or 1 to a plurality of heterocyclic groups may be substituted on the heterocyclic ring, and the kind of these substituents may be the same or different when plurally substituted. One example is an aryl group substituted by 1 to 3 alkyl groups having 1 to 4 carbon atoms, an aralkyl group or a heterocyclic group, and 1 to 4 alkoxy groups having 1 to 4 carbon atoms.
A substituted or unsubstituted aryl, aralkyl or heterocyclic group, chlorine atom, fluorine atom or other halogen atom
Examples thereof include a 5-substituted aryl group, aralkyl group and heterocyclic group. Some of the above substituents are shown below with more specific examples.

First, among the substituents which may be present in the above-mentioned aryl group, aralkyl group and heterocyclic group, the halogen atom means a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, and among them, bromine is preferred. Atom and iodine atom.

Among the substituents that may be present on the aryl group, aralkyl group and heterocyclic group, acyl groups include acetyl, ethylcarbonyl, propylcarbonyl, butylcarbonyl, pentylcarbonyl, hexylcarbonyl and the like. Benzoyl group, pt-butylbenzoyl group and the like.

The alkyl group among the substituents which may be present in the above-mentioned aryl group, aralkyl group and heterocyclic group is a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms. , Preferably having 1 carbon atom
8 alkyl groups. Specifically, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, neopentyl, 1,1, 2-dimethylpropyl group, n-hexyl group, cyclohexyl group, 1,3-dimethylbutyl group, 1-isopropylpropyl group, 1,2-dimethylbutyl group, n-
Heptyl group, 1,4-dimethylpentyl group, 2-methyl 1-isopropylpropyl group, 1-ethyl-3-methylbutyl group, n-octyl group, 2-ethylhexyl group, 3
-Methyl-1-isopropylbutyl group, 2-methyl-1
-Isopropyl group, 1-tert-butyl-2-methylpropyl group, n-nonyl group, 3,5,5-trimethylhexyl group, n-decyl group, dodecyl group, undecyl group,
Tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonidecyl, eicosyl, lauryl, stearyl, alkoxyalkyl, alkoxyalkoxyalkyl, alkoxyalkoxyalkoxyalkyl,
Alkylaminoalkyl group, dialkylaminoalkyl group, alkoxycarbonylalkyl group, alkylaminocarbonylalkyl group, alkoxysulfonylalkyl group, 3-methyl-2-butyl group, 2,3-dimethyl-2
-Butyl group, 3,3-dimethyl-2-butyl group, 2-methyl-3-pentyl group, 3-methyl-2-pentyl group,
4-methyl-2-pentyl group, 2,2-dimethyl-3-
Pentyl group, 2,3-dimethyl-3-pentyl group, 2,
4-dimethyl-3-pentyl group, 4,4-dimethyl-2
-Pentyl group, 2-methyl-3-hexyl group, 5-methyl-2-hexyl group, 2,3,3-trimethyl-2-butyl group, 3,4-dimethyl-2-pentyl group, 2,3-
Dimethyl-2-pentyl group, 3,3-dimethyl-2-pentyl group, 3-ethyl-2-pentyl group, 4-methyl-
3-hexyl group, 3-methyl-2-hexyl group, 2,2
-Dimethyl-3-hexyl group, 2,3-dimethyl-2-
Hexyl group, 2,5-dimethyl-2-hexyl group, 2,
5-dimethyl-3-hexyl group, 3,4-dimethyl-3
-Hexyl group, 3,5-dimethyl-3-hexyl group, 3
-Ethyl-2-methyl-3-pentyl group, 4-methyl-
3-heptyl group, 5-methyl-2-heptyl group, 5-methyl-3-heptyl group, 6-methyl-2-heptyl group,
6-methyl-3-heptyl group, 2,3,4-trimethyl-2-pentyl group, 2,3,4-trimethyl-3-pentyl group, 2-methyl-3-ethyl-2-pentyl group, 3
-Ethyl-3-methyl-2-pentyl group, 3-ethyl-
4-methyl-2-pentyl group, 2-ethyl-3-methyl-2-pentyl group, 2,3-dimethyl-3-hexyl group, 2,4-dimethyl-3-hexyl group, 4,5-dimethyl- 3-hexyl group, 4-ethyl-3-hexyl group,
3-ethyl-2-hexyl group, 3,4-dimethyl-2-
Hexyl group, 3,5-dimethyl-2-hexyl group, 2-
Methyl-3-heptyl group, 3-methyl-2-heptyl group, 3-methyl-4-heptyl group, 2,6-dimethyl-
4-heptyl group, 3-ethyl-2,2-dimethyl-3-
Pentyl group, 2-methyl-3-octyl group, 3,5-dimethyl-4-heptyl group, 2,4-dimethyl-3-ethyl-3-pentyl group, 2,3-dimethyl-4-heptyl group, 4 -Ethyl-2-methyl-3-hexyl group, 2,
4,5-trimethyl-3-hexyl group, 3,4,5-trimethyl-2-hexyl group, 3-ethyl-4-methyl-
2-hexyl group, 4-ethyl-3-methyl-2-hexyl group, 2,3-dimethyl-4-heptyl group, 3,7-dimethyl-3-octyl group, 3,7-dimethyl-4-octyl group 2,6-dimethyl-3-octyl group, 2-methyl-3-undecyl group, 7-ethyl-2-methyl-4-
Examples include an undecyl group, a 2-methyl-3-tridecyl group, and a 2-methyl-4-tridecyl group.

Among the substituents that may be present on the aryl group, aralkyl group and heterocyclic group, the alkoxy group is a straight-chain, branched-chain or cyclic alkoxy group having 1 to 20 carbon atoms. Is from 1 to 8 carbon atoms
Alkoxy groups. Specifically, methoxy, ethoxy, n-propoxy, isopropoxy, n-
Butoxy group, isobutoxy group, sec-butoxy group, t
ert-butoxy group, n-pentyloxy group, isopentyloxy group, neopentyloxy group, 1,2-dimethyl-propoxy group, n-hexyloxy group, cyclohexyloxy group, 1,3-dimethylbutoxy group, 1- Isopropylpropoxy group, 1,2-dimethylbutoxy group,
n-heptyloxy group, 1,4-dimethylpentyloxy group, 2-methyl-1-isopropylpropoxy group, 1
-Ethyl-3-methylbutoxy group, n-octyloxy group, 2-ethylhexyloxy group, 3-methyl-1-isopropylbutoxy group, 2-methyl-1-isopropoxy group, 1-tert-butyl-2-methyl In addition to a propoxy group, an n-nonyloxy group, an n-decyloxy group, a methoxymethoxy group, a methoxyethoxy group, an ethoxyethoxy group, a propoxyethoxy group, a butoxyethoxy group, a 3-methoxypropyloxy group, and a 3-ethoxypropyloxy group , An alkoxyalkoxy group such as a dimethoxymethoxy group, a diethoxymethoxy group, a dimethoxyethoxy group, a diethoxyethoxy group or the like, an alkoxyalkoxyalkoxy group such as a methoxyethoxyethoxy group, an ethoxyethoxyethoxy group, or a butyloxyethoxyethoxy group, or an alkoxy group Turkey alkoxy alkoxyalkoxy group, chloromethoxy group, 2,2,2 b ethoxy group, a trifluoromethoxy group, 1, 1, 1,
Examples thereof include an alkylaminoalkoxy group such as a 3,3-hexafluoro-2-propyloxy group, a dimethylaminoethoxy group, and a diethylaminoethoxy group, a dialkylaminoalkoxy group, and a hydroxyalkoxy group.

Of the substituents that may be present on the aryl group, aralkyl group and heterocyclic group, a halogenated alkyl group means a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms. Partially halogenated, preferably partly halogenated alkyl having 1 to 8 carbon atoms. Specifically, a chloromethyl group, a bromomethyl group, a dichloromethyl group, a dibromomethyl group, a trichloromethyl group, a tribromomethyl group, a 1-chloroethyl group, a 1-bromoethyl group,
Chloroethyl group, 2-bromoethyl group, 1,2-dichloroethyl group, 1,2-dibromoethyl group, 1,1-dichloroethyl group, 1,1-dibromoethyl group, 2,2-dichloroethyl group, 2, 2-dibromoethyl group, 1,1,
2-trichloroethyl group, 1,1,2-tribromoethyl group, 1,2,2-trichloroethyl group, 1,2,2-
Tribromoethyl group, 1-chloropropyl group, 1-bromopropyl group, 2-chloro-1-propyl group, 2-bromo-1-propyl group, 3-chloro-1-propyl group, 3
-Bromo-1-propyl group, 1-chloro-2-propyl group, 1-bromo-2-propyl group, 2,3-dichloro-
1-propyl group, 2,3-dibromo-1-propyl group,
1,3-dichloro-2-propyl group, 1,3-dibromo-2-propyl group, 4-chloro-1-butyl group, 4-bromo-1-butyl group, 1-chloro-1-butyl group, 1 −
Bromo-1-butyl group, 1-chloro-2-butyl group, 1
-Bromo-2-butyl group, 2-chloro-1-butyl group,
2-bromo-1-butyl group, 1,3-dichloro-2-butyl group, 1,3-dibromo-2-butyl group, 1,4-dichloro-2-butyl group, 1,4-dibromo-2- Butyl group, 5-chloro-1-pentyl group, 5-bromo-1-pentyl group, 1-chloro-1-pentyl group, 1-bromo-
1-pentyl group, 6-chloro-1-hexyl group, 6-bromo-1-hexyl group, 1-chloro-1-hexyl group,
1-bromo-1-hexyl group, 7-chloro-1-heptyl group, 7-bromo-1-heptyl group, 1-chloro-1-
Heptyl group, 1-bromo-1-heptyl group, 8-chloro-1-octyl group, 8-bromo-1-octyl group, 1-
Chloro-1-octyl group, 1-bromo-1-octyl group, 9-chloro-1-nonyl group, 9-bromo-1-nonyl group, 1-chloro-1-nonyl group, 1-bromo-1-nonyl Group, 10-chloro-1-decyl group, 10-bromo-
1-decyl group, 1-chloro-1-decyl group, 1-bromo-1-decyl group, 11-chloro-1-undecyl group, 1
1-bromo-1-undecyl group, 1-chloro-1-undecyl group, 1-bromo-1-undecyl group, 12-chloro-1-dodecyl group, 12-bromo-1-dodecyl group,
A 1-chloro-1-dodecyl group, a 1-bromo-1-dodecyl group and the like are shown.

Of the substituents which may be present on the aryl, aralkyl and heterocyclic groups, a halogenated alkoxy group means a linear, branched or cyclic alkoxy group having 1 to 20 carbon atoms. Partially halogenated, preferably partly halogenated alkoxy having 1 to 8 carbon atoms. Specifically, chloromethoxy, bromomethoxy, dichloromethoxy, dibromomethoxy, trichloromethoxy, tribromomethoxy, 1-chloroethoxy, 1
-Bromoethoxy group, 2-chloroethoxy group, 2-bromoethoxy group, 1,2-dichloroethoxy group, 1,2-
Dibromoethoxy group, 1,1-dichloroethoxy group,
1,1-dibromoethoxy group, 2,2-dichloroethoxy group, 2,2-dibromoethoxy group, 1,1,2-trichloroethoxy group, 1,1,2-tribromoethoxy group, 1,2,2 -Trichloroethoxy group, 1,2,2-
Tribromoethoxy group, 1-chloropropoxy group, 1-
Bromopropoxy group, 2-chloro-1-propoxy group,
2-bromo-1-propoxy group, 3-chloro-1-propoxy group, 3-bromo-1-propoxy group, 1-chloro-2-propoxy group, 1-bromo-2-propoxy group,
2,3-dichloro-1-propoxy group, 2,3-dibromo-1-propoxy group, 1,3-dichloro-2-propoxy group, 1,3-dibromo-2-propoxy group, 4-chloro-1- Butoxy group, 4-bromo-1-butoxy group,
1-chloro-1-butoxy group, 1-bromo-1-butoxy group, 1-chloro-2-butoxy group, 1-bromo-2-
Butoxy group, 2-chloro-1-butoxy group, 2-bromo-1-butoxy group, 1,4-dichloro-2-butoxy group, 1,4-dibromo-2-butoxy group, 5-chloro-
1-pentyloxy group, 5-bromo-1-pentyloxy group, 1-chloro-1-pentyloxy group, 1-bromo-1-pentyloxy group, 6-chloro-1-hexyloxy group, 6-bromo- 1-hexyloxy group, 1-chloro-1-hexyloxy group, 1-bromo-1-hexyloxy group, 7-chloro-1-heptyloxy group, 7-bromo-1-heptyloxy group, 1-chloro- 1-heptyloxy group, 1-bromo-1-heptyloxy group, 8-
Chloro-1-octyloxy group, 8-bromo-1-octyloxy group, 1-chloro-1-octyloxy group, 1
-Bromo-1-octyloxy group, 9-chloro-1-nonyloxy group, 9-bromo-1-nonyloxy group, 1-
Chloro-1-nonyloxy group, 1-bromo-1-nonyloxy group, 10-chloro-1-decyloxy group, 10-
Bromo-1-decyloxy group, 1-chloro-1-decyloxy group, 1-bromo-1-decyloxy group, 11-chloro-1-undecyloxy group, 11-bromo-1-undecyloxy group, 1-chloro -1-undecyloxy group, 1-bromo-1-undecyloxy group, 12-chloro-1-dodecyloxy group, 12-bromo-1-dodecyloxy group, 1-chloro-1-dodecyloxy group, 1 −
Bromo-1-dodecyloxy group, chloromethoxyethoxy group, bromomethoxyethoxy group, 1-chloroethoxyethoxy group, 1-bromoethoxyethoxy group, 1-chloro-3 ', 6'-oxaheptyloxy group, 1-bromo -3 ', 6'-oxaheptyloxy group, 1-chloro-
3 ', 6'-oxaoctyloxy group, 1-bromo-
3 ', 6'-oxaoctyloxy group, 1-chloro-
3 ', 6', 9'-oxadecyloxy group, 1-bromo-3 ', 6', 9'-oxadecyloxy group, 1-chloro-3 ', 6', 9 ', 12'-oxatri Decyloxy group, 1-bromo-3 ', 6', 9 ', 12'-oxatridecyloxy group, chloromethoxypropoxy group, bromomethoxypropoxy group, 1-chloroethoxypropoxy group, 1-bromoethoxypropoxy group, 1-chloro-4 ', 8'-oxanonyloxy group, 1-bromo-
4 ', 8'-oxanonyloxy group, 1-chloro-
4 ', 8'-oxadecyloxy group, 1-bromo-
And 4 ', 8'-oxadecyloxy.

Of the substituents which may be present on the aryl, aralkyl and heterocyclic groups, an alkylamino group means an alkylamino group having an alkyl moiety having 1 to 20 carbon atoms, preferably a carbon atom. Numbers 1-8
It is an alkylamino group having two alkyl moieties. Specifically, methylamino group, ethylamino group, n-propylamino group, n-butylamino group, sec-butylamino group, n-pentylamino group, n-hexylamino group, n-heptylamino group, n -Octylamino group, 2
-Ethylhexylamino group, dimethylamino group, diethylamino group, di-n-propylamino group, di-n-butylamino group, di-sec-butylamino group, di-n-pentylamino group, di-n-hexylamino Group, di-n-
A heptylamino group, a di-n-octylamino group, an n-decylamino group, and the like.

Among the substituents that may be present on the aryl group, aralkyl group and heterocyclic group, an alkoxycarbonyl group means a group having 1 to 8 carbon atoms which may contain a hetero atom in the alkyl group of the alkoxy group. , Preferably 1 to 5 alkoxycarbonyl, or 3 to 8 carbon atoms which may contain heteroatoms, preferably 5 to 5 carbon atoms.
Shows 8 cyclic alkoxycarbonyl. In particular,
Methoxycarbonyl group, ethoxycarbonyl group, n-propoxycarbonyl group, isopropoxycarbonyl group,
n-butoxycarbonyl group, isobutoxycarbonyl group, sec-butoxycarbonyl group, tert-butoxycarbonyl group, n-pentyloxycarbonyl group, isopentyloxycarbonyl group, neopentyloxycarbonyl group, 1,2-dimethyl-propyloxy Carbonyl group, n-hexyloxycarbonyl group, cyclohexyloxycarbonyl group, 1,3-dimethyl-butyloxycarbonyl group, 1-isopropylpropyloxycarbonyl group, 1,2-dimethylbutyloxycarbonyl group, n-heptyloxycarbonyl group 1,4-dimethylpentyloxycarbonyl group, 2-methyl-1-isopropylpropyloxycarbonyl group, 1-ethyl-3
-Methylbutyloxycarbonyl group, n-octyloxycarbonyl group, 2-ethylhexyloxycarbonyl group, 3-methyl-1-isopropylbutyloxycarbonyl group, 2-methyl-1-isopropyloxycarbonyl group, 1-tert-butyl- 2-methylpropyloxycarbonyl group, n-nonyloxycarbonyl group, methoxymethoxycarbonyl group, methoxyethoxycarbonyl group, ethoxyethoxycarbonyl group, propoxyethoxycarbonyl group, butoxyethoxycarbonyl group, diethylaminoethoxycarbonyl group, methylthioethoxycarbonyl group, Methoxypropyloxycarbonyl group, γ-methoxypropoxycarbonyl group, γ-ethoxypropoxycarbonyl group, methoxyethoxyethoxycarbonyl group, ethoxy Siethoxyethoxycarbonyl group, dimethoxymethoxycarbonyl group, diethoxymethoxycarbonyl group, dimethoxyethoxycarbonyl group,
Diethoxyethoxycarbonyl group, chloromethoxycarbonyl group, trichloroethoxycarbonyl group, trifluoromethoxycarbonyl group, hexafluoro-2-propoxycarbonyl group, (3,6,9-oxa) decyloxycarbonyl group, tetrahydrofurfuryloxycarbonyl Group, pyranoxycarbonyl group, piperidinooxycarbonyl group, piperidinoethoxycarbonyl group, tetrahydropyrroleoxycarbonyl group, tetrahydropyranmethoxycarbonyl group, tetrahydrothiophenoxycarbonyl group, cyclohexyloxycarbonyl group and the like.

Among the substituents that may be present on the aryl group, aralkyl group and heterocyclic group, the halogenated alkoxycarbonyl group includes a carbon atom which may contain a hetero atom in the alkyl group of the alkoxy group. Alkoxycarbonyl groups having 1 to 8, preferably 1 to 5 carbon atoms, are partially halogenated or 3 to 8, preferably 5 carbon atoms which may contain hetero atoms. A part of ~ 8 cyclic alkoxycarbonyl groups is halogenated. In particular,
A chloromethoxycarbonyl group, a bromomethoxycarbonyl group, a 2-chloroethoxycarbonyl group, a 2-bromoethoxycarbonyl group, a 3-chloro-1-propoxycarbonyl group, a 3-bromo-1-propoxycarbonyl group,
2-chloro-1-propoxycarbonyl group, 2-bromo-1-propoxycarbonyl group, 1-chloro-2-propoxycarbonyl group, 1-bromo-2-propoxycarbonyl group, 2,3-dichloro-1-propoxycarbonyl Group, 2,3-dibromo-1-propoxycarbonyl group, 1,3-dichloro-2-propoxycarbonyl group,
1,3-dibromo-2-propoxycarbonyl group, 1-
Chloro-2-butoxycarbonyl group, 1-bromo-2-
Butoxycarbonyl group, 2-chloro-1-butoxycarbonyl group, 2-bromo-1-butoxycarbonyl group, 4
-Chloro-1-butoxycarbonyl group, 4-bromo-1
-Butoxycarbonyl group, 1,4-dichloro-2-butoxycarbonyl group, 1,4-dibromo-2-butoxycarbonyl group, 5-chloro-1-pentyloxycarbonyl group, 5-bromo-1-pentyloxycarbonyl group ,
6-chloro-1-hexyloxycarbonyl group, 6-bromo-1-hexyloxycarbonyl group, 7-chloro-
1-heptyloxycarbonyl group, 7-bromo-1-heptyloxycarbonyl group, 8-chloro-1-octyloxycarbonyl group, 8-bromo-1-octyloxycarbonyl group, 9-chloro-1-nonyloxycarbonyl group , 9-bromo-1-nonyloxycarbonyl group, 1
0-chloro-1-decyloxycarbonyl group, 10-bromo-1-decyloxycarbonyl group, 11-chloro-
1-undecyloxycarbonyl group, 11-bromo-1
-Undecyloxycarbonyl group, 12-chloro-1-
And a dodecyloxycarbonyl group, a 12-bromo-1-dodecyloxycarbonyl group, and the like.

Among the substituents which may be present in the above-mentioned aryl group, aralkyl group and heterocyclic group, the aryl group may be any aryl group which may have a substituent. Specifically, a phenyl group, an o-methylphenyl group, an m-methylphenyl group, a p-methylphenyl group,
o-ethylphenyl group, m-ethylphenyl group, p-ethylphenyl group, o-propylphenyl group, m-propylphenyl group, p-propylphenyl group, o-isopropylphenyl group, m-isopropylphenyl group, p- Isopropylphenyl group, o-butylphenyl group, m-butylphenyl group, p-butylphenyl group, o-tert
-Butylphenyl group, m-tert-butylphenyl group, p-tert-butylphenyl group, o-methoxyphenyl group, m-methoxyphenyl group, p-methoxyphenyl group, o-ethoxyphenyl group, m-ethoxyphenyl group P-ethoxyphenyl group, o-propoxyphenyl group, m-propoxyphenyl group, p-propoxyphenyl group, o-isopropoxyphenyl group, m-isopropoxyphenyl group, p-isopropoxyphenyl group, o
-Butoxyphenyl group, m-butoxyphenyl group, p-
Butoxyphenyl group, 2,6-dimethylphenyl group,
2,6-diethylphenyl group, 2,6-dipropylphenyl group, 2,6-diisopropylphenyl group, 2,6-
Dibutylphenyl group, 2,6-ditert-butylphenyl group, 2,6-dimethoxyphenyl group, 2,6-diethoxyphenyl group, 2,6-dipropoxyphenyl group,
2,6-diisopropoxyphenyl group, 2,6-dibutoxyphenyl group, 2-fluorophenyl group, 2-chlorophenyl group, 2-bromophenyl group, 2-iodophenyl group, 3-fluorophenyl group, 3- Chlorophenyl group, 3-bromophenyl group, 3-iodophenyl group, 4
-Fluorophenyl group, 4-chlorophenyl group, 4-bromophenyl group, 4-iodophenyl group, 2,3-difluorophenyl group, 2,3-dichlorophenyl group, 2,
4-difluorophenyl group, 2,4-dichlorophenyl group, 2,4-dibromophenyl group, 2,5-difluorophenyl group, 2,5-dichlorophenyl group, 2,6-difluorophenyl group, 2,6-dichlorophenyl group ,
2,6-dibromophenyl group, 3,4-difluorophenyl group, 3,4-dichlorophenyl group, 3,5-difluorophenyl group, 3,5-dichlorophenyl group, 2,
3,4-trifluorophenyl group, 2,3,4-trichlorophenyl group, 2,3,5-trifluorophenyl group, 2,3,5-trichlorophenyl group, 2,3,6-
Trifluorophenyl group, 2,3,6-trichlorophenyl group, 2,4,6-trifluorophenyl group, 2,
4,6-trichlorophenyl group, 2,4,6-tribromophenyl group, 2,4,6-triiodophenyl group,
And 2,3,5,6-tetrafluorophenyl group, pentafluorophenyl group, pentachlorophenyl group and the like.

On the other hand, the alkyl group may be linear or branched, and may be substituted or unsubstituted. In the case of an unsubstituted alkyl group, the alkyl group has 1 to 20 carbon atoms. Alternatively, it is a branched (including a cyclic alkyl group) alkyl group, preferably an alkyl group having 1 to 8 carbon atoms. Representative examples of the unsubstituted alkyl group are as follows.

Methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-
Butyl group, tert-butyl group, n-pentyl group, isopentyl group, neopentyl group, 1,2-dimethylpropyl group, n-hexyl group, cyclohexyl group, 1,3-dimethylbutyl group, 1-isopropylpropyl group, 1 , 2
-Dimethylbutyl group, n-heptyl group, 1,4-dimethylpentyl group, 2-methyl 1-isopropylpropyl group, 1-ethyl-3-methylbutyl group, n-octyl group, 2-ethylhexyl group, 3-methyl- 1-isopropylbutyl group, 2-methyl-1-isopropyl group, 1-
tert-butyl-2-methylpropyl group, n-nonyl group, 3,5,5-trimethylhexyl group, n-decyl group, dodecyl group, undecyl group, tridecyl group, tetradecyl group, pentadecyl group, hexadecyl group, heptadecyl group Octadecyl group, nonidecyl group, eicosyl group, lauryl group, stearyl group, 3-methyl-2-butyl group, 2,3-dimethyl-2-butyl group, 3,3-dimethyl-2-butyl group, 2-methyl -3-pentyl group, 3
-Methyl-2-pentyl group, 4-methyl-2-pentyl group, 2,2-dimethyl-3-pentyl group, 2,3-dimethyl-3-pentyl group, 2,4-dimethyl-3-pentyl group, 4,4-dimethyl-2-pentyl group, 2-methyl-3-hexyl group, 5-methyl-2-hexyl group, 2,
3,3-trimethyl-2-butyl group, 3,4-dimethyl-2-pentyl group, 2,3-dimethyl-2-pentyl group, 3,3-dimethyl-2-pentyl group, 3-ethyl-
2-pentyl group, 4-methyl-3-hexyl group, 3-methyl-2-hexyl group, 2,2-dimethyl-3-hexyl group, 2,3-dimethyl-2-hexyl group, 2,5-dimethyl -2-hexyl group, 2,5-dimethyl-3-hexyl group, 3,4-dimethyl-3-hexyl group, 3,5-
Dimethyl-3-hexyl group, 3-ethyl-2-methyl-
3-pentyl group, 4-methyl-3-heptyl group, 5-methyl-2-heptyl group, 5-methyl-3-heptyl group,
6-methyl-2-heptyl group, 6-methyl-3-heptyl group, 2,3,4-trimethyl-2-pentyl group, 2,
3,4-trimethyl-3-pentyl group, 2-methyl-3
-Ethyl-2-pentyl group, 3-ethyl-3-methyl-
2-pentyl group, 3-ethyl-4-methyl-2-pentyl group, 2-ethyl-3-methyl-2-pentyl group, 2,
3-dimethyl-3-hexyl group, 2,4-dimethyl-3
-Hexyl group, 4,5-dimethyl-3-hexyl group, 4
-Ethyl-3-hexyl group, 3-ethyl-2-hexyl group, 3,4-dimethyl-2-hexyl group, 3,5-dimethyl-2-hexyl group, 2-methyl-3-heptyl group,
3-methyl-2-heptyl group, 3-methyl-4-heptyl group, 2,6-dimethyl-4-heptyl group, 3-ethyl-2,2-dimethyl-3-pentyl group, 2-methyl-3
-Octyl group, 3,5-dimethyl-4-heptyl group,
2,4-dimethyl-3-ethyl-3-pentyl group, 2,
3-dimethyl-4-heptyl group, 4-ethyl-2-methyl-3-hexyl group, 2,4,5-trimethyl-3-hexyl group, 3,4,5-trimethyl-2-hexyl group,
3-ethyl-4-methyl-2-hexyl group, 4-ethyl-3-methyl-2-hexyl group, 2,3-dimethyl-4
-Heptyl group, 3,7-dimethyl-3-octyl group,
3,7-dimethyl-4-octyl group, 2,6-dimethyl-3-octyl group, 2-methyl-3-undecyl group, 7
-Ethyl-2-methyl-4-undecyl, 2-methyl-3-tridecyl and 2-methyl-4-tridecyl.

In the case of a substituted alkyl group, typical examples of the substituent include a halogen atom, an alkoxy group, a hydroxyalkoxy group, an alkoxyalkoxy group, a halogenated alkoxy group, a nitro group, an amino group, an alkylamino group, an alkoxycarbonyl group. , An alkylaminocarbonyl group, an alkoxysulfonyl group and the like. Specific examples of these substituents are the same as the substituents that may be present in the above-mentioned aryl group, aralkyl group and heterocyclic group.

Of the above amino compounds, aniline is preferably used.

The phenol compound is represented by the general formula (4):

[0046]

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(Wherein R is a hydrogen atom, a linear or branched alkyl group having 1 to 8 carbon atoms, a hydroxyl group, a halogen atom, a nitro group, a cyano group, an amino group, a carboxyl group, an acetyl group, an alkyl ( A straight-chain or branched-chain alkyl group having 1 to 4 carbon atoms; the same applies hereinafter) ester group, aryl (benzene group or naphthalene ring aryl group; same applies hereinafter) ester, thiol group, alkylthioester, or arylthioester group; m is an integer of 0 to 5). The substituents need not all be the same, and different substituents may be substituted.

The following are typical examples of the phenol compound.

Phenol 2-methylphenol 3-methylphenol 4-methylphenol 2-ethylphenol 3-ethylphenol 4-ethylphenol 2,3-dichlorophenol 2,4-dichlorophenol 2,5-dichlorophenol ・ 2,6-dichlorophenol ・ 3,4-dichlorophenol ・ 3,5-dichlorophenol ・ 2,3-difluorophenol ・ 2,4-difluorophenol ・ 2,5-difluorophenol ・ 2 3,6-difluorophenol, 3,4-difluorophenol, 3,5-difluorophenol, 2-fluoro-4-nitrophenol, 3-fluoro-4-nitrophenol, 4-fluoro-2-nitrophenol, 5-fluoro -2-Nitrophenol ・, 4-Dinitrophenol ・ 2,5-dinitrophenol ・ 2,6-dinitrophenol ・ 2-bromophenol ・ 3-bromophenol ・ 4-bromophenol ・ 4-bromoresorcinol ・ 4-chlororesorcinol ・ 4-fluororesorcinol ・2-amino-3-nitrophenol ・ 2-amino-4-nitrophenol ・ 2-amino-5-nitrophenol ・ 4-amino-2-nitrophenol ・ 4-amino-3-nitrophenol ・ 2-tert-butylphenol -3-tert-butylphenol-4-tert-butylphenol-4-isopropyl-3-methylphenol-5-isopropyl-3-methylphenol-salicylic acid The thiol compound is represented by the general formula (5):

[0050]

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(Wherein R is a hydrogen atom, a linear or branched alkyl group having 1 to 8 carbon atoms, a hydroxyl group, a halogen atom, a nitro group, a cyano group, an amino group, a carboxyl group, an acetyl group, an alkyl ( A straight-chain or branched-chain alkyl group having 1 to 4 carbon atoms; the same applies hereinafter) ester group, aryl (benzene group or naphthalene ring aryl group; same applies hereinafter) ester, thiol group, alkylthioester, or arylthioester group; m is an integer of 0 to 5). The substituents need not all be the same, and different substituents may be substituted.

Representative examples of the thiol compound are as follows.

Benzenethiol 2-methylthiophenol 3-methylthiophenol 4-methylthiophenol 2-bromothiophenol 3-bromothiophenol 4-bromothiophenol 2-chlorothiophenol 3-chlorothio Phenol ・ 4-chlorothiophenol ・ 2-fluorothiophenol ・ 3-fluorothiophenol ・ 4-fluorothiophenol ・ 4-hydroxythiophenol ・ 1,3-dithiol ・ 1,2-dithiol ・ 2-aminothiophenol ・3-Aminothiophenol / 4-aminothiophenol In the present invention, the above-mentioned fluorine-containing phthalonitrile or fluorine-containing phthalocyanine is reacted with a nucleophilic compound such as an amino compound, a phenol compound or a thiol compound. The desired phthalonitrile or phthalocyanine compound containing a substituent is obtained by a nucleophilic substitution reaction in a medium.
In order to trap by-produced hydrogen fluoride, this nucleophilic substitution reaction is preferably performed in the presence of an alkaline earth metal compound.

The alkaline earth metal compound is not particularly limited as long as it can effectively trap hydrogen fluoride in the reaction solvent. The alkaline earth metal compound may be an oxide, hydroxide or organic compound of an alkaline earth metal. Salts, inorganic salts and the like can be used. Representative examples include calcium compounds such as calcium acetate, calcium acetylacetonate, calcium carbonate, calcium phosphate, calcium silicate, calcium citrate, calcium formate, calcium hydroxide, calcium iodide, calcium oxalate, calcium oxide and calcium stearate. Magnesium acetate;
Magnesium compounds such as magnesium acetylacetonate, magnesium carbonate, magnesium phosphate, magnesium silicate, magnesium citrate, magnesium formate, magnesium hydroxide, magnesium iodide, magnesium oxalate, magnesium oxide and magnesium stearate; barium acetate, barium acetate Barium compounds such as acetylacetonate, barium carbonate, barium phosphate, barium silicate, barium citrate, barium formate, barium hydroxide, barium iodide, barium oxalate, barium oxide and barium stearate;
Strontium compounds such as strontium acetate, strontium acetylacetonate, strontium carbonate, strontium phosphate, strontium silicate, strontium citrate, strontium formate, strontium hydroxide, strontium iodide, strontium oxalate, strontium oxide and strontium stearate. Can be mentioned. One of these may be used alone, or two or more of them may be appropriately mixed and used as long as they do not affect each other.

Among the above alkaline earth metal compounds,
The calcium salt in the calcium compound is useful because it traps hydrogen fluoride and becomes stable calcium fluoride (CaF ₂ ). Use of an alkaline earth metal carbonate is advantageous because no acid remains. In particular, calcium carbonate (CaCO ₃ ) is preferred. In this case, since the by-produced water may have an adverse effect, it is desirable to azeotropically distill the water with the reaction solvent.

Therefore, the reaction solvent used in the present invention is:
Desirably, it azeotropes with water or has a higher boiling point than water. Among the alkaline earth metal compounds, calcium carbonate is particularly preferred.

As the alkaline earth metal compound, either a naturally occurring compound or a chemically synthesized compound can be used. For example, in the case of the above-mentioned calcium carbonate, heavy calcium carbonate obtained by pulverizing what is mined as limestone and classifying it by a sieve or the like can be exemplified as a naturally occurring calcium carbonate. Examples of chemically synthesized products include light calcium carbonate obtained by roasting limestone and then carbonation, and calcium carbonate obtained by an aqueous solution reaction of calcium chloride and carbonic acid.

The amount of the alkaline earth metal compound added is
It is preferable that hydrogen fluoride generated by the nucleophilic substitution reaction can be promptly reacted with the alkaline earth metal compound and trapped. For example, as a nucleophile compound,
When the amino compound represented by the general formula (3) is used, an amount corresponding to the number of the amino substituents (—NRR ′) may be added. In the reaction for substituting one fluorine atom in the fluorinated phthalonitrile or the fluorinated phthalocyanine compound, the reaction is carried out with respect to 1 mol of the phthalonitrile or the phthalocyanine compound represented by the general formula (1) or (2). , Usually 0.4 to 5 times, preferably 1 to 3 times.
The alkaline earth metal compound may be used in a molar amount, particularly preferably in a range of 1.1 to 1.5 molar times. Therefore,
When substituting n fluorine atoms, these n
It is preferable to use it in the range of twice. If the amount of the alkali metal compound is too small, the generated hydrogen fluoride cannot be sufficiently trapped. In addition, even if used in a large amount, no further effect corresponding to excessive addition is obtained,
In addition to being industrially uneconomical, an excessive amount of calcium carbonate may inhibit the nucleophilic substitution reaction.

In the present invention, after completion of the nucleophilic substitution reaction, the reaction mixture is filtered to separate and remove solids.

The solid matter is separated from the reaction mixture by filtration.
The temperature at the time of removal (temperature of the reaction mixture) is 10 to 15
0 ° C, preferably 40 to 120 ° C, particularly preferably 50 ° C.
It can be appropriately selected from the range of -100 ° C. If the temperature is too low, the viscosity of the reaction mixture increases, and the filtration takes time. If the temperature is too high, the nucleophilic substitution reaction may proceed in the filtration step. Therefore, in the present invention, it is preferable to separate and remove solids from the reaction mixture by hot filtration at 40 ° C. or higher.

When an alkaline earth metal is used, the generated fluoride varies depending on the alkaline earth metal compound used, but examples thereof include CaF ₂ , MgF ₂ , and BeF ₂ . Since these are insoluble in the solvent, they can be easily removed from the reaction system by filtration. Unreacted alkaline earth metal compounds, such as calcium carbonate, hardly dissolve in the solvent, and thus can be easily removed by filtration.

The reaction solvent used in the present invention is not particularly limited as long as it is a solvent inert to the nucleophilic substitution reaction. However, as described above, carbonate, which is one of the preferable alkaline earth metal compounds, is used. In the case of using a salt, it is considered that water produced as a by-product may have an adverse effect. Therefore, it is preferable that such water is azeotropically distilled off. Those having a high boiling point are desirable. As such a reaction solvent, the amino compound itself represented by the general formula (3) used as a nucleophilic compound as a raw material can be used. In addition, for example, benzonitrile, tri-n-butylamine,
Tri-n-octylamine, N, N-dimethylaniline, N, N-diethylaniline, N, N-dimethylacetamide, toluene, xylene, ethylbenzene, 1-
Methyl naphthalene, 1-ethyl naphthalene, dimethyl naphthalene, tetrachloroethane, chlorobenzene, o-
Dichlorobenzene, m-dichlorobenzene, 1,2,4
-Trichlorobenzene, 1-chloronaphthalene, sulfolane, dimethylsulfoxide and the like can be used. One of these may be used alone, or two or more of them may be used as an appropriate mixture as long as they do not affect each other.

The amount of the reaction solvent used is not particularly limited and can be determined as appropriate. For example, when a reaction solvent other than the above-mentioned amino compound as a raw material is used, the amount of the fluorinated phthalonitrile or the fluorinated phthalocyanine compound is 10 to 50 parts by weight, preferably 20 parts by weight, per 100 parts by weight of the reaction solvent. It is preferred that the amount be in the range of ４０40 parts by weight. If the amount of the reaction solvent is too large, the productivity is lowered and the reaction rate is slow, so that extra time is required, which is not economically preferable. On the other hand, if the amount of the reaction solvent is too small, the slurry concentration becomes high, so that stirring becomes difficult, and a large stirrer is required. In addition, stirring efficiency is deteriorated, and uniform reaction cannot be performed. When the raw material amino compound itself is used as a reaction solvent, it is preferably in the range of 10 to 300 mol, more preferably 25 to 100 mol, per 1 mol of the fluorinated phthalonitrile or the fluorinated phthalocyanine compound. Good. If the amount of the reaction solvent is too small, the slurry concentration becomes high, so that stirring becomes difficult, and a large stirrer is required. In addition, stirring efficiency is deteriorated, and uniform reaction cannot be performed. On the other hand, if the amount of the reaction solvent is too large, the productivity is low and the reaction rate is slow, so that extra time is required, which is not economically preferable.

The ratio between the fluorinated phthalonitrile or the fluorinated phthalocyanine compound and the nucleophilic compound is appropriately determined depending on the degree of substitution with a fluorine atom. In any case, depending on the desired degree of nucleophilic substitution, the fluorine atom on the benzene nucleus of the fluorinated phthalonitrile or the benzene nucleus of the phthalocyanine skeleton of the fluorinated phthalocyanine compound and the nucleophilic compound are preferably obtained. The nucleus may be replaced. For example, when an amino compound is used as the nucleophilic compound, the amino compound is used in an amount of usually 1 to 300 moles, preferably 2 to 300 moles per mole of the fluorinated phthalonitrile or the fluorinated phthalocyanine compound.
What is necessary is just to make it into the range of 100 mol times.

The reaction conditions for carrying out the nucleophilic substitution reaction of the present invention are not particularly limited.
To 250 ° C., preferably 120 to 200 ° C. When the reaction temperature is lower than 100 ° C., it is difficult to efficiently remove azeotropically the water produced as a by-product, and the nucleophilic substitution reaction does not proceed, so that by-products increase or the reaction rate becomes remarkably slow, resulting in production. There is an adverse effect such as an extremely long time required, which is economically undesirable. On the other hand, when the temperature is higher than 250 ° C., the starting materials and the reaction solvent are oxidized and thermally decomposed, so that an increase in by-products and a decrease in the yield are not preferred.

According to the method of the present invention, for example, the nucleophilic substitution reaction of a fluorine-containing phthalocyanine compound of the general formula (2) (X = fluorine atom, R = hydrogen atom) with an amino compound of the general formula (3) In this case, general formula (6):

[0067]

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An amino-substituted phthalocyanine compound represented by the following formula is obtained.

Here, R and R ′ are respectively the same as R and R ′ defined in the above formula (3), and M and m are respectively M and m defined in the above formula (1).
And n is the number of amino compound substitutions. When m = n, the amino-substituted phthalocyanine compound obtained by the nucleophilic substitution reaction does not become a fluorine-containing compound, but the object of the present invention is to quickly trap hydrogen fluoride generated during the nucleophilic substitution reaction. In addition, such a mode is also included because the filtration of the generated fluoride can be performed quickly. In the case of a near-infrared absorbing dye, m> n.

Among the amino-substituted phthalocyanine compounds represented by the general formula (6), those in which M is metal-free (however, the present invention is not limited to this. It goes without saying that a suitable metal other than a non-metal, a metal oxide or a metal halide is also included).

Dodecafluorotetrakis (anilino)
Phthalocyanine ・ Dodecafluorotetrakis (o-toluidino) phthalocyanine ・ Dodecafluorotetrakis (p-toluidino) phthalocyanine ・ Dodecafluorotetrakis (2,4-xylidino) phthalocyanine ・ Dodecafluorotetrakis (2,6-xylidino) phthalocyanine o-methoxyanilino)
Phthalocyanine ・ Dodecafluorotetrakis (p-methoxyanilino)
Phthalocyanine ・ Dodecafluorotetrakis (m-methoxyanilino)
Phthalocyanine ・ Dodecafluorotetrakis (o-fluoroanilino)
Phthalocyanine ・ Dodecafluorotetrakis (p-fluoroanilino)
Phthalocyanine ・ Dodecafluorotetrakis (tetrafluoroanilino) phthalocyanine ・ Dodecafluorotetrakis (o-methoxycarbonylanilino) phthalocyanine ・ Dodecafluorotetrakis (p-methoxycarbonylanilino) phthalocyanine ・ Dodecafluorotetrakis (m-methoxycarbonylanilino) Phthalocyanine ・ Dodecafluorotetrakis (o-ethoxycarbonylanilino) phthalocyanine ・ Dodecafluorotetrakis (p-ethoxycarbonylanilino) phthalocyanine ・ Dodecafluorotetrakis (methylamino) phthalocyanine ・ Dodecafluorotetrakis (ethylamino) phthalocyanine ・ Dodecafluorotetrakis Butylamino) phthalocyanine ・ Dodecafluorotetrakis (octylamino) ) Phthalocyanine octafluorooctakis (anilino) phthalocyanine octafluorooctakis (o-toluidino) phthalocyanine octafluorooctakis (p-toluidino) phthalocyanine octafluorooctakis (m-toluidino) phthalocyanine octafluorooctakis ( 2,4-xylidino) phthalocyanine octafluorooctakis (2,6-xyridino) phthalocyanine octafluorooctakis (o-methoxyanilino)
Phthalocyanine Octafluorooctakis (p-methoxyanilino)
Phthalocyanine-Octafluorooctakis (m-methoxyanilino)
Phthalocyanine / octafluorooctakis (o-fluoroanilino)
Phthalocyanine Octafluorooctakis (p-fluoroanilino)
Phthalocyanine-Octafluorooctakis (tetrafluoroanilino) phthalocyanine-Octafluorooctakis (o-ethoxycarbonylanilino) phthalocyanine-Octafluorooctakis (p-ethoxycarbonylanilino) phthalocyanine-Octafluorooctakis (m-ethoxy) Carbonylanilino) phthalocyanine Octafluorooctakis (methylamino) phthalocyanine Octafluorooctakis (ethylamino) phthalocyanine Octafluorooctakis (butylamino) phthalocyanine Octafluorooctakis (octylamino) phthalocyanine Octafluorooctakis Phenylthiophthalocyanine ・ Pentadecafluoromonoanilinophthalocyanine ・ Pentadecafluoromono (o- Idino) phthalocyanine pentadecafluoromono (p-toluidino) phthalocyanine pentadecafluoromono (m-toluidino) phthalocyanine pentadecafluoromono (2,4-xyridino) phthalocyanine pentadecafluoromono (2,6-xylidino) Phthalocyanine ・ Pentadecafluoromono (o-methoxyanilino) phthalocyanine ・ Pentadecafluoromono (p-methoxyanilino) phthalocyanine ・ Pentadecafluoromono (m-methoxyanilino) phthalocyanine ・ Pentadecafluoromono (o-fluoroani Lino) phthalocyanine pentadecafluoromono (p-fluoroanilino) phthalocyanine pentadecafluoromono (tetrafluoroanilino)
Phthalocyanine ・ Pentadecafluoromono (o-ethoxycarbonylanilino) phthalocyanine ・ Pentadecafluoromono (p-ethoxycarbonylanilino) phthalocyanine ・ Pentadecafluoromono (m-ethoxycarbonylanilino) phthalocyanine ・ Pentadecafluoromono (methyl) Amino) phthalocyanine pentadecafluoromono (ethylamino) phthalocyanine pentadecafluoromono (butylamino) phthalocyanine pentadecafluoromono (octylamino) phthalocyanine tetradecafluorobis (anilino) phthalocyanine tetradecafluorobis (n-) Butylamino) phthalocyanine tetradecafluorobis (cyclohexylamino) phthalocyanine dodecafluorotetra (anilino) phthalo Anine Decafluorohexa (o-toluidino) phthalocyanine Nonafluorohepta (2,3,4,5,6-pentafluoroanilino) phthalocyanine Nonafluorohepta (2,4-xylidino) phthalocyanine Heptafluoronona (anilino ) Phthalocyanine ・ octafluoroocta (benzylamino) phthalocyanine ・ octafluoroocta (2-naphthylamino) phthalocyanine ・ octafluoroocta (2-pyridino) phthalocyanine ・ octafluoroocta (diethylamino) phthalocyanine ・ octafluoroocta (diphenylamino) phthalocyanine ・Nonafluorohepta (di-n-butylamino) phthalocyanine octafluorotetra (anilino) tetra (p-toluidino) phthalocyanine Octafluoro Rotetra (n-octylamino) tetra (m-chloroanilino) phthalocyanine octafluoropenta (anilino) tri (p-toluidino) phthalocyanine octafluorohexa (n-pentylamino) bis (p-cyanoanilino) phthalocyanine tetra (anilino) Phthalocyanine Tetra (m-nitroanilino) phthalocyanine Tetra (tert-butylamino) phthalocyanine Hexa (p-N, N-dimethylaminoanilino) phthalocyanine Octa (p-tert-butylanilino) phthalocyanine Hexafluorobis (anilino) Phthalocyanine ・ Hexafluorobis (1-naphthylamino) phthalocyanine ・ Hexafluorobis (m-bromoanilino) phthalocyanine ・ Tetrafluorotetra (anilino) Talocyanine ・ tetrafluorotetra (n-butylamino) phthalocyanine ・ tetrafluorotetra (benzyl) phthalocyanine ・ tetraphenoxide dodecafluorophthalocyanine The alkaline earth metal compound used as required in the present invention has an average particle size of at least 10 μm. Preferably 100 to 5000 μm, particularly preferably 200 to 200
It is preferred to use 0 μm particles. The average particle size in the present invention means a 50% size (D ₅₀ ) of the weight cumulative particle size distribution. By using an alkaline earth metal compound having an average particle diameter in this range, a solid material filtration operation can be rapidly performed.

The shape of the particles of the alkaline earth metal compound is not particularly limited, and various shapes can be used.

According to the method of the present invention, after completion of the reaction, a solid substance is filtered from the reaction mixture, preferably separated and removed by hot filtration at 40 ° C. or higher, and then the filtrate is concentrated. And / or an organic solvent is added, or water and / or an organic solvent is added to the concentrated solution to precipitate a phthalonitrile or phthalocyanine compound having a substituent. In particular, it is preferable to add the concentrate to water and / or an organic solvent because the time required for subsequent filtration of the precipitate can be reduced.

When the target product is precipitated or crystallized in this manner, the filtration time of the precipitate can be reduced and the filtration operation of the precipitate can be performed efficiently, as compared with the case where the filtrate is precipitated without concentration. be able to. Although the reason for this is not clear, it is considered that large crystals are obtained by concentration.

The filtrate may be concentrated by heating the filtrate to distill unreacted raw materials and / or reaction solvent. This distillation / concentration operation is preferably performed at a temperature of 150 ° C. or less.
Concentration at too high a temperature is undesirable because side reactions occur. In some cases, depending on the type of the reaction raw material and / or the reaction solvent, it may not be possible to distill at a temperature of 150 ° C. or lower under normal pressure. In this case, the distillation must be performed under reduced pressure. For example, when aniline is used as a starting material and at the same time as a reaction solvent, it is usually under reduced pressure, for example, under reduced pressure of about 20 Torr, 100 to 110
It is preferable to carry out distillation and concentration at a temperature of ° C.

The degree of concentration is within a range where crystallization of the substituted phthalonitrile or phthalocyanine compound does not occur, for example, 30% or more of the saturation concentration, and furthermore, 50%.
The concentration may be increased to the above concentration. In particular, it is preferable to concentrate the solution to a concentration at which the concentration is substantially saturated.

The amount of water and / or organic solvent used in the above-mentioned crystallization operation may be an amount sufficient to cause the precipitation, and is usually 1 to 10 times the weight of the filtrate. Excessive use is not economical.

As the organic solvent used in the above crystallization operation,
Any one can be used as long as it is inert to the substituent-containing phthalonitrile or phthalocyanine compound and can crystallize these. Among them, alcoholic organic solvents are preferable, and typical examples thereof include methanol and
Examples thereof include alcohols having 1 to 8 carbon atoms such as ethanol, n-propyl alcohol, isopropyl alcohol, n-butanol, sec-butyl alcohol and tert-butyl alcohol. These can be used alone or in combination of two or more. In addition, when using together with water, the ratio of both can be determined suitably.

The method for filtering the solids and precipitates includes:
There is no particular limitation, and it can be carried out according to a method generally used for separating and removing solids. Usually, pressure filtration is performed.

The obtained phthalonitrile or phthalocyanine compound having substituents obtained as described above is separated by an operation such as filtration, and then purified by washing with water and / or an organic solvent. This washing and purification is preferably performed repeatedly until the unreacted raw material, ie, the nucleophilic compound and the reaction solvent, as impurities are sufficiently removed. For this reason,
By performing the above concentration operation, a nucleophilic compound or a reaction solvent as an impurity can be reduced, so that a high-purity substituent-containing phthalonitrile or phthalocyanine compound can be obtained with a small number of washings. For example, when the concentration is not carried out, the washing operation is required 3 to 4 times. When the concentration is carried out to about 80% of the saturation concentration, the phthalonitrile or phthalocyanine compound having a substituent with sufficient purity can be obtained by washing twice.

As the organic solvent used for washing and purifying the above-mentioned substituent-containing phthalonitrile or phthalocyanine compound crystal, the organic solvent used for extracting the above-mentioned substituent-containing phthalonitrile or phthalocyanine compound can be used. The solvent (water and / or organic solvent) used for the above-mentioned substituent-containing phthalonitrile or phthalocyanine compound and the washing / purification of the substituent-containing phthalonitrile or phthalocyanine compound may be the same or different, but is usually And the same solvent.

[0082]

According to the method of the present invention, the filtrate obtained by filtering solids from the reaction mixture is concentrated,
The precipitate filtration time can be shortened, and the number of subsequent washings for purification can be reduced. For this reason, productivity is improved.

By performing the nucleophilic substitution reaction in the presence of an alkaline earth metal compound, hydrogen fluoride generated during the nucleophilic substitution reaction can be efficiently trapped, thereby solving the problem of corrosion of the reactor. be able to. In particular, the average particle size is 1
By using the particles of the alkaline earth metal compound having a particle size of 0 μm or more, the solid material filtration time can be reduced. For this reason, productivity is further improved.

[0084]

EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples.

Reference Example 1 30 units equipped with a stirrer, thermometer, water separation tube and cooler
In a 0 ml glass separable flask, 40 g of hexadecafluorovanadyl phthalocyanine, 214 g of aniline and 18.5 of heavy calcium carbonate (average particle size: 20 μm) were used.
g, and reacted at 170 ° C. for 2.5 hours with stirring while removing generated water outside the system. After the reaction, the reaction mixture was cooled, and subjected to pressure filtration of 1.5 kg / cm ² at 40 ° C. using a pressure filter having a diameter of 35 mm to separate solids.
Removed. The time required for separation and removal of solids by this filtration (solids filtration time) was 15 minutes.

The filtrate is poured into isopropyl alcohol,
The obtained octafluorooctakisanilinovanadyl phthalocyanine was used in the same manner as in the above reaction mixture for 1.
A pressure filtration of 5 kg / cm ² was performed. The time required for filtration of the precipitate (filtration time) was 1 hour.

Further, after washing twice with isopropyl alcohol, it was dried at 150 ° C. under reduced pressure to obtain 60 g of octafluorooctakisanilinovanadyl phthalocyanine. The yield was 90 mol%.

Reference Example 2 In Reference Example 1, the separation and removal of solids by filtration
The same operation as in Reference Example 1 was performed except that the operation was performed at 0 ° C. The solids filtration time was 5 minutes.

REFERENCE EXAMPLE 3 30 units equipped with a stirrer, thermometer, water separation tube and cooler
A 0 ml glass separable flask was charged with 40 g of tetrafluorophthalonitrile, 214 g of aniline, and 9.5 g of heavy calcium carbonate (average particle size: 20 μm).
While stirring at 50 ° C, the generated water is removed out of the system.
Allowed to react for hours. After the reaction, the reaction mixture was cooled to a diameter of 3
1.5 kg / cm ² at 70 ° C. using a 5 mm pressure filter
Was filtered under pressure to separate and remove solids. The solids filtration time was 5 minutes.

The filtrate was poured into methanol, and the 4-
Anilino-3,5,6-trifluorophthalonitrile was treated with 1.5 kg / cm as in the case of the above reaction mixture.
Pressure filtration of No. ² was performed. The filtration time of the deposit was 1 hour.

Further, after washing with methanol twice, drying under reduced pressure at 150 ° C., 52 g of 4-anilino-3,
5,6-trifluorophthalonitrile was obtained. The yield is 9
It was 5 mol%.

Reference Example 4 The same operation as in Reference Example 1 was carried out except that heavy calcium carbonate having an average particle size of 400 μm was used. The solids filtration time was 3 minutes.

Example 1 In Reference Example 1, the same operation as in Reference Example 1 was performed, except that after separating and removing the solid by filtration, aniline was distilled off from the filtrate at 20 Torr and 110 ° C. to concentrate the filtrate. Was. The amount of the distilled aniline was 85 g, and the concentration of the target substance in the concentrated liquid containing the target substance (octafluorooctakisanilinovanadyl phthalocyanine) was about 39% by weight (saturation concentration: about 45% by weight). . At this time, the filtration time of the deposit was 15 minutes.

A comparison between Reference Example 1 and Example 1 shows that concentration of the filtrate can reduce the filtration time of the precipitate.

Example 2 The same operation as in Reference Example 4 was carried out except that the solid was separated and removed by filtration, aniline was distilled off from the filtrate at 20 Torr and 110 ° C., and the filtrate was concentrated. Was. The amount of the distilled aniline was 100 g, and the concentration of the target substance in the concentrate containing the target substance (octafluorooctakisanilinovanadyl phthalocyanine) was about 43% by weight (saturation concentration: 45% by weight). At this time, the filtration time of the deposit was 10 minutes.

Example 3 The same operation as in Example 1 was performed, except that isopropyl alcohol was introduced into the concentrated solution instead of the concentrated solution being introduced into isopropyl alcohol. The filtration time of the deposit was 40 minutes.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C09B 47/10 C09B 47/10

Claims (4)

[Claims] 1. A nucleophilic substitution reaction between a phthalonitrile having at least one halogen atom or a phthalocyanine compound having at least one halogen atom on a benzene nucleus of a phthalocyanine skeleton and a nucleophilic compound in a reaction solvent. In producing the corresponding substituent-containing phthalonitrile or the substituent-containing phthalocyanine compound, the reaction mixture is filtered to separate and remove solids, and then the filtrate is concentrated. A substituent-containing phthalonitrile or a substituent-containing phthalocyanine compound, which is charged into an organic solvent, or water and / or an organic solvent is charged into the concentrated solution, whereby the substituent-containing phthalonitrile or the substituent-containing phthalocyanine compound is deposited. A method for producing a group-containing phthalocyanine compound. 2. The method according to claim 1, wherein the filtrate is concentrated at a temperature of 150 ° C. or lower. 3. The method according to claim 2, wherein the filtrate is concentrated to a concentration of at least 30% of the saturation concentration of the filtrate. 4. The method according to claim 1, wherein the nucleophilic substitution reaction is carried out in the presence of an alkaline earth metal compound.