JPH10316642A - Phthalonitrile compound and its production - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject new compound useful as an intermediate for a phthalocyanine compound containing a substituent group on a specific position on a phthalonitrile skeleton benzene nucleus. SOLUTION: This compound is substituted with 1-2 phenoxy groups among four substitutable positions of a benzene nucleus of a phthalonitrile skeleton, in which the phenoxy groups are substituted with (substituted) aryl groups, such as 4-(2-phenyl-6-(2-propyl)phenoxy)3,5,6-trifluoronitrile. The high-purity compound is efficiently obtained in high yield by reacting 2-40 pts.wt., preferably 5-20 pts.wt. of a phenol compound substituted with a (substituted) aryl group with 1-2 mols, preferably 1.1-1.5 mols of a phthalonitrile compound substituted with at least one halogen atom based on 1 mol of the phenol compound in 100 pts.wt. of an organic solvent in the presence of a catalyst at 30-250 deg.C, preferably 50-200 deg.C.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a novel phthalonitrile compound and a method for producing the same. More specifically, the present invention relates to a phthalonitrile compound which is useful as an intermediate of pharmaceuticals, agricultural chemicals, and various industrial chemicals, and is extremely useful as a raw material of a phthalocyanine compound used as an optoelectronic material, and a method for producing the same. More specifically, it has absorption in the near-infrared region of 600 to 1000 nm and has excellent solubility, and is a near-infrared ray for writing or reading in an optical recording medium using a semiconductor laser, a liquid crystal display device, an optical character reader, and the like. As a near-infrared absorbing material used as an absorbing dye, a near-infrared sensitizer, a thermal transfer agent, a light-to-heat converting agent such as a thermal paper / thermosensitive stencil, a near-infrared absorbing filter, an eye fatigue preventing agent, a photoconductive material, or an imaging device For color separation filters used in tubes, color filters for liquid crystal displays, color CRT selective absorption filters, color toners, inkjet inks, barcode inks for preventing tampering and counterfeiting, as well as microbial deactivators and photosensitive dyes for tumor treatment Phthalocyanine compounds that exhibit excellent effects when used, especially write-once optical recording for compact discs Very useful phthalonitrile compound as an intermediate of the phthalocyanine compound which exhibits very excellent effects as a near infrared absorbing dye for use in the body and a manufacturing method thereof.

[0002]

2. Description of the Related Art In recent years, the development of optical recording media such as compact disks, laser disks, optical memory disks, and optical cards using a semiconductor laser as a light source has been active. In particular, CD, PHOTO-CD or CD-RO
M is widely used as a large-capacity, high-speed access digital recording medium for storing and reproducing voices, images, code data, and the like. Each of these systems requires a so-called near-infrared absorbing dye which is sensitive to a semiconductor laser, and (1) the maximum absorption wavelength in a thin film is 70%.
0 to 730 nm (the number of peaks due to association is small, and therefore, the absorbance is high, and the sharp peak is a major constituent factor for optical properties such as reflectance). (2) Spin It can be applied on a substrate by a simple and highly productive method such as coating.
And (3) excellent heat resistance and light resistance, and (4) excellent solubility in a solvent that does not attack the substrate.
There is a demand for a compound having good characteristics such as good thermal decomposition characteristics (which is a major factor in sensitivity) and (5) excellent economical efficiency in the production method and the like. Above all, many phthalocyanine compounds which are stable to light, heat, temperature and the like and have excellent fastness have been studied.

For example, JP-A-58-56892 discloses that
A method using a perfluorophthalocyanine compound has been proposed. Also, JP-A-61-192780, JP-A-61-246091, JP-A-63-37991,
JP-A-64-42283, JP-A-2-276677
JP-A-2-91360, JP-A-2-265788
JP-A-3-215466, JP-A-4-22639
No. 0 and the like have proposed a structure in which a substituent is introduced into the benzene ring of a phthalocyanine skeleton via oxygen.
Further, Japanese Patent Application Laid-Open No. 5-1272 and the like propose a phthalocyanine in which four alkoxy groups are introduced into the α-position of phthalocyanine and a halogen compound or the like is partially introduced into the residue.

[0004] However, these compounds have poor light resistance, low reflectivity, or are often used on substrates such as polycarbonate which are commonly used, depending on the type, number and position of substituents on the benzene nucleus of the phthalocyanine skeleton. It has problems that it does not dissolve in a solvent that can be directly applied, or that it has difficulty in controlling the absorption wavelength. Further, those having a substituent introduced at the α-position have a problem in terms of economic efficiency, such as poor productivity from phthalonitrile as a raw material.

Further, the present applicants have proposed a phthalocyanine compound in which a phenoxy group having a bulky substituent is substituted at the β-position (JP-A-5-345861,
JP-A-6-107766, JP-A-6-328856 and JP-A-8-225751.

However, these compounds also have problems in reflectance, sensitivity and the like in optical recording media, and the phthalocyanine compounds proposed so far do not satisfy all of the above characteristics.

On the other hand, in order to design and develop a novel phthalocyanine compound satisfying the above characteristics, it is necessary to select the type of a substituent introduced on the benzene nucleus of the phthalocyanine skeleton,
Numbers and locations need to be specified. For this purpose, it is possible to directly introduce a desired substituent at a designed position on the benzene nucleus of the phthalocyanine skeleton such as an unsubstituted phthalocyanine compound, but when a method for directly introducing the desired substituent cannot be taken. In many cases, a new phthalocyanine compound is designed by separately synthesizing a phthalonitrile compound obtained by introducing a desired substituent at a designed position on the benzene nucleus of the phthalonitrile skeleton, and then synthesizing the phthalonitrile compound. Thus, a technique for obtaining a desired new phthalocyanine compound has been adopted. In this method, emphasis is placed on the development of a novel phthalonitrile compound that is a main raw material of a molecularly designed phthalocyanine compound and a method for producing the same. That is, a major technical problem is to introduce a desired substituent at a designed position on the benzene nucleus of the phthalonitrile skeleton at the stage of synthesizing the phthalonitrile compound to obtain a novel phthalonitrile compound.

[0008]

SUMMARY OF THE INVENTION The present invention has been made in view of the above-mentioned circumstances of the prior art. That is, an object of the present invention is a novel molecule designed so that absorption can be controlled according to the purpose in the absorption wavelength range of 600 to 1000 nm, and excellent solubility, heat resistance, light resistance and the like can be expressed. Phthalocyanine compounds, especially optical recording media,
Above all, a novel phthalocyanine that is molecularly designed so that it can exhibit various properties such as solubility, absorption wavelength, sensitivity, reflectance, light resistance, and thermal decomposition properties required for use as optical recording media for compact discs In order to synthesize a compound, a novel compound comprising one or more substituents capable of effectively exhibiting these properties at a designed position on a benzene nucleus of a phthalonitrile skeleton as a main raw material thereof. An object of the present invention is to provide a phthalonitrile compound.

Another object of the present invention is to provide a method for producing the phthalonitrile compound efficiently and with high purity.

[0010]

The above objects are achieved by (1)
One or two of the four substitutable positions of the benzene nucleus of the phthalonitrile skeleton are substituted with a phenoxy group,
And it is achieved by a phthalonitrile compound in which the phenoxy group is substituted by an aryl group which may have a substituent.

Another object of the present invention is to provide (2) one of the ortho positions of the phenoxy group which is substituted with the aryl group, wherein at least the remaining ortho positions are represented by the following (1) to (2).
(7) Substituents of the group

[0012]

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(Wherein, in the formulas of the substituents in the above groups (1) to (7), R ¹ is a halogen atom, a linear or branched chain having 1 to 20 carbon atoms which may have a substituent. Or a cyclic alkyl group or an aryl group which may have a substituent, wherein R ² , R ³ , R ⁴ and R ⁵ each independently have 1 to 20 carbon atoms which may have a substituent. R ⁶ represents a linear, branched or cyclic alkyl group or an aryl group which may have a substituent, R ⁶ represents an aryl group which may have a substituent, and A represents a CH group or a nitrogen atom. B represents an oxygen atom, a sulfur atom, a CH ₂ group, an NH group or an alkylamino group having 1 to 4 carbon atoms, a, b, c and e are integers of 1 to 5; And f are integers from 0 to 6, and g and h are each independently 1
-4. This is also achieved by the phthalonitrile compound according to the above (1), which is substituted with at least one substituent selected from the group consisting of:

Further, another object of the present invention is to provide (3) a general formula (1)

[0015]

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(In the above general formula (1), X, Y and Z represent a hydrogen atom or a fluorine atom, at least one of X, Y and Z is a fluorine atom, and W has a substituent. Represents an aryl group which may be substituted, V represents at least one substituent selected from the substituents of the groups (1) to (7) defined in the above (2), and n is an integer of 0 to 4. This is also achieved by the phthalonitrile compound according to (1) or (2) above.

Still another object of the present invention is also achieved by (4) the phthalonitrile compound according to the above (3), wherein in the general formula (1), V is an alkoxycarbonyl group containing a bromo atom. .

Still another object of the present invention is to provide (5) the above-mentioned (3), wherein in the general formula (1), V is an alkoxycarbonyl group in which a secondary or higher alkyl group is directly bonded to a carbonyl group. It is also achieved by a phthalonitrile compound.

Still another object of the present invention is to provide (6) reacting a phenol compound substituted with an aryl group which may have a substituent with a phthalonitrile compound substituted with at least one halogen atom. The method is also achieved by the method for producing a phthalonitrile compound according to any one of the above (1) to (5).

[0020]

BEST MODE FOR CARRYING OUT THE INVENTION The phthalonitrile compound according to the present invention is obtained by substituting one or two of four substitutable positions of a benzene nucleus of a phthalonitrile skeleton with a phenoxy group. Is substituted with an aryl group which may have a substituent.

In the phthalonitrile compound substituted with the phenoxy group, examples of the aryl group which may have a substituent include a phenyl group and a naphthyl group. Preferably it is a phenyl group. Substituents optionally present on the aryl group include, for example, halogen atoms, alkyl groups, alkoxy groups, halogenated alkyl groups, halogenated alkoxy groups, nitro groups, amino groups, alkylamino groups, alkoxycarbonyl groups, and the like.

Further, the phthalonitrile compound substituted with the phenoxy group may further be partially or entirely substituted with a substituent other than the phenoxy group. That is, the phthalonitrile compound substituted with the phenoxy group is not limited to one type of the phthalonitrile compound substituted only with the phenoxy group,
In addition, a phthalonitrile compound substituted with the above-described phenoxy group and further partially or entirely substituted with a substituent other than the phenoxy group may be used.

Examples of the substituent other than the phenoxy group in the phthalonitrile compound substituted with the phenoxy group include a halogen atom, an alkyl group, an aryl group, a heterocyclic group, a cyano group, a hydroxy group, a nitro group, Amino group (including substituted amino group), alkoxy group,
Acylamino group, aminocarbonylamino group, sulfamoylamino group, alkylthio group, arylthio group, alkoxycarbonylamino group, sulfonylamino group, carbamoyl group, sulfamoyl group, sulfonyl group, alkoxycarbonyl group, heterocyclic oxy group, azo group , Acyloxy group, carbamoyloxy group, silyloxy group,
Examples include an aryloxycarbonyl group, an imide group, a heterocyclic thio group, a sulfinyl group, a phosphoryl group, and an acyl group. The kind of the substituent may be one kind or two or more kinds. Preferred substituents are a halogen atom, especially a chlorine atom and a fluorine atom, especially a fluorine atom.

Preferred among the novel phthalonitrile compounds of the present invention are those represented by the above formula (1), which will be described in detail below.

In the general formula (1), the substituent on the phenoxy group represented by W represents an aryl group which may have a substituent. Examples of the aryl group include a phenyl group and a naphthyl group. Preferably it is a phenyl group. Substituents optionally present on the aryl group include, for example, halogen atoms, alkyl groups, alkoxy groups, halogenated alkyl groups, halogenated alkoxy groups, nitro groups, amino groups, alkylamino groups, alkoxycarbonyl groups, and the like.

Here, the halogen atom is fluorine, chlorine, bromine and iodine, among which bromine is preferred.

The alkyl group is a straight chain having 1 to 20 carbon atoms,
It is a branched or cyclic alkyl group, preferably an alkyl group having 1 to 8 carbon atoms. Specifically, a methyl group,
Ethyl group, n-propyl group, isopropyl group, n-butyl group, tert-butyl group, n-pentyl group, n-hexyl group, cyclohexyl group, n-octyl group, 2-ethylhexyl group, n-decyl group, lauryl And a stearyl group.

The alkoxy group is a linear, branched or cyclic alkoxy group having 1 to 20 carbon atoms, preferably an alkoxy group having 1 to 8 carbon atoms. Specifically, methoxy, ethoxy, n-propyloxy, isopropyloxy, n-butoxy, tert-butoxy, n-pentyloxy, n-hexyloxy, cyclohexyloxy, n-octyl And oxy, 2-ethylhexyloxy, n-decyloxy and the like.

A halogenated alkyl group is one having 1 to 2 carbon atoms.
Part of the 0 linear, branched or cyclic alkyl group is halogenated, and preferably a part of the alkyl group having 1 to 8 carbon atoms is halogenated. Particularly preferably, the alkyl group having 1 to 8 carbon atoms is partially brominated. Specifically, bromomethyl group, bromoethyl group, bromopropyl group, bromobutyl group, bromopentyl group, bromohexyl group, bromoheptyl group, monobromoalkyl group such as bromooctyl group,
And a dibromoalkyl group such as a 1,3-dibromopropyl group and a 1,3-dibromobutyl group.

A halogenated alkoxy group is a group having 1 to 1 carbon atoms.
20 straight-chain, branched-chain or cyclic alkoxy groups are partially halogenated, and preferably have 1 to 8 carbon atoms.
Of the above alkoxy groups are partially halogenated. Particularly preferably, the alkoxy group having 1 to 8 carbon atoms is partially brominated. Specifically, monobromoalkoxy groups such as bromomethoxy group, bromoethoxy group, bromopropoxy group, bromobutoxy group, bromopentoxy group, bromohexyloxy group, bromoheptyloxy group, and bromooctyloxy group; -Dibromopropoxy group, dibromoalkoxy group such as 1,3-dibromobutoxy group and the like.

The alkoxycarbonyl group is an alkoxycarbonyl group having 1 to 8, preferably 1 to 5 carbon atoms which may contain a hetero atom in the alkyl group portion of the alkoxy group, or 3 to 8 carbon atoms which may contain a hetero atom. It preferably represents 5 to 8 cyclic alkoxycarbonyl groups. Specifically, a methoxycarbonyl group, an ethoxycarbonyl group, n
-Butoxycarbonyl group, tert-butoxycarbonyl group, n-pentyloxycarbonyl group, n-hexyloxycarbonyl group, 2-ethylhexyloxycarbonyl group, methoxyethoxycarbonyl group, ethoxyethoxycarbonyl group, butoxyethoxycarbonyl group, diethylaminoethoxycarbonyl Group, methylthioethoxycarbonyl group, methoxypropyloxycarbonyl group, (3,6,9-oxa) decyloxycarbonyl group, tetrahydrofurfuryloxycarbonyl group, pyranoxycarbonyl group, piperidinooxycarbonyl group, piperidinoethoxy Carbonyl group, tetrahydropyrroleoxycarbonyl group, tetrahydropyranmethoxycarbonyl group, tetrahydrothiophenoxycarbonyl group, cyclohexyl Indicating, for example, alkoxycarbonyl group.

In the general formula (1), the substitution position of W on the phenoxy group is not particularly limited, but is preferably at the ortho position of the phenoxy group. Since the aryl group which may have a substituent is located at the ortho position of the phenoxy group, an absorption peak derived from an aggregate in an absorption spectrum of a thin film of the phthalocyanine compound synthesized using the phthalonitrile compound as a raw material (hereinafter, referred to as “ Association peak) can be greatly suppressed.

In the general formula (1), the substituents on the phenoxy group represented by V include the following (1) to (7)
Group substituents

[0034]

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(Wherein, in the formulas of the substituents in the above groups (1) to (7), R ¹ is a halogen atom, a linear or branched chain having 1 to 20 carbon atoms which may have a substituent. Or a cyclic alkyl group or an aryl group which may have a substituent, wherein R ² , R ³ , R ⁴ and R ⁵ each independently have 1 to 20 carbon atoms which may have a substituent. R ⁶ represents a linear, branched or cyclic alkyl group or an aryl group which may have a substituent, R ⁶ represents an aryl group which may have a substituent, and A represents a CH group or a nitrogen atom. B represents an oxygen atom, a sulfur atom, a CH ₂ group, an NH group or an alkylamino group having 1 to 4 carbon atoms, a, b, c and e are integers of 1 to 5; And f are integers from 0 to 6, and g and h are each independently 1
-4. ) Represents at least one substituent selected from

Specific examples of the substituents of groups (1) to (7) include the following substituent groups.

(1) group: fluorine, chlorine, bromine, iodine,
Methyl, ethyl, propyl, isopropyl, cyclopropyl, butyl, isobutyl, sec-butyl, tert
-Butyl, straight or branched pentyl, straight or branched hexyl, cyclohexyl, straight or branched heptyl, straight or branched octyl, straight or branched nonyl, straight or branched decyl, straight or Branched undecyl, linear or branched dodecyl, bromomethyl, dibromomethyl, tribromomethyl, 1-bromoethyl, 2-bromoethyl,
1,2-dibromoethyl, 1,1-dibromoethyl,
2,2-dibromoethyl, 1,1,2-tribromoethyl, 1,2,2-tribromoethyl, 1-bromopropyl, 2-bromo-1-propyl, 3-bromo-1-propyl, 1- Bromo-2-propyl, 2,3-dibromo-
1-propyl, 1,3-dibromo-2-propyl, 4-bromo-1-butyl, 1-bromo-1-butyl, 1-bromo-2-butyl, 2-bromo-1-butyl, 1,4-dibromo -2-butyl, 5-bromo-1-pentyl, 1-
Bromo-1-pentyl, 6-bromo-1-hexyl, 1
-Bromo-1-hexyl, 7-bromo-1-heptyl,
1-bromo-1-heptyl, 8-bromo-1-octyl, 1-bromo-1-octyl, 9-bromo-1-nonyl, 1-bromo-1-nonyl, 10-bromo-1-decyl, 1- Bromo-1-decyl, 11-bromo-1-undecyl, 1-bromo-1-undecyl, 12-bromo-
1-dodecyl, 1-bromo-1-dodecyl, phenyl,
o-methylphenyl, m-methylphenyl, p-methylphenyl, o-ethylphenyl, m-ethylphenyl,
p-ethylphenyl, o-propylphenyl, m-propylphenyl, p-propylphenyl, o-isopropylphenyl, m-isopropylphenyl, p-isopropylphenyl, o-butylphenyl, m-butylphenyl, p-butylphenyl, o-tert-butylphenyl, m-tert-butylphenyl, p-tert-butylphenyl, o-methoxyphenyl, m-methoxyphenyl, p-methoxyphenyl, o-ethoxyphenyl, m-ethoxyphenyl, p-ethoxyphenyl , O
-Propoxyphenyl, m-propoxyphenyl, p-
Propoxyphenyl, o-isopropoxyphenyl, m
-Isopropoxyphenyl, p-isopropoxyphenyl, o-butoxyphenyl, m-butoxyphenyl, p
-Butoxyphenyl, 2,6-dimethylphenyl, 2,
6 diethylphenyl, 2,6-dipropylphenyl,
2,6-diisopropylphenyl, 2,6-dibutylphenyl, 2,6-ditert-butylphenyl, 2,6
-Dimethoxyphenyl, 2,6-diethoxyphenyl,
2,6-dipropoxyphenyl, 2,6-diisopropoxyphenyl, 2,6-dibutoxyphenyl, 2-fluorophenyl, 2-chlorophenyl, 2-bromophenyl, 2-iodophenyl, 3-fluorophenyl, −
Chlorophenyl, 3-bromophenyl, 3-iodophenyl, 4-fluorophenyl, 4-chlorophenyl,
-Bromophenyl, 4-iodophenyl, 2,3-difluorophenyl, 2,3-dichlorophenyl, 2,4-
Difluorophenyl, 2,4-dichlorophenyl, 2,
4-dibromophenyl, 2,5-difluorophenyl,
2,5-dichlorophenyl, 2,6-difluorophenyl, 2,6-dichlorophenyl, 2,6-dibromophenyl, 3,4-difluorophenyl, 3,4-dichlorophenyl, 3,5-difluorophenyl, 3,5- Dichlorophenyl, 2,3,4-trifluorophenyl,
2,3,4-trichlorophenyl, 2,3,5-trifluorophenyl, 2,3,5-trichlorophenyl,
2,3,6-trifluorophenyl, 2,3,6-trichlorophenyl, 2,4,6-trifluorophenyl,
2,4,6-trichlorophenyl, 2,4,6-tribromophenyl, 2,4,6-triiodophenyl, 2,
3,5,6-tetrafluorophenyl, pentafluorophenyl, pentachlorophenyl.

Group (2): methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, isopropoxycarbonyl, butoxycarbonyl, isobutoxycarbonyl, sec-butoxycarbonyl, tert-butoxycarbonyl, linear or branched pentyloxycarbonyl, linear or Branched hexyloxycarbonyl, cyclohexyloxycarbonyl, straight or branched heptyloxycarbonyl, straight or branched octyloxycarbonyl, straight or branched nonyloxycarbonyl, straight or branched decyloxycarbonyl, straight or branched Undecyloxycarbonyl, linear or branched dodecyloxycarbonyl, cyclohexanemethoxycarbonyl, cyclohexaneethoxy Carbonyl, 3-cyclohexyl -1
-Propoxycarbonyl, tert-butylcyclohexyloxycarbonyl, bromomethoxycarbonyl, 2
-Bromoethoxycarbonyl, 3-bromo-1-propoxycarbonyl, 2-bromo-1-propoxycarbonyl, 1-bromo-2-propoxycarbonyl, 2,3-
Dibromo-1-propoxycarbonyl, 1,3-dibromo-2-propoxycarbonyl, 1-bromo-2-butoxycarbonyl, 2-bromo-1-butoxycarbonyl, 4-bromo-1-butoxycarbonyl, 1,4-dibromo -2-butoxycarbonyl, 5-bromo-1-pentyloxycarbonyl, 6-bromo-1-hexyloxycarbonyl, 7-bromo-1-heptyloxycarbonyl, 8-bromo-1-octyloxycarbonyl,
9-bromo-1-nonyloxycarbonyl, 10-bromo-1-decyloxycarbonyl, 11-bromo-1-
Undecyloxycarbonyl, 12-bromo-1-dodecyloxycarbonyl, phenoxycarbonyl, 4-methylphenoxycarbonyl, 4-chlorophenoxycarbonyl, 4-cyclohexylphenoxycarbonyl, 4
-Phenylphenoxycarbonyl, 2-fluorophenoxycarbonyl, 4-ethoxyphenoxycarbonyl.

Group (3): methoxyethoxycarbonyl,
Ethoxyethoxycarbonyl, 3 ', 6'-oxaheptyloxycarbonyl, 3', 6'-oxaoctyloxycarbonyl, 3 ', 6', 9'-oxadecyloxycarbonyl, 3 ', 6', 9 ', 12 '-Oxatridecyloxydicarbonyl.

Group (4): methoxypropyloxycarbonyl, ethoxypropyloxycarbonyl, 4 ', 8'
-Oxanonyloxycarbonyl, 4 ', 8'-oxadecyloxycarbonyl, 4', 8 ', 12'-oxatridecyloxycarbonyl.

Group (5): methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, sec
-Butoxy, tert-butoxy, linear or branched pentyloxy, linear or branched hexyloxy, cyclohexyloxy, linear or branched heptyloxy, linear or branched octyloxy, linear or branched nonyloxy, direct Chain or branched decyloxy, straight or branched undecyloxy, straight or branched dodecyloxy, bromomethoxy, dibromomethoxy, tribromomethoxy, 1-bromoethoxy, 2-bromoethoxy, 1,2-dibromoethoxy, 1,1-dibromoethoxy, 2,2-dibromoethoxy, 1,1,2-tribromoethoxy, 1,
2,2-tribromoethoxy, 1-bromopropoxy,
2-bromo-1-propoxy, 3-bromo-1-propoxy, 1-bromo-2-propoxy, 2,3-dibromo-1-propoxy, 1,3-dibromo-2-propoxy, 4-bromo-1- Butoxy, 1-bromo-1-butoxy, 1-bromo-2-butoxy, 2-bromo-1-butoxy, 1,4-dibromo-2-butoxy, 5-bromo-1-pentyloxy, 1-bromo-1 -Pentyloxy, 6-bromo-1-hexyloxy, 1-bromo-1
-Hexyloxy, 7-bromo-1-heptyloxy,
1-bromo-1-heptyloxy, 8-bromo-1-octyloxy, 1-bromo-1-octyloxy, 9-
Bromo-1-nonyloxy, 1-bromo-1-nonyloxy, 10-bromo-1-decyloxy, 1-bromo-
1-decyloxy, 11-bromo-1-undecyloxy, 1-bromo-1-undecyloxy, 12-bromo-1-dodecyloxy, 1-bromo-1-dodecyloxy, bromomethoxyethoxy, 1-bromoethoxy Ethoxy, 1-bromo-3 ', 6'-oxaheptyloxy, 1-bromo-3', 6'-oxaoctyloxy,
1-bromo-3 ', 6', 9'-oxadecyloxy,
1-bromo-3 ', 6', 9 ', 12'-oxatridecyloxy, bromomethoxypropoxy, 1-bromoethoxypropoxy, 1-bromo-4', 8'-oxanonyloxy, 1-bromo-4 ', 8'-oxadecyloxy, methoxyethoxy, ethoxyethoxy, 3',
6'-oxaheptyloxy, 3 ', 6'-oxaoctyloxy, 3', 6 ', 9'-oxadecyloxy,
3 ', 6', 9 ', 12'-oxatridecyloxy,
Methoxypropyloxy, ethoxypropyloxy,
4 ', 8'-oxanonyloxy, 4', 8'-oxadecyloxy.

Group (6): benzyloxycarbonyl, phenethyloxycarbonyl, 3-fer-1-propoxycarbonyl, 4-phenyl-1-butoxycarbonyl, 5-phenyl-1-pentoxycarbonyl, 6-phenyl-1- Hexyloxycarbonyl.

Group (7): 2-tetrahydroxyfuranoxycarbonyl, 4-tetrahydropyranoxycarbonyl, 2-pyrrolidinooxycarbonyl, 2-piperidinooxycarbonyl, 2-tetrahydrothiophenoxycarbonyl, tetrahydrofurfuryloxy Carbonyl, 4-tetrahydropyranooxycarbonyl, 2-morpholinoethoxycarbonyl, 2-pyrrolidinoethoxycarbonyl, 2-piperazinoethoxycarbonyl.

Among the substituents of the above groups (1) to (7),
Group (2) is preferable, and an alkoxycarbonyl group in which a secondary or higher alkyl group such as isopropoxycarbonyl or tert-butoxycarbonyl is directly bonded to a carbonyl group is more preferable. More preferably, 3-hexanoxycarbonyl, 6-undecanoloxycarbonyl,
2,4-dimethyl-3-pentoxycarbonyl, 2,6
An alkoxycarbonyl group having 6 or more carbon atoms and a secondary or higher alkyl group directly bonded to a carbonyl group, such as -dimethyl-4-heptoxycarbonyl, is more preferable. On the other hand, a preferred substituent is an alkoxycarbonyl group containing a bromo atom, and in particular, a brominated secondary or higher alkyl such as 1-bromo-2-propoxycarbonyl, 1,3-dibromo-2-propoxycarbonyl, etc. Alkoxycarbonyl groups having a group are more desirable. When the substituent is an alkoxycarbonyl group in which a secondary or higher alkyl group is directly bonded to a carbonyl group, or an alkoxycarbonyl group having a brominated secondary or higher alkyl group, such as reflectance and recording sensitivity, It is preferable because a phthalonitrile compound as a raw material of a novel phthalocyanine compound which can be an optical recording medium having excellent characteristics, particularly excellent recording sensitivity, can be synthesized as designed.

In the general formula (1), the substitution position of the substituent V on the phenoxy group is not particularly limited, but is preferably at the ortho position of the phenoxy group. It is preferred that both W are at the ortho position of the phenoxy group, ie, at the 2,6 positions. When the substituents V and W are located at positions 2 and 6 of the phenoxy group,
The absorption peak of the phthalocyanine compound synthesized using the phthalonitrile compound can be sharpened. Furthermore, in the phthalocyanine compound synthesized using the phthalonitrile compound, the association peak of the thin film can be significantly suppressed. That is, the phthalonitrile compound is
It can be said to be preferable because it is a raw material useful for synthesizing a phthalocyanine compound having a substituent having optical characteristics such as reflectance and recording sensitivity suitable for an optical recording medium.

Particularly preferably, the substituents V and W are located at the 2,6-positions of the phenoxy group, and the substituent V is preferably an alkoxycarbonyl group in which a secondary or higher alkyl group is directly bonded to a carbonyl group. It is particularly preferred that the alkyl group is an alkyl group containing a bromo atom or an alkyl group having 6 or more carbon atoms. This is particularly preferable because it is a raw material useful for synthesizing a novel phthalocyanine compound having a substituent having optical characteristics such as reflectance and recording sensitivity suitable for an optical recording medium.

In the general formula (1), the remaining positions where the substituents V and W are introduced into the phenoxy group are further improved in solubility or absorption of the phthalocyanine compound synthesized using the phthalonitrile compound. A new substituent may be introduced for controlling the wavelength. Examples of these substituents include a halogen atom, an alkoxycarbonyl comprising a linear or branched alkoxy having 1 to 20 carbon atoms which may be substituted with an alkoxy group, an aryloxycarbonyl group which may be substituted, A chain or branched alkyl group having 1 to 12 carbon atoms which may be substituted, a linear or branched alkoxy group having 1 to 12 carbon atoms, a linear or branched carbon group having 1 to 12 carbon atoms 20 monoalkylamino groups, linear or branched dialkylamino groups having 1 to 20 carbon atoms, cyclohexyl group,
Examples include an optionally substituted phenoxy group, an optionally substituted anilino group or a nitro group. Of these, a halogen atom is preferred, and a bromine atom is particularly preferred.

In the above general formula (1), X, Y and Z represent a hydrogen atom or a fluorine atom, and at least one of X, Y and Z is a fluorine atom. It is preferable that X, Y and Z are all fluorine atoms in that the solubility of the phthalocyanine compound synthesized using the phthalonitrile compound is excellent.

That is, in the above general formula (1), the substituents V and W are located at positions 2 and 6 of the phenoxy group, and the substituent V is an alkoxycarbonyl group in which a secondary or higher alkyl group is directly bonded to the carbonyl group. X, Y and Z
Is preferably a fluorine atom. The phthalonitrile compound can synthesize a phthalocyanine compound having excellent solubility and film-forming properties. Further, in the synthesized phthalocyanine compound, a useful substituent is introduced as designed, so that excellent optical characteristics such as reflectance and recording sensitivity can be exhibited. Therefore, this can be used for an optical recording medium, particularly an optical recording medium corresponding to a high-speed recording type compact disc.

In the general formula (1), n is 0
It is an integer of 1 to 4, preferably an integer of 1 to 2.

Specific examples of the phthalonitrile compound used in the present invention include the following compounds.

Compound 1; 4- (2-phenyl-6- (2
-Propyl) phenoxy) -3,5,6-trifluorophthalonitrile:

[0053]

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Compound 2: 4- (2,6-diphenylphenoxy) -3,5,6-trifluorophthalonitrile:

[0055]

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Compound 3: 4- (2,4-diphenylphenoxy) -3,5,6-trifluorophthalonitrile:

[0057]

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Compound 4: 4- (2,4,6-triphenylphenoxy) -3,5,6-trifluorophthalonitrile:

[0059]

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Compound 5; 4- (2- (2-propoxy)
Carbonyl-6-phenylphenoxy) -3,5,6-
Trifluorophthalonitrile:

[0061]

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Compound 6; 4- (2- (3-pentoxy)
Carbonyl-6-phenylphenoxy) -3,5,6-
Trifluorophthalonitrile:

[0063]

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Compound 7; 4- (2- (3-pentoxy)
Carbonyl-4-phenylphenoxy) -3,5,6-
Trifluorophthalonitrile:

[0065]

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Compound 8; 4- (2-tert-butoxycarbonyl-6-phenylphenoxy) -3,5,6-trifluorophthalonitrile:

[0067]

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Compound 9; 4- (2- (3-hexanoxy) carbonyl-6-phenylphenoxy) -3,5
6-trifluorophthalonitrile:

[0069]

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Compound 10; 4- (2- (6-undecanooxy) carbonyl-6-phenylphenoxy) -3,
5,6-trifluorophthalonitrile:

[0071]

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Compound 11; 4- (2- (2,4-dimethyl-3-pentoxy) carbonyl-6-phenylphenoxy) -3,5,6-trifluorophthalonitrile:

[0073]

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Compound 12; 4- (2- (2,6-dimethyl-4-heptoxy) carbonyl-6-phenylphenoxy) -3,5,6-trifluorophthalonitrile:

[0075]

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Compound 13; 4- (2,4-di (2-propoxy) carbonyl-6-phenylphenoxy) -3,
5,6-trifluorophthalonitrile:

[0077]

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Compound 14; 4- (2- (2-butoxy)
Carbonyl-6-phenylphenoxy) -3,5,6-
Trifluorophthalonitrile:

[0079]

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Compound 15; 4- (2- (2-pentoxy) carbonyl-6-phenylphenoxy) -3,5
6-trifluorophthalonitrile:

[0081]

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Compound 16: 4- (2- (3-methoxypropoxy) carbonyl-6-phenylphenoxy)-
3,5,6-trifluorophthalonitrile:

[0083]

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Compound 17: 4- (2,4-di (2-methoxyethoxy) carbonyl-6-phenylphenoxy)
-3,5,6-trifluorophthalonitrile:

[0085]

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Compound 18; 4- (2-ethoxy-6-phenylphenoxy) -3,5,6-trifluorophthalonitrile:

[0087]

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Compound 19: 4- (2,4-diethoxy-
6-phenylphenoxy) -3,5,6-trifluorophthalonitrile:

[0089]

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Compound 20: 4- (2-benzyloxycarbonyl-6-phenylphenoxy) -3,5,6-trifluorophthalonitrile:

[0091]

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Compound 21; 4- (2-phenethyloxycarbonyl-6-phenylphenoxy) -3,5,6-
Trifluorophthalonitrile:

[0093]

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Compound 22: 4- (2- (2-tetrahydrofurfuryloxy) carbonyl-6-phenylphenoxy) -3,5,6-trifluorophthalonitrile:

[0095]

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Compound 23; 4- (4- (2-tetrahydrofurfuryloxy) carbonyl-6-phenylphenoxy) -3,5,6-trifluorophthalonitrile:

[0097]

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Compound 24; 4- (2,4-di (2-tetrahydrofurfuryloxy) carbonyl-6-phenylphenoxy) -3,5,6-trifluorophthalonitrile:

[0099]

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Compound 25: 4- (6- (bromophenyl) -2-isopropoxycarbonylphenoxy)-
3,5,6-trifluorophthalonitrile:

[0101]

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Compound 26; 4- (bromo-2-isopropoxycarbonyl-6-phenylphenoxy) -3,
5,6-trifluorophthalonitrile:

[0103]

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Compound 27; 4- (6- (4-chlorophenyl) -2-isopropoxycarbonylphenoxy))
-3,5,6-trifluorophthalonitrile:

[0105]

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Compound 28; 4- (4-fluoro-2-
(2-methoxyethoxy) carbonyl-6-phenylphenoxy) -3,5,6-trifluorophthalonitrile:

[0107]

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Compound 29: 4- (6- (4-bromomethylphenyl) -2- (2-tetrahydrofurfuryloxy) carbonylphenoxy) -3,5,6-trifluorophthalonitrile:

[0109]

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Compound 30: 4- (6- (4-bromomethoxyphenyl) -2-isopropoxycarbonylphenoxy) -3,5,6-trifluorophthalonitrile:

[0111]

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Compound 31; 4- (2- (2-methoxyethoxy) carbonyl-6-phenylphenoxy) -3,
5,6-trifluorophthalonitrile:

[0113]

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Compound 32: 4,5-bis (2-isopropoxycarbonyl-6-phenylphenoxy) -3,6
-Difluorophthalonitrile:

[0115]

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Compound 33; 4,5-bis (2-tert
-Butoxycarbonyl-6-phenylphenoxy)-
3,6-difluorophthalonitrile:

[0117]

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Compound 34; 4- (4- (2-bromoethoxy) carbonyl-2-phenylphenoxy) -3,
5,6-trifluorophthalonitrile:

[0119]

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Compound 35; 4- (2- (2-bromoethoxy) carbonyl-6-phenylphenoxy) -3,
5,6-trifluorophthalonitrile:

[0121]

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Compound 36; 4- (2- (6-bromohexyloxy) carbonyl-6-phenylphenoxy)-
3,5,6-trifluorophthalonitrile:

[0123]

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Compound 37; 4- (2,4-di (6-bromohexyloxycarbonyl) -6-phenylphenoxy) -3,5,6-trifluorophthalonitrile:

[0125]

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Compound 38; 4- (2- (2-bromoethyl) -6-phenylphenoxy) -3,5,6-trifluorophthalonitrile:

[0127]

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Compound 39: 4- (4- (2-bromoethoxy) -2-isopropoxycarbonyl-6-phenylphenoxy) -3,5,6-trifluorophthalonitrile:

[0129]

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Compound 40; 4- (2- (2-bromoethoxy) -6-phenylphenoxy) -3,5,6-trifluorophthalonitrile:

[0131]

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Compound 41: 4- (2- (2-bromoethoxy) carbonyl-6-phenylphenoxy) -3,
5,6-trifluorophthalonitrile:

[0133]

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Compound 42; 4- (2- (1-bromo-2)
-Propoxycarbonyl-6-phenylphenoxy)-
3,5,6-trifluorophthalonitrile:

[0135]

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Compound 43; 4- (2- (1-bromo-1)
-Propoxy) carbonyl-6-phenylphenoxy)
-3,5,6-trifluorophthalonitrile:

[0137]

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Compound 44; 4- (2- (1,3-dibromo-2-propoxy) carbonyl-6-phenylphenoxy) -3,5,6-trifluorophthalonitrile:

[0139]

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Compound 45; 4- (2- (1,4-dibromo-2-butoxy) carbonyl-6-phenylphenoxy) -3,5,6-trifluorophthalonitrile:

[0141]

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Compound 46; 4,5-bis (4- (6-bromohexyl) -2-phenylphenoxy) -3,6-
Difluorophthalonitrile:

[0143]

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Compound 47: 4,5-bis (2- (2-bromoethoxycarbonyl) -6-phenylphenoxy)
-(2-ethoxycarbonyl-6-phenylphenoxy) -3,6-difluorophthalonitrile:

[0145]

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Compound 48; 4,5-bis (2- (2,3
-Dibromo-1-propoxy) carbonyl-6-phenylphenoxy) -3,6-difluorophthalonitrile:

[0147]

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Next, the method for producing a phthalonitrile compound of the present invention comprises the steps of: converting a phenol compound substituted with an aryl group which may have a substituent and a phthalonitrile compound substituted with at least one halogen atom. It is characterized by reacting.

Hereinafter, the method for producing the novel phthalonitrile compound of the present invention will be described in detail.

If the phthalonitrile compound represented by the general formula (1) is taken as an example, it can be synthesized according to the following formula (2).

[0151]

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In the above synthesis formula, a phthalonitrile compound represented by the following general formula (3) can be synthesized by using twice the amount of a phenol compound as a raw material.

[0153]

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In the method for producing a novel phthalonitrile compound of the present invention, the phenol compound substituted with an aryl group which may have a substituent and the phthalonitrile compound substituted with at least one halogen atom may be used. The reaction can be carried out without a solvent, but is preferably carried out using an organic solvent. The organic solvent may be any inert solvent that is not reactive with the starting materials, for example, benzene, toluene, xylene, nitrobenzene, monochlorobenzene, dichlorobenzene, trichlorobenzene,
1-chloronaphthalene, 1-methylnaphthalene, ethylene glycol, acetonitrile, benzonitrile, pyridine, N, N-dimethylformamide, N-methyl-2
-Pyrrolidinone, N, N-dimethylacetophenone, triethylamine, tri-n-butylamine, dimethylsulfoxide, sulfolane and the like can be used, and preferred are acetonitrile and benzonitrile.

In the present invention, a catalyst can be used in order to promote the progress of the reaction. Examples of such a catalyst include tertiary amine compounds such as triethylamine and tri-n-octylamine, KOH, NaO
Examples thereof include alkali metal compounds such as H, K ₂ CO ₃ , Na ₂ CO ₃ , KF, and NaF, with KF being preferred. KF is preferred because it is inactive against a phthalonitrile compound substituted with at least one halogen atom, so that a side reaction hardly occurs.

In the present invention, a phenol compound substituted with an optionally substituted aryl group is used in an amount of 2 to 40 parts per 100 parts of an organic solvent (hereinafter, referred to as parts by weight).
Parts, preferably in the range of 5 to 20 parts, from 1 to 1 mol of the phthalonitrile compound substituted with at least one halogen atom with respect to 1 mol of the phenol compound substituted with an aryl group which may have a substituent. 2 mol, preferably in the range of 1.1 to 1.5 mol, the reaction temperature is 30 to
The reaction is carried out at 250 ° C, preferably at 50 to 200 ° C. When a catalyst is present, the catalyst is used in an amount of 0.1 to 8 mol, preferably 0.5 to 4 mol, per 1 mol of the phenol compound substituted with an aryl group which may have a substituent. And reacting.

[0157]

The present invention will be described below in more detail with reference to examples.

Example 1 Exemplified Compound 11: 4- (2- (2,4-dimethyl-3-)
Pentoxy) carbonyl-6-phenylphenoxy)-
Production of 3,5,6-trifluorophthalonitrile 3.12 g (0.01 mol) of 2- (2,4-dimethyl-3-pentoxy) carbonyl-6-phenylphenol, 1.74 g of potassium fluoride (0. 03 mol), 2.00 g (0.01 mol) of tetrafluorophthalonitrile and 20 ml of acetonitrile were charged into a 100 ml four-necked flask and reacted under reflux for 4 hours. After the completion of the reaction, potassium fluoride was filtered off and acetonitrile was distilled off to obtain 4.04 g of the desired pale yellow cake (yield: 82%). The physical properties of the obtained target product are as shown in Table 1 below.

[0159]

[Table 1]

Example 2 Exemplified Compound 5: Preparation of 4- (2- (2-propoxy) carbonyl-6-phenylphenoxy) -3,5,6-trifluorophthalonitrile 2- (2-propoxy) carbonyl-6 -Charge 2.56 g (0.01 mol) of phenylphenol, 1.74 g (0.03 mol) of potassium fluoride, 2.00 g (0.01 mol) of tetrafluorophthalonitrile and 20 ml of acetonitrile into a 100 ml four-necked flask. The reaction was carried out under reflux for 4 hours. After the completion of the reaction, potassium fluoride was separated by filtration and acetonitrile was distilled off to obtain 3.80 g of the objective pale yellow cake (yield 87%). The physical properties of the obtained target product are as shown in Table 2 below.

[0161]

[Table 2]

Example 3 Exemplified compound 44: 4- (2- (1,3-dibromo-2-)
Propoxy) carbonyl-6-phenylphenoxy)-
Production of 3,5,6-trifluorophthalonitrile 4.14 g (0.01 mol) of 2- (1,3-dibromo-2-propoxy) carbonyl-6-phenylphenol, 1.74 g of potassium fluoride (0. 03 mol), 2.00 g (0.01 mol) of tetrafluorophthalonitrile and 20 ml of acetonitrile were charged into a 100 ml four-necked flask and reacted under reflux for 4 hours. After the completion of the reaction, potassium fluoride was separated by filtration and acetonitrile was distilled off to obtain 5.05 g of the objective pale yellow cake (yield: 85%). The physical properties of the obtained target product are as shown in Table 3 below.

[0163]

[Table 3]

Example 4 Exemplified Compound 10: Preparation of 4- (2- (6-undecanoxy) carbonyl-6-phenylphenoxy) -3,5,6-trifluorophthalonitrile 2- (6-undecanoxy) carbonyl-6 -Charge 3.69 g (0.01 mol) of phenylphenol, 1.74 g (0.03 mol) of potassium fluoride, 2.00 g (0.01 mol) of tetrafluorophthalonitrile and 20 ml of acetonitrile in a 100 ml four-necked flask. The reaction was carried out under reflux for 4 hours. After completion of the reaction, potassium fluoride was separated by filtration and acetonitrile was distilled off to obtain 4.28 g of a light yellow cake as a target product (yield: 78%). The physical properties of the obtained target product are as shown in Table 4 below.

[0165]

[Table 4]

[0166]

The novel phthalonitrile compound of the present invention is a molecular material designed as a raw material of a phthalocyanine compound used for an optical recording medium so as to have characteristics required for an optical recording medium. In particular, as a raw material of phthalocyanine compounds used for optical recording media compatible with compact discs, these characteristics are expressed so as to have the necessary properties such as solubility, absorption wavelength, sensitivity, reflectance, light resistance, and thermal decomposition characteristics. The obtained one or more substituents are introduced at designed positions on the benzene nucleus of the phthalonitrile skeleton. Therefore, the novel compound of the present invention has excellent absorption characteristics, solubility, light resistance, thermal decomposition characteristics and economic efficiency, and has a 650 to 900 n
A novel phthalocyanine compound having absorption in the near infrared region of m can be synthesized as designed.

According to the production method of the present invention, it is possible to introduce a substituent at a designed position on the benzene nucleus of the phthalonitrile skeleton. That is, according to the production method of the present invention, molecular design of a compound according to the use becomes possible,
In that case, there is no need to go through a complicated manufacturing process, which is industrially advantageous.

Claims (6)

[Claims] 1. An aryl in which one or two of four substitutable positions of a benzene nucleus of a phthalonitrile skeleton are substituted with a phenoxy group, and the phenoxy group may have a substituent. A phthalonitrile compound substituted with a group. 2. One of the ortho positions of the phenoxy group is substituted with the aryl group, and at least the remaining ortho position is a substituent of the following groups (1) to (7): (However, in the formulas of the substituents in the above groups (1) to (7), R ¹
Represents a halogen atom, a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms which may have a substituent or an aryl group which may have a substituent,
R ² , R ³ , R ⁴ and R ⁵ each independently have a linear, branched or cyclic alkyl group or substituent having 1 to 20 carbon atoms which may have a substituent; R ⁶ represents an aryl group which may have a substituent; A represents a CH group or a nitrogen atom; and B represents an oxygen atom, a sulfur atom, a CH ₂ group, an NH group or a carbon atom. Represents an alkylamino group having 1 to 4 atoms, a,
b, c and e are integers from 1 to 5, and d and f are 0
And g and h are each independently an integer of 1-4. 2. The phthalonitrile compound according to claim 1, wherein the phthalonitrile compound is substituted with at least one substituent selected from the group consisting of: 3. A compound of the general formula (1) (In the general formula (1), X, Y and Z represent a hydrogen atom or a fluorine atom, at least one of X, Y and Z is a fluorine atom, and W may have a substituent. Represents an aryl group, and V is (1) to (1) defined in claim 2;
(7) represents at least one substituent selected from the group consisting of substituents, and n is an integer of 0 to 4. The phthalonitrile compound according to claim 1 or 2, wherein 4. The phthalonitrile compound according to claim 3, wherein in the general formula (1), V is an alkoxycarbonyl group containing a bromo atom. 5. The phthalonitrile compound according to claim 3, wherein in the general formula (1), V is an alkoxycarbonyl group in which a secondary or higher alkyl group is directly bonded to a carbonyl group. 6. The method according to claim 1, wherein a phenol compound substituted with an aryl group which may have a substituent and a phthalonitrile compound substituted with at least one halogen atom are reacted. The method for producing a phthalonitrile compound according to any one of the above.