JP2011153277A - Method for producing aryl-substituted tetraazaporphyrin compound, compound obtained by the production method, and filter for display containing the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for producing an aryl-substituted tetraazaporphyrin compound; to provide an aryl-substituted tetraazaporphyrin compound produced by the production method; and to provide a filter for display containing the aryl-substituted tetraazaporphyrin compound. <P>SOLUTION: The method for producing an aryl-substituted tetraazaporphyrin compound comprises reacting the tetraazaporphyrin compound with an aryl compound having a leaving group in the presence of a base and a transition-metal compound. The tetraazaporphyrin compound is preferably a compound represented by formula (A), and the aryl compound having the leaving group is preferably a compound represented by formula (B): Ar-X (wherein, Ar represents an aryl group; and X represents a leaving group). In the formula, R represents a hydrogen atom, a cyano group, a nitro group, a straight chain, an alkyl group, an alkoxy group, an aryl group, an aryloxy group, an aralkyl group, an aralkyloxy group, a halogenoalkyl group, a halogenoalkoxy group, a substituted amino group, an alkoxyalkyl group, an alkoxyalkoxyalkyl group, an aryloxyalkyl group, an aralkyloxyalkyl group, a halogenoalkoxyalkyl group, or the like; m represents an integer of 0-8; and M represents two hydrogen atoms, two monovalent metal atoms, divalent metal atoms, trivalent substituted metal atoms, tetravalent substituted metal atoms, or metal oxide atoms. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to a method for producing an aryl-substituted tetraazaporphyrin compound. More specifically, the present invention relates to a method for producing an aryl-substituted tetraazaporphyrin compound useful for various functional material applications (for example, display filter applications, optical recording medium applications, ink applications, thermal transfer applications).

In recent years, with the advancement of sophistication in society, excellent functions are being developed for various functional material applications (for example, display filter applications, optical recording medium applications, ink applications, thermal transfer applications), including optoelectronic applications. The development of organic compounds has been actively conducted. As such an organic compound, a tetraazaporphyrin compound having excellent optical properties is known. For example, various tetraazaporphyrin compounds have been proposed as organic compounds for optical recording media (Patent Documents 1 to 3). Moreover, various tetraazaporphyrin compounds have been proposed as organic compounds for optical filters or display filters (Patent Documents 4 to 8). Among these tetraazaporphyrin compounds, a tetraazaporphyrin compound having an aryl group as a substituent is produced, for example, by a method of cyclizing a maleonitrile compound having an aryl group as a substituent (Patent Documents 9 to 10). ). According to the methods described in Patent Documents 9 and 10, although a tetraazaporphyrin compound having an aryl group as a substituent can be produced, the compound is produced as a mixture composed of a plurality of isomers.
In addition, it is guessed that the production | generation ratio of several isomers changes with reaction conditions, such as the temperature in the case of cyclization, the kind of substituent in a maleonitrile compound, etc. Although it is not certain whether this is due to the generation ratio of the plurality of isomers, the optical properties (for example, extinction coefficient) of the aryl-substituted tetraazaporphyrin compound produced by the methods described in Patent Documents 9 and 10 ) Turned out to be not so big.
As a large display, a plasma display attracting attention generates light (electromagnetic waves) with unnecessary intensity from the display screen due to its structure and operation principle, and it is necessary to shield the light. In order to improve such a point, for example, a compound that selectively and efficiently absorbs unnecessary light (for example, a compound that efficiently absorbs light in the wavelength range of 570 to 605 nm) is desired. Currently, there is a need for a method for producing an aryl-substituted tetraazaporphyrin compound that is stable and efficient and has excellent optical properties (eg, extinction coefficient).

JP 7-268227 A JP 9-309268 A JP 11-11015 A JP 2000-275432 A JP 2002-40233 A JP 2002-251144 A JP 2004-361551 A JP 2008-268331 A Japanese Patent Laid-Open No. 11-43619 Japanese Patent Laid-Open No. 11-100500

  An object of the present invention is to provide a novel method for producing an aryl-substituted tetraazaporphyrin compound. Furthermore, it is providing the filter for a display which has the outstanding optical characteristic containing the aryl substituted tetraazaporphyrin compound manufactured by this manufacturing method.

As a result of intensive studies on the method for producing aryl-substituted tetraazaporphyrin compounds, the present inventors have completed the present invention. That is, the present invention
(I) A method for producing an aryl-substituted tetraazaporphyrin compound obtained by reacting a tetraazaporphyrin compound with an aryl compound having a leaving group in the presence of a base and a transition metal compound,
(Ii) The tetraazaporphyrin compound relates to the production method according to (i), which is a compound represented by the general formula (A),

〔式中、Ｒは、水素原子、シアノ基、ニトロ基、直鎖、分岐または環状のアルキル基、直鎖、分岐または環状のアルコキシ基、置換または未置換のアリール基、置換または未置換のアリールオキシ基、置換または未置換のアラルキル基、置換または未置換のアラルキルオキシ基、直鎖、分岐または環状のハロゲノアルキル基、直鎖、分岐または環状のハロゲノアルコキシ基、置換アミノ基、直鎖、分岐または環状のアルコキシアルキル基、直鎖、分岐または環状のアルコキシアルコキシアルキル基、置換または未置換のアリールオキシアルキル基、置換または未置換のアラルキルオキシアルキル基、あるいは直鎖、分岐または環状のハロゲノアルコキシアルキル基を表し、さらに、隣接するＲ基は互いに結合して、置換している炭素原子と共に、置換または未置換の炭素環式脂肪族環を形成していてもよいを表し、ｍは０〜８の整数を表し（但し、ｍが８を表す場合、少なくとも１つのＲは水素原子を表す）、Ｍは２個の水素原子、２個の１価の金属原子、２価の金属原子、３価の置換金属原子、４価の置換金属原子、または酸化金属原子を表す〕

[Wherein, R represents a hydrogen atom, a cyano group, a nitro group, a linear, branched or cyclic alkyl group, a linear, branched or cyclic alkoxy group, a substituted or unsubstituted aryl group, a substituted or unsubstituted aryl group. Oxy group, substituted or unsubstituted aralkyl group, substituted or unsubstituted aralkyloxy group, linear, branched or cyclic halogenoalkyl group, linear, branched or cyclic halogenoalkoxy group, substituted amino group, linear, branched Or a cyclic alkoxyalkyl group, a linear, branched or cyclic alkoxyalkoxyalkyl group, a substituted or unsubstituted aryloxyalkyl group, a substituted or unsubstituted aralkyloxyalkyl group, or a linear, branched or cyclic halogenoalkoxyalkyl group And adjacent R groups are bonded to each other to share a substituted carbon atom. Represents an optionally substituted carbocyclic aliphatic ring, and m represents an integer of 0 to 8 (provided that when m represents 8, at least one R represents a hydrogen atom). And M represents two hydrogen atoms, two monovalent metal atoms, a divalent metal atom, a trivalent substituted metal atom, a tetravalent substituted metal atom, or a metal oxide atom]

（式中、Ａｒはアリール基を表し、Ｘは脱離基を表す）
(iv)またＡｒが置換基を有していてもよい炭素数３〜４０のアリール基である(iii)記載の製造方法であり、
(v)Ａｒが、フッ素原子、塩素原子、直鎖、分岐、または環状のアルキル基、直鎖、分岐、または環状のアルコキシ基、置換または未置換のアリール基、Ｎ，Ｎ−ジ置換アミノ基で置換されていてもよいアリール基である(iv)記載の製造方法であり、
(vi)Ｘがハロゲン原子または−ＯＳＯ_２−Ｒ_０(Ｒ_０は置換または未置換のアリール基、あるいはハロゲン原子で置換されていてもよい直鎖、分岐または環状のアルキル基を表す)である(iii)記載の製造方法であり、
(vii)前記−ＯＳＯ_２−Ｒ_０において、Ｒ_０が炭素数６〜１０の置換または未置換のアリール基、あるいは炭素数１〜１０のハロゲン原子で置換されていてもよい直鎖、分岐または環状のアルキル基である(vi)記載の製造方法に関する。
(viii)前記(ｉ)〜(vii)のいずれかに記載の製造方法により製造されるアリール置換テトラアザポルフィリン化合物に関するものである。さらには、
(ix)前記(viii)に記載のアリール置換テトラアザポルフィリン化合物を少なくとも１種含有して成るディスプレイ用フィルタに関するものである。 (iii) The aryl compound having a leaving group relates to the production method according to (i) or (ii), which is a compound represented by the general formula (B),

(In the formula, Ar represents an aryl group, and X represents a leaving group)
(iv) The production method according to (iii), wherein Ar is an aryl group having 3 to 40 carbon atoms which may have a substituent,
(v) Ar is a fluorine atom, a chlorine atom, a linear, branched, or cyclic alkyl group, a linear, branched, or cyclic alkoxy group, a substituted or unsubstituted aryl group, or an N, N-disubstituted amino group The production method according to (iv), which is an aryl group optionally substituted with
(vi) X is a halogen atom or —OSO ₂ —R ₀ (R ₀ represents a substituted or unsubstituted aryl group or a linear, branched or cyclic alkyl group which may be substituted with a halogen atom). (iii) is the production method described,
(vii) In the -OSO ₂ -R ₀ , R ₀ is a linear, branched, or substituted or unsubstituted aryl group having 6 to 10 carbon atoms, or a halogen atom having 1 to 10 carbon atoms The production method according to (vi), which is a cyclic alkyl group.
(viii) An aryl-substituted tetraazaporphyrin compound produced by the production method according to any one of (i) to (vii). Moreover,
(ix) The present invention relates to a display filter comprising at least one aryl-substituted tetraazaporphyrin compound described in (viii) above.

  The present invention makes it possible to provide a novel method for producing an aryl-substituted tetraazaporphyrin compound useful for various functional material applications (for example, display filter applications, optical recording medium applications, ink applications, thermal transfer applications). became. Furthermore, it has become possible to provide a display filter having excellent optical properties, which comprises an aryl-substituted tetraazaporphyrin compound produced by the production method.

It is typical sectional drawing of the filter for displays of this invention. It is typical sectional drawing of the filter for displays of this invention. It is typical sectional drawing of the filter for displays of this invention. It is typical sectional drawing of the filter for displays of this invention. It is typical sectional drawing of the filter for displays of this invention. It is typical sectional drawing of the filter for displays of this invention. It is typical sectional drawing of the filter for displays of this invention.

Hereinafter, the present invention will be described in detail.
The present invention relates to a method for producing an aryl-substituted tetraazaporphyrin compound obtained by reacting a tetraazaporphyrin compound with an aryl compound having a leaving group in the presence of a base and a transition metal compound.
The tetraazaporphyrin compound used in the present invention may be any compound that can introduce at least one aryl group into the tetraazaporphyrin skeleton, and the skeleton may have various substituents, preferably For example, it is a compound represented by the following general formula (A).

〔式中、Ｒは、水素原子、シアノ基、ニトロ基、直鎖、分岐または環状のアルキル基、直鎖、分岐または環状のアルコキシ基、置換または未置換のアリール基、置換または未置換のアリールオキシ基、置換または未置換のアラルキル基、置換または未置換のアラルキルオキシ基、直鎖、分岐または環状のハロゲノアルキル基、直鎖、分岐または環状のハロゲノアルコキシ基、置換アミノ基、直鎖、分岐または環状のアルコキシアルキル基、直鎖、分岐または環状のアルコキシアルコキシアルキル基、置換または未置換のアリールオキシアルキル基、置換または未置換のアラルキルオキシアルキル基、あるいは直鎖、分岐または環状のハロゲノアルコキシアルキル基を表し、さらに、隣接するＲ基は互いに結合して、置換している炭素原子と共に、置換または未置換の炭素環式脂肪族環を形成していてもよいを表し、ｍは０〜８の整数を表し（但し、ｍが８を表す場合、少なくとも１つのＲは水素原子を表す）、Ｍは２個の水素原子、２個の１価の金属原子、２価の金属原子、３価の置換金属原子、４価の置換金属原子、または酸化金属原子を表す〕

[Wherein, R represents a hydrogen atom, a cyano group, a nitro group, a linear, branched or cyclic alkyl group, a linear, branched or cyclic alkoxy group, a substituted or unsubstituted aryl group, a substituted or unsubstituted aryl group. Oxy group, substituted or unsubstituted aralkyl group, substituted or unsubstituted aralkyloxy group, linear, branched or cyclic halogenoalkyl group, linear, branched or cyclic halogenoalkoxy group, substituted amino group, linear, branched Or a cyclic alkoxyalkyl group, a linear, branched or cyclic alkoxyalkoxyalkyl group, a substituted or unsubstituted aryloxyalkyl group, a substituted or unsubstituted aralkyloxyalkyl group, or a linear, branched or cyclic halogenoalkoxyalkyl group And adjacent R groups are bonded to each other to share a substituted carbon atom. Represents an optionally substituted carbocyclic aliphatic ring, and m represents an integer of 0 to 8 (provided that when m represents 8, at least one R represents a hydrogen atom). And M represents two hydrogen atoms, two monovalent metal atoms, a divalent metal atom, a trivalent substituted metal atom, a tetravalent substituted metal atom, or a metal oxide atom]

In the present specification, the aryl group represents, for example, a carbocyclic aromatic group such as phenyl group or naphthyl group, for example, a heterocyclic aromatic group such as furyl group, thienyl group or pyridyl group, and preferably Represents a carbocyclic aromatic group.
In the compound represented by the general formula (A), R is preferably a hydrogen atom, a cyano group, a nitro group, a linear, branched or cyclic alkyl group having 1 to 24 carbon atoms, or a linear chain having 1 to 24 carbon atoms. Branched or cyclic alkoxy group, substituted or unsubstituted aryl group having 4 to 30 carbon atoms, substituted or unsubstituted aryloxy group having 4 to 30 carbon atoms, substituted or unsubstituted aralkyl group having 5 to 30 carbon atoms A substituted or unsubstituted aralkyloxy group having 5 to 30 carbon atoms, a linear, branched or cyclic halogenoalkyl group having 1 to 24 carbon atoms, a linear, branched or cyclic halogenoalkoxy group having 1 to 24 carbon atoms, N, N-disubstituted amino group having 2 to 30 carbon atoms, linear, branched or cyclic alkoxyalkyl group having 2 to 24 carbon atoms, linear, branched or cyclic alkoxyalkoxyalkyl having 3 to 24 carbon atoms Group, a substituted or unsubstituted aryloxyalkyl group having 5 to 30 carbon atoms, a substituted or unsubstituted aralkyloxyalkyl group having 6 to 30 carbon atoms, or a linear, branched or cyclic halogeno group having 2 to 24 carbon atoms Represents an alkoxyalkyl group.

In the formula represented by the general formula (A), R represents a substitution with a carbon atom at the β-position of the pyrrole ring in the tetraazaporphyrin skeleton.
Specific examples of R in the general formula (A) include, for example, a hydrogen atom, a cyano group, a nitro group, such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, sec- Butyl group, tert-butyl group, n-pentyl group, isopentyl group, neopentyl group, tert-pentyl group, 1,2-dimethylpropyl group, 1-methylbutyl group, 2-methylbutyl group, n-hexyl group, 1-methyl Pentyl group, 2-methylpentyl group, 4-methylpentyl group, 4-methyl-2-pentyl group, 1,2-dimethylbutyl group, 2,3-dimethylbutyl group, 3,3-dimethylbutyl group, 1- Ethylbutyl group, 2-ethylbutyl group, n-heptyl group, 1-methylhexyl group, 3-methylhexyl group, 5-methylhexyl group, 2,4-dimethyl Pentyl group, cyclohexylmethyl group, n-octyl group, tert-octyl group, 1-methylheptyl group, 2-ethylhexyl group, 2-propylpentyl group, 2,5-dimethylhexyl group, 2,5,5-trimethylhexyl Group, n-nonyl group, 2,2-dimethylheptyl group, 2,6-dimethyl-4-heptyl group, 3,5,5-trimethylhexyl group, n-decyl group, 4-ethyloctyl group, n-undecyl Group, 1-methyldecyl group, n-dodecyl group, 1,3,5,7-tetramethyloctyl group, n-tridecyl group, 1-hexylheptyl group, n-tetradecyl group, n-pentadecyl group, n-hexadecyl group N-heptadecyl group, n-octadecyl group, n-eicosyl group, n-tricosyl group, n-tetracosyl group, cyclopentyl group, cycl Hexyl group, 4-methylcyclohexyl group, 4-tert-butylcyclohexyl group, cycloheptyl group, straight chain, branched or cyclic alkyl groups such as cyclooctyl group,

  For example, methoxy group, ethoxy group, n-propoxy group, isopropoxy group, n-butoxy group, isobutoxy group, sec-butoxy group, n-pentyloxy group, neopentyloxy group, cyclopentyloxy group, n-hexyloxy group 3,3-dimethylbutyloxy group, 2-ethylbutyloxy group, cyclohexyloxy group, n-heptyloxy group, n-octyloxy group, 2-ethylhexyloxy group, n-nonyloxy group, n-decyloxy group, n -Undecyloxy group, n-dodecyloxy group, n-tridecyloxy group, n-tetradecyloxy group, n-pentadecyloxy group, n-hexadecyloxy group, n-heptadecyloxy group, n-octadecyl group Oxy group, n-eicosyloxy group, n-tricosyloxy group, n-tetrakoshi Linear, branched or cyclic alkoxy groups such as oxy group,

  For example, phenyl group, 2-methylphenyl group, 3-methylphenyl group, 4-methylphenyl group, 3-ethylphenyl group, 4-ethylphenyl group, 4-n-propylphenyl group, 4-isopropylphenyl group, 4 -N-butylphenyl group, 4-isobutylphenyl group, 4-tert-butylphenyl group, 4-n-pentylphenyl group, 4-isopentylphenyl group, 4-tert-pentylphenyl group, 4-n-hexylphenyl Group, 4-cyclohexylphenyl group, 4-n-heptylphenyl group, 4-n-octylphenyl group, 4-n-nonylphenyl group, 4-n-decylphenyl group, 4-n-undecylphenyl group, 4 -N-dodecylphenyl group, 4-n-tetradecylphenyl group, 4-n-hexadecylphenyl group, 4-n-octadecyl Phenyl group, 2,3-dimethylphenyl group, 2,4-dimethylphenyl group, 2,5-dimethylphenyl group, 2,6-dimethylphenyl group, 3,4-dimethylphenyl group, 3,5-dimethylphenyl group 3,4,5-trimethylphenyl group, 2,3,5,6-tetramethylphenyl group, 5-indanyl group, 1,2,3,4-tetrahydro-5-naphthyl group, 1,2,3, 4-tetrahydro-6-naphthyl group, 2-methoxyphenyl group, 3-methoxyphenyl group, 4-methoxyphenyl group, 3-ethoxyphenyl group, 4-ethoxyphenyl group, 4-n-propoxyphenyl group, 4-iso Propoxyphenyl group, 4-n-butoxyphenyl group, 4-isobutoxyphenyl group, 4-n-pentyloxyphenyl group, 4-n-hexyloxyphenyl 4-cyclohexyloxyphenyl group, 4-n-heptyloxyphenyl group, 4-n-octyloxyphenyl group, 4-n-nonyloxyphenyl group, 4-n-decyloxyphenyl group, 4-n-undecyl Oxyphenyl group, 4-n-dodecyloxyphenyl group, 4-n-tetradecyloxyphenyl group, 4-n-hexadecyloxyphenyl group, 4-n-octadecyloxyphenyl group, 2,3-dimethoxyphenyl group, 2,4-dimethoxyphenyl group, 2,5-dimethoxyphenyl group, 3,4-dimethoxyphenyl group, 3,5-dimethoxyphenyl group, 3,5-diethoxyphenyl group, 2-methoxy-4-methylphenyl group 2-methoxy-5-methylphenyl group, 3-methoxy-4-methylphenyl group, 2-methyl-4-methoxy Phenyl group, 3-methyl-4-methoxyphenyl group, 3-methyl-5-methoxyphenyl group, 2-fluorophenyl group, 3-fluorophenyl group, 4-fluorophenyl group, 2-chlorophenyl group, 3-chlorophenyl group 4-chlorophenyl group, 4-bromophenyl group, 4-trifluoromethylphenyl group, 3-trifluoromethylphenyl group, 2,4-difluorophenyl group, 3,5-difluorophenyl group, 2,4-dichlorophenyl group 3,4-dichlorophenyl group, 3,5-dichlorophenyl group, 2-methyl-4-chlorophenyl group, 2-chloro-4-methylphenyl group, 3-chloro-4-methylphenyl group, 2-chloro-4- Methoxyphenyl group, 3-methoxy-4-fluorophenyl group, 3-methoxy-4-chlorophenyl group 3-fluoro-4-methoxyphenyl group, 4-phenylphenyl group, 3-phenylphenyl group, 2-phenylphenyl group, 4- (4′-methylphenyl) phenyl group, 4- (4′-methoxyphenyl) phenyl Group, 3,5-diphenylphenyl group, 1-naphthyl group, 2-naphthyl group, 4-methyl-1-naphthyl group, 4-ethoxy-1-naphthyl group, 6-n-butyl-2-naphthyl group, 6 -Methoxy-2-naphthyl group, 7-ethoxy-2-naphthyl group, 2-furyl group, 2-thienyl group, 3-thienyl group, 2-pyridyl group, 3-pyridyl group, 4-pyridyl group, 4- ( N, N-dimethylamino) phenyl group, 3- (N, N-dimethylamino) phenyl group, 2- (N, N-dimethylamino) phenyl group, 4- (N, N-diethylamino) phenyl group 2- (N, N-diethylamino) phenyl group, 4- (N, N-di-n-butylamino) phenyl group, 4- (N, N-di-n-hexylamino) phenyl group, 4- (N -Cyclohexyl-N-methylamino) phenyl group, 4- (N, N-diethylamino) -1-naphthyl group, 4-pyrrolidinophenyl group, 4-piperidinophenyl group, 4-morpholinophenyl group, 4- Pyrrolidino-1-naphthyl group, 4- (N-benzyl-N-methylamino) phenyl group, 4- (N-benzyl-N-phenylamino) phenyl group, 4- (N-methyl-N-phenylamino) phenyl Group, 4- (N-ethyl-N-phenylamino) phenyl group, 4- (Nn-butyl-N-phenylamino) phenyl group, 4- (N, N-diphenylamino) phenyl group, 2- ( N, N-diphenylamino) phenyl group, 4- [N, N-di (4′-methylphenyl) amino] phenyl group, 4- [N, N-di (3′-methylphenyl) amino] phenyl group, 4- [N, N-di (4′-ethylphenyl) amino] phenyl group, 4- [N, N-di (4′-tert-butylphenyl) amino] phenyl group, 4- [N, N-di (4 '-N-hexylphenyl) amino] phenyl group, 4- [N, N-di (4'-methoxyphenyl) amino] phenyl group, 4- [N, N-di (4'-ethoxyphenyl) amino] phenyl 4- [N, N-di (4′-n-butoxyphenyl) amino] phenyl group, 4- [N, N-di (4′-n-hexyloxyphenyl) amino] phenyl group, 4- [N, N-di (4′-n-hexyloxyphenyl) amino] phenyl group, N, N-di (1′-naphthyl) amino] phenyl group, -[N, N-di (2'-naphthyl) amino] phenyl group, 4- [N-phenyl-N- (3'-methylphenyl) amino] phenyl group, 4- [N-phenyl-N- (4 '-Methylphenyl) amino] phenyl group, 4- [N-phenyl-N- (4'-octylphenyl) amino] phenyl group, 4- [N-phenyl-N- (4'-methoxyphenyl) amino] phenyl 4- [N-phenyl-N- (4′-ethoxyphenyl) amino] phenyl group, 4- [N-phenyl-N- (4′-n-hexyloxyphenyl) amino] phenyl group, 4- [N-phenyl-N- (4′-n-hexyloxyphenyl) amino] phenyl group, N-phenyl-N- (4′-fluorophenyl) amino] phenyl group, 4- [N-phenyl-N- (1′-naphthyl) amino] phenyl group, 4- [N-phenyl-N- (2 ′ -Naphthyl) amino] fe 4- [N-phenyl-N- (4′-phenylphenyl) amino] phenyl group, 4- (N, N-diphenylamino) -1-naphthyl group, 6- (N, N-diphenylamino) A substituted or unsubstituted aryl group such as a 2-naphthyl group, 4- (N-carbazolyl) phenyl group, 4- (N-phenoxadiyl) phenyl group,

  For example, phenyloxy group, 2-methylphenyloxy group, 3-methylphenyloxy group, 4-methylphenyloxy group, 3-ethylphenyloxy group, 4-ethylphenyloxy group, 4-n-propylphenyloxy group, 4-isopropylphenyloxy group, 4-n-butylphenyloxy group, 4-isobutylphenyloxy group, 4-tert-butylphenyloxy group, 4-n-pentylphenyloxy group, 4-isopentylphenyloxy group, 4 -Tert-pentylphenyloxy group, 4-n-hexylphenyloxy group, 4-cyclohexylphenyloxy group, 4-n-heptylphenyloxy group, 4-n-octylphenyloxy group, 4-n-nonylphenyloxy group 4-n-decylphenyloxy group, 4-n-undecyl Nyloxy group, 4-n-dodecylphenyloxy group, 4-n-tetradecylphenyloxy group, 4-n-hexadecylphenyloxy group, 4-n-octadecylphenyloxy group, 2,3-dimethylphenyloxy group, 2,4-dimethylphenyloxy group, 2,5-dimethylphenyloxy group, 2,6-dimethylphenyloxy group, 3,4-dimethylphenyloxy group, 3,5-dimethylphenyloxy group, 3,4,5 -Trimethylphenyloxy group, 2,3,5,6-tetramethylphenyloxy group, 5-indanyloxy group, 1,2,3,4-tetrahydro-5-naphthyloxy group, 1,2,3,4 -Tetrahydro-6-naphthyloxy group, 2-methoxyphenyloxy group, 3-methoxyphenyloxy group, 4-methoxyphenyloxy Group, 3-ethoxyphenyloxy group, 4-ethoxyphenyloxy group, 4-n-propoxyphenyloxy group, 4-isopropoxyphenyloxy group, 4-n-butoxyphenyloxy group, 4-isobutoxyphenyloxy group, 4-n-pentyloxyphenyloxy group, 4-n-hexyloxyphenyloxy group, 4-cyclohexyloxyphenyloxy group, 4-n-heptyloxyphenyloxy group, 4-n-octyloxyphenyloxy group, 4- n-nonyloxyphenyloxy group, 4-n-decyloxyphenyloxy group, 4-n-undecyloxyphenyloxy group, 4-n-dodecyloxyphenyloxy group, 4-n-tetradecyloxyphenyloxy group, 4-n-hexadecyloxyphenyloxy group, 4-n-octa Decyloxyphenyloxy group, 2,3-dimethoxyphenyloxy group, 2,4-dimethoxyphenyloxy group, 2,5-dimethoxyphenyloxy group, 3,4-dimethoxyphenyloxy group, 3,5-dimethoxyphenyloxy group 3,5-diethoxyphenyloxy group, 2-methoxy-4-methylphenyloxy group, 2-methoxy-5-methylphenyloxy group, 3-methoxy-4-methylphenyloxy group, 2-methyl-4- Methoxyphenyloxy group, 3-methyl-4-methoxyphenyloxy group, 3-methyl-5-methoxyphenyloxy group, 2-fluorophenyloxy group, 3-fluorophenyloxy group, 4-fluorophenyloxy group, 2- Chlorophenyloxy group, 3-chlorophenyloxy group, 4-chlorophenyloxy group Group, 4-bromophenyloxy group, 4-trifluoromethylphenyloxy group, 3-trifluoromethylphenyloxy group, 2,4-difluorophenyloxy group, 3,5-difluorophenyloxy group, 2,4-dichlorophenyl Oxy group, 3,4-dichlorophenyloxy group, 3,5-dichlorophenyloxy group, 2-methyl-4-chlorophenyloxy group, 2-chloro-4-methylphenyloxy group, 3-chloro-4-methylphenyloxy group 2-chloro-4-methoxyphenyloxy group, 3-methoxy-4-fluorophenyloxy group, 3-methoxy-4-chlorophenyloxy group, 3-fluoro-4-methoxyphenyloxy group, 4-phenylphenyloxy group , 3-phenylphenyloxy group, 2-phenylphenyloxy 4- (4′-methylphenyl) phenyloxy group, 4- (4′-methoxyphenyl) phenyloxy group, 3,5-diphenylphenyloxy group, 1-naphthyloxy group, 2-naphthyloxy group, 4- Methyl-1-naphthyloxy group, 4-ethoxy-1-naphthyloxy group, 6-n-butyl-2-naphthyloxy group, 6-methoxy-2-naphthyloxy group, 7-ethoxy-2-naphthyloxy group, A substituted or unsubstituted aryloxy group such as 2-furyloxy group, 2-thienyloxy group, 3-thienyloxy group, 2-pyridyloxy group, 3-pyridyloxy group, 4-pyridyloxy group,

  For example, benzyl group, α-methylbenzyl group, α-ethylbenzyl group, α, α-dimethylbenzyl group, α-phenylbenzyl group, α, α-diphenylbenzyl group, phenethyl group, α-methylphenethyl group, β- Methylphenethyl group, α, α-dimethylphenethyl group, 4-methylphenethyl group, 4-methylbenzyl group, 3-methylbenzyl group, 2-methylbenzyl group, 4-ethylbenzyl group, 2-ethylbenzyl group, 4- Isopropylbenzyl group, 4-tert-butylbenzyl group, 2-tert-butylbenzyl group, 4-tert-pentylbenzyl group, 4-cyclohexylbenzyl group, 4-n-octylbenzyl group, 4-tert-octylbenzyl group, 4-phenylbenzyl group, 4- (4′-methylphenyl) benzyl group, 4- (4′-tert) -Butylphenyl) benzyl group, 4- (4'-methoxyphenyl) benzyl group, 4-methoxybenzyl group, 3-methoxybenzyl group, 2-ethoxybenzyl group, 4-n-butoxybenzyl group, 4-n-heptyl Oxybenzyl group, 3,4-dimethoxybenzyl group, 4-fluorobenzyl group, 2-fluorobenzyl group, 4-chlorobenzyl group, 3-chlorobenzyl group, 2-chlorobenzyl group, 3,4-dichlorobenzyl group, A substituted or unsubstituted aralkyl group such as a 2-furfuryl group, a 1-naphthylmethyl group, and a 2-naphthylmethyl group,

  For example, benzyloxy group, α-methylbenzyloxy group, α-ethylbenzyloxy group, α, α-dimethylbenzyloxy group, α-phenylbenzyloxy group, α, α-diphenylbenzyloxy group, phenethyloxy group, α -Methylphenethyloxy group, β-methylphenethyloxy group, α, α-dimethylphenethyloxy group, 4-methylphenethyloxy group, 4-methylbenzyloxy group, 3-methylbenzyloxy group, 2-methylbenzyloxy group, 4-ethylbenzyloxy group, 2-ethylbenzyloxy group, 4-isopropylbenzyloxy group, 4-tert-butylbenzyloxy group, 2-tert-butylbenzyloxy group, 4-tert-pentylbenzyloxy group, 4- Cyclohexylbenzyloxy group, 4-n-octylben Zyloxy group, 4-tert-octylbenzyloxy group, 4-phenylbenzyloxy group, 4- (4′-methylphenyl) benzyloxy group, 4- (4′-tert-butylphenyl) benzyloxy group, 4- ( 4′-methoxyphenyl) benzyloxy group, 4-methoxybenzyloxy group, 3-methoxybenzyloxy group, 2-ethoxybenzyloxy group, 4-n-butoxybenzyloxy group, 4-n-heptyloxybenzyloxy group, 3,4-dimethoxybenzyloxy group, 4-fluorobenzyloxy group, 2-fluorobenzyloxy group, 4-chlorobenzyloxy group, 3-chlorobenzyloxy group, 2-chlorobenzyloxy group, 3,4-dichlorobenzyl Oxy group, 2-furfuryloxy group, 1-naphthylmethyloxy group, 2 A substituted or unsubstituted aralkyl group such as naphthylmethyl group,

For example, fluoromethyl group, 3-fluoropropyl group, 6-fluorohexyl group, 8-fluorooctyl group, trifluoromethyl group, 1,1-dihydro-perfluoroethyl group, 1,1-dihydro-perfluoro-n -Propyl group, 1,1,3-trihydro-perfluoro-n-propyl group, 2-hydro-perfluoro-2-propyl group,
1,1-dihydro-perfluoro-n-butyl group, 1,1-dihydro-perfluoro-n-pentyl group, 1,1-dihydro-perfluoro-n-hexyl group, 6-fluorohexyl group, 4- Fluorocyclohexyl group, 1,1-dihydro-perfluoro-n-octyl group, 1,1-dihydro-perfluoro-n-decyl group, 1,1-dihydro-perfluoro-n-dodecyl group, 1,1- Dihydro-perfluoro-n-tetradecyl group, 1,1-dihydro-perfluoro-n-hexadecyl group, perfluoroethyl group, perfluoro-n-propyl group, perfluoro-n-pentyl group, perfluoro-n- Hexyl group, 2,2-bis (trifluoromethyl) propyl group,
Linear, branched or cyclic such as dichloromethyl group, 2-chloroethyl group, 3-chloropropyl group, 4-chlorocyclohexyl group, 7-chloroheptyl group, 8-chlorooctyl group, 2,2,2-trichloroethyl group A halogenoalkyl group of

For example, fluoromethyloxy group, 3-fluoropropyloxy group, 6-fluorohexyloxy group, 8-fluorooctyloxy group, trifluoromethyloxy group, 1,1-dihydro-perfluoroethyloxy group, 1,1- Dihydro-perfluoro-n-propyloxy group, 1,1,3-trihydro-perfluoro-n-propyloxy group, 2-hydro-perfluoro-2-propyloxy group,
1,1-dihydro-perfluoro-n-butyloxy group, 1,1-dihydro-perfluoro-n-pentyloxy group, 1,1-dihydro-perfluoro-n-hexyloxy group, 6-fluorohexyloxy group 4-fluorocyclohexyloxy group, 1,1-dihydro-perfluoro-n-octyloxy group, 1,1-dihydro-perfluoro-n-decyloxy group, 1,1-dihydro-perfluoro-n-dodecyloxy group 1,1-dihydro-perfluoro-n-tetradecyloxy group, 1,1-dihydro-perfluoro-n-hexadecyloxy group, perfluoroethyloxy group, perfluoro-n-propyloxy group, Fluoro-n-pentyloxy group, perfluoro-n-hexyloxy group, 2,2-bis (trifluoromethyl Propyl group, dichloromethyloxy group, 2-chloroethyloxy group, 3-chloropropyloxy group, 4-chlorocyclohexyloxy group, 7-chloroheptyloxy group, 8-chlorooctyloxy group, 2,2, A linear, branched or cyclic halogenoalkoxy group such as a 2-trichloroethyloxy group,

  For example, N, N-dimethylamino group, N, N-diethylamino group, N, N-di-n-butylamino group, N, N-di-n-hexylamino group, N, N-di-n-octyl Amino group, N, N-di-n-decylamino group, N, N-di-n-dodecylamino group, N-methyl-N-ethylamino group, N-ethyl-Nn-butylamino group, N- Methyl-N-phenylamino group, N-ethyl-N-phenylamino group, Nn-butyl-N-phenylamino group, N-benzyl-N-phenylamino group, N, N-diphenylamino group, N, N-di (3-methylphenyl) amino group, N, N-di (4-methylphenyl) amino group, N, N-di (4-ethylphenyl) amino group, N, N-di (4-tert- Butylphenyl) amino group, N, N-di (4-n-hex) Ruphenyl) amino group, N, N-di (4-methoxyphenyl) amino group, N, N-di (4-ethoxyphenyl) amino group, N, N-di (4-n-butoxyphenyl) amino group, N , N-di (4-n-hexyloxyphenyl) amino group, N, N-di (1-naphthyl) amino group, N, N-di (2-naphthyl) amino group, N-phenyl-N- (3 -Methylphenyl) amino group, N-phenyl-N- (4-methylphenyl) amino group, N-phenyl-N- (4-octylphenyl) amino group, N-phenyl-N- (4-methoxyphenyl) amino Group, N-phenyl-N- (4-ethoxyphenyl) amino group, N-phenyl-N- (4-n-hexyloxyphenyl) amino group, N-phenyl-N- (4-fluorophenyl) amino group, N-feni -N- (1-naphthyl) amino group, N-phenyl-N- (2-naphthyl) amino group, N-phenyl-N- (3-phenylphenyl) amino group, N-phenyl-N- (4-phenyl) Phenyl) amino group, N-carbazolyl group, N-phenoxadiyl group, substituted amino group such as N-phenothiadiyl group,

  For example, methoxymethyl group, ethoxymethyl group, n-butoxymethyl group, n-pentyloxymethyl group, n-hexyloxymethyl group, (2-ethylbutyloxy) methyl group, n-heptyloxymethyl group, n-octyl Oxymethyl group, n-decyloxymethyl group, n-dodecyloxymethyl group, 2-methoxyethyl group, 2-ethoxyethyl group, 2-n-propoxyethyl group, 2-isopropoxyethyl group, 2-n-butoxy Ethyl group, 2-n-pentyloxyethyl group, 2-n-hexyloxyethyl group, 2- (2′-ethylbutyloxy) ethyl group, 2-n-heptyloxyethyl group, 2-n-octyloxyethyl group Group, 2- (2′-ethylhexyloxy) ethyl group, 2-n-decyloxyethyl group, 2-n-dodecyloxyethyl 2-n-tetradecyloxyethyl group, 2-cyclohexyloxyethyl group, 2-methoxypropyl group, 3-methoxypropyl group, 3-ethoxypropyl group, 3-n-propoxypropyl group, 3-isopropoxypropyl group 3-n-butoxypropyl group, 3-n-pentyloxypropyl group, 3-n-hexyloxypropyl group, 3- (2′-ethylbutoxy) propyl group, 3-n-octyloxypropyl group, 3- (2′-ethylhexyloxy) propyl group, 3-n-decyloxypropyl group, 3-n-dodecyloxypropyl group, 3-n-tetradecyloxypropyl group, 3-cyclohexyloxypropyl group, 4-methoxybutyl group 4-ethoxybutyl group, 4-n-propoxybutyl group, 4-isopropoxybutyl group, 4- -Butoxybutyl group, 4-n-hexyloxybutyl group, 4-n-octyloxybutyl group, 4-n-decyloxybutyl group, 4-n-dodecyloxybutyl group, 5-methoxypentyl group, 5-ethoxy Pentyl group, 5-n-propoxypentyl group, 5-n-pentyloxypentyl group, 6-methoxyhexyl group, 6-ethoxyhexyl group, 6-isopropoxyhexyl group, 6-n-butoxyhexyl group, 6-n -Hexyloxyhexyl group, 6-n-decyloxyhexyl group, 4-methoxycyclohexyl group, 7-methoxyheptyl group, 7-ethoxyheptyl group, 7-isopropoxyheptyl group, 8-methoxyoctyl group, 8-ethoxyoctyl group Group, 9-methoxynonyl group, 9-ethoxynonyl group, 10-methoxydecyl group, 10-ethoxy group Sidecyl group, 10-n-butoxydecyl group, 11-methoxyundecyl group, 11-ethoxyundecyl group, 12-methoxydodecyl group, 12-ethoxydodecyl group, 12-isopropoxide decyl group, 14-methoxytetradecyl group , Linear, branched or cyclic alkoxyalkyl groups such as tetrahydrofurfuryl group

For example, (2-methoxyethoxy) methyl group, (2-ethoxyethoxy) methyl group, (2-n-butyloxyethoxy) methyl group, (2-n-hexyloxyethoxy) methyl group, (3-methoxypropyloxy) ) Methyl group, (3-ethoxypropyloxy) methyl group, (3-n-butyloxypropyloxy) methyl group, (3-n-pentyloxypropyloxy) methyl group, (4-methoxybutyloxy) methyl group, (6-methoxyhexyloxy) methyl group, (10-ethoxydecyloxy) methyl group, 2- (2′-methoxyethoxy) ethyl group, 2- (2′-ethoxyethoxy) ethyl group, 2- (2′-) n-butoxyethoxy) ethyl group, 3- (2′-ethoxyethoxy) propyl group,
3- (2′-methoxypropyloxy) propyl group, 3- (2′-isopropyloxypropyloxy) propyl group, 3- (3′-methoxypropyloxy) propyl group, 3- (3′-ethoxypropyloxy) A linear, branched or cyclic alkoxyalkoxyalkyl group such as a propyl group,

  For example, phenyloxymethyl group, 4-methylphenyloxymethyl group, 3-methylphenyloxymethyl group, 2-methylphenyloxymethyl group, 4-ethylphenyloxymethyl group, 4-n-propylphenyloxymethyl group, 4 -N-butylphenyloxymethyl group, 4-tert-butylphenyloxymethyl group, 4-n-hexylphenyloxymethyl group, 4-n-octylphenyloxymethyl group, 4-n-decylphenyloxymethyl group, 4 -Methoxyphenyloxymethyl group, 4-ethoxyphenyloxymethyl group, 4-butoxyphenyloxymethyl group, 4-n-pentyloxyphenyloxymethyl group, 4-fluorophenyloxymethyl group, 3-fluorophenyloxymethyl group, 2-Fluorophenyloxymethyl 3,4-difluorophenyloxymethyl group, 4-chlorophenyloxymethyl group, 2-chlorophenyloxymethyl group, 4-phenylphenyloxymethyl group, 1-naphthyloxymethyl group, 2-naphthyloxymethyl group, 2-furyl Oxymethyl group, 1-phenyloxyethyl group, 2-phenyloxyethyl group, 2- (4′-methylphenyloxy) ethyl group, 2- (4′-ethylphenyloxy) ethyl group, 2- (4′- n-hexylphenyloxy) ethyl group, 2- (4′-methoxyphenyloxy) ethyl group, 2- (4′-n-butoxyphenyloxy) ethyl group, 2- (4′-fluorophenyloxy) ethyl group, 2- (4′-chlorophenyloxy) ethyl group, 2- (4′-bromophenyloxy) ethyl group, 2- (1 ′ Naphthyloxy) ethyl group, 2- (2′-naphthyloxy) ethyl group, 2-phenyloxypropyl group, 3-phenyloxypropyl group, 3- (4′-methylphenyloxy) propyl group, 3- (2 ′ -Naphthyloxy) propyl group, 4-phenyloxybutyl group, 4- (2'-ethylphenyloxy) butyl group, 4-phenyloxypentyl group, 5-phenyloxypentyl group, 5- (4'-tert-butyl) Phenyloxy) pentyl group, 6-phenyloxyhexyl group, 6- (2′-chlorophenyloxy) hexyl group, 8-phenyloxyoctyl group, 10-phenyloxydecyl group, 10- (3′-methylphenyloxy) decyl Substituted or unsubstituted aryloxyalkyl groups such as groups,

  For example, benzyloxymethyl group, phenethyloxymethyl group, 4-methylbenzyloxymethyl group, 3-methylbenzyloxymethyl group, 4-n-propylbenzyloxymethyl group, 4-n-octylbenzyloxymethyl group, 4- Methoxybenzyloxymethyl group, 4-ethoxybenzyloxymethyl group, 4-n-butoxybenzyloxymethyl group, 4-fluorobenzyloxymethyl group, 3-fluorobenzyloxymethyl group, 2-fluorobenzyloxymethyl group, 4- Chlorobenzyloxymethyl group, 4-phenylbenzyloxymethyl group, 2-benzyloxyethyl group, 2-phenethyloxyethyl group, 2- (4′-methylbenzyloxy) ethyl group, 2- (2′-methylbenzyloxy) ) Ethyl group, 2- (4′-fluoroben) Ruoxy) ethyl group, 2- (4′-chlorobenzyloxy) ethyl group, 3-benzyloxypropyl group, 3- (4′-methoxybenzyloxy) propyl group, 4-benzyloxybutyl group, 4- (4 ′ A substituted or unsubstituted aralkyloxyalkyl group such as -phenylbenzyloxy) butyl group, 5- (4'-methylbenzyloxy) pentyl group, 6-benzyloxyhexyl group, and 8-benzyloxyoctyl group;

  For example, fluoromethyloxymethyl group, 3-fluoro-n-propyloxymethyl group, 6-fluoro-n-hexyloxymethyl group, trifluoromethyloxymethyl group, 1,1-dihydro-perfluoroethyloxymethyl group, 1,1-dihydro-perfluoro-n-propyloxymethyl group, 2-hydro-perfluoro-2-propyloxymethyl group, 1,1-dihydro-perfluoro-n-butyloxymethyl group, 1,1- Dihydro-perfluoro-n-pentyloxymethyl group, 1,1-dihydro-perfluoro-n-hexyloxymethyl group, 1,1-dihydro-perfluoro-n-octyloxymethyl group, 1,1-dihydro- Perfluoro-n-decyloxymethyl group, 1,1-dihydro-perfluoro-n-tetradecyl Xymethyl group, 2,2-bis (trifluoromethyl) propyloxymethyl group, 3-chloro-n-propyloxymethyl group, 2- (8-fluoro-n-octyloxy) ethyl group, 2- (1,1 -Dihydro-perfluoroethyloxy) ethyl group, 2- (1,1,3-trihydro-perfluoro-n-propyloxy) ethyl group, 2- (1,1-dihydro-perfluoro-n-pentyloxy) Ethyl group, 2- (6-fluoro-n-hexyloxy) ethyl group, 2- (1,1-dihydro-perfluoro-n-octyloxy) ethyl group, 3- (4-fluorocyclohexyloxy) propyl group, 3- (1,1-dihydro-perfluoroethyloxy) propyl group, 3- (1,1-dihydro-perfluoro-n-dodecyloxy) propyl group 4- (perfluoro-n-hexyloxy) butyl group, 4- (1,1-dihydro-perfluoroethyloxy) butyl group, 6- (2-chloroethyloxy) hexyl group, 6- (1,1- Mention may be made of linear, branched or cyclic halogenoalkoxyalkyl groups such as (dihydro-perfluoroethyloxy) hexyl group.

In the compound represented by the general formula (A), R is more preferably a hydrogen atom, a linear, branched or cyclic alkyl group having 1 to 16 carbon atoms, a linear, branched or cyclic group having 1 to 16 carbon atoms. An alkoxy group, a substituted or unsubstituted aryl group having 4 to 24 carbon atoms, a substituted or unsubstituted aryloxy group having 4 to 24 carbon atoms, a substituted or unsubstituted aralkyl group having 5 to 24 carbon atoms, a carbon number of 5 to 5 24 substituted or unsubstituted aralkyloxy groups, linear, branched or cyclic halogenoalkyl groups having 1 to 16 carbon atoms, linear, branched or cyclic halogenoalkoxy groups having 1 to 16 carbon atoms, and 2 to 16 carbon atoms A linear, branched or cyclic alkoxyalkyl group, a linear, branched or cyclic alkoxyalkoxyalkyl group having 3 to 16 carbon atoms, a substituted or unsubstituted aryloxy group having 5 to 24 carbon atoms It represents an alkyl group, a substituted or unsubstituted aralkyloxy group having 6 to 24 carbon atoms or straight-chain having 2 to 16 carbon atoms, branched or cyclic halogenoalkoxy group.
In the compound represented by the general formula (A), R is more preferably a hydrogen atom, a linear, branched or cyclic alkyl group having 1 to 12 carbon atoms, or a substituted or unsubstituted aryl group having 6 to 16 carbon atoms. Particularly preferably a hydrogen atom, a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms, or a substituted or unsubstituted aryl group having 6 to 12 carbon atoms. Further, adjacent R groups may be bonded to each other to form a substituted or unsubstituted carbocyclic aliphatic ring together with a substituted carbon atom, and preferably a substituted group having 4 to 20 carbon atoms in total. Alternatively, an unsubstituted carbocyclic aliphatic ring may be formed, more preferably a substituted or unsubstituted carbocyclic aliphatic ring having 6 to 10 carbon atoms may be formed, and further preferably. May form a cyclopentane ring or a cyclohexane ring.

In the general formula (A), m represents an integer of 0 to 8, and when m represents 8, at least one R represents a hydrogen atom. In addition, when m represents 0, it represents that all the carbon atoms of the β-position of the pyrrole ring in the tetraazaporphyrin skeleton are substituted with hydrogen atoms. More preferably, m represents an integer of 0 to 4, and more preferably 4. When m represents an integer of 2 or more, R may be the same group or different groups.
In the general formula (A), M represents two hydrogen atoms, two monovalent metal atoms, a divalent metal atom, a trivalent substituted metal atom, a tetravalent substituted metal atom, or a metal oxide atom. And more preferably two hydrogen atoms, a divalent metal atom, or a metal oxide atom, and still more preferably a divalent metal atom or a metal oxide atom. Examples of the monovalent metal atom represented by M include Na, K, and Li. Examples of the divalent metal atom represented by M include Cu, Zn, Fe, Co, Ni, Ru, Rh, Pd, Pt, Mn, Mg, Ti, Be, Ca, Ba, Cd, Hg, and Pb. , Sn and the like. Examples of the trivalent substituted metal atom represented by M include Al—F, Al—Cl, Al—Br, Al—I, Ga—F, Ga—Cl, Ga—Br, Ga—I, and In—. F, In-Cl, In- Br, In-I, Tl-F, Tl-Cl, Tl-Br, Tl-I, Al-C 6 H 5, Al-C 6 H 4 (CH 3), In- _{C 6 H 5, In-C} 6 H 4 (CH 3), Mn (OH), Mn (OC 6 H 5)
, Mn [OSi (CH ₃ ) ₃ ], Fe—Cl, Ru—Cl, Rh—Cl, and the like. The tetravalent substituted metal atom represented by M, for _{example, CrCl 2, SiCl 2, SiBr} 2, SiF 2, SiI 2, ZrCl 2, ZrI 2, GeCl 2, GeBr 2, GeF 2, GeI 2, SnCl ₂ , SnF ₂ , SnBr ₂ , TiCl ₂ , TiBr ₂ , TiF ₂ , Si (OH) ₂ , Ge (OH) ₂ , Zr (OH) ₂ , Mn (OH) ₂ , Sn (OH) ₂ , Ti (R) ₀₀₀ ) ₂ , Cr (R ₀₀₀ ) ₂ , Si (R ₀₀₀ ) ₂ , Sn (R ₀₀₀ ) ₂ , Ge (R ₀₀₀ ) ₂ [wherein R ₀₀₀ represents an alkyl group, a phenyl group, a naphthyl group, or Represents a derivative], Si (OR ₁₁₁ ) ₂ , Sn (OR ₁₁₁ ) ₂ , Ge (OR ₁₁₁ ) ₂ , Ti (OR ₁₁₁ ) ₂ , Cr (OR ₁₁₁ ) ₂ [ In the formula, R ₁₁₁ represents an alkyl group, a phenyl group, a naphthyl group, a trialkylsilyl group, a dialkylalkoxysilyl group, or a derivative thereof.
Sn (SR ₂₂₂ ) ₂ , Ge (SR ₂₂₂ ) ₂ [wherein R ₂₂₂ represents an alkyl group, a phenyl group, a naphthyl group, or a derivative thereof]. Examples of the metal oxide atom represented by M include VO, MnO, TiO and the like.

In the general formula (A), M is more preferably Cu, Zn, Fe, Co, Ni, Pd, Mn, Mg, VO, TiO, and more preferably Cu, Ni, Pd, VO, Particularly preferred are Cu and VO.
The tetraazaporphyrin compound used in the production method of the present invention is more preferably a compound represented by the following general formula (1).

（式中、Ｒ_１〜Ｒ_４はそれぞれ独立に、水素原子、シアノ基、ニトロ基、直鎖、分岐または環状のアルキル基、直鎖、分岐または環状のアルコキシ基、置換または未置換のアリール基、置換または未置換のアリールオキシ基、置換または未置換のアラルキル基、置換または未置換のアラルキルオキシ基、直鎖、分岐または環状のハロゲノアルキル基、直鎖、分岐または環状のハロゲノアルコキシ基、置換アミノ基、直鎖、分岐または環状のアルコキシアルキル基、直鎖、分岐または環状のアルコキシアルコキシアルキル基、置換または未置換のアリールオキシアルキル基、置換または未置換のアラルキルオキシアルキル基、あるいは直鎖、分岐または環状のハロゲノアルコキシアルキル基を表し、Ｍ_１は２個の水素原子、２個の１価の金属原子、２価の金属原子、３価の置換金属原子、４価の置換金属原子、または酸化金属原子を表す）

Wherein R _{1 to} R ₄ are each independently a hydrogen atom, a cyano group, a nitro group, a linear, branched or cyclic alkyl group, a linear, branched or cyclic alkoxy group, a substituted or unsubstituted aryl group Substituted, unsubstituted aryloxy group, substituted or unsubstituted aralkyl group, substituted or unsubstituted aralkyloxy group, linear, branched or cyclic halogenoalkyl group, linear, branched or cyclic halogenoalkoxy group, substituted Amino group, linear, branched or cyclic alkoxyalkyl group, linear, branched or cyclic alkoxyalkoxyalkyl group, substituted or unsubstituted aryloxyalkyl group, substituted or unsubstituted aralkyloxyalkyl group, or linear, Represents a branched or cyclic halogenoalkoxyalkyl group, and M ₁ represents two hydrogen atoms, two monovalent metals. An atom, a divalent metal atom, a trivalent substituted metal atom, a tetravalent substituted metal atom, or a metal oxide atom)

In the compound represented by the general formula (1), R _{1 to} R ₄ are each independently a hydrogen atom, a cyano group, a nitro group, a linear, branched or cyclic alkyl group, a linear, branched or cyclic alkoxy group. Substituted, unsubstituted aryl group, substituted or unsubstituted aryloxy group, substituted or unsubstituted aralkyl group, substituted or unsubstituted aralkyloxy group, linear, branched or cyclic halogenoalkyl group, linear, branched Or a cyclic halogenoalkoxy group, a substituted amino group, a linear, branched or cyclic alkoxyalkyl group, a linear, branched or cyclic alkoxyalkoxyalkyl group, a substituted or unsubstituted aryloxyalkyl group, a substituted or unsubstituted aralkyl Represents an oxyalkyl group or a linear, branched or cyclic halogenoalkoxyalkyl group, preferably , A hydrogen atom, a cyano group, a nitro group, a linear, branched or cyclic alkyl group having 1 to 24 carbon atoms, a linear, branched or cyclic alkoxy group having 1 to 24 carbon atoms, a substitution having 4 to 30 carbon atoms, or An unsubstituted aryl group, a substituted or unsubstituted aryloxy group having 4 to 30 carbon atoms, a substituted or unsubstituted aralkyl group having 5 to 30 carbon atoms, a substituted or unsubstituted aralkyloxy group having 5 to 30 carbon atoms, C1-C24 linear, branched or cyclic halogenoalkyl group, C1-C24 linear, branched or cyclic halogenoalkoxy group, C2-C30 N, N-disubstituted amino group, carbon A linear, branched or cyclic alkoxyalkyl group having 2 to 24 carbon atoms, a linear, branched or cyclic alkoxyalkoxyalkyl group having 3 to 24 carbon atoms, and a substituted or unsubstituted aryl having 5 to 30 carbon atoms Kishiarukiru group represents a linear, branched or cyclic halogenoalkoxy group of substituted or unsubstituted aralkyloxy group having 6 to 30 carbon atoms or 2 to 24 carbon atoms.

In the compound represented by the general formula (1), more preferably, R _{1 to} R ₄ are a hydrogen atom, a straight chain having 1 to 16 carbon atoms, a branched or cyclic alkyl group, or a straight chain having 1 to 16 carbon atoms. Branched or cyclic alkoxy group, substituted or unsubstituted aryl group having 4 to 24 carbon atoms, substituted or unsubstituted aryloxy group having 4 to 24 carbon atoms, substituted or unsubstituted aralkyl group having 5 to 24 carbon atoms A substituted or unsubstituted aralkyloxy group having 5 to 24 carbon atoms, a linear, branched or cyclic halogenoalkyl group having 1 to 16 carbon atoms, a linear, branched or cyclic halogenoalkoxy group having 1 to 16 carbon atoms, A linear, branched or cyclic alkoxyalkyl group having 2 to 16 carbon atoms, a linear, branched or cyclic alkoxyalkoxyalkyl group having 3 to 16 carbon atoms, a substituted or unsubstituted aryl group having 5 to 24 carbon atoms. Lumpur oxyalkyl group represents a linear, branched or cyclic halogenoalkoxy group of substituted or unsubstituted aralkyloxy group having 6 to 24 carbon atoms or 2 to 16 carbon atoms.

In the compound represented by the general formula (1), R _{1 to} R ₄ are more preferably a linear, branched or cyclic alkyl group having 1 to 12 carbon atoms, or a substituted or unsubstituted group having 6 to 16 carbon atoms. And particularly preferably a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms, or a substituted or unsubstituted aryl group having 6 to 12 carbon atoms. A linear, branched or cyclic alkyl group represented by R _{1 to} R ₄ , a linear, branched or cyclic alkoxy group, a substituted or unsubstituted aryl group, a substituted or unsubstituted aryloxy group, substituted or unsubstituted An aralkyl group, a substituted or unsubstituted aralkyloxy group, a linear, branched or cyclic halogenoalkyl group, a linear, branched or cyclic halogenoalkoxy group, a substituted amino group, a linear, branched or cyclic alkoxyalkyl group, Specific examples of the linear, branched or cyclic alkoxyalkoxyalkyl group, the substituted or unsubstituted aryloxyalkyl group, the substituted or unsubstituted aralkyloxyalkyl group, or the linear, branched or cyclic halogenoalkoxyalkyl group include
For example, a linear, branched or cyclic alkyl group, a linear, branched or cyclic alkoxy group, a substituted or unsubstituted aryl group, a substituted or unsubstituted aryloxy group, substituted Or an unsubstituted aralkyl group, a substituted or unsubstituted aralkyloxy group, a linear, branched or cyclic halogenoalkyl group, a linear, branched or cyclic halogenoalkoxy group, a substituted amino group, a linear, branched or cyclic alkoxy List alkyl groups, linear, branched or cyclic alkoxyalkoxyalkyl groups, substituted or unsubstituted aryloxyalkyl groups, substituted or unsubstituted aralkyloxyalkyl groups, or linear, branched or cyclic halogenoalkoxyalkyl groups. Can do.

In the general formula (1), M ₁ represents two hydrogen atoms, two monovalent metal atoms, a divalent metal atom, a trivalent substituted metal atom, a tetravalent substituted metal atom, or a metal oxide atom. More preferably, they are two hydrogen atoms, a bivalent metal atom, or a metal oxide atom, More preferably, they are Cu or VO. Specific examples of the two monovalent metal atoms, divalent metal atoms, trivalent substituted metal atoms, tetravalent substituted metal atoms, or oxidized metal atoms represented by M ₁ include, for example, the general formula ( The two monovalent metal atoms, the bivalent metal atom, the trivalent substituted metal atom, the tetravalent substituted metal atom, or the metal oxide atom mentioned in M of A) can be exemplified.
In addition, in the manufacturing method of this invention, the tetraaza porphyrin compound to be used may be used individually by 1 type, or may use multiple together.
Moreover, in this specification, the compound represented by General formula (1) is actually 1 type chosen from the compound represented by the following general formula (1-A)-general formula (1-D). Or a mixture of two or more isomers [see, for example, Chem. Heterocycl. Comp. , 24, 1043 (1988), JP-A-11-43619]. In describing the structure of such a mixture of a plurality of isomers, in this specification, for example, one structural formula represented by the general formula (1) is described for convenience.

〔式中、Ｒ_１〜Ｒ_４、およびＭ_１は、一般式（１）の場合と同じ意味を表す〕

[Wherein R _{1 to} R ₄ and M ₁ represent the same meaning as in the general formula (1)]

The tetraazaporphyrin compound used in the production method of the present invention is, for example, one compound selected from compounds represented by general formula (1-A) to general formula (1-D), or two or more isomers. Mixtures of the body can be used. The tetraazaporphyrin compound used in the production method of the present invention can be produced by referring to a method known per se. That is, for example, US Pat. No. 2,850,505, British Patent No. 689387, J. Pat. Gen. Chem. USSR, 47, 1954 (1977) and JP-A 2006-321925 can be used for the production.
Although it does not specifically limit as an aryl compound which has a leaving group used in the manufacturing method of this invention, Preferably, it is a compound represented by general formula (B).

（式中、Ａｒはアリール基を表し、Ｘは脱離基を表す）

一般式（Ｂ）で表わされる化合物において、Ａｒはアリール基を表し、好ましくは、置換基を有していてもよい炭素数３〜４０のアリール基を表し、より好ましくは、置換基を有していてもよい炭素数４〜３５のアリール基を表す。Ａｒは置換基を有していてもよく、例えば、フッ素原子、塩素原子、直鎖、分岐、または環状のアルキル基、直鎖、分岐、または環状のアルコキシ基、置換または未置換のアリール基、Ｎ，Ｎ−ジ置換アミノ基などで置換されていてもよいアリール基を表す。
Ａｒの具体例としては、例えば、フェニル基、１−ナフチル基、２−ナフチル基、２−アントラセニル基、９−アントラセニル基、９−メチル−１０−アントラセニル基、９−フェニル−１０−アントラセニル基、１−フェナントレニル基、２−フェナントレニル基、３−フェナントレニル基、４−フェナントレニル基、９−フェナントレニル基、９−メチル−１０−フェナントレニル基、９−フェニル−１０−フェナントレニル基、１−メチル−９−フェナントレニル基、１−フェニル−９−フェナントレニル基、２−メチル−９−フェナントレニル基、２−フェニル−９−フェナントレニル基、１，８−ジメチル−９−フェナントレニル基、１，８−ジフェニル−９−フェナントレニル基、２，７−ジメチル−９−フェナントレニル基、２，７−ジフェニル−９−フェナントレニル基、２，７，９−トリメチル−１０−フェナントレニル基、２，７，９−トリフェニル−１０−フェナントレニル基、４−キノリニル基、１−ピレニル基、４−ピリジニル基、３−ピリジニル基、２−ピリジニル基、３−フラニル基、２−フラニル基、３−チエニル基、２−チエニル基、２−オキサゾリル基、２−チアゾリル基、２−ベンゾオキサゾリル基、２−ベンゾチアゾリル基、２−ベンゾイミダゾリル基、４−メチルフェニル基、３−メチルフェニル基、２−メチルフェニル基、４−エチルフェニル基、３−エチルフェニル基、２−エチルフェニル基、４−ｎ−プロピルフェニル基、４−イソプロピルフェニル基、２−イソプロピルフェニル基、４−ｎ−ブチルフェニル基、４−イソブチルフェニル基、４−ｓｅｃ−ブチルフェニル基、２−ｓｅｃ−ブチルフェニル基、４−ｔｅｒｔ−ブチルフェニル基、３−ｔｅｒｔ−ブチルフェニル基、２−ｔｅｒｔ−ブチルフェニル基、４−ｎ−ペンチルフェニル基、４−イソペンチルフェニル基、２−ネオペンチルフェニル基、４−ｔｅｒｔ−ペンチルフェニル基、４−ｎ−ヘキシルフェニル基、４−（２’−エチルブチル）フェニル基、４−ｎ−ヘプチルフェニル基、４−ｎ−オクチルフェニル基、４−（２’−エチルヘキシル）フェニル基、４−ｔｅｒｔ−オクチルフェニル基、４−ｎ−デシルフェニル基、４−ｎ−ドデシルフェニル基、４−ｎ−テトラデシルフェニル基、４−シクロペンチルフェニル基、４−シクロヘキシルフェニル基、４−（４’−メチルシクロヘキシル）フェニル基、４−（４’−ｔｅｒｔ−ブチルシクロヘキシル）フェニル基、３−シクロヘキシルフェニル基、２−シクロヘキシルフェニル基、４−エチル−１−ナフチル基、６−ｎ−ブチル−２−ナフチル基、２，４−ジメチルフェニル基、３，５−ジメチルフェニル基、２，６−ジメチルフェニル基、２，４−ジエチルフェニル基、２，３，５−トリメチルフェニル基、２，３，６−トリメチルフェニル基、３，４，５−トリメチルフェニル基、２，６−ジエチルフェニル基、２，５−ジイソプロピルフェニル基、２，６−ジイソブチルフェニル基、２，４−ジ−ｔｅｒｔ−ブチルフェニル基、２，５−ジ−ｔｅｒｔ−ブチルフェニル基、４，６−ジ−ｔｅｒｔ−ブチル−２−メチルフェニル基、５−ｔｅｒｔ−ブチル−２−メチルフェニル基、４−ｔｅｒｔ−ブチル−２，６−ジメチルフェニル基、４−メトキシフェニル基、３−メトキシフェニル基、２−メトキシフェニル基、４−エトキシフェニル基、３−エトキシフェニル基、２−エトキシフェニル基、４−ｎ−プロポキシフェニル基、３−ｎ−プロポキシフェニル基、４−イソプロポキシフェニル基、３−イソプロポキシフェニル基、２−イソプロポキシフェニル基、４−ｎ−ブトキシフェニル基、４−イソブトキシフェニル基、２−ｓｅｃ−ブトキシフェニル基、４−ｎ−ペンチルオキシフェニル基、４−イソペンチルオキシフェニル基、２−イソペンチルオキシフェニル基、４−ネオペンチルオキシフェニル基、２−ネペンチルオキシフェニル基、４−ｎ−ヘキシルオキシフェニル基、２−（２’−エチルブチルオキシ）フェニル基、４−ｎ−オクチルオキシフェニル基、４−ｎ−デシルオキシフェニル基、４−ｎ−ドデシルオキシフェニル基、４−ｎ−テトラデシルオキシフェニル基、４−シクロヘキシルオキシフェニル基、２−シクロヘキシルオキシフェニル基、２−メトキシ−１−ナフチル基、４−メトキシ−１−ナフチル基、４−ｎ−ブトキシ−１−ナフチル基、５−エトキシ−１−ナフチル基、６−メトキシ−２−ナフチル基、６−エトキシ−２−ナフチル基、６−ｎ−ブトキシ−２−ナフチル基、６−ｎ−ヘキシルオキシ−２−ナフチル基、７−メトキシ−２−ナフチル基、７−ｎ−ブトキシ−２−ナフチル基、２−メチル−４−メトキシフェニル基、２−メチル−５−メトキシフェニル基、３−メチル−５−メトキシフェニル基、３−エチル−５−メトキシフェニル基、２−メトキシ−４−メチルフェニル基、３−メトキシ−４−メチルフェニル基、２，４−ジメトキシフェニル基、２，５−ジメトキシフェニル基、２，６−ジメトキシフェニル基、３，４−ジメトキシフェニル基、３，５−ジメトキシフェニル基、３，５−ジエトキシフェニル基、３，５−ジ−ｎ−ブトキシフェニル基、２−メトキシ−４−エトキシフェニル基、２−メトキシ−６−エトキシフェニル基、３，４，５−トリメトキシフェニル基、４−フェニルフェニル基、３−フェニルフェニル基、２−フェニルフェニル基、４−（４’−メチルフェニル）フェニル基、４−（３’−メチルフェニル）フェニル基、４−（４’−メトキシフェニル）フェニル基、４−（４’−ｎ−ブトキシフェニル）フェニル基、２−（２’−メトキシフェニル）フェニル基、３−メチル−４−フェニルフェニル基、３−メトキシ−４−フェニルフェニル基、４−フルオロフェニル基、３−フルオロフェニル基、２−フルオロフェニル基、３，４−ジフルオロフェニル基、２，４−ジフルオロフェニル基、２，６−ジフルオロフェニル基、２−フルオロ−４−メチルフェニル基、２−メチル−４−フルオロフェニル基、２−クロロフェニル基、４−Ｎ，Ｎ−ジメチルアミノフェニル基、４−Ｎ，Ｎ−ジエチルアミノフェニル基、４−Ｎ，Ｎ−ジフェニルアミノフェニル基、４−Ｎ−フェニル−Ｎ−（１’−ナフチル）アミノフェニル基、４−（４’−Ｎ，Ｎ−ジメチルアミノフェニル）フェニル基、４−〔４’−Ｎ−フェニル−Ｎ−（１”−ナフチル）アミノフェニル〕フェニル基、４−〔４’−Ｎ，Ｎ−ジ（１”−ナフチル）−アミノフェニル〕フェニル基、ジベンゾチオフェン−３−イル基、３−（Ｎ，Ｎ−ジフェニルアミノ）ジベンゾチオフェン−６−イル基、３−〔Ｎ−フェニル−Ｎ−（１’−ナフチル）アミノ〕ジベンゾチオフェン−６−イル基、３−〔Ｎ，Ｎ−ジ（１’−ナフチル）アミノ〕ジベンゾチオフェン−６−イル基、９Ｈ−フルオレン−２−イル基、９，９−ジメチル−９Ｈ−フルオレン−２−イル基、９，９−ジ−ｎ−ヘキシル−９Ｈ−フルオレン−２−イル基、９，９−ジ−ｎ−オクチル−９Ｈ−フルオレン−２−イル基などのアリール基を挙げることができる。

(In the formula, Ar represents an aryl group, and X represents a leaving group)

In the compound represented by the general formula (B), Ar represents an aryl group, preferably an optionally substituted aryl group having 3 to 40 carbon atoms, more preferably a substituent. Represents an optionally substituted aryl group having 4 to 35 carbon atoms. Ar may have a substituent, for example, a fluorine atom, a chlorine atom, a linear, branched, or cyclic alkyl group, a linear, branched, or cyclic alkoxy group, a substituted or unsubstituted aryl group, An aryl group which may be substituted with an N, N-disubstituted amino group or the like is represented.
Specific examples of Ar include, for example, phenyl group, 1-naphthyl group, 2-naphthyl group, 2-anthracenyl group, 9-anthracenyl group, 9-methyl-10-anthracenyl group, 9-phenyl-10-anthracenyl group, 1-phenanthrenyl group, 2-phenanthrenyl group, 3-phenanthrenyl group, 4-phenanthrenyl group, 9-phenanthrenyl group, 9-methyl-10-phenanthrenyl group, 9-phenyl-10-phenanthrenyl group, 1-methyl-9-phenanthrenyl Group, 1-phenyl-9-phenanthrenyl group, 2-methyl-9-phenanthrenyl group, 2-phenyl-9-phenanthrenyl group, 1,8-dimethyl-9-phenanthrenyl group, 1,8-diphenyl-9-phenanthrenyl group 2,7-dimethyl-9-phenanthrenyl group, , 7-diphenyl-9-phenanthrenyl group, 2,7,9-trimethyl-10-phenanthrenyl group, 2,7,9-triphenyl-10-phenanthrenyl group, 4-quinolinyl group, 1-pyrenyl group, 4-pyridinyl group Group, 3-pyridinyl group, 2-pyridinyl group, 3-furanyl group, 2-furanyl group, 3-thienyl group, 2-thienyl group, 2-oxazolyl group, 2-thiazolyl group, 2-benzoxazolyl group, 2-benzothiazolyl group, 2-benzimidazolyl group, 4-methylphenyl group, 3-methylphenyl group, 2-methylphenyl group, 4-ethylphenyl group, 3-ethylphenyl group, 2-ethylphenyl group, 4-n- Propylphenyl group, 4-isopropylphenyl group, 2-isopropylphenyl group, 4-n-butylphenyl group, 4-isobuty Phenyl group, 4-sec-butylphenyl group, 2-sec-butylphenyl group, 4-tert-butylphenyl group, 3-tert-butylphenyl group, 2-tert-butylphenyl group, 4-n-pentylphenyl group 4-isopentylphenyl group, 2-neopentylphenyl group, 4-tert-pentylphenyl group, 4-n-hexylphenyl group, 4- (2′-ethylbutyl) phenyl group, 4-n-heptylphenyl group, 4-n-octylphenyl group, 4- (2′-ethylhexyl) phenyl group, 4-tert-octylphenyl group, 4-n-decylphenyl group, 4-n-dodecylphenyl group, 4-n-tetradecylphenyl Group, 4-cyclopentylphenyl group, 4-cyclohexylphenyl group, 4- (4'-methylcyclohexyl) phenyl Group, 4- (4′-tert-butylcyclohexyl) phenyl group, 3-cyclohexylphenyl group, 2-cyclohexylphenyl group, 4-ethyl-1-naphthyl group, 6-n-butyl-2-naphthyl group, 2, 4-dimethylphenyl group, 3,5-dimethylphenyl group, 2,6-dimethylphenyl group, 2,4-diethylphenyl group, 2,3,5-trimethylphenyl group, 2,3,6-trimethylphenyl group, 3,4,5-trimethylphenyl group, 2,6-diethylphenyl group, 2,5-diisopropylphenyl group, 2,6-diisobutylphenyl group, 2,4-di-tert-butylphenyl group, 2,5- Di-tert-butylphenyl group, 4,6-di-tert-butyl-2-methylphenyl group, 5-tert-butyl-2-methylphenyl group, 4- tert-butyl-2,6-dimethylphenyl group, 4-methoxyphenyl group, 3-methoxyphenyl group, 2-methoxyphenyl group, 4-ethoxyphenyl group, 3-ethoxyphenyl group, 2-ethoxyphenyl group, 4- n-propoxyphenyl group, 3-n-propoxyphenyl group, 4-isopropoxyphenyl group, 3-isopropoxyphenyl group, 2-isopropoxyphenyl group, 4-n-butoxyphenyl group, 4-isobutoxyphenyl group, 2-sec-butoxyphenyl group, 4-n-pentyloxyphenyl group, 4-isopentyloxyphenyl group, 2-isopentyloxyphenyl group, 4-neopentyloxyphenyl group, 2-nepentyloxyphenyl group, 4 -N-hexyloxyphenyl group, 2- (2'-ethylbutyloxy) pheny Group, 4-n-octyloxyphenyl group, 4-n-decyloxyphenyl group, 4-n-dodecyloxyphenyl group, 4-n-tetradecyloxyphenyl group, 4-cyclohexyloxyphenyl group, 2-cyclohexyl Oxyphenyl group, 2-methoxy-1-naphthyl group, 4-methoxy-1-naphthyl group, 4-n-butoxy-1-naphthyl group, 5-ethoxy-1-naphthyl group, 6-methoxy-2-naphthyl group 6-ethoxy-2-naphthyl group, 6-n-butoxy-2-naphthyl group, 6-n-hexyloxy-2-naphthyl group, 7-methoxy-2-naphthyl group, 7-n-butoxy-2- Naphthyl group, 2-methyl-4-methoxyphenyl group, 2-methyl-5-methoxyphenyl group, 3-methyl-5-methoxyphenyl group, 3-ethyl-5-metho Siphenyl group, 2-methoxy-4-methylphenyl group, 3-methoxy-4-methylphenyl group, 2,4-dimethoxyphenyl group, 2,5-dimethoxyphenyl group, 2,6-dimethoxyphenyl group, 3,4 -Dimethoxyphenyl group, 3,5-dimethoxyphenyl group, 3,5-diethoxyphenyl group, 3,5-di-n-butoxyphenyl group, 2-methoxy-4-ethoxyphenyl group, 2-methoxy-6- Ethoxyphenyl group, 3,4,5-trimethoxyphenyl group, 4-phenylphenyl group, 3-phenylphenyl group, 2-phenylphenyl group, 4- (4′-methylphenyl) phenyl group, 4- (3 ′ -Methylphenyl) phenyl group, 4- (4'-methoxyphenyl) phenyl group, 4- (4'-n-butoxyphenyl) phenyl group, 2- (2'-methoxy) Ciphenyl) phenyl group, 3-methyl-4-phenylphenyl group, 3-methoxy-4-phenylphenyl group, 4-fluorophenyl group, 3-fluorophenyl group, 2-fluorophenyl group, 3,4-difluorophenyl group 2,4-difluorophenyl group, 2,6-difluorophenyl group, 2-fluoro-4-methylphenyl group, 2-methyl-4-fluorophenyl group, 2-chlorophenyl group, 4-N, N-dimethylamino Phenyl group, 4-N, N-diethylaminophenyl group, 4-N, N-diphenylaminophenyl group, 4-N-phenyl-N- (1′-naphthyl) aminophenyl group, 4- (4′-N, N-dimethylaminophenyl) phenyl group, 4- [4′-N-phenyl-N- (1 ″ -naphthyl) aminophenyl] phenyl group, 4- [4′- N, N-di (1 ″ -naphthyl) -aminophenyl] phenyl group, dibenzothiophen-3-yl group, 3- (N, N-diphenylamino) dibenzothiophen-6-yl group, 3- [N-phenyl] -N- (1'-naphthyl) amino] dibenzothiophen-6-yl group, 3- [N, N-di (1'-naphthyl) amino] dibenzothiophen-6-yl group, 9H-fluoren-2-yl Group, 9,9-dimethyl-9H-fluoren-2-yl group, 9,9-di-n-hexyl-9H-fluoren-2-yl group, 9,9-di-n-octyl-9H-fluorene- An aryl group such as a 2-yl group can be mentioned.

In the compound represented by the general formula (B), X represents a leaving group, and preferably represents a halogen atom or —OSO ₂ —R ₀ . The halogen atom which is a preferable leaving group represented by X represents a chlorine atom, a bromine atom or an iodine atom, and more preferably a bromine atom or an iodine atom. In —OSO ₂ —R ₀ which is a preferred leaving group represented by X, R ₀ represents a substituted or unsubstituted aryl group, or a linear, branched or cyclic alkyl group which may be substituted with a halogen atom. More preferably, it represents a substituted or unsubstituted aryl group having 6 to 10 carbon atoms, or a linear, branched or cyclic alkyl group which may be substituted with a halogen atom having 1 to 10 carbon atoms, and more preferably Represents a linear, branched or cyclic alkyl group which may be substituted with a halogen atom having 1 to 8 carbon atoms. Specific examples of the substituted or unsubstituted aryl group represented by R ₀ include the aryl groups listed as specific examples of Ar in the general formula (B).
Specific examples of the linear, branched or cyclic alkyl group which may be substituted with a halogen atom represented by R ₀ include, for example, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, and an n-butyl group. , Isobutyl group, tert-butyl group, n-pentyl group, cyclopentyl group, cyclohexyl group, n-octyl group, n-decyl group and other alkyl groups, trifluoromethyl group, chlorodifluoromethyl group, dichlorofluoromethyl group, penta Examples thereof include alkyl groups substituted with halogen atoms such as a fluoroethyl group and an n-nonafluorobutyl group. The -OSO ₂ -R ₀ is the preferred leaving group represented by X, more preferably, a benzene sulfonyloxy group, p- toluenesulfonyloxy group, methanesulfonyloxy group, a trifluoromethanesulfonyloxy group.

  The amount of the aryl compound having a leaving group is not particularly limited, and the amount necessary to produce an aryl-substituted tetraazaporphyrin compound at a desired ratio with respect to the raw material tetraazaporphyrin compound is used. can do. For example, when four aryl groups are introduced into a tetraazaporphyrin compound, the amount of the aryl compound having a leaving group is generally 2.0 to 7 with respect to 1 mol of the tetraazaporphyrin compound. It is preferable to use about 0.0 mol, and more preferably about 3.0 to 6.0 mol. Further, as the tetraazaporphyrin compound, for example, in the general formula (A), R is a substituent other than a hydrogen atom, for example, an alkyl group or an aryl group, and m is 4, When a group is introduced, the aryl compound having a leaving group may be used in a large excess amount. For example, an amount exceeding 7.0 mol may be used per 1 mol of the tetraazaporphyrin compound. it can.

  Examples of the base used in the production method of the present invention include inorganic bases such as sodium carbonate, potassium carbonate, cesium carbonate, sodium hydroxide, potassium hydroxide, potassium phosphate, sodium bicarbonate, and potassium bicarbonate, such as sodium. -Tert-butoxide, potassium-tert-butoxide, sodium methoxide, potassium methoxide, sodium ethoxide, potassium ethoxide, sodium (2,4,6-tri-tert-butylphenolate), potassium (2,4,4) Metal alkoxides such as potassium (2,6-di-tert-butyl-4-methylphenolate), potassium acetate, sodium acetate, triethylamine, triisopropylamine, tri- n-Butyl A , Tetra-n-butylammonium bromide, 1,8-diazabicyclo [5.4.0] -7-undecene (DBU), 1,5-diazabicyclo [4.3.0] -5-nonene (DBN), Examples thereof include organic bases such as N, N, N ′, N′-tetramethylethylenediamine.

Such bases may be used alone or in combination. The amount of the base used is not particularly limited, but is generally 0.5 to 3.0 mol, preferably 0.8 to 2.5, per 1 mol of the aryl compound having a leaving group. Use mol.
The transition metal compound used in the production method of the present invention is not particularly limited, but is preferably a compound containing a metal atom selected from Group 7 to Group 11, more preferably Group 10 It is a compound containing the metal atom selected from these. The compound containing a metal atom selected from Group 10 is preferably a compound containing a palladium atom (hereinafter abbreviated as a palladium compound) or a compound containing a nickel atom (hereinafter abbreviated as a nickel compound). More preferably, it is a palladium compound. The transition metal compound used in the production method of the present invention is not particularly limited. For example, examples of the palladium compound include palladium chloride, palladium bromide, palladium iodide, palladium acetate, bis (2, 4-pentadionate) palladium, K ₂ PdCl ₄ , K ₂ PdCl ₆ , K ₂ Pd (NO ₃ ) ₄ , tris (dibenzylideneacetone) dipalladium, dichlorobis (ethylene) palladium, Pd (π-C ₅ H ₅ ) Inorganic and organic ligand complexes such as ₂ , for example, bis (ethylenediamine) palladium dichloride, PdCl ₂ (NH ₃ ) ₂ , PdCl ₂ [N (C ₂ H ₅ ) ₃ ] ₂ , Pd (NO ₃ ) ₂ ( NH _3), such as ₆ N-coordination complexes,
For example, Pd [P (CH ₃ ) ₃ ] ₄ , Pd [P (C ₂ H ₅ ) ₃ ] ₄ , Pd [P (n-C ₃ H ₇ ) ₃ ] ₄ , Pd [P (iso-C ₃ H) _{7) 3] 4, Pd [} P (n-C 4 H 9) 3] 4, Pd [P (tert-C 4 H 9) 3] 4, Pd [P (Cyc-C 6 H 11) 3] 4 _{, Pd [P (C 6 H} 5) 3] 4, Pd [P (o-CH 3 -C 6 H 4) 3] 4, PdCO 2 [P (C 6 H 5) 3] 4, Pd (C 2 _{H 4) [P (C 6} H 5) 3] 2, PdCl 2 [P (C 6 H 5) 3] 2, PdCl 2 [P (n-C 4 H 9) 3] 2, PdCl 2 [P ( _{tert-C 4 H 9) 3} ] 2, PdBr 2 [P (C 6 H 5) 3] 2, PdBr 2 [P (n-C 4 H 9) 3] 2, P _{Br 2 [P (tert-C} 4 H 9) 3] 2, PdCl 2 [P (OCH 3) 3] 2, PdBr 2 [P (OCH 3) 3] 2, PdI 2 [P (OCH 3) 3] ₂ , trivalent phosphine coordination complexes such as PdCl (C ₆ H ₅ ) [P (C ₆ H ₅ ) ₃ ] _2, and palladium compounds such as Pd / carbon.

Examples of the nickel compound include inorganic and organic ligand complexes such as nickel chloride, nickel bromide, and bis (2,4-pentadionate) nickel, such as Ni [P (C ₆ H ₅ ) ₃ ]. ₄ , nickel compounds such as trivalent phosphine coordination complexes such as NiCl ₂ [P (C ₆ H ₅ ) ₃ ] ₂ . Such transition metal compounds may be used alone or in combination. The amount of the transition metal compound used is not particularly limited, but a so-called catalytic amount may be used, and is generally 30 mol% or less, preferably 20 mol per mol of the aryl compound having a leaving group. It is less than mol%, and more preferably 0.0001-15 mol% is used.
The production method of the present invention is a method for producing an aryl-substituted tetraazaporphyrin compound using a tetraazaporphyrin compound, an aryl compound having a leaving group, a base, and a transition metal compound. For the purpose, it is preferable to carry out the reaction in the presence of a phosphorus ligand. Although it does not specifically limit as a phosphorus ligand, For example, the compound represented by general formula (C) or general formula (D) can be mentioned.

（式中、Ｒ_１１〜Ｒ_１３はそれぞれ独立に、直鎖、分岐または環状のアルキル基、置換または未置換のアリール基、あるいは置換または未置換のアラルキル基を表す）

(Wherein R _{11 to} R ₁₃ each independently represents a linear, branched or cyclic alkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted aralkyl group)

（式中、Ｒ_１４〜Ｒ_１７はそれぞれ独立に、直鎖、分岐または環状のアルキル基、置換または未置換のアリール基、あるいは置換または未置換のアラルキル基を表し、Ｚは連結基を表す）
一般式（Ｃ）および一般式（Ｄ）において、Ｒ_１１〜Ｒ_１７はそれぞれ独立に、直鎖、分岐または環状のアルキル基、置換または未置換のアリール基、あるいは置換または未置換のアラルキル基を表し、より好ましくは、直鎖、分岐または環状のアルキル基、あるいは置換または未置換のアリール基である。一般式（Ｃ）および一般式（Ｄ）において、Ｒ_１１〜Ｒ_１７で表される直鎖、分岐または環状のアルキル基としては、好ましくは、炭素数１〜２４の直鎖、分岐または環状のアルキル基である。Ｒ_１１〜Ｒ_１７で表される直鎖、分岐または環状のアルキル基の具体例としては、例えば、一般式（Ａ）のＲで例示した直鎖、分岐または環状のアルキル基を挙げることができる。Ｒ_１１〜Ｒ_１７で表される直鎖、分岐または環状のアルキル基としては、より好ましくは、例えば、メチル基、エチル基、ｎ−プロピル基、イソプロピル基、ｎ−ブチル基、ｔｅｒｔ−ブチル基、ｎ−ヘキシル基、ｎ−オクチル基、ｎ−デシル基、シクロペンチル基、シクロヘキシル基などの炭素数１〜１０の直鎖、分岐または環状のアルキル基を挙げることができる。

(Wherein R _{14 to} R ₁₇ each independently represents a linear, branched or cyclic alkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted aralkyl group, and Z represents a linking group)
In General Formula (C) and General Formula (D), R _{11 to} R ₁₇ are each independently a linear, branched or cyclic alkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted aralkyl group. And more preferably a linear, branched or cyclic alkyl group, or a substituted or unsubstituted aryl group. In the general formula (C) and the general formula (D), the linear, branched or cyclic alkyl group represented by R _{11 to} R ₁₇ is preferably a linear, branched or cyclic alkyl group having 1 to 24 carbon atoms. It is an alkyl group. Specific examples of the linear, branched or cyclic alkyl group represented by R _{11 to} R ₁₇ include, for example, the linear, branched or cyclic alkyl group exemplified for R in the general formula (A). . The linear, branched or cyclic alkyl group represented by R _{11 to} R ₁₇ is more preferably, for example, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, or a tert-butyl group. , N-hexyl group, n-octyl group, n-decyl group, cyclopentyl group, cyclohexyl group and the like, and straight-chain, branched or cyclic alkyl groups having 1 to 10 carbon atoms.

In general formula (C) and general formula (D), the substituted or unsubstituted aryl group represented by R _{11 to} R ₁₇ is preferably a substituted or unsubstituted aryl group having 4 to 30 carbon atoms. . Specific examples of the substituted or unsubstituted aryl group represented by R _{11 to} R ₁₇ include the substituted or unsubstituted aryl group exemplified for R in the general formula (A). More preferably, the substituted or unsubstituted aryl group represented by R _{11 to} R ₁₇ has, for example, 6 to 6 carbon atoms such as a phenyl group, a 4-methylphenyl group, a 2-methoxyphenyl group, and a 1-naphthyl group. There may be mentioned 10 substituted or unsubstituted aryl groups.
In general formula (C) and general formula (D), the substituted or unsubstituted aralkyl group represented by R _{11 to} R ₁₇ is preferably a substituted or unsubstituted aralkyl group having 5 to 30 carbon atoms. . Specific examples of the substituted or unsubstituted aralkyl group represented by R _{11 to} R ₁₇ include a substituted or unsubstituted aralkyl group exemplified for R in the general formula (A). More preferably, the substituted or unsubstituted aralkyl group represented by R _{11 to} R ₁₇ includes, for example, a substituted or unsubstituted aralkyl group having 7 to 10 carbon atoms such as a benzyl group and a 4-methylbenzyl group. be able to.

  In the general formula (D), Z represents a linking group, and preferably represents a linear, branched, or cyclic alkylene group, an alkylene group containing an aromatic ring, or a substituted or unsubstituted arylene group, more preferably. Represents a linear, branched or cyclic alkylene group having 1 to 10 carbon atoms, an alkylene group containing an aromatic ring having 8 to 10 carbon atoms, or a substituted or unsubstituted arylene group having 6 to 30 carbon atoms, More preferably, a linear, branched or cyclic alkylene group having 2 to 8 carbon atoms, an alkylene group containing an aromatic ring having 8 to 10 carbon atoms, or a substituted or unsubstituted arylene group having 6 to 20 carbon atoms. To express. Specific examples of the linear, branched, or cyclic alkylene group that is a preferable linking group represented by Z include, for example, a methylene group, a 1,2-ethylene group, a 1,3-propylene group, and 1,4-butylene. Group, 1,5-pentylene group, 1,6-hexylene group, 1,7-heptylene group, 1,8-octylene group, 1,9-nonylene group, 1,10-decylene group, 1,2-propylene group 2,3-butylene group, 2,5-hexylene group, 1,4-cyclohexylene group and the like. Specific examples of the alkylene group containing an aromatic ring which is a preferred linking group represented by Z include, for example, 1,4-xylylene group, 1,3-xylylene group, 1,2-xylylene group and the like. More preferred are a 1,3-xylylene group and a 1,2-xylylene group. Specific examples of the substituted or unsubstituted arylene group which is a preferable linking group represented by Z include, for example, 1,2-phenylene group, 1,1′-binaphthyl-2,2′-diyl group, 9,9 -Dimethyl-xanthene-4,5-diyl group, benzophenone-2,2'-diyl group, diphenyl ether-2,2'-diyl group, ferrocene-1,1'-diyl group and the like. Examples of the compound represented by the general formula (C) which is a preferable phosphorus ligand include trimethylphosphine, triethylphosphine, tri-n-propylphosphine, triisopropylphosphine, tri-n-butylphosphine, triisobutylphosphine, Tri-tert-butylphosphine, trioctylphosphine, tricyclopentylphosphine, tricyclohexylphosphine, di-tert-butylmethylphosphine, tert-butyldicyclohexylphosphine, tert-butyldiisopropylphosphine, di-tert-butylneopentylphosphine, tribenzyl Phosphine, tris (4-methylbenzyl) phosphine, triphenylphosphine, tri (1-naphthyl) phosphine, tris (2-furyl) phosphine, di Enyl-2-pyridylphosphine, tri (4-methylphenyl) phosphine, tri (3-methylphenyl) phosphine, tri (2-methylphenyl) phosphine, tri (2,4,6-trimethylphenyl) phosphine, diphenyl (4 -Methylphenyl) phosphine, diphenyl (2-methylphenyl) phosphine, tris (4-methoxyphenyl) phosphine, tris (2,6-dimethoxyphenyl) phosphine, tris (2,4,6-trimethoxyphenyl) phosphine, diphenyl (2-methoxyphenyl) phosphine, tris (4-fluorophenyl) phosphine, tris (4-chlorophenyl) phosphine, tris (4-trifluoromethylphenyl) phosphine, tris (3,5-bistrifluoromethylphenyl) phosphi , Tris (pentafluorophenyl) phosphine, diphenyl-2-pyridylphosphine, methyldiphenylphosphine, dimethylphenylphosphine, ethyldiphenylphosphine, diethylphenylphosphine, n-propyldiphenylphosphine, di-n-propylphenylphosphine, isopropyldiphenylphosphine, Diisopropylphenylphosphine, n-butyldiphenylphosphine, di-n-butylphenylphosphine, tert-butyldiphenylphosphine, di-tert-butylphenylphosphine, n-hexyldiphenylphosphine, di-n-hexylphenylphosphine, n-octyldiphenyl Phosphine, di-n-octylphenylphosphine, cyclohexyldiphenylphosphine, dicyclohexyl Ruphenylphosphine, di-tert-butyl- (2-phenylphenyl) phosphine, di-tert-butyl- (2-cyclohexylphenyl) phosphine, di-tert-butyl- [2- (2′-dimethylaminophenyl) phenyl ] Phosphine, dicyclohexyl (2-phenylphenyl) phosphine, dicyclohexyl (2-cyclohexylphenyl) phosphine, dicyclohexyl [2- (2′-dimethylamino) phenyl] phosphine, dicyclohexyl [2- (2′-methylphenyl) phenyl] phosphine , Dicyclohexyl [2- (2′-isopropylphenyl) phenyl] phosphine, benzyldiphenylphosphine, and the like.

  Examples of the compound represented by the general formula (D) which is a preferable phosphorus ligand include bis (dimethylphosphino) methane, 1,2-bis (dimethylphosphino) ethane, and 1,2-bis (diethylphosphine). Fino) ethane, 1,3-bis (dimethylphosphino) propane, 1,3-bis (diethylphosphino) propane, 1,4-bis (dimethylphosphino) butane, 1,2-bis (di-tert-) Butylphosphino) ethane, 1,3-bis (di-tert-butylphosphino) propane, 1,4-bis (di-tert-butylphosphino) butane, bis (dicyclohexylphosphino) methane, 1,2- Bis (dicyclohexylphosphino) ethane, 1,3-bis (dicyclohexylphosphino) propane, 1,4-bis (dicyclohexylphosphino) Tan, (2R, 3R) -bis (dicyclohexylphosphino) butane, (2S, 3S) -bis (dicyclohexylphosphino) butane, bis (diphenylphosphino) methane, 1,2-bis (diphenylphosphino) ethane, 1,3-bis (diphenylphosphino) propane, 1,4-bis (diphenylphosphino) butane, 1,5-bis (diphenylphosphino) pentane, 1,6-bis (diphenylphosphino) hexane, 1, 2-bis (di-tert-butylphosphinomethyl) benzene, 1,2-bis (dicyclohexylphosphinomethyl) benzene, 1,2-bis (diphenylphosphinomethyl) benzene, 1,3-bis (di-tert) -Butylphosphinomethyl) benzene, 1,3-bis (dicyclopentylphosphinomethyl) benzene, 1,2-bis ( Diphenylphosphino) benzene, 1,3-bis (di-tert-butylphosphino) benzene, 2,2′-bis (di-tert-butylphosphino) -1,1′-binaphthyl, 2,2′- Bis (dicyclohexylphosphino) -1,1′-binaphthyl, 2,2′-bis (diphenylphosphino) -1,1′-binaphthyl, 2,2′-bis (4 ″ -methylphenylphosphino) -1 , 1′-binaphthyl, 9,9-dimethyl-4,5-bis (di-tert-butylphosphino) xanthene, 9,9-dimethyl-4,5-bis (diphenylphosphino) xanthene, 2,2 ′ -Bis (diphenylphosphino) benzophenone, 2,2'-bis (di-tert-butylphosphino) diphenyl ether, 2,2'-bis (dicyclohexylphosphite) ) Diphenyl ether, 2,2′-bis (diphenylphosphino) diphenyl ether, 1,1′-bis (di-tert-butylphosphino) ferrocene, 1,1′-bis (diisopropylphosphino) ferrocene, 1,1 ′ -Bis (dimethylphosphino) ferrocene etc. can be mentioned.

In the production method of the present invention, as the phosphorus ligand, the compounds represented by the general formula (C) and the general formula (D) may be used singly or in combination. The amount of phosphorus ligand used is not particularly limited, but in general, the ratio of the transition metal compound to the phosphorus ligand is the same as the palladium atom when the transition metal compound is a palladium compound. In terms of the ratio of phosphorus atoms, it is about 1: 0.001 to 1:20, preferably about 1: 0.01 to 1: 4. Some of the phosphorus ligands are available as commercially available reagents. Org. Chem. , 65, 1158 (2000), J. Am. Amer. Chem. Soc. , 120, 7369 (1998), J. Am. Amer. Chem. Soc. 121, 4369 (1999) and the like.
The production method of the present invention can be carried out in the absence of an organic solvent, but can be carried out in the presence of an organic solvent if desired. Examples of the organic solvent include aliphatic hydrocarbon solvents such as pentane, hexane, octane, and cyclohexane, benzene, toluene, o-xylene, m-xylene, p-xylene, mixed xylene, mesitylene, cumene, pseudocumene, tetralin, and the like. Aromatic hydrocarbon solvents such as 1,4-dioxane, tetrahydrofuran, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, diethylene glycol dimethyl ether, diisopropyl ether, diisobutyl ether, cyclopentyl methyl ether, anisole, diphenyl ether and the like, for example, Dimethyl sulfoxide, sulfolane, N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolide , 1,3-dimethyl-2-imidazolidinone, it may be mentioned acetonitrile, an organic solvent such as an aprotic polar solvent such as propionitrile, more preferably an aprotic polar solvent. These organic solvents may be used alone or in combination.

In the production method of the present invention, the amount of the organic solvent used as desired is not particularly limited, but the amount of the aromatic compound having a leaving group is generally 0.1M to 5M. More preferably, the amount is adjusted to 0.25M to 2M. When the production method of the present invention is carried out, the tetraazaporphyrin compound, the aryl compound having a leaving group, the base, and the transition metal compound, and the method for supplying the phosphorus ligand to be used as desired are particularly limited. However, for example, (1) a mixture of a tetraazaporphyrin compound, a base, and a transition metal compound, and a phosphorus ligand to be used, if necessary, is stirred and mixed in the presence of an organic solvent, and then eliminated. A method for supplying an aryl compound having a group,
(2) A mixture of a tetraazaporphyrin compound, a base, a transition metal compound, and an aryl compound having a leaving group is stirred and mixed in the presence of an organic solvent, if desired, and then a phosphorus ligand to be used is optionally added. Supply method,
(3) A tetraazaporphyrin compound, an aryl compound having a leaving group, a base, and a transition metal compound, and a phosphorus ligand to be used as required are inserted all together, and if desired, stirred and mixed in the presence of an organic solvent. Methods for carrying out the reaction, etc. can be applied.

The production method of the present invention can be carried out in an air atmosphere, but in general, it is preferably carried out in the presence of an inert gas (for example, nitrogen, argon, helium). The reaction temperature is preferably about room temperature to about 200 ° C, more preferably about 50 to 180 ° C. In addition, the reaction may be carried out at normal pressure, and, if necessary, can be carried out under reduced pressure or pressurized conditions. Preferably, it is carried out at normal pressure. In carrying out the production method of the present invention, the type and form of the reaction apparatus to be used are not particularly limited, but generally tank-type, tube-type and tower-type reaction apparatuses can be used. Moreover, a manufacturing process can be implemented by a batch type (batch type), and also can be implemented continuously. Moreover, the reaction apparatus used for manufacture can be equipped with various stirring apparatuses. Such stirrers include, for example, paddle type stirrers, propeller type stirrers, turbine type stirrers, homogenizers, homomixers, line mixers, line homomixers, and other high speed stirrers, as well as static mixers, colloid mills, and orifice mixers. And a flow jet mixer. The progress of the reaction can be followed by methods such as thin layer chromatography, high performance liquid chromatography, gas chromatography and the like. After completion of the reaction, the aryl-substituted tetraazaporphyrin compound produced by the method of the present invention, for example, after distilling off the organic solvent, if necessary, the product is a generally known method such as a chromatography method or a recrystallization method. Can be isolated and purified. The structure of the product can be identified by various analysis methods such as elemental analysis, MS (FD-MS) analysis, IR analysis, ¹ H-NMR, ¹³ C-NMR.

  In the production method of the present invention, for example, a compound represented by the general formula (A) is used as the starting tetraazaporphyrin compound, and an aryl compound having a leaving group is represented by, for example, the general formula (B). When the compound is used, the produced aryl-substituted tetraazaporphyrin compound is a compound represented by the general formula (E).

〔式中、Ｒ、ｍおよびＭは、一般式（Ａ）の場合と同じ意味を表し、Ａｒは一般式（Ｂ）の場合と同じ意味を表し、ｎは１〜８の整数を表す（但し、ｍ＋ｎは１〜８の整数を表す）〕
一般式（Ｅ）において、ｎは１〜８の整数を表し、より好ましくは、１〜４の整数を表し、さらに好ましくは、２〜４の整数を表し、特に好ましくは４を表す。但し、ｍ＋ｎは１〜８の整数を表す。
本発明の製造方法において、テトラアザポルフィリン化合物として、例えば、一般式（１）で表される化合物を使用し、脱離基を有するアリール化合物として、例えば、一般式（Ｂ）で表される化合物を使用した場合、製造されるアリール置換テトラアザポルフィリン化合物は、一般式（２）で表される化合物である。

[Wherein, R, m and M represent the same meaning as in formula (A), Ar represents the same meaning as in formula (B), and n represents an integer of 1 to 8 (provided that M + n represents an integer of 1 to 8)]
In general formula (E), n represents the integer of 1-8, More preferably, the integer of 1-4 is represented, More preferably, the integer of 2-4 is represented, Most preferably, 4 is represented. However, m + n represents the integer of 1-8.
In the production method of the present invention, as the tetraazaporphyrin compound, for example, a compound represented by the general formula (1) is used, and as an aryl compound having a leaving group, for example, a compound represented by the general formula (B) Is used, the produced aryl-substituted tetraazaporphyrin compound is a compound represented by the general formula (2).

〔式中、Ｒ_１〜Ｒ_４およびＭ_１は、一般式（１）の場合と同じ意味を表し、Ａｒは一般式（Ｂ）の場合と同じ意味を表し、ｎは一般式（Ｅ）の場合と同じ意味を表す〕
なお、一般式（Ｅ）および一般式（２）で表される式において、Ａｒは、テトラアザポルフィリン骨格内のピロール環のβ位の炭素原子に置換していることを表している。例えば、テトラアザポルフィリン化合物として、例えば、一般式（１−Ａ）〜一般式（１−Ｄ）で表される化合物から選ばれる１種の化合物、または２種以上の異性体から成る混合物を使用し、脱離基を有するアリール化合物として、例えば、一般式（Ｂ）で表される化合物を使用し、４つのアリール基が置換されたアリール置換テトラアザポルフィリン化合物が製造される場合は、その生成物は、一般式（２−Ａ）〜一般式（２−Ｄ）で表される化合物から選ばれる１種の化合物、または２種以上の異性体から成る混合物である。

[Wherein R _{1 to} R ₄ and M ₁ represent the same meaning as in the general formula (1), Ar represents the same meaning as in the general formula (B), and n represents the general formula (E). (Same meaning as in the case)
In the formulas represented by the general formula (E) and the general formula (2), Ar represents substitution with a carbon atom at the β-position of the pyrrole ring in the tetraazaporphyrin skeleton. For example, as the tetraazaporphyrin compound, for example, one compound selected from the compounds represented by the general formula (1-A) to the general formula (1-D) or a mixture composed of two or more isomers is used. When an aryl-substituted tetraazaporphyrin compound in which four aryl groups are substituted is produced using, for example, a compound represented by the general formula (B) as an aryl compound having a leaving group, formation thereof The product is one compound selected from the compounds represented by the general formula (2-A) to the general formula (2-D), or a mixture composed of two or more isomers.

〔式中、Ｒ_１〜Ｒ_４およびＭ_１は、一般式（１）の場合と同じ意味を表し、Ａｒは一般式（Ｂ）の場合と同じ意味を表す〕

[Wherein R _{1 to} R ₄ and M ₁ represent the same meaning as in the general formula (1), and Ar represents the same meaning as in the general formula (B)].

  In general formulas (2-A) to (2-D), the aryl groups represented by Ar may be the same group or different groups. According to such a production method of the present invention, an aryl-substituted tetraazaporphyrin compound having excellent optical properties can be produced. The aryl-substituted tetraazaporphyrin compound produced by the method of the present invention includes not only crystals but also amorphous (amorphous). Further, the extinction coefficient of the aryl-substituted tetraazaporphyrin compound produced by the method of the present invention has an excellent optical characteristic that it is larger than the extinction coefficient of the aryl-substituted tetraazaporphyrin compound produced by a known method. ing. The aryl-substituted tetraazaporphyrin compound produced by the method of the present invention is hereinafter abbreviated as “compound A” according to the present invention.

  The compound A according to the present invention can be used for various functional materials (for example, display filter applications, optical recording medium applications, ink applications, thermal transfer applications), and the compound A according to the present invention includes one kind. They may be used alone or in combination. As a functional material, for example, when used for a filter for a display, the compound A according to the present invention may be used alone or in combination. Of course, the compound A according to the present invention, which is a mixture of a plurality of isomers, can be used for the display filter. Further, if desired, each isomer can be separated from the mixture, and one of the isomers can be used, and a plurality of isomers having an arbitrary ratio can be used in combination. When the compound A according to the present invention is used for the display filter, the compound having the absorption maximum at 570 to 605 nm is preferable among the compounds A according to the present invention in consideration of the required characteristics of the display filter. More preferably, among the compounds represented by the general formula (E), compounds having an absorption maximum at 570 to 605 nm, and more preferably among the compounds represented by the general formula (2), from 570 to 605 nm. A compound having an absorption maximum can be suitably used for a display filter.

  The display filter according to the present invention is a filter applicable to various displays such as a plasma display, a liquid crystal display, an organic electroluminescence display, a field emission display (FED), and a cathode ray tube (CRT). Used by wearing. In addition, in a liquid crystal display, it can apply to various aspects, such as a transmission type and a reflection type, for example. The display filter of the present invention functions as a light control film having a characteristic of correcting the visible light spectrum of the display screen by containing at least one compound A according to the present invention. Further, the display filter of the present invention further functions as an electromagnetic wave shield having a characteristic of blocking electromagnetic waves from the display screen by providing a transparent conductive layer having a surface resistance of 0.01 to 30Ω / □. The display filter of the present invention further functions as a near-infrared cut filter having a characteristic of blocking near-infrared rays from the display screen by containing a near-infrared absorbing compound having an absorption maximum at a wavelength of about 800 to 1100 nm. To do. When the display filter of the present invention is applied to, for example, a plasma display filter, the configuration is not particularly limited, but in general, the functional transparent layer (A), the substrate (B), and the transparent adhesive layer It is a filter consisting of (C). The filter for plasma display comprises at least one compound A according to the present invention in at least one layer or member constituting the functional transparent layer, the substrate and the transparent adhesive layer. The plasma display filter is provided on the plasma display screen, and generally has a functional transparent layer (A) provided on the outside air side, and a transparent adhesive layer (C) provided on the display side and adhered to the screen. The substrate (B) is provided between the functional transparent layer (A) and the transparent adhesive layer (C) (FIG. 1). Further, for the purpose of shielding electromagnetic waves generated from the plasma display, it is preferable that the plasma display filter is further provided with a transparent conductive layer (D). In this case, the transparent conductive layer (D) is provided between the functional transparent layer (A) and the substrate (B) (FIG. 2). The transparent conductive layer (D) may be provided between the base (B) and the transparent adhesive layer (C) (FIG. 3).

Of course, when configuring the plasma display filter, various other configurations can be made in consideration of desired required characteristics. For example, the filter for plasma displays can be provided with a hard coat layer and a further transparent adhesive layer as desired. Moreover, it can also be set as the filter for plasma displays which provides a some functional transparent layer. These layers may also contain the compound A according to the present invention.
When the display filter of the present invention is applied to, for example, a liquid crystal display filter, the configuration is generally
(1) Filter comprising the substrate (B) (FIG. 4)
(2) Filter comprising a transparent adhesive layer (C) (FIG. 5)
(3) Filter comprising the substrate (B) and the transparent adhesive layer (C) (FIG. 6)
(4) There is a filter (FIG. 7) composed of a substrate (B) and a functional transparent layer (A).
The filter for liquid crystal displays comprises at least one compound A according to the present invention in at least one layer or member constituting the functional transparent layer, the substrate and the transparent adhesive layer. The liquid crystal display filter is provided in an arbitrary path from the light source in the display to the outermost surface of the visual recognition unit. For example, in the case of a transmissive liquid crystal display, the liquid crystal display filter is not only on the liquid crystal display screen, but for example, a light guide plate, a backlight, a polarizing plate, a color filter, etc., with a transparent adhesive layer interposed, for example. Provided.

Hereinafter, the functional transparent layer (A) will be described.
The display filter of the present invention has an antireflection function, an antiglare function, an antireflection antiglare function, a hard coat function (friction resistance function), an antistatic function, an antistatic function, depending on the installation method for the display and the required functions. A functional transparent layer having at least one of a soiling function, a gas barrier function, and an ultraviolet ray cutting function and transmitting visible light is provided. The functional transparent layer is a functional film itself having one or more of the above functions, or a support formed by applying a functional film to the coating method, printing method, or various conventionally known film forming methods, and further having each function. Supports can be used. The support is preferably a transparent support, and is generally a transparent glass or a transparent polymer film. In addition, as a transparent polymer film, the transparent polymer film illustrated by the base | substrate (B) mentioned later can be mentioned, for example.
The thickness of the support is not particularly limited. In addition, for example, a compound A according to the present invention can be contained in a support made of a transparent polymer film.
Even when the functional transparent layer is the functional film itself, the compound A according to the present invention can be contained in the film.

  The functional transparent layer has either an anti-reflection (AR: anti-reflection) function for suppressing external light reflection, an anti-glare (AG: anti-glare) function, or an anti-reflection / anti-glare (ARAG) function having both functions. It is preferable to have such a function. The functional transparent layer having the antireflection function can determine the constituent members of the antireflection film and the film thickness of each constituent member by optical design in consideration of the optical characteristics of the support that forms the antireflection film. As the functional transparent layer having an antireflection function, for example, a thin film such as fluorine-based transparent polymer resin having a refractive index of 1.5 or less in the visible light region, magnesium fluoride, silicon-based resin, silicon oxide, Single layer formed with optical wavelength of ¼ wavelength, inorganic compound thin film made of metal oxide, fluoride, silicide, boride, carbide, nitride, sulfide, etc. with different refractive index, or silicon-based Some organic compound thin films made of a resin, an acrylic resin, a fluorine-based resin, and the like are laminated in the order of a high refractive index layer and a low refractive index layer when viewed from the support. As a method for forming the inorganic compound thin film, for example, a known method such as a sputtering method, an ion plating method, a vacuum deposition method, or a wet coating method can be applied. As a method for forming the organic compound thin film, for example, a known method such as a bar coating method, a reverse coating method, a gravure coating method, a die coating method, a roll coating method, or a comma coating method can be applied. The visible light reflectance of the surface of the functional transparent layer having antireflection properties is generally adjusted to 2% or less, preferably 1.3% or less, and more preferably 0.8% or less.

The functional transparent layer having an antiglare function is generally a transparent layer with respect to a visible light region having a minute uneven surface state of about 0.1 μm to 10 μm. The functional transparent layer having an antiglare function is, for example, an acrylic resin, a silicon resin, a melamine resin, a urethane resin, an alkyd resin, a fluorine resin, or a thermosetting resin, or a photocurable resin. Inorganic particles such as silica and organic silicon compounds, or inks formed by dispersing organic compound particles such as melamine and acrylic, for example, bar coating method, reverse coating method, gravure coating method, die coating method, roll coating method It can be formed by coating and curing on a support by a method such as a comma coating method. The average particle diameter of the inorganic compound particles and the organic compound particles is generally 1 to 40 μm.
The functional transparent layer having an antiglare function is, for example, a thermosetting resin such as an acrylic resin, a silicon resin, a melamine resin, a urethane resin, an alkyd resin, a fluorine resin, or a photocurable resin. Can be formed by pressing a mold having a desired haze or surface state and curing the surface to irregularities. The haze value that serves as an index of the antiglare function is generally 0.5 to 20%. The functional transparent layer having an antireflection antiglare function can be prepared by forming an antireflection film on a film having an antiglare function or a support having an antiglare function. The visible light reflectance of the surface of the functional transparent layer having an antireflection antiglare function is generally adjusted to 1.5% or less, preferably 1.0% or less.

For the purpose of adding scratch resistance performance to the display filter of the present invention, it is preferable that the functional transparent layer has a hard coat function (friction resistance function). The functional transparent layer having a hard coat function can be prepared by forming a film having a hard coat function or a hard coat film on a support. Examples of the hard coat film include thermosetting resins such as acrylic resins, silicon resins, melamine resins, urethane resins, alkyd resins, and fluorine resins, or photocurable resins. The thickness of the hard coat film is generally about 1 to 100 μm. The hard coat film can also be used for a high refractive index layer or a low refractive index layer of a transparent functional layer having an antireflection function. Further, an antireflection film may be formed on the hard coat film, and the functional transparent layer may have both an antireflection function and a hard coat function. Similarly, the functional transparent layer may have both functions of an antiglare function and a hard coat function. A functional transparent layer having both an antiglare function and a hard coat function can be prepared, for example, by forming an antireflection film on a hard coat film having irregularities by dispersing particles or the like. As for the surface hardness of the functional transparent layer having a hard coat function, the pencil hardness according to JISK5600 is at least H or more, preferably 2H or more. Generally, a display filter is easily charged with static electricity, and an antistatic function may be required in consideration of prevention of dust adhesion and prevention of adverse effects on the human body. In this case, in order to provide an antistatic function, the functional transparent layer may have a certain conductivity. In general, the conductivity may be about 10 ¹¹ Ω / □ or less in terms of surface resistance. Examples of the conductive material include a known transparent conductive film such as ITO (Indium Tin Oxide), and a conductive film in which conductive ultrafine particles such as ITO ultrafine particles and tin oxide ultrafine particles are dispersed. Moreover, it is preferable that the layer which comprises the functional transparent layer which has any one or more functions of an antireflection function, an anti-glare function, an anti-glare function, and a hard-coat function has electroconductivity. It is preferable that the functional transparent film has a gas barrier function with respect to, for example, environmental substances or moisture. The required gas barrier function is generally 10 g / m ² in terms of moisture permeability.
-Day or less. Examples of the film having a gas barrier function include silicon oxide, aluminum oxide, tin oxide, indium oxide, yttrium oxide, magnesium oxide, or a mixture thereof, or a metal oxide thin film obtained by adding other elements to these, Examples thereof include films made of various resins such as vinylidene chloride, acrylic resin, silicon resin, melamine resin, urethane resin, and fluorine resin. The thickness of the film having a gas barrier function is generally 10 to 200 nm in the case of a metal oxide thin film, and is generally 1 to 100 μm in the case of a resin. Note that the film having a gas barrier function may have a single-layer structure or a multilayer structure. Examples of the film having a gas barrier function against moisture include, for example, polyethylene, polypropylene, nylon, polyvinylidene chloride, vinylidene chloride and vinyl chloride, vinylidene chloride and acrylonitrile copolymers, and various resins such as fluorine resins. Mention may be made of membranes. Further, the layer constituting the functional transparent layer having any one or more of the antireflection function, the antiglare function, the antireflection antiglare function, the antistatic function, and the hard coat function further serves as a gas barrier function. It can be. Furthermore, an antifouling function can be imparted to the surface of the functional transparent layer so that fingerprints and the like can be easily prevented or removed. Those having an antifouling function are compounds having non-wetting properties with respect to water and / or fats and oils, and examples thereof include fluorine compounds and silicon compounds. In addition, by forming, for example, an inorganic thin film single layer that absorbs ultraviolet rays, or an antireflection film composed of an inorganic thin film multilayer, or a transparent film containing an ultraviolet absorbing compound, on the functional transparent layer, Furthermore, an ultraviolet cut function can be imparted. When the functional transparent layer is the functional film itself, for example, it may be formed on the main surface of the transparent conductive layer by various film forming methods such as a coating method and a printing method.
In the case where the functional transparent layer is a transparent substrate on which a functional film is formed or a transparent substrate having each function, the functional transparent layer may be formed, for example, on the main surface of the transparent conductive layer via an adhesive.

Hereinafter, the substrate (B) will be described.
The substrate functions as a filter support, and generally transparent glass or transparent polymer film is used in the visible light region. Examples of the transparent polymer film include polyethylene terephthalate, polyether sulfone, polystyrene, polyethylene naphthalate, polyarylate, polyether ether ketone, polycarbonate, polyethylene, polypropylene, nylon 6 and other celluloses, polyimide, triacetyl cellulose and the like. Resins, polyurethane resins, fluorine resins such as polytetrafluoroethylene, vinyl compounds such as polyvinyl chloride, polyacrylic acid, polyacrylic acid esters, polyacrylonitrile, addition polymers of vinyl compounds, polymethacrylic acid, polymethacrylic acid esters , Vinylidene compounds such as polyvinylidene chloride, vinyl compounds such as vinylidene fluoride / trifluoroethylene copolymer, ethylene / vinyl acetate copolymer Or copolymers of fluorine-based compound, polyether such as polyethylene oxide, epoxy resins, polyvinyl alcohol, polyvinyl butyral, but is not limited thereto. The substrate generally has a thickness of 10 to 250 μm, preferably 50 to 250 μm. From the viewpoint of production efficiency, the substrate is preferably a flexible transparent polymer film, and the filter using the transparent polymer film directly bonded to the display surface as a substrate is made of the substrate glass of the display. When broken, there is an advantage that the glass can be prevented from scattering. In the present invention, the surface of the substrate may be subjected to etching treatment such as sputtering treatment, corona treatment, flame treatment, ultraviolet ray irradiation and electron beam irradiation, or undercoating treatment. A hard coat layer may be formed on at least one main surface of the substrate. Examples of the hard coat film that becomes the hard coat layer include thermosetting resins such as acrylic resins, silicon resins, melamine resins, urethane resins, alkyd resins, and fluorine resins, or photocurable resins. Can be mentioned. The thickness of the hard coat layer is about 1 to 100 μm. Further, the hard coat layer may contain one or more compounds A according to the present invention. The display filter of the present invention, particularly the plasma display filter, preferably functions as an electromagnetic wave shielding body having a property of shielding electromagnetic waves from the display screen. The plasma display filter includes a functional transparent layer, a substrate, a transparent In addition to the adhesive layer, a transparent conductive layer (D) is preferably provided.

Hereinafter, the transparent conductive layer (D) will be described.
When the display filter is in the form of an electromagnetic wave shield, a transparent conductive layer is formed on one main surface of the substrate. The transparent conductive layer in the present invention is a transparent conductive layer composed of a single layer or a multilayer thin film. In the electromagnetic wave shield, electrical connection between the transparent conductive layer and the outside is necessary. For example, the functional transparent layer, the transparent adhesive layer, and the like secure the conducting portion while leaving the peripheral portion of the transparent conductive layer. It will be necessary. As a single transparent conductive layer, there are a conductive mesh such as a metal mesh and a conductive grid pattern film, and a transparent conductive thin film such as a metal thin film and an oxide semiconductor thin film. As the transparent conductive layer composed of a multilayer thin film, there is a multilayer thin film in which a metal thin film and a high refractive index transparent thin film are laminated. Multi-layer thin film composed of metal thin film and high refractive index transparent thin film prevents the reflection of metal in the specific wavelength region by the high-refractive index transparent thin film, the conductivity of silver and other metals and the near-infrared reflection characteristics due to free electrons. Since it can be performed, it has preferable characteristics with respect to conductivity, near-infrared cut function, and visible light transmittance. In order to obtain a display filter having an electromagnetic wave shielding function and a near-infrared cut function, a metal thin film having a high conductivity for electromagnetic wave absorption and a reflective interface for electromagnetic wave reflection and a high refractive index transparent thin film were laminated. A transparent conductive layer comprising a multilayer thin film is preferred. In order to have an electromagnetic wave shielding function necessary for a plasma display in addition to a high visible light transmittance and a low visible light reflectance, the transparent conductive layer generally has a surface resistance of 0.01 to 30Ω / □, more preferably It is desirable to be 0.1 to 15Ω / □, more preferably 0.1 to 5Ω / □. Also, the transparent conductive layer itself can have a near-infrared cut function, and the light transmittance minimum in the near-infrared wavelength region, for example, 800 to 1100 nm, can be 20% or less. In the present invention, a preferred transparent conductive layer is 2 on the one main surface of the substrate, in the order of the high refractive index transparent thin film layer (Dt) and the metal thin film layer (Dm), with (Dt) / (Dm) as repeating units. The film is repeatedly laminated 4 times, and further formed thereon by laminating at least a high refractive index transparent thin film layer, and the surface resistance of the transparent conductive layer is 0.1 to 5Ω / □. The material for the metal thin film layer is preferably silver, gold, platinum, palladium, copper, indium, tin, or an alloy of silver and gold, platinum, palladium, copper, indium or tin. Although the content rate of the silver in the alloy containing silver is not specifically limited, Generally, it is 50 to less than 100 mass%. In the case of a metal thin film composed of a plurality of layers, at least one layer should be used without alloying silver, or only the metal thin film layer in the first layer and / or the outermost layer as viewed from the substrate is an alloy of silver. It can be. The metal thin film layer is required to be in a continuous state rather than a discontinuous island structure from the viewpoint of conductivity, and the thickness is preferably 4 to 30 nm. In the case of a metal thin film composed of a plurality of layers, it is not necessary that all the layers have the same thickness, and further, all the layers may not be silver or a silver alloy having the same composition. Examples of the method for forming the metal thin film layer include known methods such as sputtering, ion plating, vacuum deposition, and plating. The transparent thin film forming the high refractive index transparent thin film layer is not particularly limited as long as it has transparency in the visible light region and has an effect of preventing light reflection in the visible light region of the metal thin film layer. In general, a material having a refractive index with respect to visible light of 1.6 or more, preferably 1.8 or more is used. Examples of the material for forming such a transparent thin film include oxides such as indium, titanium, zirconium, bismuth, tin, zinc, antimony, tantalum, cerium, neodymium, lanthanum, thorium, magnesium, gallium, and the like. And zinc sulfide, and more preferably zinc oxide, titanium oxide, indium oxide, and a mixture of indium oxide and tin oxide (ITO). The thickness of the high refractive index transparent thin film layer is not particularly limited, but is generally 5 to 200 nm. Examples of the method for forming the high refractive index transparent thin film layer include known methods such as sputtering, ion plating, ion beam assist, vacuum deposition, and wet coating. For the purpose of improving the environmental resistance of the transparent conductive layer, a protective layer made of an organic or inorganic material can be provided on the surface of the transparent conductive layer to such an extent that various properties such as conductivity and optical properties are not significantly impaired. In addition, in order to improve the environmental resistance of the metal thin film layer and the adhesion between the metal thin film layer and the high refractive index transparent thin film layer, conductivity, optical characteristics, etc. are provided between the metal thin film layer and the high refractive index transparent thin film layer. An inorganic layer can be provided to such an extent that these properties are not impaired. In addition, as a material which forms an inorganic substance layer, copper, nickel, chromium, gold | metal | money, platinum, zinc, zirconium, titanium, tungsten, tin, palladium etc. or the alloy which consists of 2 or more types of these materials is mentioned, for example. . The thickness of the inorganic layer is preferably about 0.2 to 2 nm. As a method for forming the transparent conductive layer, there is a method using a conductive mesh in addition to a method using a transparent conductive thin film. A single-layer metal mesh will be described as an example of the conductive mesh. As a single-layer metal mesh, for example, there is one in which a copper mesh layer is formed on a base. Generally, a single layer of metal mesh is formed by bonding a copper foil on a base and then processing it into a mesh. As the copper foil, rolled copper or electrolytic copper is used, and a porous copper foil having a pore diameter of 0.5 to 5 μm is preferable. The porosity of the copper foil is preferably 0.01 to 20%, more preferably 0.02 to 5%. The porosity is a value defined by P / R where R is the volume and P is the pore volume. The copper foil may be subjected to various surface treatments (for example, chromate treatment, roughening treatment, pickling, zinc / chromate treatment). The thickness of the copper foil is generally 3 to 30 μm. The aperture ratio of the light transmission portion of the metal mesh is generally 60 to 95%. The shape of the opening is not particularly limited, but it is preferably in the form of a regular triangle, a regular square, a regular hexagon, a circle, a rectangle, a rhombus, and the like, and is arranged in the plane. In general, it is preferable that one side or diameter of the opening of the light transmitting portion is 5 to 200 μm. Further, the width of the metal in the portion where the opening is not formed is preferably 5 to 50 μm. The substantial sheet resistance of the metal layer having the light transmitting portion is preferably 0.01 to 0.5Ω / □. In order to electrically connect the transparent conductive layer and the ground portion (ground conductor) of the display device, a conductive adhesive layer is provided. Examples of the conductive adhesive and conductive adhesive used for the conductive adhesive layer include acrylic adhesives, silicon adhesives, urethane adhesives, polyvinyl butyral adhesives (PVB), and ethylene-vinyl acetate adhesives. There are materials in which metal particles such as carbon, Cu, Ni, Ag, and Fe are dispersed as conductive particles based on (EVA), polyvinyl ether, saturated polyester, melamine resin, and the like. The volume specific resistance of the conductive adhesive and the conductive adhesive is generally 1 × 10 ⁻⁴ to 1 × 10 ³ Ω · cm. Examples of the conductive adhesive and the conductive pressure-sensitive adhesive include a sheet form and a liquid form. As the conductive adhesive material, a sheet-like pressure sensitive adhesive material can be suitably used. After pasting the sheet-like adhesive material, or after applying the adhesive, it is laminated and pasted. The liquid conductive adhesive can be cured by treatment at room temperature or high temperature after application and bonding, or by irradiation with ultraviolet rays. Examples of the method for applying the liquid conductive adhesive include known methods such as a screen printing method, a bar coating method, a reverse coating method, a gravure coating method, a die coating method, a roll coating method, and a comma coating method. it can. In addition, the thickness of the conductive adhesive layer is set in consideration of the volume resistivity and necessary conductivity, and is generally 0.5 to 50 μm, preferably 1 to 30 μm. A double-sided adhesive type conductive tape having conductivity on both sides can also be used.

Hereinafter, the transparent adhesive layer (C) will be described.
In the present invention, the transparent adhesive layer is a layer made of any transparent adhesive material (adhesive, adhesive). The transparent adhesive layer is, for example, an acrylic adhesive, a silicon adhesive, a urethane adhesive, a polyvinyl butyral adhesive (PVB), an ethylene-vinyl acetate adhesive (EVA), a polyvinyl ether, a saturated polyester, a melamine resin. Formed from. In addition, as an adhesive material, a sheet form or a liquid form can be used. For example, when using a sheet-like pressure-sensitive adhesive material as the adhesive material, the sheet-like adhesive material is laminated or laminated after the adhesive is applied. For example, when a liquid adhesive is used as the adhesive, it is cured and bonded by treatment at room temperature or high temperature after application and bonding, or by ultraviolet irradiation. Examples of the coating method include known methods such as a screen printing method, a bar coating method, a reverse coating method, a gravure coating method, a die coating method, a roll coating method, and a comma coating method. Although the thickness of a transparent adhesion layer is not specifically limited, Generally, it is 0.5-50 micrometers. The surface on which the transparent adhesive layer is formed and the surface to be bonded are preferably subjected to an easy adhesion treatment such as an easy adhesion coat or a corona discharge treatment in advance. Furthermore, after bonding through the transparent adhesive layer, the air mixed between the members at the time of bonding is defoamed or dissolved in the adhesive material to further improve the adhesion between the members. It is preferable to perform the treatment under pressure and heating conditions. The compound A according to the present invention can be contained in at least one layer of the transparent adhesive layer. The display filter of the present invention contains at least one compound A according to the present invention. In addition, in this specification, the content includes not only those contained in each layer consisting of various members or films, or the inside of the transparent adhesive material, but also the state of being applied to the surface of the member or each layer. is there. Examples of the method for incorporating the compound A according to the present invention into a display filter include the following methods (1) to (4).
(1) A method of adding to a transparent adhesive material and including it in a transparent adhesive layer,
(2) A method of kneading and containing the polymer resin,
(3) A method in which the compound A according to the present invention is dispersed or dissolved in an organic solvent containing a polymer resin or a resin monomer, and various members are cast on each layer, for example,
(4) There is a method in which the compound A according to the present invention is added to an organic solvent containing a binder resin, and various members are coated as paints and coated on each layer.
In the above method (1), the content of the compound A according to the present invention is not particularly limited. %. In the methods (2) and (3), the content of the compound A according to the present invention is not particularly limited, but is generally 10 ppm to 30% by mass with respect to the polymer resin or resin monomer. Preferably, it is 10 ppm to 20% by mass. In the method (4), the content of the compound A according to the present invention is not particularly limited. %. Moreover, generally binder resin density | concentration is 1-50 mass% with respect to the whole coating material. In the display filter of the present invention, in addition to the compound A according to the present invention, one or more light absorbing compounds can be used in combination as long as the desired effects of the present invention are not impaired. Examples of such a light absorbing compound include, but are not limited to, compounds having desired absorption in the visible light region, such as anthraquinone compounds, phthalocyanine compounds, methine compounds, azomethine compounds, oxazine compounds, Examples include azo compounds, styryl compounds, coumarin compounds, porphyrin compounds, dibenzofuranone compounds, diketopyrrolopyrrole compounds, rhodamine compounds, xanthene compounds, and pyromethene compounds. Furthermore, when the display filter of the present invention is in the form of a near-infrared cut filter, it may further contain one or more near-infrared absorbing compounds. In addition, as a near-infrared absorption compound, Preferably, it is a compound which has an absorption maximum in about 800-1100 nm. The near-infrared absorbing compound is not particularly limited. For example, phthalocyanine compounds (for example, metal phthalocyanine complexes), naphthalocyanine compounds (for example, metal naphthalocyanine complexes), anthraquinone compounds, dithiol compounds (for example, nickel dithiol) Complex) and diiminium salt compounds. The concentration of these light-absorbing compounds and near-infrared-absorbing compounds should be set arbitrarily in consideration of the absorption wavelength and extinction coefficient of the compound, and the desired optical characteristics (for example, color purity and transmission characteristics) of the display filter. Can do. The display filter of the present invention has, for example, excellent transmission characteristics without significantly impairing the brightness and visibility of the plasma display, and can improve the optical characteristics (for example, color purity and contrast) of the plasma display. it can. The display filter of the present invention can improve, for example, the optical characteristics (for example, color purity) of a liquid crystal display.

  EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited to these.

Example 1
A mixture of the compounds represented by formulas (a-1) to (a-4) 6.0 g, palladium acetate 0.28 g, potassium acetate 6.0 g, bromobenzene 7.8 g and N, N-dimethylacetamide 50 ml To the mixture, 0.35 g of triphenylphosphine was added under a nitrogen atmosphere, and then the mixture was stirred at 120 ° C. for 8 hours. Thereafter, N, N-dimethylacetamide was distilled off under reduced pressure, 200 ml of methanol water (1: 1 volume ratio) was added to the residue, and the precipitated solid was separated by filtration. After this solid was dissolved in toluene, it was purified by silica gel column chromatography [developing solution: toluene / n-hexane (volume ratio: 2/1)] and expressed by the formulas (b-1) to (b-4). 4.2 g of a mixture consisting of the compounds represented was obtained as a blue solid. This mixture had an absorption maximum at 604 nm in toluene with a molar extinction coefficient of 142000.

(Example 2)
In Example 1, instead of using bromobenzene, according to the procedure described in Example 1, except that 8.8 g of 2-fluorobromobenzene was used, the formulas (c-1) to (c-4) 3.6 g of a mixture consisting of the compounds represented was obtained as a blue solid. This mixture had an absorption maximum at 594 nm with a molar extinction coefficient of 156000 in toluene.

(Example 3)
In Example 1, except that 12.4 g of 1-bromonaphthalene was used instead of using bromobenzene, the compounds represented by formula (d-1) to formula (d-4) were prepared according to the procedure described in Example 1. 5.3 g of a mixture consisting of the compounds obtained was obtained as a blue solid. This mixture had an absorption maximum at 598 nm with a molar extinction coefficient of 154000 in toluene.

Example 4
In Example 1, instead of using a mixture of compounds represented by formula (a-1) to formula (a-4), a compound represented by formula (e-1) to formula (e-4) Except that 8.2 g of the mixture consisting of was used, 6.7 g of the mixture consisting of the compounds represented by formula (f-1) to formula (f-4) was converted as a blue solid according to the procedure described in Example 1. Obtained. This mixture had an absorption maximum at 618 nm with a molar extinction coefficient of 88300 in toluene.

(Example 5)
In Example 1, instead of using a mixture consisting of compounds represented by formula (a-1) to formula (a-4), compounds represented by formula (g-1) to formula (g-4) In accordance with the procedure described in Example 1, except that 9.0 g of a mixture consisting of 4 and 4-tert-butylbromobenzene was used instead of bromobenzene, 5.8 g of a mixture consisting of the compound represented by h-5) was obtained as a blue solid. This mixture had an absorption maximum at 614 nm in toluene with a molar extinction coefficient of 122000.

(Example 6)
6.0 g of a mixture composed of the compounds represented by formula (a-1) to formula (a-4) described in Example 1, 0.60 g of PdCl ₂ [P (C ₆ H ₅ ) ₃ ] ₂ , 1 , 8-diazabicyclo [5.4.0] -7-undecene (DBU) 9.2 g, 11.5 g of trifluoromethanesulfonyloxybenzene and 50 ml of N, N-dimethylformamide under nitrogen atmosphere. -0.56 g of bis (dicyclohexylphosphino) ethane was added, and then the mixture was stirred at 140 ° C for 12 hours. Then, N, N-dimethylformamide was distilled off under reduced pressure, 200 ml of methanol water (1: 1 volume ratio) was added to the residue, and the precipitated solid was separated by filtration. After this solid was dissolved in toluene, it was purified by silica gel column chromatography [developing solution: toluene / n-hexane (volume ratio: 2/1)],
4.5 g of a mixture consisting of the compounds represented by formula (b-1) to formula (b-4) described in Example 1 was obtained as a blue solid. This mixture had an absorption maximum at 604 nm in toluene with a molar extinction coefficient of 140500.

(Comparative Example 1)
Under a nitrogen atmosphere, a mixture of 2.28 g of 2-tert-butyl-3- (2′-fluorophenyl) maleonitrile, 30 ml of n-pentanol and 0.33 g of cuprous chloride was heated at 90 ° C. 1.52 g of 8-diazabicyclo [5.4.0] -7-undecene (DBU) was added dropwise over 30 minutes. After the addition, the mixture was stirred at 125 ° C. for 8 hours. The reaction mixture was cooled to room temperature, 100 ml of methanol was added, and 50 ml of water was further added dropwise. The precipitated solid was filtered off. This solid was dissolved in toluene, and then purified by silica gel column chromatography [developing solution: toluene / n-hexane (volume ratio: 2/1)], and the formula (c-1) to formula described in Example 2 were used. 1.4 g of a mixture consisting of the compound represented by (c-4) was obtained as a blue solid. This mixture exhibited an absorption maximum at 594 nm with a molar extinction coefficient of 129000 in toluene. The molar extinction coefficient of this mixture was found to be smaller than the molar extinction coefficient of the mixture produced by the method described in Example 2.

(Comparative Example 2)
In a nitrogen atmosphere, a mixture of 1.5 g of 2-n-octyl-3-phenylmaleonitrile and 20 ml of ethylene glycol was heated to 70 ° C., and then 1,8-diazabicyclo [5.4.0] -7-undecene was added to the mixture. (DBU) 0.52 g and bis (2,4-pentanedionate) vanadium oxide 500 mg were added. The mixture was then stirred at reflux for 6 hours. After cooling the reaction mixture to room temperature, 200 ml of ether was added to extract the desired product, and the ether layer was washed with 100 ml of water. After separating the ether layer, the ether was distilled off under reduced pressure. After the residue was dissolved in toluene, the residue was purified by silica gel column chromatography [developing solution: toluene / n-hexane (volume ratio: 2/1)], and the formula (f-1) to formula ( 110 mg of a mixture consisting of the compound represented by f-4) was obtained as a blue solid. This mixture had an absorption maximum at 618 nm in toluene with a molar extinction coefficient of 76700. The molar extinction coefficient of this mixture was found to be smaller than the molar extinction coefficient of the mixture produced by the method described in Example 4.

(Example 7) Production of display filter of the present invention A triacetylcellulose (TAC) film (thickness: 80 μm) is used as a base, and the following functional transparent film is rolled as a functional transparent layer on one surface thereof. -Continuously formed by two rolls. That is, a photopolymerization initiator is added to a polyfunctional methacrylate resin, and a coating liquid in which ITO fine particles (average particle size: 10 nm) are further dispersed is applied with a gravure coater and UV cured to form a conductive hard coat film. (Film thickness: 3 μm) was formed. A fluorine-containing organic compound solution is coated on the microgravure coater, dried at 90 ° C and thermally cured to form an antireflective film (film thickness: 100 nm) with a refractive index of 1.4. Hard coat function (Pencil hardness: 2H), antireflection function (surface visible light reflectance: 0.9%), antistatic function (surface resistance: 7 × 10 ⁹ Ω / □), functional transparent film having antifouling property Formed.
On the other hand, a mixture of the compounds represented by the formulas (c-1) to (c-4) produced in Example 2 was dissolved in an ethyl acetate / toluene (50: 50% by mass) solvent to prepare a diluent. did. A functional transparent film is prepared by mixing an acrylic pressure-sensitive adhesive (80% by mass) and a diluent (20% by mass) containing a mixture of the compounds represented by formulas (c-1) to (c-4). / The TAC surface of the TAC film was coated with a comma coater to a dry film thickness of 25 μm and dried to form a transparent adhesive layer. A release film was laminated on the surface of the transparent adhesive layer and wound into a roll to produce a display filter having a release film. In addition, the dilution liquid was prepared so that the mixture which consists of a compound represented by Formula (c-1)-Formula (c-4) might contain 1500 (mass) ppm in the dry adhesive material. Furthermore, the display filter was cut into a sheet shape, the release film was peeled off, and was bonded to the front surface of the plasma display panel (display portion 920 mm × 520 mm) using a single wafer laminator. At this time, sheet cutting and bonding position alignment were performed so that the transparent adhesive layer portion was bonded to the entire display portion. After pasting, it was autoclaved at 60 ° C. and 2 × 10 ⁵ Pa to obtain a display device equipped with a display filter.

(Comparative Example 3) Preparation of display filter for comparison In Example 7, the adhesive layer was formed by the compounds represented by formula (c-1) to formula (c-4) produced in Production Example 2. Instead of using the mixture, a display comprising the compounds represented by formula (c-1) to formula (c-4) produced in Comparative Example 1 was used, and the display according to the method described in Example 7 was performed. A filter for display was produced, and a display device equipped with the display filter was obtained.

[Characteristic Evaluation of Display Filters Produced in Example 7 and Comparative Example 3]
The display filters produced in Example 7 and Comparative Example 3 were measured and evaluated for the following characteristics as compared to before the display filter was mounted. The results are shown in Table 1.
(1) Brightness contrast ratio of plasma display (maximum luminance / minimum luminance ratio)
The plasma display after mounting the display filter was evaluated. When the ambient brightness is 100 lx, the maximum luminance (cd / m ² ) at the time of white display on the plasma display and the minimum luminance (cd / m ² ) at the time of black display are measured with a luminance meter (LS-) manufactured by Minolta Co., Ltd. 110), and the contrast ratio (maximum luminance / minimum luminance ratio) was determined. The contrast ratio before the display filter was mounted was 20. The results are shown in Table 1.
(2) Ratio of 595 nm to 610 nm transmittance of display filter
A small piece of a filter for display was measured using a spectrophotometer (U-300) manufactured by Hitachi, Ltd., and the ratio (%) of the transmission at 595 nm to the transmission at 610 nm (transmission at 595 nm / 610 nm Transmittance × 100) was determined. It shows that the smaller the value of transmittance, the more efficiently absorbing unnecessary electromagnetic waves emitted from the plasma display. The results are shown in Table 1.

第１表から、本発明の方法により製造したアリール置換テトラアザポルフィリン化合物を含有してなるディスプレイ用フィルタは、従来の方法により製造したアリール置換テトラアザポルフィリン化合物を含有してなるディスプレイ用フィルタに比べ、５９５ｎｍの６１０ｎｍに対する透過率が小さいことが判る。このことより、本発明のディスプレイ用フィルタは、プラズマディスプレイから発せられる不要な電磁波を効率よく吸収し、ディスプレイ用フィルタとしての性能が優れていることが判る。

From Table 1, the display filter containing the aryl-substituted tetraazaporphyrin compound produced by the method of the present invention is compared with the display filter containing the aryl-substituted tetraazaporphyrin compound produced by the conventional method. It turns out that the transmittance | permeability with respect to 610 nm of 595 nm is small. From this, it can be seen that the display filter of the present invention efficiently absorbs unnecessary electromagnetic waves emitted from the plasma display and is excellent in performance as a display filter.

(Example 8) Preparation of filter for display of the present invention It is represented by formula (c-1) to formula (c-4) produced in Example 2 in an ethyl acetate / toluene (50:50 mass%) solvent. A mixture of the compounds was dissolved to obtain a diluted solution. An acrylic pressure-sensitive adhesive (80% by mass) and a diluent (20% by mass) containing a mixture composed of the compounds represented by formulas (c-1) to (c-4) are mixed, and a polyethylene terephthalate film ( A filter for display was manufactured by coating and drying on a surface of 75 μm) to a dry film thickness of 20 μm using a die coater. In addition, the dilution liquid was prepared so that the mixture which consists of a compound represented by Formula (c-1)-Formula (c-4) might contain 1200 (mass) ppm in the dry adhesive material. In this display filter, the transmittance at 595 nm was 19% with respect to the transmittance at a wavelength of 610 nm. When this display filter is attached to a transmissive liquid crystal display screen (with a color filter) whose red chromaticity (x, y) is (0.612, 0.335), the red chromaticity is (0 .617, 0.332). That is, when the display filter of the present invention is mounted, the red chromaticity approaches the red chromaticity (0.670, 0.330) determined by the NTSC system.

  The present invention makes it possible to provide a method for producing an aryl-substituted tetraazaporphyrin compound that is stable, efficient, and excellent in optical properties. The aryl-substituted tetraazaporphyrin compound produced by the method of the present invention has excellent optical properties, and is used for various functional materials (for example, display filter use, optical recording medium use, ink use, thermal transfer use). ) Can be used. In addition, the display filter containing the aryl-substituted tetraazaporphyrin compound produced by the method of the present invention is excellent in optical properties and can be used as various display filters.

11: Functional transparent layer (A)
12: Substrate (B)
13: Transparent adhesive layer (C)

21: Functional transparent layer (A)
22: Substrate (B)
23: Transparent adhesive layer (C)
24: Transparent conductive layer (D)

31: Functional transparent layer (A)
32: Substrate (B)
33: Transparent adhesive layer (C)
34: Transparent conductive layer (D)

42: Substrate (B)

53: Transparent adhesive layer (C)

62: Substrate (B)
63: Transparent adhesive layer (C)

71: Functional transparent layer (A)
72: Substrate (B)

Claims (9)

  A process for producing an aryl-substituted tetraazaporphyrin compound comprising reacting a tetraazaporphyrin compound with an aryl compound having a leaving group in the presence of a base and a transition metal compound. The process according to claim 1, wherein the tetraazaporphyrin compound is a compound represented by the general formula (A).

[Wherein, R represents a hydrogen atom, a cyano group, a nitro group, a linear, branched or cyclic alkyl group, a linear, branched or cyclic alkoxy group, a substituted or unsubstituted aryl group, a substituted or unsubstituted aryl group. Oxy group, substituted or unsubstituted aralkyl group, substituted or unsubstituted aralkyloxy group, linear, branched or cyclic halogenoalkyl group, linear, branched or cyclic halogenoalkoxy group, substituted amino group, linear, branched Or a cyclic alkoxyalkyl group, a linear, branched or cyclic alkoxyalkoxyalkyl group, a substituted or unsubstituted aryloxyalkyl group, a substituted or unsubstituted aralkyloxyalkyl group, or a linear, branched or cyclic halogenoalkoxyalkyl group And adjacent R groups are bonded to each other to share a substituted carbon atom. Represents an optionally substituted carbocyclic aliphatic ring, and m represents an integer of 0 to 8 (provided that when m represents 8, at least one R represents a hydrogen atom). And M represents two hydrogen atoms, two monovalent metal atoms, a divalent metal atom, a trivalent substituted metal atom, a tetravalent substituted metal atom, or a metal oxide atom] The method according to claim 1 or 2, wherein the aryl compound having a leaving group is a compound represented by the general formula (B).

(In the formula, Ar represents an aryl group, and X represents a leaving group)
  The process according to claim 3, wherein Ar is an aryl group having 3 to 40 carbon atoms which may have a substituent.   Ar is substituted with a fluorine atom, a chlorine atom, a linear, branched, or cyclic alkyl group, a linear, branched, or cyclic alkoxy group, a substituted or unsubstituted aryl group, or an N, N-disubstituted amino group. The method according to claim 4, wherein the aryl group may be an aryl group. X is a halogen atom or —OSO ₂ —R ₀ (R ₀ represents a substituted or unsubstituted aryl group, or a linear, branched or cyclic alkyl group which may be substituted with a halogen atom). 3. Manufacturing method of 3. In the -OSO ₂ -R _{0, R 0} is a substituted or unsubstituted aryl group having 6 to 10 carbon atoms or optionally straight optionally substituted by a halogen atom having 1 to 10 carbon atoms, alkyl branched or cyclic The manufacturing method of Claim 6 which is group.   The aryl substituted tetraazaporphyrin compound manufactured by the manufacturing method in any one of Claims 1-7.   A display filter comprising at least one aryl-substituted tetraazaporphyrin compound according to claim 8.

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