JP2007039378A - Method for producing phthalocyanine - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for mildly and easily producing in high yield a phthalocyanine useful as a new material for image formation, infrared-sensitive recording use, optical recording devices and optical film, etc. <P>SOLUTION: The method for producing the phthalocyanine comprises conducting a reaction between a compound(component A) of the general formula(I) or (II), a metal salt(component B) and a disilazane compound(component C) of the general formula(III):HN(SiR<SP>31</SP>R<SP>32</SP>R<SP>33</SP>)<SB>2</SB>. In the formulas(I), (II) and (III), R<SP>1</SP>is a substituent; n<SB>1</SB>is an integer of 0 or ≥1; Q<SB>1</SB>is a nonmetal atom group forming a ring through condensing with a benzene ring; R<SB>2</SB>is a substituent; n<SB>2</SB>is an integer of 0 or ≥1; Q<SB>2</SB>is a nonmetal atom group forming a ring through condensing with a benzene ring; A<SB>21</SB>, A<SB>22</SB>and A<SB>23</SB>are each an oxygen atom or NH; R<SP>31</SP>, R<SP>32</SP>and R<SP>33</SP>are each an aliphatic or aromatic group. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a method for producing phthalocyanines useful as a novel image forming material, an infrared thermosensitive recording material, an optical recording element, an optical film material and the like. The present invention relates to a method for producing a phthalocyanine having a condensed ring.

  Phthalocyanines are widely used as pigments. Among them, phthalocyanines having a condensed ring have been extensively studied as near-infrared absorbing dyes.

  Conventionally, as a method for producing phthalocyanines, a method of heating phthalic anhydride or phthalimide at 200 to 300 ° C. in the presence of urea, a method of heating phthalonitrile together with ammonia or a catalyst at 150 to 250 ° C., etc. are widely known. (For example, refer nonpatent literature 1). As these improved methods, there are methods that improve the addition method and the like (see, for example, Patent Document 1 and Non-Patent Document 2). Furthermore, a method of coexisting a silazane derivative has been known (see, for example, Patent Document 2, Non-Patent Documents 3 and 4).

However, there is no effective knowledge about the production method of phthalocyanines having a condensed ring other than a benzene ring and naphthalocyanines having a substituent at positions 1 and 4, and these are produced in a high yield under mild and simple conditions. A method was sought.
JP-A-6-228449 JP 2002-226482 A Journal of Chemical Society, Parkin Transaction, I, pages 2453-2458 (issued in 1988) Journal of Organic Chemistry, 55, 2155-2159 (issued in 1990) Journal of Organic Chemistry, 68, 8736-8738 (issued in 2003) Sinlet, 1649 pages (issued in 2002)

The present invention has been made in view of the above-described conventional problems, and an object thereof is to achieve the following object. That is,
An object of the present invention is to provide a mild, simple and high-yield production method of phthalocyanines useful as a novel image forming material, infrared thermosensitive recording material, optical recording element, optical film material and the like.

  As a result of intensive studies, the present inventors have found that the above object of the present invention can be achieved by the following means.

(1) A compound (component A) represented by the following general formula (I) or the following general formula (II), a metal salt (component B), and a disilazane compound represented by the following general formula (III) (component C) ) Is reacted with phthalocyanines.

［一般式（Ｉ）中、Ｒ¹は置換基を表し、ｎ₁は０または１以上の整数を表し、Ｑ₁はベンゼン環と縮合して環を形成する非金属原子群を表す。ｎ₁が２以上の場合、複数のＲ¹は同一でも異なっていてもよく、互いに結合して環を形成してもよい。ただし、Ｑ₁によってベンゼン環と縮合して形成される環がナフタレン環の場合、ｎ₁は１以上の整数を表す。］

[In General Formula (I), R ¹ represents a substituent, n ₁ represents 0 or an integer of 1 or more, and Q ₁ represents a nonmetallic atom group that forms a ring by condensation with a benzene ring. When n ₁ is 2 or more, a plurality of R ¹ may be the same or different and may be bonded to each other to form a ring. However, when the ring formed by condensing with the benzene ring by Q ₁ is a naphthalene ring, n ₁ represents an integer of 1 or more. ]

［一般式（II）中、Ｒ²は置換基を表し、ｎ₂は０または１以上の整数を表し、Ｑ₂はベンゼン環と縮合して環を形成する非金属原子群を表す。ｎ₂が２以上の場合、複数のＲ²は同一でも異なっていてもよく、互いに結合して環を形成してもよい。Ａ₂₁、Ａ₂₂、及びＡ₂₃は各々独立に酸素原子またはＮＨを表す。ただし、Ｑ₂によってベンゼン環と縮合して形成される環がナフタレン環の場合、ｎ₂は１以上の整数を表す。］

[In General Formula (II), R ² represents a substituent, n ₂ represents 0 or an integer of 1 or more, and Q ₂ represents a nonmetallic atom group that forms a ring by condensation with a benzene ring. When n ₂ is 2 or more, a plurality of R ² may be the same or different and may be bonded to each other to form a ring. A ₂₁ , A ₂₂ , and A ₂₃ each independently represent an oxygen atom or NH. However, when the ring formed by condensing with the benzene ring by Q ₂ is a naphthalene ring, n ₂ represents an integer of 1 or more. ]

General formula (III)
HN (SiR ³¹ R ³² R ³³ ) ₂
[In the general formula (III), R ³¹ , R ³² and R ³³ each independently represents an aliphatic group or an aromatic group. ]

(2) The method for producing a phthalocyanine according to (1) above, wherein the component (A) is a compound represented by the following general formula (IV) or the following general formula (V).

［一般式（IV）中、Ｒ⁴は置換基を表し、ｎ₄は１〜６の整数を表す。ｎ₄が２以上の場合、複数のＲ⁴は同一でも異なっていてもよく、互いに結合して環を形成してもよい。］

[In General Formula (IV), R ⁴ represents a substituent, and n ₄ represents an integer of 1 to 6. When n ₄ is 2 or more, the plurality of R ⁴ may be the same or different and may be bonded to each other to form a ring. ]

［一般式（Ｖ）中、Ｒ⁵は置換基を表し、ｎ₅は１〜６の整数を表す。ｎ₅が２以上の場
合、複数のＲ⁵は同一でも異なっていてもよく、互いに結合して環を形成していてもよい。Ａ₅₁、Ａ₅₂、及びＡ₅₃は各々独立に酸素原子またはＮＨを表す。］

[In General Formula (V), R ⁵ represents a substituent, and n ₅ represents an integer of 1 to 6. When n ₅ is 2 or more, the plurality of R ⁵ may be the same or different, and may be bonded to each other to form a ring. A ₅₁ , A ₅₂ , and A ₅₃ each independently represent an oxygen atom or NH. ]

(3) The production of the phthalocyanines according to (1) or (2), wherein the component (A) is a compound represented by the following general formula (VI) or the following general formula (VII): Is the method.

［一般式（VI）中、Ｒ⁶¹及びＲ⁶²は各々独立に置換基を表す。］

[In General Formula (VI), R ⁶¹ and R ⁶² each independently represent a substituent. ]

［一般式（VII）中、Ｒ⁷¹、及びＲ⁷²は各々独立に置換基を表し、Ａ₇₁、Ａ₇₂、及びＡ₇₃は各々独立に酸素原子またはＮＨを表す。］

[In general formula (VII), ^R71 and ^R72 each independently represent a substituent, and _A71 , _A72 and _A73 each independently represent an oxygen atom or NH. ]

(4) In the general formulas (I), (II), (IV) to (VII), R ¹ , R ² , R ⁴ , R ⁵ , R ⁶¹ , R ⁶² , R ⁷¹ , and R ⁷² are The production of phthalocyanines according to any one of (1) to (3) above, which is a group selected from the group consisting of groups represented by formulas (VIII-1) to (VIII-3) Is the method.
Formula (VIII-1)
-NR ⁸¹ R ⁸²
General formula (VIII-2)
-O-R ⁸³
General formula (VIII-3)
-SR ⁸⁴
[In the general formulas (VIII-1) to (VIII-3), R ^{81 to} R ⁸⁴ each independently represents a hydrogen atom, an aliphatic group or an aromatic group. ]

(5) Any of (1) to (4) above, wherein the disilazane compound represented by the general formula (III) is 1,1,1,3,3,3-hexamethyldisilazane The method for producing phthalocyanines described in 1. above.

(6) The method for producing a phthalocyanine according to any one of (1) to (5), wherein the reaction is performed at 50 to 250 ° C.

(7) The phthalocyanines according to any one of (1) to (6), wherein the reaction temperature of the reaction is 65 to 130 ° C., and the reaction temperature is changed during the reaction. It is a manufacturing method.

(8) The method for producing a phthalocyanine according to any one of (1) to (7), wherein the reaction solvent for the reaction is an amide solvent.

(9) The method for producing a phthalocyanine according to any one of (1) to (7), wherein a reaction solvent for the reaction is 1-butanol or pentanol.

  ADVANTAGE OF THE INVENTION According to this invention, the manufacturing method which can manufacture phthalocyanine useful as a novel image forming material, an infrared thermosensitive recording material, an optical recording element, an optical film material, etc. in a mild, simple and high yield can be provided. .

Hereinafter, embodiments of the present invention will be described in detail.
In the present specification, the aliphatic group means an alkyl group, a substituted alkyl group, an alkenyl group, a substituted alkenyl group, an alkynyl group, a substituted alkynyl group, an aralkyl group, and a substituted aralkyl group. The alkyl group means a linear, branched, or cyclic (for example, cycloalkyl group) alkyl group, preferably having 1 to 20 carbon atoms, and more preferably 1 to 18. The alkyl part of the substituted alkyl group is the same as the above alkyl group. An alkenyl group means a linear, branched, or cyclic (eg, cycloalkenyl group) alkenyl group, preferably having 2 to 20 carbon atoms, and more preferably 2 to 18 carbon atoms. The alkenyl part of the substituted alkenyl group is the same as the above alkenyl group. The alkynyl group means a linear, branched, or cyclic (eg, cycloalkynyl group) alkynyl group, preferably having 2 to 20 carbon atoms, and more preferably 2 to 18 carbon atoms. The alkynyl part of the substituted alkynyl group is the same as the above alkynyl group. The alkyl part of the aralkyl group and the substituted aralkyl group is the same as the above alkyl group. The aryl part of the aralkyl group and the substituted aralkyl group is the same as the following aryl group.

  The substituent of the alkyl part of the substituted alkyl group, the substituted alkenyl group, the substituted alkynyl group and the substituted aralkyl group includes a halogen atom (for example, a chlorine atom, a bromine atom, an iodine atom); an alkyl group [straight chain, branched, cyclic substitution Alternatively, it represents an unsubstituted alkyl group. They are alkyl groups (preferably alkyl groups having 1 to 30 carbon atoms such as methyl, ethyl, n-propyl, isopropyl, t-butyl, n-octyl, eicosyl, 2-chloroethyl, 2-cyanoethyl, 2-ethylhexyl). A cycloalkyl group (preferably a substituted or unsubstituted cycloalkyl group having 3 to 30 carbon atoms, such as cyclohexyl, cyclopentyl, 4-n-dodecylcyclohexyl), a bicycloalkyl group (preferably having 5 to 30 carbon atoms). A substituted or unsubstituted bicycloalkyl group, that is, a monovalent group obtained by removing one hydrogen atom from a bicycloalkane having 5 to 30 carbon atoms, for example, bicyclo [1,2,2] heptan-2-yl, bicyclo [2,2,2] octane-3-yl), a tricyclo structure with more ring structures Domo is intended to cover. An alkyl group (for example, an alkyl group of an alkylthio group) in the substituents described below also represents such an alkyl group. ];

Alkenyl group [represents a linear, branched or cyclic substituted or unsubstituted alkenyl group. They are alkenyl groups (preferably substituted or unsubstituted alkenyl groups having 2 to 30 carbon atoms, such as vinyl, allyl, prenyl, geranyl, oleyl), cycloalkenyl groups (preferably substituted or substituted groups having 3 to 30 carbon atoms). An unsubstituted cycloalkenyl group, that is, a monovalent group obtained by removing one hydrogen atom of a cycloalkene having 3 to 30 carbon atoms (for example, 2-cyclopenten-1-yl, 2-cyclohexen-1-yl), Bicycloalkenyl group (a substituted or unsubstituted bicycloalkenyl group, preferably a substituted or unsubstituted bicycloalkenyl group having 5 to 30 carbon atoms, that is, a monovalent group obtained by removing one hydrogen atom of a bicycloalkene having one double bond. For example, bicyclo [2,2,1] hept-2-en-1-yl, bicyclo 2,2,2] oct-2-en-4-yl). An alkynyl group (preferably a substituted or unsubstituted alkynyl group having 2 to 30 carbon atoms, such as ethynyl, propargyl, trimethylsilylethynyl group); an aryl group (preferably a substituted or unsubstituted aryl having 6 to 30 carbon atoms) Groups such as phenyl, p-tolyl, naphthyl, m-chlorophenyl, o-hexadecanoylaminophenyl); heterocyclic groups (preferably 5- or 6-membered substituted or unsubstituted aromatic or non-aromatic heterocycles A monovalent group obtained by removing one hydrogen atom from a compound, more preferably a 5- or 6-membered aromatic heterocyclic group having 3 to 30 carbon atoms, such as 2-furyl, 2-thienyl, 2-pyrimidinyl, 2-benzothiazolyl);

A cyano group; a hydroxyl group; a nitro group; a carboxyl group; an alkoxy group (preferably a substituted or unsubstituted alkoxy group having 1 to 30 carbon atoms such as methoxy, ethoxy, isopropoxy, t-butoxy, n-octyloxy, 2-methoxyethoxy); aryloxy groups (preferably substituted or unsubstituted aryloxy groups having 6 to 30 carbon atoms such as phenoxy, 2-methylphenoxy, 4-t-butylphenoxy, 3-nitrophenoxy, 2 -Tetradecanoylaminophenoxy); a silyloxy group (preferably a silyloxy group having 3 to 20 carbon atoms, such as trimethylsilyloxy, t-butyldimethylsilyloxy); a heterocyclic oxy group (preferably having 2 to 30 carbon atoms) Substituted or unsubstituted heterocyclic oxy group, 1- Acyltetrazol-5-oxy, 2-tetrahydropyranyloxy); acyloxy group (preferably formyloxy group, substituted or unsubstituted alkylcarbonyloxy group having 2 to 30 carbon atoms, substituted or unsubstituted group having 6 to 30 carbon atoms) Arylcarbonyloxy group of, for example, formyloxy, acetyloxy, pivaloyloxy, stearoyloxy, benzoyloxy, p-methoxyphenylcarbonyloxy); carbamoyloxy group (preferably substituted or unsubstituted carbamoyloxy having 1 to 30 carbon atoms) Groups such as N, N-dimethylcarbamoyloxy, N, N-diethylcarbamoyloxy, morpholinocarbonyloxy, N, N-di-n-octylaminocarbonyloxy, Nn-octylcarbamoyloxy) An alkoxycarbonyloxy group (preferably a substituted or unsubstituted alkoxycarbonyloxy group having 2 to 30 carbon atoms, such as methoxycarbonyloxy, ethoxycarbonyloxy, t-butoxycarbonyloxy, n-octylcarbonyloxy); aryloxycarbonyloxy group (Preferably a substituted or unsubstituted aryloxycarbonyloxy group having 7 to 30 carbon atoms, such as phenoxycarbonyloxy, p-methoxyphenoxycarbonyloxy, pn-hexadecyloxyphenoxycarbonyloxy);

An amino group (preferably an amino group, a substituted or unsubstituted alkylamino group having 1 to 30 carbon atoms, a substituted or unsubstituted anilino group having 6 to 30 carbon atoms, such as amino, methylamino, dimethylamino, anilino, N-methyl-anilino, diphenylamino); acylamino group (preferably formylamino group, substituted or unsubstituted alkylcarbonylamino group having 1 to 30 carbon atoms, substituted or unsubstituted arylcarbonylamino group having 6 to 30 carbon atoms) Groups such as formylamino, acetylamino, pivaloylamino, lauroylamino, benzoylamino, 3,4,5-tri-n-octyloxyphenylcarbonylamino); aminocarbonylamino groups (preferably substituted with 1 to 30 carbons) Or unsubstituted aminocarbonyl , For example, carbamoylamino, N, N-dimethylaminocarbonylamino, N, N-diethylaminocarbonylamino, morpholinocarbonylamino); alkoxycarbonylamino group (preferably a substituted or unsubstituted alkoxycarbonylamino group having 2 to 30 carbon atoms) , For example, methoxycarbonylamino, ethoxycarbonylamino, t-butoxycarbonylamino, n-octadecyloxycarbonylamino, N-methyl-methoxycarbonylamino); aryloxycarbonylamino group (preferably having 7 to 30 carbon atoms substituted or Unsubstituted aryloxycarbonylamino groups such as phenoxycarbonylamino, p-chlorophenoxycarbonylamino, mn-octyloxyphenoxycarbonylamino); Famoylamino group (preferably a substituted or unsubstituted sulfamoylamino group having 0 to 30 carbon atoms, such as sulfamoylamino, N, N-dimethylaminosulfonylamino, Nn-octylaminosulfonylamino) Alkyl and arylsulfonylamino groups (preferably substituted or unsubstituted alkylsulfonylamino having 1 to 30 carbon atoms, substituted or unsubstituted arylsulfonylamino having 6 to 30 carbon atoms, such as methylsulfonylamino, butylsulfonylamino, Phenylsulfonylamino, 2,3,5-trichlorophenylsulfonylamino, p-methylphenylsulfonylamino);

A mercapto group; an alkylthio group (preferably a substituted or unsubstituted alkylthio group having 1 to 30 carbon atoms, such as methylthio, ethylthio, n-hexadecylthio); an arylthio group (preferably a substituted or unsubstituted arylthio group having 6 to 30 carbon atoms). , For example, phenylthio, p-chlorophenylthio, m-methoxyphenylthio); a heterocyclic thio group (preferably a substituted or unsubstituted heterocyclic thio group having 2 to 30 carbon atoms, such as 2-benzothiazolylthio, 1 -Phenyltetrazol-5-ylthio); a sulfamoyl group (preferably a substituted or unsubstituted sulfamoyl group having 0 to 30 carbon atoms such as N-ethylsulfamoyl, N- (3-dodecyloxypropyl) sulfamoyl, N, N-dimethylsulfamoyl, N-acetyl Sulfamoyl, N-benzoylsulfamoyl, N- (N′-phenylcarbamoyl) sulfamoyl); sulfo group; alkyl and arylsulfinyl group (preferably substituted or unsubstituted alkylsulfinyl group having 1 to 30 carbon atoms, from 6 30 substituted or unsubstituted arylsulfinyl groups such as methylsulfinyl, ethylsulfinyl, phenylsulfinyl, p-methylphenylsulfinyl); alkyl and arylsulfonyl groups (preferably substituted or unsubstituted alkyl having 1 to 30 carbon atoms) Sulfonyl group, 6-30 substituted or unsubstituted arylsulfonyl group such as methylsulfonyl, ethylsulfonyl, phenylsulfonyl, p-methylphenylsulfonyl); acyl group (preferably formyl group, carbon number) To a substituted or unsubstituted alkylcarbonyl group having 7 to 30 carbon atoms, a substituted or unsubstituted arylcarbonyl group having 7 to 30 carbon atoms, or a heterocyclic ring bonded to the carbonyl group at a substituted or unsubstituted carbon atom having 4 to 30 carbon atoms A carbonyl group such as acetyl, pivaloyl, 2-chloroacetyl, stearoyl, benzoyl, pn-octyloxyphenylcarbonyl, 2-pyridylcarbonyl, 2-furylcarbonyl);

An aryloxycarbonyl group (preferably a substituted or unsubstituted aryloxycarbonyl group having 7 to 30 carbon atoms, such as phenoxycarbonyl, o-chlorophenoxycarbonyl, m-nitrophenoxycarbonyl, pt-butylphenoxycarbonyl); An alkoxycarbonyl group (preferably a substituted or unsubstituted alkoxycarbonyl group having 2 to 30 carbon atoms, such as methoxycarbonyl, ethoxycarbonyl, t-butoxycarbonyl, n-octadecyloxycarbonyl); a carbamoyl group (preferably having 1 carbon atom) To 30 substituted or unsubstituted carbamoyl such as carbamoyl, N-methylcarbamoyl, N, N-dimethylcarbamoyl, N, N-di-n-octylcarbamoyl, N- (methylsulfonyl) carba Aryl) and heterocyclic azo groups (preferably substituted or unsubstituted arylazo groups having 6 to 30 carbon atoms, substituted or unsubstituted heterocyclic azo groups having 3 to 30 carbon atoms, such as phenylazo, p-chlorophenylazo , 5-ethylthio-1,3,4-thiadiazol-2-ylazo); an imide group (preferably N-succinimide, N-phthalimide); a phosphino group (preferably a substituted or unsubstituted group having 2 to 30 carbon atoms) A phosphino group such as dimethylphosphino, diphenylphosphino, methylphenoxyphosphino); a phosphinyl group (preferably a substituted or unsubstituted phosphinyl group having 2 to 30 carbon atoms such as phosphinyl, dioctyloxyphosphinyl, di Ethoxyphosphinyl); phosphinyloxy group (preferably Or a substituted or unsubstituted phosphinyloxy group having 2 to 30 carbon atoms, such as diphenoxyphosphinyloxy, dioctyloxyphosphinyloxy); a phosphinylamino group (preferably having 2 to 3 carbon atoms). 30 substituted or unsubstituted phosphinylamino groups such as dimethoxyphosphinylamino, dimethylaminophosphinylamino); silyl groups (preferably substituted or unsubstituted silyl groups having 3 to 30 carbon atoms such as , Trimethylsilyl, t-butyldimethylsilyl, phenyldimethylsilyl).

  Among the above functional groups, those having a hydrogen atom may be substituted with the above groups by removing this. Examples of such functional groups include an alkylcarbonylaminosulfonyl group, an arylcarbonylaminosulfonyl group, an alkylsulfonylaminocarbonyl group, and an arylsulfonylaminocarbonyl group. Specific examples thereof include methylsulfonylaminocarbonyl, p-methylphenylsulfonylaminocarbonyl, acetylaminosulfonyl, and benzoylaminosulfonyl groups.

  Examples of the substituent of the aryl moiety of the substituted aralkyl group include the same groups as the substituents of the following substituted aryl group.

  In the present specification, the aromatic group means an aryl group and a substituted aryl group. These aromatic groups may be condensed with an aliphatic ring, another aromatic ring or a heterocyclic ring. The number of carbon atoms in the aromatic group is preferably 6 to 40, more preferably 6 to 30, and still more preferably 6 to 20. Among them, the aryl group is preferably phenyl or naphthyl, particularly preferably phenyl.

  The aryl part of the substituted aryl group is the same as the above aryl group. Examples of the substituent of the substituted aryl group include those exemplified above as the substituent of the alkyl part of the substituted alkyl group, the substituted alkenyl group, the substituted alkynyl group and the substituted aralkyl group.

Next, the compounds represented by the general formulas (I) to (VIII) will be described.
In the general formula (I), R ¹ represents a substituent, and examples of the substituent are the same as those described above as the substituent of the alkyl part of the substituted alkyl group, substituted alkenyl group, substituted alkynyl group and substituted aralkyl group. Things. R ¹ is preferably a halogen atom, alkyl group, alkenyl group, alkynyl group, aryl group, cyano group, hydroxyl group, nitro group, carboxyl group, alkoxy group, aryloxy group, silyloxy group, acyloxy group, carbamoyloxy group, alkoxy Carbonyloxy group, aryloxycarbonyloxy group, amino group, acylamino group, aminocarbonylamino group, alkoxycarbonylamino group, aryloxycarbonylamino group, sulfamoylamino group, alkyl or arylsulfonylamino group, mercapto group, alkylthio group , Arylthio group, sulfamoyl group, sulfo group, alkyl or arylsulfinyl group, alkyl or arylsulfonyl group, acyl group, aryloxycarbonyl group, alkyl A xycarbonyl group, a carbamoyl group, an imide group, a phosphino group, a phosphinyl group, a phosphinyloxy group, a phosphinylamino group, and a silyl group, more preferably a halogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group Cyano group, hydroxyl group, nitro group, carboxyl group, alkoxy group, aryloxy group, silyloxy group, acyloxy group, amino group, acylamino group, mercapto group, alkylthio group, arylthio group, sulfo group, alkyl or arylsulfinyl group, Alkyl or arylsulfonyl group, acyl group, imide group, phosphino group, silyl group, more preferably halogen atom, alkyl group, aryl group, cyano group, hydroxyl group, alkoxy group, aryloxy group, silyloxy group, An amino group, an alkylthio group, an arylthio group, and a silyl group, more preferably a chlorine atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, and 6 carbon atoms. An aryloxy group having 1 to 20 carbon atoms, a silyloxy group having 1 to 20 carbon atoms, an amino group having 2 to 20 carbon atoms, an alkylthio group having 1 to 20 carbon atoms, an arylthio group having 6 to 20 carbon atoms, and a hydroxy group, and more preferably An alkoxy group having 1 to 10 carbon atoms, an aryloxy group having 6 to 10 carbon atoms, an amino group having 2 to 10 carbon atoms, an alkylthio group having 1 to 10 carbon atoms, and an arylthio group having 6 to 10 carbon atoms. R ¹ is more preferably an alkoxy group having 1 to 10 carbon atoms, an amino group having 2 to 10 carbon atoms, or an alkylthio group having 1 to 10 carbon atoms. Most preferred R ¹ is an alkoxy group having 1 to 5 carbon atoms.

n ₁ represents 0 or an integer of 1 or more. When n ₁ is an integer of 2 or more, the plurality of R ¹ may be the same as or different from each other. n ₁ is preferably an integer of 0 to 4, more preferably 1 to 3, and most preferably 2. Further, n ₁ is 2, and R ¹ is preferably substituted at two positions in the ortho position of the two cyano groups. However, when the ring formed by condensing with the benzene ring by Q ₁ is a naphthalene ring, n ₁ represents an integer of 1 or more.

Q ₁ represents a nonmetallic atom group that forms a ring by condensing with a benzene ring. Preferred examples of Q ₁ include the following.

［式中、＊および＊＊はベンゼン環との結合位置を表す。なお、上記は基本の原子連結を示したものであり、結合の不足している原子には水素原子または置換基が置換するものである。］

[Wherein, * and ** represent a bonding position with a benzene ring. In addition, the above shows basic atomic connection, and a hydrogen atom or a substituent is substituted for an atom having insufficient bonds. ]

More preferable Q ₁ is (A), (B), (N), (Q), (R), (S), (T), (Y), (Z) and (AA) among the above. (A), (N), (Q), (R), (S), (T), (Y), and (Z) are more preferable, and (A), (N), ( Q) and (Y), more preferably (A), (N), (Q), and (Y) having no substituent on Q ₁ , and most preferred Q ₁ is on Q ₁ (A) which has no substituent.

In the general formula (II), R ² , n ₂ and Q ₂ are the same as R ¹ , n ₁ and Q ₁ , respectively, and preferred ranges are also the same. In addition, it is preferable that R ² is substituted at two positions at the ortho position of the carbon atom which is n ₂ and is condensed with a 5-membered ring containing A _{21 to} A ₂₃ . A _{21 to} A ₂₃ each independently represents an oxygen atom or NH, and A ₂₁ and A ₂₂ are preferably the same.

In the general formula (III), R ^{31 to} R ³³ each independently represents an aliphatic group or an aromatic group. These aliphatic groups and aromatic groups are as described above, and R ^{31 to} R ³³ are preferably an aliphatic group having 1 to 6 carbon atoms and an aromatic group having 6 to 8 carbon atoms, more preferably carbon. An alkyl group having 1 to 6 carbon atoms and an aryl group having 6 to 8 carbon atoms, more preferably an alkyl group having 1 to 4 carbon atoms and an unsubstituted phenyl group, and more preferably an alkyl group having 1 to 4 carbon atoms. And most preferably a methyl group.

In the general formula (IV), R ⁴ has the same meaning as R ¹ in the general formula (I), and the preferred range is also the same. n ₄ represents an integer of 1 to 6, preferably an integer of 1 to 4, more preferably 1 to 3, and most preferably n ₄ is 2. Further, n ₄ is 2, and R ⁴ is preferably substituted at two positions in the ortho position of the two cyano groups.

In the general formula (V), R ⁵ and n ₅ have the same meanings as R ⁴ and n ₄ , respectively, and preferred ranges are also the same. Further, n ₅ is 2, and R ⁵ is preferably substituted at two positions at the ortho position of the carbon atom condensed with the 5-membered ring containing A _{51 to} A ₅₃ . A _{51 to} A ₅₃ are synonymous with A _{21 to} A ₂₃ , and preferred ranges are also the same.

In the general formulas (VI) and (VII), R ⁶¹ , R ⁶² , R ⁷¹ , and R ⁷² are synonymous with R ¹ , and preferred ranges are also the same. A _{71 to} A ₇₃ are synonymous with A _{21 to} A ₂₃ , and preferred ranges are also the same.

In the general formulas (I), (II), (IV) to (VII), R ¹ , R ² , R ⁴ , R ⁵ , R ⁶¹ , R ⁶² , R ⁷¹ , and R ⁷² are represented by the following general formula: A group selected from the groups represented by (VIII-1) to (VIII-3) is preferable.
Formula (VIII-1)
-NR ⁸¹ R ⁸²
General formula (VIII-2)
-O-R ⁸³
General formula (VIII-3)
-SR ⁸⁴
[In the general formulas (VIII-1) to (VIII-3), R ^{81 to} R ⁸⁴ each independently represents a hydrogen atom, an aliphatic group or an aromatic group. ]

R ^{81 to} R ⁸⁴ are preferably an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms, more preferably an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 10 carbon atoms. More preferably an alkyl group having 1 to 6 carbon atoms or an unsubstituted phenyl group. Most preferred R ^{81 to} R ⁸⁴ are alkyl groups having 1 to 5 carbon atoms.

The metal salt (component B) used in the production method of the present invention is preferably an organic or inorganic compound containing a group 1 to 15 and a lanthanoid metal. Here, the metal is preferably Li, Na, Mg, Al, K, Ca, Si, Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Ge, Ga, Ru, Sn, and Pb, more preferably Li, Na, Mg, Al, K, Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu and Zn, more preferably Li, Na, Mg, K, Sc, Ti, V, Cr, Mn, Fe, Co , Ni, Cu and Zn. Components other than the metal forming the metal salt are preferably halogen ions (for example, F ⁻ , Cl ⁻ , Br ⁻ ), CN ⁻ , SO ₄ ²⁻ , HO ⁻ , NO ₃ ⁻ , CO ₃ ²⁻ , carboxylate ions ( For example, acetate ion, oxalate ion), sulfonate ion (for example, methanesulfonate ion, benzenesulfonate ion), phosphate ion, alkoxy ion (for example, methoxy ion, ethoxy ion, isopropoxy ion, phenoxy ion) and the like. . More preferably, Cl ⁻ , CN ⁻ , SO ₄ ²⁻ , HO ⁻ , CO ₃ ²⁻ , acetate ions, and alkoxy ions are more preferable, and Cl ⁻ , CN ⁻ , SO ₄ ²⁻ , HO ⁻ , acetate ions, Alkoxy ion.

  Next, specific examples of the compounds represented by the general formulas (I), (II) and (IV) to (VII) of the present invention are shown, but the present invention is not limited thereto.

  Next, specific examples of the compound represented by the general formula (III) of the present invention are shown, but the present invention is not limited thereto.

  The ratio of the raw material used for the reaction is preferably 0.01 to 10 mol, more preferably 0.1 to 5 mol, and still more preferably 0.2 to 0.1 mol with respect to 1 mol of component A. 2 moles, most preferably 0.25 to 1 mole. The amount of component C is preferably 0.1 to 50 mol, more preferably 0.5 to 20 mol, still more preferably 1.0 to 10 mol, and still more preferably 1 mol of component A. Is 1.5 to 5 moles, most preferably 1.75 to 3 moles.

  Component C used for the reaction may be carried out by batch addition, divided addition, dropwise addition, or a combination of these addition methods.

  Examples of the solvent used in the reaction include a disilazane solvent, an amide solvent (for example, N, N-dimethylformamide (DMA), N, N-dimethylacetamide (DMAc), 1-methyl-2-pyrrolidone), a sulfone solvent (for example, sulfolane). Sulfoxide solvents (eg dimethyl sulfoxide), ureido solvents (eg tetramethyl urea), ether solvents (eg dioxane, cyclopentyl methyl ether), ketone solvents (eg acetone, cyclohexanone), hydrocarbon solvents (eg toluene, xylene) ), Halogen solvents (eg tetrachloroethane, chlorobenzene), alcohol solvents (eg 1-butanol, pentanol, ethylene glycol, cyclohexanol), pyridine solvents (eg pyridine, γ-picoline) Using 2,6-lutidine) alone or in combination. Preferred are amide solvents, sulfone solvents, ureido solvents, ether solvents, halogen solvents, alcohol solvents, pyridine solvents, and more preferred are amide solvents, sulfone solvents, ether solvents, halogen solvents. An alcohol solvent, more preferably an amide solvent (preferably N, N-dimethylformamide, N, N-dimethylacetamide), an alcohol solvent (preferably 1-butanol or pentanol, more preferably 1-butanol). The most preferred solvent is an amide solvent.

  The reaction temperature is preferably 0 to 250 ° C., more preferably 50 to 250 ° C., further preferably 50 to 150 ° C., most preferably 65 to 130 ° C., and the reaction time is 5 minutes to 30 hours. It is preferable that Note that changing the reaction temperature in the middle of the reaction is after the addition of Component A, Component B, and Component C and after the reaction temperature is reached (specifically, the solvent distillation). It is to change the temperature of the reaction system until the last operation).

  In the present invention, it is preferable to change the reaction temperature during the reaction (for example, the first half 50 ° C., the second half 120 ° C.). For example, it is preferable to react at a relatively low temperature until a raw material that is easily decomposed in the reaction system is converted into an intermediate that is difficult to decompose, and in this respect, it is preferable to change the reaction temperature in the middle. Moreover, as a timing which changes reaction temperature, the stage which the raw material and intermediate body which are comparatively easy to decompose | dissolve has disappeared is preferable. And it is preferable that the substantially second half of the reaction is higher than the first half. The temperature difference between the first half and the second half of the reaction is preferably 10 to 50 ° C. It is particularly effective when an amide solvent is used alone or in combination, and the case where the first half is 65 to 80 ° C and the second half is 80 to 130 ° C is preferable.

  During the reaction, when by-product water and other refluxable components are by-produced, it is also preferable to react while removing from the system, a method of distilling alone or with a solvent under reduced pressure or normal pressure, Alternatively, a method using an absorbent such as molecular sieve, a method using a dehydrating condensing agent such as acetic anhydride or orthoester, or the like is preferably used. In addition, this reaction is also preferably performed in a closed system.

  The present invention will be described in more detail with reference to the following examples, but the present invention is not limited thereto.

Example 1
In a three-necked flask, 38.7 g of the exemplified compound (S-1), 8.1 g of copper chloride, 58.1 g of 1,1,1,3,3,3-hexamethyldisilazane and 300 ml of DMF were placed, and the internal temperature was 70. The mixture was stirred at 90 ° C. for 3 hours and then stirred at 90 ° C. for 2 hours. After distilling off the solvent under reduced pressure, 4 l of chloroform was added, 3 l of water was added, and 20 ml of sulfuric acid was further added for extraction. The obtained chloroform solution was washed by adding 3 l of water three times, then concentrated with a rotary evaporator, 500 ml of methanol was added to the resulting residue, and the resulting crystals were suction filtered. By drying, 30.9 g of the target naphthalocyanine compound (central metal: copper) was obtained (yield 76%). The spectral absorption of a diluted solution of this in THF was measured and found to be λmax = 945 nm.

(Example 2)
In a three-necked flask, 38.7 g of the exemplified compound (S-1), 57.6 g of lithium butoxide, 58.1 g of 1,1,1,3,3,3-hexamethyldisilazane, 150 ml of 1-butanol, and 150 ml of DMF were added. After stirring for 3 hours at an internal temperature of 70 ° C., the mixture was stirred for 2 hours at 90 ° C. After the solvent was distilled off under reduced pressure, 4 l of chloroform was added, 3 l of water was added, and 130 g of acetic acid was further added for extraction. The obtained chloroform solution was washed by adding 3 l of water three times, then concentrated with a rotary evaporator, 500 ml of methanol was added to the resulting residue, and the resulting crystals were suction filtered. Drying yielded 31.8 g of the desired naphthalocyanine compound (metal free) (yield 82%). The spectral absorption of a dilute solution in THF of this product was measured and found to be λmax = 860 nm.

(Example 3)
Using the exemplified compound (S-2), the target naphthalocyanine compound was prepared in exactly the same manner as in Example 2 above, except that lithium butoxide and 1-butanol were changed to equivalent amounts of lithium pentoxide and pentanol. 25.6 g of (metal-free body) was obtained (yield 66%). The spectral absorption of a dilute solution in THF of this product was measured and found to be λmax = 860 nm.

Example 4
In a three-necked flask, 38.7 g of the exemplified compound (S-1), 10.4 g of vanadium oxytrichloride, 96.8 g of 1,1,1,3,3,3-hexamethyldisilazane and 300 ml of DMF were added, and the internal temperature After stirring for 3 hours at 70 ° C., the mixture was stirred for 2 hours at 90 ° C. After distilling off the solvent under reduced pressure, 4 l of chloroform was added, 3 l of water was added, and 20 ml of sulfuric acid was further added for extraction. The obtained chloroform solution was washed by adding 3 l of water three times, then concentrated with a rotary evaporator, 500 ml of methanol was added to the resulting residue, and the resulting crystals were suction filtered. By drying, 28.5 g of the target naphthalocyanine compound (central metal: VO) was obtained (yield 70%). The spectral absorption of a dilute solution in THF of this product was measured and found to be λmax = 906 nm.

(Example 5)
In a three-necked flask, 40.7 g of the exemplified compound (S-21), 8.1 g of copper chloride, 48.4 g of 1,1,1,3,3,3-hexamethyldisilazane and 200 ml of DMAc were placed, and the internal temperature was 85 ° C. And stirred for 8 hours. After distilling off the solvent under reduced pressure, 4 l of chloroform was added, 3 l of water was added, and 20 ml of sulfuric acid was further added for extraction. The obtained chloroform solution was washed by adding 3 l of water three times, then concentrated with a rotary evaporator, 500 ml of methanol was added to the resulting residue, and the resulting crystals were suction filtered. By drying, 32.5 g of the corresponding naphthalocyanine compound (central metal: copper) of interest was obtained (yield 80%). The spectral absorption of a diluted solution of this in THF was measured and found to be λmax = 945 nm.

(Example 6)
In a three-necked flask, 44.0 g of the exemplified compound (S-22), 76.8 g of lithium butoxide, 58.1 g of 1,1,1,3,3,3-hexamethyldisilazane, 150 ml of 1-butanol and 150 ml of DMF are placed. After stirring for 3 hours at an internal temperature of 70 ° C., the mixture was stirred for 2 hours at 90 ° C. After the solvent was distilled off under reduced pressure, 4 l of chloroform was added, 3 l of water was added, and 173 g of acetic acid was further added for extraction. The obtained chloroform solution was washed by adding 3 l of water three times, then concentrated with a rotary evaporator, 500 ml of methanol was added to the resulting residue, and the resulting crystals were suction filtered. Drying yielded 38.6 g of the desired naphthalocyanine compound (metal free) (yield 85%). The spectral absorption of a diluted solution of this in THF was measured and found to be λmax = 861 nm.

(Example 7)
In a three-necked flask, 41.0 g of exemplary compound (S-41), 57.6 g of lithium butoxide, 58.1 g of 1,1,1,3,3,3-hexamethyldisilazane and 1.5 l of 1-butanol were added. After heating and stirring at an internal temperature of 70 ° C. for 3 hours, the internal temperature was raised to boil, and the mixture was heated and stirred for 2 hours while distilling out butanol. The total amount of butanol distilled out was 1 liter. After the solvent was distilled off under reduced pressure, 4 l of chloroform was added, 3 l of water was added, and 130 g of acetic acid was further added for extraction. The obtained chloroform solution was washed by adding 3 l of water three times, then concentrated with a rotary evaporator, 500 ml of methanol was added to the resulting residue, and the resulting crystals were suction filtered. It was dried to obtain 29.8 g (yield 77%) of the corresponding naphthalocyanine compound (metal-free). The spectral absorption of a dilute solution in THF of this product was measured and found to be λmax = 860 nm.

(Example 8)
In a three-necked flask, 41.1 g of exemplary compound (S-42), 57.6 g of lithium butoxide, 58.1 g of 1,1,1,3,3,3-hexamethyldisilazane, 50 g of 3Å molecular sieve and 1-butanol 1.5 l was added, and the mixture was heated and stirred at an internal temperature of 85 ° C. for 9 hours. After the solvent was distilled off under reduced pressure, 4 l of chloroform was added, 3 l of water was added, 130 g of acetic acid was further added, and the mixture was filtered and extracted. The obtained chloroform solution was washed by adding 3 l of water three times, then concentrated with a rotary evaporator, 500 ml of methanol was added to the resulting residue, and the resulting crystals were suction filtered. By drying, 22.5 g (yield 58%) of the target naphthalocyanine compound (metal-free) was obtained. The spectral absorption of a dilute solution in THF of this product was measured and found to be λmax = 860 nm.

(Comparative Example 1)
38.7 g of Exemplified Compound (S-1), 8.1 g of copper chloride and 300 ml of DMF were placed in a three-necked flask, heated and stirred at an internal temperature of 70 ° C. for 3 hours, and then stirred at 90 ° C. for 2 hours. After distilling off the solvent under reduced pressure, 4 l of chloroform was added, 3 l of water was added, and 20 ml of sulfuric acid was further added for extraction. The operation of adding 3 l of water to the obtained chloroform solution and washing was performed three times, followed by concentration with a rotary evaporator, adding 500 ml of methanol to the resulting residue, and filtering the obtained crystals by suction, It dried and 11.4g of target naphthalocyanine compounds (center metal: copper) were obtained (yield 28%). The spectral absorption of a diluted solution of this in THF was measured and found to be λmax = 945 nm.

(Comparative Example 2)
38.7 g of Exemplified Compound (S-1), 57.6 g of lithium butoxide, 150 ml of 1-butanol, and 150 ml of DMF are placed in a three-necked flask, heated and stirred at an internal temperature of 70 ° C. for 3 hours, and then at 90 ° C. for 2 hours. Stir with heating. After the solvent was distilled off under reduced pressure, 4 l of chloroform was added, 3 l of water was added, and 130 g of acetic acid was further added for extraction. The obtained chloroform solution was washed by adding 3 l of water three times, then concentrated with a rotary evaporator, 500 ml of methanol was added to the resulting residue, and the resulting crystals were suction filtered. It dried and 6.2 g of target naphthalocyanine compounds (metal-free body) were obtained (yield 16%). The spectral absorption of a dilute solution in THF of this product was measured and found to be λmax = 860 nm.

(Comparative Example 3)
In a three-necked flask, 41.0 g of the exemplified compound (S-41), 57.6 g of lithium butoxide and 1.5 l of 1-butanol were placed, and after heating and stirring at an internal temperature of 70 ° C. for 3 hours, the internal temperature was raised. The mixture was boiled and stirred for 2 hours while distilling off 1-butanol. The total amount of 1-butanol distilled out was 1 liter. After the solvent was distilled off under reduced pressure, 4 l of chloroform was added, 3 l of water was added, and 130 g of acetic acid was further added for extraction. The obtained chloroform solution was washed by adding 3 l of water three times, then concentrated with a rotary evaporator, 500 ml of methanol was added to the resulting residue, and the resulting crystals were suction filtered. Drying yielded 3.5 g of the desired naphthalocyanine compound (metal free) (yield 9%). The spectral absorption of a dilute solution in THF of this product was measured and found to be λmax = 860 nm.

(Comparative Example 4)
In a three-necked flask, 41.1 g of exemplary compound (S-42), 57.6 g of lithium butoxide, 50 g of 3 mol molecular sieve and 1.5 l of 1-butanol were placed, and the mixture was heated and stirred at an internal temperature of 85 ° C. for 9 hours. After the solvent was distilled off under reduced pressure, 4 l of chloroform was added, 3 l of water was added, 130 g of acetic acid was further added, and the mixture was filtered and extracted. The obtained chloroform solution was washed by adding 3 l of water three times, then concentrated with a rotary evaporator, 500 ml of methanol was added to the resulting residue, and the resulting crystals were suction filtered. By drying, 7.3 g of the desired corresponding naphthalocyanine compound (metal-free) was obtained (yield 19%). The spectral absorption of a dilute solution in THF of this product was measured and found to be λmax = 860 nm.

  From the results of the above Examples and Comparative Examples, it can be seen that the phthalocyanines can be produced in a mild, simple and high yield according to the method for producing phthalocyanines of the present invention.

Claims (9)

A compound (component A) represented by the following general formula (I) or the following general formula (II), a metal salt (component B), and a disilazane compound (component C) represented by the following general formula (III) A process for producing a phthalocyanine characterized by reacting.

[In General Formula (I), R ¹ represents a substituent, n ₁ represents 0 or an integer of 1 or more, and Q ₁ represents a nonmetallic atom group that forms a ring by condensation with a benzene ring. When n ₁ is 2 or more, a plurality of R ¹ may be the same or different and may be bonded to each other to form a ring. However, when the ring formed by condensing with the benzene ring by Q ₁ is a naphthalene ring, n ₁ represents an integer of 1 or more. ]

[In General Formula (II), R ² represents a substituent, n ₂ represents 0 or an integer of 1 or more, and Q ₂ represents a nonmetallic atom group that forms a ring by condensation with a benzene ring. When n ₂ is 2 or more, a plurality of R ² may be the same or different and may be bonded to each other to form a ring. A ₂₁ , A ₂₂ , and A ₂₃ each independently represent an oxygen atom or NH. However, when the ring formed by condensing with the benzene ring by Q ₂ is a naphthalene ring, n ₂ represents an integer of 1 or more. ]
General formula (III)
HN (SiR ³¹ R ³² R ³³ ) ₂
[In the general formula (III), R ³¹ , R ³² and R ³³ each independently represents an aliphatic group or an aromatic group. ] The said component (A) is a compound represented by the following general formula (IV) or the following general formula (V), The manufacturing method of the phthalocyanines of Claim 1 characterized by the above-mentioned.

[In General Formula (IV), R ⁴ represents a substituent, and n ₄ represents an integer of 1 to 6. When n ₄ is 2 or more, the plurality of R ⁴ may be the same or different and may be bonded to each other to form a ring. ]

[In General Formula (V), R ⁵ represents a substituent, and n ₅ represents an integer of 1 to 6. When n ₅ is 2 or more, the plurality of R ⁵ may be the same or different, and may be bonded to each other to form a ring. A ₅₁ , A ₅₂ , and A ₅₃ each independently represent an oxygen atom or NH. ] The method for producing a phthalocyanine according to claim 1 or 2, wherein the component (A) is a compound represented by the following general formula (VI) or the following general formula (VII).

[In General Formula (VI), R ⁶¹ and R ⁶² each independently represent a substituent. ]

[In General Formula (VII), R ⁷¹ and R ⁷² each independently represent a substituent, and A ₇₁ , A ₇₂ , and A ₇₃ each independently represent an oxygen atom or NH. ] In the general formulas (I), (II), (IV) to (VII), R ¹ , R ² , R ⁴ , R ⁵ , R ⁶¹ , R ⁶² , R ⁷¹ , and R ⁷² are represented by the following general formula (VIII The method for producing phthalocyanines according to any one of claims 1 to 3, wherein the group is a group selected from the group consisting of groups represented by -1) to (VIII-3).
Formula (VIII-1)
-NR ⁸¹ R ⁸²
General formula (VIII-2)
-O-R ⁸³
General formula (VIII-3)
-SR ⁸⁴
[In the general formulas (VIII-1) to (VIII-3), R ^{81 to} R ⁸⁴ each independently represents a hydrogen atom, an aliphatic group or an aromatic group. ]   The phthalocyanine according to any one of claims 1 to 4, wherein the disilazane compound represented by the general formula (III) is 1,1,1,3,3,3-hexamethyldisilazane. Manufacturing method.   The said reaction is performed at 50-250 degreeC, The manufacturing method of phthalocyanines of any one of Claims 1-5 characterized by the above-mentioned.   The reaction temperature of the said reaction is 65-130 degreeC, Comprising: Reaction temperature is changed in the middle of reaction, The manufacturing method of the phthalocyanines of any one of Claims 1-6 characterized by the above-mentioned.   The method for producing phthalocyanines according to any one of claims 1 to 7, wherein a reaction solvent for the reaction is an amide solvent.   The method for producing phthalocyanines according to any one of claims 1 to 7, wherein a reaction solvent for the reaction is 1-butanol or pentanol.