JP2005290282A - Process for producing phthalocyanine - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a process for producing a metal-free phthalocyanine safely under moderate conditions and in a high yield without impairing substituents by using a lithium salt and to provide a process for simply converting the resulting metal-free phthalocyanine into a variety of metal phthalocyanines. <P>SOLUTION: The process for producing a metal-free phthalocyanine comprises adding a lithium salt to a compound selected from the group consisting of compounds represented by formulae (1)-(6) to effect a reaction and then performing post-treatment to produce a metal-free phthalocyanine of formula (7). The process for producing a metal phthalocyanine comprises mixing the resulting metal-free phthalocyanine with a metal source. In formulae (1)-(7), R<SB>11</SB>-R<SB>14</SB>each independently denote a hydrogen atom or a substituent and R<SB>201</SB>-R<SB>216</SB>each independently denote a hydrogen atom or a substituent. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to an inkjet ink, a sublimation transfer color copy, an ink dye, a color filter, a silver halide photosensitive material, printing, a metal-free phthalocyanine used for an optical recording medium, and a method for producing a metal phthalocyanine derived therefrom. It is. Among them, the present invention relates to a novel compound suitable for an optical information recording medium capable of recording and reproducing information using a laser beam. In particular, the present invention relates to a dye suitable for a heat mode type optical information recording medium suitable for recording information using a short wavelength laser beam having a wavelength of 450 nm or less.

  As a method for synthesizing metal-free phthalocyanine, (1) a method in which phthalonitrile is reacted in the presence of a strong base, (2) a method in which metallic lithium is dissolved in an alcohol solvent, and then phthalonitrile is added, (3) diiminoisoindoline is added. A method obtained by a method of heating at a high temperature and (4) an electrolyte method using lithium chloride as an electrolyte are common (Non-Patent Document 1.2, etc.). In addition, a system using cerium trichloride as an additive (Non-Patent Document 3) and a system using hydroquinone (Non-Patent Document 4) have been reported. A method for obtaining an asymmetric metal-free phthalocyanine using subphthalocyanine and diiminoisoindoline has also been reported (Non-Patent Document 5). A method for converting the central metal of metal phthalocyanine has also been reported (Patent Document 1.2). Furthermore, when unsubstituted phthalonitrile, 1,8-diazabicyclo [5,4,0] -7-undecene and lithium compound are heated and stirred in an alcohol solvent, monolithium phthalocyanine and 1,8-diazabicyclo [5,4,0]- There is also a report that a higher-order compound composed of 7-undecene is obtained (Patent Document 3).

  Among these methods, according to the study by the present inventors, when phthalonitrile has an electron withdrawing substituent, the methods (1) and (3) among the above general methods are extremely difficult. The yield was found to be low. Further, (2) is unsuitable for production from the viewpoint of the safety of metallic lithium, and the method (4) is not practical from the viewpoint of production volume. Even in a system using cerium trichloride or hydroquinone as an additive, when phthalonitrile has an electron-attracting substituent, there is a disadvantage that the yield is low. In addition, when synthesizing symmetrical metal-free phthalocyanine using subphthalocyanine and diiminoisoindoline, there is a drawback that isoindoline must be used in excess. The method for converting the central metal of metal phthalocyanine requires extremely high temperatures (about 250 to 300 degrees). The method of heating and stirring phthalonitrile having an electron-attracting substituent in 1,8-diazabicyclo [5,4,0] -7-undecene and an alcohol solvent in the presence of lithium chloride was a low yield. Therefore, it was necessary to develop a new manufacturing method.

  Typical methods for synthesizing metal phthalocyanines are (1) a method in which phthalonitrile and a metal source are reacted at a high temperature in the presence of a strong base, and (2) a method in which diiminoisoindoline and a metal source are reacted at a high temperature. .

However, in order to obtain metal phthalocyanine in a good yield by the above method, a metal with high Lewis acidity must be used. When a metal with low Lewis acidity is used, the yield is low, and when a strong Lewis acid is used. In some cases, the substituents were damaged, and it was difficult to obtain various substituted metal phthalocyanines in good yield.
Shirai-Kobayashi, published by IPC Co., Ltd. “Phthalocyanine: Chemistry and Function”, pages 1-62 CC Leznoff-Co-authored by ABP Lever, published by VCH 'Phtalocyanines and Properties and Applications' pages 1-54 Tetrahedron Lett. 2003, 43, 4211. J. Am. Chem. Soc., 1984, 106, 1579. J. Org. Chem. 1996, 61, 8591. Japanese Unexamined Patent Publication No. 6-2100175 JP 7-33995 A JP-A-61-186386

  The present invention provides a method for obtaining a metal-free phthalocyanine, which is a useful precursor for metal phthalocyanine synthesis, in a high yield safely under mild conditions and without impairing substituents.

  Furthermore, the present invention provides a method for easily converting into various metal phthalocyanines using a metal-free phthalocyanine.

  The inventors focused on dilithiophthalocyanine, which can be converted to metal-free phthalocyanine by treatment with acid. A general synthesis method of dilithiophthalocyanine is a method of adding phthalonitrile after dissolving lithium metal in an alcohol solvent to prepare an alkoxide in the system. However, since metallic lithium is used, there is a problem in terms of production suitability. Here, among the lithium alkoxides generated in the system, the alkoxide serves as a base that promotes the reaction, and the lithium cation coordinates to nitrogen to promote phthalocyanine skeleton formation. In addition, the present inventors considered that the lithium salt is not so high in Lewis acidity as to impair the substituent, and has appropriate Lewis acidity. Thus, as a result of intensive studies, the present inventors have found that a metal-free phthalocyanine can be synthesized in a high yield if a lithium salt is allowed to coexist, thereby completing the present invention.

  In addition, a group of substituted metal phthalocyanines having a variety of central metals can be synthesized by synthesizing metal-free phthalocyanines having substituents and using them as templates.

That is, the present invention includes (1) adding at least one lithium salt to at least one compound in the compound group represented by any one of the general formulas (1) to (6), performing a reaction, and performing post-treatment. A process for producing a metal-free phthalocyanine represented by the following general formula (7):

(Wherein R _{11 to} R ₁₄ each independently represents a hydrogen atom or a substituent)
General formula (7)

(Wherein R _{201 to} R ₂₁₆ each independently represents a hydrogen atom or a substituent)

(2) The method for producing a metal-free phthalocyanine according to (1), wherein at least one of R _{201 to} R ₂₁₆ in the general formula (7) is the following general formula (8) or (9).

(In the formula, R ₃₁ , R ₄₁ and R ₄₂ independently represent a hydrogen atom or a substituent.)

(3) The substituent represented by the general formula (8) or (9) is any of R ₂₀₁ , R ₂₀₄ , R ₂₀₅ , R ₂₀₈ , R ₂₀₉ , R ₂₁₂ , R ₂₁₃ , and R _{216 in} the general formula (7). The method for producing a metal-free phthalocyanine according to (2), characterized by comprising:

(4) The metal-free phthalocyanine according to any one of (1) to (3), wherein the post-treatment is performed with an acid (preferably hydrochloric acid or sulfuric acid, more preferably sulfuric acid) that neutralizes the reaction. Production method.
(5) The method for producing a metal-free phthalocyanine according to any one of (1) to (3), wherein an inorganic base is allowed to coexist before the post-treatment.

(6) A lithium salt and an alkoxide derivative (preferably a metal alkoxide, more preferably a sodium alkoxide) are added to the compound represented by the general formula (1) (1) )-(4) The manufacturing method of the metal-free phthalocyanine in any one of.

(7) A lithium salt is added to the compound represented by the general formula (4) and reacted in a coordinating organic solvent (1) to (4) represented by the general formula (7) The manufacturing method of the metal-free phthalocyanine in any one of.

(8) A method for producing metal phthalocyanine, comprising mixing a metal source with a metal-free phthalocyanine obtained by the production method shown in (1) to (7).

(9) The metal species contained in the mixed metal source is magnesium, manganese, iron, cobalt, nickel, copper, zinc, gallium, molybdenum, ruthenium, palladium, tin, platinum, titanium, vanadium, europium, lutetium, cerium, or these (8) The method for producing a metal phthalocyanine according to (8).

(10) The method for producing a metal phthalocyanine according to (8) or (9), wherein a base is added to the reaction system.

  The present invention provides a method for obtaining a metal-free phthalocyanine safely under mild conditions and in a high yield without impairing substituents. Furthermore, this invention provides the method of converting into various metal phthalocyanines simply using a metal-free phthalocyanine.

In the general formulas (1) to (7), R _{11 to} R ₁₄ and R _{201 to} R ₂₁₆ are each independently a hydrogen atom, a halogen atom, an alkyl group (including a cycloalkyl group or a bicycloalkyl group), an alkenyl group (cyclo Alkynyl group, bicycloalkenyl group), alkynyl group, aryl group, heterocyclic group, hydroxyl group, nitro group, carboxyl group, alkoxy group, aryloxy group, silyloxy group, heterocyclic oxy group, acyloxy group, carbamoyloxy group , Alkoxycarbonyloxy group, aryloxycarbonyloxy, amino group (including anilino group), acylamino group, aminocarbonylamino group, alkoxycarbonylamino group, aryloxycarbonylamino group, sulfamoylamino group, alkyl and arylsulfonylamino Group, mercap Group, alkylthio group, arylthio group, heterocyclic thio group, sulfamoyl group, sulfo group, alkyl and arylsulfinyl group, alkyl and arylsulfonyl group, acyl group, aryloxycarbonyl group, alkoxycarbonyl group, carbamoyl group, aryl and heterocyclic ring Examples include azo group, imide group, phosphino group, phosphinyl group, phosphinyloxy group, phosphinylamino group, and silyl group. R _{11 to} R ₁₄ and R _{201 to} R ₂₁₆ may be connected to each other to form a ring.

More specifically, R _{11 to} R ₁₄ and R _{201 to} R ₂₁₆ are each independently a hydrogen atom, a halogen atom (for example, a chlorine atom, a bromine atom, an iodine atom), an alkyl group [straight chain, branched, cyclic substitution or An unsubstituted alkyl group is represented. 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. ], An 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), hydroxyl group, nitro group, carboxyl group, alkoxy group (preferred Is a substituted or unsubstituted alkoxy group having 1 to 30 carbon atoms such as methoxy, ethoxy, isopropoxy, t-butoxy, n-octyloxy, 2-methoxyethoxy), aryloxy group (preferably having 6 carbon atoms) To 30 substituted or unsubstituted aryloxy groups such as phenoxy, 2-methylphenoxy, 4-t-butylphenoxy, 3-nitrophenoxy, 2-tetradecanoylaminophenoxy), silyloxy groups (preferably having a carbon number) 3 to 20 silyloxy groups such as trimethylsilyloxy, t-butyldimethylsilyloxy, heterocyclic oxy groups (preferably substituted or unsubstituted heterocyclic oxy groups having 2 to 30 carbon atoms, 1-phenyltetrazole-5 -Oxy, 2-tetrahydropyranyloxy), reed An oxy group (preferably formyloxy group, substituted or unsubstituted alkylcarbonyloxy group having 2 to 30 carbon atoms, substituted or unsubstituted arylcarbonyloxy group having 6 to 30 carbon atoms, such as formyloxy, acetyloxy, pivaloyloxy , Stearoyloxy, benzoyloxy, p-methoxyphenylcarbonyloxy), a carbamoyloxy group (preferably a substituted or unsubstituted carbamoyloxy group having 1 to 30 carbon atoms, such as N, N-dimethylcarbamoyloxy, N, N -Diethylcarbamoyloxy, morpholinocarbonyloxy, N, N-di-n-octylaminocarbonyloxy, Nn-octylcarbamoyloxy), an alkoxycarbonyloxy group (preferably substituted with 2 to 30 carbon atoms or Unsubstituted alkoxycarbonyloxy group such as methoxycarbonyloxy, ethoxycarbonyloxy, t-butoxycarbonyloxy, n-octylcarbonyloxy), aryloxycarbonyloxy group (preferably substituted or unsubstituted aryl having 7 to 30 carbon atoms) An oxycarbonyloxy group such as phenoxycarbonyloxy, p-methoxyphenoxycarbonyloxy, pn-hexadecyloxyphenoxycarbonyloxy), an amino group (preferably an amino group, a substituted or unsubstituted group having 1 to 30 carbon atoms) An alkylamino group, a substituted or unsubstituted anilino group having 6 to 30 carbon atoms, such as amino, methylamino, dimethylamino, anilino, N-methyl-anilino, diphenylamino), an 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, such as formylamino, acetylamino, pivaloylamino, lauroylamino, benzoyl Amino, 3,4,5-tri-n-octyloxyphenylcarbonylamino), an aminocarbonylamino group (preferably a substituted or unsubstituted aminocarbonylamino having 1 to 30 carbon atoms such as carbamoylamino, N, N -Dimethylaminocarbonylamino, N, N-diethylaminocarbonylamino, morpholinocarbonylamino), alkoxycarbonylamino group (preferably a substituted or unsubstituted alkoxycarbonylamino group having 2 to 30 carbon atoms such as methoxy Cicarbonylamino, ethoxycarbonylamino, t-butoxycarbonylamino, n-octadecyloxycarbonylamino, N-methyl-methoxycarbonylamino), aryloxycarbonylamino group (preferably substituted or unsubstituted having 7 to 30 carbon atoms) Aryloxycarbonylamino group, for example, phenoxycarbonylamino, p-chlorophenoxycarbonylamino, mn-octyloxyphenoxycarbonylamino), sulfamoylamino group (preferably substituted or unsubstituted having 0 to 30 carbon atoms) Sulfamoylamino groups such as sulfamoylamino, N, N-dimethylaminosulfonylamino, Nn-octylaminosulfonylamino), alkyl and arylsulfonylamino groups (preferably having 1 to 1 carbon atoms) 30 substituted or unsubstituted alkylsulfonamides, substituted or unsubstituted arylsulfonylamino having 6 to 30 carbon atoms, such as methylsulfonylamino, butylsulfonylamino, phenylsulfonylamino, 2,3,5, -trichlorophenylsulfonyl Amino, p-methylphenylsulfonylamino), mercapto group, alkylthio group (preferably a substituted or unsubstituted alkylthio group having 1 to 30 carbon atoms, such as methylthio, ethylthio, n-hexadecylthio), arylthio group (preferably carbon number) 6 to 30 substituted or unsubstituted arylthio, 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, example For example, 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-acetylsulfamoyl, N-benzoylsulfamoyl, N- (N′-phenylcarbamoyl) sulfamoyl), sulfo group, alkyl and arylsulfinyl A group (preferably a substituted or unsubstituted alkylsulfinyl group having 1 to 30 carbon atoms, a substituted or unsubstituted arylsulfinyl group having 6 to 30 carbon atoms, such as methylsulfinyl, ethylsulfinyl, phenylsulfinyl, p-methylphenylsulfinyl) , Alkyl and And an arylsulfonyl group (preferably a substituted or unsubstituted alkylsulfonyl group having 1 to 30 carbon atoms, a substituted or unsubstituted arylsulfonyl group having 6 to 30 carbon atoms such as methylsulfonyl, ethylsulfonyl, phenylsulfonyl, p-methyl Phenylsulfonyl), acyl group (preferably formyl group, substituted or unsubstituted alkylcarbonyl group having 2 to 30 carbon atoms, substituted or unsubstituted arylcarbonyl group having 7 to 30 carbon atoms, substituted or unsubstituted 4 to 30 carbon atoms, Heterocyclic carbonyl groups bonded to carbonyl groups at unsubstituted carbon atoms, such as acetyl, pivaloyl, 2-chloroacetyl, stearoyl, benzoyl, pn-octyloxyphenylcarbonyl, 2-pyridylcarbonyl, 2-furyl Carbonyl), aryloxy A carbonyl group (preferably a substituted or unsubstituted aryloxycarbonyl group having 7 to 30 carbon atoms, such as phenoxycarbonyl, o-chlorophenoxycarbonyl, m-nitrophenoxycarbonyl, pt-butylphenoxycarbonyl), alkoxycarbonyl A 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 1 to 30 carbon atoms). Substituted or unsubstituted carbamoyl such as carbamoyl, N-methylcarbamoyl, N, N-dimethylcarbamoyl, N, N-di-n-octylcarbamoyl, N- (methylsulfonyl) carbamoyl), a And a heterocyclic azo group (preferably a substituted or unsubstituted arylazo group having 6 to 30 carbon atoms, a substituted or unsubstituted heterocyclic azo group having 3 to 30 carbon atoms, such as phenylazo, p-chlorophenylazo, 5 -Ethylthio-1,3,4-thiadiazol-2-ylazo), imide group (preferably N-succinimide, N-phthalimide), phosphino group (preferably a substituted or unsubstituted phosphino group having 2 to 30 carbon atoms) Dimethylphosphino, diphenylphosphino, methylphenoxyphosphino), phosphinyl group (preferably a substituted or unsubstituted phosphinyl group having 2 to 30 carbon atoms, eg phosphinyl, dioctyloxyphosphinyl, diethoxyphosphine Finyl), phosphinyloxy group (preferably carbon A substituted or unsubstituted phosphinyloxy group having a number of 2 to 30 such as diphenoxyphosphinyloxy, dioctyloxyphosphinyloxy, a phosphinylamino group (preferably a substituted or An unsubstituted phosphinylamino group such as dimethoxyphosphinylamino, dimethylaminophosphinylamino), a silyl group (preferably a substituted or unsubstituted silyl group 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. Examples thereof include methylsulfonylaminocarbonyl, p-methylphenylsulfonylaminocarbonyl, acetylaminosulfonyl, and benzoylaminosulfonyl groups. R _{11 to} R ₁₄ and R _{201 to} R ₂₁₆ may be further substituted with a substituent.

In the general formulas (1) to (7), R _{11 to} R ₁₄ and R _{201 to} R ₂₁₆ are more preferably halogen atoms, alkyl groups, alkoxy groups, aryloxy groups, alkyl and arylthio groups, alkyl and arylsulfonyl groups, It is a sulfamoyl group.

In the general formula (8), each R ₃₁ is independently a hydrogen atom, an alkyl group (including a cycloalkyl group or a bicycloalkyl group), an alkenyl group (including a cycloalkenyl group or a bicycloalkenyl group), an alkynyl group, an aryl group, a hetero group Ring group, hydroxyl group, alkoxy group, aryloxy group, silyloxy group, heterocyclic oxy group, acyloxy group, carbamoyloxy group, alkoxycarbonyloxy group, aryloxycarbonyloxy group, mercapto group, alkylthio group, arylthio group, heterocyclic ring Examples include a thio group, an acyl group, an aryloxycarbonyl group, an alkoxycarbonyl group, a carbamoyl group, and a silyl group. R ₃₁ may be further substituted with a substituent.

R ₃₁ is more preferably an alkyl group, alkenyl group, alkynyl group, aryl group, heterocyclic group, carboxyl group, alkoxy group, aryloxy group, acylamino group, carbamoyl group, alkyl group, alkenyl group, alkynyl group, aryl A group, a heterocyclic group, a carboxyl group, an acyl group, an aryloxycarbonyl group, and an alkoxycarbonyl group are more preferable.

  Most preferred are a substituted or unsubstituted alkyl group having 1 to 18 carbon atoms and a substituted or unsubstituted aryl group having 6 to 30 carbon atoms.

In the general formula (9), R ₄₁ and R ₄₂ are each independently a hydrogen atom, an alkyl group (including a cycloalkyl group and a bicycloalkyl group), an alkenyl group (including a cycloalkenyl group and a bicycloalkenyl group), an alkynyl group, and an aryl Group, heterocyclic group, carboxyl group, acyl group, aryloxycarbonyl group, alkoxycarbonyl group and carbamoyl group. R ₄₁ and R ₄₂ may be connected to each other to form a ring. R ₄₁ and R ₄₂ may be further substituted with a substituent.

R ₄₁ and R ₄₂ are more preferably a branched alkyl group, most preferably a tertiary alkyl group.

The substitution position of the general formulas (8) and (9) substituted with the phthalocyanine derivative is preferably the α-position of the phthalocyanine ring. The α-position of the phthalocyanine ring generally refers to the substitution position on the side close to the pyrrole ring in the benzopyrrole ring, which is a partial structure forming the phthalocyanine ring. Specifically, in the following general structural formula (7), R ₂₀₁ , R ₂₀₄ , R ₂₀₅ , R ₂₀₈ , R ₂₀₉ , R ₂₁₂ , R ₂₁₃ , and R ₂₁₆ are substituted positions.
In the following general structure, R ₂₀₁ , R ₂₀₄ , R ₂₀₅ , R ₂₀₈ , R ₂₀₉ , R ₂₁₂ , R ₂₁₃ , R ₂₁₆ and R ₂₀₂ , R ₂₀₃ , R ₂₀₆ , R ₂₀₇ , R ₂₁₀ , R ₂₁₁ , R ₂₁₄ , R ₂₁₅ adjacent to each other may form a ring, but R ₂₀₁ , R ₂₀₄ , R ₂₀₅ , R ₂₀₈ , R ₂₀₉ , R ₂₁₂ , R ₂₁₃ , R ₂₁₆ and R ₂₀₂ , R ₂₀₃ , R ₂₀₆ , R ₂₀₇ , R ₂₁₀ , R ₂₁₁ , R ₂₁₄ and R ₂₁₅ are preferably all not forming a ring.
General formula (7)

The phthalocyanine derivative of the present invention may have a substituent other than those represented by the general formulas (8) and (9), and examples thereof include those exemplified as examples of R _{11 to} R ₁₄ and R _{201 to} R _216. It is done.

  Although the compounds represented by (1) to (6) used in the present invention are listed in the following list, the present invention is not limited to these. In the case of no substitution, that is, when a hydrogen atom is substituted, the notation is omitted.

  Moreover, the synthesis method of these compounds has detailed description in the following literature.

(1) JP 2003-94828 A (2) JP 2002-301870 (3) JP 2001-64283 (4) Synthesis, 1993, p. 194.

  Preferred lithium salts used for the synthesis of the metal-free phthalocyanine of the general formula (7) are lithium chloride, lithium bromide, lithium iodide, lithium fluoride, lithium acetate, lithium acetylacetonate, lithium formate, lithium oxide Lithium sulfate, lithium trifluoroacetate, lithium trifluoromethanesulfonate, and the like. More preferred is lithium halide, and most preferred is lithium chloride.

  The amount of the lithium salt to be added is preferably 0.25 to 100 times the mole of the compound represented by the general formulas (1) to (6). More preferably, it is 0.5-5 times mole. Most preferably, it is 0.5-1 times mole.

  The inorganic base used in the synthesis of the metal-free phthalocyanine of the general formula (7) is preferably a metal alkoxide (for example, sodium alkoxide, lithium alkoxide, etc.) or an alkoxide derivative formed from an alcohol solvent (for example, a general-purpose alcohol solvent). (Eg, formed from methanol, ethanol, propanol, butanol, isopropanol, tert-butanol, cyclopentanol, cyclohexanol, etc.) and a metal (eg, sodium, potassium, lithium, etc.), alkyl metal (eg, methyl lithium, n -Butyl lithium and the like). More preferred is a metal alkoxide. Most preferred is sodium alkoxide or a solution thereof. Strong organic bases such as 1,8-diazabicyclo [5,4,0] -7-undecene and 1,5-diazabicyclo [4,3,0] -5-nonene are unfavorable because they impair the substrate.

The solvent used may be any solvent as long as it does not inhibit this reaction. For example, alcohols (for example, methanol, ethanol, propanol, isopropyl alcohol, butanol, sec-butanol, tert-butanol, n-pentanol, n-hexanol, cyclohexanol, 2-methyl-1-pentanol, 1-heptanol, 2-heptanol, 1-octanol, 2-ethylhexanol, benzyl alcohol, ethoxyethanol, propoxyethanol, butoxyethanol, 2-dimethylaminoethanol 2-methylaminoethanol, ethylene glycol, propylene glycol, 1,4-butanediol, etc.), basic organic solvents (for example, methylamine, ethylamine, n-propylamine, isopropylamine) Isobutylamine, cyclohexylamine, morpholine, pyrrolidine, piperidine, aniline, 1-aminonaphthalene, pyridine, quinoline, 2-methoxyethyleneamine, ethylenediamine, 1,3-propanediamine, 1,4-butanediamine, etc.), phenols (Phenol, o-cresol, etc.), alkyl thiols (ethane thiol, n-butane thiol, sec-butane thiol, tert-butane thiol, etc.) aryl thiols (thiophenol, 4-mercaptopyridine, etc.), ureas (urea N, N-dimethylimidazolidinone, etc.), polar aprotic solvents (for example, formamide, N, N-dimethylformamide, sulfolane, dimethyl sulfoxide, N, N-dimethylacetamide, acetonitrile, N-methylpyrrolidone, etc.), chain Organic acids such as above or cyclic ethers (eg diethyl ether, diisopropyl ether, dimethoxyethane, tetrahydrofuran, dioxane, diethylene glycol dimethyl ether), aromatics (eg toluene, xylene, nitrobenzene, chloronaphthalene, dichlorobenzene), carboxylic acids (Eg acetic acid, propionic acid, trifluoroacetic acid, etc.), nitro compounds (eg nitromethane, nitroethane etc.), ester compounds (eg ethyl acetate, butyl acetate etc.), ketones (acetone, methyl ethyl ketone etc.), aliphatic hydrocarbons (eg Hexane, octane), alicyclic hydrocarbons (eg cyclopentane, cyclohexane, methylcyclohexane, etc.), halogenated hydrocarbons (chloroform, dichloromethane, dichloroethane, tetrachloride) Arsenide), water, ammonia, a mixed solvent thereof and the like. Preferred are alcohols such as methanol, ethanol, propanol, butanol, pentanol, 2-dimethylaminoethanol, ethylene glycol, and more preferred are ethanol, 2-dimethylaminoethanol, and ethylene glycol.
However, in the general formulas (2), (3), (5), (6), a urea solvent or a formamide solvent in the presence of a base is used, or ammonia (gas, liquid or aqueous solution) may be used in the above solvent. It is preferable to use together.

  The amount of the solvent used is preferably 1 to 100 times, more preferably 3 to 50 times that of the compounds represented by the general formulas (1) to (6). Most preferably, it is 5 to 20 times by mass.

  The optimum reaction temperature varies depending on the type of reactant used, but is preferably -20 to 200 ° C, more preferably 0 to 170 ° C. Most preferably, it is 20 degreeC-150 degreeC. Moreover, although reaction time changes with temperature etc., 10 minutes-20 hours are preferable, and 30 minutes-10 hours are more preferable.

  Acids used for the post-treatment include mineral acids (for example, sulfuric acid, hydrochloric acid, hydrobromic acid, nitric acid, phosphoric acid, etc.), organic carboxylic acids (for example, acetic acid, oxalic acid, formic acid, propionic acid, benzoic acid, etc.), sulfonic acids ( For example, methanesulfonic acid, ethanesulfonic acid, benzenesulfonic acid, p-toluenesulfonic acid, etc.) are preferably used, more preferably sulfuric acid, hydrochloric acid, hydrobromic acid, and acetic acid, and most preferably sulfuric acid and hydrochloric acid. . In addition, you may use these acids individually or in mixture of 2 or more types.

  As the alkoxide derivative used for synthesizing the metal-free phthalocyanine of the general formula (7) from the compound represented by the general formula (1), a metal alkoxide (for example, sodium alkoxide (for example, sodium methoxide, a methanol solution thereof or sodium ethoxy) is preferable. And alkoxide derivatives formed from alcohol solvents (for example, general-purpose alcohol solvents (for example, methanol, ethanol, propanol, butanol, isopropanol, tert-butanol, cyclopentanol, cyclopentanol, etc.) Hexanol, etc.) and metals (for example, those formed from sodium, potassium, lithium, etc.). More preferred is sodium alkoxide, and most preferred are sodium methoxide and its methanol solution and sodium ethoxide and its ethanol solution. Strong organic bases such as 1,8-diazabicyclo [5,4,0] -7-undecene and 1,5-diazabicyclo [4,3,0] -5-nonene are unfavorable because they impair the substrate.

  The coordinating organic solvent used in synthesizing the metal-free phthalocyanine of the general formula (7) from the general formula (4) is a chain or cyclic diol (for example, ethylene glycol, propylene glycol, 1,4-butanediol, Cis and trans-1,2-cyclohexanediol, cis and trans-1,2-cyclopentanediol, etc.), catechols (catechol, 3-methylcatechol, etc.), on-chain or cyclic diamines (eg ethylenediamine, 1, 3-propanediamine, 1,4-butanediamine, cis and trans-1,2-cyclohexanediamine, cis and trans-1,2-cyclopentanediamine, etc.), 1,2-phenylenediamine, or oxygen and nitrogen atoms (For example, 2-dimethylaminoethanol, - methylamino ethanol, 2-methoxy ethylene amine), these are preferred. More preferably ethylene glycol, propylene glycol, cis-1,2-cyclohexanediol, cis-1,2-cyclopentanediol, ethylenediamine, 1,3-propanediamine, 2-dimethylaminoethanol, 2-methoxyethyleneamine. Most preferred are ethylene glycol, 2-dimethylaminoethanol, and ethylenediamine.

  Next, the central metal of the metal phthalocyanine that can be converted from the metal-free phthalocyanine represented by the general formula (7) is not particularly limited, but the metal may be an oxide or may have a ligand. Preferably, lithium, sodium, aluminum, silicon, phosphorus, calcium, germanium, rubidium, strontium, zircon, rhodium, ruthenium, indium, iridium, magnesium, manganese, iron, cobalt, nickel, copper, zinc, gallium, molybdenum, ruthenium Palladium, tin, platinum, titanium, vanadium, europium, lutetium, cerium, strontium, and barium. These oxides may have a ligand. Most preferably magnesium, manganese, iron, cobalt, nickel, copper, zinc, gallium, molybdenum, ruthenium, palladium, tin, platinum, titanium, vanadium, europium, lutetium, cerium, and even these oxides, You may have a ligand.

  The base used for converting the metal-free phthalocyanine of the general formula (7) to metal phthalocyanine is preferably an organic base, an alkyl metal, a metal hydride (for example, sodium hydride) and the like. More preferred are triethylamine and sodium hydride. Most preferred is triethylamine.

  The solvent used may be any solvent as long as it does not inhibit this reaction, but is preferably an aprotic polar solvent, and most preferably N, N-dimethylacetamide.

  The amount of the solvent used is preferably 1 to 100 times by mass, more preferably 3 to 50 times by mass of the compound represented by the general formula (7). Most preferably, it is 5 to 20 times by mass.

  The optimum reaction temperature varies depending on the type of reactant used, but is preferably -20 to 200 ° C, more preferably 0 to 170 ° C. Most preferably, it is 20 degreeC-150 degreeC.

  The phthalocyanine derivative of the present invention may be bonded at an arbitrary position to form a multimer. In this case, each unit may be the same as or different from each other, and polystyrene, polymethacrylate, polyvinyl alcohol, cellulose, etc. It may be bonded to a polymer chain.

  As the phthalocyanine derivative of the present invention, a specific derivative may be used alone, or plural kinds of different structures may be mixed and used.

Although the preferable specific example of the metal-free phthalocyanine which can be synthesize | combined with the method of this invention is given to the following, this invention is not limited to these.
In Table 1 below, for example, the notation R ₂₀₁ / R ₂₀₄ represents the meaning of either R ₂₀₁ or R ₂₀₄ , and therefore a compound having this notation is a mixture of substitutional position isomers. In the case of no substitution, that is, when a hydrogen atom is substituted, the notation is omitted.
Table 1 Examples of metal-free phthalocyanines that can be synthesized by the method of the present invention

[Example]
EXAMPLES Next, although an Example demonstrates this invention still in detail, this invention is not limited to a following example.
[Synthesis of Compound (I-1)]

  25 ml of ethanol is added to 2.5 g of 3-sec butylsulfonylphthalonitrile and 0.21 g of lithium chloride, and the mixture is heated and stirred at 60 ° C. To this, 0.5 g of a 28% sodium methoxide methanol solution is added and heated and stirred at 80 ° C. for 4 hours. When the reaction solution is cooled to room temperature and an amount of sulfuric acid neutralized by the reaction system is added, precipitation of crystals is confirmed. The crude crystals obtained by filtration were recrystallized from methanol and dimethyl sulfoxide to obtain 0.8 g of Compound (I-1) (yield 32%). The structure was confirmed by MALDI-MS.

  25 ml of 2-dimethylaminoethanol is added to 2.5 g of 3-secbutylsulfonyl-1,3-diiminoisoindoline and 0.21 g of lithium chloride, and the mixture is heated and stirred under reflux for 4 hours under reflux. The reaction solution is cooled to room temperature, methanol and water are added, and precipitation of crystals is confirmed by adding an amount of sulfuric acid that neutralizes the reaction system. The crude crystals obtained by filtration were washed with methanol to obtain 1.0 g (yield 40%) of compound (I-1). The structure was confirmed by MALDI-MS.

[Comparative Example 1]
25 ml of butanol is added to 2.5 g of 3-sec butylsulfonylphthalonitrile, and the mixture is heated and stirred at 60 ° C. To this was added 0.5 g of 1,8-diazabicyclo [5,4,0] -7-undecene, and the mixture was heated and stirred at 80 ° C. for 4 hours, but no dye component could be confirmed.

[Comparative Example 2]
Add 15 ml of quinoline to 2.5 sec of 3-secbutylsulfonyl-1,3-diiminoisoindoline, and stir at 180 ° C. for 2 hours. The reaction solution is cooled to room temperature, and when isopropyl alcohol is added, crystal precipitation is confirmed. The crystals obtained by filtration were washed with isopropyl alcohol and purified by a silica gel column to obtain 0.2 g of Compound (I-1) (yield 8%). The structure was confirmed by MALDI-MS.

[Comparative Example 3]
25 ml of pentanol is added to 2.5 g of 3-sec butylsulfonylphthalonitrile and 0.15 g of cerium trichloride, and the mixture is heated and stirred at 60 ° C. To this was added 6.0 g of 1,8-diazabicyclo [5,4,0] -7-undecene, and the mixture was heated and stirred at 160 ° C. for 4 hours, but only a small amount of the dye component could be confirmed.

[Comparative Example 4]
Add 25 ml of pentanol to 2.5 g of 3-secbutylsulfonylphthalonitrile and 0.27 g of hydroquinone, and heat and stir at 80 ° C. To this was added 6.0 g of 1,8-diazabicyclo [5,4,0] -7-undecene, and the mixture was heated and stirred at 140 ° C. for 4 hours, but only a small amount of the dye component could be confirmed.

[Comparative Example 5]
To 0.93 g of 3-secbutylsulfonylphthalonitrile and 0.42 g of tris (3-secbutylsulfonyl) subphthalocyanine, add 1.25 ml of 1-chloronaphthalene and 2.5 ml of dimethyl sulfoxide, and heat and stir at 80 ° C. The reaction solution is returned to room temperature, crystals are precipitated with isopropyl alcohol and filtered. 0.04 g (35% yield based on subphthalocyanine) of compound (I-1) was obtained.

[Comparative Example 6]
25 ml of butanol is added to 2.5 g of 3-sec butylsulfonylphthalonitrile and 0.21 g of lithium chloride, and the mixture is heated and stirred at 60 ° C. To this was added 0.5 g of 1,8-diazabicyclo [5,4,0] -7-undecene, and the mixture was heated and stirred at 80 ° C. for 4 hours. The dye component was confirmed, but the system became complicated and could not be separated. It was.
[Synthesis of Compound (I-2)]

  25 ml of ethanol is added to 2.5 g of 3-tertbutylsulfonylphthalonitrile and 0.21 g of lithium chloride, and the mixture is heated and stirred at 60 ° C. To this, 0.5 g of a 28% sodium methoxide methanol solution is added and heated and stirred at 80 ° C. for 4 hours. When the reaction solution is cooled to room temperature and an amount of sulfuric acid neutralized by the reaction system is added, precipitation of crystals is confirmed. The crude crystals obtained by filtration were recrystallized from methanol and dimethyl sulfoxide to obtain 0.8 g of Compound (I-2) (yield 32%). The structure was confirmed by MALDI-MS.

  25 ml of 2-dimethylaminoethanol is added to 2.5 g of 3-tertbutylsulfonyl-1,3-diiminoisoindoline and 0.21 g of lithium chloride, and the mixture is heated and stirred under reflux for 4 hours under reflux. When the reaction solution is cooled to room temperature, methanol and water are added, and an amount of sulfuric acid that neutralizes the reaction system is added to confirm the precipitation of crystals. The crude crystals obtained by filtration were washed with methanol to obtain 0.8 g of Compound (I-2) (yield 32%). The structure was confirmed by MALDI-MS.

[Comparative Example 7]
25 ml of butanol is added to 2.5 g of 3-tertbutylsulfonylphthalonitrile, and the mixture is heated and stirred at 60 ° C. To this was added 0.5 g of 1,8-diazabicyclo [5,4,0] -7-undecene, and the mixture was heated and stirred at 80 ° C. for 4 hours, but no dye component could be confirmed.

[Comparative Example 8]
Add 15 ml of quinoline to 2.5-tert-butylsulfonyl-1,3-diiminoisoindoline and stir at 190 ° C. for 2 hours. The reaction solution is cooled to room temperature, and isopropyl alcohol is added to confirm crystal precipitation. The crystals obtained by filtration were washed with isopropyl alcohol and purified by a silica gel column to obtain 0.2 g of Compound (I-1) (yield 8%). The structure was confirmed by MALDI-MS.

[Comparative Example 9]
25 ml of butanol is added to 2.5 g of 3-tertbutylsulfonylphthalonitrile and 0.21 g of lithium chloride, and the mixture is heated and stirred at 60 ° C. To this was added 0.5 g of 1,8-diazabicyclo [5,4,0] -7-undecene, and the mixture was heated and stirred at 80 ° C. for 4 hours. The dye component was confirmed, but the system became complicated and could not be separated. It was.
[Synthesis of Compound (I-3)]

  23 ml of ethanol is added to 2.3 g of 3-isopropylsulfonylphthalonitrile and 0.21 g of lithium chloride, and the mixture is heated and stirred at 60 ° C. To this, 0.5 g of a 28% sodium methoxide methanol solution is added and heated and stirred at 80 ° C. for 4 hours. When the reaction solution is cooled to room temperature and an amount of sulfuric acid neutralized by the reaction system is added, precipitation of crystals is confirmed. The crude crystals obtained by filtration were recrystallized from methanol and dimethyl sulfoxide to obtain 0.7 g (yield 30%) of compound (I-3). The structure was confirmed by MALDI-MS.

Add 25 ml of 2-dimethylaminoethanol to 2.5 g of 3-isopropylsulfonyl-1,3-diiminoisoindoline and 0.21 g of lithium chloride, and heat and stir for 4 hours under reflux under reflux. When the reaction solution is cooled to room temperature, methanol and water are added, and an amount of sulfuric acid that neutralizes the reaction system is added to confirm the precipitation of crystals. The crude crystals obtained by filtration were washed with methanol to obtain 1.0 g of Compound (I-3) (yield 43%). The structure was confirmed by MALDI-MS.
[Synthesis of Compound (I-4)]

23 ml of ethanol is added to 2.3 g of 3-npropylsulfonylphthalonitrile and 0.21 g of lithium chloride, and the mixture is heated and stirred at 60 ° C. To this, 0.5 g of a 28% sodium methoxide methanol solution is added and heated and stirred at 80 ° C. for 4 hours. When the reaction solution is cooled to room temperature and an amount of sulfuric acid neutralized by the reaction system is added, precipitation of crystals is confirmed. The crude crystals obtained by filtration were recrystallized from methanol and dimethyl sulfoxide to obtain 0.8 g of Compound (I-3) (yield 34%). The structure was confirmed by MALDI-MS.
[Synthesis of Compound (I-5)]

25 ml of ethanol is added to 2.2 g of 3-ethylsulfonylphthalonitrile and 0.21 g of lithium chloride, and the mixture is heated and stirred at 60 ° C. To this, 0.5 g of a 28% sodium methoxide methanol solution is added and heated and stirred at 80 ° C. for 4 hours. When the reaction solution is cooled to room temperature and an amount of sulfuric acid neutralized by the reaction system is added, precipitation of crystals is confirmed. The crude crystals obtained by filtration were recrystallized from methanol and dimethyl sulfoxide to obtain 0.9 g (yield 41%) of Compound (I-4). The structure was confirmed by MALDI-MS.
[Synthesis of Compound (I-6)]

Add 29 ml of 2-dimethylaminoethanol to 2.9 g of 3-phenylsulfonyl 1,3-diiminoisoindoline and 0.21 g of lithium chloride, and heat and stir for 4 hours under reflux. The reaction solution is cooled to room temperature, methanol and water are added, and precipitation of crystals is confirmed by adding an amount of sulfuric acid that neutralizes the reaction system. The crude crystals obtained by filtration were washed with methanol to obtain 1.3 g (yield 48%) of compound (I-5). The structure was confirmed by MALDI-MS.
[Synthesis of Compound (I-7)]

  Add 29 ml of 2-dimethylaminoethanol to 2.9 g of 3-pyridylsulfonyl 1,3-diiminoisoindoline and 0.21 g of lithium chloride, and heat and stir under reflux for 4 hours under reflux. When the reaction solution is cooled to room temperature, methanol and water are added, and an amount of sulfuric acid that neutralizes the reaction system is added to confirm the precipitation of crystals. The crude crystals obtained by filtration were washed with methanol to obtain 1.3 g (yield 48%) of compound (I-6). The structure was confirmed by MALDI-MS.

Table 2 below lists the examples and comparative examples.
Table 2

* Yield based on tris (3-secbutylsulfonyl) subphthalocyanine ** Inseparable because it gave a complex mixture.

  As shown in the above table, according to the present invention, it was possible to provide a method for obtaining a metal-free phthalocyanine safely under mild conditions and in a high yield without impairing substituents.

Next, examples in which the central metal is introduced into the metal-free phthalocyanine will be described in detail, but the present invention is not limited to the following examples. In addition, the compound synthesize | combined in each of Examples 11-29 was made into the compound (II-1)-the compound (II-19), respectively.
[Synthesis of Compound (II-1)]

8 ml of N, N-dimethylacetamide is added to 1.0 g of compound (I-1) and 1.2 g of copper iodide, and the mixture is heated and stirred at 80 ° C. for 5 hours. The reaction solution is cooled to room temperature, water is added and the precipitated crystals are filtered. The obtained crude crystals were separated and purified using silica gel column chromatography to obtain 0.8 g (yield 76%) of compound (II-1). The structure was confirmed by MALDI-MS.
[Synthesis of Compound (II-2)]

10 ml of N, N-dimethylacetamide is added to 1.0 g of compound (I-1) and 0.27 g of vanadyl acetylacetonate, and the mixture is heated and stirred at 100 ° C. for 6 hours. The reaction solution is cooled to room temperature, water is added, and the precipitated crystals are filtered. The obtained crude crystals were separated and purified using silica gel column chromatography to obtain 0.7 g (yield 66%) of compound (II-2). The structure was confirmed by MALDI-MS.
[Synthesis of Compound (II-3)]

10 ml of N, N-dimethylacetamide is added to 1.0 g of compound (I-2) and 0.27 g of vanadyl acetylacetonate, and the mixture is heated and stirred at 100 ° C. for 6 hours. The reaction solution is cooled to room temperature, water is added, and the precipitated crystals are filtered. The obtained crude crystals were separated and purified using silica gel column chromatography to obtain 0.7 g (yield 66%) of compound (II-3). The structure was confirmed by MALDI-MS.
[Synthesis of Compound (II-4)]

6 ml of N, N-dimethylacetamide is added to 0.6 g of compound (I-3) and 0.26 g of vanadyl acetylacetonate, and the mixture is heated and stirred at 140 ° C. for 5 hours. The reaction solution is cooled to room temperature, water is added, and the precipitated crystals are filtered. The obtained crude crystals were washed with water and methanol to obtain 0.3 g (yield 47%) of compound (II-4). The structure was confirmed by MALDI-MS.
[Synthesis of Compound (II-5)]

10 ml of N, N-dimethylacetamide is added to 1.0 g of compound (I-1) and 0.34 g of titanium (IV) butoxide, and the mixture is heated and stirred at 130 ° C. for 2 hours. The reaction solution is cooled to room temperature, water is added, and the precipitated crystals are filtered. The resulting crude crystals were separated and purified using silica gel column chromatography to obtain 0.3 g (yield 28%) of compound (II-5). The structure was confirmed by MALDI-MS.
[Synthesis of Compound (II-6)]

  Add 5 ml of N, N-dimethylacetamide to 0.25 g of compound (I-1) and 0.35 g of dichloro (1,5-cyclooctadiene) platinum (II), and further add 0.1 g of triethylamine dropwise at 100 ° C. Stir for 8 hours. The reaction solution is cooled to room temperature, partitioned between dilute hydrochloric acid and ethyl acetate, and the organic layer is concentrated with an evaporator. The obtained crude crystals were separated and purified using silica gel column chromatography to obtain 0.2 g (yield 84%) of compound (II-6). The structure was confirmed by MALDI-MS. [Synthesis of Compound (II-7)]

To 0.5 g of compound (I-1) and 0.15 g of manganese (II) acetate, 10 ml of N, N-dimethylacetamide is added and stirred at room temperature for 30 minutes. The mixture is partitioned between water and ethyl acetate, and the organic layer is concentrated with an evaporator. The obtained crude crystals were separated and purified using silica gel column chromatography to obtain 0.2 g (yield 38%) of compound (II-7). The structure was confirmed by MALDI-MS.
[Synthesis of Compound (II-8)]

10 ml of N, N-dimethylacetamide was added to 0.5 g of compound (I-1) and 0.22 g of dichloro (1,5-cyclooctadiene) ruthenium (II) polymer, and further 0.1 ml of triethylamine was added dropwise at room temperature. Stir for 6 hours. Water is added to the reaction solution, and the precipitated crystals are filtered. The obtained crude crystals were separated and purified using silica gel column chromatography to obtain 0.32 g (yield 50%) of compound (II-8). The structure was confirmed by MALDI-MS and ₁ HNMR.

[Synthesis of Compound (II-9)]

10 ml of N, N-dimethylacetamide is added to 0.5 g of compound (I-1) and 0.14 g of tin (II) dichloride, followed by heating and stirring at 140 ° C. for 3 hours. The reaction solution is cooled to room temperature, water is added to the reaction solution, the precipitated crystals are filtered, and further washed with dichloroethane to remove the inorganic salt. The resulting solution was concentrated, and the crude crystals were recrystallized using dichloroethane and ethanol to obtain 0.3 g of Compound (II-9) (yield 54%). The structure was confirmed by MALDI-MS.
[Synthesis of Compound (II-10)]

To 0.4 g of the compound (I-1) and 0.35 g of gallium trichloride (5 ml), 5 ml of quinoline is added and heated and stirred at 150 ° C. for 2 hours. The reaction solution was cooled to room temperature, diluted hydrochloric acid was added to the reaction solution, the precipitated crystals were filtered, and the resulting crude crystals were separated and purified using silica gel column chromatography to obtain 0.18 g (yield) of compound (II-10). 42%). The structure was confirmed by MALDI-MS.
[Synthesis of Compound (II-11)]

10 ml of N, N-dimethylacetamide is added to 1.0 g of compound (I-1) and 0.55 g of bis (1,5-cyclooctadiene) nickel (O), and the mixture is heated and stirred at 100 ° C. for 2 hours. The reaction solution is cooled to room temperature, water is added, and the precipitated crystals are filtered. The obtained crude crystals were separated and purified using silica gel column chromatography to obtain 0.5 g (yield 48%) of compound (II-11). The structure was confirmed by MALDI-MS.
[Synthesis of Compound (II-12)]

5 ml of N, N-dimethylacetamide is added to 0.5 g of compound (I-1) and 0.22 g of zinc acetate (II), and the mixture is heated and stirred at 140 ° C. for 1 hour. The reaction solution was cooled to room temperature, water was added, and the precipitated crystals were filtered to obtain 0.4 g of Compound (II-12) (yield 76%). The structure was confirmed by MALDI-MS.
[Synthesis of Compound (II-13)]

5 ml of N, N-dimethylacetamide is added to 0.5 g of compound (I-1) and 0.23 g of magnesium acetate (II) tetrahydrate, and the mixture is heated and stirred at 140 ° C. for 5 hours. The reaction solution was cooled to room temperature, water was added, the precipitated crystals were filtered, and the obtained crystals were stirred and washed with methanol to obtain 0.45 g (yield 88%) of Compound (II-13). The structure was confirmed by MALDI-MS.
[Synthesis of Compound (II-14)]

Add 5 ml of N, N-dimethylacetamide to 0.5 g of compound (I-2) and 0.23 g of magnesium acetate (II) tetrahydrate, and heat and stir at 140 ° C. for 5 hours. The reaction solution was cooled to room temperature, water was added, the precipitated crystals were filtered, and the obtained crystals were stirred and washed with methanol to obtain 0.45 g (yield 88%) of compound (II-14). The structure was confirmed by MALDI-MS.
[Synthesis of Compound (II-15)]

Add 5 ml of N, N-dimethylacetamide to 0.6 g of compound (I-3) and 0.27 g of magnesium acetate (II) tetrahydrate, and heat and stir at 140 ° C. for 1 hour. The reaction solution was cooled to room temperature, water was added, the precipitated crystals were filtered, and the obtained crystals were stirred and washed with methanol to obtain 0.53 g (yield 86%) of Compound (II-15). The structure was confirmed by MALDI-MS.
[Synthesis of Compound (II-16)]

Add 5 ml of N, N-dimethylacetamide to 0.6 g of compound (I-4) and 0.27 g of magnesium acetate (II) tetrahydrate, and stir at 140 ° C. for 1 hour. The reaction solution was cooled to room temperature, water was added, the precipitated crystals were filtered, and the obtained crystals were stirred and washed with methanol to obtain 0.6 g (yield 98%) of Compound (II-16). The structure was confirmed by MALDI-MS.
[Synthesis of Compound (II-17)]

5 ml of N, N-dimethylacetamide is added to 0.5 g of compound (I-5) and 0.23 g of magnesium acetate (II) tetrahydrate, and the mixture is heated and stirred at 140 ° C. for 5 hours. The reaction solution was cooled to room temperature, water was added, the precipitated crystals were filtered, and the obtained crystals were stirred and washed with methanol to obtain 0.45 g (yield 88%) of Compound (II-17). The structure was confirmed by MALDI-MS.
[Synthesis of Compound (II-18)]

7 ml of N, N-dimethylacetamide is added to 0.7 g of compound (I-6) and 0.28 g of magnesium acetate (II) tetrahydrate, followed by heating and stirring at 140 ° C. for 3 hours. The reaction solution is cooled to room temperature, water is added, and the precipitated crystals are filtered. The obtained crude crystals were separated and purified using silica gel column chromatography to obtain 0.25 g (yield 28%) of compound (II-18). The structure was confirmed by MALDI-MS.
[Synthesis of Compound (II-19)]

  Add 0.3 ml of compound (I-1), 0.42 g of europium (2,2,6,6-tetramethyl-3,5, -heptanedionato), 3 ml of N, N-dimethylacetamide, and heat at 140 ° C. for 1 hour. Stir. The reaction mixture is cooled to room temperature, water is added, the precipitated crystals are filtered, extracted with ethyl acetate, and partitioned between water and saturated brine. The obtained solution was dehydrated with sodium sulfate and concentrated with an evaporator to obtain 0.25 g (yield 63%) of Compound (II-19). The structure was confirmed by MALDI-MS.

Table 3 below provides a list of examples. In Table 3 below, M represents a central metal, meaning that it has a metal oxide or ligand.
Table 3

* DMAc Abbreviation of N, N-dimethylacetamide ** tmhd 2,2,6,6, -Tetramethyl-3,5-heptadionate

  As shown in the above table, the metal-free phthalocyanine obtained in the present invention can be easily converted into various metal phthalocyanines.

Claims (10)

The following general formula, wherein at least one lithium salt is added to at least one compound in the compound group represented by any one of the general formulas (1) to (6), the reaction is performed, and post-treatment is performed. (7) A method for producing a metal-free phthalocyanine.

(Wherein R _{11 to} R ₁₄ each independently represents a hydrogen atom or a substituent)
General formula (7)

(Wherein R _{201 to} R ₂₁₆ each independently represents a hydrogen atom or a substituent) At least one of R ₂₀₁ to R ₂₁₆ in formula (7), characterized in that a following general formula (8) or (9), method for producing metal-free phthalocyanine according to claim 1.

(In the formula, R ₃₁ , R ₄₁ and R ₄₂ independently represent a hydrogen atom or a substituent.) The substituent represented by the general formula (8) or (9) has any one of R ₂₀₁ , R ₂₀₄ , R ₂₀₅ , R ₂₀₈ , R ₂₀₉ , R ₂₁₂ , R ₂₁₃ , and R _{216 in} the general formula (7). The method for producing a metal-free phthalocyanine according to claim 2, wherein:   The method for producing a metal-free phthalocyanine according to any one of claims 1 to 3, wherein the post-treatment is performed with an acid that neutralizes the reaction.   The method for producing a metal-free phthalocyanine according to any one of claims 1 to 4, wherein an inorganic base is allowed to coexist before the post-treatment.   The method for producing a metal-free phthalocyanine according to claim 1, which is represented by the general formula (7), wherein a lithium salt and an alkoxide derivative are added to the compound represented by the general formula (1).   The metal-free metal according to any one of claims 1 to 4, represented by the general formula (7), wherein a lithium salt is added to the compound represented by the general formula (4) and reacted in a coordinating organic solvent. A method for producing phthalocyanine.   A method for producing metal phthalocyanine, comprising mixing a metal source with a metal-free phthalocyanine obtained by the production method shown in claim 1.   The metal species contained in the mixed metal source is magnesium, manganese, iron, cobalt, nickel, copper, zinc, gallium, molybdenum, ruthenium, palladium, tin, platinum, titanium, vanadium, europium, lutetium, cerium or oxides thereof The method for producing metal phthalocyanine according to claim 8, wherein:   The method for producing a metal phthalocyanine according to claim 8 or 9, wherein a base is added to the reaction system.