JPH0735482B2 - Phthalocyanine derivative - Google Patents

Description

TECHNICAL FIELD The present invention relates to a novel phthalocyanine derivative.

(Prior Art and Problems Thereof) Phthalocyanine compounds are extremely stable to light, heat, humidity and the like and have excellent robustness.

In particular, phthalocyanine or metal phthalocyanine is widely used as various dyes or pigments because of its high stability and vivid color tone. Further, it is well known that metal phthalocyanine exerts the functions of electric conductivity, photoconductivity, energy conversion, electrophotographic charge adjusting agent, catalyst, etc., because a metal atom exists in a large π-electron conjugated system. ing. In particular, it has recently attracted attention as a thin film polymer material with a high level of functionality by blending with a polymer.
Various studies have been conducted. But phthalocyanine,
Alternatively, metal phthalocyanines have poor solubility in organic solvents, which is a major problem for application to products using phthalocyanine compounds.

Various studies have been conducted to improve the solubility (oil solubility) of phthalocyanines and metal phthalocyanines in organic solvents, especially non-polar solvents, but none of them have sufficient solubility.

For example, a phthalocyanine sulfonylamine derivative (II) as found in JP-B-54-3372, JP-B-54-1464
There is known a phthalocyanine sulfonamide derivative (III) as disclosed in Japanese Patent Publication No. Furthermore, Japanese Examined Japanese Patent Publication Sho 39-16787
No. 54-62227, secondary or tertiary aminoalkyl phthalocyanines (IV and V)
Is also proposed.

Further, phthalocyanine acylamino derivatives (VI, VII) as seen in JP-A-58-69255 and 61-183358.
It has been known. In addition, Japanese Patent Laid-Open No.
51-106125, phthalocyanine derivatives (VIII, IX, X) as disclosed in JP-A-60-209583 and JP-A-61-252769 are known.

(Problems to be Solved by the Invention) However, none of the compounds exhibits satisfactory solubility in a nonpolar solvent.

(Object of the Invention) An object of the present invention is to provide a phthalocyanine derivative which exhibits good solubility in an organic solvent, particularly a nonpolar solvent.

(Means for Solving the Problem) As a result of various studies by the present inventors, the phthalocyanine derivative represented by the following general formula (1) effectively achieves the above-mentioned object and overcomes the drawbacks of the prior art, It has been found that it exhibits a sufficiently satisfactory solubility in organic solvents.

In the above formula, M represents hydrogen (2H), a metal, a metal oxide, or a metal halide, and the groups W, X, Y, and Z are any of the 2-position, 3-position, 4-position, and 5-position of the benzene ring of phthalocyanine. Are hydrogen atoms or _{one of the following} general formulas S ₁ or S ₂ , and at least one of W, X, Y and Z is a general formula S ₁ or It is one of S ₂ .

In the general formula S ₁ , R ¹ represents a hydrogen atom, an aliphatic group, an acyl group or a sulfonyl group, A represents a divalent aliphatic group, R ² represents a hydrogen atom, a halogen atom, a cyano group, a nitro group, Hydroxyl group, alkyl group, acylamino group, sulfonylamino group, acyl group, alkoxy group, alkoxycarbonyl group, carbamoyl group, sulfamoyl group,
It represents an aryl group, an alkylsulfonyl group, an arylsulfonyl group, an alkylthio group, or an arylthio group.

n represents 0 or an integer of 1 to 5.

X represents an oxygen atom or a sulfur atom.

In the general formula S ₂ , R ³ represents a hydrogen atom, an alkyl group, an acyl group or a sulfonyl group.

R ⁴ represents a halogen atom, an alkoxy group, an aryloxy group, an amino group, an alkylthio group or an arylthio group.

R ⁵ is a hydrogen atom, a halogen atom, an alkyl group, an aryl group, a heterocyclic group, a cyano group, a hydroxyl group, an alkoxy group, an aryloxy group, a heterocyclic oxy group, an acylamino group, an anilino group, an amino group, a ureido group, It represents a sulfamoylamino group, an alkylthio group, an arylthio group, a sulfonamide group, a carbamoyl group, an acyl group, a sulfamoyl group, a sulfonyl group or an alkoxycarbonyl group.

n'represents an integer of 1 to 5 and m represents 0 or an integer of 1 to 4.

In addition, an aliphatic group of R ¹ , an acyl group, a sulfonyl group, an aliphatic group of A, an alkyl group of R ² , an alkoxy group, an alkoxycarbonyl group, a carbamoyl group, a sulfamoyl group, an aryl group, an alkylsulfonyl group, and an arylsulfonyl group. , Heterocyclic group, thio group, R ³ alkyl group, R ⁴ alkoxy group, aryloxy group, alkylthio group, arylthio group, R ⁵ alkyl group, aryl group, alkoxy group, aryloxy group, alkylthio group, arylthio group The group and the alkoxy group may be further substituted.

The structural feature of the phthalocyanine derivative represented by the general formula (1) of the present invention is that the benzene ring of the phthalocyanine has a substituent represented by the general formulas S ₁ and S ₂ .

This substituent group, JP-A-60-212763, JP-A-60-229029,
It is publicly known from No. 61-105545, No. 61-9653, No. 61-4046, etc. Providing diffusion resistance to photographic couplers (eg, acetylacetone, pyrazolone, and phenol derivatives), high-boiling organic solvents (eg, phthalates,
Phosphoric acid or phosphonic acid ester, benzoic acid ester,
It is a fact well known to those skilled in the art that it is very useful for improving solubility in alcohol or phenol, aliphatic carboxylic acid ester, aniline, hydrocarbon, etc.). However, up to now, no phthalocyanine derivative having a substituent such as those represented by the general formulas S ₁ and S ₂ has been known at all. In addition, it is totally unexpected that the diffusion resistance and oil-solubilizing group of a photographic coupler, which has a completely different molecular structure from phthalocyanines and solubility in organic solvents, is effective for improving the solubility of phthalocyanines. It was a good fact.

Hereinafter, the phthalocyanine derivative represented by the general formula (1) of the present invention will be described in detail.

The metal of the phthalocyanine derivative of the present invention, the metal oxide metal halide is not particularly limited, Zn, P
b, Cu, Ni, Fe, Co, Sr, Ca, Yb, Ru, Sm, Tb, Dy,
U, Tl, Cs, Pd, Nd, Ga, In, Sn, Si, Pt, Mn, Ge, A
l, V, VO, Mg, Ti, Cr, Mo, etc. may be mentioned, and they may be metal-free.

The aliphatic group represented by R ¹ in the general formula S ₁ and the acyl group are described in more detail. The aliphatic group has 1 to 36 carbon atoms.
And aliphatic groups including linear and branched alkyl groups, alkenyl groups, aralkyl groups, cycloalkyl groups, alkynyl groups and cycloalkenyl groups, which are described below. Acyl group is acetyl group, propionyl group,
2-methylpropionyl group, benzoyl group (2,4-di-t
ert-amylphenoxy) acetyl group and the like. Each of the substituents described below may be bonded to these. The sulfonyl group is a methanesulfonyl group, an octanesulfonyl group, a benzenesulfonyl group, (2-octyloxy-5-tert-
It represents an octyl) phenylsulfonyl group or the like, to which a substituent described below may be bonded.

Substituents allowed for the aliphatic group, acyl group, and sulfonyl group represented by R ₁ further include a halogen atom (eg, chlorine atom, bromine atom, etc.), alkyl group (eg, methyl group, propyl group, 1-butyl). Group, trifluoromethyl group, tridecyl group, 3- (2,4-di-t-aminophenoxy) propyl group, 2-dodecyloxyethyl group, 3-
Phenoxypropyl group, 2-hexylsulfonyl-ethyl group, cyclopentyl group, benzyl group, etc.), aryl group (for example, phenyl group, 4-t-butylphenyl group,
2,4-di-t-amylphenyl group, 4-tetradecanamidophenyl group, etc.), heterocyclic group (for example, 2-furyl group, 2-thienyl group, 2-pyrimidinyl group, 2-benzothiazolyl group, etc.) , A cyano group, an alkoxy group (for example, a methoxy group, an ethoxy group, a 2-methoxyethoxy group,
2-dodecyloxyethoxy group, 2-methanesulfonylethoxy group, etc.), aryloxy group (eg, phenoxy group, 2-methylphenoxy group, 4-t-butylphenoxy group, etc.), heterocyclic oxy group (eg, 2- Benzimidazolyloxy group, etc.), acylamino group (for example, acetamide group, benzamide group, tetradecanamide group, α- (2,4-di-t-amylphenoxy) butylamide group, γ- (3-t-butyl-4-) Hydroxyphenoxy) butyramide group, α- {4- (4-hydroxyphenylsulfonyl) phenoxy} decanamide group,
Etc.), anilino group (for example, phenylamino group, 2-chloroanilino group, 2-chloro-5-tetradecanamidoanilino group, 2-chloro-5-dodecyloxycarbonylanilino group, N-acetylanilino group, 2-chloro). -5
-{Α- (3-t-butyl-4-hydroxyphenoxy) dodecanamide} anilino group, etc.), ureido, etc. (eg, phenylureido group, methylureido group, N,
N-dibutylureido group, etc.), imide group (eg, N
-Succinimide group, 3-benzylhydantoinyl group,
4- (2-ethylhexanoylamino) phthalimide group, etc.), sufamoylamino group (eg, N, N-dipropylsulfamoylamino group, N-methyl-N-decylsulfamoylamino group, etc.) ), Alkylthio group (for example, methylthio group, octylthio group, tetradecylthio group, 2-phenoxyethylthio group, 3-phenoxypropylthio group, 3- (4-t-butylphenoxy))
Propylthio group, etc., arylthio group (for example, phenylthio group, 2-butoxy-5-t-octylphenylthio group, 3-pentadecylphenylthio group, 2-carboxyphenylthio group, 4-tetradecanamide phenyl group) Nylthio group, etc.), heterocyclic thio group (eg, 2-benzothiazolylthio group, etc.), sulfonamide group (eg, methanesulfonamide group, hexadecanesulfonamide group, benzenesulfonamide group, p-toluenesulfone) Amide group, octadecanesulfonamide group, 2-methyloxy-5-t-butylbenzenesulfonamide group,
Etc.), carbamoyl group (for example, N-ethylcarbamoyl group, N, N-dibutylcarbamoyl group, N- (2-dodecyloxyethyl) carbamoyl group, N-methyl-N-)
Dodecylcarbamoyl group, N- (3- (2,4-di-tert
-Amylphenoxy) propyl) carbamoyl group,
Etc.), an acyl group (eg, an acetyl group, (2,4-di-ter
t-amylphenoxy) acetyl group, benzoyl group,
Etc.), a sulfamoyl group (eg, N-ethylsulfamoyl group, N, N-dipropylsulfamoyl group, N-
(2-dodecyloxyethyl) sulfamoyl group, N-
Ethyl-N-dodecylsulfamoyl group, N, N-diethylsulfamoyl group, etc.), sulfonyl group (eg, methanesulfonyl group, octanesulfonyl group, benzenesulfonyl group, toluenesulfonyl group, etc.), alkoxycarbonyl group (Eg, methoxycarbonyl group, butyloxycarbonyl group, dodecylcarbonyl group, octadecylcarbonyl group, etc.).

The divalent aliphatic group represented by A is a chain or cyclic alkylene group having preferably 1 to 22 carbon atoms (for example,
Methylene group, propylene group, propylidene group, tritylidene group, cyclohexylidene group, 1,1-propylene group,
Represents an ethylene group, a 1,3-propylene group, a 1,6-cyclohexylene group, a hexylmethylene group, etc., and A represents an alkyl group, an aryl group, a heterocyclic group, an alkoxy group (for example,
Methoxy group, 2-methoxyethoxy group, etc.), aryloxy group (eg, phenoxy group, 2,4-di-tert-amylphenoxy group, 2-chlorophenoxy group, etc.), carbonyl group (eg, acetyl group, benzoyl group) Etc.), ester group (eg, methoxycarbonyl group, phenoxycarbonyl group, acetoxy group, benzoyloxy group, butoxysulfonyl group, toluenesulfonyloxy group, etc.), amide group (eg, acetylamino group, ethylcarbamoyl group, dimethyl group) Carbamoyl group, methanesulfonamide group, butylsulfamoyl group etc.), sulfamide group (eg dipropylsulfamoylamino group etc.), imide group (eg succinimide group, hydantoinyl group etc.), ureido group (eg phenylureido) Group, dimethylure Id group), a sulfonyl group (for example, a methanesulfonyl group, etc.), a hydroxy group,
Cyano group, nitro group, halogen atom, thio group (for example,
It may be substituted with a substituent selected from an ethylthio group, a phenylthio group and the like). R ₂ is a halogen atom, a hydroxy group, a cyano group, a nitro group, an alkyl group (for example, a methyl group, a butyl group, a dodecyl group, etc.), an acylamino group (for example, an acetylamino group, a benzoylamino group, a tetradecanamide group, α- (2,4-di-t-amylphenoxy) butyramide group, γ- (3-t-butyl-4-hydroxyphenoxy) butyramide group, α-
{4- (4-hydroxyphenylsulfonyl) phenoxy} decanamide group, etc.), sulfonylamino group (eg, butylsulfonamide group, benzenesulfonamide group, methanesulfonamide group, hexadecanesulfonamide group, p-toluenesulfonamide) Group, octadecanesulfonamide group, 2-methoxy-5-t-butylbenzenesulfonamide group, etc.), acyl group (for example,
Acetyl group, benzoyl group etc.), aryl group, heterocyclic group, alkoxy group (eg methoxy group, 2-methoxyethoxy group etc.), aryloxy group (eg phenoxy group, 2,4-di-tert-amylphenoxy group) , 2-chlorophenoxy group, etc.), alkoxycarbonyl (eg, methoxycarbonyl group, phenoxycarbonyl group,
Acetoxy group, benzoyloxy group, butoxysulfonyl group, toluenesulfonyloxy group, etc.), carbamoyl group (eg, ethylcarbamoyl group, dimethylcarbamoyl group, sulfamoyl group, butylsulfamoyl group, dioctylsulfamoyl group, etc.), alkylsulfo Represents a digroup or an arylsulfonyl group (eg, methanesulfonyl group, p-hydroxyphenylsulfonyl group, etc.), thio group (eg, ethylthio group, phenylthio group, etc.), and R _{2 is} a substitutable group. It may be substituted with the substituents described above, and n represents an integer of 0 to 5.

In the general formula S ₁ , the cyano group represented by R ² is It is preferable that the ortho-position or the para-position and the halogen atom are substituted in the ortho-position relative to the group. X is preferably an oxygen atom.

In the general formula S ₂ , R ³ represents a hydrogen atom, a substituted or unsubstituted alkyl group (eg, methyl group, ethyl group, n-hexyl group, 2-ethylhexyl group, 2-dodecyloxyethyl group, benzyl group, 2- Methanesulfonylethyl group, etc.),
Acyl group (for example, acetyl group, phenoxyacetyl group, benzoyl group, dodecanoyl group, etc.), sulfonyl group (for example, methanesulfonyl group, octanesulfonyl group,
Benzenesulfonyl group, (2-octyloxy-5-te
rt-octyl) phenylsulfonyl group and the like, to which the substituent described below may be bonded.

R ⁴ is a halogen atom (for example, fluorine atom, chlorine atom, bromine atom, etc.), a substituted or unsubstituted alkoxy group (the alkyl residue may be linear or branched, or cyclic) Well, it may be a saturated alkyl residue or an unsaturated alkyl residue. ] (For example, methoxy group, butoxy group, hexyloxy group, octyloxy group, allyloxy group, 2-dodecylthioethoxy group, 2
-Propyneoxy group, 2-methoxyethoxy group, 2-
(N, N-diethylamino) ethoxy group, etc.), aryloxy group (eg, phenoxy group, 2-methoxyphenoxy group, 4-tert-butylphenoxy group, 2-phenylphenoxy group, etc.), amino A group (for example, an amino group, N,
N-dimethylamino group, N-methyl-N-butylamino group, pyrrolidinyl group, morpholino group, N-methylanilino group, 2-chloroanilino group, 2-methoxy-5-methylanilino group, N, N-dibutylamino group, N , N-bis (2
-Propyloxyethyl) amino group, etc.), a substituted or unsubstituted alkylthio group [this alkyl residue may be linear, branched, or cyclic] (for example, dodecylthio group, 2- Butoxyethylthio group, 2-
(N, N-diethyl) aminoethylthio group, 2- [2-
(2-ethoxy) ethoxy] ethylthio group, etc.) or an arylthio group (for example, phenylthio group, 2-butoxyphenylthio group, 4-tert-octylphenylthio group, 2-butoxy-5-tert-octylphenyl group). A ruthio group, etc.).

R ⁵ is a hydrogen atom, a halogen atom (eg, chlorine atom, bromine atom, fluorine atom, etc.), a substituted or unsubstituted alkyl group (eg, methyl group, ethyl group, i-propyl group, t-
Butyl group, trifluoromethyl group, dodecyl group, 3-
(2,4-di-tert-amylphenoxy) propyl group, allyl group, 2-dodecyloxyethyl group, cyclopentyl group, benzyl group, etc., aryl group (for example, phenyl group, 4-t-butylphenyl group, 2, 4-di-t-amylphenyl group, 4-tetradecanamidophenyl group,
Etc.), a heterocyclic group (for example, a 2-furyl group, a 2-thienyl group, a 2-pyrimidinyl group, a 2-benzothiazolyl group,
Etc.), cyano group, hydroxyl group, substituted or unsubstituted alkoxy group (for example, methoxy group, ethoxy group, i-propoxy group, 2-methoxyethoxy group, 2-dodecyloxyethoxy group, 2-methanesulfonylethoxy group,
Etc.), an aryloxy group (for example, a phenoxy group, 2-
Methylphenoxy group, 4-t-butylphenoxy group,
Etc.), heterocyclic oxy group (eg, 2-benzimidazolyloxy group, etc.), acylamino group (eg, acetamide group, benzamide group, tetradecanamide group, α)
-(2,4-di-t-amylphenoxy) butyramide group, γ- (3-t-butyl-4-hydroxyphenoxy) butyramide group, α- {4- (4-hydroxyphenylsulfonyl) phenoxy} decanamide Group, etc.),
Anilino group (for example, phenylamino group, 2-chloroanilino group, 2-chloro-5-tetradecanamidoanilino group, 2-chloro-5-dodecyloxycarbonylanilino group, N-acetylanilino group, 2-chloro-5 −
{Α- (3-t-butyl-4-hydroxyphenoxy)
Dodecane amide} anilino group, etc.), amino group (eg, ethylamino group, dimethylamino group, methyloctylamino group, etc.), ureido group (eg, phenylureido group, methylureido group, N, N-dimethylureido group,
N, N dibutylureido group, etc.), sulfamoylamino group (for example, N, N-dipropylsulfamoylamino group, N-methyl-N-decylsulfamoylamino group,
Etc.), a substituted or unsubstituted alkylthio group (eg, methylthio group, octylthio group, tetradecylthio group, 2-phenoxyethylthio group, 3-phenoxypropylthio group, 3- (4-t-butylphenoxy) propylthio group Groups, etc.), arylthio groups (eg, phenylthio groups,
2-butoxy-5-t-octylphenylthio group, 3-
Pentadecylphenylthio group, 2-carboxyphenylthio group, 4-tetradecanamidophenylthio group,
Etc.), heterocyclic thio group (eg, 2-benzothiazolylthio group, etc.), substituted or unsubstituted alkoxycarbonylamino group (eg, methoxycarbonylamino group, tetradecyloxycarbonylamino group, etc.), amide group ( For example, methanesulfonamide group, hexadecanesulfonamide group, benzenesulfonamide group, p-toluenesulfonamide group, octadecanesulfonamide group,
2-methoxy-5-t-butylbenzenesulfonamide group, etc., carbamoyl group (for example, N-ethylcarbamoyl group, N, N-dibutylcarbamoyl group, N- (2-
Dodecyloxyethyl) carbamoyl group, N-methyl-
N-dodecylcarbamoyl group, N- {3- (2,4-di-t
ert-amylphenoxy) propyl} carbamoyl group,
Etc.), an acyl group (eg, an acetyl group, (2,4-di-ter
t-amylphenoxy) acetyl group, benzoyl group,
Etc.), a sulfamoyl group (eg, N-ethylsulfamoyl group, N, N-dipropylsulfamoyl group, N-
(2-dodecyloxyethyl) sulfamoyl group, N-
Ethyl-N-dodecylsulfamoyl group, N, N-diethylsulfamoyl group, etc.), sulfonyl group (eg, methanesulfonyl group, octanesulfonyl group, benzenesulfonyl group, toluenesulfonyl group, etc.), substituted or unsubstituted Substituted alkoxycarbonyl group (for example, methoxycarbonyl group, butyloxycarbonyl group, dodecyloxycarbonyl group, octadecyloxycarbonyl group,
Etc.), more preferred in the general formula S ₂ , R ⁴ is an alkoxy group or an aryloxy group, It is bonded to the ortho position of the group.

Next, specific examples of the compound represented by the general formula (1) will be shown, but the compound is not limited thereto.

Table 1 shows the compounds when W, X, Y and Z in the general formula (1) are each S ₁ . Ie Table 1 shows specific examples of R ¹ , R ² , A, and M.

Table 2 shows the compounds when W, X, Y and Z in the general formula (1) are each S ₂ .

Ie Table 2 shows specific examples of R ³ , R ⁴ , R ⁵ , and M.

Example 1 Compound No. 2 was obtained by the following synthetic route.

Compounds a , b , c , d and compound No. 2 were synthesized by the following methods.

1-1 Synthesis of compound a Organic Syntheses Collective volum from phthalimide
It was synthesized by the method described in eII P459 (1966). Yield 60% 1-2 Synthesis of compound b It was synthesized from compound a by the method described in Coloring Materials Society Journal 38 (3), 99, (1965). Yield 75% 1-3 Synthesis of compound c As in the case of compound b , it was synthesized by the method described in Coloring Materials Society Journal 38 (3), 99, (1965). Yield 80% 1-4 Synthesis of compound d Synthesized by the method described in JP-A-60-24547. Yield 80
% 1-5 Synthesis of Compound No. 2 Compound c 3 g, pyridine 30 ml and dimethylacetamide 30
While stirring the suspension containing ml, the compound d was mixed at 10 ° C or lower.
10 g was dropped. After completion of the dropwise addition, the reaction mixture was stirred at 20 to 30 ° C. for 5 hours and allowed to stand overnight.

The reaction mixture was extracted with 300 ml of CHCl _{3 and} 300 ml of 9% HClaq, and the organic layer was washed again with 300 ml of 9% HClaq and washed 3 times with water. The organic layer was passed and the liquid was concentrated to dryness under reduced pressure. 300 ml of methanol was added to the residue and the precipitated crystals were filtered and washed with methanol to obtain 7 g of crude crystals.

The crude crystals were purified by flash column chromatography (silica gel: CHCl ₃ / n-hexane = 10/1 = V / V) to obtain 2.5 g of the title compound 2. Yield 27% mp311 ℃ (decomposition) Example 2 Compound No. 3 was obtained by the following synthetic route.

Compounds e , f , g , h , i , j and compound No. 3 were synthesized by the following methods.

2-1 Synthesis of Compound e While stirring a suspension containing 126.6 g of 3-nitrophthalic acid, 216 g of urea, and 380 ml of diethylene glycol dimethyl ether, 33.7 ml of cH ₂ SO _{4 was} added. 100 parts of this reaction mixture
The mixture was heated and stirred at ˜110 ° C. for 2 hours and at 130 to 140 ° C. for 3 hours, and then poured into ice water 3. After the precipitated crystals are washed with water and washed, 80
Dry overnight at ° C. Yield 85 g Yield 70% 2-2 Synthesis of compound f 85 g of compound e synthesized above and 400 ml of dimethylformamide
While stirring the solution containing and, 100 ml of 28% NH ₃ aq was added. After stirring for 3 hours as it was, water 1.5 was added to the reaction solution, and the precipitated crystals were washed with water and dried at 80 ° C. overnight.
Yield 65 g Yield 70% 2-3 Synthesis of compound g Compound f 44 g previously synthesized was added to 100 ml of dimethylformamide.
While stirring the suspension containing
55 ml was added dropwise at 10 ° C or lower. After completion of dropping, stirring was continued at 10 ° C or lower for 2 hours, and then the reaction mixture was poured into ice water 1 with stirring, and the precipitated crystals were washed with water and kept at 80 ° C for 1 hour.
Dry at night.

Yield 34 g Yield 93% 2-4 Synthesis of compound h 0.5 g of 28% CH ₃ ONa MeOH solution was added to 400 ml of methanol solution containing 20 g of compound f synthesized above and NH ₃ was added with stirring.
Gas was introduced (about 2 / min). After 1 hour, heat the reaction mixture to a gentle reflux and let it stand at room temperature.
Reacted for hours. The precipitated crystals were collected while hot and washed with methanol. Air dried at room temperature.

Yield 15 g Yield 74% 2-5 Synthesis of compound j 10 g of compound h synthesized above and 100 ml of dichlorobenzene and
The suspension containing 2.6 g of CuCl was stirred at 130 to 140 ° C. for 3 hours. The precipitated crystals were taken while hot and washed with acetone. The crude crystals were taken out and washed twice with 100 ml of 15% HCl aqueous solution at room temperature and then taken out and washed once in 100 ml of dimethylacetamide at 60 to 70 ° C.

Yield 8g Yield 84% 2-6 Synthesis of Compound j Similar to Compound c synthesized above, Journal of Coloring Materials Society 38 (3), 9
9, 93% yield synthesized by the method described in (1965) 2-7 Synthesis of compound 3 Compound 3 was synthesized by a method of synthesizing compound 2 from compound j and compound d .

Yield 2.5g Yield 27% mp128-9 ° C Example 3 Compound No. 17 was obtained by the following synthetic route.

Compounds k , l , m , n and compound No. 17 were synthesized by the following methods.

3-1 in a method of synthesizing a compound g of synthetic compounds e compound k, to synthesize a compound k from compound a synthesized previously.

3-2 Synthesis of compound l A suspension of 50 g of reduced iron and 250 ml of acetic acid was stirred and 50 g of compound k synthesized above was added little by little while paying attention to heat generation. After heating at 80 ° C. for 1 hour after completion of addition, the reaction mixture was washed with Celite and 100 ml of acetic acid. The liquid was poured into 1.5 of water with stirring. The precipitated crystals are collected, washed with water, 80 ℃
It was dried overnight.

Yield 25 g Yield 60% 3-3 Synthesis of compound m t-octylphenol 33 g, potassium carbonate 33.2 g, acetonitrile 80 ml, and polyethylene glycol 400 (PEG-40
0) A suspension containing 8 g was heated to reflux with stirring. To this, 32.4 g of n-octyl bromide was added dropwise over 2 hours. The mixture was heated as it was for 3 hours and left overnight. The reaction mixture was passed through to remove insoluble materials.

The liquid was extracted with 150 ml of n-hexane / 100 ml of water, and the organic layer was I
After washing twice with 100 ml each of NNaOHaq, it was washed with 100 ml of saturated saline. After drying the organic layer with Na ₂ SO ₄ , n-hexane was distilled off, 150 ml of dichloromethane was added, and 12.8 ml of chlorosulfonic acid was added dropwise at 5 ° C. or lower over 1.5 hours while stirring.

After completion of the dropping, the reaction was carried out at 5 to 10 ° C for 0.5 hour, and then dichloromethane was distilled off. To this residue were added 150 ml of acetonitrile and 50 ml of dimethylacetamide, and 17.6 ml of phosphorus oxychloride was added dropwise over 2 hours while stirring. After reacting at 45 to 47 ° C for 0.5 hour, the mixture was poured into 300 ml of ice water with stirring. Extracted precipitated oil in n- hexane 160ml and water 100 ml, the separated after the organic layer was dried over Na ₂ SO _4, over the removed Na ₂ SO _4, from the liquid was distilled off n- hexane.

61.8 g (yield 92%) of an oily substance was obtained.

3-4 Synthesis of compound n While stirring a suspension containing 6 g of compound l and 50 ml of pyridine, 26 g of compound m was added dropwise at 5 ° C or lower. 1 below 5 ° C
After that, the mixture was left at 20 to 30 ° C. for 3 hours and then left overnight. The reaction mixture was extracted with 100 ml of ethyl acetate and 100 ml of 9% HClaq, and washed twice with water.

The organic layer was evaporated under reduced pressure, 100 ml of methanol was added, and the mixture was ice-cooled.
The precipitated crystals were collected and washed with cold methanol.

Yield 12g Yield 59% 3-5 Synthesis of Compound 17 A suspension containing compound n 12g, urea 20g, cuprous chloride 2.3g, ammonium molybdate 0.1g and dichlorobenzene 50ml was stirred at 150-60 ° C. Heated for 6 hours. The reaction mixture was poured into methanol 2. The precipitated crystals were collected, dried and purified by flash column chromatography (silica gel / CHCl ₃ ). Yield 1.9g Yield 15
% Mp158 ~ 9 ℃ As described above, the phthalocyanine derivative of the present invention can be synthesized by the synthetic method shown in Examples 1 to 3. For the synthesis of the compound of the present invention, reference was made to the following documents and patents.

1. J. Heterocycl. Chem. 7 1403 (1970) 2. Zh. Obsch. Khimi. Vol41 (12) 2735 3. Journal of Coloring Materials 38 (3), 99, (1965) 4. JP-A-61-183358 No. 5. 〃 60-185951 6. 〃 60-249102 No. 7. 〃 60-55340 No. 8. 〃 60-41042 9. 〃 60-24547 10. 〃 59-222837 11. 〃 59-178460 12.〃50-19435 13. Frank H. Moser, Arthur L. Thomas, The Phthalocyan
ines VolI, VolII, CRC Press.Inc. The above synthesis is for tetra-substituted compounds, but for mono-, di-, or tri-substituted compounds, the reaction conditions are controlled in the phthalocyanine cyclization reaction (for example, the Journal of Coloring Materials 38 (2), 99, 1965), the compound can be synthesized under the same conditions as in the above-described synthesis example.

Reference Example 1 The compound of the present invention exhibits good solubility in non-polar solvents such as benzene, toluene and chloroform crocin.

Table 3 shows examples of the solubility of the compound-17 of the invention in various organic solvents.

Example of solubility measurement method In a 50 ml sample tube, 2 g of the phthalocyanine compound of the present invention,
Add 2 ml of solvent and heat in an ultrasonic cleaner at 40 ° C for 1 hour. After allowing to cool to room temperature, pass the toluene solution and The solubility was calculated more. The results are shown in Table-3 and Table-4.

When the solubility is 30% or more, it is indicated by ⊚, when it is 10% or more and less than 30%, it is indicated by ◯, when it is 1% or more and less than 10%, it is indicated by Δ, and less than 1% is indicated by ×.

Reference Example 2 Table 4 shows examples of specific solubility of the compound of the present invention in toluene.

Comparative compound W, X, Y, Z And a compound in which M is Cu was used as a comparative compound.

Next, examples in which the compound of the present invention is used as an ink coloring material are shown.

Reference Example 3 20 g of a 45% toluene solution of polymerized rosin polyhydric alcohol ester was added to 60 g of a 38% gilsonite toluene solution, and 12 g of the compound No. 17 of the present invention was added to a rosin-modified carboxylic acid resin 42.
20 g of a solution of 88% toluene solution was added and kneaded to prepare a special gravure ink.

Gravure printing was performed using this gravure ink to obtain a cyan printed matter.

In addition to this, it is also possible to make a cellophane-based gravure ink by adding a compound of the present invention to a vehicle using a rosin-modified resin mainly composed of nitrocellulose and using an ester-based organic solvent.

Further, when the conventional phthalocyanine is used in a solvent type ink, it may be unstable due to the stability of the crystal form, and sometimes the color may change due to crystal growth or the coloring power may be reduced, but the compound of the present invention is soluble in a solvent. Eliminating such instability is also a great advantage.

As described above, it is understood that the phthalocyanine derivative of the present invention has good solubility in a nonpolar solvent. Further, the phthalocyanine derivative of the present invention was able to dye thermoplastic resins such as polyethylene, polypropylene, polystyrene and polycarbonate uniformly and in high density. Further, since the phthalocyanine derivative of the present invention is soluble in many organic solvents, it is easy to dye the resin in a state of being dissolved in the organic solvent when the resin is colored, and the colored film can be obtained by using the cast method or a coater. Could also be created. Further, the phthalocyanine derivative of the present invention can be used also as a colorant for an organic solvent-based ink, and when used as a colorant for an ink jet ink using an organic solvent as a solvent, there is no clogging, color reproducibility and light fastness. I was able to obtain a good image.

Claims (1)

[Claims] 1. A phthalocyanine derivative represented by the following general formula (I): In the formula, M represents hydrogen (2H), a metal, a metal oxide, or a metal halide, and the groups W, X, Y, and Z are any of the 2-position, 3-position, 4-position, and 5-position of the benzene ring of phthalocyanine. And is a hydrogen atom or _{one of the} general formulas S ₁ or S ₂ shown below, and W,
At least one of X, Y and Z is represented by the general formula S ₁ or S ₂
Is one of. In the general formula S ₁ , R ¹ is a hydrogen atom, an aliphatic group, an acyl group,
Represents a sulfonyl group, A represents a divalent aliphatic group,
R ² is a hydrogen atom, halogen atom, cyano group, nitro group, hydroxyl group, alkyl group, acylamino group, sulfonylamino group, acyl group, alkoxy group, alkoxycarbonyl group, carbamoyl group, sulfamoyl group, aryl group, alkylsulfonyl group Represents a sulfonyl group, an alkylthio group, and an arylthio group. n represents 0 or an integer of 1 to 5. X represents an oxygen atom or a sulfur atom. In the general formula S ₂ , R ³ represents a hydrogen atom, an alkyl group, an acyl group or a sulfonyl group. R ⁴ represents a halogen atom, an alkoxy group, an aryloxy group, an amino group, an alkylthio group or an arylthio group. R ⁵ is a hydrogen atom, a halogen atom, an alkyl group, an aryl group, a heterocyclic group, a cyano group, a hydroxyl group, an alkoxy group, an aryloxy group, a heterocyclic oxy group, an acylamino group, an anilino group, an amino group, a ureido group, It represents a sulfamoylamino group, an alkylthio group, an arylthio group, a sulfonamide group, a carbamoyl group, an acyl group, a sulfamoyl group, a sulfonyl group or an alkoxycarbonyl group. n'represents an integer of 1 to 5 and m represents 0 or an integer of 1 to 4.