JP2014065670A - Simple production method of trifluoromethyl phthalonitrile and phthalocyanine derivative - Google Patents

Abstract

An object of the present invention is to provide a simple method for producing a trifluoromethylphthalonitrile derivative and to provide a phthalocyanine derivative.
The inventors have succeeded in synthesizing a simple trifluoromethylphthalonitrile by using an aromatic coupling reaction with an existing compound, iodophthalonitrile. This is a raw material of trifluoromethyl phthalocyanine, and is a functional dye applicable to pharmaceuticals, photosensitized solar cells, and optical materials.
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Description

The present invention relates to a simple method for producing a trifluoromethylphthalonitrile derivative and a phthalocyanine derivative.

Phthalocyanines have been used as blue and green pigments. Due to its excellent physical properties, it is a functional dye used as a charge generating material and a dye for magneto-optical disks. Furthermore, applications in various fields such as photosensitizers for photodynamic therapy and nonlinear optical materials are expected. However, phthalocyanine derivatives generally have a problem of poor solubility in organic solvents. Accordingly, phthalocyanines into which a trifluoromethyl group has been introduced have been synthesized with the aim of improving solubility (Non-Patent Documents 1, 2, and 3). Thereafter, Fujiwara et al. Also reported a new method for producing trifluoromethylphthalonitrile (Patent Document 1), but there are also steps with low yields, which are not easy.

Japanese Patent Laid-Open No. 06-041137

Barkanova, SV; Iodko, SS, Kaliya, OL; Kondratenko, NV; Luk'yanets, EA; Oksengendler, IG; Tomilova, LG; Yagupol'skii, LM; Zhurnal Organicheskoi Khimii, 1979, 15 (8), 1770-1773 . Oksengendler, I. G .; Kondratenko, N. V .; Luk'yanets, E. A .; Yagupol'skii, L. M. Zhurnal Organicheskoi Khimii, 1977, 13 (7), 1554-1558. George, P .; Michael, H .; Synthesis communication, 1981, 11 (5), 351-363

Existing methods for synthesizing trifluoromethylphthalonitrile have a large number of steps and yields at each stage are not satisfactory.
The problem to be solved by the present invention is to provide a simple and regioselective synthesis method of trifluoromethylphthalonitrile.

In order to achieve the above-mentioned objective, we facilitated the trifluoromethylation reaction for aromatics, which has made remarkable progress in recent years, especially the coupling reaction using Yagorovsky reagent and copper reported in 2011 (Non-patent Document 4). And we succeeded in synthesizing phthalonitrile with trifluoromethyl at various positions in high yield.
(Non-Patent Document 4) Cheng-Pan, Z .; Zong-Ling, W .; Qing-Yun, C .; Chun-Tao, Z .; Yu-Cheng, G .; Ji-Chang, X .; Angew. Chem. Int. Ed. 2011, 50, 1896-1900
In view of the above problems, an object of the present invention is to provide a method for simply introducing a trifluoromethyl group using various iodophthalonitriles as raw materials.

  In order to achieve the above object, according to the first aspect of the invention, perfluoroalkylation is performed on 4-iodophthalonitrile by a coupling reaction. That is, the invention according to claim 1 has the following general formula (1)

(Wherein R represents a lower perfluoroalkyl group and n represents 1 to 4), which is a method for producing 4-perfluoroalkylphthalonitrile represented by Comprising the step of reacting copper with a perfluoroalkylating agent.
The above process is expressed by the following formula when halogen is iodine.

The invention according to claim 2 has the following general formula (1 ')

Wherein the halogen moiety of the 4-halogenphthalonitrile is selected from the group consisting of chlorine, bromine and iodine, and a Yagolovsky reagent as a perfluoroalkylating agent The method according to claim 1, wherein
The invention according to claim 3 has the following general formula (2)

(Wherein R and n are the same as those in claim 1), which is a method for producing 3-perfluoroalkylphthalonitrile, which is a zero-valent copper and a perfluoroalkylating agent with respect to 3-halogenphthalonitrile. Comprising the step of reacting.
The invention according to claim 4 is the following general formula (2 ′).

Wherein the halogen moiety of the 3-halogenphthalonitrile is selected from the group consisting of chlorine, bromine and iodine, and a Yagolovsky reagent is used as the perfluoroalkylating agent. The method according to claim 3 used.
The invention according to claim 5 has the following general formula (3)

(Wherein R and n are the same as those in claim 1), which is a process for producing 4,5-di (perfluoroalkyl) phthalonitrile, which is based on 4,5-di (halogen) phthalonitrile. It consists of a step of reacting zero-valent copper with a perfluoroalkylating agent.
The invention according to claim 6 is the following general formula (3 ′).

Wherein the halogen moiety of the 4,5-di (halogen) phthalonitrile is selected from the group consisting of chlorine, bromine, and iodine. The method according to claim 5, wherein a Yagorovsky reagent is used as the perfluoroalkylating agent.
The invention according to claim 7 has the following general formula (4)

(Wherein R and n are the same as in claim 1), which is a process for producing 3,6-di (perfluoroalkyl) phthalonitrile, wherein 3,6-di (halogen) phthalonitrile is It consists of a step of reacting zero-valent copper with a perfluoroalkylating agent.
The invention according to claim 8 is the following general formula (4 ′).

Wherein the halogen moiety of the 3,6-di (halogen) phthalonitrile is selected from the group consisting of chlorine, bromine, and iodine. The method according to claim 7, wherein a Yagolovsky reagent is used as the perfluoroalkylating agent.
The invention according to claim 9 has the following general formula (5)

(In the formula, R represents a lower perfluoroalkyl group, n represents 1 to 4, M represents a hydrogen atom, metal element, metalloid element, metal oxide, metalloid oxide, metal hydroxide, metalloid) Wherein 4-perfluoroalkylphthalonitrile produced by the method according to claim 1 together with a metal salt in a solvent is a method for producing a phthalocyanine derivative represented by hydroxide, metal halide, and metalloid halide. It consists of the process of making it react at 100 degreeC or more.
The invention according to claim 10 is the following general formula (5 ′).

(Wherein R, n and M are the same as those in claim 9), wherein the 4-perfluoroalkylphthalonitrile is used as the 4-perfluoroalkylphthalonitrile. The method according to claim 9, wherein 4-trifluoromethylphthalonitrile produced by the method is used.
The invention according to claim 11 has the following general formula (6)

(Wherein R, n and M are the same as in claim 9), wherein 3-perfluoroalkylphthalonitrile prepared by the method according to claim 3 is mixed with a metal salt as a solvent. It consists of the process made to react at 100 degreeC or more inside.
The invention according to claim 12 is the following general formula (6 ′).

(Wherein R, n and M are the same as in claim 9), wherein the 3-perfluoroalkylphthalonitrile is produced by the method according to claim 4. The method according to claim 11, wherein the produced 3-trifluoromethylphthalonitrile is used.
The invention according to claim 13 has the following general formula (7)

(Wherein R, n and M are the same as those in claim 9), and a 4,5-di (perfluoroalkyl) phthalonitrile produced by the method according to claim 5. And a metal salt in a solvent at 100 ° C. or higher.
The invention according to claim 14 is the following general formula (7 ′).

(Wherein R, n and M are the same as in claim 9), a process for producing a β, β-octa (trifluoromethyl) phthalocyanine derivative represented by the above 4,5-di (perfluoroalkyl) The method according to claim 13, wherein 4,5-di (trifluoromethyl) phthalonitrile produced by the method according to claim 6 is used as phthalonitrile.
The invention according to claim 15 is the following general formula (8)

(Wherein R, n and M are the same as those in claim 9), and a 3,6-di (perfluoroalkyl) phthalonitrile produced by the method according to claim 7. And a metal salt in a solvent at 100 ° C. or higher.
The invention according to claim 16 is the following general formula (8 ′).

(Wherein R, n and M are the same as in claim 9), wherein the 3,6-di (perfluoroalkyl) is a method for producing an α, α-octa (trifluoromethyl) phthalocyanine derivative represented by The method according to claim 15, wherein 3,6-di (trifluoromethyl) phthalonitrile produced by the method according to claim 8 is used as the phthalonitrile.
Furthermore, the inventions of claims 17 to 24 reside in the phthalocyanine derivative produced in claims 9 to 16.

4-iodophthalonitrile as a raw material is a commercial product and can be easily obtained. Other iodophthalonitriles can be synthesized by the following method with reference to the literature (Non-Patent Documents 5 and 6).
Alexandre, AP; Qingping, T .; Richard, CL; J. Org. Chem. 2002, 67, 9276-9287 Dmitri, ST; Kieran, JMN; Colin, RM; Clifford, CL; J. Org. Chem. 1996, 61, 3034-3040

From the starting material iodophthalonitrile to the perfluoroalkane-substituted phthalonitrile derivative according to claim 1, it can be converted as follows using a coupling reaction.

The halogenated perfluoroalkanes used in the synthesis of the general formulas (1), (2), (3), and (4) have an alkyl chain of 1 to 4, and chlorine, bromine, and iodine can be used for the halogen moiety. It is. Copper to be used is zero-valent copper, and powdered copper is preferably used. The type of solvent is not particularly limited, but ether solvents such as diethyl ether, diisopropyl ether, n-butyl methyl ether, tert-butyl methyl ether, tetrahydrofuran and dioxane; hydrocarbon solvents such as heptane, hexane, cyclopentane and cyclohexane Halogenated hydrocarbon solvents such as chloroform, carbon tetrachloride, methylene chloride, dichloroethane, and trichloroethane; aromatic solvents such as benzene, toluene, xylene, cumene, cymene, mesitylene, diisopropylbenzene, pyridine, pyrimidine, pyrazine, and pyridazine Ester solvents such as ethyl acetate; ketone solvents such as acetone and methyl ethyl ketone; solvents such as dimethyl sulfoxide and dimethylformamide; methanol, ethanol, propanol, isopropyl alcohol Alcohol solvents such as alcohol, aminoethanol, N, N-dimethylaminoethanol; supercritical carbon dioxide, ionic liquids, and dimethylformamide is most preferred. The reaction temperature can be between room temperature and 100 ° C, preferably 60 ° C.

  The synthesis of trifluoromethylphthalonitrile is represented by the general formula (9)

It is possible to synthesize | combine as follows using the Yagorovsky reagent represented by these, and copper.

Copper used for the synthesis of the general formulas (1 ′), (2 ′), (3 ′), and (4 ′) is zero-valent copper, and it is preferable to use powdered copper. The type of solvent is not particularly limited, but ether solvents such as diethyl ether, diisopropyl ether, n-butyl methyl ether, tert-butyl methyl ether, tetrahydrofuran and dioxane; hydrocarbon solvents such as heptane, hexane, cyclopentane and cyclohexane Halogenated hydrocarbon solvents such as chloroform, carbon tetrachloride, methylene chloride, dichloroethane, and trichloroethane; aromatic solvents such as benzene, toluene, xylene, cumene, cymene, mesitylene, diisopropylbenzene, pyridine, pyrimidine, pyrazine, and pyridazine Ester solvents such as ethyl acetate; ketone solvents such as acetone and methyl ethyl ketone; solvents such as dimethyl sulfoxide and dimethylformamide; methanol, ethanol, propanol, isopropyl alcohol Alcohol solvents such as alcohol, aminoethanol, N, N-dimethylaminoethanol; supercritical carbon dioxide, ionic liquids, and dimethylformamide is most preferred. The reaction temperature can be between room temperature and 100 ° C, preferably 60 ° C.
Hereinafter, the synthesis of trifluoromethylphthalonitrile of the present invention will be specifically described with reference to embodiments, but the scope of the present invention is not limited to the following embodiments.
(Embodiment 1)
Synthesis of 4-trifluoromethylphthalonitrile:
In a 30-ml eggplant flask with nitrogen replacement, 150 mg (0.59 mmol) of 4-iodophthalonitrile, 477 mg (1.2 mmol) of Yagorovsky reagent and 113 mg (1.8 mmol) of copper were dissolved in 5.0 ml of dimethylformamide and heated to 60 ° C. did. After stirring overnight, the mixture was cooled to room temperature, water was added, and extraction was performed three times with ethyl acetate. The organic layer was washed with saturated brine, dried over sodium sulfate, and purified by silica gel column chromatography (Hex / AcOEt = 8/2) to obtain 103 mg of the desired product (yield 89%).
¹ H NMR (300MHz, CDCl ₃ ): 8.01 (s, 2H), 8.09 (s, 1H)
¹⁹ F NMR (282 MHz, CDCl ₃ ): -64.1 (s, 3F)
(Embodiment 2)
Synthesis of 3-trifluoromethylphthalonitrile:
Place 25 mg (0.10 mmol) of 3-iodophthalonitrile, 81 mg (0.20 mmol) of Yagorovsky reagent, and 19 mg (0.30 mmol) of copper into a nitrogen-substituted test tube, dissolve in 1.0 ml of dimethylformamide, and heat to 60 ° C. did. After stirring overnight, the mixture was cooled to room temperature, water was added, and extraction was performed three times with ethyl acetate. The organic layer was washed with saturated brine, dried over sodium sulfate, and purified by silica gel column chromatography (Hex / AcOEt = 7/3) to obtain 17.9 mg (yield 91%) of the desired product.
¹ H NMR (300MHz, CDCl ₃ ): 7.93 (t, J = 7.8 Hz, 1H), 8.07 (t, J = 7.8 Hz, 2H)
¹⁹ F NMR (282 MHz, CDCl ₃ ): -62.7 (s, 3F)
(Embodiment 3)
Synthesis of 4,5-di (trifluoromethyl) phthalonitrile:
To a 30 ml eggplant flask purged with nitrogen, add 190 mg (0.50 mmol) of 4,5-diiodophthalonitrile, 810 mg (2.0 mmol) of Yagorovsky reagent, 190 mg (3.0 mmol) of copper, dissolve in 5.0 ml of dimethylformamide and dissolve at 60 ° C. Heated. After stirring overnight, the mixture was cooled to room temperature, water was added, and extraction was performed three times with ethyl acetate. The organic layer was washed with saturated brine, dried over sodium sulfate, and purified by silica gel column chromatography (Hex / AcOEt = 9/1) to obtain 105 mg of the desired product (yield 79%).
¹ H NMR (300MHz, CDCl ₃ ): 8.31 (s, 2H)
¹⁹ F NMR (282 MHz, CDCl ₃ ): -60.6 (s, 3F)
(Embodiment 4)
Synthesis of 3,6-di (trifluoromethyl) phthalonitrile:
Nitrogen-substituted 30 ml eggplant flask was charged with 3,5-diiodophthalonitrile 38 mg (0.10 mmol), Yagolovsky reagent 162 mg (0.4 mmol), copper 38 mg (0.6 mmol) and dissolved in 1.0 ml dimethylformamide at 60 ° C. Heated. After stirring overnight, the mixture was cooled to room temperature, water was added, and extraction was performed three times with ethyl acetate. The organic layer was washed with saturated brine, dried over sodium sulfate, and purified by silica gel column chromatography (Hex / AcOEt = 8/2) to obtain 22 mg of the desired product (yield 82%).
¹ H NMR (300MHz, CDCl ₃ ): 8.23 (s, 2H)
¹⁹ F NMR (282 MHz, CDCl ₃ ): -63.1 (s, 3F)
(Embodiment 5)
Synthesis of β-tetra (trifluoromethyl) zinc phthalocyanine:
In a nitrogen-substituted test tube, 4-trifluoromethylphthalonitrile 68 mg (0.35 mmol) and zinc chloride 16 mg (0.12 mmol) were dissolved in 1.0 ml of N, N-dimethylaminoethanol, heated to 140 ° C. and stirred overnight. . After cooling to room temperature, saturated aqueous ammonium chloride was added and the precipitated crystals were collected by filtration, washed with water and dried under reduced pressure in a desiccator. Thereafter, recrystallization was performed with ethyl acetate and hexane to obtain 17 mg (yield 24%) of the desired product.
¹ H NMR (300MHz, d-acetone): 8.45-9.11 (m, 12H)
¹⁹ F NMR (282 MHz, d-acetone): -61.3 (12F)
MALDI-TOF calculated forC36H12F12N8Zn (MH ⁺ ) ^- 848.03 found 849.39
(Embodiment 6)
Synthesis of α-tetra (trifluoromethyl) zinc phthalocyanine:
In a nitrogen-substituted test tube, dissolve 30 mg (0.15 mmol) of 3-trifluoromethylphthalonitrile and 6.9 mg (0.051 mmol) of zinc chloride in 1.0 ml of N, N-dimethylaminoethanol and heat to 140 ° C overnight. Stir. After cooling to room temperature, saturated aqueous ammonium chloride was added, and the mixture was extracted 3 times with ethyl acetate. The organic layer was washed with saturated aqueous ammonium chloride and saturated brine, dried over sodium sulfate, and purified by silica gel column chromatography (Hex / Acetone = 7/3) to obtain 23 mg of the desired product (yield 72%). Obtained.
¹ H NMR (300MHz, d-acetone): isomer 2: 8.04-8.13 (m, 12H), isomer 1: 8.35 (t, J = 7.35 Hz, 4H), 8.50 (d, J = 7.2 Hz, 4H), 9.53 (s, 4H)
¹⁹ F NMR (282 MHz, d-acetone), isomer 1 / isomer 2 = 73/28: -58.9 (s, 12F), -60.4 (s, 12F)
MALDI-TOF calculated forC36H12F12N8Zn (MH ⁺ ) ^- 848.03 found 849.74
(Embodiment 7)
Synthesis of β, β-octa (trifluoromethyl) zinc phthalocyanine:
4,5-di (trifluoromethyl) phthalonitrile 70 mg (0.27 mmol) and zinc chloride 12 mg (0.089 mmol) were dissolved in 1.0 ml of N, N-dimethylaminoethanol, heated to 140 ° C. and stirred overnight. After cooling to room temperature, saturated aqueous ammonium chloride was added and the mixture was extracted three times with ethyl acetate. The organic layer was washed with saturated aqueous ammonium chloride and saturated brine, dried over sodium sulfate, and recrystallized from ethyl acetate and hexane to obtain the desired product (38 mg, yield 51%).
¹ H NMR (300MHz, d-acetone): 9.41 (s, 8H)
¹⁹ F NMR (282 MHz, d-acetone): -58.3 (s, 24F)
MALDI-TOF calculated forC40H8F24N8Zn (MH ⁺ ) ^- 1119.98 found 1121.78
(Embodiment 8)
Synthesis of α, α-octa (trifluoromethyl) zinc phthalocyanine:
In a nitrogen-substituted test tube, 23 mg (0.087 mmol) and zinc chloride 4.0 mg (0.029 mmol) were dissolved in 1.0 ml of N, N-dimethylaminoethanol, heated to 140 ° C. and stirred overnight. After cooling to room temperature, saturated aqueous ammonium chloride was added and the mixture was extracted three times with ethyl acetate. The organic layer was washed with saturated aqueous ammonia chloride and saturated brine, dried over sodium sulfate and extracted three times with diethyl ether. The organic layer was washed with saturated aqueous ammonia chloride and saturated brine, and then sodium sulfate. It was dried and purified by silica gel column chromatography (Hex / AcOEt = 8/2) to obtain 12 mg (yield 50%) of the target compound.
¹ H NMR (300MHz, CDCl ₃ ): 8.16 (s, 8H)
¹⁹ F NMR (282 MHz, CDCl ₃ ): -61.9 (s, 24F)
MALDI-TOF calculated forC40H8F24N8Zn (MH ⁺ ) ^- 1119.98 found 1121.63

Claims (24)

The following general formula (1)

(Wherein R represents a lower perfluoroalkyl group and n represents 1 to 4), which is a method for producing 4-perfluoroalkylphthalonitrile represented by A process comprising the step of reacting copper with a perfluoroalkylating agent. The following general formula (1 ')

Wherein the halogen moiety of the 4-halogenphthalonitrile is selected from the group consisting of chlorine, bromine and iodine, and a Yagolovsky reagent as a perfluoroalkylating agent The manufacturing method of Claim 1 using this. The following general formula (2)

(Wherein R and n are the same as those in claim 1), which is a method for producing 3-perfluoroalkylphthalonitrile, which is a zero-valent copper and a perfluoroalkylating agent with respect to 3-halogenphthalonitrile. The manufacturing method which consists of the process of reacting. The following general formula (2 ')

Wherein the halogen moiety of the 3-halogenphthalonitrile is selected from the group consisting of chlorine, bromine and iodine, and a Yagolovsky reagent is used as the perfluoroalkylating agent. The manufacturing method of Claim 3 used. The following general formula (3)

(Wherein R and n are the same as those in claim 1), which is a process for producing 4,5-di (perfluoroalkyl) phthalonitrile, which is based on 4,5-di (halogen) phthalonitrile. A production method comprising a step of reacting zero-valent copper with a perfluoroalkylating agent. The following general formula (3 ')

Wherein the halogen moiety of the 4,5-di (halogen) phthalonitrile is selected from the group consisting of chlorine, bromine, and iodine. The production method according to claim 5, wherein a Yagolovsky reagent is used as the perfluoroalkylating agent. The following general formula (4)

(Wherein R and n are the same as in claim 1), which is a process for producing 3,6-di (perfluoroalkyl) phthalonitrile, wherein 3,6-di (halogen) phthalonitrile is A production method comprising a step of reacting zero-valent copper with a perfluoroalkylating agent. The following general formula (4 ')

Wherein the halogen moiety of the 3,6-di (halogen) phthalonitrile is selected from the group consisting of chlorine, bromine, and iodine. The production method according to claim 7, wherein a Yagorovsky reagent is used as the perfluoroalkylating agent. The following general formula (5)

(In the formula, R represents a lower perfluoroalkyl group, n represents 1 to 4, M represents a hydrogen atom, metal element, metalloid element, metal oxide, metalloid oxide, metal hydroxide, metalloid) Wherein 4-perfluoroalkylphthalonitrile produced by the method according to claim 1 together with a metal salt in a solvent is a method for producing a phthalocyanine derivative represented by hydroxide, metal halide, and metalloid halide. The manufacturing method which consists of the process made to react at 100 degreeC or more. The following general formula (5 ')

(Wherein R, n, and M are the same as in claim 9). Β-tetra (trifluoromethyl) phthalonitrile represented by claim 2, wherein the 4-perfluoroalkylphthalonitrile is claim 2. The manufacturing method of Claim 9 using the 4-trifluoromethyl phthalonitrile manufactured by the method of description. The following general formula (6)

(Wherein R, n and M are the same as in claim 9), wherein 3-perfluoroalkylphthalonitrile prepared by the method according to claim 3 is mixed with a metal salt as a solvent. The manufacturing method which consists of the process made to react at 100 degreeC or more inside. The following general formula (6 ')

(Wherein R, n and M are the same as in claim 9), wherein α-tetra (trifluoromethyl) phthalocyanine is represented by claim 4 as the 3-perfluoroalkylphthalonitrile. The manufacturing method of Claim 11 using the 3-trifluoromethyl phthalonitrile manufactured by the method of. The following general formula (7)

(Wherein R, n and M are the same as those in claim 9), and a 4,5-di (perfluoroalkyl) phthalonitrile produced by the method according to claim 5. The manufacturing method which consists of the process of making a metal salt react with 100 degreeC or more with a metal salt. The following general formula (7 ')

(Wherein R, n and M are the same as in claim 9), a process for producing a β, β-octa (trifluoromethyl) phthalocyanine derivative represented by the above 4,5-di (perfluoroalkyl) The production method according to claim 13, wherein 4,5-di (trifluoromethyl) phthalonitrile produced by the method according to claim 6 is used as phthalonitrile. The following general formula (8)

(Wherein R, n and M are the same as those in claim 9), and a 3,6-di (perfluoroalkyl) phthalonitrile produced by the method according to claim 7. The manufacturing method which consists of the process of making a metal salt react with 100 degreeC or more with a metal salt. The following general formula (8 ')

(Wherein R, n and M are the same as in claim 9), wherein the 3,6-di (perfluoroalkyl) is a method for producing an α, α-octa (trifluoromethyl) phthalocyanine derivative represented by The production method according to claim 15, wherein 3,6-di (trifluoromethyl) phthalonitrile produced by the method according to claim 8 is used as phthalonitrile. A phthalocyanine derivative represented by the following general formula (5).

(In the formula, R, n and M are the same as in claim 9.) A β-tetra (trifluoromethyl) phthalonitrile derivative represented by the following general formula (5 ′).

(In the formula, R, n and M are the same as in claim 9.) A phthalocyanine derivative represented by the following general formula (6).

(In the formula, R, n and M are the same as in claim 9.) An α-tetra (trifluoromethyl) phthalocyanine derivative represented by the following general formula (6 ′):

(In the formula, R, n and M are the same as in claim 9.) A phthalocyanine derivative represented by the following general formula (7):

(In the formula, R, n and M are the same as in claim 9.) A β, β-octa (trifluoromethyl) phthalocyanine derivative represented by the following general formula (7 ′):

(In the formula, R, n and M are the same as in claim 9.) A phthalocyanine derivative represented by the general formula (8).

(In the formula, R, n and M are the same as in claim 9.) Α, α-octa (trifluoromethyl) phthalocyanine derivative represented by the general formula (8 ′)

(In the formula, R, n and M are the same as in claim 9.)