JP2014051452A - Procedures for synthesis of phthalocyanine with 3,5-bis(pentafluorosulfanyl)-phenyl group and novel phthalocyanine - Google Patents

Abstract

PROBLEM TO BE SOLVED: To synthesize (3,5-bis-pentafluorosulfanyl-phenyl)-phthalocyanine.SOLUTION: Introduction of a substituent on the α position for suppression of aggregation increases a Lewis basicity of the imino nitrogen, resulting in easy decomposition. In this invention, we have suppressed the aggregation of phthalocyanine by the use of 3,5-bis(pentafluorosulfanyl)phenyl group and have succeeded in suppressing the protonation. An improvement of the durability of phthalocyanine itself is anticipated due to the fact that the basicity of the imino nitrogen of phthalocyanine was decreased.

Description

The present invention relates to a method for producing a phthalocyanine having a 3,5-bis (pentafluorosulfanyl) -phenyl group.

Phthalocyanine is an artificial organic blue pigment that has been known for a long time and is used as a paint and pigment in various everyday situations. In addition, phthalocyanine has unique optical properties because it has a widely conjugated π space, and is expected to be used as an organic material such as dye-sensitized solar cells, n-type organic semiconductors, optical disks, and pharmaceuticals for photodynamic therapy. It is a compound. However, phthalocyanine is easily agglomerated due to its π-electron system, causing problems such as a decrease in solubility and loss of functionality. Therefore, when applying phthalocyanine as an organic material, it is most important how to suppress aggregation. Introduction of a substituent at the α-position is effective in suppressing aggregation, and various α-substituted phthalocyanines have been synthesized so far (Non-Patent Documents 1-4).

Cook, M. J .; Daniel, M. F .; Harrison, K. J .; McKeown, N. B .; Thompson, A. J. J. Chem. Soc., Chem. Commun. 1987, 1086. Cammidge, A. N .; Cook, M. J .; Harrison, K. J .; McKeown, N. B. J. Chem. Soc., Perkin Trans. 1 1991, 3053. Cook, M. J .; Dunn, A. J .; Howe, S. D .; Thompson, A. J .; Harrison, K. J. J. Chem. Soc., Perkin Trans. 1 1988, 2453. Cook, M. J. J. Mater. Sci .: Mater. Electron. 1994, 5, 117.

However, α-substituted phthalocyanines, particularly phthalocyanines containing an electron-donating group at the α-position, have a problem in that the reactivity of phthalocyanine itself increases and is easily decomposed by increasing the Lewis basicity of imino nitrogen.
Therefore, we thought that aggregation could be suppressed while suppressing Lewis basicity of imino nitrogen of phthalocyanine using pentafluorosulfanyl group (SF ₅ ) which is a strong electron withdrawing group and very bulky substituent. With reference to Sugimori et al.'S report on a phthalocyanine introduced with a phenyl group at the α-position (Non-Patent Document 5 below), 4- (3,5-bis-pentafluorosulfanyl-phenyl) phthalontri, 3- (3,5- Bis-pentafluorosulfanyl-phenyl) phthalonitrile was synthesized, and phthalocyanine was synthesized therefrom.
(Non-Patent Document 5) Sugimori, T .; Okamoto, S .; Kotoh, N .; Honda, M .; Kasuga, K .; Chem. Lett. 2000, 1200
In view of the above problems, the present invention provides a method for producing phthalocyanine and a novel phthalocyanine in which a 3,5-bis (pentafluorosulfanyl) -phenyl group is introduced into the β-position and α-position of phthalonitrile by a coupling reaction, respectively. For the purpose.

In order to achieve the above object, the invention described in claim 1 is a method for producing a phthalonitrile derivative represented by the general formula (1), wherein 3,5-bis This comprises a step of reacting a (pentafluorosulfanyl) -phenylboronic acid derivative with a phthalonitrile derivative having a leaving group at the 4-position and a Suzuki-Miyaura coupling reaction.

The invention according to claim 2 is the method according to claim 1, wherein the 3,5-bis (pentafluorosulfanyl) -phenylboronic acid derivative is selected from the group consisting of boronic acid, boronic acid ester, and trifluoroborate. is there.
The invention according to claim 3 is characterized in that the leaving group of the phthalonitrile derivative having a leaving group at the 4-position is selected from the group consisting of fluorine, chlorine, bromine, halogen atoms of iodine, tosylate, triflate and mesitylate. It is in the method of 1 or 2.
The invention according to claim 4 is a method for producing a phthalonitrile derivative represented by the general formula (2), and 3,5-bis (pentafluorosulfanyl) -phenylboron as shown in the following reaction formula (Chemical Formula 3) It consists of a step of reacting an acid derivative with a phthalonitrile derivative having a leaving group at the 3-position and a Suzuki-Miyaura coupling reaction.

The invention according to claim 5 is the method according to claim 4, wherein the 3,5-bis (pentafluorosulfanyl) -phenylboronic acid derivative is selected from the group consisting of boronic acid, boronic acid ester and trifluoroborate.
The invention according to claim 6 is characterized in that the leaving group of the phthalonitrile derivative having a leaving group at the 3-position is selected from the group consisting of fluorine, chlorine, bromine, halogen atoms of iodine, tosylate, triflate and mesitylate. It is in the method of 4 or 5.
The invention according to claim 7 is a method for producing a phthalocyanine derivative represented by the following general formula (3) and general formula (4), wherein (3,5-bis -It comprises a step of reacting a pentafluorosulfanyl-phenyl) -phthalonitrile derivative with a metal compound.

(In the formula, M represents a hydrogen atom, a metal element, a metalloid element, a metal oxide, a metalloid oxide, a metal hydroxide, a metalloid hydroxide, a metal halide, or a metalloid halide.)
The invention according to claim 8 is the method according to claim 7, wherein 4- (3,5-bispentafluorosulfanylphenyl) -phthalonitrile is used as the (3,5-bis-pentafluorosulfanyl-phenyl) -phthalonitrile derivative. is there.
The invention according to claim 9 is the method according to claim 7, wherein 3- (3,5-bispentafluorosulfanylphenyl) -phthalonitrile is used as the (3,5-bis-pentafluorosulfanyl-phenyl) -phthalonitrile derivative. is there.
The invention according to claim 10 resides in a phthalocyanine derivative represented by the following general formula (3).

The invention according to claim 11 resides in a phthalocyanine derivative represented by the following general formula (4).

The raw material phthalonitrile can be synthesized by Suzuki-Miyaura coupling with reference to Non-Patent Document 5.

As the raw material boron derivative, boronic acid, boronic acid ester and trifluoroborate can be used, and boronic acid is preferable. As the leaving group of the aromatic derivative, a substituent having a large leaving ability such as a halogen atom of chlorine, bromine or iodine, tosylate, triflate or mesytilate can be used, and it is desirable to use iodine and triflate. The metal catalyst to be used is not particularly limited, and zero-valent palladium or the like can be used. A catalyst prepared in advance can be used, or a catalyst prepared in the system can be used. Although the ligand of the catalyst is not particularly limited, a phosphine ligand can be used, such as triphenylphosphine, trimethylphosphine, triiso-propylphosphine, tritert-butylphosphine, diphenylphosphinoferrocene, diphenylphosphinopentacene, etc. Can be used. Uses weak bases such as potassium carbonate, sodium carbonate, sodium bicarbonate, cesium carbonate, sodium phosphate, potassium phosphate, and strong bases such as lithium hydroxide, sodium hydroxide, potassium hydroxide, barium hydroxide can do.
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 Alcoholic solvents such as alcohol, aminoethanol, N, N-dimethylaminoethanol; ionic liquids and water, and mixed solvents thereof can also be used. The reaction temperature can be between room temperature and 150 ° C, but is preferably 80 ° C.

The phthalocyanine derivative can be synthesized using a phthalonitrile derivative as a raw material.

As the metal element represented by M, alkali metal, alkaline earth metal, transition metal, lanthanoid metal, and actinoid metal can be used. Specifically, lithium, sodium, potassium, magnesium, calcium, scandium, yttrium, titanium, zirconium, chromium, manganese, molybdenum, iron, ruthenium, cobalt, rhodium, nickel, palladium, nickel, copper, zinc, aluminum, gallium , Indium, tin, lanthanum, uranium, and the like.
Examples of the metalloid element represented by M include boron, silicon, arsenic, germanium, and lead.
As the metal oxide represented by M, oxides of alkali metals, alkaline earth metals, transition metals, lanthanoid metals, and actinoid metals can be used. Specifically, lithium oxide, magnesium oxide, calcium oxide, titanium oxide, chromium oxide, manganese oxide, molybdenum oxide, iron oxide, ruthenium oxide, copper oxide, zinc oxide, aluminum oxide, gallium oxide, lanthanum oxide, uranium oxide, etc. Can be mentioned.
Examples of the metalloid oxide represented by M include boron oxide, silicon oxide, arsenic oxide, germanium oxide, lead oxide, and the like.

  As the metal hydroxide represented by M, hydroxides of alkali metals, alkaline earth metals, transition metals, lanthanoid metals, and actinoid metals can be used. For example, aluminum hydroxide, indium hydroxide, thallium hydroxide, etc. can be mentioned.

Examples of the metalloid hydroxide represented by M include boron hydroxide, silicon hydroxide, arsenic hydroxide, germanium hydroxide, lead hydroxide, and the like.
As the metal halide represented by M, halides of alkali metals, alkaline earth metals, transition metals, lanthanoid metals, and actinoid metals can be used. As a halogen atom, any of a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom may be sufficient.

Examples of the metalloid halide represented by M include boron halide, silicon halide, arsenic halide, germanium halide, lead halide and the like. As a halogen atom, any of a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom may be sufficient.
There are four types of structural isomers in the compounds of the present invention, and these isomers are all included in the scope of the present invention. Also, any mixture of structural isomers is within the scope of the present invention. The pentafluorosulfanyl phthalocyanine of the present invention may form a salt depending on the type and may exist as a hydrate or a solvate, but these substances are all included in the scope of the present invention.
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, aminoethanol, N, N-dimethylaminoethanol and the like; supercritical carbon dioxide, ionic liquids, and the like, with N, N-dimethylaminoethanol being most preferred.

It is a figure which shows the UV / Vis spectrum and fluorescence spectrum of the synthetic | combination phthalocyanine, Comprising: It is a UV / Vis spectrum in the methylene chloride of (beta)-(3,5-bis-pentafluorosulfanyl-phenyl) -zinc phthalocyanine. It is a figure which shows the UV / Vis spectrum and fluorescence spectrum of the synthesize | combined phthalocyanine, Comprising: It is a UV / Vis spectrum in the methylene chloride of (alpha)-(3,5-bis-pentafluorosulfanyl-phenyl) -zinc phthalocyanine. FIG. 2 is a diagram showing UV / Vis spectrum and fluorescence spectrum of a synthesized phthalocyanine, wherein α- (3,5-bis-pentafluorosulfanyl-phenyl) -zinc phthalocyanine, α- (3,5-bis-trifluoromethyl- It is a UV / Vis spectrum of (phenyl) -zinc phthalocyanine and α-phenyl-zinc phthalocyanine. It is a figure which shows the UV / Vis spectrum and fluorescence spectrum of the synthesize | combined phthalocyanine, Comprising: It is a fluorescence spectrum in the methylene chloride of (beta)-(3,5-bis-pentafluorosulfanyl-phenyl) -zinc phthalocyanine. It is a figure which shows the UV / Vis spectrum and fluorescence spectrum of the synthesize | combined phthalocyanine, Comprising: It is a fluorescence spectrum in the methylene chloride of (alpha)-(3,5-bis-pentafluorosulfanyl-phenyl) -zinc phthalocyanine. The UV / Vis spectrum and fluorescence spectrum of the synthesized phthalocyanines are shown and described in Tables 1 to 5 below. Table 1 is a UV / Vis spectrum of β- (3,5-bis-pentafluorosulfanyl-phenyl) -zinc phthalocyanine in methylene chloride. Table 2 is a UV / Vis spectrum of α- (3,5-bis-pentafluorosulfanyl-phenyl) -zinc phthalocyanine in methylene chloride. (Table 1) β- (3,5-bis-pentafluorosulfanyl UV / Vis spectrum of -phenyl) -zinc phthalocyanine in methylene chloride

Table 2 UV / Vis spectra of α- (3,5-bis-pentafluorosulfanyl-phenyl) -zinc phthalocyanine in methylene chloride.

From Table 1 and Table 2
It was found from the UV / Vis spectrum that β- (3,5-bis-pentafluorosulfanyl-phenyl) -zinc phthalocyanine was strongly aggregated in the solution. This is thought to be due to the fact that the π plane was expanded and the stacking became stronger due to the introduction of the phenyl group. On the other hand, it was revealed that α- (3,5-bis-pentafluorosulfanyl-phenyl) -zinc phthalocyanine does not show any aggregating action. This is probably because the rotation of the phenyl group is hindered by the bulky pentafluorosulfanyl group, so that the phenyl group exists at an angle close to perpendicular to the phthalocyanine surface and inhibits aggregation. In order to examine the effect of the pentafluorosulfanyl group in detail, a comparison was made with phthalocyanines having a phenyl group and a 3,5-bis (trifluoromethyl) phenyl group.
Table 3 shows the UV of α- (3,5-bis-pentafluorosulfanyl-phenyl) -zinc phthalocyanine, α- (3,5-bis-trifluoromethyl-phenyl) -zinc phthalocyanine, α-phenyl-zinc phthalocyanine. / Vis spectrum.
(Table 3) Comparison of UV / Vis spectra of pentafluorosulfanyl, trifluoromethyl and phenyl groups

From Table 3
In the phthalocyanine into which the Ph group has been introduced, protonation is caused by protons in the solvent, causing a red shift. Protonation occurs in the 3,5-bis (trifluoromethyl) phenyl group, but no protonation occurs in the phthalocyanine having the 3,5-bis (pentafluorosulfanyl) phenyl group. This is thought to be because protons are prevented from approaching by the bulky substituent 3,5-bis (pentafluorosulfanyl) phenyl group. If the basicity of phthalocyanine on nitrogen increases and protonation tends to occur, phthalocyanine is likely to decompose, which is not preferable from the viewpoint of durability. The synthesized phthalocyanine is expected to improve durability because protonation is suppressed.
Table 4 is the fluorescence spectrum of β- (3,5-bis-pentafluorosulfanyl-phenyl) -zinc phthalocyanine in methylene chloride.
Table 5 is the fluorescence spectrum of α- (3,5-bis-pentafluorosulfanyl-phenyl) -zinc phthalocyanine in methylene chloride.

From Tables 4 and 5, β- (3,5-bis-pentafluorosulfanyl-phenyl) -zinc phthalocyanine resulted in a low fluorescence quantum yield due to aggregation. On the other hand, α- (3,5-bis-pentafluorosulfanyl-phenyl) -zinc phthalocyanine was not aggregated and thus showed a high fluorescence quantum yield. This result is consistent with the UV / Vis spectrum result.

Hereinafter, the present invention will be described more specifically with reference to embodiments, but the scope of the present invention is not limited to the following embodiments.

(First embodiment)
Synthesis of 4- (3,5-bis-pentafluorosulfanyl-phenyl) -phthalonitrile Into a nitrogen-substituted 50 ml eggplant flask, 200 mg (0.787 mmol) of 4-iodophthalonitrile, 3,5-bis (pentafluorosulfanyl) ) -Phenylboronic acid 324 mg (0.866 mmol), palladium acetate 17.7 mg (0.0787 mmol), triphenylphosphine 83 mg (0.315 mmol), potassium phosphate 501 mg (2.362 mg), fully degassed toluene / water = 17 ml of a mixed solvent of 1/1 was added and the reaction was carried out at 90 ° C for 10 hours. After confirming the disappearance of the raw materials by thin-layer silica gel chromatography, the mixture was cooled to room temperature, diluted with water and extracted with ethyl acetate. The organic layer was washed with saturated brine, dried over sodium sulfate and concentrated. The crude product was purified by silica gel column chromatography (hexane / ethyl acetate = 8/2) to obtain 223 mg (yield 62%) of the desired product.
¹ H NMR (300 MHz, CDCl3): δ = 7.93-8.043 (m, 3H), 8.09 (d, 2H, J = 1.8 Hz), 8.27 (t, 1H, J = 2.4 Hz, 1.8Hz)
¹⁹ F NMR (282 MHz, CDCl3): δ = -149.9 (quintet, 2F, J = 151 Hz) -167.3 (d, 8F, J = 149 Hz)
(Second Embodiment)
Synthesis of 3- (3,5-bis-pentafluorosulfanyl-phenyl) -phthalonitrile Into a nitrogen-substituted 50 ml eggplant flask, trifluorosulfonic acid 2,3-dicyano-phenyl ester 210 mg (0.761 mmol), 3,5 -Bis (pentafluorosulfanyl) -phenylboronic acid 285 mg (0.761 mmol), palladium acetate 8.7 mg (0.0390 mmol), triphenylphosphine 40.7 mg (0.155
mmol), potassium phosphate (485 mg, 2.28 mmol), 17 ml of a fully degassed mixed solvent of toluene / water = 1/1 were added, and the reaction was carried out at 90 ° C. for 2.5 hours. After confirming the disappearance of the raw materials by thin layer silica gel chromatography, the mixture was cooled to room temperature, diluted with water and extracted with ethyl acetate. The organic layer was washed with saturated brine, dried over sodium sulfate and concentrated. The crude product was purified by silica gel column chromatography (hexane / ethyl acetate = 7/3) to obtain 212 mg of the desired product (yield 61%).
¹ H NMR (300 MHz, CDCl3): δ = 7.82 (d, 1H, J = 6.5 Hz), 7.92 (q, 1H, J = 7.7 Hz), 7.96 (d, 1H, J = 6.5 Hz), 8.11 ( s, 2H), 8.30 (s, 1H)
¹⁹ F NMR (282 MHz, CDCl3): δ = -150.0 (quintet, 2F, J = 150.8 Hz), -167.3 (d, 8F, J = 150.8 Hz)

(Third embodiment)
Synthesis of β- (3,5-bis-pentafluorosulfanyl-phenyl) -zinc phthalocyanine 90 mg (0.197 of 4- (3,5-bis-pentafluorosulfanyl-phenyl) -phthalonitrile was added to a nitrogen-substituted 20 ml eggplant flask. mmol), zinc chloride 6.7 mg (0.0493 mmol), N, N-dimethylaminoethanol 1 ml was added, and the reaction was carried out at 135 ° C. After reacting for 5 hours, the mixture was cooled to room temperature, and water was added to precipitate crystals. The crystals were collected by filtration, washed with water, and dried in a desiccator with diphosphorus pentoxide. The crude crystals were dissolved in ethyl acetate and purified by adding hexane to crystallize to obtain 55 mg (yield 59%) of the desired product.
IR (KBr): 3417, 2928, 2857, 1718, 1603, 1445, 1395, 1097, 874, 731, 662, 595, 468 cm-1
MALDI-TOF calculated for C ₅₆ H ₂₄ F ₄ 0N ₈ S ₈ Zn [MH ⁺ ] ^- 1890.69 found 1889.50

(Fourth embodiment)
Synthesis of α- (3,5-bis-pentafluorosulfanyl-phenyl) -phthalocyanine 3- (3,5-bis-pentafluorosulfanyl-phenyl) -phthalonitrile 50.0 mg (0.110 mmol) in a nitrogen-substituted test tube Then, 5.0 mg (0.0365 mmol) of zinc chloride was added and the mixture was stirred well and then heated at 230 ° C. for 90 minutes. After the reaction, the reaction mixture was cooled to room temperature and purified by silica gel column chromatography (hexane / ethyl acetate 8/2) to obtain 24 mg (yield 35%) of the desired product.
¹ H NMR (300 MHz, CDCl3): δ = 8.18 (d, 4H, J = 6.9Hz), 8.22 (s, 4H) 8.53 (d, 4H, J = 6.9 Hz) 8.92 (s, 4H), 9.02 ( s, 8H)
¹⁹ F NMR (282 MHz, CDCl3): δ = -146.9 (quintet, 2F, J = 149.4 Hz), -165.5 (d, 8F, J = 149.5 Hz)
MALDI-TOF calculated for C ₅₆ H ₂₄ F ₄ 0N ₈ S ₈ Zn [MH ⁺ ] ^- 1890.69 found 1889.42

Claims (11)

This is a method for producing a phthalonitrile derivative represented by the general formula (1), and the 3,5-bis (pentafluorosulfanyl) -phenylboronic acid derivative is removed at the 4-position as shown in the following reaction formula (Chemical Formula 1). A production method comprising a step of reacting a phthalonitrile derivative having a leaving group with a Suzuki-Miyaura coupling reaction.

2. The method of claim 1, wherein the 3,5-bis (pentafluorosulfanyl) -phenylboronic acid derivative is selected from the group consisting of boronic acid, boronic acid ester, and trifluoroborate. The method according to claim 1 or 2, wherein the leaving group of the phthalonitrile derivative having a leaving group at the 4-position is selected from the group consisting of fluorine, chlorine, bromine, iodine halogen atoms, tosylate, triflate and mesylate. . A method for producing a phthalonitrile derivative represented by the general formula (2), in which the 3,5-bis (pentafluorosulfanyl) -phenylboronic acid derivative is removed at the 3-position as shown in the following reaction formula (Chemical Formula 3) A production method comprising a step of reacting a phthalonitrile derivative having a leaving group with a Suzuki-Miyaura coupling reaction.

5. The method of claim 4, wherein the 3,5-bis (pentafluorosulfanyl) -phenylboronic acid derivative is selected from the group consisting of boronic acid, boronic acid ester, and trifluoroborate. 6. The method according to claim 4, wherein the leaving group of the phthalonitrile derivative having a leaving group at the 3-position is selected from the group consisting of fluorine, chlorine, bromine, iodine halogen atoms, tosylate, triflate, and mesylate. . A method for producing a phthalocyanine derivative represented by the following general formula (3) and general formula (4), as shown in the following reaction formula (Chemical Formula 5) (3,5-bis-pentafluorosulfanyl-phenyl) A production method comprising a step of reacting a phthalonitrile derivative and a metal compound.
(In the formula, M represents a hydrogen atom, a metal element, a metalloid element, a metal oxide, a metalloid oxide, a metal hydroxide, a metalloid hydroxide, a metal halide, or a metalloid halide.) 8. The method according to claim 7, wherein 4- (3,5-bis-pentafluorosulfanyl-phenyl) -phthalonitrile is used as the (3,5-bis-pentafluorosulfanyl-phenyl) -phthalonitrile derivative. 8. The method according to claim 7, wherein 3- (3,5-bis-pentafluorosulfanyl-phenyl) -phthalonitrile is used as the (3,5-bis-pentafluorosulfanyl-phenyl) -phthalonitrile derivative. Phthalocyanine derivatives represented by the following general formula (3)
Phthalocyanine derivative represented by the following general formula (4)