JP2014051453A - Procedures for synthesis of subphthalocyanine with 3,5-bis(pentafluorosulfanyl)-phenyl group and novel subphthalocyanine with 3,5-bis(pentafluorosulfanyl)-phenyl group - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide synthetic procedures for subphthalocyanine with pentafluorosulfanyl group having suppression effects of aggregation and to provide novel subphthalocyanine with 3,5-bis(pentafluorosulfanyl)-phenyl group.SOLUTION: We have synthesized subphthalocyanine with 3,5-bis(pentafluorosulfanyl)-phenyl group, which is a bulky substituent, at the α and β positions for suppression of the aggregation. By this synthesis, we have succeeded in controlling the aggregation of subphthalocyanine. Furthermore, spectroscopic measurement revealed an extremely high fluorescence quantum yield. Due to these properties, this compound is expected to have a potential for the development of optical materials.

Description

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

  Subphthalocyanine is a compound expected to be used as a functional dye, such as an optical material, an organic semiconductor, and a photosensitizer for photodynamic therapy. Subphthalocyanine is a phthalocyanine analog compound having a boron atom in the center, and phthalocyanine has a planar structure having four diiminoisoindoline units, while subphthalocyanine has only three of them. It has a three-dimensional structure of the mold (Non-Patent Document 1). In addition, in the UV-visible absorption spectrum, the maximum absorption wavelength of phthalocyanine is around 700 nm, whereas that of subphthalocyanine is characterized by being blue-shifted from 500 nm to 600 nm, which is larger than phthalocyanine. When considering the application of subphthalocyanine, it is necessary to suppress the aggregation action in the solution state. This is because, when aggregation occurs, the optical properties peculiar to subphthalocyanine are lost.

Claessens, G. C; Gonzalez-Rodrigues, D; Torres. T; Chem. Rev, 2002, 102, 835-853

   In view of the above points, the present invention uses a bulky substituent 3,5-bis (pentafluorosulfanyl) -phenyl group to suppress aggregation, and the α-position and β-position of phthalonitrile by Suzuki-Miyaura coupling reaction. It is an object of the present invention to provide a method for producing a phthalocyanine having a pentafluorosulfanyl group having a substituent suppressing effect by introducing a substituent at the position and a novel subphthalocyanine having a 3,5-bis (pentafluorosulfanyl) -phenyl group.

In order to achieve the above object, according to the first aspect of the present invention, 1,3-bis (pentafluorosulfanyl) -5-bromobenzene is used as a boronic acid derivative, which is coupled to the β-position and α of phthalonitrile by a coupling reaction. Each was introduced. That is, the invention according to claim 1 has the following general formula (1)

Is a method for producing a subphthalocyanine derivative represented by:
(1) First, a Suzuki-Miyaura coupling reaction of a 3,5-bis (pentafluorosulfanyl) phenylboronic acid derivative with a phthalonitrile derivative having a leaving group at the 4-position in the presence of a zero-valent palladium catalyst and a base And (2) a method for synthesizing a subphthalocyanine including a second step of reacting the compound with a boron compound after the first step.
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. .
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 chlorine, bromine, iodine halogen atoms, tosylate, triflate and mesitylate. Or in the method described in 2.
The invention according to claim 4 has the following general formula (2)

Is a method for producing a subphthalocyanine derivative represented by:
(1) Suzuki-Miyaura coupling reaction of a 3,5-bis (pentafluorosulfanyl) -phenylboronic acid derivative with a phthalonitrile derivative having a leaving group at the 3-position in the presence of a zero-valent palladium catalyst and a base One step and (2) a method for synthesizing subphthalocyanine comprising a second step of reacting the compound with a boron compound after the first step.
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 chlorine, bromine, iodine halogen atoms, tosylate, triflate and mesitylate. It is in the method of 4 or 5.
The inventions according to claims 7 and 8 reside in the subphthalocyanine derivatives represented by the general formulas (1) and (2).
The starting phthalonitrile can be synthesized by Suzuki-Miyaura coupling with reference to Non-Patent Document 2 below.
(Non-Patent Document 2) Sugimori, T .; Okamoto, S .; Kotoh, N .; Honda, M .; Kasuga, K .; Chem. Lett. 2000, 1200

The 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 synthesis of the subphthalocyanine derivative can be performed using the phthalonitrile derivative as a raw material with reference to Non-Patent Document 3 below.
(Non-Patent Document 3) Claessens, GC; Gonzalez-Rodrigues, D .; Rey, DB; Torres. T .; Mark, G .; Schuchmann, H .; Sonntag, v. C; MacDonald, GJ; Nohr, SR; Eur. J. Org. Chem. 2003, 2547-2551

There are three types of structural isomers or rotational 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 subphthalocyanine having a 3,5-bis (pentafluorosulfanyl) -phenyl group of the present invention may form a salt depending on the type, and may exist as a hydrate or solvate. Any substance is within the scope of the present invention.
As the boron compound to be used, boron trichloride, boron tribromide, boron trifluoride, triphenylborane, and phenylboron dichloride can be used, but boron trichloride is preferred. Further, the number of equivalents of the reagent can be used from 0.33 equivalents to the starting phthalonitrile, but preferably 3.0 equivalents.
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 other alcohol solvents; supercritical carbon dioxide, ionic liquids, and the like, with p-xylene being most preferred.

  The reaction temperature can be between room temperature and 150 ° C, but is preferably 140 ° C.

It is a figure which shows the UV / Vis spectrum and fluorescence spectrum of the synthetic | combination subphthalocyanine, Comprising: It is a UV / Vis spectrum in the methylene chloride of (beta)-(3,5-bis-pentafluorosulfanyl-phenyl) -subphthalocyanine. It is a figure which shows the UV / Vis spectrum and fluorescence spectrum of the synthetic | combination subphthalocyanine, Comprising: It is a UV / Vis spectrum in the methylene chloride of (alpha)-(3,5-bis-pentafluorosulfanyl-phenyl) -subphthalocyanine. It is a figure which shows the UV / Vis spectrum and fluorescence spectrum of the synthetic | combination subphthalocyanine, Comprising: It is a fluorescence spectrum in the methylene chloride of (beta)-(3,5-bis-pentafluorosulfanyl-phenyl) -subphthalocyanine. It is a figure which shows the UV / Vis spectrum and fluorescence spectrum of the synthetic | combination subphthalocyanine, Comprising: It is a fluorescence spectrum in the methylene chloride of (alpha)-(3,5-bis-pentafluorosulfanyl-phenyl) -subphthalocyanine. FIGS. 1 to 4 show the UV / Vis spectrum and fluorescence spectrum of the synthesized phthalocyanine. Table 1 below shows the UV / Vis spectrum of β- (3,5-bis-pentafluorosulfanyl-phenyl) -subphthalocyanine.

Table 2 below shows the UV / Vis spectrum of α- (3,5-bis-pentafluorosulfanyl-phenyl) -subphthalocyanine.

Comparing the maximum absorption wavelengths of subphthalocyanines into which substituents are introduced at the β-position and α-position respectively in FIGS. 1 and 2, there is almost no difference between the two. This is considered to be because the phenyl group introduced at the α-position exists at an angle close to a right angle instead of a plane due to steric hindrance, thereby cutting the conjugate plane. Further, since no change in the spectrum is observed even when pyridine is added, it can be seen that these subphthalocyanines are not aggregated in the solution.
Table 3 below shows the fluorescence spectrum of β- (3,5-bis-pentafluorosulfanyl-phenyl) -subphthalocyanine.

Table 4 below shows the fluorescence spectrum of α- (3,5-bis-pentafluorosulfanyl-phenyl) -subphthalocyanine.

It should be noted that the fluorescence quantum yield is remarkably high in the fluorescence spectrum according to FIGS. The fluorescence quantum yield was almost quantitative for each subphthalocyanine. In general, the fluorescence quantum yield of subphthalocyanine in which chlorine is introduced into boron tends to be high, but a value close to 1.0 is observed.

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) -subphthalocyanine In a 10 ml eggplant flask with argon substitution, 100 mg of 4- (3 ′, 5′-bispentafluorosulfanylphenyl) -phthalonitrile ( 0.219 mmol), 0.8 ml (0.789 mmol) of 1 mol / l p-xylene solution of boron trichloride was added and heated to 140 ° C. After reacting for 8 hours, it was cooled to room temperature and purged with argon twice. The mixture was diluted with water and extracted with ethyl acetate. The organic layer was washed with saturated brine, dried over sodium sulfate, and concentrated. This was purified by adsorption silica gel column chromatography (hexane / ethyl acetate = 9/1) to obtain the desired product in a yield of 6.9%. The isomer was obtained in a yield of 7.8%.
1H NMR (300 MHz, CDCl3): δ = 8.48 (s, 3H), 8.58 (d, 3H, J = 8.1 Hz), 8.84 (s, 6H), 9.10 (d, 3H, J = 8.1 Hz), 9.42 (s, 3H)
19F NMR (282 MHz, CDCl3): δ = -149.8 (quintet, 6F J = 150.9 Hz), -167.3 (d, 24F, J = 150.3 Hz)
IR (KBr): 3853, 3735, 2649, 3446, 3116, 2933, 2873, 1717, 1654, 1558, 1457, 1558, 1457, 1185, 1139,
MALDI-TOF calculated for C ₄₂ H ₁₈ BClF ₃₀ N ₆ S ₆ [MH ⁺ ] ^- 1413.92 found 1413.77
(Fourth Embodiment) Synthesis of α- (3,5-bis-pentafluorosulfanyl-phenyl) -subphthalocyanine Argon In a substituted 30 ml eggplant flask with 3- (3 ′, 5′-bispentafluorosulfanylphenyl) -Phthalonitrile 100 mg (0.219 mmol), 0.8 ml (0.789 mmol) of 1 mol / l p-xylene solution of boron trichloride was added and heated to 140 ° C. After reacting for 5 hours, the mixture was cooled to room temperature and purged with argon twice. The mixture was diluted with water and extracted with ethyl acetate. The organic layer was washed with saturated brine, dried over sodium sulfate, and concentrated. This was purified by silica gel chromatography (hexane / ethyl acetate = 9/1 → 7/3) to obtain the desired product in a yield of 15%.
¹ H NMR (300 MHz, CDCl3): δ = 7.96 (d, 3H, J = 6.9 Hz), 8.05 (t, 3H, J = 7.5 Hz), 8.47 (s, 3H), 8.61 (d, 3H, J = 8.4 Hz), 8.80 (s, 6H)
¹⁹ F NMR (282 MHz, CDCl3): δ = -148.2 (q, 1F, J = 150 Hz), -167.11 (d, 4F, J = 150 Hz)
MALDI-TOF calculated for C ₄₂ H ₁₈ BClF ₃₀ N ₆ S ₆ [MH ⁺ ] ^- 1413.92 found 1415.55

Claims (8)

The following general formula (1)

Is a method for producing a subphthalocyanine derivative represented by:
(1) a first step in which a 3,5-bis (pentafluorosulfanyl) -phenylboronic acid derivative is subjected to a Suzuki-Miyaura coupling reaction with a phthalonitrile derivative having a leaving group at the 4-position; and (2) the first step. A method for synthesizing a subphthalocyanine comprising a second step of reacting the compound with a metal salt. 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 ester, and trifluoroborate. 3. The method according to claim 1, wherein the leaving group of the phthalonitrile derivative having a leaving group at the 4-position is selected from the group consisting of chlorine, bromine, iodine halogen atoms, tosylate, triflate, and mesycylate. The following general formula (2)

Is a method for producing a subphthalocyanine derivative represented by:
(1) a first step in which a 3,5-bis (pentafluorosulfanyl) -phenylboronic acid derivative is subjected to a Suzuki-Miyaura coupling reaction with a phthalonitrile derivative having a leaving group at the 3-position; and (2) the first step. A method for synthesizing a subphthalocyanine comprising a second step of reacting the compound with a metal salt. 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. The method according to claim 4 or 5, wherein the leaving group of the phthalonitrile derivative having a leaving group at the 3-position is selected from the group consisting of chlorine, bromine, iodine halogen atoms, tosylate, triflate, and mesycylate. A subphthalocyanine derivative represented by the following general formula (1).
A subphthalocyanine derivative represented by the following general formula (2).