JPH0747695B2 - Method for producing soluble phthalocyanine complex benzo-substituted at selective position - Google Patents

Description

TECHNICAL FIELD The present invention relates to a method for producing a soluble benzo-substituted phthalocyanine complex having an absorption maximum at 700 nm to 800 nm.

[Conventional technology]

BACKGROUND ART Conventionally, a phthalocyanine metal complex and a metal complex of naphthalocyanine, which is a benzotetrasubstituted product thereof, have been used as a photoreceptor for electrophotography. However, the alignment control of the complex necessary for reproducing the characteristics of the photoconductor has not been sufficiently satisfied. Further, studies have been made on a compact disk, a circuit forming method and the like using these complexes for forming a thin film or a fine pattern, but it is still problematic in that orientation control is difficult.

These problems result from the properties of the metal complex of phthalocyanine and naphthalocyanine. In general,
The phthalocyanine complex has a large intermolecular interaction. Therefore, it is poorly soluble in organic solvents, has several crystal polymorphs, and is difficult to control its physical and chemical properties. Also, a metal complex of naphthalocyanine having a structure in which one benzene ring is equally benzo-substituted,
Like the phthalocyanine metal complex, it is sparingly soluble in organic solvents. Naphthalocyanine metal complex also easily associates,
Therefore, polymorphism is likely to occur.

Such a property is due to the phthalocyanine and naphthalocyanine molecules having 4-fold axial symmetry. Therefore, by breaking this symmetry, the above characteristics are lost,
It can be soluble in organic solvents. It has been disclosed in Japanese Patent Application No. 63-208568 that the solubility in an organic solvent is increased by making the naphthalocyanine skeleton asymmetric.

As a conventional method for producing naphthalocyanine, there are JP-A-60-23451, JP-A-60-184565, JP-A-61-215663, and JP-A-61-186384.
The methods disclosed in JP-A No. 63-91290 and the like can be mentioned. However, this is a method for producing a naphthalocyanine compound having an equivalent substituent or no substituent.

[Problems to be Solved by the Invention]

A study of naphthalocyanines containing a naphthalene ring was conducted in 1934.
This is the first paper reported by R.P. Lindstead et al. In this paper, Linsted et al. State that eutectic 1,2-dicyanonaphthalene with a metal salt should yield the various propeller-like naphthalocyanines shown in Figures 1a-1e. There is. Here, FIGS. 1b to 1e schematically show the structures of the corresponding naphthalocyanines. However, at the time of publication of the paper, there was no separation technique with high accuracy such as liquid chromatography, so that the separation was not actually successful and only the existence of these isomers was expected. Such a mixture of various isomers cannot be used for forming an alignment film, forming a fine pattern, controlling crystal polymorphism and the like.

In addition, sulfonated naphthalocyanine aluminum (II
I) and zinc (II) complexes have also been reported by Dee Phillips et al. (J. Photochem. Phtobiol., 45
Vol. 1, No. 1, 187 (1986)). However, it is extremely unstable in the aqueous solution column of these complexes.

In addition to metal complexes, the synthesis, electrochemical properties and chemiluminescent development of the naphthalocyanine silicon (IV) complex shown in Fig. 2 have been reported by ME Keny et al. (J.
Amer. Chem. Soc., 106, 24, 7404 (1984) and J. Amer. Chem. Soc., 111, 6, 2362 (1989).
Year)). In this naphthalocyanine silicon (IV) complex,
Three silicon bonded through siloxane bonds to form a shaft ligand bonded are three n-C ₃ H ₁₃ groups each silicon at both ends. This complex has been shown to be benzene soluble and chemically stable due to its unique structure. Even in metal complexes, copper (II), iron (I
I), iron (III), cobalt (III), nickel (II) ions, etc. are known to have relatively strong axial coordination. That is, by using these ions as the central metal ion, a benzo-substituted phthalocyanine complex such as naphthalocyanine that is axially coordinated can be obtained relatively easily. However, when the axial coordination occurs, the ligands interfere with the stacking of ene-substituted phthalocyanine rings such as naphthalocyanine with each other, which is preferable for orientation control, orientation thin film formation, and crystal polymorphism control of these complexes. is not.

Further, from the viewpoint of application, the absorption maximum of the dye is preferably around 750 nm, but the absorption maximum of the conventional phthalocyanine complex is around 650 nm, which is a little too short.

Therefore, the present invention provides a method for producing a phthalocyanine complex benzo-substituted at a selective position, which is soluble in an ordinary organic solvent, is easy to control the orientation, and has an absorption maximum at 700 to 800 nm. The purpose is to

[Means for Solving the Problems]

The present inventors, as a result of earnest research in view of the above circumstances, 1,2-
It has been found that the above object can be achieved by mixing dicyanonaphthalene or 2,3-dicyanonaphthalene and phthalonitrile and heating in the presence of zinc (II) acetate or magnesium (II) acetate.

In the method of the present invention, the mixing ratio of 1,2-dicyanonaphthalene or 2,3-dicyanonaphthalene and phthalonitrile is such that phthalonitrile is mixed with 1 mol part of 1,2-dicyanonaphthalene or 2,3-dicyanonaphthalene. It is preferably 15 to 25 parts by mol, and particularly preferably 19 parts by mol. This mixing ratio is less than 15 parts by mole or
If it exceeds 25 parts by mole, compounds other than the target phthalocyanine complex are likely to be produced.

The reaction of 1,2-dicyanonaphthalene or 2,3-dicyanonaphthalene with phthalonitrile is preferably carried out at a temperature of 200 ° C to 300 ° C, particularly 250 ° C.
Is preferred.

In the method of the present invention, in addition to the above compounds, various additives can be further added, if necessary. Examples of such additives include antioxidants such as hydroquinone.

After the above reaction is completed, the target phthalocyanine complex is separated and purified. Separation and purification of the phthalocyanine complex is usually carried out by chromatography or the like, but reverse phase liquid chromatography using a binary liquid as a mobile phase under a linear gradient condition is particularly preferable. Further, as a column used in this reversed phase liquid chromatography, a column packed with octadecylsilane (ODS column) is preferable.

The benzo-substituted phthalocyanine complex obtained by the production method of the present invention is soluble in an ordinary solvent and has a light absorption maximum shifted to the long wavelength side. Therefore, it is expected to be widely applied to the technical field in which optical and electrical characteristics are involved. Examples of such technical fields include electrophotographic materials, disk coating materials, materials for fine light processing, organic high-performance thin film materials, and electrode materials.

[Action]

In the present invention, the present inventors have established a method for producing a phthalocyanine complex having a benzo-substituted phthalocyanine ring at a predetermined position. That is, according to the present invention, it becomes possible to benzo-substitute one or two predetermined positions of the phthalocyanine ring. In the present invention, benzo substitution at a predetermined position of the phthalocyanine ring reduces the symmetry of the phthalocyanine ring. As a result, the association property between the phthalocyanine rings is remarkably reduced, and the solubility of the hardly soluble phthalocyanine complex in an organic solvent such as tetrahydrofuran, acetone or acetonitrile is increased. Further, in the same manner, it became possible to control the orientation of the phthalocyanine complex, which had been difficult to control the orientation, by using a magnetic field, an electric field, an interface, or the like.

〔Example〕

Hereinafter, the present invention will be described in more detail with reference to Examples.

Example 1 0.12-g (0.00056 mol) of 1,2-dicyanonaphthalene or 2,3-dicyanonaphthalene, and 1.37 g of phthalonitrile
(0.0107 mol) (molar ratio 19.01: 1) was placed in a test tube, and 0.17 g (0.0033 mol) of zinc acetate dihydrate and 0.32 g (0.0029 mol) of hydroquinone were added to the test tube. Next, the test tube was immersed in a metal bath set at 270 ° C. for several minutes to completely solidify the contents. Then, the obtained reaction product was finely crushed in an agate mortar and added to 1000 ml of tetrahydrofuran, and dissolved as much as possible. This solution was filtered with a membrane filter (0.45 μm), and the filtrate was a column packed with basic alumina (length 10 cm, inner diameter 2.
Impurities were adsorbed to the column and removed by passing through 5 cm). The obtained filtrate was filtered through a membrane filter again, and then the volume concentrated by a rotary evaporator was reduced to 10
It was set to 0 ml. Then, by leaving it for several hours, green crystals were obtained.

The results of elemental analysis of the obtained crystals are as follows.

Elemental analysis value: C 69.06%, H 3.06%, N 17.30% Silicic acid value: C 68.85%, H 2.89%, N 17.84%
84% of the target zinc 2,3-benzophthalocyanine (I
It was I). The structural formula is shown below.

A, 2,3-benzophthalocyanine zinc (II) In the above formula, the left side shows the formal structural formula, and the right side shows the structural formula in abbreviated form.

Example 2 1.00 g (0.0056 mol) of 1,2-dicyanonaphthalene or 2,3-dicyanonaphthalene and 0.72 g (0.0056 of phthalonitrile)
Mol), 0.68 g (0.0031 mol) of zinc acetate dihydrate and 0.31 g (0.0028 mol) of hydroquinone were reacted in the same manner as in Example 1 at 270 ° C. for several minutes. After the reaction, the obtained reaction product was finely pulverized in an agate mortar and added to tetrahydrofuran 400, and dissolved as much as possible.
Various benzo-substituted phthalocyanines are remarkably easily dissolved in tetrahydrofuran in the presence of 2,3-benzophthalocyanine. Then, this tetrahydrofuran solution was filtered with a membrane filter in the same manner as in Example 1,
The filtrate was then packed with a column of basic alumina (length 10
cm, inner diameter 2.5 cm) to adsorb and remove impurities. The obtained filtrate was filtered through a membrane filter again, concentrated with a rotary evaporator until the volume became 100 ml, and left in a refrigerator for several hours to obtain blue-green crystals.

The crystals thus obtained were collected using a membrane filter, dissolved in a small amount of tetrahydrofuran,
Chromatography was performed to separate each benzophthalocyanine complex. The chromatogram measured at three wavelengths of 250 nm, 340 nm and 670 nm is shown in FIG. At this time, a reversed-phase ODS column (Finepak SIL C18T-5) was used as the column, and tetrahydrofuran / water was used as the mobile phase in a volume ratio.
It was used under the condition of a linear gradient from 50:50 to 100: 0.

Each phthalocyanine complex shown below was purified by recrystallization from each fraction.

A.2,3-Benzophthalocyanine zinc (II) B. Phthalocyanine zinc (II) C.2,3: 7,8-Dibenzophthalocyanine zinc (II) D.2,3: 12,13-dibenzophthalocyanine zinc (II) E.2,3: 7,8: 12,13-tribenzophthalocyanine zinc (I
I) F.2,3: 7,8: 12,13: 17,18-Tetrabenzophthalocyanine zinc (II) G.1,2-Benzophthalocyanine zinc (II) H.1,2: 7,8: 12,13: 17,18-Tetrabenzophthalocyanine zinc (II) In each of the above formulas, the left side shows the formal structural formula, and the right side shows the structural formula in abbreviated form.

Elemental analysis of the benzophthalocyanine complex represented by C, D, E, and F was performed. The results are shown below.

C.2,3: 7,8-Dibenzophthalocyanine zinc (II) Elemental analysis: C 69.96%, H 3.05%, N 15.89% Calculated: C 70.86%, H 2.97%, N 16.53% D.2,3 : 12,13-Dibenzophthalocyanine zinc (II) Elemental analysis: C 69.96%, H 3.32%, N 15.65% Calculated: C 70.86%, H 2.97%, N 16.53% E.2,3: 7,8: 12,13-Tribenzophthalocyanine zinc (I
I) Elemental analysis value: C 73.50%, H 3.16%, N 15.33% Calculated value: C 72.58%, H 3.05%, N 15.39% F.2,3: 7,8: 12,13: 17,18-tetra Benzophthalocyanine zinc (II) Elemental analysis value: C 72.61%, H 3.15%, N 13.82% Calculated value: C 74.09%, H 3.11%, N 14.40% Each benzophthalocyanine zinc (II) complex represented by the above A to H The electronic absorption spectrum of is shown in FIG. FIG. 4 also shows the structure of the benzophthalocyanine zinc (II) complex showing each spectrum curve. As is clear from FIG. 4, 67 found in phthalocyanine zinc (II)
The absorption band near 0 nm shifts to the longer wavelength side as the number of substituted benzene rings increases.

Further, FIG. 5 shows the measurement results of the proton nuclear magnetic resonance spectrum of each of the benzophthalocyanine zinc (II) complexes represented by A to H above. FIG. 5 also shows the structure of the benzophthalocyanine zinc (II) complex showing each spectrum curve. Further, the reference numeral attached to each peak of the spectrum curve in FIG. 5 indicates that the peak is a proton peak at the position indicated by the same reference numeral in the structural formula on the left side of the drawing. FIG. 5 shows that the above-mentioned benzophthalocyanine zinc (II) complex is sufficiently separated and purified, and clarifies that each spectrum is the target complex.

Among the benzophthalocyanine zinc (II) complexes obtained by the production method of the present invention, the 2,3: 12,13-dibenzophthalocyanine zinc (II) complex has two broad absorption bands split around a wavelength of 700 nm. It has a high polarization property and is promising as a nonlinear optical material.

[Effects of the Invention] As described above, according to the method of the present invention, it is soluble in an ordinary organic solvent, orientation control is easy, and the absorption maximum is at 700 to 800 nm. A benzo-substituted phthalocyanine complex can be obtained.

[Brief description of drawings]

FIG. 1a is a diagram showing a structure of a phthalocyanine containing a naphthalene ring, which has been conventionally reported, and FIGS. 1b to 1e are schematic diagrams showing a conventionally reported structure of a phthalocyanine containing another naphthalene ring. FIG. 2 is a view showing a structure of a naphthalocyanine silicon (IV) complex which has been reported, and FIG. 3 is a chromatogram of a mixture of various benzophthalocyanine complexes produced according to an embodiment of the present invention. FIG. 4 is a diagram showing an absorption spectrum of each benzophthalocyanine complex separated from the mixture whose chromatogram is shown in FIG. 3, and FIG. 5 is each benzophthalocyanine separated from the mixture whose chromatogram is shown in FIG. It is a figure which shows each magnetic resonance spectrum of a complex.

Claims (2)

[Claims] 1. 1,2-Dicyanonaphthalene or 2,3-dicyanonaphthalene and phthalonitrile are mixed with zinc (II) acetate.
A method for producing a benzo-substituted phthalocyanine complex, comprising: a step of heating in the presence of benzene to form a benzo-substituted phthalocyanine complex; and a step of separating and purifying the benzo-substituted phthalocyanine complex using reverse phase liquid chromatography. 2. The dose of phthalonitrile is 15 to 25 parts by mole with respect to 1 part by mole of 1,2-dicyanonaphthalene or 2,3-dicyanonaphthalene, and heating is performed at 200 ° C. to 300 ° C.
The method for producing a benzo-substituted phthalocyanine according to claim 1, wherein