JP2513965B2 - Method for producing benzodisubstituted phthalocyanine complex - Google Patents

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for selectively producing a benzodisubstituted phthalocyanine complex having a polarization structure effective as a nonlinear optical material.

[0002]

2. Description of the Related Art Conventionally, a phthalocyanine complex and its benzotetrasubstituted naphthalocyanine complex have been used as electrophotographic photoreceptors. However, when it is used as a nonlinear optical material, it is indispensable to sufficiently control the orientation of the phthalocyanine complex and to impart a polarization structure.

The difficulty in controlling the orientation and the difficulty in imparting a polarization structure are due to the structural characteristics of the metal complex of phthalocyanine and naphthalocyanine. Generally, metal complexes of phthalocyanine and naphthalocyanine are 4
It has a symmetry axis and has a large intermolecular interaction. For this reason,
It is poorly soluble in organic solvents. On the other hand, due to this high symmetry, it has several crystalline polymorphs, which makes it difficult to control its physical and chemical properties. Further, a metal complex of naphthalocyanine in which one benzene ring is equally benzo-substituted is more difficult to dissolve than a metal complex of phthalocyanine. By destroying this symmetry, the above properties are lost and the compound is made soluble in an organic solvent.
It has just been disclosed in No. 23627.

According to the present invention, a solvent such as tetrahydrofuran, toluene, acetone or methylene chloride, which is more suitable for large-scale production than the liquid chromatography method disclosed in Japanese Patent Application No. Hei 2-223627, is used alone or in a mixture, and a recrystallization method is used.
From the mixed system of several compounds, the target 2,3: 7,8
-Dibenzophthalocyanine or 2,3: 12,13
A strictly defined molar ratio of 2,3-dicyanonaphthalene to phthalonitrile in the template reaction so that the metal complex of dibenzophthalocyanine can be easily purified 2,3:
7,8-dibenzophthalocyanine or 2,3: 1
It is a method for producing a metal complex of 2,13-dibenzophthalocyanine.

[0005]

DISCLOSURE OF THE INVENTION 2,3-Dicyanonaphthalene and phthalonitrile are treated in the presence of a zinc salt such as zinc acetate or magnesium acetate or a magnesium salt in an inert solvent such as quinoline or n-amyl alcohol or without any solvent. By heating with a solvent, the following six types of compounds are obtained. A. Phthalocyanine zinc (II) or phthalocyanine magnesium (II) B. 2,3-benzophthalocyanine zinc (II) or 2,3-benzophthalocyanine magnesium (I
I) C.I. 2,3: 7,8-dibenzophthalocyanine zinc (I
I) or 2,3: 7,8-dibenzophthalocyanine magnesium (II) D.I. 2,3: 12,13-dibenzophthalocyanine zinc (II) or 2,3: 12,13-dibenzophthalocyanine magnesium (II) E. 2,3: 7,8: 12,13-tribenzophthalocyanine zinc (II) or 2,3: 7,8: 12,1
3-Tribenzophthalocyanine magnesium (II) F.I. Naphthalocyanine zinc (II) or naphthalocyanine magnesium (II)

A (phthalocyanine complex) and F (naphthalocyanine complex) have four-fold axial symmetry and are insoluble or hardly soluble in an organic solvent and easily separated. B (2,3-benzophthalocyanine complex), E (2,3: 7,8: 12,13-
Tribenzonaphthalocyanine complex) is 2,3-dicyanonaphthalene or phthalonitrile with respect to the other 15
It is relatively easy to obtain by carrying out the template reaction using a molar amount of 25 to 25 times. This is due to the disclosure of the above-mentioned application publication No. 2-55.
It is easier to understand than No. 769.

As the nonlinear optical material described in the field of industrial application, there are polarized structures such as C (2,3: 7,8-dibenzophthalocyanine complex) and D (2,3: 12,13-dibenzophthalocyanine complex). It is necessary to selectively synthesize a complex having a and other compounds to be easily separated.

The separation and purification methods include recrystallization, alumina column chromatography, gel filtration chromatography and the like.

As the recrystallization solvent for the 2,3: 7,8-dibenzophthalocyanine complex and the 2,3: 12,13-dibenzophthalocyanine complex of the present invention, a solvent such as tetrahydrofuran, toluene, acetone or methylene chloride may be used alone or It can be mixed and used.

The central metals of the 2,3: 7,8-dibenzophthalocyanine complex and the 2,3: 12,13-dibenzophthalocyanine complex of the present invention include zinc, magnesium, titanium oxide, vanadium oxide, sodium and lithium. , Lanthanoid elements, copper, silicon, cobalt and the like.

The present invention uses a recrystallization method most suitable for large-scale purification.

When C (2,3: 7,8-dibenzophthalocyanine complex) is purified, D (2,3: 12,13-
Dibenzophthalocyanine complex), E (2,3: 7,8:
It is easy to separate from (12,13-tribenzophthalocyanine complex), but B (2,3-benzophthalocyanine complex)
Hard to separate from. On the other hand, D (2,3: 12,13-dibenzophthalocyanine complex) and E (2,3: 7,8: 1)
2,13-tribenzophthalocyanine complex) is difficult to separate.

Therefore, according to the present invention, when a solvent such as tetrahydrofuran, toluene, acetone or methylene chloride is used alone or in combination as a recrystallization solvent, coexistence of a complex having similar solubility is avoided as much as possible.
It is a method for producing a benzodisubstituted phthalocyanine complex in which a molar ratio of 2,3-dicyanonaphthalene and phthalonitrile, which is a raw material in a template reaction for synthesizing a phthalocyanine derivative, is strictly defined. Incidentally, prior to the separation by the above-mentioned recrystallization method, impurities that interfere with the recrystallization may be removed by alumina column chromatography or silica gel column chromatography.

[0014]

The present invention defines the molar ratio of 2,3-dicyanonaphthalene and phthalonitrile to 0.4: 0.6 to 0.7: 0.3, zinc acetate or magnesium acetate. In the presence of a zinc salt or a magnesium salt such as, a template reaction is performed by heating in an inert solvent such as quinoline or n-amyl alcohol or without a solvent, and then tetrahydrofuran, toluene, acetone,
A method for producing a benzodisubstituted phthalocyanine complex, which comprises separating a 2,3: 7,8-dibenzophthalocyanine complex by a recrystallization method using a solvent such as methylene chloride alone or mixed, and 2,3-dicyanonaphthalene. The molar ratio of phthalonitrile to 0.2: 0.8 to 0.5
Specified as 0.5, quinoline, n-, in the presence of zinc salts such as zinc acetate or magnesium acetate, magnesium salts.
A template reaction is carried out by heating in an inert solvent such as amyl alcohol or in the absence of a solvent, and then a solvent such as tetrahydrofuran, toluene, acetone, methylene chloride is used alone or in a mixture, and a recrystallization method is used to prepare a 2: 3: 1 mixture.
The present invention relates to a method for producing a benzodisubstituted phthalocyanine complex, which comprises separating a 2,13-dibenzophthalocyanine complex.

[0015]

In order to efficiently obtain C (2,3: 7,8-dibenzophthalocyanine complex) or D (2,3: 12,13-dibenzophthalocyanine complex) using 2,3-dicyanonaphthalene and phthalonitrile. Is C (2,
3: 7,8-dibenzophthalocyanine complex) or D
(2,3: 12,13-dibenzophthalocyanine complex)
It is necessary to increase the production ratio of s as much as possible and efficiently separate and purify it from other products. In addition, C (2,3: 7,8−
Dibenzophthalocyanine complex)
The presence of (2,3-benzophthalocyanine complex) is
(2,3: 12,13-dibenzophthalocyanine complex)
The presence of E (2,3: 7,8: 12,13-tribenzophthalocyanine complex) interferes with the purification of the respective target compound.

Using probability theory, the above A, B, C, D,
The calculated production ratios of the six compounds E and F were obtained. Two
When the molar amount of 3-dicyanonaphthalene is W and the molar amount of phthalonitrile is (1-W), A, B, C, D,
Table 1 shows the production ratio (%) of E and F.

[0017]

[Table 1]

When W = 0.5, C (2,3: 7,8-dibenzophthalocyanine complex) and D (2,3: 12,13)
-Dibenzophthalocyanine complex) has the highest production ratio, but A (phthalocyanine complex) and B (2,
3: benzophthalocyanine complex) or E (2,3:
7,8: 12,13-tribenzophthalocyanine complex)
And F (naphthalocyanine complex) are present. As the value of W increases, A (phthalocyanine complex) and B (2,
The production ratio of 3-benzophthalocyanine complex) decreases, but the production ratio of C (2,3: 7,8: 12,13-dibenzophthalocyanine complex) also decreases. As the value of W decreases, the production ratio of E (2,3: 7,8: 12,13-tribenzophthalocyanine complex) and F (naphthalocyanine complex) decreases, but D (2,3: 12, 13
-Dibenzophthalocyanine complex) production ratio is also reduced.
However, here, as an example, orthophthalonitrile, 2,
Considering the case of the reaction of 3-dicyanonaphthalene and zinc acetate, expensive 2,3-dicyanonaphthalene is used as a fixed amount, and the amount of orthophthalonitrile is changed within the range of W value of 0.2 to 0.8. When A, B, C,
The calculated production amounts of the six compounds D, E and F are shown in Table 2 below.

[0019]

[Table 2]

The above calculation results are obtained. C (2,
When it is desired to obtain (3: 7,8: 12,13-dibenzophthalocyanine complex), the production amount is about the same amount between W = 0.2 to 0.5, but A (phthalocyanine complex) and B (2 , 3-benzophthalocyanine complex) is produced in an amount of W
It increases as the value of decreases. Therefore, W = 0.
Preferable results are obtained by carrying out the reaction at around 4 to 0.7. When it is desired to obtain D (2,3: 12,13-dibenzophthalocyanine complex), the production amount is about the same amount between W = 0.2 and 0.5, but E (2,3:
7,8: 12,13-tribenzophthalocyanine complex)
The amount of F and naphthalocyanine complex formed remarkably decreases as the value of W decreases. Therefore, it is preferable to carry out the reaction in the vicinity of W = 0.2 to 0.5.

[0021]

EXAMPLES The present invention will be described in more detail below with reference to examples.

Example 1 2.00 g (0.0056) 2,3-dicyanonaphthalene
Mol), orthophthalonitrile 1.44 g (0.011
2 mol), zinc acetate dihydrate 1.02 g (0.0047
Mol) mixture was added to 25 ml of quinoline, and the mixture was stirred at 180 to 190 ° C. for 1 hour, cooled, and cooled, and then methanol 4
After adding 00 ml, filtering and washing with methanol, the crystals were dissolved in 400 ml of tetrahydrofuran, filtered, the filtrate was applied to an alumina column, and 1540 mg of the residue obtained by distilling tetrahydrofuran was recrystallized from tetrahydrofuran to give D ( 2,3: 12,13-dibenzophthalocyanine zinc) could be purified with good purity.

Example 2 1.00 g (0.0056) of 2,3-dicyanonaphthalene
Mol), orthophthalonitrile 0.36 g (0.002
8 mol), 0.50 g of zinc acetate dihydrate (0.0023
(Mole) mixture was added to 20 ml of quinoline, and the mixture was stirred at 180 to 190 ° C. for 1 hour, and crystals 802 obtained in the same manner
C was obtained by recrystallizing mg from tetrahydrofuran.
(2,3: 7,8-dibenzophthalocyanine zinc) could be purified with good purity.

Example 3 2.00 g (0.0056) of 2,3-dicyanonaphthalene
Mol), orthophthalonitrile 1.44 g (0.011
2 mol), 1.01 g of magnesium acetate tetrahydrate (0.
(0047 mol) and DBU (2.56 g) were added to n-amyl alcohol (40 ml) and the mixture was stirred at 140 to 150 ° C. for 3 hours, and 1630 mg of crystals obtained in the same manner was recrystallized from tetrahydrofuran to give D (2,3:
(12,13-dibenzophthalocyanine magnesium) could be purified with good purity.

Example 4 2.00 g (0.0056) of 2,3-dicyanonaphthalene
Mol), orthophthalonitrile 0.36 g (0.002
8 mol), 0.49 g of magnesium acetate tetrahydrate (0.
(0023 mol) and DBU (1.28 g) were added to n-amyl alcohol (40 ml) and the mixture was stirred at 140 to 150 ° C. for 3 hours, and then 821 mg of crystals obtained in the same manner was recrystallized from tetrahydrofuran to give C (2,3:
7,8-dibenzophthalocyanine magnesium) could be purified with good purity.

Example 5 2.00 g (0.0056) of 2,3-dicyanonaphthalene
Mol), orthophthalonitrile 1.44 g (0.011
2 mol), zinc acetate dihydrate 1.02 g (0.0047
Mole) mixture to a test tube and then this tube
It was immersed in a metal bath set at 70 ° C. for several minutes to completely solidify the contents. After cooling, 400 ml of tetrahydrofuran
1420 mg of crystals obtained in the same manner as above was recrystallized from tetrahydrofuran to give D (2,3: 1).
2,13-dibenzophthalocyanine zinc) could be purified with good purity.

Example 6 2.00 g (0.0056) 2,3-dicyanonaphthalene
Mol), orthophthalonitrile 0.72 g (0.005
6 mol) and 0.64 g of magnesium acetate tetrahydrate (0.
(0030 mol) and DBU (1.56 g) were added to n-amyl alcohol (40 ml), and the mixture was stirred at 140 to 150 ° C. for 3 hours, and 1012 mg of crystals obtained in the same manner was recrystallized from toluene to give C (2,3: 7,8-dibenzophthalocyanine magnesium) could be purified with good purity.

[0028]

According to the present invention, a 2,3: 7,8-dibenzophthalocyanine chain and a 2,3: 12,13-dibenzophthalocyanine chain are efficiently separated and purified from a mixed system of compounds. be able to.

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Claims (2)

(57) [Claims] 1. A molar ratio of 2,3-dicyanonaphthalene and phthalonitrile of 0.4: 0.6 to 0.7: 0.3.
In the presence of a zinc salt such as zinc acetate or magnesium acetate, or a magnesium salt, a template reaction is performed by heating in an inert solvent such as quinoline or n-amyl alcohol or without a solvent, and then tetrahydrofuran, It is characterized in that a 2,3: 7,8-dibenzophthalocyanine complex is separated by a recrystallization method using a solvent such as toluene, acetone, or methylene chloride alone or mixed.
Method for producing 2,3: 7,8-dibenzophthalocyanine complex . 2. A molar ratio of 2,3-dicyanonaphthalene and phthalonitrile of 0.2: 0.8 to 0.5: 0.5.
Defined, or zinc acetate zinc salt such as magnesium acetate, in the presence of a magnesium salt, quinoline, after performing template reaction by heating in an inert solvent or without a solvent such as n- amyl alcohol, tetrahydrofuran Solvents such as toluene, toluene, acetone, and methylene chloride may be used alone or in a mixture to prepare a recrystallization method.
A method for producing a 2,3: 12,13-dibenzophthalocyanine complex, which comprises separating the dibenzophthalocyanine complex .