JP4079234B2 - Method for producing metal phthalocyanines - Google Patents

Description

[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a method for producing metal phthalocyanines, and more particularly to a method for producing metal phthalocyanines capable of selectively producing asymmetric metal phthalocyanines by controlling the formation of isomers of metal phthalocyanines. is there.
[0002]
[Prior art]
Metal phthalocyanines are useful compounds as materials for paints, printing inks, colorants, electrophotographic photoreceptors, and optical disks, and so far many compounds have been synthesized. Methods for producing metal phthalocyanines have been known for a long time and are described in detail in “Phtharocyanine (vol. 1 to 4)” (˜1996) by Lezonoff et al. These methods are roughly divided into the following three methods.
The first method is a method in which a mixture of phthalic anhydrides and a metal or a metal halide and urea is heated in the presence of a high boiling point solvent or in the absence of a solvent. In this case, a catalyst such as ammonium molybdate is used in combination as necessary.
The second method is a method in which phthalonitriles and metal halides are heated in the presence of a high-boiling solvent or in a solvent-free condition. This method is used for the production of metal phthalocyanines that cannot be produced by the first method, such as phthalocyanines having a central metal such as aluminum, indium, oxovanadium, oxotitanium, and zirconium.
In the third method, phthalic anhydrides or phthalonitriles are first reacted with ammonia to produce an intermediate such as 1,3-diiminoisoindoline, and then it is combined with a metal halide in a high-boiling solvent. It is the method of making it react in it.
[0003]
By the way, various problems arise when metal phthalocyanines are used industrially, but they are deeply related to the structure of metal phthalocyanines. For example, when metal phthalocyanines are used for optical recording materials, phthalocyanines having a long-chain alkyl group (for example, Japanese Patent Application Laid-Open No. Hei 2) in order to have solubility in an organic solvent in addition to thermal and optical characteristics. No. -187468) and naphthalocyanines having an increased aromatic ring (for example, JP-A-2-289653) have been studied.
In addition, when metal phthalocyanines are used in an electrophotographic photoreceptor, the crystallinity of the metal phthalocyanines affects the electrophotographic characteristics, and this also has an important relationship with the substituent of the metal phthalone anines.
[0004]
When phthalonitrile having a substituent at the 3-position is used for the production of metal phthalocyanines, (a) symmetric type, (b) asymmetric type 1, (c) asymmetric type 2, and (D) Four types of metal phthalocyanines of asymmetric type 3 are produced (where R represents a substituent).
In the normal manufacturing method, these four kinds of mixtures are manufactured. However, the metal required depending on the intended characteristics, such as an asymmetric type as an optical recording material and a symmetric type as an electrophotographic photosensitive member. Phthalocyanines are different. Therefore, controlling the production of metal phthalocyanine isomers according to the reaction conditions becomes important for improving the yield.
[0005]
[Table 1]
[0006]
[Problems to be solved by the invention]
As described above, in a normal production method, various isomers are produced simultaneously and obtained as a mixture of metal phthalocyanines. Therefore, the target compound must be separated and purified by column chromatography or a solution method. come. For this reason, the manufacturing process is lengthened, which has the disadvantage that it leads to high costs from an industrial point of view.
Accordingly, an object of the present invention is to solve such problems and provide a method for producing metal phthalocyanines capable of selectively producing asymmetric metal phthalocyanines.
[0007]
[Means for Solving the Problems]
According to the present invention, a solution containing the first, in the method for producing a metal phthalocyanines reacting a Futaroniriru such asymmetric metal halide, a compound represented by the phthalonitrile asymmetric and the following general formula (1) Further, there is provided a method for producing metal phthalocyanines, characterized in that a base is added dropwise under heating and then a metal halide is added and reacted.
[0008]
[Chemical 2]
[0009]
(In the formula, R represents a hydrogen atom or an organic group, and X represents an oxygen atom or a sulfur atom.)
[0010]
Secondly, in the method for producing a metal phthalocyanine described in the first aspect, there is provided a method for producing a metal phthalocyanine characterized in that vanadium chloride is used as a metal halide.
[0011]
Thirdly, the method for producing metal phthalocyanines according to the first or second method described above, wherein the reaction is carried out in an organic solvent.
[0012]
Fourthly, in the method for producing metal phthalocyanines according to the third aspect, there is provided a method for producing metal phthalocyanines, wherein an alcohol solvent is used as the organic solvent.
[0013]
Fifth, the method for producing metal phthalocyanines according to the fourth aspect, wherein benzyl alcohol is used as the organic solvent.
[0014]
Sixth, in the method for producing a metal phthalocyanine according to any one of the first to fifth, a method for producing a metal phthalocyanine characterized by using a vanadium trichloride THF complex as a metal halide is provided. .
[0015]
Seventh, in the method for producing a metal phthalocyanine according to any one of the first to sixth, there is provided a method for producing a metal phthalocyanine characterized by using a 3-position substituted phthalonitrile as an asymmetric phthalonitrile. Provided.
[0016]
Eighth, in the method for producing a metal phthalocyanine according to any one of the first to seventh, a compound in which the organic group R is an amino group, an alkyl group, or an aryl group as the compound represented by the general formula (1). There is provided a method for producing metal phthalocyanines characterized by being used.
[0017]
Ninth, in the method for producing a metal phthalocyanine according to any one of the first to eighth aspects, the compound represented by the general formula (1) is selected from the group consisting of urea, aliphatic amide, and aromatic amide. There is provided a method for producing metal phthalocyanines characterized by using one or more compounds.
[0018]
Tenth, in the method for producing a metal phthalocyanine according to any one of the first to ninth, a method for producing a metal phthalocyanine characterized in that the reaction temperature is 60 to 150 ° C.
[0019]
The present invention is described in more detail below.
When producing metal phthalocyanines, when using unsubstituted or symmetric phthalonitriles, there is only one kind of metal phthalocyanine, so there is no problem with isomers, but asymmetric phthalonitriles are used. In such a case, it becomes a mixture of several isomers as described above. Accordingly, the present inventors have conducted extensive studies to establish a method for selectively producing asymmetric metal phthalocyanines, and as a result, reacted phthalonitriles with the compound of the general formula (1) or ammonia. Then, in the method for producing metal phthalocyanines via 1,3-diiminoisoindolines, a base is dropped under heating to carry out an isoindolineation reaction, and then a metal halide is added to cause the reaction. The present inventors have found that it is possible to selectively produce high-yield metal phthalocyanines and to produce asymmetric metal phthalocyanines with higher yields by using specific metal halides and solvents.
[0020]
The phthalonitriles used in the present invention are generally phthalonitriles having a substituent at the 3-position, but basically any phthalonitriles may be used as long as they are asymmetric phthalonitriles. .
Examples of such phthalonitriles include, but are not limited to, those shown in Table 2 below.
[0021]
[Table 2]
[0022]
As the metal halide used in the present invention, vanadium trichloride is generally used. However, the use of a THF complex of vanadium trichloride which is easy to handle further promotes the production of an asymmetric isomer.
[0023]
Examples of the compound represented by the general formula (1) include aliphatic amides such as formamide, acetamide, propionamide, and butyramide, aromatic amides such as benzamide, urea, thiourea, thioacetamide, and thiobenzamide. Can be mentioned.
[0024]
Examples of the base used in the present invention include sodium alcoholates such as sodium methylate and sodium ethylate.
[0025]
Examples of the organic solvent include alcohols such as 1-propanol, 2-propanol, 1-butanol, isobutanol, 1-pentanol, 1-hexanol, cyclohexanol, 1-heptanol, 1-octanol, and benzyl alcohol. An organic solvent is mentioned, but when benzyl alcohol is used as a solvent, production of a symmetrical isomer can be suppressed.
[0026]
Furthermore, the method for producing metal phthalocyanines of the present invention has the advantage that metal phthalocyanines can be obtained at a lower temperature than conventional methods. The reaction temperature when a base is added dropwise to a solution containing phthalonitriles and the compound represented by the above general formula (1) or ammonia under heating and then a metal halide is added and reacted is 60 ° C. to 150 ° C. A range of ° C can be selected. If the reaction temperature is too high, the decomposition product of phthalonitriles increases, so the range of 80 ° C to 130 ° C is particularly recommended. Although the reaction time depends on the reaction temperature and phthalonitriles, it cannot be generally stated, but it is in the range of 1 to 24 hours.
[0027]
[Action]
In the method for producing metal phthalocyanines of the present invention, the reaction mechanism for selectively obtaining a specific isomer is not necessarily clear, but is presumed as follows. That is, dimerization by reaction of indoline and phthalonitrile is performed in a reaction via reaction of 1,3-diiminoisoindolines with a compound represented by the above general formula (1) or ammonia by reacting phthalonitriles. It is believed that the product is further dimerized to form a template for the phthalocyanine ring, and by performing the initial reaction while hot, a preferentially symmetric dimer is generated. In the next dimerization reaction, an asymmetric isomer template is inevitably selectively formed, and thus the metal phthalocyanines produced are presumed to be asymmetric isomers.
[0028]
【Example】
EXAMPLES The present invention will be specifically described below with reference to examples, but is not limited thereto.
[0029]
Example 1
1.37 g (0.015 mol) of phthalonitrile of Example Compound (4), 0.34 g (0.0075 mol) of formamide and 50 ml of n-pentanol were heated to 70 ° C. to obtain a methanol solution of 20% sodium methylate. 90 g (0.015 mol) was added dropwise. The mixture was further stirred at this temperature for 30 minutes, and then heated to 90 ° C., and 0.67 g (0.0042 mol) of vanadium trichloride was added. The mixture was further heated to 100 ° C. and stirred at this temperature for 6 hours. After cooling to room temperature, 150 ml of methanol was added to the reaction mixture, and 80 ml of water was added dropwise thereto to precipitate crystals. After stirring for 2 hours, the crystals were separated by filtration.
The crystals separated by filtration were washed with a small amount of methanol / water (3/1) and THF, and then dried at 80 ° C. under reduced pressure to obtain 2.46 g of vanadyl phthalocyanine (yield 83.0%). A high-speed liquid chromatograph confirmed that asymmetric vanadyl phthalocyanine was selectively produced.
[0030]
Example 2
1. A phthalonitrile (3.00 g, 0.015 mol), formamide (0.68 g, 0.015 mol) and n-pentanol (50 ml) of the exemplified compound (5) are heated to 70 ° C. to give a methanol solution of 20% sodium methylate. 90 g (0.015 mol) was added dropwise. The mixture was further stirred at this temperature for 30 minutes, and then heated to 90 ° C., and 0.67 g (0.0042 mol) of vanadium trichloride was added. The mixture was further heated to 100 ° C. and stirred at this temperature for 4 hours. After cooling to room temperature, 150 ml of methanol was added to the reaction mixture, and 80 ml of water was added dropwise thereto to precipitate crystals. After stirring for 2 hours, the crystals were separated by filtration.
The crystals separated by filtration were washed with a small amount of methanol / water (3/1) and THF, and then dried at 80 ° C. under reduced pressure to obtain 3.10 g of vanadyl phthalocyanine (yield 85.7%). A high-speed liquid chromatograph confirmed that asymmetric vanadyl phthalocyanine was selectively produced.
[0031]
Example 3
1. 55% (0.015 mol) of phthalonitrile of Exemplified Compound (15), 0.34 g (0.0075 mol) of formamide and 50 ml of n-pentanol were heated to 70 ° C. to give a methanol solution of 20% sodium methylate. 90 g (0.015 mol) was added dropwise. The mixture was further stirred at this temperature for 30 minutes, and then heated to 90 ° C., and 0.67 g (0.0042 mol) of vanadium trichloride was added. The mixture was further heated to 100 ° C. and stirred at this temperature for 6 hours. After cooling to room temperature, 150 ml of methanol was added to the reaction mixture, and 80 ml of water was added dropwise thereto to precipitate crystals. After stirring for 2 hours, the crystals were separated by filtration.
The crystals separated by filtration were washed with a small amount of methanol / water (3/1) and THF, and then dried at 80 ° C. under reduced pressure to obtain 4.64 g of vanadyl phthalocyanine (yield 80.0%). A high-speed liquid chromatograph confirmed that asymmetric vanadyl phthalocyanine was selectively produced.
[0032]
Example 4
5.55 g (0.015 mol) of phthalonitrile of Example Compound (15), 0.68 g (0.015 mol) of formamide and 50 ml of benzyl alcohol were heated to 70 ° C. to obtain 2.90 g of a methanol solution of 20% sodium methylate ( 0.015 mol) was added dropwise. The mixture was further stirred at this temperature for 30 minutes, and then heated to 90 ° C., and 0.67 g (0.0042 mol) of vanadium trichloride was added. The mixture was further heated to 100 ° C. and stirred at this temperature for 6 hours. After cooling to room temperature, 150 ml of methanol was added to the reaction mixture, and 80 ml of water was added dropwise thereto to precipitate crystals. After stirring for 2 hours, the crystals were separated by filtration.
[0033]
The crystals separated by filtration were washed with a small amount of methanol / water (3/1) and THF, and then dried at 80 ° C. under reduced pressure to obtain 4.80 g of vanadyl phthalocyanine (yield 82.8%). The high-speed liquid chromatograph of the obtained vanadyl phthalocyanine is shown in FIG. In FIG. 1, (b) Peak 1 indicating vanadium phthalocyanine of asymmetric type 1 and (c) Peak 2 indicating vanadyl phthalocyanine of asymmetric type 2 are observed, and the asymmetric type vanadyl phthalocyanine is selectively produced. It was confirmed that it was done.
[0034]
Example 5
5.55 g (0.015 mol) of phthalonitrile of Example Compound (15), 0.68 g (0.015 mol) of formamide and 50 ml of benzyl alcohol were heated to 70 ° C. to obtain 2.90 g of a methanol solution of 20% sodium methylate ( 0.015 mol) was added dropwise. After stirring at this temperature for another 30 minutes, the mixture was heated to 90 ° C. and 1.60 g (0.0042 mol) of vanadium trichloride THF complex was added. The mixture was further heated to 100 ° C. and stirred at this temperature for 6 hours. After cooling to room temperature, 150 ml of methanol was added to the reaction mixture, and 80 ml of water was added dropwise thereto to precipitate crystals. After stirring for 2 hours, the crystals were separated by filtration.
[0035]
The crystals separated by filtration were washed with a small amount of methanol / water (3/1) and THF, and then dried at 80 ° C. under reduced pressure to obtain 5.04 g of vanadyl phthalocyanine (yield 86.7%). The high-speed liquid chromatograph of the obtained vanadyl phthalocyanine is shown in FIG. FIG. 2 shows (b) peak 1 indicating vanadyl phthalocyanine of asymmetric type 1 and (c) peak 2 indicating vanadyl phthalocyanine of asymmetric type 2 in Table 1, and selectively producing asymmetric type vanadyl phthalocyanine. It was confirmed that it was done.
[0036]
Comparative Example 1
5.55 g (0.015 mol) of phthalonitrile of Example Compound (15), 0.34 g (0.0075 mol) of formamide, 2.90 g (0.015 mol) of a 20% sodium methylate in methanol, and 50 ml of n-pentanol The mixture was heated to 50 ° C. and stirred at this temperature for 1 hour. Next, the mixture was heated to 90 ° C. and 0.67 g (0.0042 mol) of vanadium trichloride was added, and further heated to 100 ° C. and stirred at this temperature for 6 hours. After cooling to room temperature, 150 ml of methanol was added to the reaction mixture, and 80 ml of water was added dropwise thereto to precipitate crystals. After stirring for 2 hours, the crystals were separated by filtration.
[0037]
The crystals separated by filtration were washed with a small amount of methanol / water (3/1) and THF, and then dried at 80 ° C. under reduced pressure to obtain 3.68 g of vanadyl phthalocyanine (yield 63.4%). The obtained high-speed liquid chromatograph of vanadyl phthalocyanine is shown in FIG. In FIG. 3, (a) Peak 3 indicating symmetric vanadyl phthalocyanine in Table 1, (b) Peaks 1 and 2 indicating asymmetric type 1 and (c) asymmetric type 2 vanadyl phthalocyanine are observed. It was confirmed that no vanadyl phthalocyanine was selectively produced.
[0038]
Comparative Example 2
5.55 g (0.015 mol) of phthalonitrile of exemplary compound (15), 0.59 g (0.0038 mol) of vanadium trichloride and 50 ml of n-pentanol were heated to 105 ° C. while stirring. When the reaction temperature exceeded 100 ° C., 4.00 g (0.02625 mol) of 1,8-diazabicyclo [5.4.0] undec-7-ene (DBU) was added dropwise over about 10 minutes, and then 104 to 106 The mixture was stirred for 4 hours while maintaining the temperature between ° C. After cooling to room temperature, 150 ml of methanol was added to the reaction mixture, and 80 ml of water was added dropwise thereto to precipitate crystals. After stirring for 2 hours, the crystals were separated by filtration.
[0039]
The crystals separated by filtration were washed with a small amount of methanol / water (3/1) and THF, and then dried at 80 ° C. under reduced pressure to obtain 3.48 g of vanadyl phthalocyanine (yield 60%).
A high-speed liquid chromatograph of the obtained vanadyl phthalocyanine is shown in FIG. In FIG. 4, peak 3 showing (a) symmetric vanadyl phthalocyanine in Table 1 was observed, and it was confirmed that asymmetric vanadyl phthalocyanine was not selectively produced.
[0040]
【The invention's effect】
According to the present invention, asymmetric metal phthalocyanines can be selectively produced.
In addition, according to the present invention, asymmetric metal phthalocyanines can be selectively produced in high yield.
[Brief description of the drawings]
1 is a high-performance liquid chromatograph of vanadyl phthalocyanine obtained in Example 4. FIG.
2 is a high-performance liquid chromatograph of vanadyl phthalocyanine obtained in Example 5. FIG.
3 is a high performance liquid chromatograph of vanadyl phthalocyanine obtained in Comparative Example 1. FIG.
4 is a high performance liquid chromatograph of vanadyl phthalocyanine obtained in Comparative Example 2. FIG.
[Explanation of symbols]
1 (b) Peak 2 showing asymmetric type 1 vanadyl phthalocyanine in Table 1 Peak 3 showing (c) asymmetric type 2 vanadyl phthalocyanine in Table 1 Peak showing (a) symmetrical type vanadyl phthalocyanine in Table 1

Claims (10)

In the method for producing a metal phthalocyanine in which an asymmetric phthalonitrile and a metal halide are reacted, a base is added dropwise to a solution containing the asymmetric phthalonitrile and a compound represented by the following general formula (1) under heating. Then, a method for producing a metal phthalocyanine, characterized by adding a metal halide and reacting.
(In the formula, R represents a hydrogen atom or an organic group, and X represents an oxygen atom or a sulfur atom.)   2. The method for producing a metal phthalocyanine according to claim 1, wherein vanadium chloride is used as the metal halide.   The method for producing a metal phthalocyanine according to claim 1 or 2, wherein the reaction is carried out in an organic solvent.   4. The method for producing a metal phthalocyanine according to claim 3, wherein an alcohol solvent is used as the organic solvent.   The method for producing metal phthalocyanines according to claim 4, wherein benzyl alcohol is used as the organic solvent.   6. The method for producing a metal phthalocyanine according to claim 1, wherein a vanadium trichloride THF complex is used as the metal halide. The method for producing metal phthalocyanines according to any one of claims 1 to 6, wherein 3-position substituted phthalonitriles are used as the asymmetric phthalonitriles.   8. The method for producing a metal phthalocyanine according to claim 1, wherein the compound represented by the general formula (1) is a compound in which the organic group R is an amino group, an alkyl group or an aryl group.   9. The metal according to claim 1, wherein at least one compound selected from the group consisting of urea, aliphatic amides and aromatic amides is used as the compound represented by the general formula (1). A method for producing phthalocyanines.   The method for producing a metal phthalocyanine according to any one of claims 1 to 9, wherein the reaction temperature is 60 to 150 ° C.