JP4372991B2 - Porphyrazine compound and method for producing the same - Google Patents

Description

[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a novel porphyrazine (tetraazaporphyrin) compound and a method for producing the same. By using the compound, a write-once type optical recording medium having a high recording density and excellent in light resistance and storage stability is provided. Is possible.
[0002]
[Prior art]
In the current write-once optical disc system, the laser used has an oscillation wavelength of 770 to 790 nm, and the recording medium is set so that recording and reproduction can be performed at the above wavelength. In the future, as the amount of information increases, it is essential to increase the capacity of recording media, and laser wavelengths used for recording and reproduction are becoming shorter. However, a recording material that has excellent light resistance and storage stability and can be recorded and reproduced with an optical pickup using a laser of 700 nm or less has not been developed yet.
[0003]
In addition, current CDs and CD-ROMs are coated with Al on the unevenness of the substrate itself, and the wavelength dependence of the reflectance of Al is small, so that it can be reproduced even if the laser wavelength is shortened in the future. It is. However, in the case of CD-R, a dye having a maximum absorption wavelength at 680 to 750 nm is used for the recording layer, and a high reflectance is set to 770 to 790 nm depending on its optical constant and film thickness configuration. In the wavelength region of 700 nm or less, the reflectance is extremely low, and when the laser wavelength is shortened, there is a possibility that the currently recorded information cannot be reproduced by a future system.
[0004]
Porphyrazine compounds are azaannulene dyes similar to phthalocyanine dyes that are sometimes used in CD-R recording layers, and have a smaller π-electron system and shorter light absorption wavelength than phthalocyanine dyes. If it can be used for this recording layer, it is expected that a recording medium corresponding to the short wavelength laser as described above can be produced. However, porphyrazine compounds having no substituent have low solubility in organic solvents, and it is difficult to form a recording layer by a solvent coating method.
On the other hand, a porphyrazine compound having a substituent is not always easy to synthesize. In particular, when it is used as a write-once type optical recording material, it needs to have an appropriate thermal decomposability, and such a compound is more difficult to synthesize.
[0005]
[Problems to be solved by the invention]
The present invention improves such drawbacks of conventional porphyrazine compounds, provides a dye material suitable as a high-capacity write-once optical recording material, and simultaneously synthesizes such a dye material with high yield. It is an object of the present invention to provide a manufacturing method.
[0006]
[Means for Solving the Problems]
  The inventors of the present invention have so far conducted research on porphyrazine compounds and have already proposed in JP-A-9-267562, JP-A-10-860, and JP-A-11-43619. As a result of repeated studies, the present invention has been achieved. That is, according to the present invention, a polyphyrazine compound represented by the following general formula (I) is provided.
[Chemical 6]
[In the above formula, X₁~ X₄Each independently represents a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted phenyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted aryloxy group, and Y₁~ Y₄Each independentlyIt represents a hetero five-membered ring represented by the following general formula (III).Mt represents two hydrogen atoms, or represents a divalent, trivalent, or tetravalent metal atom optionally having an oxygen, halogen atom, or other ligand]
[Chemical 7]
[In the above formula, Z ₅ ~ Z ₇ Is a substituted or unsubstituted carbon atom or nitrogen atom that forms a hetero five-membered ring together with the carbon atom or nitrogen atom to which it is bonded. However, Z ₅ ~ Z ₇ Are not all carbon atoms and are bonded to the porphyrazine ring at the nitrogen atom. Z ₈ ~ Z ₁₁ Represents a carbon atom or a nitrogen atom, Z ₈ ~ Z ₁₁ Two or more of them are carbon atoms. W ₁ ~ W ₄ Are each independently a hydrogen atom, halogen atom, nitro group, cyano group, hydroxyl group, carboxy group, substituted or unsubstituted alkyl group, substituted or unsubstituted alkoxy group, substituted or unsubstituted aryl group, substituted or unsubstituted Represents an amino group or a substituted or unsubstituted acyl group]
[0007]
The compound of the present invention has the following features due to the effect of its unique substituent. First, since the solubility in an organic solvent is high, it is easy to form a recording film by a solvent coating method. Further, since it has an absorption maximum at a short wavelength as compared with a dye used for a CD-R recording layer, it can be applied to a high-density optical disk system using a semiconductor laser having a short oscillation wavelength. Moreover, since the light resistance and storage stability are high, the stored information is excellent in storage stability. Furthermore, since the decomposition temperature is moderately low and the decomposition speed is high, it is possible to increase the sensitivity and speed of recording. Moreover, although it has such an appropriate thermal decomposability, it can be synthesized in a high yield by using a production method as described below.
[0008]
The porphyrazine compound of the present invention is not necessarily impossible to synthesize by a conventionally known method for synthesizing a porphyrazine derivative, but if a method such as that shown in the present invention is used, it is extremely easy to obtain a high yield. Can be synthesized.
In the synthesis of porphyrazine compounds, in many cases, side reactions and decomposition reactions are likely to occur during the ring formation reaction. Therefore, in the present invention, side reactions and decomposition are less likely to occur during ring formation. A method for obtaining various porphyrazine derivatives by first synthesizing such a porphyrazine compound and then converting the fluorine-substituted alkoxy group of the compound into another substituent is proposed. As a result, even a porphyrazine derivative with low thermal stability can be easily synthesized without reducing the yield.
[Chemical 6]
[In the above formula, X1 to X4 and Mt represent the same as those in the general formula (I). R represents an alkoxy group in which part or all of hydrogen is fluorine-substituted]
[0009]
The above general formula (I) representing the compound of the present invention is more specifically represented by the following formulas (Ia) to (Id). These represent isomer structures and are usually formed as a mixture in a single reaction and can be used in various applications as a mixture, but each can also be isolated and used as necessary. It is.
[Chemical 7]
[0010]
Examples of the alkyl group in the general formula (I) and the general formulas (II) and (III) and the alkyl group in the alkoxy group include a methyl group, an ethyl group, an n-propyl group, an n-butyl group, Isobutyl group, n-pentyl group, neopentyl group, isoamyl group, 2-methylbutyl group, n-hexyl group, 2-methylpentyl group, 3-methylpentyl group, 4-methylpentyl group, 2-ethylbutyl group, n-heptyl Group, 2-methylhexyl group, 3-methylhexyl group, 4-methylhexyl group, 5-methylhexyl group, 2-ethylpentyl group, n-octyl group, 2-methylheptyl group, 3-methylheptyl group, 4 -Primary alkyl group such as methylheptyl group, 5-methylheptyl group, 2-ethylhexyl group, n-nonyl group, n-decyl group, isopropyl group, sec-butyl group, -Ethylpropyl group, 1-methylbutyl group, 1,2-dimethylbutyl group, 1,3-dimethylbutyl group, 1-ethyl-2-methylpropyl group, 1-methylhexyl group, 1-ethylpentyl group, 1-propyl Butyl group, 1-isopropyl-2-methylpropyl group, 1-ethyl-2-methylbutyl group, 1-isopropylbutyl group, 1-methylheptyl group, 1-ethylhexyl group, 1-propylpentyl group, 1-isopropylpentyl group Secondary alkyl groups such as 1-propyl-2-methylbutyl group, 1-methyloctyl group, 1-ethylheptyl group, 1-propylhexyl group, 1-isobutyl-3-methylbutyl group, tert-butyl group, tert- Tertiary alkyl groups such as amyl group, tert-heptyl group, tert-octyl group, cyclopentyl group, cycl Hexyl group, methylcyclohexyl group, dimethylcyclohexyl group, such as cycloalkyl groups such as cycloheptyl group, and these alkyl groups may be substituted by a halogen atom or other substituents.
[0011]
As the aryl group, phenyl group, methylphenyl group, dimethylphenyl group, trimethylphenyl group, ethylphenyl group, butylphenyl group, tert-butylphenyl group, di (tert-butyl) phenyl group, methoxyphenyl group, dimethoxyphenyl Group, trimethoxyphenyl group, butoxyphenyl group, naphthyl group and the like, and these aryl groups may be substituted with a halogen atom or other substituents.
[0012]
Examples of Y1 to Y4 in the general formula (I) include hetero five-membered ring system substituents such as imidazolyl group, pyrazolyl group, triazolyl group and tetrazolyl group, and these include various alkyl groups as described above. And may be substituted with a substituent such as an aryl group or a halogen atom. The hetero five-membered ring may be condensed with another aromatic ring, and a part of the aromatic ring may be substituted with a hetero atom such as nitrogen. More specific examples of such heterocyclic substituents include the following. That is, an imidazolyl group, 2-methylimidazolyl group, 4 or 5-methylimidazolyl group, 2-phenylimidazolyl group, 4 or 5-phenylimidazolyl group, 4,5-diphenylimidazolyl group, 4 or 5-nitroimidazolyl group, 4 Or 5- (methoxycarbonyl) imidazolyl group, 4 or 5- (ethoxycarbonyl) -5 or 4-methylimidazolyl group, 4 or 5-bromoimidazolyl group, 4,5-dicyanoimidazolyl group, pyrazolyl group, 3 or 5- Methylpyrazolyl group, 3,5-dimethylpyrazolyl group, 3,5-bis (trifluoromethyl) pyrazolyl group, 4-bromopyrazolyl group, 1,2,3-triazolyl group, 4-bromo-1,2,3- Triazolyl group, 1,2,4-triazolyl group, tetrazolyl group, 5-methyltetrazo Group, 5-phenyltetrazolyl group, benzoimidazolyl group, 2-methylbenzimidazolyl group, 5,6-dimethylbenzimidazolyl group, 5,6-dimethoxybenzimidazolyl group, 5 or 6-chlorobenzoimidazolyl group, 5 or 6-nitrobenzimidazolyl Group, 5 or 6-cyanobenzimidazolyl group, 5 or 6- (ethoxyethoxy) benzimidazolyl group, naphthimidazolyl group, 4 or 7-azabenzimidazolyl group, 4,6 or 5,7-diazabenzimidazolyl group, indazolyl group, 1 2,3-benzotriazolyl group, 5 or 6-chloro-1,2,3-benzotriazolyl group, 5 or 6-bromo-1,2,3-benzotriazolyl group, 5 or 6 -Fluoro-1,2,3-benzotriazolyl group, 5 or 6- (trifluoro (Romethyl) -1,2,3-benzotriazolyl group, 5,6-difluoro-1,2,3-benzotriazolyl group, 4 or 7-aza-1,2,3-benzotriazolyl group 5 or 6-aza-1,2,3-benzotriazolyl group and the like.
[0013]
Examples of Mt in the compound of the general formula (I) include H₂, Cu, Ni, Zn, Co, Pd, Pt, VO, TiO, Mg, Cd, Sn, SnX₂, AlX, GaX, InX, RhX, GeX₂[X represents a monovalent ligand], SiCl₂, Si (OSiR1R2R3)₂, Si (OPOR4R5)₂, Si (OCOR6)₂[R1 to R6 each represents an alkyl group] and the like, and Cu, Ni, Zn, Co, Pd, Pt, VO, Mg, etc. are particularly preferable from the viewpoint of synthesis and physical properties.
[0014]
Specific examples of the compounds of the above general formula (I) are shown in the following table.
[Table 1]
[Table 2]
[Table 3]
[0015]
In order to synthesize the compound of general formula (I) as described above, a method of cyclizing a maleonitrile derivative having the same substituent as the target porphyrazine compound by a known method is also possible. As described above, when the method of first synthesizing the porphyrazine compound represented by the general formula (IV) and reacting it with various heterocyclic compounds, the target product is obtained in high yield.
[0016]
The porphyrazine compound represented by the general formula (IV) is a method described in the literature Zhurnal Organicheskoi Khimii, Vol.28, No.10, p.2149-2155, etc. It can also be synthesized by applying a known method as a method for synthesizing a porphyrazine derivative.
That is, a method in which a porphyrazine derivative containing magnesium at the center is prepared by heating a maleonitrile derivative and magnesium alkoxide in an alcohol solvent, and the central metal is later replaced, or the maleonitrile derivative is converted to urea and metal in the presence of ammonium molybdate. A method of heating together with a chloride, or a method of heating a maleonitrile derivative and a metal chloride in an alcohol solvent in the presence of a basic substance such as sodium alkoxide, potassium alkoxide, DBU or the like. In any case, it is possible to use a single type or a plurality of types of maleonitrile derivatives. When a plurality of types are used, compounds in which X1 to X4 in the general formula (IV) are not the same are obtained.
[0017]
More specifically, the structure of the compound of the general formula (IV) is represented by the following formulas (IV-a) to (IV-d). These represent isomer structures, and they are usually produced as a mixture in a single reaction and can be used as they are, but they can also be isolated and used as necessary.
[Chemical 8]
[0018]
Specific examples of the compound of the general formula (IV) include those shown in the following table.
[Table 4]
[0019]
Specific examples of the heterocyclic compound that reacts with the compound of the general formula (IV) to give the compound of the general formula (I) include azole compounds as shown in the following table.
[Table 5]
[0020]
The amount of these heterocyclic compounds used in the reaction may be 1 mole or more, preferably 4 moles or more per mole of the porphyrazine compound, but may be used in excess thereof in order to increase the reaction rate. It is also possible to accelerate the reaction by removing the fluorinated alcohol produced during the reaction by vacuum distillation or the like.
[0021]
The kind of the heterocyclic compound used in the reaction may be single or plural, and when a plurality of heterocyclic compounds are used, a compound in which Y1 to Y4 in the general formula (I) are not the same can be obtained. If the amount of the heterocyclic compound used is less than 4 moles per mole of porphyrazine, a compound in which Y1 to Y4 are not the same and a heterocyclic substituent and a fluorine-substituted alkoxy group are mixed can be obtained.
In addition, even when a single heterocyclic compound is reacted, the reaction position on the heterocyclic ring may be different. In this case, compounds in which Y1 to Y4 are not the same but are in a structural isomerism relationship with each other can be obtained. Compound No. 1 in Table 1 above. The structure notation such as P-4, P-9 to 18, Q-1 represents this last case.
[0022]
This reaction is promoted by a basic substance. For example, the following can be used as inorganic bases. That is, potassium carbonate, sodium carbonate, calcium carbonate, sodium hydrogen carbonate, sodium acetate, sodium nitrite, potassium nitrite, sodium sulfite and the like. These may be anhydrides or hydrates, but it is preferable to use anhydrides to prevent hydrolysis during the reaction. As the organic base, triethylamine, tributylamine, diazabicycloundecene (DBU) and the like can be used, and alkoxides such as potassium tert-butoxide and sodium tert-butoxide can also be used. The base may be used in an amount of 1 equivalent or more, but it may be used in excess.
[0023]
The reaction solvent is not particularly limited, but N, N-dimethylformamide, N, N-dimethylacetamide, dimethyl sulfoxide, sulfolane, diethyl ether, tetrahydrofuran, 1,4-dioxane, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, acetone An aprotic solvent having a high dielectric constant such as methyl butyl ketone, ethyl acetate and butyl acetate is preferred.
[0024]
Although reaction temperature can be selected from the range of 0-150 degreeC according to the kind of reaction material and solvent, Preferably it is room temperature-100 degreeC. At lower temperatures, the reaction is slow, and at higher temperatures, decomposition tends to occur.
[0025]
【Example】
Hereinafter, the present invention will be specifically described with reference to examples. First, a synthesis example of the compound of the general formula (IV) will be shown, then a synthesis example of the compound of the general formula (I) will be shown, and finally, an example of making an optical disk using the compound of the general formula (I) will be shown. I will decide.
[0026]
1. Synthesis of compounds of general formula (IV)
Synthesis example 1
Synthesis of Compound A-1
Operation 1) Synthesis of 1-tert-butyl-2-chloro-1,2-dicyanoethylene 11.3 g (0.15 mol) of chloroacetonitrile and pivaloyl cyanide in a reaction flask equipped with a condenser and a stirrer. 7 g (0.15 mol) and 450 ml of dichloromethane were charged and cooled to 0 ° C. with stirring. While stirring this, 84.1 g (0.45 mol) of titanium tetrachloride was added dropwise over 90 minutes while maintaining the temperature of -5 ° C to 0 ° C. After stirring for 5 minutes, 91 g (0.90 mol) of N-methylmorpholine was added dropwise at −10 to 0 ° C. for 3 hours. After stirring for 30 minutes, cooling was stopped and stirring was performed for 3 hours while returning to room temperature. Stirring was stopped, the reaction solution was poured into 1000 ml of ice water, 200 ml of chloroform was added and stirred, and then transferred to a separatory funnel to separate the organic layer. The organic layer was washed with water, dried over magnesium sulfate. After filtering off magnesium sulfate, the organic layer was concentrated with an evaporator to obtain 18.9 g of a residual oil. This was purified by silica gel column chromatography (developing solvent toluene) to obtain 14.7 g of the desired product. Two peaks presumed to be a cis form and a trans form, respectively, were detected by GC analysis, and the area ratio was 12:88. A molecular ion peak (m / e 169) was confirmed for each component by GC / MS analysis.
In addition, the cis isomer (maleonitrile) and the trans isomer (fumaronitrile) of the dicyanoethylene derivative as described above are distinguished from each other by carrying out a cyclization reaction to produce a porphyrazine dye. Can be identified as a trans form. However, in the reaction of the present invention, the cis isomer and trans isomer can be used as they are without being separated, and this is also the case in the following synthesis examples.
[0027]
Operation 2) Synthesis of 1-tert-butyl-2- (2,2,2-trifluoroethoxy) -1,2-dicyanoethylene
A reaction flask was charged with 6.4 g (0.064 mol) of 2,2,2-trifluoroethanol, 53 ml of N, N-dimethylformamide (hereinafter abbreviated as DMF), and 8.8 g (0.064 mol) of anhydrous potassium carbonate. 1-tert-butyl-2-chloro-1,2-dicyanoethylene (9.0 g, 0.053 mol) obtained in the operation 1) was charged over 1 hour with stirring. After stirring for 4 hours, the mixture was poured into 500 ml of water and extracted with 80 ml of toluene. The extract was washed with water and concentrated with an evaporator. The remaining oil was allowed to stand and gradually crystallized. The yield was 11.6 g and the yield was 94%. Two peaks estimated to be a cis form and a trans form, respectively, were detected by GC analysis, and the area ratio was 78:22. A molecular ion peak (m / e 232) was confirmed for each component by GC / MS analysis.
[0028]
Operation 3) Synthesis of tetra-tert-butyl-tetrakis (2,2,2-trifluoroethoxy) copper porphyrazine (Compound A-1)
11.6 tert-butyl-2- (2,2,2-trifluoroethoxy) -1,2-dicyanoethylene obtained in operation 2) in a reaction flask 11.6 g (0.05 mol), 2,2,2 -100 ml of trifluoroethanol, 2.3 g (0.05 mol) of formamide, and 5.6 g (0.05 mol) of potassium tert-butoxide were added and stirred at 50 ° C for 30 minutes. The cuprous chloride 1.4g (0.014mol) was prepared there, and it heated up at 80 degreeC, stirring, filled nitrogen gas in the system, and stirred at 75-80 degreeC for 15 hours. After stopping the heating and cooling to room temperature, the reaction solution was poured into 400 ml of water, and the precipitated crystals were collected by filtration and dried. This was purified by silica gel column chromatography (developing solvent n-hexane: toluene = 20: 1) to obtain the desired dye. The yield was 5.0 g and the yield was 40%. A molecular ion peak (m / e992) was confirmed by LC / MS.
[0029]
Synthesis example 2
Synthesis of Compound A-2
In the same manner as in Synthesis Example 1 except that anhydrous nickel chloride having the same mole number was used instead of cuprous chloride in Synthesis Example 1 and Operation 3), 1.8 g of the target dye was obtained.
[0030]
Synthesis example 3
Synthesis of Compound A-3
Procedure 1) Synthesis of tetra-tert-butyl-tetrakis (2,2,2-trifluoroethoxy) magnesium porphyrazine
A reaction flask was charged with 160 ml of 1-propanol, 1.9 g (0.078 mol) of magnesium, and 10 mg of iodine, and stirred at the reflux temperature of the solvent for 6 hours. It was once cooled and 37 g of 1-tert-butyl-2- (2,2,2-trifluoroethoxy) -1,2-dicyanoethylene obtained by the same operation as in operation 2) of Synthesis Example 1 (0. 16 mol), and then heated again and stirred at 90 ° C. for 4 hours, and then the heating was stopped. A small amount of the reaction solution was taken and thin layer chromatography confirmed the formation of a blue dye component.
[0031]
Operation 2) Synthesis of tetra-tert-butyl-tetrakis (2,2,2-trifluoroethoxy) porphyrazine
While stirring the reaction liquid in operation 1), the reaction liquid was cooled to 0 ° C., and 160 g of trifluoroacetic acid was gradually added thereto and stirred at 5 ° C. or lower for 1 hour. After cooling, the reaction solution was poured into 2000 ml of water, and 200 ml of ethyl acetate was added and stirred. The organic layer was separated with a separatory funnel, washed with water, and then concentrated with an evaporator. The residue was purified by silica gel column chromatography (developing solvent n-hexane: toluene = 10: 1) to obtain 11 g of a dye.
[0032]
Operation 3) Synthesis of tetra-tert-butyl-tetrakis (2,2,2-trifluoroethoxy) zinc porphyrazine (Compound A-3)
In a reaction flask, 0.89 g (0.96 mmol) of the metal-free dye obtained in operation 2), 7 ml of DMF, 0.60 g (2.7 mmol) of zinc acetate dihydrate, and a catalytic amount of ammonium molybdate tetrahydrate. Was stirred at 80 ° C. for 2 hours. Thereafter, the reaction solution was diluted with water, and the precipitated crystals were collected by filtration and dried, and purified by silica gel column chromatography (developing solvent toluene) to obtain 0.88 g of a dye. A molecular ion peak (m / e993) was confirmed by LC / MS.
[0033]
Synthesis example 4
Synthesis of Compound A-4
1.1 g of the target dye was obtained in the same manner as in Synthesis Example 3 except that the same molar number of anhydrous cobalt (II) chloride was used in place of zinc acetate dihydrate in Operation 3) of Synthesis Example 3.
[0034]
Synthesis example 5
Synthesis of Compound A-5
0.91 g of the target dye was obtained in the same manner as in Synthesis Example 3 except that palladium chloride and sodium acetate of the same mole number were used in place of the zinc acetate dihydrate of Synthesis Example 3 and Operation 3).
[0035]
Synthesis Example 6
Synthesis of Compound A-6
In the same manner as in Synthesis Example 3 except that platinum chloride having the same number of moles was used instead of the zinc acetate dihydrate in Synthesis Example 3 and Operation 3), 0.34 g of the target dye was obtained.
[0036]
Synthesis example 7
Synthesis of Compound A-7
In the same manner as in Synthesis Example 3 except that vanadium trichloride having the same number of moles was used instead of the zinc acetate dihydrate of Synthesis Example 3 and Operation 3), 1.3 g of the target dye was obtained.
[0037]
Synthesis Example 8
Synthesis of Compound A-8
Operation 1) Synthesis of 1-tert-butyl-2- (2,2,3,3,3-pentafluoropropoxy) -1,2-dicyanoethylene
The same number of moles of 2,2,3,3,3-pentafluoropropanol was used in place of 2,2,2-trifluoroethanol in the operation 2) of Synthesis Example 1, and the other operations were the same as the operation 2) of Synthesis Example 1. The same operation was performed to obtain the desired dicyanoethylene derivative in a yield of 96%. Two peaks estimated to be a cis form and a trans form, respectively, were detected by GC analysis, and the area ratio was 67:33. A molecular ion peak (m / e 282) was confirmed for each component by GC / MS analysis.
[0038]
Operation 2) Synthesis of tetra-tert-butyl-tetrakis (2,2,3,3,3-pentafluoropropoxy) copper porphyrazine (compound A-8)
5.6 g (0.02 mol) of 1-tert-butyl-2- (2,2,3,3,3-pentafluoropropoxy) -1,2-dicyanoethylene obtained in operation 1) was added to the reaction flask. , 2,3,3,3-pentafluoropropanol, 0.9 g (0.02 mol) formamide, and 2.2 g (0.02 mol) potassium tert-butoxide were added and stirred at 50 ° C. for 30 minutes. Thereto was added 0.56 g (0.0057 mol) of cuprous chloride, the temperature was raised to 80 ° C. while stirring, the system was filled with nitrogen gas, and the mixture was stirred at 75-80 ° C. for 15 hours. After stopping the heating and cooling, the reaction solution was poured into 300 ml of water, and the precipitated crystals were collected by filtration and dried. This was purified by silica gel column chromatography (developing solvent n-hexane: toluene = 30: 1) to obtain the desired dye. The yield was 2.1 g and the yield was 35%. A molecular ion peak (m / e 1192) was confirmed by LC / MS.
[0039]
Synthesis of Compound A-9
Operation 1) Synthesis of 1-chloro-2-phenyl-1,2-dicyanoethylene
A reaction flask equipped with a condenser and a stirrer was charged with 11.3 g (0.15 mol) of chloroacetonitrile, 19.7 g (0.15 mol) of benzoylcyanide and 450 ml of dichloromethane, and cooled to 0 ° C. with stirring. To this, 84.1 g (0.45 mol) of titanium tetrachloride was added dropwise over 90 minutes while maintaining a temperature of -5 ° C to 0 ° C. After stirring for 5 minutes, 91 g (0.90 mol) of N-methylmorpholine was added dropwise at −10 to 0 ° C. for 3 hours. After stirring for 30 minutes, cooling was stopped and stirring was performed overnight at room temperature. Stirring was stopped, the reaction solution was poured into 1000 ml of ice water, 200 ml of chloroform was added and stirred, and then transferred to a separatory funnel to separate the organic layer. The organic layer was washed with water, separated, dried over magnesium sulfate. After filtering off magnesium sulfate, the solvent was distilled off with an evaporator to obtain 21.3 g of a residual oil content. This was purified by silica gel column chromatography (developing solvent toluene) to obtain 18.4 g of the desired product. Two peaks presumed to be a cis isomer and a trans isomer, respectively, were detected by GC analysis, and the area ratio was 14:86. A molecular ion peak (m / e189) was confirmed for each component by GC / MS analysis.
[0040]
Operation 2) Synthesis of 1-phenyl-2- (2,2,2-trifluoroethoxy) -1,2-dicyanoethylene
The reaction flask was charged with 6.4 g (0.064 mol) of 2,2,2-trifluoroethanol, 50 ml of DMF, and 8.8 g (0.064 mol) of anhydrous potassium carbonate, and stirred at room temperature. -Chloro-2-phenyl-1,2-dicyanoethylene 10 g (0.053 mol) was charged over 30 minutes. After stirring for 4 hours, the mixture was poured into 500 ml of water and extracted with 100 ml of toluene. The extract was washed with water and concentrated with an evaporator to obtain the desired product. The yield was 12 g and the yield was 90%. Two peaks estimated to be a cis form and a trans form, respectively, were detected by GC analysis, and the area ratio was 71:29. A molecular ion peak (m / e 252) was confirmed for each component by GC / MS analysis.
[0041]
Operation 3) Synthesis of tetraphenyl-tetrakis (2,2,2-trifluoroethoxy) copper porphyrazine (Compound A-9)
12.6 g (0.05 mol) of 1,2-phenyl-2- (2,2,2-trifluoroethoxy) -1,2-dicyanoethylene obtained in operation 2) was added to the reaction flask. 100 ml of fluoroethanol, 2.3 g (0.05 mol) of formamide and 5.6 g (0.05 mol) of potassium tert-butoxide were charged and stirred at 50 ° C. for 30 minutes. Thereto was added 1.4 g (0.014 mol) of cuprous chloride, the temperature was raised to 80 ° C. while stirring, the system was filled with nitrogen gas, and the mixture was stirred at 75-80 ° C. for 16 hours. After stopping the heating and cooling to room temperature, the reaction solution was poured into 300 ml of water, and the precipitated crystals were collected by filtration and dried. This was purified by silica gel column chromatography (developing solvent n-hexane: toluene = 20: 1) to obtain the desired dye. The yield was 4.1 g and the yield was 31%. A molecular ion peak (m / e1072) was confirmed by LC / MS.
[0042]
2. Synthesis of compounds of general formula (I)
Example 1
Synthesis of tetra-tert-butyl-tetriimidazolyl copper porphyrazine (compound P-1)
A reaction flask equipped with a condenser and a stirrer was charged with 0.99 g (1 mmol) of compound A-1, 0.68 g (10 mmol) of imidazole, 0.69 g (5 mmol) of anhydrous potassium carbonate, and 15 ml of DMF and heated while stirring. And stirred at 50 ° C. for 4 hours. Heating and stirring were stopped, and the reaction solution was poured into 500 ml of water and extracted with 100 ml of chloroform. The extract was transferred to a separatory funnel, washed with 1% aqueous sodium hydroxide solution, and further washed repeatedly with water. The organic layer was then concentrated with an evaporator, and the residue was subjected to silica gel column chromatography (developing solvent chloroform: methanol = 30: 1). ) To obtain 0.64 g of a dye. A molecular ion peak (m / e864) was confirmed by LC / MS. This compound was dissolved in an organic solvent such as ethanol, tetrahydrofuran, ethyl acetate, chloroform, 2-ethoxyethanol or the like at 1% or more at room temperature. The absorption maximum wavelength in chloroform was 595 nm, and the molar extinction coefficient at that wavelength was 140000. The infrared absorption spectrum of this compound is shown in FIG. When this compound was subjected to differential scanning calorimetry (hereinafter abbreviated as DSC), an endothermic peak such as an extrapolation start temperature (hereinafter abbreviated as Tid) of 380 ° C. and a peak temperature (hereinafter abbreviated as Tpd) of 395 ° C. was observed. Further, in thermogravimetric analysis (hereinafter abbreviated as TGA), a weight loss curve such as an extrapolated weight loss starting temperature (hereinafter abbreviated as Tig) of 370 ° C. was observed. These thermal analyzes were conducted under a nitrogen atmosphere at a heating rate of 10 ° C./min.
[0043]
Example 2
Synthesis of tetra-tert-butyl-tetrapyrazolyl copper porphyrazine (compound P-2)
Into a reaction flask, 0.99 g (1 mmol) of compound A-1, 0.41 g (6 mmol) of pyrazole, 0.69 g (5 mmol) of anhydrous potassium carbonate, and 15 ml of DMF were charged and heated with stirring and stirred at 50 ° C. for 6 hours. . Heating and stirring were stopped, and the reaction solution was poured into 500 ml of water and extracted with 100 ml of ethyl acetate. The extract was transferred to a separatory funnel, washed with 1% aqueous sodium hydroxide solution and repeatedly washed with water. The organic layer was concentrated with an evaporator and purified by silica gel column chromatography (developing solvent: toluene: methanol = 50: 1). As a result, 0.59 g of a dye was obtained. A molecular ion peak (m / e864) was confirmed by LC / MS. This compound was dissolved in an organic solvent such as ethanol, tetrahydrofuran, ethyl acetate, chloroform, 2-ethoxyethanol or the like at 1% or more at room temperature. The absorption maximum wavelength in chloroform was 595 nm. For this compound, an endothermic peak at Tid = 382 ° C. and Tpd = 394 ° C. was observed by DSC, and a weight loss curve at Tig = 400 ° C. was observed by TGA.
[0044]
Example 3
Synthesis of tetra-tert-butyl-tetrabenzotriazolyl nickel porphyrazine (compound Q-1)
A reaction flask was charged with 0.99 g (1 mmol) of compound A-2, 1.4 g (12 mmol) of 1,2,3-benzotriazole, 0.83 g (6 mmol) of anhydrous potassium carbonate, and 15 ml of DMF and heated while stirring. Stir at 75 ° C. for 4 hours. Heating and stirring were stopped, and the reaction solution was poured into 500 ml of water and extracted with 100 ml of toluene. The extract was transferred to a separatory funnel, washed with a 1% aqueous sodium hydroxide solution, and further washed repeatedly with water. The organic layer was then concentrated with an evaporator, and the residue was subjected to silica gel column chromatography (developing solvent toluene: ethyl acetate = 20: 1 to 10: 1) to obtain 0.82 g of a dye. Molecular ion peak (m / e1063) was confirmed by LC / MS. Moreover, the analysis result of 1H-NMR (300 MHz, CDCl3) was as follows. δ (ppm from TMS) 1.19-1.38 (18H, m), 1.96-2.15 (18H, m), 6.83-7.07 (2H, m), 7.24-7 .62 (10H, m), 7.81-8.04 (2H, m), 8.31-8.44 (2H, m). This compound was dissolved in 2-ethoxyethanol by 1% or more at room temperature. The maximum absorption wavelength in chloroform was 598 nm. With this compound, an exothermic peak with Tid = 275 ° C. and Tpd = 295 ° C. was observed by DSC, and a weight loss curve with Tig = 307 ° C. was observed by TGA.
[0045]
Example 4
Synthesis of tetra-tert-butyl-tetrabenzotriazolyl copper porphyrazine (compound P-4)
The compound A-1 was used in place of the compound A-2 in the operation of Example 3, and 0.70 g of a dye was obtained in the same manner as in Example 3. A molecular ion peak (m / e 1068) was confirmed by LC / MS. This compound was dissolved in 2-ethoxyethanol by 1% or more at room temperature. The absorption maximum wavelength in chloroform was 599 nm, and the molar extinction coefficient at that wavelength was 150,000. With respect to this compound, an exothermic peak with Tid = 275 ° C. and Tpd = 295 ° C. was observed by DSC, and a decrease in Tig = 305 ° C. was observed with TGA. The infrared absorption spectrum of this compound is shown in FIG.
[0046]
Examples 5-25
The reaction examples similar to the above are shown in the table below together with the values of Examples 1 to 4.
[0047]
[Table 6]
[0048]
The maximum absorption wavelength λmax of the porphyrazine compound obtained above in chloroform is shown in the table below.
[Table 7]
[0049]
Comparative Example 1 (Comparative Example of Compound)
Synthesis of octaphenyl copper porphyrazine.
A reaction flask was charged with 1.7 g (7.5 mmol) of 1,2-diphenylmaleonitrile, 0.36 g (7.9 mmol) of formamide, 0.9 g (7.9 mmol) of potassium tert-butoxide, and 20 ml of 1-propanol. While stirring, the temperature was raised to 50 ° C. and stirred for 30 minutes. Furthermore, it heated to 90 degreeC, 0.25 g (2.5 mmol) of cuprous chloride was added, and it stirred at 100 degreeC under nitrogen atmosphere for 5 hours. After allowing to cool, the reaction solution was poured into water, and the precipitated crystals were collected by filtration and dried. This was purified by silica gel column chromatography (developing solvent toluene) to obtain 0.087 g of a dye. The yield was 4.7%. This compound has low solubility in organic solvents, for example, solubility in 2-ethoxyethanol was less than 0.1% at room temperature.
[0050]
Comparative Example 2 (Comparative Example of Manufacturing Method)
Synthesis of Compound P-1
Operation 1) Synthesis of 1-tert-butyl-2-imidazolyl-1,2-dicyanoethylene
The reaction flask was charged with 13.6 g (0.2 mol) of imidazole, 60 ml of DMF, and 9.8 g (0.071 mol) of anhydrous potassium carbonate, and 1-tert obtained in the same manner as in Operation 1) of Synthesis Example 1). -10 g (0.06 mol) of butyl-2-chloro-1,2-dicyanoethylene was charged. The temperature was raised to 60 ° C., stirred for 5 hours, poured into 500 ml of water, and extracted with chloroform. The extract was washed with water and concentrated with an evaporator to obtain an oil. The yield was 2.5 g and the yield was 21%. Two peaks presumed to be isomers were detected by GC analysis, and molecular ion peaks (m / e200) were confirmed for each component by GC / MS analysis.
[0051]
Operation 2) Synthesis of Compound P-1
To the reaction flask, 2.0 g (0.01 mol) of 1-tert-butyl-2-imidazolyl-1,2-dicyanoethylene obtained in operation 1), 25 ml of 1-pentanol, and 1.5 g (0.01 mol) of DBU were added. The temperature was raised to 80 ° C. while charging and stirring. Thereto was added 0.30 g (0.003 mol) of cuprous chloride, the temperature was raised to 100 ° C. while stirring, and the mixture was stirred at 100 ° C. for 5 hours in a nitrogen atmosphere. When a small amount of the reaction solution was collected and analyzed by thin layer chromatography, many brown components presumed to be decomposed products were detected. On the other hand, almost no pigment component was produced, and the synthesis was unsuccessful.
[0052]
In analyzing the compounds of the above Examples and Comparative Examples, the following analyzers were used.
GC / MS: GCMS-QP2000GF manufactured by Shimadzu Corporation
LC / MS: LCMS-QP8000 manufactured by the same company
IR: FTIR-8000PC manufactured by the company
DSC: Company DSC-50
TGA: TGA-50 manufactured by the company
NMR: FT-NMR spectrometer Λ300 manufactured by JEOL Ltd.
[0053]
3. Example of optical disc creation
Example d-1
Compound No. The porphyrazine compound represented by P-7 is dissolved 1.8% in ethylcyclohexane, and the above solution is spin-coated on a polycarbonate substrate having a track pitch of 0.74 μm, a groove width (half value) of 0.28 μm, and a depth of 1700 mm. As a result, a homogeneous film having a thickness of 900 to 400 mm was obtained, and a disk was prepared by sputtering Au with 1000 mm and further providing a protective layer with an acrylic photopolymer. The above disk was recorded and reproduced satisfactorily by a disk evaluation apparatus having a pickup of 635 nm and NA = 0.6.
[0054]
Example d-2
Compound No. The porphyrazine compound represented by P-1 was dissolved in a mixed solvent of ethylcyclohexane / 1-methoxy-2-propanol = 1/1 (weight ratio) 1.8%, and the solution was mixed with a track pitch of 0.74 μm and a groove width ( (Half-value) A homogenous film of 900 to 600 mm is obtained by spin-coating on a polycarbonate substrate having a depth of 0.28 μm and a depth of 1700 mm, and a disk on which a protective layer is formed by sputtering 1000 μg of Au and acrylic photopolymer. It was created. The above disk was recorded and reproduced satisfactorily by a disk evaluation apparatus having a pickup of 635 nm and NA = 0.6.
[0055]
Example d-3
Compound No. A porphyrazine compound represented by P-4 is dissolved in an ethylcyclohexane / 1-methoxy-2-butanol = 1/1 (weight ratio) mixed solvent at 2.0%, and the solution is mixed with a track pitch of 0.74 μm and a groove width ( (Half-value) A homogenous film of 900 to 600 mm is obtained by spin-coating on a polycarbonate substrate having a depth of 0.28 μm and a depth of 1700 mm, and a disk on which a protective layer is formed by sputtering 1000 μg of Au and acrylic photopolymer. It was created. The above disk was recorded and reproduced satisfactorily by a disk evaluation apparatus having a pickup of 635 nm and NA = 0.6.
[0056]
Comparative Example d-1
The octaphenyl copper porphyrazine synthesized in Comparative Example 1 was dissolved in ethylcyclohexane and a mixed solvent of ethylcyclohexane and cellosolve used in Examples d-1 to 3 above, but all had a solubility of 0.3% or less. In addition, it was impossible to form a film on a polycarbonate by a solvent coating method.
[0057]
【The invention's effect】
Since the novel porphyrazine compound of the present invention has an absorption maximum at a short wavelength as compared with a dye used in a CD-R recording layer, it can be applied to a high-density optical disk system using a semiconductor laser having a short oscillation wavelength. is there. Further, when this porphyrazine compound is applied to an optical recording medium, it has excellent light resistance and storage stability, and therefore, the recorded information has excellent storage stability. Furthermore, since the decomposition temperature is moderately low and the decomposition speed is high, it is possible to increase the sensitivity and speed of recording.
Moreover, according to the manufacturing method of the porphyrazine compound of this invention, it becomes possible to synthesize | combine with a high yield, although the porphyrazine compound has moderate thermal decomposability.
[Brief description of the drawings]
1 is an infrared absorption spectrum of the porphyrazine compound synthesized in Example 1. FIG.
2 is an infrared absorption spectrum of the porphyrazine compound synthesized in Example 4. FIG.

Claims (8)

A porphyrazine compound represented by the following general formula (I):
[Wherein, X _{1 to} X ₄ each independently represents a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted phenyl group, a substituted or unsubstituted alkoxy group, or a substituted or unsubstituted aryl. Represents an oxy group, and Y _{1 to} Y ₄ each independently represents a hetero five-membered ring represented by the following general formula (III). Mt represents two hydrogen atoms, or represents a divalent, trivalent, or tetravalent metal atom optionally having an oxygen, halogen atom, or other ligand]
[In the above formula, Z _{5 to} Z ₇ are each a substituted or unsubstituted carbon atom or nitrogen atom which forms a hetero five-membered ring together with the carbon atom or nitrogen atom to which each is bonded. However, Z _{5 to} Z ₇ are not all carbon atoms and are bonded to the porphyrazine ring at the nitrogen atom. Z _{8 to} Z ₁₁ represent a carbon atom or a nitrogen atom, and two or more of Z _{8 to} Z ₁₁ are carbon atoms. W _{1 to} W ₄ are each independently a hydrogen atom, halogen atom, nitro group, cyano group, hydroxyl group, carboxy group, substituted or unsubstituted alkyl group, substituted or unsubstituted alkoxy group, substituted or unsubstituted aryl group, Represents a substituted or unsubstituted amino group or a substituted or unsubstituted acyl group] The porphyrazine compound according to claim 1 , wherein X _{1 to} X ₄ are each independently a substituted or unsubstituted alkyl group. Porphyrazine compound according to any one of claims 1-2, characterized in that X ₁ to X ₄ is a branched alkyl group having a substituted or unsubstituted independently. The porphyrazine compound according to any one of claims 1 to 3 , wherein X _{1 to} X ₄ are all the same substituent. The porphyrazine compound according to any one of claims 1 to 4 , wherein Y _{1 to} Y ₄ are all the same or have a relation of structural isomerism. The porphyrazine compound according to any one of claims 1 to 5 , wherein Mt is any one of Cu, Ni, Zn, Pd, Pt, VO, Co, and Mg. A method for producing a porphyrazine compound according to any one of claims 1 to 6 , wherein a porphyrazine compound represented by the following general formula (IV) is used as a precursor , and the complex five represented by the following general formula (IIIa): Production of a porphyrazine compound characterized by reacting a member ring compound to convert the fluorine-substituted substituent R of the general formula (IV) into a hetero five-membered ring represented by the general formula (IIIa) Method.
[Wherein, X _{1 to} X ₄ and Mt represent the same as those in the general formula (I). R represents an alkoxy group in which part or all of hydrogen is fluorine-substituted]
[In the above formula, Z _{5 to} Z ₇ are each a substituted or unsubstituted carbon atom or nitrogen atom which forms a hetero five-membered ring together with the carbon atom or nitrogen atom to which each is bonded. However, Z _{5 to} Z ₇ are not all carbon atoms and are bonded to the porphyrazine ring at the nitrogen atom. Z _{8 to} Z ₁₁ represent a carbon atom or a nitrogen atom, and two or more of Z _{8 to} Z ₁₁ are carbon atoms. W _{1 to} W ₄ are each independently a hydrogen atom, halogen atom, nitro group, cyano group, hydroxyl group, carboxy group, substituted or unsubstituted alkyl group, substituted or unsubstituted alkoxy group, substituted or unsubstituted aryl group, Represents a substituted or unsubstituted amino group or a substituted or unsubstituted acyl group] The method for producing a porphyrazine compound according to claim 7 , wherein the substituent R of the compound of the general formula (IV) used as a precursor is represented by the following formula.
R = —OCH ₂ (CF ₂ ) _n F or —OCH ₂ (CF ₂ ) _n H (wherein n represents an integer of 1 to 4)