JPH1135837A - Tetrazaporphyrin compound and its precursor, and production of tetrazaporphyrin compound - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a new compound useful for a recording material for an optical recording medium excellent in light exposure properties and shelf stability, applicable to an optical disk system for highly densified recording using semiconductor laser having oscillating wave length in the short wave range. SOLUTION: This compound is expressed by formula I [X is H or a (substituted) alkyl], e.g. 3,3-dimethyl-1,1,2-tricyano-1-butane. The compound is obtained by reacting an alkylaldehyde with malononitrile and then with potassium cyanide, followed by dehydrogenation. It is preferable to produce a tetrazaporphyrin compound of formula II [ M is two Hs, metal or a (substituted)alkyl; X<1> -X<4> are each H or a (substituted)alkyl] by reacting the compound of the formula I with a metal or its derivative.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel tetraazaporphyrin compound and a precursor thereof, and a method for producing the tetraazaporphyrin compound.
The present invention relates to a novel tetraazaporphyrin compound useful as a material for optical recording media, such as a photoelectric functional material, a recording and storage material, and a method for producing a novel alkyl-substituted tricyanoethylene compound and a tetraazaporphyrin compound which are precursors thereof.

[0002]

2. Description of the Related Art The current write-once optical disk system (WO
RM, CD-R), the oscillation wavelength of the laser used is 770.
nm to 790 nm, and the recording medium records at the above wavelength,
It is configured to be able to reproduce. In the future, it is indispensable to increase the capacity of the recording medium as the amount of information increases. Therefore, it is easily expected that the wavelength of the laser used for recording and reproduction will inevitably be shortened.

[0003] However, those using a phthalocyanine dye as a recordable optical disk recording material for data are disclosed in
1-1150243, JP-A-61-177287, JP-A-61-154888, JP-A-61-246091
JP-A-62-39286, JP-A-63-3779
No. 1, JP-A-63-39888, and the like, and those using a phthalocyanine dye as a compact disk recording material include JP-A-1-176585, JP-A-3-215466, and JP-A-4-113886. JP-A-4-226390, JP-A-5-1272, JP-A-5-171052, JP-A-5-116456, JP-A-5-69860 and JP-A-5-139944. However, it has excellent light resistance and storage stability,
At present, a recording material that can be recorded and reproduced by an optical pickup using a laser of 700 nm or less has not yet been developed.

Unsubstituted tetraazaporphyrins, which are analogous to phthalocyanines, are stable to light and heat and have high absorption, but have poor solubility in organic solvents and are difficult to be formed into thin films. Was. The synthesis of 4-substituted alkyltetraazaporphyrins is described in J. Am. Ge
n. Chem. Although it is described in USSR 1977, 47, 1954, it does not describe formation of isomers. The method for producing the α-substituted phthalocyanine is described in JP-A-3-62878 and JP-A-3-2154.
No. 66, JP-A-4-226390, JP-A-4-348
No. 168, JP-A-5-25177, etc., but there is no description of the application of tetraazaporphyrin and the possibility thereof.

[0005]

SUMMARY OF THE INVENTION Accordingly, the present invention has been made in view of the above situation, and has a high density optical disk using a semiconductor laser having an oscillation wavelength shorter than that of the conventional system. It is an object of the present invention to provide a compound useful as a recording material for an optical recording medium having excellent light resistance and storage stability which can be applied to a system and a method for producing the same.

[0006]

Means for Solving the Problems As a result of intensive studies, the present inventors have found that by providing a recording layer containing a specific tetraazaporphyrin compound as a main component, an oscillation wavelength of 700 nm can be obtained.
The present inventors have found that the compound can be applied to a high-density optical disk system using a semiconductor laser of nm or less, and that the above compound can be efficiently produced by addition of a synthesis temperature, a catalyst, and the like, and have completed the present invention.

That is, according to the present invention, first, an alkyl-substituted tricyanoethylene compound represented by the following general formula (I) is provided.

Embedded image (In the formula, X is a hydrogen atom or a linear or branched alkyl group, and may be substituted with another substituent.) Second, the following general formulas (II) -a to (II)- There is provided a halogenated tetraazaporphyrin compound comprising one or a mixture of two or more of the four compounds represented by d.

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Embedded image [Wherein, M and X ^{1 to} X ⁴ each represent the following. M: two hydrogen atoms, or a divalent, trivalent or tetravalent metal atom which may have an oxygen atom or a halogen atom,
Or a substituted or unsubstituted alkyl group, aryl group, alkoxy group, aryloxy group,-(OPR ¹¹ R ¹² ) t
^{Group, (- OPOR 13 R 14)} t group, - (OSiR ¹⁵ R ¹⁶ R
¹⁷⁾ t group, - (OCOR ¹⁸⁾ t group, - (OR ¹⁹⁾ t group,
-(OCOCOR ²⁰ ) t group,-(OCOCOR ²¹ ) t
R ^{11 to} R ²³ each independently represent a hydrogen atom, a substituted or unsubstituted monovalent aliphatic hydrocarbon group or a substituted or unsubstituted group, or a metal atom which may have a — (OCONR ²² R ²³ ) t group. A t is an integer of 0 to 2, X ^{1 to} X ⁴ are each independently a hydrogen atom or a substituted or unsubstituted linear or branched alkyl group, provided that all are hydrogen It cannot be an atom. Third, the alkyl-substituted tricyanoethylene compound represented by the general formula (I) is reacted with a metal or a metal derivative, and the general formulas (II) -a to (I)
A method for producing at least one tetraazaporphyrin compound represented by I) -d is provided. Fourthly, in the third aspect, there is provided a method for producing a tetraazaporphyrin compound, wherein the reaction is performed in an organic solvent. Fifth, in the fourth aspect, there is provided a method for producing a tetraazaporphyrin compound, wherein the organic solvent is an aromatic hydrocarbon or a halogenated aromatic hydrocarbon. Sixth, in any of the above third to fifth,
A method for producing a tetraazaporphyrin compound is provided, wherein the metal or metal derivative is a transition metal, a transition metal halide or a transition metal carboxylate. Seventh, in any one of the third to sixth aspects, the reaction temperature is 9
A method for producing a tetraazaporphyrin compound, which is performed at a temperature of 0 to 220 ° C. is provided. Eighth, in any one of the third to seventh aspects, the amount of the solvent used is 1 to 10 based on the alkyl-substituted tricyanoethylene compound.
There is provided a method for producing a tetraazaporphyrin compound, which is a 0-fold amount. Ninthly, there is provided a method for producing a tetraazaporphyrin compound according to any one of the third to eighth aspects, wherein ammonium molybdate is coexistent. Tenth, in any of the third to ninth above, after forming a ring as the central metal as Mg, metal exchange or elimination of Mg to obtain a desired metal tetraazaporphyrin or H ₂ tetraazaporphyrin A method for producing a tetraazaporphyrin compound is provided. Eleventh, in the tenth,
A tetraazaporphyrin characterized in that metal exchange or Mg elimination is carried out by coexisting at least one of an organic solvent, ammonium molybdate and an acid with the metal or metal derivative described in the sixth and Mg tetraazaporphyrin. A method for producing a compound is provided.

The above general formulas (II) -a to (II)-of the present invention
The tetraazaporphyrin represented by d has a structure in which the precursor structure does not give cis and trans structural isomers, and the desired tetraazaporphyrin can be obtained in high yield, which is very useful industrially. It is. In particular, the general formula (II)
In the case of the isomer mixture represented by -a to (II) -d, the solubility in an organic solvent is improved without impairing the inherent stability of tetraazaporphyrin, and solvent coating with high productivity is possible. Tetraazaporphyrin compound.
More specifically, the compound represented by the general formula (II) -a has high crystallinity, and it is difficult to apply the compound alone with a solvent. However, any of the three isomers represented by the general formulas (II) -b to (II) -d can be coated with a single solvent. Therefore, even in the case of a mixture of four isomers, a mixture in which the content of the isomers represented by the general formula (II) -a is as small as possible is advantageous when a film is formed by solvent coating.

[0009]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below in detail.
The present invention relates to a tetraazaporphyrin compound comprising one of four compounds represented by the following general formulas (II) -a to (II) -d or a mixture of two or more thereof, and a method for producing the same.

[0010]

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In the above general formulas (II) -a to (II) -d, M represents two hydrogen atoms, or a divalent, trivalent or tetravalent metal atom which may have an oxygen atom or a halogen atom. Or a substituted or unsubstituted alkyl group, aryl group, alkoxy group, aryloxy group,-(OPR ¹¹ R
¹² ) t group, (-OPOR ¹³ R ¹⁴ ) t group,-(OSiR ¹⁵
R ¹⁶ R ¹⁷ ) t group,-(OCOR ¹⁸ ) t group,-(OR ¹⁹ )
t group, - (OCOCOOR ²⁰⁾ t group, - (OCOCOR
²¹⁾ t group or - represents an metal atom which may have a (OCONR ²² R ²³⁾ t group. R ^{11 to} R ²³ each independently represent a hydrogen atom, a substituted or unsubstituted monovalent aliphatic hydrocarbon group or a substituted or unsubstituted monovalent aromatic hydrocarbon group, and t represents an integer of 0 to 2. Represent. X ^{1 to} X ⁴ each independently represent a hydrogen atom or a substituted or unsubstituted linear or branched alkyl group, but not all hydrogen atoms.

The conditions for synthesizing the tetraazaporphyrin ring are as follows: 1 to 4 monoalkyltricyanoethylene compounds represented by the following general formula (I) as raw materials and a metal or a metal derivative are mixed in a solvent at 90 to 350. Heat reaction at ℃.

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The monoalkyl tricyanoethylene compound represented by the general formula (I) is a novel substance. When this monoalkyl tricyanoethylene compound is used as a precursor, cis and trans structural isomers are not taken. There is no drop in the yield when only the cis-isomer is fractionated or when the reaction is carried out with a trans-isomer mixture, and this has an industrially excellent advantage.

The preferred reaction temperature is 90 to 220 ° C.
When the temperature is lower than 90 ° C., the reaction does not progress easily,
If the temperature exceeds 220 ° C., a large amount of decomposed products is generated, which causes a decrease in yield. Furthermore, it should be noted that the reaction temperature was 15
When the temperature is 0 ° C. or higher, the formation of a metal-free body or the general formula (I
I) The production ratio of the isomer component represented by -a is increased, which is not preferable for applications requiring high solubility, and conversely, products suitable for applications requiring crystallinity can be obtained. .

The amount of the solvent used is 1 to 100 times by weight, preferably 5 to 100 times the weight of the monoalkyltricyanoethylene compound.
１５15 weight times. The solvent may have a boiling point of 100 ° C. or higher, but preferably has a boiling point of 135 ° C. or higher. Specific examples include N, N-dimethylformamide, N, N-dimethylacetamide, dimethylsulfoxide, 1-methyl-2-pyrrolidone, 1-chloronaphthalene, tetrahydronaphthalene, benzyl alcohol, quinoline, N, N-dimethylaminoethanol Examples thereof include aliphatic alcohols, i.e., n-amyl alcohol, n-hexanol, cyclohexanol, 2-methyl-1-pentanol, 1-heptanol, 2-heptanol, 1-octanol, and the like. 2-ethylhexanol, ethylene glycol, propylene glycol, ethoxyethanol, propoxyethanol and the like.

The metal or metal derivative used in the reaction includes Al, Si, Ca, Ti, V, Mn, Fe, Co,
Ni, Cu, Zn, Ge, Mo, Ru, Rh, Pd, I
n, Sn, Pt, Pb, Mg and halides thereof, carboxylic acid derivatives, sulfates, nitrates, carbonyl compounds,
Oxides, complexes and the like can be mentioned. Preferably, copper chloride, copper bromide, copper iodide, copper acetate, nickel chloride, nickel bromide, nickel acetate, palladium chloride, palladium acetate,
Platinum chloride, zinc chloride, platinum bromide, zinc acetate, titanium (IV) chloride, vanadium trichloride, silicon tetrachloride, vanadium acetylacetone and the like.

At the time of tetraazaporphyrin ring formation, the addition of a base shortened the reaction time and improved the synthesis yield, and was found to be very effective. In other words, when no base is added, the reaction temperature does not increase until the reaction temperature is increased or the reaction time is increased, and in the former case, the yield decreases due to the generation of metal-free form and decomposition products. In the latter case, the reaction temperature must be higher than that of the base addition, and the reaction time is 3 to 10 times longer, which leads to a decrease in productivity. As the base, ammonium molybdate is particularly preferable, and the amount of these used is based on the amount of the starting material monoalkyltricyanoethylene compound.
0.0001 to 1.0 mol is sufficient, and preferably 0.1 to 1.0 mol.
0005 to 0.01 mol.

Further, after forming a ring with tetraazaporphyrin using Mg as a central metal, Mg can be converted into a desired metal tetraazaporphyrin by a metal exchange reaction or Mg can be eliminated to obtain H ₂ tetraazaporphyrin. Alternatively, a desired metal tetraazaporphyrin can be obtained by an H ₂ tetraazaporphyrin metal insertion reaction. That is, Mg tetraazaporphyrin can be obtained in good yield by reacting Mg alkoxide with the tricyanoethylene compound of the present invention at 90 to 160 ° C. in an organic solvent. And metal-exchange to obtain the desired metal tetraazaporphyrin. Here, at the time of the metal exchange reaction, the reaction yield can be improved due to the presence of ammonium molybdate and the acid. Specific acids include acetic acid, hydrochloric acid, trifluoroacetic acid, sulfuric acid, phosphoric acid, and the like.
g is a weight ratio of 0.01 to 1000 times, preferably 0.5 to 50 times the weight of tetraazaporphyrin, and the amount of ammonium molybdate added is Mg
0.000001 to 1.0 for tetraazaporphyrin.
It is a 0-fold weight ratio. In addition, since Mg tetraazaporphyrin is rapidly converted into H ₂ tetraazaporphyrin by heat treatment in the above acid, H ₂ tetraazaporphyrin and a metal derivative are acted on to obtain a desired metal tetraazaporphyrin. Is also good.

The monoalkyltricyanoethylene compound is prepared by reacting an alkyl aldehyde with malononitrile to give 1,1-dicyano-2-alkylethylene and then with potassium cyanide to give 1,1,2-tricyanoethylene. It is obtained by dehydrogenating -2-alkylethane.

In the general formulas (II) -a to (II) -d, X ¹ to
Specific examples of the alkyl group for X ⁴ include the following. Note that these alkyl groups may be substituted with a substituent such as a halogen atom. Methyl group, ethyl group, n-propyl group, 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,
3-ethylpentyl group, n-octyl group, 2-methylheptyl group, 3-methylheptyl group, 4-methylheptyl group, 5-methylheptyl group, 2-ethylhexyl group, 3
-Ethylhexyl group, n-nonyl group, n-decyl group, n
A primary alkyl group such as a dodecyl group; an isopropyl group, s
ec-butyl group, 1-ethylpropyl group, 1-methylbutyl group, 1,2-dimethylpropyl group, 1-methylheptyl group, 1-ethylbutyl group, 1,3-dimethylbutyl group, 1,2-dimethylbutyl group , 1-ethyl-2-methylpropyl group, 1-methylhexyl group, 1-ethylheptyl group, 1-propylbutyl group, 1-isopropyl-2
-Methylpropyl group, 1-ethyl-2-methylbutyl group, 1-propyl-2-methylpropyl group, 1-methylheptyl group, 1-ethylhexyl group, 1-propylpentyl group, 1-isopropylpentyl group, 1- Isopropyl-2-methylbutyl group, 1-isopropyl-3-methylbutyl group, 1-methyloctyl group, 1-ethylheptyl group, 1-propylhexyl group, 1-isobutyl-3-
Secondary alkyl group such as methylbutyl group; tert-butyl group, tert-hexyl group, tert-amyl group, te
tertiary alkyl groups such as rt-octyl group; cyclohexyl group, 4-methylcyclohexyl group, 4-ethylcyclohexyl group, 4-tert-butylcyclohexyl group, 4
A cycloalkyl group such as-(2-ethylhexyl) cyclohexyl group, bornyl group, isobornyl group and adamantane group; Examples of the unsaturated alkyl group include an ethylene group, a propylene group, a butylene group, a hexene group, an octene group, a dodecene group, a cyclohexene group, and a butylhexene group.

In the definitions of R ^{11 to} R ²³ in the general formulas (II) -a to (II) -d, the monovalent aliphatic hydrocarbon group includes a methyl group, an ethyl group, a propyl group and an isopropyl group. Butyl group, isobutyl group, sec-butyl group, te
rt-butyl group, amyl group, hexyl group, octyl group,
Examples include an alkyl group such as a decyl group, a dodecyl group, and an octadecyl group, and an alkenyl group such as a vinyl group, an allyl group, an isopropenyl group, a 1-butenyl group, a 2-butenyl group, and a 2-pentenyl group. Examples of the monovalent aromatic hydrocarbon group include a phenyl group and a benzyl group. Examples of the substituent include a halogen atom such as fluorine, chlorine, and bromine, a carbon trifluoride group, a cyano group, and an ester group.

Specific examples of the compound represented by formula (II) -a include those shown in Table 1. Although the isomers of the compounds shown in Table 1 are not described, there are actually four isomers as described above.

[0023]

[Table 1]

[0024]

Hereinafter, the present invention will be described with reference to Examples.
The present invention is not limited to these.

Synthesis Example 1 Malononitril in 110 ml of dry ethanol
28.1 g (426 mmol 1.2 eq) are dissolved and stirred. This is Pivalaldehyde
30.5 g (355 mmol) and Piperidin
e A mixture of 1.6 ml and 4.6 ml of acetic acid was gradually added dropwise, and the mixture was refluxed for 1.5 hours. After lowering the temperature to room temperature and continuing stirring for 2 hours, chloroform 700
Extract with ml. This was washed with water two or three times, an appropriate amount of magnesium sulfate was added, and the filtrate was concentrated and purified with a chloroform / silica gel column to obtain 38.15 g of white crystals [compound represented by the following structural formula (A)] ( Yield 8
0.3%).

[0026]

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The results of elemental analysis of the white crystals were as follows. FIG. 1 shows the IR spectrum of the above compound.

Synthesis Example 2 Potassium cyanide 31.25 g (480 mmol 2
eq) is added to ethanol / water = 250 ml / 250 ml and stirred to dissolve. In addition, 3,3-dimethyl-1,1- represented by the structural formula (A) synthesized in Synthesis Example 1
32.16 g of Dicyano-1-butene (2
40 mmol) and stirred at about 50 ° C. for 2 to 3 minutes and at room temperature for 20 minutes, and then water / acetic acid = 200 ml / 50 ml.
, And the mixture was extracted with 1000 ml of chloroform. The chloroform layer was washed with saturated saline and then with water, an appropriate amount of magnesium sulfate was added, and the filtrate was concentrated. The precipitated crystals were washed with 100 ml of toluene / hexane = 2/1.
By recrystallizing the mixture, 29.43 g of white crystals [compound represented by the following structural formula (B)] (yield: 91.5 g)
%).

[0029]

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The results of elemental analysis of the white crystals were as follows. FIG. 2 shows the IR spectrum of the above compound.

EXAMPLE 1 3,3-Dimethyl- represented by the structural formula (B) synthesized in Synthesis Example 2 in 70 ml of Dry Prydine
1,1,2-Tricyanobutane 6.44m
g (40 mmol) was dissolved in an ice bath, cooled to 0-5 ° C., and stirred with Fluorotrichloromethane.
6.71 g of bromine dissolved in 48 ml of ne (42 mmo)
1) is slowly added dropwise. After completion of dropping, at 0-5 ° C 2
Continue stirring at room temperature for 15 minutes for about 3 minutes
And pour into water. This was extracted with 500 ml of toluene and washed repeatedly with water. An appropriate amount of magnesium sulfate was added to the toluene layer, the mixture was stirred, the filtrate was concentrated, purified by a chloroform / silica gel column, and the solid was washed with hexane to give white crystals. [The following structural formula (C)
3.98 g (yield 62.58%) was obtained.

[0032]

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The results of elemental analysis of the white crystals were as follows. FIG. 3 shows the IR spectrum of the above compound.

Example 2 The 3,3 compound represented by the structural formula (C) synthesized in Example 1
-Dimethyl-1,1,2-Tricyano-
1.59 mg (10 mmol) of 1-butane was mixed with 4 g of 1,2,4-trichlorobenzene, 0.003 g of ammonium molydebnate and 0.248 of cuprous chloride.
g (2.5 mmol 0.25 eq) and mix at a temperature of 15
Stirred at 0 ° C. for 4 hours. The reaction product was purified using a hexane / silica gel column to remove trichlorobenzene, and the developing solvent was changed to chloroform.
Purification by a silica gel column gave 0.5 g of crystals (yield 28.6%), which is a mixture of the four isomers shown below.

[0035]

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The λmax of the mixture of the four isomers in chloroform was 608 nm and ε = 101000. The results of elemental analysis of the above compound were as follows. FIG. 4 shows the IR spectrum of the above compound.

Example 3 0.243 g (10 mmol) of shaved metal magnesium was dispersed in Dry n-Pentanol, and the mixture was heated under reflux for 1 hour. Then, the temperature was lowered slightly, and the 3,3-Dimet represented by the structural formula (C) synthesized in Example 1 was obtained.
hyl-1,1,2-Tricyano-1-bute
After adding 1.59 mg (10 mmol) of ne, heating reflux was continued for 4 hours again, and then the mixture was cooled to room temperature, only chloroform-soluble components of the reaction product were separated by filtration, chloroform was distilled off, and 400 ml of a 1/10 mixed solution of methanol / water was added. The crystals were collected by filtration. After drying the crystals, the crystals were purified by a chloroform / silica gel column to obtain 1.3 g (yield: 78.7%) of crystals as a mixture of four isomers shown below.

[0038]

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The λmax of the four isomer mixtures in chloroform was 621 nm and ε = 100000. The results of elemental analysis of the above compound were as follows.

Example 4 0.7 g (1.05 mmol) of the Mg tetraazaporphyrin isomer mixture synthesized in Example 3, 0.454 g (3.5 mmol) of nickel chloride anhydride, 8 ml of acetic acid and 25 ml of 1,1 , 4-Trichioroben
Mix and heat to reflux for 3 hours. This is subjected to 1,2,4-Trichior using a hexane / silica gel column.
After removing benzene, the solvent was purified by changing the developing solvent to chloroform to obtain 0.66 g (yield: 89.6%) of a crystal as a mixture of four isomers shown below.

[0041]

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The chloroform mixture of the four isomers had λmax of 606 nm and ε = 105000. The results of elemental analysis of the above compound were as follows.

Example 5 0.243 g (10 mmol) of shaved metallic magnesium was dispersed in Dry n-Butanol, and the mixture was heated under reflux for 3 hours. Then, the temperature was lowered slightly, and iodine was slightly added to 3-methyl-1,1,2-tricyano-1.
After adding 1.45 mg (10 mmol) of -butene and continuing heating reflux again for 6 hours, the reaction mixture was cooled to room temperature, only the chloroform-soluble component of the reaction product was filtered off, chloroform was distilled off, and 400 ml of a 1/10 mixed solution of methanol / water was added. The crystals were collected by filtration. After drying, the crystals were purified by a chloroform / silica gel column to obtain 1.2 g (yield: 79.3%) of a crystal as a mixture of four isomers shown below.

[0044]

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The resulting mixture of four isomers had a λmax in chloroform of 620 nm and ε = 108000
Met. The results of elemental analysis of the above compound were as follows.

[0046]

When the alkyl-substituted tricyanoethylene compound of claim 1 is used as a precursor of tetraazaporphyrin, it does not take cis or trans structural isomers, so that the desired product can be obtained in high yield. Is industrially very useful as a precursor of tetraazaporphyrin.

The tetraazaporphyrin compound according to claim 2 has at least one structure represented by the general formulas (II) -a to (II) -d, and is therefore applicable to a high-density optical disk system. It is useful as a recording material for an optical recording medium having excellent light resistance and storage stability.

The method for producing a tetraazaporphyrin compound according to claim 3 comprises reacting the alkyl-substituted tricyanoethylene compound represented by the general formula (I) with a metal (derivative). According to this, at least one compound represented by the above general formulas (II) -a to (II) -d can be easily obtained in high yield.

In the method for producing a tetraazaporphyrin compound according to claims 4 and 5, since the reaction according to claim 3 is carried out in a solvent or an alcohol, the desired product can be obtained under milder conditions. .

In the method for producing a tetraazaporphyrin compound according to claim 6, since the transition metal, transition metal halide or transition metal carboxylate is used as the metal (derivative), the desired product can be obtained more easily. .

According to the method for producing a tetraazaporphyrin compound of the present invention, since the reaction temperature is 90 to 220 ° C., the production of a highly crystalline isomer can be suppressed, and the target product can be obtained efficiently.

In the method for producing a tetraazaporphyrin compound according to claim 8, since the amount of the solvent is 1 to 100 times the amount of the raw material, the target product can be obtained more efficiently.

In the method for producing a tetraazaporphyrin compound according to the ninth aspect, the target product can be efficiently obtained at lower temperature because ammonium molybdate coexists in the reaction system.

In the method for producing a tetraazaporphyrin compound according to claim 10, after forming a ring with the central metal as Mg,
Since the desired metal tetraazaporphyrin or H ₂ tetraazaporphyrin is obtained by metal exchange or elimination of Mg, the desired product can be obtained more efficiently.

The method for producing a tetraazaporphyrin compound according to the eleventh aspect is characterized in that at least one of an organic solvent, ammonium molybdate and an acid coexists with the metal or metal derivative according to the sixth aspect and Mg tetraazaporphyrin. Since the metal is exchanged or Mg is eliminated, the target substance can be obtained even more efficiently.

[Brief description of the drawings]

FIG. 1 is an IR spectrum of the compound obtained in Synthesis Example 1.

FIG. 2 is an IR spectrum of the compound obtained in Synthesis Example 2.

FIG. 3 is an IR spectrum of the compound obtained in Example 1.

FIG. 4 is an IR spectrum of the compound obtained in Example 2.

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[Procedure amendment]

[Submission date] October 15, 1997

[Procedure amendment 1]

[Document name to be amended] Statement

[Correction target item name] Name of invention

[Correction method] Change

[Correction contents]

Patent application title: Tetraazaporphyrin compound and precursor thereof and method for producing tetraazaporphyrin compound

 ──────────────────────────────────────────────────続 き Continued on the front page (72) Inventor Noboru Sasa 1-3-6 Nakamagome, Ota-ku, Tokyo Inside Ricoh Company (72) Inventor Yasunobu Ueno 1-3-6 Nakamagome, Ota-ku, Tokyo Share Inside the company Ricoh

Claims (11)

[Claims] 1. An alkyl-substituted tricyanoethylene compound represented by the following general formula (I). Embedded image (In the formula, X is a hydrogen atom or a linear or branched alkyl group, and may be substituted with another substituent.) 2. A halogenated tetraazaporphyrin compound comprising one or a mixture of two or more of the four compounds represented by the following general formulas (II) -a to (II) -d. Embedded image Embedded image Embedded image Embedded image [Wherein, M and X ^{1 to} X ⁴ each represent the following. M: two hydrogen atoms, or a divalent, trivalent or tetravalent metal atom which may have an oxygen atom or a halogen atom,
Or a substituted or unsubstituted alkyl group, aryl group, alkoxy group, aryloxy group,-(OPR ¹¹ R ¹² ) t
^{Group, (- OPOR 13 R 14)} t group, - (OSiR ¹⁵ R ¹⁶ R
¹⁷⁾ t group, - (OCOR ¹⁸⁾ t group, - (OR ¹⁹⁾ t group,
-(OCOCOR ²⁰ ) t group,-(OCOCOR ²¹ ) t
R ^{11 to} R ²³ each independently represent a hydrogen atom, a substituted or unsubstituted monovalent aliphatic hydrocarbon group or a substituted or unsubstituted group, or a metal atom which may have a — (OCONR ²² R ²³ ) t group. A t is an integer of 0 to 2, X ^{1 to} X ⁴ are each independently a hydrogen atom or a substituted or unsubstituted linear or branched alkyl group, provided that all are hydrogen It cannot be an atom. ] 3. The general formula (II) -a, wherein the alkyl-substituted tricyanoethylene compound represented by the general formula (I) is reacted with a metal or a metal derivative.
To (II) -d, a method for producing at least one tetraazaporphyrin compound. 4. The method for producing a tetraazaporphyrin compound according to claim 3, wherein the reaction is performed in an organic solvent. 5. The method for producing a tetraazaporphyrin compound according to claim 4, wherein the organic solvent is an aromatic hydrocarbon or a halogenated aromatic hydrocarbon. 6. The method for producing a tetraazaporphyrin compound according to claim 3, wherein the metal or the metal derivative is a transition metal, a transition metal halide or a transition metal carboxylate. 7. The method for producing a tetraazaporphyrin compound according to claim 3, wherein the reaction temperature is 90 to 220 ° C. 8. The process for producing a tetraazaporphyrin compound according to claim 3, wherein the amount of the solvent used is 1 to 100 times the amount of the alkyl-substituted tricyanoethylene compound. . 9. The method for producing a tetraazaporphyrin compound according to claim 3, wherein ammonium molybdate is present. 10. The method according to claim 3, wherein after forming a ring as the central metal as Mg, the metal is exchanged or Mg is eliminated to obtain a desired metal tetraazaporphyrin or H ₂ tetraazaporphyrin. A method for producing a tetraazaporphyrin compound, comprising: 11. The metal exchange or Mg desorption according to claim 10, wherein at least one of an organic solvent, ammonium molybdate and an acid is present in combination with the metal or metal derivative according to claim 6 and Mg tetraazaporphyrin. A process for producing a tetraazaporphyrin compound.