JPH11116574A - Halogenated tetraazaporphyrin compound and method for producing (halogenated) tetraazaporphyrin compound - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a compound useful as a recording material for an optical recording medium having excellent light resistance and storage stability applicable to a high-density optical disk system, and a method for producing the same. SOLUTION: A halogenated tetraazaporphyrin compound comprising 1 to 4 kinds of compounds including the following general formula (I) -a and its isomer, and (halogenation) from a substituted maleonitrile or a substituted 2,5-diiminopyrrole A method for producing a tetraazaporphyrin compound. Embedded image

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a method for producing a novel halogenated tetraazaporphyrin compound and a (halogenated) tetraazaporphyrin compound, and more particularly to dyes, pigments, photoelectrically functional materials, recording and storage materials, and the like. The present invention relates to a halogenated tetraazaporphyrin compound and a method for producing a (halogenated) tetraazaporphyrin compound useful as a material for an optical recording medium.

[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.

On the other hand, methods for producing α-substituted phthalocyanines are described in JP-A-3-62878 and JP-A-3-21.
5466, JP-A-4-226390, JP-A-4-3
48168, JP-A-5-25177, etc., and halogenated phthalocyanines and their production methods are described in JP-A-4-15263, JP-A-4-15264, and JP-A-4-15265. , JP-A-4
No. -15266, JP-A-5-1272, JP-A 5-1
No. 7700, JP-A-5-17477, JP-A-5-25
No. 179, JP-A-5-86301, JP-A-5-171
No. 052, JP-A-5-247363 and the like.

[0005] 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. Further, in the above-mentioned publications relating to a method for synthesizing phthalocyanine and a method for halogenating the phthalocyanine, there is no description about the application of tetraazaporphyrin and the possibility thereof.

[0006]

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.

[0007]

Means for Solving the Problems As a result of intensive studies, the present inventors have found that by providing a recording layer containing a halogenated tetraazaporphyrin compound as a main component, an oscillation wavelength of 7
It has been found that it can be applied to a high-density optical disk system using a semiconductor laser of 00 nm or less.
The present inventors have found that the above compound can be efficiently produced by adding an organic base, controlling halogenation, and the like, and have completed the present invention.

That is, according to the present invention, first, a tetrahalide comprising one or a mixture of two or more of the four compounds represented by the following general formulas (I) -a to (I) to (d): An azaporphyrin compound is provided.

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Embedded image [Wherein, M, R ^{1 to} R ⁴ , X and n 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. T: an integer of 0 to 2; R ^{1 to} R ⁴ each independently represent a hydrogen atom or a substituted or unsubstituted linear or branched alkyl group;
X: chlorine, bromine or iodine atom, except when all of ^{1 to} R ⁴ are hydrogen atoms, n: the number of substitution of the above halogen atom, and an integer of 1 to 4. Second, an alkyl-substituted maleonitrile represented by the following general formula (III) -a or 1 to 4 alkyl-substituted 2,5-diiminopyrroles represented by the following general formula (III) -b, and a metal or metal derivative And a method for producing at least one tetraazaporphyrin compound represented by the following general formulas (II) -a to (II) -d.

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Embedded image (Wherein, R and R ′ each independently represent a hydrogen atom or a substituted or unsubstituted linear or branched alkyl group.
However, at least one of R and R 'is a hydrogen atom, and all eight substitution positions do not become hydrogen atoms when the tetraazaporphyrin compound is formed. )

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Embedded image [Wherein, M and R ^{1 to} R 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. T: an integer of 0 to 2; R ^{1 to} R ⁴ each independently represent a hydrogen atom or a substituted or unsubstituted linear or branched alkyl group;
All ¹ to R ⁴ excluding a case where the hydrogen atom. Third, there is provided a method for producing a tetraazaporphyrin compound according to the second aspect, wherein the reaction is carried out in an organic solvent. Fourth, in the third aspect, there is provided a method for producing a tetraazaporphyrin compound, wherein the organic solvent is an alcohol. Fifth, in the second to fourth aspects, there is provided a method for producing a tetraazaporphyrin compound, wherein the metal or metal derivative is a transition metal, a transition metal halide or a transition metal carboxylate. Sixth, there is provided a method for producing a tetraazaporphyrin compound according to any one of the above second to fifth aspects, wherein the reaction temperature is 90 to 220 ° C. Seventh, in the second to sixth, the amount of the solvent used is 1 to 100 times the amount of the alkyl-substituted maleonitrile or the alkyl-substituted 2,5-diiminopyrrole, A manufacturing method is provided. Eighth, in the above second to seventh,
There is provided a method for producing a tetraazaporphyrin compound, which comprises coexisting an organic base. Ninthly, there is provided the method for producing a tetraazaporphyrin compound according to the eighth aspect, wherein the organic base is diazabicycloundecene or diazabicyclononene. Tenthly, one or a mixture of two or more of tetraazaporphyrins represented by the general formulas (II) -a to (II) -d is halogenated at 0 to 90 ° C. in a mixed solvent of an organic solvent and water. Wherein said compound is reacted with an agent.
A method for producing at least one halogenated tetraazaporphyrin compound represented by (I) -d is provided. Eleventh, there is provided a halogenated tetraazaporphyrin compound according to the first aspect, wherein X is bromine. Twelfthly, there is provided a method for producing a halogenated tetraazaporphyrin compound according to the tenth aspect, wherein the organic solvent is substantially immiscible with water. Thirteenth, the method for producing a halogenated tetraazaporphyrin compound according to the twelfth aspect, wherein the organic solvent is one or more selected from saturated hydrocarbons, ethers, and halogenated hydrocarbons. Provided.
Fourteenthly, there is provided a method for producing a halogenated tetraazaporphyrin compound according to the tenth aspect, wherein the halogenating agent is bromine. Fifteenthly, there is provided a method for producing a halogenated tetraazaporphyrin compound according to the fourteenth aspect, wherein the amount of bromine used is 1 to 5 molar ratio with respect to the tetraazaporphyrin compound.

The general formulas (I) -a to (I)-of the present invention.
The halogenated tetraazaporphyrin represented by d has a feature that the thermal decomposition temperature is lower than that of the non-halogenated one, and furthermore, the thermal decomposition occurs rapidly, and the recording is excellent in the recording sensitivity and the uniformity of the recording pit shape. Material. In particular, when the isomer mixture represented by the general formulas (I) -a to (I) -d is used, the solubility of the tetraazaporphyrin in an organic solvent is improved without deteriorating the inherent stability of the tetraazaporphyrin. It becomes a halogenated tetraazaporphyrin compound which can be coated with a highly soluble solvent. More specifically, the compound represented by the general formula (I) -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 (I) -b to (I) -d can be coated with a single solvent. Therefore, even in the case of a mixture of four isomers, it is advantageous when a mixture in which the content of the isomer represented by the general formula (I) -a is as small as possible is formed by solvent coating.

[0010]

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

[0011]

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In the above general formulas (I) -a to (I) -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. R ^{1 to} R ⁴ each independently represent a hydrogen atom or a substituted or unsubstituted linear or branched alkyl group. However, it is excluded when all of R ^{1 to} R ⁴ are hydrogen atoms. X represents a chlorine, bromine or iodine atom, n represents the number of substitutions of the halogen atom,
It is an integer of 1 to 4.

Further, the present invention provides a compound of the general formula (I) -a
(I) In order to obtain a halogen-free tetraazaporphyrin which is a precursor for obtaining the compound represented by -d, from 1 to 4 types of alkyl-substituted maleonitrile or alkyl-substituted 2,5-diiminopyrrole which is a precursor thereof And a metal or a metal derivative to react with the following general formula (I)
The present invention relates to a production method for obtaining I) -a to (II) -d.

[0014]

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The above general formulas (II) -a to (II) -d
Wherein M is two hydrogen atoms, or an oxygen atom or
Divalent, trivalent or tetravalent gold which may have a halogen atom
Genus atom, or substituted or unsubstituted alkyl group, aryl
, An alkoxy group, an aryloxy group,-(OPR¹¹
R¹²) T group, (-OPOR¹³R¹⁴) T group,-(OSiR)
^FifteenR¹⁶R¹⁷) T group,-(OCOR)¹⁸) T group,-(O
R¹⁹) T group,-(OCOCOOR²⁰) T group,-(OCO
COR^{twenty one}) T group or-(OCONR)^{twenty two}R^{twenty three}) T group
Represents a metal atom which may be present. R¹¹~ R^{twenty three}Is German
A hydrogen atom, a substituted or unsubstituted monovalent aliphatic carbon
Hydrogen group or substituted or unsubstituted monovalent aromatic hydrocarbon
Represents a group, and t represents an integer of 0 to 2. R¹~ R^FourEach
Independently a hydrogen atom or a substituted or unsubstituted linear or
Represents a branched alkyl group. Where R ¹~ R^FourEverything is water
It is excluded if it is an elementary atom.

The conditions for synthesizing the tetraazaporphyrin ring are as follows: the starting material is an alkyl-substituted maleonitrile represented by the following general formula (III) -a or the following general formula (III)
-Alkyl-substituted 2,5-diiminopyrroles represented by -b and metal or metal derivative in a solvent at 90 to 3
Heat reaction at 50 ° C.

[0017]

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Embedded image In the general formulas (III) -a and (III) -b, R,
R ′ each independently represents a hydrogen atom or a substituted or unsubstituted linear or branched alkyl group. Where R,
At least one of R ′ is a hydrogen atom, and all eight substitution positions do not become hydrogen atoms when the tetraazaporphyrin compound is formed. In the present invention,
The compound represented by the general formula (III) -a has no particular problem even if it is in a trans form.

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, preferably 5 to 15 times the weight of the alkyl-substituted maleonitrile or the alkyl-substituted 2,5-diiminopyrrole.
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-
Examples thereof include dimethylaminoethanol, and particularly preferred examples are aliphatic alcohols, that is, n-amyl alcohol, n-hexanol, cyclohexanol,
2-methyl-1-pentanol, 1-heptanol, 2
-Heptanol, 1-octanol, 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, vanadium trichloride, silicon tetrachloride, acetylacetone vanadium and the like.

For the synthesis of alkyl-substituted maleonitriles, see J. Mol. Gen. Chem. USSR 1977,4
7, 1954, etc., and alkyl-substituted 2,
For 5-diiminopyrrole, the method of obtaining 1,3-diiminoisoindoline from phthalonitrile can be applied as it is. That is, the target substituted 2,5-diiminopyrrole is obtained by reacting the corresponding maleonitrile with ammonia in the presence of sodium in an alcohol.

It has been found that the addition of an organic base during the formation of the tetraazaporphyrin ring can reduce the reaction time and improve the synthesis yield, and is very effective. That is, when no organic base is added, the reaction does not easily proceed to the end point unless the reaction temperature is increased or the reaction time is increased.
In the former case, the yield is reduced due to the formation of a metal-free body and a decomposition product, and in the latter case, the reaction temperature must be higher than that of the addition of the organic base, and the reaction time takes 3 to 10 times, This leads to a decrease in productivity. Examples of the organic base include 1,8-diazabicyclo [5,4,0] -7-undecene (hereinafter abbreviated as DBU) and 1,5-diazabicyclo [4,3,0] -5-nonene (hereinafter abbreviated as DBN). Preferably, the amount of these used is 0.5 to 2.5 mol, preferably 0.1 mol, based on the starting material alkyl-substituted maleonitrile or alkyl-substituted 2,5-diiminopyrrole.
7 to 1.5 mol.

Further, according to the present invention, the necessary number of halogen atoms (1
４4). That is, when a halogen atom is introduced into tetraazaporphyrin, the absorption wavelength becomes longer, and the degree of the longer wavelength shifts as the halogen introduction rate increases. According to the present invention, since the halogen introduction rate can be controlled, it is very excellent in wavelength matching.

As a specific halogen introduction method, a tetraazaporphyrin compound represented by the general formulas (II) -a to (II) -d is prepared by mixing a tetraazaporphyrin compound in an organic solvent and water in a mixed solvent of 0 to 0;
Reaction with a halogenating agent at 90 ° C. to give a compound of the general formula (I) -a
(I) A halogenated tetraazaporphyrin compound represented by -d is obtained. In the present invention, by reacting a tetraazaporphyrin compound and a halogenating agent in a mixed solvent of water and an organic solvent that is substantially immiscible with water, a reaction by-product hydrogen halide or a salt of the halogenating agent is produced. This prevents the tetraazaporphyrin compound from precipitating out of the organic solvent, which is a reaction solvent, together with the reaction by-products, because the compounds are dissolved in water. In order to obtain more (3- or 4-substituted) tetraazaporphyrins having a higher halogenation rate, the presence of water is important. A product with a high rate cannot be obtained efficiently.

In the halogenated tetraazaporphyrin compounds represented by the general formulas (I) -a to (I) -d, X represents a halogen, and as the halogen atom, F, Cl, Br, I
And preferably Br. Specific examples of the halogenating agent include chlorine, bromine, iodine, sulfuryl chloride, thionyl chloride, antimony chloride, FeCl ₃ , phosphorus pentachloride, phosphorus oxychloride, t-butyl hypochlorite, N-bromosuccinimide, Examples thereof include iodine chloride, cupric bromide, quaternary ammonium bromide, N-chlorosuccinimide, quaternary ammonium iodide, and potassium triiodide. Among them, bromine is most preferred.

The reaction temperature is 0 to 90 ° C., preferably 20 to 60 ° C. If the reaction temperature is lower than 20 ° C., the reaction does not proceed well. If the reaction temperature is higher than 90 ° C., it becomes difficult to control the halogenation rate, and the generation of decomposition products increases to lower the yield. cause. Regarding the ratio of the halogenating agent to act, the halogenating rate can be controlled by applying 1 to 5 moles to the tetraazaporphyrin. That is, the halogenating agent to be actuated is 4
When the molar ratio is less than or equal to 1, the halogenation rate of the obtained halogenated tetraazaporphyrin is obtained as a mixture of 1 to 4,
When the halogenating agent is used in an amount of 4 mol or more, a high substitution ratio halogenated tetraazaporphyrin of only 3 to 4 or 4 having a high halogenation ratio can be produced. 5 halogenating agents
Even when the compound is used in a molar excess, only the tetrasubstituted product is obtained, and the tetraazaporphyrin itself may be decomposed, which may lower the yield.

In the halogenation, the organic solvent to be used is substantially immiscible with water, that is, one which forms two layers with water, and is represented by the general formula (I) -a to (I) -d. A solvent capable of dissolving tetraazaporphyrin, preferably one or more selected from saturated hydrocarbons, ethers, and halogenated hydrocarbons. More preferably, n-hexane, n-pentane, n-octane, cyclohexane, methylcyclohexane, tetrahydrofuran, n-butyl ether, n-propyl ether, isopropyl ether, carbon tetrachloride, chloroform, methylene chloride, 1,1-dichloroethane, , 2-
Dichloroethane, 1,1,1-trichloroethane, 1,
One or more selected from 1,2-trichloroethane and 1,1,2,2-tetrachloroethane.

The amount of the organic solvent is 3 to 350 times by weight, preferably 4 to 350 times the weight of the starting material tetraazaporphyrin.
It is necessary to completely dissolve the tetraazaporphyrin, and if the amount is less than 3 times, solids are liable to precipitate during the reaction, which hinders the progress of the reaction.
If it exceeds 50 times, the reaction will be too slow, leading to a decrease in productivity. The amount of water is 0.1
It is 10 to 10 times by weight, preferably 0.5 to 3 times by weight, and it is necessary that the ratio is such that many interfaces between water and the organic solvent are formed. If the amount of water added is less than 0.1 weight times,
There is no effect of adding water, and a solid precipitates out during the reaction, hindering the progress of the reaction. On the other hand, if it is added in an amount exceeding 10 times by weight, the amount of the solvent becomes too large, and the reaction efficiency is reduced.

The general formulas (I) -a to (I) -d and (I)
In I) -a to (II) -d, specific examples of the alkyl group of R ^{1 to} R ⁴ include the following. In addition,
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
Primary alkyl groups such as -nonyl group, n-decyl group, n-dodecyl group; isopropyl group, sec-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 ,
Secondary alkyl groups such as 1-isopropyl-3-methylbutyl group, 1-methyloctyl group, 1-ethylheptyl group, 1-propylhexyl group, 1-isobutyl-3-methylbutyl group; tert-butyl group, tert-hexyl Tertiary alkyl groups such as a tert-amyl group and a tert-octyl group; cyclohexyl group, 4-methylcyclohexyl group, 4-ethylcyclohexyl group, 4-tert
-Butylcyclohexyl group, 4- (2-ethylhexyl) cyclohexyl group, bornyl group, isobornyl group,
A cycloalkyl group such as an 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 definition of R ^{11 to} R ²³ in formulas (I) -a to (I) -d and (II) -a to (II) -d, the monovalent aliphatic hydrocarbon group is , Methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, amyl, hexyl, octyl, decyl, dodecyl, octadecyl and other alkyl groups And alkenyl groups such as vinyl group, allyl group, isopropenyl group, 1-butenyl group, 2-butenyl group and 2-pentenyl group. As the monovalent aromatic hydrocarbon group, 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 (I) -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.

[0032]

[Table 1]

[0033]

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

Example 1 1,2-dicyano-3,3-dimethyl-1-butene
03 g (45 mmol) are dispersed in 15 g of dry pentanol and the temperature is raised. DB at about 70 ℃
5.47 g (45 × 0.8 mmol) of U are added and the temperature is raised further. When the temperature reached 90 ° C., 1.12 g (45/4 mmol) of cuprous chloride was added, and the temperature was increased to 120 ° C.
The heating and stirring are continued at a temperature of from 125C to 125C for 20 hours. After cooling the reaction product, the components insoluble in chloroform were filtered off, chloroform was distilled off, 650 ml of water / methanol = 1/1 (volume ratio) was added thereto, and the crystals were collected by filtration.
After washing with 1/1 and drying, this was purified with a hexane / chloroform = 4/1 silica gel column to obtain four purple components. The total yield of these four components was 4.26 g, and the yield was 63.2%.

[0035]

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The above four components are the four components shown in (1) to (4).
Are the two isomers, from the development ratio at the time of the column, about (1):
(2) :( 3) :( 4) = 20: 75: 5: 5.
In addition, λma in chloroform of this four isomer mixture
x was 585 nm and ε = 1110,000. Also,
The results of elemental analysis of the above compound were as follows.

[Table 2] FIG. 1 shows the IR spectrum of the above compound.

Example 2 1,2-dicyano-3,3-dimethyl-1-butene
03 g (45 mmol) are dispersed in 20 g of Dryn-hexanol and the temperature is raised. At a temperature of about 70 ° C., 6.71 g (45 × 1.2 mmol) of DBN is added, and the temperature is further raised. When the temperature reaches 85 ° C., 2.00 g (45/4 mmol) of palladium (II) chloride is added, and heating and stirring are continued at a temperature of 120 ° C. to 130 ° C. for 20 hours. After cooling the reaction product, components insoluble in chloroform were filtered off, chloroform was distilled off, and 650 ml of water / methanol = 1/1 (volume ratio) was added thereto. After washing with 1 and drying, this was purified with a hexane / chloroform = 4/1 silica gel column,
Four purple components were obtained. The total yield of these four components is 4.1
9 g and a yield of 55.5%.

[0038]

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The above four components are the four components shown in (5) to (8).
Two isomers, which are approximately (5):
(6) :( 7) :( 8) = 15: 80: 5: 0.
In addition, λma in chloroform of this four isomer mixture
x was 576 nm and ε = 108000. Also,
The results of elemental analysis of the above compound were as follows.

[Table 3] FIG. 2 shows the IR spectrum of the above compound.

Example 3 6.89 g of 3-butyl-2,5-diiminopyrrole (4
5 mmol) is dispersed in 25 g of dry ethylene glycol and the temperature is increased. DBU at a temperature of about 70 ° C
6.71 g (45 × 1.2 mmol) are added and the temperature is further increased. When the temperature reaches 85 ° C., 2.98 g (45/4 mmol) of vanadium acetylacetone is added, and heating and stirring are continued at a temperature of 120 ° C. to 135 ° C. for 24 hours. After cooling the reaction product, components insoluble in chloroform were filtered off and chloroform was distilled off.
700 ml of 1/1 (volume ratio) was added, and the crystals were filtered.
After washing with methanol = 1/1 and drying, this was purified with a hexane / chloroform = 3/2 silica gel column to obtain four blue-green components. The total yield of these four components is 4.5
6 g, and the yield was 67.2%.

[0041]

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The above four components are the four isomers shown in (9) to (12), and from the developing ratio at the time of the column, about (9) :( 10) :( 11) :( 12) = 15: 80:
5: 0. The λmax of the four isomer mixtures in chloroform was 596 nm and ε = 109000. The results of elemental analysis of the above compound were as follows.

[Table 4]

Example 4 1,2-dicyano-3,3-dimethyl-1-butene
Disperse 03 g (45 mmol) in 10 g Dry 1-chloronaphthalene and raise the temperature. When the temperature reached 90 ° C., 1.12 g of cuprous chloride (45/4 mmol)
l) Add and continue heating and stirring at a temperature of 155 ° C to 175 ° C for 72 hours. After cooling the reaction product, components insoluble in chloroform were filtered off, chloroform was distilled off, and 850 ml of water / methanol = 1/1 (volume ratio) was added thereto. After washing with 1 and drying, this was purified with a hexane / chloroform = 4/1 silica gel column to obtain four purple components. The total yield of these four components was 2.36 g, and the yield was 35.0%.

[0044]

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The above four components are the four components shown in (1) to (4).
Are the two isomers, from the development ratio at the time of the column, about (1):
(2) :( 3) :( 4) = 40: 45: 10: 5. In this example, the reaction temperature was higher and the reaction time was longer and the yield was lower than in Example 1 because no DBU was added to the reaction system.

Example 5 800 mg (1.33 m) of the mixture of the above (1) to (4)
mol) is 1,1,2-trichloroethane / hexane /
Dissolved in a mixed solvent of water = 80g / 8g / 90g,
10 g of 1,1,2-trichloroethane at 0 ° C. to 45 ° C.
0.85 g (1.33 × 4 mmol) of bromine dissolved in water is slowly added dropwise over 30 minutes. 45 after dropping
Stir at 30 ° C to 50 ° C for 30 minutes and cool. This is poured into 500 ml of toluene, 200 g of a 10% aqueous solution of sodium hydrogen sulfite, and then 20% of an aqueous solution of 5% sodium hydrogen carbonate.
After washing with 0 g and washing twice with water, drying over magnesium sulfate, filtration, toluene was distilled off, and the residue was purified with a toluene / hexane = 2/3 silica gel column.
19 g were obtained. (The yield is 97.4, based on a bromination ratio of 4.
%)

Incidentally, the λmax in chloroform of the obtained mixture of four isomers was 601 nm, and ε = 112000
Met. The results of elemental analysis of the above compound were as follows.

[Table 5] FIG. 3 shows the IR spectrum of the above compound.

Example 6 964 mg (1.5 mm) of the mixture of the above (5) to (8)
ol) with tetrahydrofuran / hexane / water = 45 g /
It is dissolved in a mixed solvent of 45 g / 90 g, and the temperature is 40 ° C. to 50 ° C.
0.7 g of bromine dissolved in 10 g of tetrahydrofuran
2 g (1.5 × 3 mmol) is slowly added dropwise over 30 minutes. After completion of the dropwise addition, the mixture is stirred at 45 ° C to 55 ° C for 30 minutes and cooled. This was poured into 500 ml of toluene, washed with 200 g of a 10% aqueous solution of sodium hydrogen sulfite and then with 200 g of a 5% aqueous solution of sodium hydrogen carbonate, washed twice with water, dried over magnesium sulfate, filtered, and toluene was distilled off to remove toluene / toluene. Purification with a hexane = 2/3 silica gel column gave 1.28 g of blue-violet crystals. (The yield is 97.0% when the bromination ratio is set to 3.)

The λmax in chloroform of the obtained mixture of four isomers was 590 nm and ε = 111000
Met. The results of elemental analysis of the above compound were as follows.

[Table 6] FIG. 4 shows the IR spectrum of the above compound.

Example 7 904 mg (1.5 m) of the mixture of the above (9) to (12)
mol) in chloroform / hexane / water = 80 g / 10
g / 90 g of a mixed solvent, and 0.72 g of bromine dissolved in 10 g of chloroform at a temperature of 40 ° C. to 50 ° C. (1.
5 × 4 mmol) is slowly added dropwise over 30 minutes. After completion of the dropwise addition, the mixture is stirred at 45 ° C to 55 ° C for 30 minutes and cooled. This was poured into 500 ml of toluene, washed with 200 g of a 10% aqueous solution of sodium hydrogen sulfite and then with 200 g of a 5% aqueous solution of sodium hydrogen carbonate, washed twice with water, dried over magnesium sulfate, filtered, and toluene was distilled off to remove toluene / toluene. Purification with a hexane = 3/2 silica gel column gave 1.30 g of blue-black crystals. (The yield is 94.4% when the bromination ratio is set to 4.)

The λmax in chloroform of the obtained mixture of four isomers was 611 nm, and ε = 1110,000.
Met. The results of elemental analysis of the above compound were as follows.

[Table 7]

TG-DTA charts of the unbrominated product of Example 1 and the brominated product of Example 5 are shown in FIGS. 5 and 6, respectively. 7 and 8 show TG-DTA charts of the unbrominated product of Example 2 and the brominated product of Example 6, respectively.
5 and 6, and FIGS. 7 and 8 show that the brominated product has a lower decomposition temperature and a more rapid thermal decomposition behavior than the non-brominated product.

[0053]

According to the present invention, the halogenated tetraazaporphyrin compound has at least one structure represented by the general formulas (I) -a to (I) -d. It is useful as a recording material for optical recording media that is excellent in light resistance and storage stability applicable to the system.

The method for producing a tetraazaporphyrin compound according to claim 2 is characterized in that the alkyl-substituted maleonitrile represented by the general formula (III) -a or the general formula (III) -b
Alkyl-substituted 2,5-diiminopyrrole 1 to
Since four kinds are reacted with a metal (derivative), according to the present production method, it is easily represented by the general formulas (II) -a to (II) -d which are the precursors of claim 1. At least one compound can be obtained.

In the method for producing a tetraazaporphyrin compound according to claims 3 and 4, since the reaction according to claim 2 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 5, 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. .

In the method for producing a tetraazaporphyrin compound according to claim 6, since the reaction temperature is 90 to 220 ° C., the desired product can be obtained more efficiently.

In the method for producing a tetraazaporphyrin compound according to claim 7, since the amount of the solvent is 1 to 100 times the amount of the raw material, the desired product can be obtained more efficiently.

In the method for producing a tetraazaporphyrin compound according to claims 8 and 9, since an organic base, particularly diazabicycloundecene or diazabicyclononene, is allowed to coexist in the reaction system, the reaction is carried out at a lower temperature, particularly in a crystalline state. The production of a high isomer can be suppressed, and the highly soluble target compound can be efficiently obtained.

The method for producing a halogenated tetraazaporphyrin compound according to claim 10 is the method of formula (II) -a.
(II) 1-tetraazaporphyrin represented by -d
Since the four kinds are reacted with the halogenating agent in a mixed solvent of an organic solvent and water at 0 to 90 ° C., the desired product can be easily obtained in high yield.

The halogenated tetraazaporphyrin compound of the eleventh aspect is the most preferable in terms of thermal decomposition behavior because the halogen is bromine.

The method for producing a halogenated tetraazaporphyrin compound according to the twelfth and thirteenth aspects is based on the fact that an organic solvent which is substantially immiscible with water, particularly a saturated hydrocarbon, ether or halogenated hydrocarbon is used. The object can be obtained efficiently.

In the method for producing a halogenated tetraazaporphyrin compound according to claims 14 and 15, bromine is used as a halogenating agent, and in particular, it is used in a molar ratio of 1 to 5 with respect to the raw material. Things can be obtained more efficiently.

[Brief description of the drawings]

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

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

FIG. 3 is an IR spectrum of the compound obtained in Example 5.

FIG. 4 is an IR spectrum of the compound obtained in Example 6.

FIG. 5 is a TG-DTA chart of the compound obtained in Example 1.

FIG. 6 is a TG-DTA chart of the compound obtained in Example 5.

FIG. 7 is a TG-DTA chart of the compound obtained in Example 2.

FIG. 8 is a TG-DTA chart of the compound obtained in Example 6.

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[Procedure amendment]

[Submission date] July 30, 1998

[Procedure amendment 2]

[Document name to be amended] Statement

[Correction target item name] Name of invention

[Correction method] Change

[Correction contents]

Title: Halogenated tetraazaporphyrin compound and method for producing (halogenated) tetraazaporphyrin compound

 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Yasunobu Ueno 1-3-6 Nakamagome, Ota-ku, Tokyo Stock inside Ricoh Company (72) Inventor Yasuhiro Higashi 1-3-6 Nakamagome, Ota-ku, Tokyo Stock Inside the company Ricoh

Claims (15)

[Claims] 1. A halogenated tetraazaporphyrin compound comprising one or a mixture of two or more of the four compounds represented by the following general formulas (I) -a to (I) -d. Embedded image Embedded image Embedded image Embedded image [Wherein, M, R ^{1 to} R ⁴ , X and n 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. T: an integer of 0 to 2; R ^{1 to} R ⁴ each independently represent a hydrogen atom or a substituted or unsubstituted linear or branched alkyl group;
X: chlorine, bromine or iodine atom, except when all of ^{1 to} R ⁴ are hydrogen atoms, n: the number of substitution of the above halogen atom, and an integer of 1 to 4. ] 2. An alkyl-substituted maleonitrile represented by the following general formula (III) -a or the following general formula (III) -a
alkyl-substituted 2,5-diiminopyrrole 1 represented by b
A method for producing at least one tetraazaporphyrin compound represented by the following general formulas (II) -a to (II) -d, characterized by reacting at least four types with a metal or a metal derivative. Embedded image Embedded image (Wherein, R and R ′ each independently represent a hydrogen atom or a substituted or unsubstituted linear or branched alkyl group.
However, at least one of R and R 'is a hydrogen atom, and all eight substitution positions do not become hydrogen atoms when the tetraazaporphyrin compound is formed. ) Embedded image Embedded image Embedded image [Wherein, M and R ^{1 to} R 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. T: an integer of 0 to 2; R ^{1 to} R ⁴ each independently represent a hydrogen atom or a substituted or unsubstituted linear or branched alkyl group;
All ¹ to R ⁴ excluding a case where the hydrogen atom. ] 3. The method for producing a tetraazaporphyrin compound according to claim 2, wherein the reaction is performed in an organic solvent. 4. The method for producing a tetraazaporphyrin compound according to claim 3, wherein the organic solvent is an alcohol. 5. The method for producing a tetraazaporphyrin compound according to claim 2, wherein the metal or metal derivative is a transition metal, a transition metal halide or a transition metal carboxylate. 6. The method according to claim 2, wherein the reaction temperature is 90.
A method for producing a tetraazaporphyrin compound, which is carried out at a temperature of from -220 ° C. 7. The tetraazaporphyrin compound according to claim 2, wherein the amount of the solvent used is 1 to 100 times the amount of the alkyl-substituted maleonitrile or the alkyl-substituted 2,5-diiminopyrrole. Production method. 8. The method for producing a tetraazaporphyrin compound according to claim 2, wherein an organic base is present. 9. The method for producing a tetraazaporphyrin compound according to claim 8, wherein the organic base is diazabicycloundecene or diazabicyclononene. 10. The compounds represented by the general formulas (II) -a to (II)-
reacting one or a mixture of two or more tetraazaporphyrins represented by d with a halogenating agent in a mixed solvent of an organic solvent and water at 0 to 90 ° C. A method for producing at least one halogenated tetraazaporphyrin compound represented by (I) -d. 11. The halogenated tetraazaporphyrin compound according to claim 1, wherein X is bromine. 12. The method for producing a halogenated tetraazaporphyrin compound according to claim 10, wherein the organic solvent is not substantially mixed with water. 13. The method for producing a halogenated tetraazaporphyrin compound according to claim 12, wherein the organic solvent is one or more selected from saturated hydrocarbons, ethers, and halogenated hydrocarbons. 14. The method for producing a halogenated tetraazaporphyrin compound according to claim 10, wherein the halogenating agent is bromine. 15. The method for producing a halogenated tetraazaporphyrin compound according to claim 14, wherein the bromine is used in a molar ratio of 1 to 5 with respect to the tetraazaporphyrin compound.