JPH1180574A - Tetraazaporphyrin compound and its production - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject compound capable of exhibiting excellent light resistance and storage stability and useful for optical density optical disks using semiconductor lasers having start wavelengths in short wavelengths by introducing a (substituted) phenyl group and a metal (derivative) to the specific sites of a tetaazaporphyrin compound. SOLUTION: A compound of formula I [Mt is two H atoms, a di- to tetra-valent metal atom (containing O or a halogen) or the like; R1 -R5 , R1 '-R5 ', R1 "-R5 ", R1 '''-R5 ''' are each H, a halogen, a (branched) alkyl (substituted by a halogen) or the like], its prescribed structural isomer or their mixture. The compound is obtained e.g. by reacting a compound of formula II or III with a metal (derivative) (e.g. a transition metal, its halide salt or carboxylate salt) in an organic solvent at a temperature of 90-220 deg.C.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a novel and useful tetraazaporphyrin compound and a method for producing the same.

[0002]

2. Description of the Related Art As optical disk materials, in particular, write-once optical disks, there are many Te-based phase-change type materials and perforated type materials using Te metal, while organic dyes having a lower thermal conductivity than Te are used. Perforated type used,
Attention has been paid to a bubble forming type (a vapor sandwich type), and a part of the bubble forming type using a cyanine dye, for example, has been put to practical use. In particular, organic materials as write-once optical disk materials include diphenylmethane-based materials, polymethine-based materials (thiapyryliums, cyanines, azulene, pentamethine, squarylium,
Croconiums, etc., quinones (anthraquinones, naphthoquinones, etc.), dithiols (benzenedithiol metal salts, dithiobenzyls, etc.), polyfins (metal phthalocyanines, metal naphthalocyanines, polyfins, etc.)
It has been known.

[0003] Organic materials as optical disk materials have more preferable properties as optical disk materials because their thermal conductivity and thermal diffusion coefficient are one or two orders of magnitude lower than metals such as Te, and their melting points are lower than that of Te metals. Have. For this reason, for example, the practical use of optical disks using phthalocyanine dyes has been studied, but such conventional polyfins not only have a lower light reflectance than metal-based ones, but also have an ordinary semiconductor property. It did not have strong absorption in the laser oscillation light spectrum region.

[0004]

SUMMARY OF THE INVENTION An object of the present invention is to provide a novel tetraazaporphyrin compound and a method for producing the same, and a substituted maleeonitrile compound and a 2,5-diiminopyrrole compound as precursors. The tetraazaporphyrin of the present invention has excellent light resistance and storage stability, and is extremely useful for a high-density optical disk system using a semiconductor laser having a starting wavelength shorter than the conventional wavelength range.

[0005]

Means for Solving the Problems The object of the present invention is to provide (1) a tetraaza comprising one or a mixture of two or more of the four compounds represented by the following formulas (I) a to (I) d: Porphyrin compounds.

[0006]

Embedded image

[0007]

Embedded image

[0008]

Embedded image

[0009]

Embedded image (Wherein, Mt is two hydrogen atoms or divalent, trivalent or tetravalent metal atoms optionally having oxygen or halogen, or (OR ₆ ) _p , (OSiR ₇ R ₈ R ₉ ) _q , (OPOR
₁₀ R ₁₁ ) _r and (OCOR ₁₂ ) represent a metal atom which may have _s . R _{6 to} R ₁₂ independently represent a hydrogen atom, a substituted or unsubstituted aliphatic or aromatic hydrocarbon group, p, q,
r and s represent an integer of 0 to 2. R _{1 to} R ₅ ,
_{R 1 '~R 5', R} 1 "~R 5", R 1 '''~R5''' are each independently a hydrogen atom, a halogen atom, halogen-substituted unsubstituted linear or branched alkyl group, Alkyl alkoxy group,
It represents an unsubstituted halogen-substituted alkoxy group or an unsubstituted halogen-substituted aryl group, alkylamino group, alkylthio group, alkylsilyl group, hydroxyl group, nitro group, or cyano group. ) ", (2)" Formula (II)-which is a precursor of the tetraazaporphyrin compound shown in the above item (1).
a substituted maleonitrile compound represented by a and a substituted 2,5-diiminopyrrole compound represented by formula (II) -b:

[0010]

Embedded image

[0011]

Embedded image (Wherein, R _{1 to} R ₅ , R ₁ ′ to R ₅ ′, R ₁ ″ to R ₅ ″,
R ₁ ′ ″ to R ₅ ″ are each independently a hydrogen atom, a halogen atom, a halogen-substituted unsubstituted linear or branched alkyl group,
Alkyl alkoxy group, halogen-substituted unsubstituted alkoxy group or halogen-substituted unsubstituted aryl group, alkylamino group, alkylthio group, alkylsilyl group, hydroxyl group,
Represents a nitro group and a cyano group. )), (3) "In order to obtain one or a mixture of two or more of the four types represented by the formulas (I) a to (I) d, the corresponding precursor is a substituted maleonitrile or substituted A method for producing a tetraazaporphyrin compound of formulas (I) a to (I) d by reacting a 2,5-diiminopyrrole compound with a metal or a metal derivative. ", (4)" The reaction is carried out in an organic solvent. (5) The method according to (3), wherein the organic solvent is an aromatic hydrocarbon or a halogenated aromatic hydrocarbon. (4) The method according to (3) or (6), wherein the metal or metal derivative is a transition metal, a transition metal halide, or a transition metal carboxylate. The production method according to the item 4). ", (7) The reaction Wherein said item (3) to (5) The method according to any one of claim degrees is characterized in that it is a 90 to 220 ° C.. (8) "A production method according to any one of the above (3) to (7), wherein ammonium molybdate is coexistent.", (9) "A coexistence of an organic base." And (10) "the organic base is diazabicycloundecene or diazabicyclononene." The manufacturing method according to the above mode (7), "

That is, the term (1) is represented by the following formulas (I) a to
(I) A tetraazaporphyrin compound represented by d, which is useful for high-density optical recording media and the like. The above item (2) is a precursor capable of obtaining a tetraazaporphyrin compound in high yield. The item (3) is a basic method for producing the tetraazaporphyrin compound shown in item (1). The items (4) and (5) are the solvent and the optimum temperature during the production, and the item (6) is the optimum condition of the central metal (or oxide) raw material for obtaining the target product. ,
The item (7) relates to the optimum conditions for the production of an efficient target compound, and the item (8), the item (9),
And the above-mentioned item (10) relates to an auxiliary agent for efficiently obtaining a target substance at a low temperature during production and its limited conditions.

Mt in the above formulas (I) a to (I) d represents two hydrogen atoms or divalent or trivalent optionally having oxygen or halogen.
Valent or tetravalent metal or (OR ₆ ) _p , (OSiR ₇ R ₈
R ₉ ) _q , (OPOR ₁₀ R ₁₁ ) _r , and a metal atom which may have (OCOR ₁₂ ) _s , and R _{6 to} R ₁₂ are each independently a hydrogen atom, or a substituted or unsubstituted aliphatic, Represents an aromatic hydrocarbon group, and p, q, r, and s represent an integer of 0 to 2. R _{1 to} R ₅ , R ₁ ′ to R ₅ ′, R ₁ ″ to R ₅ ″,
R ₁ ′ ″ to R ₅ ″ are each independently a hydrogen atom, a halogen atom, a halogen-substituted unsubstituted linear or branched alkyl group,
Alkyl alkoxy group, halogen-substituted unsubstituted alkoxy group or halogen-substituted unsubstituted aryl group, alkylamino group, alkylthio group, alkylsilyl group, hydroxyl group,
Represents a nitro group and a cyano group.

The conditions for synthesizing the tetraazaporphyrin compound are as follows: the substituted maleonitrile compound (formula (II) -a) or the alkyl-substituted 2,5-diiminopyrrole compound (formula (II) -b) One to four kinds are heated and reacted with a metal or a metal derivative in a solvent at 90 to 350 ° C. In the formulas (II) -a and (II) -b, R _{1 to} R ₅ and R ₁ ′
_{~R 5 ', R 1 "~R} 5", R 1''' ~R 5 ''' are each independently a hydrogen atom, a halogen atom, halogen-substituted unsubstituted linear or branched alkyl group, alkyl alkoxy group A halogen-substituted unsubstituted alkoxy group or a halogen-substituted unsubstituted aryl group, an alkylamino group, an alkylthio group, an alkylsilyl group, a hydroxyl group, a nitro group, and a cyano group.

In the case of ordinary substituted maleonitrile, there are cis-form and trans-form, but in order to obtain the desired tetraazaporphyrin compound in high yield, it is necessary to use only the cis-maleonitrile as a raw material. Is done. Therefore, it was necessary to fractionate only the cis form or convert the trans form to the cis form. In the present invention, the formula (II) -a has the same structure of the cis-form and the trans-form, so that a tetraazaporphyrin compound can be synthesized in a higher yield than before.

The preferred reaction temperature is 90 to 22.
0 ° C., the reaction does not proceed so much below 90 ° C.
When the temperature exceeds 20 ° C., a complicated product which is considered to be a decomposition product is given, and the yield is reduced. The solvent has a boiling point of 100
The boiling point is preferably at least 135 ° C. Specific examples include N, N-dimethylformamide, N, N-dimethylacetamide, dimethylsulfoxide, 1-methyl-2-pyrrolidone, 1-chloronaphthalene, tetrahydronaphthalene, benzyl alcohol,
Quinoline, N, N-dimethylaminoethanol and the like. Particularly preferred examples are aromatic hydrocarbons and halogenated aromatic hydrocarbons, that is, benzene, chlorobenzene, 1,2-dichlorobenzene, 1,3-dichlorobenzene, 1,4-dichlorobenzene, 1,2,3- Trichlorobenzene, 1,2,4-trichlorobenzene, 1,
3,5-trichlorobenzene, 1-chloronaphthalene,
2-chloronaphthalene 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, Mg and their halides, carboxylic acid derivatives, sulfates, nitrates, carbonyl compounds, oxides, complexes and the like. 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 2,5-diiminopyrrole, the method of synthesizing 1,3-diiminoisoindoline from phthalonitrile can be applied as it is. That is, by reacting the corresponding maleonitrile with ammonia in the presence of sodium in alcohol, the desired substituted 2,2
5-Diiminopyrrole is obtained.

It has been found that the addition of an organic base or ammonium molybdate during the formation of the tetraazaporphyrin ring can shorten the reaction time and improve the synthesis yield, and is very effective. That is, in the case where no organic base or ammonium molybdate is added, the reaction does not proceed to the end point unless the reaction temperature is raised or the reaction time is increased, and in the former case, the yield is due to the formation of a metal-free substance and a decomposition product. In the latter case, the reaction temperature must be high, and the reaction time takes 3 to 10 times, resulting in 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 DBN). These are preferably used in an amount of 0.5 to 2.5 molar equivalents relative to the starting material, substituted maleonitrile or 2,5-diiminopyrrole.
Preferably it is 0.7 to 1.5 molar equivalents. The amount of ammonium molybdate may be 0.0001 to 10 molar equivalents, preferably 0.001 to 0.01 molar equivalents, relative to substituted maleonitrile or 2,5-diiminopyrrole.

Formulas (I) -a to (I) -d, Formula (II)-
a to R _{1 to} R ₅ , R ₁ ′ to R ₅ ′ and R ₁ ″ in formula (II) -b
To R ₅ ", the alkyl group is a methyl group _{R 1 '''~R5'} '', an ethyl group, n- propyl group, n- butyl group, an 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, primary alkyl group such as n-decyl group, isopropyl group, sec-butyl group,
1-ethylpropyl group, 1-methylbutyl group, 1,2-
Dimethylpropyl group, 1-methylheptyl group, 1-ethylbutyl group, 1,2-dimethylbutyl group, 1,3-dimethylbutyl group, 1-ethyl-2-methylpropyl group, 1
-Methylhexyl group, 1-ethylpentyl group, 1-propylbutyl 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, 1-isopropyl-2-methylbutyl group, 1-
Secondary alkyl groups such as methyloctyl group, 1-ethylheptyl group, 1-propylhexyl group, 1-isobutyl-3-methylbutyl group, and tertiary alkyl groups such as tert-butyl group, tert-amyl group and tert-heptyl group. And cycloalkyl groups such as cyclohexyl, 4-methylcyclohexyl, 4-ethylcyclohexyl, 4-tert-butylcyclohexyl, 4- (2-ethylhexyl) cyclohexyl, bornyl, isobornyl and adamantane. These alkyl groups may be substituted with a substituent such as halogen. 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, an ethynyl group, and a tert-butylacetylene group.

[0022]

EXAMPLES The present invention will now be described specifically with reference to examples, but the present invention is not limited to these examples. Example 1 Synthesis of tetraazaporphyrin compound (Compound No. 1) 120 mg (4.90 mmol) of Mg was diffused in 30 ml of n-pentanol, and the mixture was heated under reflux for 5 hours. Then 1,
1.20 g (4.85 mmol) of 1,2-tricyano-2- (3-trifluoromethylphenyl) ethylene is added, and the mixture is further heated under reflux for 4 hours. After completion of the reaction, the mixture was cooled to room temperature, hexane was added, the precipitate was filtered, and the filtrate was purified by silica gel chromatography (developing solvent: chloroform). 1.00 g of a dark blue solid magnesium tetraazaporphyrin as a mixture of four isomers (8
3%). (Compound No. 1)

[0023]

Embedded image

[0024]

Embedded image

[0025]

Embedded image

[0026]

Embedded image

The λmax of the mixture of the four isomers in chlorophore was ε = 92200 at 626 nm.
The elemental analysis result of the above compound showed a theoretical value of C: 55.9%,
H: 1.63%, N: 17.0%, measured value C: 5
6.3%, H: 1.68%, N: 16.8%.
FIG. 1 shows the IR spectrum and FIG. 4 shows the UV spectrum of the compound.

Example 2 Synthesis of tetraazaporphyrin compound (Compound No. 2) 1,1,2-Tricyano-2- (2-methylphenyl)
300 mg (1.55 mmol) of ethylene, 30.8 mg (0.31 mmol) of CuCl, and 1 mg of ammonium molybdate are dissolved in 3 ml of trichlorobenzene, and the mixture is heated under reflux for 5 hours. After completion of the reaction, the mixture was cooled to room temperature, hexane was added, the precipitate was filtered, and the filtrate was purified by silica gel chromatography (developing solvent: chloroform). 20 mg of copper tetraazaporphyrin, a dark blue solid, as a mixture of four isomers as described in Example 1
(0.4%). (Compound No. 2) The λmax of the mixture of four isomers in chlorophore
Was ε = 89500 at 635 nm. The results of elemental analysis of the above compound were as follows: theoretical value C: 68.9%, H: 3.37
%, N: 20.1%, measured value C: 68.3%,
H: 3.42%, N: 19.8%. FIG. 2 shows the IR spectrum and FIG. 5 shows the UV spectrum of the compound.

Example 3 Synthesis of tetraazaporphyrin compound (Compound No. 4) Magnesium tetraazaporphyrin 100 mg (0.1 mg)
10 mmol), 43 mg of cobalt chloride (0.33 mm
ol), 1 mg of ammonium molybdate and 0.1 mg of acetic acid.
2 ml is added to 2 ml of dichlorobenzene, and the mixture is refluxed for 3 hours. After completion of the reaction, the mixture was cooled to room temperature, hexane was added, the precipitate was filtered, and the filtrate was purified by silica gel chromatography (developing solvent: chloroform). 75 mg (78%) of a dark blue solid cobalt tetraazaporphyrin as a mixture of four isomers as shown in Example 1.
I got (Compound No. 4) The λmax of the mixture of four isomers in chlorophore
Was ε = 86300 at 599 nm. The results of elemental analysis of the above compound were as follows: theoretical value C: 54.0%, H: 1.58
%, N: 16.4%, measured value C: 54.6%,
H: 1.62%, N: 15.8%. FIG. 3 shows the IR spectrum and FIG. 6 shows the UV spectrum of the compound. The compound examples are shown below. 1-30
No isomer is described for the compound shown in (1), but there are actually four isomers as shown in Example 1.

[0030]

[Table 1-1]

[0031]

[Table 1-2]

[0032]

As is apparent from the detailed and concrete description, according to the present invention, a semiconductor laser having excellent light resistance and storage stability and having a starting wavelength shorter than the conventional wavelength range is used. A novel tetraazaporphyrin compound, which is extremely useful for a high-density optical disk system, is provided, a precursor capable of obtaining the compound in high yield is provided, and a method for producing the same is provided. Provided, as well as optimal manufacturing conditions,
Further, an extremely excellent effect that the use of the compound for a high-density optical disk system is provided is exhibited.

[Brief description of the drawings]

FIG. 1 shows an infrared spectrum of a compound according to the present invention.

FIG. 2 shows an infrared spectrum of another compound according to the present invention.

FIG. 3 shows an infrared spectrum of still another compound according to the present invention.

FIG. 4 shows an ultraviolet spectrum of the compound according to the present invention.

FIG. 5 shows an ultraviolet spectrum of another compound according to the present invention.

FIG. 6 shows an ultraviolet spectrum of still another compound according to the present invention.

 ──────────────────────────────────────────────────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 (10)

[Claims] 1. A compound represented by the following formulas (I) a to (I) d:
A tetraazaporphyrin compound comprising one or a mixture of two or more species. Embedded image Embedded image Embedded image Embedded image (Wherein, Mt is two hydrogen atoms or divalent, trivalent or tetravalent metal atoms optionally having oxygen or halogen, or (OR ₆ ) _p , (OSiR ₇ R ₈ R ₉ ) _q , (OPOR
₁₀ R ₁₁ ) _r and (OCOR ₁₂ ) represent a metal atom which may have _s . R _{6 to} R ₁₂ independently represent a hydrogen atom, a substituted or unsubstituted aliphatic or aromatic hydrocarbon group, p, q,
r and s represent an integer of 0 to 2. R _{1 to} R ₅ ,
_{R 1 '~R 5', R} 1 "~R 5", R 1 '''~R5''' are each independently a hydrogen atom, a halogen atom, halogen-substituted unsubstituted linear or branched alkyl group, Alkyl alkoxy group,
It represents an unsubstituted halogen-substituted alkoxy group or an unsubstituted halogen-substituted aryl group, alkylamino group, alkylthio group, alkylsilyl group, hydroxyl group, nitro group, or cyano group. ) 2. A substituted maleonitrile compound represented by the formula (II) -a and a substituted 2,5-diimino compound represented by the formula (II) -b, which are precursors of the tetraazaporphyrin compound represented by claim 1. Pyrrole body. Embedded image Embedded image (Wherein, R _{1 to} R ₅ , R ₁ ′ to R ₅ ′, R ₁ ″ to R ₅ ″,
R ₁ ′ ″ to R ₅ ″ are each independently a hydrogen atom, a halogen atom, a halogen-substituted unsubstituted linear or branched alkyl group,
Alkyl alkoxy group, halogen-substituted unsubstituted alkoxy group or halogen-substituted unsubstituted aryl group, alkylamino group, alkylthio group, alkylsilyl group, hydroxyl group,
Represents a nitro group and a cyano group. ) 3. A compound represented by the formula (I) a to (I) d:
Formula (I) by reacting a metal or a metal derivative with a corresponding precursor, a substituted maleonitrile or substituted 2,5-diiminopyrrole, to obtain a mixture of one or more of the species. Methods for producing the tetraazaporphyrin compounds of a to (I) d. 4. The method according to claim 3, wherein the reaction is performed in an organic solvent. 5. The method according to claim 4, wherein the organic solvent is an aromatic hydrocarbon or a halogenated aromatic hydrocarbon. 6. The method 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 according to claim 3, wherein the reaction temperature is 90 to 220 ° C. 8. The method according to claim 3, wherein ammonium molybdate coexists. 9. The method according to claim 3, wherein an organic base coexists. 10. The method according to claim 7, wherein the organic base is diazabicycloundecene or diazabicyclononene.