JP4435520B2 - μ-Oxo-triazacoloratosilane derivative and process for producing the same - Google Patents

Description

  The present invention relates to a μ-oxo-triazacoloratosilane derivative that can be used in the field of photoelectronics such as photoelectric functional materials and optical recording media, and a method for producing the same.

  As the laser light for recording and reproducing with respect to the optical information recording medium, those in the red to near-infrared region are used, and recording media corresponding to this are widely used. For example, a disc-shaped optical information recording medium (CD-R, DVD-R) that can be written by a user such as a write-once optical information recording medium is an example.

  In laser light, the minimum diameter of a laser spot depends on its wavelength. The size of the laser spot is related to the density of optical information that can be recorded. When the spot is smaller, higher-density optical information recording is possible. Laser light having a long wavelength in the red to infrared region is limited in reducing the diameter of the laser spot, and so-called super-resolution technology is also used to increase the amount of information recorded in a certain area.

  On the other hand, in recording / reproduction with respect to an optical information recording medium, an attempt has been made to increase the information recording density by using a laser beam having a shorter wavelength. In recent years, semiconductor lasers in the blue light region have been put into practical use, and it is becoming possible to increase the recording information density without using super-resolution technology. The range of the transmission wavelength of such a semiconductor laser is about 350 to 500 nm, and a recording material having wavelength absorption within this range is required in the production of an optical information recording medium. However, organic materials having a maximum absorption wavelength of about 350 to 450 nm generally have a small molecular skeleton, and therefore have a low molecular extinction coefficient, and few materials exceed 100,000.

  One of the materials that can solve these problems is a porphyrin derivative. A porphyrin derivative is a derivative of cyclic tetrapyrrole (porphine), and includes a porphyrin complex having a central metal coordinated by an atomic group. The porphyrin derivative has a specific absorption band generated from the conjugated system in the ring structure in the absorption spectrum, and among these, the one on the short wavelength side is called a soret band (S band). This Soret band has a very large molecular extinction coefficient of 100,000 or more, and by using this large absorption band, highly sensitive optical recording in the blue light region is possible. In JP-A-7-304256 (Patent Document 1), JP-A-7-304257 (Patent Document 2), and JP-A-8-127174 (Patent Document 3), a recording layer containing a porphyrin derivative is formed. An optical recording medium is described.

  In general, a recording layer constituting an optical information recording medium can be easily formed by applying a solution obtained by dissolving a recording material in a solvent onto a substrate by a spin coating method or the like. However, porphyrin derivatives are easily crystallized due to the symmetry of their structure and are hardly soluble in solvents. For this reason, it is difficult to spin-coat as a solution, and there has been a problem that, when forming a film as a recording layer, a vacuum deposition method must be used.

  Japanese Patent Application Laid-Open No. 2001-277723 (Patent Document 4), Japanese Patent Application Laid-Open No. 11-144411 (Patent Document 5) and Japanese Patent Application Laid-Open No. 11-14412 (Patent Document 6) include porphyrazine dyes (tetraazaporphyrin compounds). Is described. This dye is suitable for recording / reproducing information with a red semiconductor laser beam having a wavelength of 630 to 680 nm, but cannot cope with a blue semiconductor laser beam having a wavelength of 350 to 450 nm, which enables ultrahigh density recording.

  Japanese Patent Application Laid-Open No. 2000-343823 (Patent Document 7) and Japanese Patent Application Laid-Open No. 2002-264520 (Patent Document 8) describe an optical information recording medium having a recording layer made of a corol derivative. Japanese Patent Application Laid-Open No. 2002-137547 (Patent Document 9) describes an optical recording medium containing a porphycene compound which may be metal-complexed in a recording layer.

  Japanese Patent Application Laid-Open No. 2001-039032 (Patent Document 10) describes an optical information recording medium characterized by a recording layer made of a compound having a bridge structure via a binding site in a cyclic compound having four pyrrole rings. . This bridge structure portion is composed of a divalent hydrocarbon bonding group, a transition metal, or the like.

JP-A-7-304256 JP-A-7-304257 JP-A-8-127174 JP 2001-277723 A JP-A-11-144411 Japanese Patent Laid-Open No. 11-144312 JP 2000-343823 A JP 2002-264520 A JP 2002-137547 A JP 2001-039032 A

  The present invention provides a μ-oxo-triazacoloratosilane derivative that can be used as a recording material of an optical information recording medium using a purple to blue laser beam, which is expected to be used in the field of optical information recording. Objective.

  That is, the present invention provides a μ-oxo-triazacoloratosilane derivative represented by the following formula (I), whereby the above object is achieved.

[Wherein R ^{1 to} R ⁸ are each independently a hydrogen atom, a halogen atom, a nitro group, a cyano group, a substituted or unsubstituted alkyl group or cycloalkyl group, a substituted or unsubstituted alkoxy group or an aryloxy group. Represents a substituted or unsubstituted aryl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted acyl group, a substituted or unsubstituted alkoxycarbonyl group or a heterocyclic residue, and R ¹ and R ² , R ³ and Any pair of R ⁴ , R ⁵ and R ⁶ and R ⁷ and R ⁸ may be linked to form one aliphatic ring. ]

The present invention also provides:
Formula (II)

[Wherein, R ^{1 to} R ⁸ are as defined above. ]
And a step of purifying the tetraazaporphyrin derivative represented by the formula: and a step of purifying the product, and a method for producing the μ-oxo-triazacholoratosilane derivative. Achieved.

  Triazacoloratosilane constituting the μ-oxo-triazacoloratosilane derivative is one type of corrole derivative having a corrole ring structure. The corrole derivative has a structure in which one meso-position atom of the porphyrin derivative is formally removed.

  The compound of the present invention (μ-oxo-triazacoloratosilane derivative) has a light absorption characteristic different from that of porphyrin, and can provide various materials as a functional color material. The compound of the present invention is useful as a recording material contained in a recording layer constituting an optical information recording medium using a violet to blue laser beam capable of recording / reproducing information at an ultra-high density. Further, since the compound of the present invention is soluble in various organic solvents, when the compound of the present invention is used as a recording material in an optical information recording medium, the optical information recording medium can be obtained by a simple coating method such as a spin coating method. A recording layer can be created.

  The μ-oxo-triazacoloratosilane derivative of the present invention has a structure represented by the following formula (I).

In the above formula (I), R ^{1 to} R ⁸ are each independently a hydrogen atom, a halogen atom, a nitro group, a cyano group, a substituted or unsubstituted alkyl group or cycloalkyl group, a substituted or unsubstituted alkoxy group or An aryloxy group, a substituted or unsubstituted aryl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted acyl group, a substituted or unsubstituted alkoxycarbonyl group or a heterocyclic residue, R ¹ and R ² , Any pair of R ³ and R ⁴ , R ⁵ and R ⁶ and R ⁷ and R ⁸ may be linked to form one aliphatic ring. Examples of the substituent that may be contained in R ^{1 to} R ^{8 and the} like include a halogen atom.

Specific examples of R ^{1 to} R ⁸ in formula (I) include, for example, a hydrogen atom; a nitro group; a cyano group; a halogen atom such as chlorine, bromine, fluorine, and iodine; a methyl group, an ethyl group, a propyl group, and an isopropyl group. , Butyl, tert-butyl, amyl, isoamyl, hexyl, heptyl, octyl, tert-octyl, 2-ethyl-hexyl, nonyl, dodecyl, 3-butoxy-propyl, tri A substituted or unsubstituted alkyl group such as a fluoromethyl group; a substituted or unsubstituted cycloalkyl group such as a cyclohexyl group or 4-ethylcyclohexyl group; a substituted or unsubstituted methoxy group such as a methoxy group, an ethoxy group, a propoxy group, a butoxy group, or a phenoxy group; Unsubstituted alkoxy group or aryloxy group; phenyl group, tolyl group, diphenyl group, fluorophenyl A substituted or unsubstituted aryl group such as a group; a substituted or unsubstituted aralkyl group such as a benzyl group or a phenethyl group; an acetyl group, a propionyl group, a butyryl group, a valeryl group, a stearoyl group, a benzoyl group, or a toluoyl group; A substituted or unsubstituted alkoxycarbonyl group such as an unsubstituted acyl group, a methoxycarbonyl group, an ethoxycarbonyl group, or an isopropoxycarbonyl group; a heterocyclic residue such as a furyl group, a thienyl group, a pyrrolyl group, a thiazolyl group, or a pyridyl group; Can be mentioned.

One aliphatic ring that may be formed by linking any one of R ¹ and R ² , R ³ and R ⁴ , R ⁵ and R ⁶ , R ⁷ and R ⁸ is a cyclohexyl ring or Examples include a methylcyclohexyl ring.

Any one of R ^{1 to} R ⁸ is preferably an alkyl group. This is because the μ-oxo-triazacoloratosilane derivative having an alkyl group has excellent solubility in a solvent. Examples of the alkyl group include an alkyl group having 1 to 20 carbon atoms, preferably an alkyl group having 1 to 12 carbon atoms (for example, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a tert-butyl group, an amyl group, Isoamyl group, hexyl group, heptyl group, octyl group, tert-octyl group, 2-ethyl-hexyl group, nonyl group, dodecyl group), more preferably an alkyl group having 3 to 6 carbon atoms (for example, propyl group, isopropyl group, Butyl group, tert-butyl group, amyl group, isoamyl group, hexyl group), particularly preferably tert-butyl group.

One of the preferred embodiments is that each of R ¹ and R ² , R ³ and R ⁴ , R ⁵ and R ⁶ and R ⁷ and R ⁸ is one of the above alkyl groups and the other is a hydrogen atom. . In this case, the alkyl group is most preferably a tert-butyl group. This is because the solubility in a solvent is particularly excellent in this case.

  The solvent includes an organic solvent usually used for preparing a solution containing a recording material in a coating method such as a spin coating method. Examples of such solvents include alcohol solvents such as methanol, ethanol, isopropyl alcohol, octafluoropentanol, allyl alcohol, methyl cellosolve, ethyl cellosolve, and tetrafluoropropanol, hexane, heptane, octane, decane, cyclohexane, and methylcyclohexane. , Aliphatic or alicyclic hydrocarbon solvents such as ethylcyclohexane and dimethylcyclohexane, aromatic hydrocarbon solvents such as toluene, xylene and benzene, halogenated hydrocarbons such as carbon tetrachloride, chloroform, tetrachloroethane and dibromoethane Solvents, ether solvents such as diethyl ether, dibutyl ether, diisopropyl ether, dioxane, acetone, 3-hydroxy-3-methyl-2-butanone, etc. Ton solvents, ethyl acetate, and ester solvents such as methyl lactate.

  Of these solvents, the μ-oxo-triazacoloratosilane derivative of the present invention is, for example, an aromatic hydrocarbon solvent, a halogenated hydrocarbon solvent, particularly an organic solvent such as toluene or chloroform. Excellent solubility.

  Specific examples of the μ-oxo-triazacoloratosilane derivative of the present invention include the following compounds, but are not limited thereto.

(+ Represents a tert-butyl group.)

(+ Represents a tert-butyl group.)

(+ Represents a tert-butyl group.)

  The tetraazaporphyrin derivative (also referred to as the following formula (II), also referred to as porphyrazine derivative) used as a starting material in the production of the μ-oxo-triazacoloratosilane derivative of the present invention may be synthesized or commercially available. It may be.

[Wherein, R ^{1 to} R ⁸ are as defined above. ]

スキーム１ For example, tetra-tert-butyltetraazaporphyrin, which is an example of a tetraazaporphyrin derivative, can be synthesized by the following scheme 1.

Scheme 1

  The μ-oxo-triazacoloratosilane derivative represented by the formula (I) of the present invention can be synthesized by a method including a step of reacting a tetraazaporphyrin derivative with trichlorosilane; and a step of purifying. (Scheme 2).

スキーム２

Scheme 2

  As the tetraazaporphyrin derivative used in this reaction, one having no central metal (metal-free tetraazaporphyrin derivative) is used.

  The amount of trichlorosilane used for the reaction with the tetraazaporphyrin derivative is 1 mol or more, generally 2 to 10 mol per mol of the tetraazaporphyrin derivative.

  A reaction solvent that can be used in this reaction may be any solvent that can dissolve the tetraazaporphyrin derivative. For example, aromatic solvents such as benzene, toluene and xylene; hydrocarbon solvents such as hexane, pentane and cyclohexanemethylcyclohexane;

  The reaction temperature is preferably the solvent reflux temperature. The reaction time is typically 3 hours or longer, preferably 5 to 24 hours, until no remaining tetraazaporphyrin derivative used as a raw material is observed.

  A purification process may be performed by the method used normally, for example, can be performed by a silica gel column chromatogram.

  The production of the corol ring in the μ-oxo-triazacoloratosilane derivative produced according to the present invention is described in J. Org. Am. Chem. Soc. Vol. 108, 1532-1536, 1986, the generation of a triazatetrabenzcorol ring by a phthalocyanine ring contraction reaction can be referred to.

  Since the μ-oxo-triazacholoratosilane derivative of the present invention has a Soret band similar to porphyrin, it can be used as a recording material for optical information recording media using purple to blue semiconductor laser light. The μ-oxo-triazacoloratosilane derivative also has an absorption wavelength (wavelength 550 to 660 nm) that can also correspond to red semiconductor laser light.

  Note that the creation and reproduction of an optical information recording medium using a blue semiconductor laser (wavelength 400 to 450 nm) is described in JP 2002-264520 A, JP 2000-343823 A, JP 2002-137547 A, and the like. Has been. The μ-oxo-triazacoloratosilane derivative of the present invention can be used as a recording material contained in a recording layer constituting an optical information recording medium as described therein.

  EXAMPLES Hereinafter, although an Example demonstrates this invention concretely, this invention is not limited to this.

Example 1
Synthesis of μ-oxo-{(tetrakis-tert-butyl) triazacolorato} silane derivative To 30 ml of dry benzene, 0.5 g of metal-free tetrakis-tert-butyltetraazaporphyrin derivative and 1.0 ml of trichlorosilane were added and refluxed for 5 hours. Then, 1.0 ml of trichlorosilane was further added. After confirming that no tetraazaporphyrin derivative remained, the solvent was distilled off under reduced pressure. The obtained sticky solid was stirred and dissolved overnight by adding 10 ml of a solution of pyridine: concentrated aqueous ammonia = 10: 1. The main spot of this solution was collected on a silica gel column chromatogram, and the solvent was distilled off and dried. As a result, 0.36 g of a purple solid compound represented by the following formula (Ia) was obtained.

Molecular weight of compound (theoretical value): C ₆₄ H ₈₀ N ₁₄ OSi ₂ (1116.6)

  Elemental analysis

  The MCD (magnetic circular dichroism spectrum) and electronic absorption spectrum (ultraviolet-visible) of the obtained compound are shown in FIG.

The ¹ H-NMR spectrum of the obtained compound is shown in FIG.

The TOF-MS spectrum of the obtained compound is shown in FIG.
Upper: measured value of the compound of Example 1 Lower: theoretical value

  The obtained compound had a molecular extinction coefficient ε at λ = 380.2 nm of 122,000, and the molecular extinction coefficient ε at λ = 595.9 nm was 32,000.

It is MCD (magnetic circular dichroism spectrum) of Example 1, and an electronic absorption spectrum (ultraviolet-visible). 1 is a ¹ H-NMR spectrum of Example 1. 2 is a TOF-MS spectrum of Example 1.

Claims (5)

Formula (I)

[Wherein R ^{1 to} R ⁸ are each independently a hydrogen atom, a halogen atom, a nitro group, a cyano group, a substituted or unsubstituted alkyl group or cycloalkyl group, a substituted or unsubstituted alkoxy group or an aryloxy group. Represents a substituted or unsubstituted aryl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted acyl group, a substituted or unsubstituted alkoxycarbonyl group or a heterocyclic residue, and R ¹ and R ² , R ³ and Any pair of R ⁴ , R ⁵ and R ⁶ and R ⁷ and R ⁸ may be linked to form one aliphatic ring. ]
A [mu] -oxo-triazacoloratosilane derivative represented by: The μ-oxo-triazacoloratosilane derivative according to claim 1, wherein any one of R ^{1 to} R ⁸ is an alkyl group. The μ- of claim 1, wherein in each of the groups R ¹ and R ² , R ³ and R ⁴ , R ⁵ and R ⁶ and R ⁷ and R ⁸ , either one is an alkyl group and the other is a hydrogen atom. Oxo-triazacoloratosilane derivatives.   The μ-oxo-triazacoloratosilane derivative according to claim 3, wherein the alkyl group is a tert-butyl group. Formula (II)

[Wherein R ^{1 to} R ⁸ are each independently a hydrogen atom, a halogen atom, a nitro group, a cyano group, a substituted or unsubstituted alkyl group or cycloalkyl group, a substituted or unsubstituted alkoxy group or an aryloxy group. Represents a substituted or unsubstituted aryl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted acyl group, a substituted or unsubstituted alkoxycarbonyl group or a heterocyclic residue, and R ¹ and R ² , R ³ and Any pair of R ⁴ , R ⁵ and R ⁶ and R ⁷ and R ⁸ may be linked to form one aliphatic ring. ]
A method for producing a μ-oxo-triazacholoratosilane derivative, comprising: a step of reacting a tetraazaporphyrin derivative represented by the formula:

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