JPH1067780A - Photochromic pyrazolyl fulgide compounds - Google Patents

Abstract

(57) [Summary] (Modified) [Problem] To provide a fulgide compound having an absorption wavelength region having a long wavelength (it is desired to have absorption at 700 nm or more) and having high chemical stability. . A photochromic pyrazolyl fulgide compound represented by the following general formula [I]: (Wherein R ¹ is an alkyl group having 1 to 30 carbon atoms, 6 carbon atoms)
R ² and R ³ , such as a phenyl group of 1 to 12, have 1 to 1 carbon atoms.
R groups such as 0 alkyl groups and phenyl groups having 6 to 12 carbon atoms;
⁴ is a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, 6 carbon atoms
R ⁵ is an alkyl group having 1 to 30 carbon atoms, such as a phenyl group having 6 to 12 carbon atoms, and R ⁶ is an alkyl group having 1 to 10 carbon atoms, a phenyl group having 6 to 12 carbon atoms. , X is a group containing a nitrogen atom for an oxygen atom or N-R ^7, R ⁷ represents a an alkyl group, a phenyl group having 6 to 12 carbon atoms having from 1 to 30 carbon atoms)

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a novel fulgide compound having photochromic properties, and can be used in various fields such as recording materials and optical element materials.

[0002]

2. Description of the Related Art Various photochromic compounds exhibiting a reversible structural change by light are known, and are introduced in "Photochromism" by GH Brown.

Recently, fulgide compounds have been studied as photochromic compounds having high thermal stability. Among them, techniques for phenylfulgide, furylfulgide and thienylfulgide have been disclosed in Japanese Patent Publication Nos. 60-52150 and 61-1425. It is disclosed in gazettes and the like. These compounds have been shown to have very low thermal back reactions and to be capable of long term record keeping. In addition, studies have been made on optical recording disks using these compounds, and it has been shown that a recording density of 30 million bits / cm ² has a repeatability of 8,000 times or more. (I, E, E, Proc. 16
Vol. 0, Pt. I, No. 5, 1983).

A recent optical disk recording medium is required to have absorption in a semiconductor laser region (780 to 830 nm), which is disclosed in JP-A-61-267578. It is described that pyrylfulgide and fulgimide have an absorption band near the semiconductor laser region and have a maximum absorption (λmax = 620 nm) in a considerably long wavelength region.

[0005]

However, these compounds have the following drawbacks in practical applications.

[0006] Phenylfulgide, furylfulgide and thienylfulgide are chemically stable, but have a problem that the absorption wavelength region is short.

[0007] Further, although 3-pyrylfulgide has a long absorption wavelength region, it has a problem that it is very easily oxidized and chemically unstable. The present invention is intended to solve the above-mentioned drawbacks of the prior art, and has a long absorption wavelength region (desired to have absorption at 700 nm or more) and high chemical stability. It is intended to provide a fulgide compound.

[0008]

The present invention has the following arrangement to achieve the above object.

"A photochromic pyrazolyl fulgide compound represented by the following general formula [I]:

[0010]

Embedded image (Wherein R ¹ is an alkyl group having 1 to 30 carbon atoms, 6 carbon atoms)
12 phenyl group, a substituted phenyl group, a substituted group selected from aralkyl and substituted aralkyl group, R ²
And R ³ are an alkyl group having 1 to 10 carbon atoms, a phenyl group having 6 to 12 carbon atoms, a substituted phenyl group, an aralkyl group, a substituted aralkyl group and a substituent selected from a hydrogen atom.

Embedded image Represents an adamantylidene group. R ⁴ is a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a phenyl group having 6 to 12 carbon atoms,
It represents a substituent selected from a substituted phenyl group, an aralkyl group, a substituted aralkyl group, and halogen. R ⁵ is an alkyl group having 1 to 30 carbon atoms, a phenyl group having 6 to 12 carbon atoms,
R ⁶ represents a substituent selected from a substituted phenyl group, an aralkyl group, a substituted aralkyl group and a hydrogen atom;
And a substituent selected from an alkyl group having 10 to 10, a phenyl group having 6 to 12 carbon atoms, a substituted phenyl group, an aralkyl group, a substituted aralkyl group, a substituted amino group, a halogen and a hydrogen atom. X represents a group containing a nitrogen atom for an oxygen atom or N-R ^7, R ⁷ is an alkyl group having 1 to 30 carbon atoms, a phenyl group having 6 to 12 carbon atoms, a substituted phenyl group, aralkyl group, substituted aralkyl And a substituent selected from a group, an alkyl (meth) acrylate group having 3 to 30 carbon atoms, and a hydrogen atom. (Provided that R ² and R ³ are a substituent selected from an alkyl group having 1 to 10 carbon atoms, a phenyl group having 6 to 12 carbon atoms, a substituted phenyl group, an aralkyl group, a substituted aralkyl group and a hydrogen atom, And R ⁵ is an alkyl group having 1 to 30 carbon atoms, and 6 to 1 carbon atoms.
2 of the phenyl group, a substituted phenyl group, an aralkyl group, a substituted group selected from substituted aralkyl group and a hydrogen atom, and a group containing a nitrogen atom which X is represented by an oxygen atom or N-R ^7, R ⁷ Represents an alkyl group having 1 to 30 carbon atoms, a phenyl group having 6 to 12 carbon atoms, a substituted phenyl group, an aralkyl group, a substituted aralkyl group and a substituent selected from a hydrogen atom. )) "

[0011]

BEST MODE FOR CARRYING OUT THE INVENTION In the general formula [I], R ² and R ³
May be the same or different.

Although various methods are available for producing the fulgide compound of the present invention, the most common and high-yield methods include acetylpyrazole derivatives represented by the following general formula [II]: This is based on Stobbe condensation with a succinic ester derivative represented by the general formula [III].

[0013]

Embedded image (Wherein R ¹ to R ⁶ represents a R ¹ description Street to R ^6, R ⁸ is an alkyl group in the general formula [I].) Stobbe condensation, Ya dispersion solution as sodium hydride and a catalyst Or by refluxing the reaction in t-butanol containing alkali metal t-butoxy. The product at this stage is a half ester, ie one of the groups R ⁸ is a hydrogen atom. This product is converted to a dicarboxylic acid by hydrolysis. The dicarboxylic acid is converted to an acid anhydride by a dehydration reaction with an acid chloride by heating. These acid anhydrides are converted to the corresponding imide compounds by a dehydration reaction with an appropriate primary amine. Purification of these fulgide compounds can be achieved by a suitable purification method such as a column method or a recrystallization method.

Coloring is caused by irradiating the compound with ultraviolet light and irradiating with visible light to form a colorless body. In the application to optical recording, for example, red light of 600 to 650 nm by a helium neon laser is used. Use of light or the like is preferred.

The fulgide compound of the present invention can be used by dispersing it in a suitable medium such as a solvent or plastic, or by introducing an appropriate polymerizable functional group into the fulgide compound and copolymerizing it with another monomer to obtain a polymer. Is a preferred method. Further, it is also a preferable method to introduce a long-chain alkyl group or the like into the fulgide compound to form an LB film, or to use a thin film by vapor deposition or sputtering.

The fulgide compound of the present invention is used for various purposes, for example, storage and display of information, and is also useful for hologram recording.

[0017]

EXAMPLES The present invention will be described in more detail with reference to Examples, but the present invention is not limited thereto.

Example 1 5.0 g of 4-acetyl-1,3,5-trimethylpyrazole (3
3 mmol) and 7.0 g (33 mmol) of diethylisopropylidene succinate were reacted dropwise at 60 ° C. in a 100 ml benzene solution in which 2.0 g of sodium hydride (60% oil) was dispersed. After the reaction was completed, benzene was distilled off, then water was added to the residue, and further acid was added to make it weakly acidic.

Next, the released half ester was subjected to solvent extraction using toluene. The half ester was converted to a dicarboxylic acid by boiling with 10% ethanolic potassium hydroxide. After removing the water, the dicarboxylic acid was converted to the compound of formula (A) by boiling with acetyl chloride.

[0020]

Embedded image The compound of formula (A) was obtained as a yellow solid by column purification and recrystallization with petroleum ether. Formula (A)
1 equivalent of the compound and 1 equivalent of 2-aminoethanol were boiled in toluene. After completion of the reaction, the solvent was concentrated, 1 equivalent of acetyl chloride was added, and the mixture was left at room temperature for 1 hour. The solvent was distilled off, and the compound of the formula (B) was obtained by a column purification method.

[0021]

Embedded image One equivalent of the compound of the formula (B), 1.1 equivalents of triethylamine and 1.1 equivalents of methacryloyl chloride were reacted in toluene at room temperature. The solvent was distilled off, and the compound of the formula (C) was obtained by a column purification method.

[0022]

Embedded image The compound of the formula (C) was dissolved in acetonitrile, and when it was irradiated with ultraviolet light, it was colored red-purple. This color returned to the source of white light. This operation could be repeated many times.

Example 2 In place of 4-acetyl-1,3,5-trimethylpyrazole,
Using acetyl-5-methyl-1-phenylpyrazole,
A compound of the formula (D) was obtained in the same manner as in Example 1 except that acryloyl chloride was used instead of methacryloyl chloride.

[0024]

Embedded image When the compound of the formula (D) was dissolved in acetonitrile and irradiated with ultraviolet light, it was colored reddish purple (λmax = 555 nm). This color was restored by irradiation with white light. This operation could be repeated many times.

Example 3 5.0 g of 4-acetyl-1,3,5-trimethylpyrazole (3
3 mmol) and 10.0 g (33 mmol) of diethyl adamantylidene succinate were reacted dropwise at 60 ° C. in a 100 ml benzene solution in which 2.0 g of sodium hydride (60% oil) was dispersed. After the reaction was completed, benzene was distilled off, then water was added to the residue, and further acid was added to make it weakly acidic.

Next, the released half ester was subjected to solvent extraction using toluene. The half ester was converted to a dicarboxylic acid by boiling with 10% ethanolic potassium hydroxide. After removal of the water, the dicarboxylic acid was converted to the compound of formula (E) by boiling with acetyl chloride.

[0027]

Embedded image The compound of the formula (E) was purified by a column method. Formula (E)
Was dissolved in acetonitrile, and the compound was colored red-purple when irradiated with ultraviolet light. This color was restored by irradiation with white light. This operation could be repeated many times.

Example 4 In place of 4-acetyl-1,3,5-trimethylpyrazole,
A compound of the formula (F) was obtained in the same manner as in Example 3 except that acetyl-5-methyl-1-phenylpyrazole was used.

[0029]

Embedded image When the compound of formula (F) was dissolved in acetonitrile and irradiated with ultraviolet light, the compound was colored red-purple. This color was restored by irradiation with white light. This operation could be repeated many times.

Example 5 The compound of the formula (C) obtained in Example 1 (10 parts by weight), butyl methacrylate (90 parts by weight), and 2,2'-azobis (2,4-dimethylvaleronitrile) (0.1 parts by weight) was placed in a glass ampoule. After removing the dissolved oxygen by a freeze degassing method, the ampule was sealed and polymerized at 75 ° C. for 7 hours. After the polymerization, the polymer was taken out and irradiated with ultraviolet light, so that the polymer was colored reddish purple. This color was restored by irradiation with white light. This operation could be repeated many times.

Example 6 Instead of the compound of formula (C), the compound of formula (D) obtained in Example 2
A polymer was polymerized in the same manner as in Example 5 except that the compound of the formula (1) was used. When the obtained polymer was irradiated with ultraviolet light, it was colored red-purple. This color was restored by irradiation with white light. This operation could be repeated many times.

[0032]

According to the present invention, the absorption wavelength region has a long wavelength (it is desired to have absorption at 700 nm or more).
And a fulgide compound having high chemical stability could be provided.

Claims (1)

[Claims] 1. A photochromic pyrazolyl fulgide compound represented by the following general formula [I]. Embedded image (Wherein R ¹ is an alkyl group having 1 to 30 carbon atoms, 6 carbon atoms)
12 phenyl group, a substituted phenyl group, a substituted group selected from aralkyl and substituted aralkyl group, R ²
And R ³ are each a substituent selected from an alkyl group having 1 to 10 carbon atoms, a phenyl group having 6 to 12 carbon atoms, a substituted phenyl group, an aralkyl group, a substituted aralkyl group and a hydrogen atom, or a group represented by the following formula: Represents an adamantylidene group. R ⁴ is a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a phenyl group having 6 to 12 carbon atoms,
It represents a substituent selected from a substituted phenyl group, an aralkyl group, a substituted aralkyl group, and halogen. R ⁵ is an alkyl group having 1 to 30 carbon atoms, a phenyl group having 6 to 12 carbon atoms,
R ⁶ represents a substituent selected from a substituted phenyl group, an aralkyl group, a substituted aralkyl group and a hydrogen atom;
And a substituent selected from an alkyl group having 10 to 10, a phenyl group having 6 to 12 carbon atoms, a substituted phenyl group, an aralkyl group, a substituted aralkyl group, a substituted amino group, a halogen and a hydrogen atom. X represents a group containing a nitrogen atom for an oxygen atom or N-R ^7, R ⁷ is an alkyl group having 1 to 30 carbon atoms, a phenyl group having 6 to 12 carbon atoms, a substituted phenyl group, aralkyl group, substituted aralkyl And a substituent selected from a group, an alkyl (meth) acrylate group having 3 to 30 carbon atoms, and a hydrogen atom. (Provided that R ² and R ³ are a substituent selected from an alkyl group having 1 to 10 carbon atoms, a phenyl group having 6 to 12 carbon atoms, a substituted phenyl group, an aralkyl group, a substituted aralkyl group and a hydrogen atom, And R ⁵ is an alkyl group having 1 to 30 carbon atoms, and 6 to 1 carbon atoms.
2 represents a substituent selected from a phenyl group, a substituted phenyl group, an aralkyl group, a substituted aralkyl group and a hydrogen atom, and X represents an oxygen atom or a group containing a nitrogen atom represented by NR ⁷ , and R ⁷ represents Excludes the case where it represents a substituent selected from an alkyl group having 1 to 30 carbon atoms, a phenyl group having 6 to 12 carbon atoms, a substituted phenyl group, an aralkyl group, a substituted aralkyl group and a hydrogen atom. ))