JPH0381278A - Photochromic compound - Google Patents

Abstract

NEW MATERIAL:Photochromic compounds shown by formula I and formula II (R1 to R3 are 1-20C alkyl, 1-20C alkoxy, aralkyl or aryl; R4 to R12 are H, 1-20C alkyl, 1-20C alkoxy, aralkyl, aryl, halogen, nitro, dialkylamino, sulfone or hydroxyl group; A is 1-10C alkylene, 8-16C arylalkylene, O, ether bond- containing 2-10C alkylene). EXAMPLE:5,5''-Methanediyl-bis {1-octadecyl-3,3-dimethylspiro[indoline2,3'-naphtho[2,1-b] (1,4)oxazine]}. USE:Useful as various recording materials, memory materials, printing sensitized materials, etc., photosensitive materials such as materials for optical filter, decoration, etc., having stability of colored state. PREPARATION:For example, a bis type indoline compound shown by formula III is condensed with 1-nitroso-2-naphthol shown by formula IV to give a com pound shown by formula I.

Description

[Detailed Description of the Invention] [Field of Industrial Application] The present invention relates to a novel photochromic compound, and more particularly to a spironaphthoxazine-based photochromic compound that has excellent stability in a coloring state. be.

[Conventional technology]

Spiropyran-based photochromic compounds have: 1) high absorbance in the colored form, 2) a large difference in the absorption wavelength between the colored and decolored forms, 2) the absorption wavelength of the colored form can be changed arbitrarily by substituents, and 2) coloring and decoloring. Since it can repeat colors, it is expected to be used as a rewritable optical recording material or display material.

However, spiropyran photochromic compounds have
There was a problem with durability over repeated color development and fading.

In recent years, spironaphthoxazine, which has the basic skeleton shown below in which the C and C double bonds in the pyrazole/ring are changed to C and N double bonds, has been attracting attention as a compound with excellent repeat durability. There is.

[Problem to be solved by the invention]

However, spirooxazine-based photochromic compounds such as spironaphthoxazine have excellent repeat durability, but their apparent absorbance during coloring is low;
The problem is that the stability of the colored body is poor. Therefore, when applied as a recording material, there was a problem in storage stability of the recording. The reason for this is that the colored substance ring-opened by light returns to its original colorless substance due to a thermal reaction, and this thermal reaction is extremely fast in the case of spirooxazine-based photochromic compounds. Since the colored body has a polar structure, it is relatively stable in a polar atmosphere. To achieve a polar atmosphere, it is possible to mix L. dispersed in a polar matrix with other components having polar groups, but this method is limited to very specific uses.

Therefore, the object of the present invention is to provide a photochromic compound with excellent stability of colored bodies. ], (As shown in III, - is characterized by having two spironaphthoxazine skeletons in the molecule, and these spironaphthoxazine skeletons are covalently bonded to each other through indoline moieties.

... CI) (wherein R1, R2, R3 are an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aralkyl group, an aryl group, R4, R5, R6, R7, R8, R9, RI
OlRll, R12 represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aralkyl group, an aryl group, a halogen atom, a nitro group, a dialkylamino group, a sulfone group, or a hydroxyl group; Carbon number 1-1
0 alkylene group, an arylalkylene group having 8 to 16 carbon atoms, an oxygen atom, and 2 to 10 carbon atoms having an ether bond.
represents an alkylene group. ) ...... [■] (In the formula, R1, R2, R3 are an alkyl group having 1 to 2 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aralkyl group, an aryl group, R4, R5, R6, R7, R8, R9, R1
0% R11 and R12 represent a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aralkyl group, an aryl group, a halogen atom, a nitro group, a dialkylamino group, a sulfone group, a hydroxyl group, A is carbon number l~1
0 alkylene group, C8-16 alkylene group, oxygen atom, carbon number 2-1 having an ether bond
0 alkylene group. ) The photochromink compound represented by the general formula [I] can be obtained by condensing a bis-type indoline compound with substituted or unsubstituted l-nitroso-2-naphthol. The compound of general formula CI) can be synthesized according to the following reaction formula.

(In the formula, R1, R2, R3 are an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aralkyl group, an aryl group, R4, R5, R6, R7, R8, R9, RI
OlRll, R12 represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aralkyl group, an aryl group, a rogen atom, a nitro group, a dialkylamino group, a sulfone group, a hydroxyl group, A has 1 or more carbon atoms
10 alkylene groups, an arylalkylene group having 8 to 16 carbon atoms, an oxygen atom, and 2 to 1 carbon atoms having an ether bond.
0 alkylene group. ) In addition, the photochromic compound represented by the general formula [■] is a bis-type indoline compound and a substituted or unsubstituted 2
- Obtained by condensing nitrone-1-naphthol. The compound of the general formula [■] can be synthesized according to the following reaction formula.

(In the formula, R1, R2, R3 are an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aralkyl group, an aryl group, R4, R5, R6, R7, R8, R9, RI
O, R11, and R12 represent a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aralkyl group, an aryl group, a rogen atom, a nitro group, a dialkylamino group, a sulfone group, or a hydroxyl group. A is carbon number 1-
10 alkylene groups, an arylalkylene group having 8 to 16 carbon atoms, an oxygen atom, and 2 to 1 carbon atoms having an ether bond.
0 alkylene group. ) Of the above reaction formula, the bis-type indoline compound is synthesized according to the following reaction formula using the corresponding bis-type aniline as a starting material.

(In the formula, R1, R2, and R3 are alkyl groups having 1 to 20 carbon atoms, alkoxy groups having 1 to 20 carbon atoms, aralkyl groups, and aryl groups; R4, R5, and R6 are hydrogen atoms, and 1 to 2 carbon atoms;
0 alkyl group, alkoxy group having 1 to 20 carbon atoms, aralkyl group, aryl group, halogen atom, nitro group, dialkylamino group, sulfone group, hydroxyl group, A is an alkylene group having 1 to 10 carbon atoms, carbon number It represents an arylalkylene group having 8 to 16 carbon atoms, an oxygen atom, and an alkylene group having 2 to 10 carbon atoms having an ether bond. ) That is, bis-type aniline is dissolved in hydrochloric acid, diazotized with sodium nitrite, and the obtained diazonium salt is reduced to obtain bis-type hydrazine. Bis-type indolenine is obtained by heating and refluxing 2-propanone having a substituent at the 1-position and bis-type hydrazine in twice the molar amount relative to bis-type hydrazine under an acid catalyst. The target bis-type indoline compound can be obtained by allowing a halide having a substituent to be introduced into the N-position of indolenine to act on bis-type indoline in twice the molar amount and then desalting with sodium hydroxide.

Some specific examples of the photochromic compound of the present invention represented by the above-mentioned symbol [■] obtained by such a synthesis method are illustrated below.

Cl8H3? l8H37 CH.

eH.

Further, some specific examples of the photochromic compound of the present invention represented by the above-mentioned -Momona (II) are illustrated below.

The present invention is not limited to the above specific examples.

For example, carbon number 1 to 20 indicated by R1 to RIO
Examples of the alkyl group include methyl group, ethyl group, n-propyl group, is□-propyl group, n-butyl group, 1s(1
-butyl group, 5ee-butyl group, t-butyl group, pentyl group, hexyl group, hephthyl group, octyl group, decyl group, dodecyl group, hexadecyl group, octadecyl group, icosyl group, etc., and have 1 to 20 carbon atoms. Examples of the alkoxy group include methoxy group, ethoxy group, propoxy group, butoxy group, pentoxy group, hexyloxy group, icosyloxy group, etc., and examples of the aralkyl group include benzyl group, diphenylmethyl group, trityl group, phenethyl group,
Examples of the aryl group include a phenylpropyl group, and examples of the aryl group include a phenyl group, tolyl group, xylyl group, mesityl group, naphthyl group, anthryl group, phenanthryl group, and pyrenyl group. Examples of the halogen atom represented by R4 to RIO include a chlorine atom, a bromine atom, a fluorine atom, and an iodine atom, and examples of the dialkylamino group include a dimethylamino group, a diethylamino group, and a methylethylamino group.

The photochromic compound of the present invention can be used in various recording and storage materials, photoreceptors for printing, photoreceptors for holography, and the like. It can also be used as a material for optical filters, display materials, masking materials, light meters, decorations, etc.

The photochromic compound of the present invention includes alcohols such as methanol, ethanol, and isopropyl alcohol;
Ketones such as acetone, methyl ethyl ketone, cyclohexane, and none; ethers such as ethyl ether, dioxane, and tetrahydrofuran; esters such as ethyl acetate and n-butyl acetate; aromatic solvents such as benzene, toluene, and xylene; chloroform, and dichloromethane. It dissolves in various solvents such as halogenated solvents, n-hexane, cyclohexane, acetonitrile, dimethylformamide, dimethylsulfoxide, and mixed solvents thereof.

In order to use the photochromic compound of the present invention as a photosensitive material, it can be dissolved in the above-mentioned solvent together with a polymeric substance, coated and dried on a support, directly mixed and dissolved in a polymeric substance to form a film, or It can be used by mixing with a molecular substance and then polymerizing and molding the low molecular substance. Further, it is also possible to form a film on the support by a vacuum evaporation method or a LB method.

〔Example〕

Next, the present invention will be explained in more detail with reference to Examples.

(Example 1) 5.5-methanediyl-bis(1-octadecyl-3,
3-dimethylspiro[indoline-2゜3-naphtho(2
, 1-b] (x, 4) oxazine]) The photochromic compound of this example can be synthesized as follows.

Dissolve in liquid by heating, then cool rapidly. An aqueous solution of IJium (nitrous acid) was added dropwise thereto over about 30 minutes, and the mixture was stirred for a while to effect diazotization. An aqueous solution of tin chloride was added to the reaction solution, heated to 60° C., and reacted for 5 hours.

After the reaction was completed, concentrated hydrochloric acid was added and the mixture was cooled, and a white precipitate appeared. This precipitate was suction filtered to obtain 4,4-dihydrazinodiphenylmethane hydrochloride. (Yield 86.5%) The obtained 4,4-dihydrazinodiphenylmethane hydrochloride was heated under reflux with isopropyl methyl ketone in ethanol under a sulfuric acid catalyst. After the reaction was completed, ethanol was removed under reduced pressure, and the mixture was treated with alkali and extracted with ethyl ether to obtain 5,5-methanediyl-bis(2,3,3-)lynchylindolenine). (Yield 91.8%) The obtained 5,5-methanediyl-bis(2,3゜3-trimethylindolenine) and octadecane iodide were heated under reflux in n-butanol for 4 hours, and then the solvent was removed under reduced pressure. , 5゜5-methanediyl-bis(1-octadecyl-3゜3-dimethyl-2-methyleneindoline) was obtained by alkali treatment.

(Yield 30.2%) In an ethanol solution of 1-nitroso-2-naphthol,
5,5-methanediyl-bis(1-octadecyl-3,
An ethanol solution of 3-dimethyl-2-methyleneindoline (3-dimethyl-2-methyleneindoline) was added dropwise and the reaction was carried out under reflux for 3 hours. The reaction solution was concentrated and separated by thin layer chromatography (developing solvent: benzene) to obtain the desired photochromic compound. (Yield 9.1%) The assignment of the H-NMR spectrum of the compound of this example is shown below. Note that tetramethylsilane was used as an internal standard and deuterated chloroform was used as a solvent.

δ (ppm) Oi33-1.12 6Ht Methyl hydrogen at the end of alkyl chain 1.13-1.38 76Hm Methylene hydrogen of alkyl chain and methyl at 3- and 3-positions 2.95 3.93 Group hydrogen bonded to N of indoline Methylene hydrogen J = 8 Hz - Methylene hydrogen in the part 682 to 7.75 8.50 8H aromatic hydrogen and hydrogen in the 2nd and 2nd positions Hydrogen in the 10th and 10th positions J = 8.5 Hz (Example 2 Using 4,4-diaminodiphenyl ether as the starting material aniline, the reaction was carried out in the same manner as in Example 1 except for the other conditions, and the desired photochromic compound was obtained. (Yield 10.
1%) (Example 3) 4,4-diaminodiphenyl-p to the starting material aniline
- Using xylene, the reaction was carried out in the same manner as in Example 1 except for the other conditions, to obtain the desired photochromic compound. (Yield 9.7%) (Example 4) Bis-type indoline 5,5 was prepared in the same manner as in Example 1.
-Methanediyl-bis(1-octadecyl-3,3-dimethyl-2-methyleneindoline) was synthesized. In an ethanol solution of 2-nitroso-1-naphthol, 5,5-
An ethanol solution of methanediyl-bis(1-octadecyl-3,3-dimethyl-2-methyleneindoline) was added dropwise and the reaction was carried out under reflux for 3 hours. The reaction solution was concentrated and separated by thin layer chromatography (developing solvent: dibenzene) to obtain the desired photochromink compound.

(Yield 13.7%) (Example 5) Bis-type indoline was synthesized in the same manner as in Example 2.

The obtained ethanol solution of bis-type indoline was added dropwise to an ethanol solution of 2-nitroso-1-naphthol, and the reaction was carried out under reflux for 3 hours. The reaction solution was concentrated and separated by thin layer chromatography (developing solvent: benzene) to obtain the desired photochromink compound. (Yield: 18.6%) (Example 6) Bis-type indoline was prepared in the same manner as in Example 3.

The obtained ethanol solution of bis-type indoline was added dropwise to an ethanol solution of 2-nitroso-1-naphthol-4-sulfonic acid, and the reaction was carried out under reflux for 3 hours. The reaction solution was concentrated and separated by thin layer chromatography (developing solvent: benzene) to obtain the desired photochromic compound. (Yield 7.9%) Polyester 1 containing 5% by weight of the spironaphthoxazine photochromic compound thus obtained
A 0% by weight solution was applied onto a quartz glass substrate using a spinner, and 6
After vacuum drying at 0° C. for 12 hours, a sample with a film thickness of 1 μm was prepared.

7. A sample was prepared by depositing the obtained spironaphthoxazine-based photochromic compound on a quartz galanium substrate by vacuum deposition.

Furthermore, since the spironaphthoxazine photochromic compound of this example has an alkyl long chain at the N-position, it is possible to form a monomolecular film on the water surface.

A Y-type LB film sample with 22 layers on both sides was produced on a quartz glass substrate at a mixing ratio of 1:2 with stearic acid using an LB film production apparatus.

Light from a xenon lamp at so low temperature was applied to these samples.
Ultraviolet light around 360 nm and 60 nm using an optical filter
It was divided into visible light around 0 nm and each light was irradiated alternately. When irradiated with ultraviolet light, the sample changes to a deep blue color, and in the dark, the color changes and fades fairly stably, and when it is irradiated with ultraviolet light again, it turns dark blue. This cycle could be repeated.

〔Effect of the invention〕

As described above, the photochromic compound of the present invention is
Since it has two spironaphthoxazine skeletons in one molecule, stabilization of the colored product was achieved with a mutual L-polar structure during coloring. Therefore, the present invention makes it possible to provide recording and display materials with good storage stability.

Claims (2)

[Claims] (1) A photochromic compound represented by the following general formula [I]. ▲There are mathematical formulas, chemical formulas, tables, etc.▼ ......[I] (In the formula, R1, R2, R3 are alkyl groups having 1 to 20 carbon atoms, alkoxy groups having 1 to 20 carbon atoms, aralkyl groups, Aryl group, R4, R5, R6, R7, R8, R9, R1
0, R11 and R12 represent a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aralkyl group, an aryl group, a halogen atom, a nitro group, a dialkylamino group, a sulfone group, a hydroxyl group, A has 1 to 1 carbon atoms
0 alkylene group, an arylalkylene group having 8 to 16 carbon atoms, an oxygen atom, and 2 to 10 carbon atoms having an ether bond.
represents an alkylene group. ) (2) A photochromic compound represented by the following general formula [II]. ...[II] (wherein R1, R2, R3 are an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aralkyl group, an aryl group, R4, R5, R6, R7, R8, R9, R1
0, R11 and R12 represent a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aralkyl group, an aryl group, a halogen atom, a nitro group, a dialkylamino group, a sulfone group, a hydroxyl group, A has 1 to 1 carbon atoms
0 alkylene group, an arylalkylene group having 8 to 16 carbon atoms, an oxygen atom, and 2 to 10 carbon atoms having an ether bond.
represents an alkylene group. )