JPH07300484A - Spiropyrans - Google Patents

Abstract

PURPOSE:To obtain a novel compound which has its maximum absorption wavelength at 400-500nm and shows high sensitivity to the light in this wavelength range and reverse photochromism useful for optical materials. CONSTITUTION:This spiropyran compound is expressed by formula I [R<1> is a 1-20C alkyl, an aralkyl, hydroxyethyl, acryloxyethyl; R<2> and R<4> are H, a 1-6C alkyl, an aryl, an aralkyl, a 1-5 C alkoxy, a halogen; R<3> and R<5> are H, a 1-6C alkyl, an aryl, an aralkyl; R<6> and R<7> are H, a 1-6C alkyl, an aryl, an aralkyl, a halogen; R<8> is H, vinyl, group-CH2OR<9> (R<9> is H, a l-4C alkyl); X is O, S] and its salt with an acidic compound, for example, 3,5-dimethyl-6'- nitrospiro[benzoselenazoline-2,2'(2'H)-1'-benzopyran]. The compound of formula I is obtained, for example, by condensation reaction of a benzo-selenazolenium salt derivative of formula II (Y is a halogen) with a 5-nitrosalicylaldehyde derivative of formula III.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a spiropyran compound exhibiting reverse photochromism.

[0002]

2. Description of the Related Art Photochromism is a phenomenon in which two states having different absorption spectra are reversibly changed by light, and a spiropyran derivative is best known as a typical organic compound exhibiting this phenomenon. . Specific examples and physical properties of such derivatives are, for example, Brown (G.
H. "Photochromism" by Brown (Phot)
ochromism, John Wiley & So
ns, Inc. 1971). Most of these derivatives do not normally develop color, but have a property of developing color when they are irradiated with ultraviolet rays, that is, so-called positive photochromism.

On the other hand, on the contrary, the color is usually developed,
A benzoselenazoline-based spiropyran compound is known as a representative compound exhibiting so-called reverse photochromism, which is decolorized when irradiated with visible light and subsequently reverts to its original colored state reversibly by irradiation with ultraviolet light or heat. Are disclosed in, for example, JP-A-2-78685 and JP-A-2-289.
No. 587 and Japanese Patent Publication No. 3-813072. However, the maximum absorption wavelengths of these known compounds are all in the range of 500 to 600 nm, and
A compound having high sensitivity to visible light or laser light in the region of 0 to 500 nm has not been found yet.

In recent years, attempts have been made to use compounds exhibiting photochromism (hereinafter referred to as "photochromic compounds") as optical materials such as optical information recording media and optical filters. However, the conventionally known photochromic compound has a maximum absorption wavelength of 500 nm or more as described above, and it is required to increase the recording density, and the second high-frequency generating material that shortens the wavelength of semiconductor laser light or converts the wavelength. (Hereinafter referred to as “SHG material”, Second-Harm
With the progress of development of sonic generation), photochromic compounds that are sensitive (or responsive) to light in a shorter wavelength region are required.

[0005]

The object of the present invention is 40
It is intended to provide a compound having a maximum absorption wavelength in the range of 0 to 500 nm and showing high sensitivity to light in this wavelength region.

[0006]

The compound of the present invention is a novel compound not described in the literature, and is a benzoselenazoline-based spiropyran compound represented by the following general formula (1) (hereinafter simply referred to as "spiropyran compound (1)"). )) And an acidic compound.

[0007]

[Chemical 2]

[In the formula, R ¹ represents an alkyl group having 1 to 20 carbon atoms, an aralkyl group, a hydroxyethyl group, an acryloxyethyl group or a methacryloxyethyl group. R ² and R ⁴ are the same or different and each represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an aryl group, an aralkyl group, an alkoxy group having 1 to 5 carbon atoms, a halogen atom, a cyano group, a trichloromethyl group, or trifluoro. Shows a methyl group or a nitro group. R ³
And R ⁵ are the same or different and each is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an aryl group, an aralkyl group, or 1 to 5 carbon atoms.
And an alkoxy group, a halogen atom, a cyano group, a trichloromethyl group, a trifluoromethyl group, a nitro group, an amino group, a dimethylamino group or a diethylamino group. R
⁶ and R ⁷ are the same or different and each represents a hydrogen atom or a carbon number of 1 to 6
Represents an alkyl group, an aryl group, an aralkyl group, a halogen atom, a cyano group or a nitro group. R ⁸ is a hydrogen atom, a vinyl group, a group —CH ₂ OR ⁹ or a group —CH ₂ OCOC (R
¹⁰ ) = CH ₂ and R ⁹ is hydrogen atom or 1 to 4 carbon atoms.
R ¹⁰ is a hydrogen atom or a methyl group. X
Represents an oxygen atom or a sulfur atom. ] In the general formula (1), the number of carbon atoms represented by R ¹ is 1 to
The alkyl group of 20 is a linear or branched alkyl group having 1 to 20 carbon atoms, specifically, a methyl group, an ethyl group, an n-propyl group, an iso-propyl group, an n-butyl group, Examples thereof include sec-butyl group, tert-butyl group, n-pentyl group, n-hexyl group, n-octyl group, n-decyl group and n-octadecyl group.

The aralkyl group represented by R ^{1 to} R ⁷ includes, for example, a benzyl group, a 1-phenethyl group, a 2-phenethyl group, a 3-phenylpropyl group, a 4-phenylbutyl group and the like, whose alkyl moiety has 1 carbon atom. A phenylalkyl group which is a linear or branched alkyl group having about 4 to 4 carbon atoms, and a linear or branched alkyl group having about 1 to 4 carbon atoms and about 1 to 4 carbon atoms on the phenyl ring. 1 or 2 or more kinds of linear or branched alkoxy groups, halogen atoms such as chlorine, bromine and iodine, nitro groups and the like may be substituted.

Examples of the alkyl group having 1 to 6 carbon atoms represented by R ^{2 to} R ⁷ include, for example, methyl group, ethyl group and n-
Propyl group, iso-propyl group, n-butyl group, se
c-butyl group, tert-butyl group, n-pentyl group,
A linear or branched alkyl group such as an n-hexyl group can be mentioned.

Examples of the aryl group represented by R ^{2 to} R ⁷ include a phenyl group and a naphthyl group, and a phenyl group is preferable. Further, on the aromatic ring of these groups, a linear or branched alkyl group having about 1 to 4 carbon atoms, a linear or branched alkoxy group having about 1 to 4 carbon atoms, chlorine, bromine, iodine, etc. The halogen atom, the nitro group or the like may be substituted with one kind or two or more kinds.

Examples of the halogen atom represented by R ^{2 to} R ⁷ include chlorine, bromine, iodine and the like.

The alkoxy group having 1 to 5 carbon atoms represented by R ^{2 to} R ⁵ includes, for example, methoxy group, ethoxy group, n-propoxy group, iso-propoxy group, n-butoxy group, sec-butoxy group, Examples thereof include linear or branched alkoxy groups such as tert-butoxy group and n-pentyloxy group.

Examples of the alkyl group having 1 to 4 carbon atoms represented by R ⁹ include methyl group, ethyl group, n-propyl group, iso-propyl group, n-butyl group, sec-butyl group, tert-butyl group. Examples thereof include linear or branched alkyl groups such as groups.

The salt of the spiropyran compound (1) of the present invention with an acidic compound (hereinafter simply referred to as "spiropyran compound salt") has a maximum absorption wavelength at 400 to 500 nm and shows high sensitivity to light in this wavelength range. , Which can be a desired photochromic compound. The spiropyran compound salt of the present invention is usually colored, and exhibits so-called reverse photochromism in which it is rapidly decolorized by irradiation with visible light and returned to its original colored state by irradiation with ultraviolet light or heat. This reverse photochromism cycle is stably repeated and reproduced even in various organic solvents and resins.

The spiropyran compound salt of the present invention is, for example, based on the above characteristics, a high density optical recording material, a recording / reading element, an optical filter, an optical switch, a pH sensor, a gas sensor, an image forming material, a photosensitive material, a non-linear material. It can be used as a raw material for various optical materials such as optical elements, and is also expected to be used in fields such as mechanical energy conversion of light energy. Further, it can be used not only as an optical material but also as a decorative material.

Furthermore, if the spiropyran compound salt of the present invention is used, a light source combining a semiconductor laser and an SHG material, which could not be used because it is not sensitive to conventional compounds, such as a mercury lamp (405,436 nm) and an Ar laser (458). 477 nm), Kr laser (40
7, 468 nm), Cd laser (442 nm), etc. that generate visible light can be used as a light source for the photochromic reaction.

Among the spiropyran compound salts of the present invention, in the general formula (1), R ¹ is a methyl group, an ethyl group or n-
Propyl group, n-octadecyl group, hydroxyethyl group or methacryloxyethyl group, R ² is hydrogen atom, R ³ is hydrogen atom, methyl group, methoxy group, nitro group, amino group, dimethylamino group or diethylamino group, R ⁴ Is a hydrogen atom, a methyl group or a methoxy group, R ⁵ is a hydrogen atom, a nitro group, an amino group, a dimethylamino group or a diethylamino group, R ⁶ and R ⁷ are hydrogen atoms, and R ⁸ is a hydrogen atom, a vinyl group, a hydroxymethyl group. Alternatively, a salt of a spiropyran compound (1) in which a methacryloxymethyl group and X is an oxygen atom or a sulfur atom and an acidic compound is preferable.

The spiropyran compound salt of the present invention can be produced by a known method, for example, by reacting the spiropyran compound (1) with an acidic compound. In particular, when the spiropyran compound (1) having an amino group as a substituent on its aromatic ring is used as a starting material, a salt with an acidic compound can be more easily produced.

As the acidic compound acting on the spiropyran compound (1), conventionally known compounds can be widely used as long as they can cause a neutralization reaction with the spiropyran compound (1) which can be regarded as an organic base. Protonic acid, Lewis acid, etc. can be mentioned, and among them, protic acid can be preferably used. A wide variety of known protic acids can be used, such as hydrochloric acid, sulfuric acid,
Perchloric acid, benzenesulfonic acid, toluenesulfonic acid,
Examples thereof include chlorobenzene sulfonic acid and sulfonic acid ion exchange resins. Among them, hydrochloric acid, sulfuric acid,
Toluenesulfonic acid and the like can be particularly preferably used.

Although such an acidic compound may be used in a large excess with respect to the spiropyran compound (1), the nitrogen atom on the selenazole ring in the spiropyran compound (1) and an amino group (n, Here, since n is an integer of 0 to 2) participates in the neutralization reaction, it is usually about 0.01 to (n + 5) equivalents, preferably 0.1 to (n + 1) with respect to 1 mol of the spiropyran compound (1). It is recommended to use the equivalent amount.

The acidic compound may be allowed to act on the spiropyran compound (1) in the absence of a solvent, but it is preferably carried out in the presence of a solvent. The solvent used here is not particularly limited, but for example, lower alcohols such as methanol, ethanol and propanol,
Examples thereof include ethers such as tetrahydrofuran, dioxane and dimethoxyethane, halogenated hydrocarbons such as dichloromethane and chloroform, dimethylformamide, dimethylsulfoxide and the like, and mixed solvents thereof.

The amount of the spiropyran compound (1) to be dissolved in these solvents is not particularly limited, but is usually about 0.1 to 30 g, preferably 0.5 per 100 ml of the solvent.
It may be about 10 g.

This salt-forming reaction can be carried out at a temperature similar to that of a general salt-forming reaction, usually at any temperature around 0 ° C. to room temperature, but it is usually preferable to carry out at room temperature.

The spiropyran compound salt of the present invention is instantly produced when the spiropyran compound (1) and the acidic compound come into contact with each other. Therefore, it is possible to use the product formed in a solvent in a solution state without isolation, and when isolation as a salt is required, simply distilling off the solvent used, the salt of the present invention can be obtained. Can be taken out.

In this way, the spiropyran compound salt of the present invention can be obtained.

The spiropyran compound (1), which is the main raw material for obtaining the spiropyran compound salt of the present invention, is also a photochromic compound having a maximum absorption wavelength in the wavelength region of usually 500 to 600 nm.

The spiropyran compound (1) can be obtained, for example, from JP-A-2-78685 and JP-A-2-289T87.
It can be produced according to a known method described in Japanese Patent Publication No. 3-813072, etc.

As an example, as shown in the following reaction formula-1, a benzoselenazolenium salt derivative represented by the general formula (2) and a 5-nitrosalicylaldehyde derivative represented by the general formula (3). It is easily produced by condensing and.

[0030]

[Chemical 3]

[Wherein R¹, R², R³, R^Four, R^Five, R
⁶, R⁷, R⁸And X are the same as above. Y is a halogen atom
Or group R¹¹SO₃-Indicates R¹¹Is a halogen atom or C
₁~ C _FourPheny which may have an alkyl group as a substituent
Represents a radical. ] In the general formula (2), a halogen atom represented by Y
For example, chlorine, bromine, iodine, etc. may be mentioned.
Of these, iodine is preferred. In addition, Y is a group R¹¹SO₃
R when −¹¹Also as a halogen atom indicated by
The same as the above can be mentioned. Group R¹¹SO₃− Of
As a preferable specific example, for example, p-toluene sulfone
Acid, p-chlorobenzene sulfonic acid, etc.
Wear.

Condensation of a benzoselena zolenium salt derivative of the general formula (2) (hereinafter referred to as "compound (2)") and a 5-nitrosalicylaldehyde derivative of the general formula (3) (hereinafter referred to as "compound (3)") The reaction is usually performed in a solvent in the presence of an amine. The ratio of the compound (2) to the compound (3) used is not particularly limited, but usually 0.9 to 1.1 mol of the compound (2) may be used with respect to 1 mol of the compound (3). A wide variety of known amines can be used, for example, piperidine, morpholine, triethylamine, pyridine, lutidine, 1,4-diazabicyclo [2,2,2] octane, 1,5-diazabicyclo [4,3,0] nonene- 5,1,8-diazabicyclo [5,4,0] undecene-7 and the like can be mentioned. The amount of such amine used can be appropriately selected from a wide range, but it is usually 1 to 10 times mol per 1 mol of compound (2). The solvent is not particularly limited as long as it can dissolve the compound (2) and the compound (3), and examples thereof include methanol, acetone, methyl ethyl ketone, ethyl acetate, butyl acetate, dichloromethane, dimethylformamide and the like. it can. This condensation reaction is carried out in the temperature range of room temperature to the boiling temperature of the solvent used,
It usually finishes in about 1 to 24 hours. The spiropyran compound (1) thus obtained can be easily isolated and purified from the reaction mixture by a conventional separation and purification means.

Among the spiropyran compounds represented by the general formula (1), particularly preferable compounds are the following compounds.

3,5-Dimethyl-6'-nitrospiro [benzoselenazoline-2,2 '(2'H) -1'-benzopyran] 8'-methacryloxymethyl-3-methyl-6'-nitrospiro [benzo Selenazoline-2,2 '(2'H)-
1'-benzopyran] 8'-methacryloxymethyl-3,5-dimethyl-6 '
-Nitrospiro [benzoselenazoline-2,2 '(2'
H) -1'-benzopyran] 8'-methacryloxymethyl-5-methoxy-3-methyl-6'-nitrospiro [benzoselenazoline-2,
2 '(2'H) -1'-benzopyran] 8'-methacryloxymethyl-6'-nitro-3-octadecyl spiro [benzoselenazoline-2,2' (2 '
H) -1'-Benzopyran] 6-amino-3,5-dimethyl-6'-nitrospiro [benzoselenazoline-2,2 '(2'H) -1'-benzopyran] 6-methylamino-3,5 -Dimethyl-6'-nitrospiro [benzoselenazoline-2,2 '(2'H) -1'
-Benzopyran] 6-dimethylamino-3,5-dimethyl-6'-nitrospiro [benzoselenazoline-2,2 '(2'H)-
1'-benzopyran] 6-dimethylamino-3-octadecyl-6'-nitrospiro [benzoselenazoline-2,2 '(2'H)-
1'-benzopyran] 6-dimethylamino-3-isopropyl-6'-nitrospiro [benzoselenazoline-2,2 '(2'H)-
1'-benzopyran] 8'-methacryloxymethyl-6-dimethylamino-
3,5-Dimethyl-6'-nitrospiro [benzoselenazoline-2,2 '(2'H) -1'-benzopyran] 8'-vinyl-6-dimethylamino-3,5-dimethyl-6'-nitrospiro [Benzoselenazoline-2,2 '
(2'H) -1'-Benzopyran] 8'-hydroxymethyl-6-dimethylamino-3,5
-Dimethyl-6'-nitrospiro [benzoselenazoline-2,2 '(2'H) -1'-benzopyran] 4,6-di (dimethylamino) -3,5-dimethyl-
6'-nitrospiro [benzoselenazoline-2,2 '
(2′H) -1′-Benzopyran] 6-dimethylamino-3-hydroxyethyl-6′-nitrospiro [benzoselenazoline-2,2 ′ (2′H)
-1'-benzopyran] 6-dimethylamino-3-methacryloxyethyl-6 '
-Nitrospiro [benzoselenazoline-2,2 '(2'
H) -1′-benzopyran] 3-methacryloxyethyl-5-methoxy-6-dimethylamino-6′-nitrospiro [benzoselenazoline-
2,2 '(2'H) -1'-benzopyran] 8'-methacryloxymethyl-6-dimethylamino-5
-Methyl-6'-nitro-3-octadecylspiro [benzoselenazoline-2,2 '(2'H) -1'-benzopyran] 8'-vinyl-6-dimethylamino-5-methyl-6'
-Nitro-3-octadecyl spiro [benzoselenazoline-2,2 '(2'H) -1'-benzopyran] 6-dimethylamino-3,5-dimethyl-6'-nitrospiro [benzoselenazoline-2,2 '(2'H)-
1'-benzothiopyran] 8'-methacryloxymethyl-6-dimethylamino-
3,5-Dimethyl-6'-nitro-3-octadecylspiro [benzoselenazoline-2,2 '(2'H) -1'
-Benzothiopyran] The compound (2), which is a raw material for synthesizing the spiropyran compound (1), is a known compound. For example, the corresponding 2-methylbenzoselenazole derivative and a 1-fold molar amount or more, preferably 1. 05 to 1.5 times the molar amount of the general formula R
¹ Y [In the formula, R ¹ and Y are the same as defined above. ] In a solvent such as chloroform in a sealed tube and a compound represented by
It can be easily produced by reacting in a temperature range of about 150 ° C. for about 10 to 48 hours. The 2-methylbenzoselenazole derivative is described in, for example, Ber. , 46, 94
(1913), J. Amer. Chem. Soc. , 6
8,1536 (1946), British Patent No. 14111957.
It is a known compound described in the specification or the like, or a compound that can be easily produced according to the methods described in these documents.

Further, as will be more concretely shown in Reference Examples 1 to 5 below, a commercially available or synthetic benzoselenazole derivative is used as it is, or a desired substitution is performed on the aromatic ring of the commercially available or synthetic product. A group may be introduced.
The introduction of the substituent can be performed according to a conventional method. For example, (a) nitration with the action of concentrated nitric acid, sodium nitrate, etc., (b) amination, (c) alkylation, and (d) particularly with an alkylating agent such as alkyl iodide or toluene sulfonate. It can be carried out by appropriately combining known methods such as alkylation.

The compound (3), which is the other one of the starting materials, is also a known compound and is a compound that can be easily synthesized or obtained. The following reaction formula-2 shows an example of synthesis.

[0037]

[Chemical 4]

[In the formula, R ⁶ , R ⁷ and R ⁸ are the same as defined above.
R ¹² represents a group —OR ⁹ or a group —OCOC (R ¹⁰ ) ═CH ₂ . R ⁹ and R ¹⁰ are the same as above. That is, the salicylic aldehyde derivative (3a) is reacted with chloromethyl methyl ether to give 3-chloromethyl-
A 5-nitrosalicylaldehyde derivative (4) was obtained, and this was used as a compound of the general formula R ¹² M [wherein R ¹² is the same as above. M represents a metal atom or a hydrogen atom. ] The 5-nitrosalicyl aldehyde derivative (3b) whose X is an oxygen atom can be obtained by making it react with the compound represented by this. Here, in the above general formula, examples of the metal atom represented by M include alkali metal, alkaline earth metal, and silver. Specific examples of the compound represented by the general formula R ¹² M include:
For example, silver acrylate, silver methacrylate, sodium acrylate, sodium methacrylate, sodium methylate, sodium ethylate, sodium n-propylate, sodium iso-propylate, sodium n.
-Butyrate, sodium iso-butyrate, sodium tert-butyrate, acrylic acid, methacrylic acid, methanol, ethanol, n-propanol, is
Examples thereof include o-propanol, n-butanol, iso-butanol, tert-butanol and the like.

Next, a compound (3c) in which X is a sulfur atom
To obtain the compound, a 5-nitrosalicylaldehyde derivative (3
b) is reacted with N, N-dimethylthiocarbamoyl halide in the same manner as described in, for example, JP-A-60-54388 to produce a 2-O- (N, N-dimethylthiocarbamoyl) benzaldehyde derivative ( 5) is obtained, which is heated to be isomerized to lead to a 2-S- (N, N-dimethylthiocarbamoyl) benzaldehyde derivative (6), followed by an alkali hydrolysis treatment.

Further, a compound (3) in which R ⁸ is a nitro group
Are disclosed, for example, in Japanese Patent Laid-Open No. 61-76490 and Japanese Patent Publication No.
It is easily manufactured according to the method described in Japanese Patent No. 813072. That is, the 3-chloromethyl-5-nitrosalicylaldehyde derivative (4) obtained by the above reaction formula-2 is reacted with triphenylphosphine to form a triphenylphosphonium chloride derivative, and then paraformaldehyde is converted into an alkali metal hydroxide or the like. It is easily produced by reacting in the presence of a base.

Further, the compound (3) in which R ⁸ is a hydroxymethyl group is obtained by hydrolyzing the above-mentioned 3-chloromethyl-5-nitrosalicylaldehyde derivative (4) in the presence of silver nitrate, sodium hydrogen carbonate and the like according to a conventional method. It can also be manufactured by

The spiropyran compound salt of the present invention is No. 1
One kind or two or more kinds can be used as an optical material by mixing with a suitable matrix material such as resin and organic solvent. The matrix resin used at this time is not particularly limited as long as the salt of the present invention is uniformly dispersed therein. Specific examples of the matrix resin, polymethacrylic acid, polyacrylic acid, C ₁ -C ₈ alkyl esters of polymethacrylic acid or polyacrylic acid, polyacrylonitrile, polyacrylic acid amide, poly N, N
-Dimethyl acrylamide, polyvinyl acetate, polystyrene, poly α-methyl styrene, polyvinyl toluene,
Examples thereof include polyvinyl alcohol, polyvinyl butyral, polyvinyl pyrrolidone, polyvinyl chloride, polyvinylidene chloride, polycarbonate, polyethylene oxide, nylon, polyurethane, various polyolefins, ethyl cellulose and the like. In addition, 2 of these resins
It is also possible to use a mixture of two or more species. At this time, the compounding amount of the spiropyran compound salt of the present invention is not particularly limited and can be appropriately selected from a wide range, but is usually about 0.01 to 30% by weight, preferably 0.1 to 30% by weight of the total amount of the salt and the resin. 15
It may be about wt%. When the spiropyran compound salt of the present invention is mixed with a resin or an organic solvent, various additives that have been conventionally used in compositions for optical materials can be added as long as the characteristics are not impaired.

The resin composition containing the spiropyran compound salt of the present invention may be molded into a desired shape as it is, or may be coated on a suitable base material such as metal, ceramics, plastics and papers. . The coating can be performed by various methods such as a spin coating method, a spray method, a dipping method, a flow coating method and a bar coating method. A transparent protective coating may be coated on the coating made of the resin composition containing the spiropyran compound salt of the present invention.

The optical material containing the spiropyran compound salt of the present invention can be used by encapsulating it according to a known method or enclosing it in a suitable container. The capsules can be used in admixture with resins and other matrix materials.

Further, among the spiropyran compound salts of the present invention, those having a polymerizable group as a substituent can be polymerized by homopolymerization or copolymerization with a comonomer copolymerizable therewith. Examples of the copolymerizable monomer include methacrylic acid, acrylic acid, methacrylic acid or C ₁ -C ₈ alkyl ester of acrylic acid, acrylonitrile, acrylic acid amide, N, N-dimethylacrylamide, vinyl acetate, styrene, α-methylstyrene. , Vinyltoluene and the like are preferably used. The obtained polymer can be applied to optical elements and mechanical elements.

[0046]

INDUSTRIAL APPLICABILITY According to the present invention, there is provided a compound which has a maximum absorption wavelength in the range of 400 to 500 nm and shows high sensitivity to light in this wavelength region, which is very useful as an optical material.

[0047]

EXAMPLES The present invention will be specifically described below with reference to Reference Examples and Examples.

Reference Example 1 Synthesis of 2,5-dimethyl-6-nitrobenzoselenazole To 25 ml of ice-cooled sulfuric acid, 4.94 g of 2,5-dimethylbenzoselenazole was added and dissolved by stirring. Then, a solution prepared by dissolving 2.27 g of sodium nitrate in 20 ml of sulfuric acid and cooling was added dropwise to this solution, and the mixture was stirred for 2 hours under ice cooling. The reaction solution was ice-cooled, and 650 ml of 3N aqueous sodium hydroxide solution.
It was dripped in and the pH of the reaction liquid was 11 or more. Extract with benzene, wash the extract with saturated brine, dry over anhydrous sodium sulfate, evaporate the solvent, and remove the solvent as a light yellow solid 2,5-dimethyl-6-nitrobenzoselenazole and 2,5-dimethyl-4. -A mixture of nitrobenzoselenazole 5.8
8 g was obtained (yield 100%, but from ¹ H-NMR, 6-
Nitro form: 4-nitro form = 58:42).

¹ H-NMR (400 MHz, CDC
l ₃ ): δ ppm; 6-nitro form; 2.70 (s, 5-CH ₃ , 3H),
_{2.89 (s, 2-CH 3} , 3H), 7.88 (s, phenyl, 1H), 8.52 (s, phenyl, IH) 4-nitro compound; 2.45 (s, 5-CH 3 , 3H),
_{2.87 (s, 2-CH 3} , 3H), 7.20 (d, phenyl, 1H), 7.83 (d, phenyl, IH).

Reference Example 2 Synthesis of 6-amino-2,5-dimethylbenzoselenazole 5.88 g of 2,5-dimethylnitrobenzoselenazole of the mixture obtained in Example 1 was added to 143 ml of ice-cooled hydrochloric acid.
Was added and stirred. After slowly adding 5.47 g of tin powder to this solution, the mixture was further stirred under ice cooling for 2.5 hours. The reaction solution was added dropwise to ice-cooled 3N aqueous sodium hydroxide solution (650 ml) to adjust the pH of the reaction solution to 11 or more. It was extracted with benzene, the extract was washed with saturated brine, dried over sodium carbonate, and the solvent was distilled off to obtain 5.18 g of a pale yellowish white solid (crude yield 100%). This was separated and purified by silica gel column chromatography to give 6-amino- as a pale yellowish white solid.
2.55 g of 2,5-dimethylbenzoselenazole was obtained (yield 50%).

¹ H-NMR (400 MHz, CDC
l ₃ ): δppm; 2.26 (s, 5-CH ₃ , 3H), 2.77 (s, 2)
_{-CH 3, 3H), 3.70 (} s, amino, 2H),
7.09 (s, phenyl, 1H), 7.64 (s, phenyl, 1H).

Reference Example 3 Synthesis of 6-dimethylamino-2,5-dimethylbenzoselenazole 6-amino-2,5-dimethylbenzoselenazole 2.
24 g was dissolved in 114 ml of acetonitrile and 14.3 ml of 37% formalin with stirring. To this, 2.64 g of sodium cyanoborohydride and 1.14 ml of acetic acid were added, and after stirring at room temperature for 2.5 hours, 1.14 ml of acetic acid was added and further stirred at room temperature for 1 hour. After distilling off the solvent and the like under reduced pressure, 300 ml of diethyl ether was added and the mixture was washed successively with 1N sodium hydroxide and saturated saline and dried over potassium carbonate, and then the solvent was distilled off to obtain 2.69 g of a yellow viscous substance. This was separated and purified by silica gel column chromatography to obtain 2.16 g of light yellow oil 6-dimethylamino-2,5-dimethylbenzoselenazole (yield 86.
%).

¹ H-NMR (400 MHz, CDC
l ₃ ): δppm; 2.42 (s, 5-CH ₃ , 3H), 2.73 (s, dimethylamino, 6H), 2.81 (s, 2-CH ₃ , 3)
H), 7.46 (s, phenyl, 1H), 7.74
(S, phenyl, 1H).

Reference Example 4 Synthesis of 6-dimethylamino-2,3,5-trimethylbenzoselenazolenium iodide 1.06 g of 6-dimethylamino-2,5-dimethylbenzoselenazole and methyl iodide in an autoclave. Four
After charging 2 g and 45 ml of chloroform and replacing the atmosphere with argon gas, the tube was sealed. After reacting at 80 ° C. for 8 days, the solvent was distilled off and the residue was washed with diethyl ether to obtain 1.55 g of 6-dimethylamino-2,3,5-trimethylbenzoselenazolenium iodide as a pale yellow solid (yield). 94%).

¹ H-NMR (400 MHz, DMSO-
_{d 6): δppm; 2.46 (} s, 5-CH 3, 3H), 2.73 (s, dimethylamino, 6H), 3.08 (s, 2-CH 3, 3
_{H), 4.07 (s, 3} -CH 3, 3H), 8.00
(S, phenyl, 1H), 8.04 (s, phenyl, 1
H).

Example 1 6-Dimethylamino-3,5-dimethyl-6'-nitrospiro [benzoselenazoline-2,2 '(2'H)-
1'-benzopyran] 6-dimethylamino-2,3,5-in the dark under nitrogen gas
Trimethylbenzoselena zolenium iodide 2.95
g and 1.27 g of 5-nitrosalicylaldehyde were suspended in 900 ml of dry methanol. Piperidine 1.0
After dropping 1 g, the mixture was reacted at 80 ° C. for 23 hours. After the solvent was distilled off, the product was washed with water and dried to give 6-dimethylamino-3,5-dimethyl-6'-nitrospiro [benzoselenazoline-2,2 '(2'H) -1'-benzopyran as a dark purple solid. ] 2.76 g was obtained (89% yield).

¹ H-NMR (400 MHz, DMSO-
_{d 6): δppm; 2.41 (} s, 5-CH 3, 3H), 2.72 (s, dimethylamino, 6H), 4.02 (s, 3-CH 3, 3
H), 6.18 (d, phenyl, 1H), 7.76 (d
d, phenyl, 1H), 7.83 (s, phenyl, 1
H), 7.90 (s, phenyl, 1H), 7.98
(D, olefin, 1H), 8.42 (d, phenyl,
1H), 8.60 (d, olefin, 1H).

The UV-visible absorption spectrum of the obtained compound in a methanol solution is shown in FIG.

UV (CH ₃ OH): λmax = 512n
m, e = 29500 M ^-1 cm ^-1 .

Example 2 6-Dimethylamino-3,5-dimethyl-6'-nitrospiro [benzoselenazoline-2,2 '(2'H)-
Synthesis of 1'-benzopyran] dihydrochloride 6-Dimethylamino-3,5-dimethyl-6 'in the dark
-Nitrospiro [benzoselenazoline-2,2 '(2'
H) -1'-benzopyran] 2.71 g was suspended in a mixed solvent of 300 ml of chloroform and 180 ml of methanol. 2% hydrochloric acid / methanol (170 m
l) The solution was added dropwise to give a red solution. The solvent and excess hydrochloric acid were distilled off under reduced pressure, the residue was thoroughly washed with diethyl ether, and then dried to give brown solid 6-dimethylamino-3,5-dimethyl-6'-nitrospiro [benzoselenazoline-2, 2.18 g of 2 '(2'H) -1'-benzopyran] .dihydrochloride was obtained (yield 100%).

¹ H-NMR (400 MHz, DMSO-
_{d 6): δppm; 2.48 (} s, 5-CH 3, 3H), 2.81 (s, dimethylamino, 6H), 4.25 (s, 3-CH 3, 3
H), 7.32 (d, phenyl, 1H), 8.07
(S, phenyl, 1H), 8.14-8.16 (olefin + phenyl, 3H), 8.23 (dd, phenyl,
1H), 8.89 (d, phenyl, 1H) ¹ H-NMR (400 MHz, CD ₃ OD): δpp
m; 2.78 (s, 5- CH 3, 3H), 3.36 (s, dimethylamino, 6H), 4.36 (s, 3-CH 3, 3
H), 7.13 (d, phenyl, 1H), 8.21
(S, olefin, 1H), 8.26 (s, phenyl,
1H), 8.29 (dd, phenyl, 1H), 8.37
(D, olefin, 1H), 8.68 (s, phenyl,
1H), 8.83 (d, phenyl, 1H).

The UV-visible absorption spectrum of the obtained compound in a methanol solution is shown in FIG.

UV (CH ₃ OH): λmax = 420n
m, e = 17100 M ^-1 cm ^-1 .

Reference Example 5 Synthesis of 3-hydroxymethyl-5-nitrosalicylic aldehyde 0.5 ml of 3-chloromethyl-5-nitrosalicylic aldehyde in a dark place at room temperature in 4 ml of acetone and 1 ml of distilled water.
A solution prepared by dissolving 0.40 g of silver nitrate in 2 ml of distilled water was gradually added dropwise thereto. After stirring at room temperature for 1.5 hours, the precipitated white solid was filtered off and thoroughly washed with acetone. The obtained acetone solution was distilled off under reduced pressure and then dried to obtain 0.37 g of 3-hydroxymethyl-5-nitrosalicylaldehyde as a pale ocher solid (yield 87
%).

¹ H-NMR (400 MHz, DMSO-
d ₆ ): δ ppm; 4.64 (s, CH ₂ , 2H), 8.50 (phenyl,
2H), 10.04 (s, aldehyde, 3H), 11.
70 (br, phenolic OH, 1H).

Example 3 8'-Hydroxymethyl-6-dimethylamino-3,5
-Synthesis of dimethyl-6'-nitrospiro [benzoselenazoline-2,2 '(2'H) -1'-benzopyran] 6-dimethylamino-2,3,5-in the dark under nitrogen gas
Trimethylbenzoselena zolenium iodide 0.30
and 0.16 g of 3-hydroxymethyl-5-nitrosalicylaldehyde were suspended in 30 ml of dry methanol. After dropping 0.022 g of piperidine for 1 hour at room temperature,
Then, the mixture was reacted at 70 ° C. for 11 hours. After allowing to cool, the precipitated solid was filtered off, washed with cold methanol and dried to give a dark reddish brown solid of 8'-hydroxymethyl-6-dimethylamino-.
3,5-Dimethyl-6'-nitrospiro [benzoselenazoline-2,2 '(2'H) -1'-benzopyran]
0.27 g was obtained (80% yield).

¹ H-NMR (400 MHz, DMSO-
_{d 6): δppm; 2.43 (} s, 5-CH 3, 3H), 2.73 (s, dimethylamino, 6H), 4.04 (s, 3-CH 3, 3
H), 4.37 (s, CH ₂ , 2H), 7.84 (s,
Phenyl, 1H), 7.88 (d, phenyl, 1H),
7.92 (s, phenyl, 1H), 8.03 (d, olefin, 1H), 8.42 (d, phenyl, 1H),
8.61 (d, olefin, 1H) UV (CH ₃ OH): λmax = 521 nm, e = 29
400 M ^-1 cm ^-1 .

Example 4 8'-Hydroxymethyl-6-dimethylamino-3,5
-Dimethyl-6'-nitrospiro [benzoselenazoline-2,2 '(2'H) -1'-benzopyran] -monohydrochloride synthesis 8'-hydroxymethyl-6-dimethylamino-3, in the dark 5-Dimethyl-6'-nitrospiro [benzoselenazoline-2,2 '(2'H) -1'-benzopyran]
0.059 g was suspended in 4.0 ml of tetrahydrofuran. 0.112 N hydrochloric acid was added to this suspension. After dropping 0 ml, the mixture was stirred at room temperature for 8 hours. The precipitated floating solid was separated by filtration, washed thoroughly with diethyl ether, and dried. After dissolving this solid in 1.0 ml of methanol, 20 m of diethyl ether
The resulting solid was filtered off and dried to obtain a reddish brown solid of 8′-hydroxymethyl-6-dimethylamino-3,5-dimethyl-6′-nitrospiro [benzoselenazoline-2, 2 '(2'H) -1'-benzopyran]. Monohydrochloride 0.041 g was obtained (yield 76
%).

¹ H-NMR (400 MHz, DMSO-
_{d 6): δppm; 2.49 (} s, 5-CH 3, 3H + DMSO), 2.7
8 (s, dimethylamino, 6H), 4.29 (s, 3-
CH ₃ , 3H), 4.63 (s, CH ₂ , 2H), 8.
04-8.06 (s + d, phenyl, 2H), 8.12
(D, olefin, 1H), 8.30-8.34 (s +
d, phenyl + olefin, 2H), 8.85 (d, phenyl, 1H) UV (CH ₃ OH): λmax = 456 nm, e = 18
700 M ^-1 cm ^-1 .

8'-Hydroxymethyl-6-dimethylamino-3,5-dimethyl-6'-nitrospiro [benzoselenazoline-2,2 '(2'H) -1'-benzopyran] monohydrochloride 2. When 14 mg was dissolved in 100 ml of methanol, a spectrum having a maximum absorption at 456 nm was obtained (Fig. 3-A).

When 1 equivalent of triethylamine / methanol solution was added to this solution, the maximum absorption wavelength was 521 nm.
The wavelength was shifted to a long wavelength (Fig. 3-B). When 1 equivalent of hydrochloric acid / methanol solution was added to this solution, the maximum absorption wavelength returned to the original 456 nm.

Example 5 8'-Hydroxymethyl-6-dimethylamino-3,5
-Synthesis of dimethyl-6'-nitrospiro [benzoselenazoline-2,2 '(2'H) -1'-benzopyran] dihydrochloride 8'-hydroxymethyl-6-dimethylamino-3, in the dark 5-Dimethyl-6'-nitrospiro [benzoselenazoline-2,2 '(2'H) -1'-benzopyran]
0.050 g was suspended in 4.0 ml of tetrahydrofuran. 3N hydrochloric acid was added to this suspension. After dropping 0 ml, the mixture was stirred at room temperature for 8 hours. The precipitated floating solid was separated by filtration, washed thoroughly with diethyl ether, and dried. This solid was dissolved in 1.0 ml of methanol, added dropwise to 20 ml of diethyl ether, and the precipitated solid was separated by filtration and dried to give a yellow solid 8'-hydroxymethyl-6-dimethylamino-.
3,5-Dimethyl-6′-nitrospiro [benzoselenazoline-2,2 ′ (2′H) -1′-benzopyran].
0.041 g of dihydrochloride was obtained (70% yield).

¹ H-NMR (400 MHz, DMSO-
_{d 6): δppm; 2.49 (} s, 5-CH 3, 3H + DMSO), 2.7
9 (s, dimethylamino, 6H), 4.30 (s, 3-
CH ₃ , 3H), 4.63 (s, CH ₂ , 2H), 8.
05-8.07 (s + d, phenyl, 2H), 8.12
(D, olefin, 1H), 8.30 (s, phenyl,
1H), 8.36 (d, olefin, 1H), 8.86
(D, phenyl, 1H) UV (CH ₃ OH): λmax = 435 nm, e = 30
200 M ^-1 cm ^-1 .

Example 6 8'-methacryloxymethyl-6-dimethylamino-
Synthesis of 3,5-dimethyl-6'-nitrospiro [benzoselenazoline-2,2 '(2'H) -1'-benzopyran] 6-dimethylamino-2,3,5-in the dark under nitrogen gas
Trimethylbenzoselena zolenium iodide 0.30
0 g and 0.204 g of 3-methacryloxymethyl-5-nitrosalicylaldehyde were suspended in 30 ml of dry methanol. After dropwise adding 0.063 g of piperidine, the mixture was reacted at room temperature for 11 hours. After allowing to cool, the precipitated solid was filtered off,
After washing with cold methanol and drying, 8'-methacryloxymethyl-6-dimethylamino-3,5-dimethyl-6'-nitrospiro [benzoselenazoline-
2,2 '(2'H) -1'-benzopyran] 0.333
g was obtained (yield 82%).

¹ H-NMR (400 MHz, DMSO-
_{d 6): δppm; 1.91 (} s, CH 3, 3H), 2.42 (s, 5-C
H ₃ , 3H), 2.73 (s, dimethylamino, 6
_{H), 4.05 (s, 3} -CH 3, 3H), 5.03
(S, CH ₂ , 2H), 5.70 (s, vinyl, 1
H), 6.06 (s, vinyl, 1H), 7.85 (s,
Phenyl, 1H), 7.86 (d, phenyl, 1H),
7.92 (s, phenyl, 1H), 8.03 (d, olefin, 1H), 8.46 (d, phenyl, 1H),
8.64 (d, olefin, 1H) UV (CH ₃ OH): λmax = 519 nm, e = 28
000 M ^-1 cm ^-1 .

Chloroform was added to 1.95 mg of 8'-methacryloxymethyl-6-dimethylamino-3,5-dimethyl-6'-nitrospiro [benzoselenazoline-2,2 '(2'H) -1'-benzopyran]. When dissolved in 100 ml, a spectrum having a maximum absorption at 583 nm was obtained (Fig. 4-A). When this solution was irradiated with visible light for 10 seconds using a 500 W ultra-high pressure mercury lamp equipped with a cut-off filter that transmits visible light of 400 nm or more, its maximum absorption wavelength disappeared and a colorless transparent solution was obtained (No. Fig. 4-B). Keeping this solution at 25 ° C gives 1
It returned to the original blue-violet transparent solution after a while. Further, the above cycle of erasing by visible light and developing at room temperature could be repeated with good reproducibility.

Example 7 8'-methacryloxymethyl-6-dimethylamino-
3,5-Dimethyl-6′-nitrospiro [benzoselenazoline-2,2 ′ (2′H) -1′-benzopyran].
Synthesis of monohydrochloride 8'-methacryloxymethyl-6-dimethylamino-3,5-dimethyl-6'-nitrospiro [benzoselenazoline-2,2 '(2'H) -1'-benzopyran in the dark ] 0.059 g was suspended in 4.0 ml of tetrahydrofuran. 0.112 N hydrochloric acid was added to this suspension. After dropping 0 ml, the mixture was stirred at room temperature for 7 hours. The precipitated floating solid was separated by filtration, washed thoroughly with diethyl ether, and dried. This solid was dissolved in 1.0 ml of methanol, added dropwise to 20 ml of diethyl ether, and the precipitated solid was separated by filtration and dried to give a red-brown solid of 8'-methacryloxymethyl-.
6-Dimethylamino-3,5-dimethyl-6'-nitrospiro [benzoselenazoline-2,2 '(2'H)-
0.044 g of 1'-benzopyran]. Monohydrochloride was obtained (yield 71%).

¹ H-NMR (400 MHz, DMSO-
_{d 6): δppm; 1.92 (} s, CH 3, 3H), 2.46 (s, 5-C
H ₃ , 3H), 2.77 (s, dimethylamino, 6
_{H), 4.23 (s, 3} -CH 3, 3H), 5.22
(S, CH ₂ , 2H), 5.74 (s, vinyl, 1
H), 6.08 (s, vinyl, 1H), 7.99-8.
00 (s + d, phenyl, 2H), 8.18-8.22
(S + d, phenyl + olefin, 2H), 8.31
(D, olefin, 1H), 8.81 (d, phenyl,
1H) UV (CH ₃ OH): λmax = 448 nm, e = 18
700 M ^-1 cm ^-1 .

Example 8 8'-methacryloxymethyl-6-dimethylamino-
3,5-Dimethyl-6′-nitrospiro [benzoselenazoline-2,2 ′ (2′H) -1′-benzopyran].
Synthesis of dihydrochloride 8'-methacryloxymethyl-6-dimethylamino-3,5-dimethyl-6'-nitrospiro [benzoselenazoline-2,2 '(2'H) -1'-benzopyran in the dark ] 0.059 g was suspended in 4.0 ml of tetrahydrofuran. 3N hydrochloric acid was added to this suspension. After dropping 0 ml,
Stir at room temperature for 8 hours. The precipitated floating solid was separated by filtration, washed thoroughly with diethyl ether, and dried. This solid was dissolved in 1.0 ml of methanol, then added dropwise to 20 ml of diethyl ether, and the precipitated solid was separated by filtration and dried,
Red-brown solid 8'-methacryloxymethyl-6-dimethylamino-3,5-dimethyl-6'-nitrospiro [benzoselenazoline-2,2 '(2'H) -1'-benzopyran] dihydrochloride 0.029 g was obtained (yield 43
%).

¹ H-NMR (400 MHz, DMSO-
_{d 6): δppm; 1.92 (} s, CH 3, 3H), 2.46 (s, 5-C
H ₃ , 3H), 2.77 (s, dimethylamino, 6
_{H), 4.24 (s, 3} -CH 3, 3H), 5.22
(S, CH ₂ , 2H), 5.74 (s, vinyl, 1
H), 6.08 (s, vinyl, 1H), 7.99-8.
00 (s + d, phenyl, 2H), 8.18-8.22
(S + d, phenyl + olefin, 2H), 8.29
(D, olefin, 1H), 8.80 (d, phenyl,
1H) UV (CH ₃ OH): λmax = 443 nm, e = 17
100 M ^-1 cm ^-1 .

Example 9 Synthesis of 3,5-dimethyl-6'-nitrospiro [benzoselenazoline-2,2 '(2'H) -1'-benzopyran] 2,3,5 in the dark under nitrogen gas 0.18 g of trimethylbenzoselenazolenium iodide and 0.09 g of 5-nitrosalicylaldehyde were suspended in 30 ml of dry methanol. After dropwise adding 0.05 g of piperidine, the mixture was reacted at 70 ° C. for 5 hours. After the solvent was distilled off, the residue was washed with water and dried to give 3,5-dimethyl-6'-nitrospiro [benzoselenazoline-2,2 '(2'H)-as a dark reddish brown solid.
1'-benzopyran] 0.17 g was obtained (yield 87
%).

¹ H-NMR (400 MHz, DMSO-
_{d 6): δppm; 2.36 (} s, 5-CH 3, 3H), 4.06 (s, 3
_{-CH 3, 3H), 6.22 (} d, phenyl, 1H),
7.41 (d, phenyl, 1H), 7.77 (dd, phenyl, 1H), 7.90 (s, phenyl, 1H),
8.09 (d, olefin, 1H), 8.16 (d, phenyl, 1H), 8.49 (d, phenyl, 1H),
8.66 (d, olefin, 1H) UV (CH ₃ OH): λmax = 513 nm.

Example 10 3,5-Dimethyl-6'-nitrospiro [benzoselenazoline-2,2 '(2'H) -1'-benzopyran].
Synthesis of Hydrochloride 3,5-Dimethyl-6′-nitrospiro [benzoselenazoline-2,2 ′ (2′H) -1′-benzopyran]
0.05 g was suspended in a mixed solvent of 5 ml of chloroform and 5 ml of tetrahydrofuran. After 1.0 ml of 6N hydrochloric acid was added dropwise to this suspension, the mixture was stirred at room temperature for 8 hours. The precipitated solid was filtered off, washed thoroughly with diethyl ether, and dried to give a yellow solid of 2,5-dimethyl-6'-nitrospiro [benzoselenazoline-2,2 '(2'H)-.
1'-benzopyran] .hydrochloride (0.023 g) was obtained (yield 44%).

¹ H-NMR (200 MHz, DMSO-
_{d 6): δppm; 1.72 (} s, 5-CH 3, 3H), 3.46 (s, 3
_{-CH 3, 3H), 6.43 (} d, olefin, 1
H), 6.73 (d, phenyl, 1H), 7.35
(D, phenyl, 1H), 7.35 (d, phenyl, 1
H), 7.39 (s, phenyl, 1H), 7.42 (d
d, phenyl, 1H), 7.50 (d, olefin, 1
H), 8.09 (d, 1H , _{phenyl, 1H) UV (CH 3 OH} ): λmax = 402nm.

When one equivalent of a triethylamine / methanol solution was added to a methanol solution of this compound, the maximum absorption wavelength shifted to 513 nm (FIG. 5). When 1 equivalent of hydrochloric acid / methanol solution was added to this solution,
The maximum absorption wavelength returned to the original 402 nm (Fig. 6).

[Brief description of drawings]

FIG. 1 is an ultraviolet-visible absorption spectrum of the compound obtained in Example 1 in a methanol solution.

FIG. 2 is an ultraviolet-visible absorption spectrum of the compound obtained in Example 2 in a methanol solution.

FIG. 3 is an ultraviolet-visible absorption spectrum in Example 4.

FIG. 4 is an ultraviolet-visible absorption spectrum in Example 6.

5 is an ultraviolet-visible absorption spectrum in Example 10. FIG.

6 is an ultraviolet-visible absorption spectrum in Example 10. FIG.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification number Office reference number FI technical display location (C07D 517/10 293: 10 333: 54)

Claims (2)

[Claims] 1. A general formula: [In the formula, R ¹ represents an alkyl group having 1 to 20 carbon atoms, an aralkyl group, a hydroxyethyl group, an acryloxyethyl group or a methacryloxyethyl group. R ² and R ⁴ are the same or different and each represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an aryl group, an aralkyl group, an alkoxy group having 1 to 5 carbon atoms,
It represents a halogen atom, a cyano group, a trichloromethyl group, a trifluoromethyl group or a nitro group. R ³ and R ⁵ are the same or different and each represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms,
An aryl group, an aralkyl group, an alkoxy group having 1 to 5 carbon atoms, a halogen atom, a cyano group, a trichloromethyl group, a trifluoromethyl group, a nitro group, an amino group, a dimethylamino group or a diethylamino group is shown. R ⁶ and R ⁷ are the same or different and each represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms,
An aryl group, an aralkyl group, a halogen atom, a cyano group or a nitro group is shown. R ⁸ is a hydrogen atom, vinyl group, or group -C
H ₂ OR ⁹ or a group —CH ₂ OCOC (R ¹⁰ ) ═CH ₂ is shown, R ⁹ is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms,
R ¹⁰ represents a hydrogen atom or a methyl group. X represents an oxygen atom or a sulfur atom. ] The salt of the spiropyran compound and acidic compound represented by these. 2. R ¹ is a methyl group, ethyl group, n-propyl group, n-octadecyl group, hydroxyethyl group or methacryloxyethyl group, R ² is a hydrogen atom, R ³ is a hydrogen atom, a methyl group, a methoxy group. , A nitro group, an amino group, a dimethylamino group or a diethylamino group, R ⁴ is a hydrogen atom,
A methyl group or a methoxy group, R ⁵ is a hydrogen atom, a nitro group,
Amino group, dimethylamino group or diethylamino group, R
The salt of the spiropyran compound and the acidic compound according to claim 1, wherein ⁶ and R ⁷ are hydrogen atoms, R ⁸ is a hydrogen atom, a vinyl group, a hydroxymethyl group or a methacryloxymethyl group, and X is an oxygen atom or a sulfur atom.