JPH0570468A - Spironaphthooxazine derivative - Google Patents

Abstract

PURPOSE:To provide a new compound having an excellent coloration performance, a good optically coloration and decoloration-repeating characteristic, a good dispersing property in the copolymers or resins of other polymerizable monomers, and useful as a photochromic material for recording materials, a photochromic material for optical equipments, etc. CONSTITUTION:A compound having a Se at the 1 position and represented by formula I. For example, 3-Methyl-9'-hydroxy-spiro[benzoselenazoline2,3'(3'H) naphtho-[2,1-b]-1,4-oxadine]. The compound of formula I is obtained by adding methyl iodide to 2-methylbenzoselenazole and subsequently reacting the produced 2,3-dimethylbenzoselenazolenium iodide of formula III with 1-nitro-2,7- dihydroxynaphthalene of formula IV in the presence of triethylamine.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a novel spironaphthoxazine compound useful as a photochromic material for recording materials, a photochromic material for optical devices, a photochromic material or clothing for image formation, and a photochromic material for ornaments. ..

[0002]

2. Description of the Related Art Spiropyran compounds are known as typical ones of photochromic compounds (GH Brown,
"Photochemism", Techniques of Chemistry Vol. III,
Wiley Interscience, New York, 1971).

Further, JP-B-45-28892, JP-B-49-48631, JP-A-48-23787, JP-A-55-36284, JP-A-60-53586, and JP-A-61-53288. , JP-A-61-138686
No. 61-263982 and 61-501.
145 and JP-A-63-250381, 1,3,3-trimethyl-spiro [indoline-
2,3 '-(3H) -naphtho [2,1-b] -1,4-
Oxazine] and substituted derivatives thereof are disclosed.

[0004]

However, the spiropyran compound has a big problem in durability in repeated use of photocoloring and erasing. In addition, the known spirooxazine compound is extremely excellent in the repeating property of photobleaching and decoloring as compared with the above-mentioned compound, but the coloring species are thermally unstable, are weak to oxygen, and are naturally fading even when stored in the dark. There was a property to do.

The present invention is intended to solve such problems, and its purpose is to exhibit a variety of color tone changes, a large molar absorption coefficient, excellent durability, and other polymerizable monomers. It is intended to provide a photochromic compound excellent in retention in a resin by copolymerization.

[0006]

The present invention provides the following formula (I):
The present invention relates to a spironaphthoxazine compound having Se.

[0007]

[Chemical 2]

[Wherein R ₁ represents a hydrogen atom, an acryloyl group or a methacryloyl group, and R ₂ and R ₃ are the same or different, a hydrogen atom, a lower alkyl group having 1 to 3 carbon atoms, and 1 to 3 carbon atoms. And 3 represents a lower alkoxy group, a halogen atom, a nitro group or a cyano group, and R ₄ represents an alkyl group having 1 to 18 carbon atoms]

The present inventors have found that the spironaphthoxazine compound having Se at the 1-position of the present invention is novel and has excellent optical properties which are unprecedented as a photochromic compound, and arrived at the present invention.

The spironaphthoxazine compound of the formula (I) of the present invention is superior in the repeating characteristic of photo-color erasing and decoloring in both photon mode and thermal mode as compared with the conventional spironaphthoxazine compounds. It is possible to reversibly convert from color to color. In addition, the molar extinction coefficient of the colored species is extremely large, and it has excellent color forming performance.

Since the compound of formula (I) of the present invention has Se as a basic skeleton structure, it can be used in a non-polar solvent (n-hexane, cyclohexane, carbon tetrachloride, toluene, benzene, dioxane, ethyl acetate, etc.). , Shows positive photochromism by UV irradiation, and in polar solvents (alcohol, acetonitrile, dimethylsulfoxide, dimethylacetamide, dimethylformamide, etc.),
It exhibits reverse photochromism when exposed to visible light. In an intermediate polar solvent (methylene chloride, acetone, etc.),
It exhibits unique optical behaviors that conventional spironaphthoxazine compounds do not have, such as normal and reverse intermediate photochromism.

Further, the compound in which the substituent R ₁ has a polymerizable group such as an acryloyl group or a methacryloyl group can be copolymerized with other polymerizable monomers and can be blended with an optically transparent resin. It is possible to improve the dispersibility, and it is also possible to stabilize the thermally unstable metastable type (coloring species) by controlling the higher-order structure of the polymer.

As the polymerizable monomer copolymerizable with the compound of the formula (I) of the present invention, any generally used polymerizable monomer having a vinyl group can be used. For example, acrylic acid, methacrylic acid, acrylic acid ester, methacrylic acid ester, styrene, vinyl acetate, acrylonitrile, bisallyl carbonate, vinyl chloride, vinylidene chloride and the like can be mentioned. Furthermore, it is also possible to use two or more of these polymerizable monomers at the same time.

The addition of an antioxidant, an oxygen quencher, and an ultraviolet absorber to the mixture of the compound of formula (I) of the present invention and the polymerizable monomer is effective for prolonging the life of photochromic performance and color tone. Effective for change.

Further, as a polymerization initiator for copolymerizing the above-mentioned polymerizable monomer, other than organic peroxides such as ketone peroxide, peroxyketal, hydroperoxide, dialkyl peroxide, diacyl peroxide, peroxydicarbonate and peroxyester. ,
Polymerization initiators such as azobisisobutyronitrile are suitable.

As the resin which can be blended with the compound of the formula (I) of the present invention, any generally used optically transparent resin can be used. For example, diethylene glycol bisallyl carbonate polymer, polymethacrylate or copolymers thereof; celluloses, polyvinyl acetate, polyvinyl alcohol, polyvinyl butyral, polyester resin, polycarbonate, polystyrene or copolymers thereof; epoxy resin, halogenated bisphenol A Di (methacrylate) polymer or copolymer thereof; urethane modified di (methacrylate) polymer of halogenated bisphenol A or copolymer thereof; nylon resin, polyvinylidene fluoride or copolymer thereof; vinylidene cyanide Or a copolymer thereof; or polyurethane is preferably used.

The compound of the formula (I) of the present invention or the copolymer of the compound of the formula (I) and the polymerizable monomer of the present invention may be incorporated into the resin by various methods such as a dyeing method, a solvent kneading method or a heating roll kneading method. The method of can be applied.

The proportion of the compound of the formula (I) of the present invention in the copolymer and the resin blend is preferably changed depending on the purpose of use.

[0019]

EXAMPLES The present invention will be described in more detail by way of examples, but the present invention is not limited thereto.

Example 1 3-Methyl-9'-hydroxy-spiro [benzoselenazoline-2,3 '(3'H) naphtho- [2,1-b]-
1,4-oxazine] (II).

(1) Synthesis of 2,3-dimethylbenzoselenazolenium iodide

[0022]

[Chemical 3]

0.80 g of 2-methylbenzoselenazole
(4.1 mmol) was dissolved in 3 ml of chloroform, 1.13 g (7.9 mmol) of methyl iodide was added, and the tube was sealed.
The reaction was performed at 12 ° C for 12 hours. After completion of the reaction, the mixture was filtered, and the residue was washed 3 times with 15 ml of chloroform and 3 times with 10 ml of ether, and dried to obtain 1.36 g (4.0 mmol) of 2,3-dimethylbenzoselenazolenium iodide as a white powder. Obtained in% yield. ¹ H-NMR (D ₂ O) δ ppm: 3.24 (s, C-CH ₃ , 3H), 4.28 (s,
N-CH ₃ , 3H), 7.73 ~ 8.43 (m, aromatic, 4H)

(2) Synthesis of 1-nitroso-2,7-dihydroxynaphthalene

[0025]

[Chemical 4]

2,7-dihydroxynaphthalene 8.00
g (50.0 mmol) was dissolved in a mixed solvent of 50 ml of acetone and 100 ml of acetic acid and cooled to 0 ° C. with an ice bath. Sodium nitrite 10.35 g (150 mmol) in water 50 ml
The solution dissolved in was added dropwise over 2 hours. Then 15
After reacting for a period of time, the deposited precipitate was filtered off and washed with ether 50
Wash 3 times with 30 ml and 3 times with 30 ml of water to give 9.66 crude product.
got g.

5.68 g of this product was dissolved in 15 ml of dimethylsulfoxide, 10 ml of water was added thereto, the mixture was allowed to stand for 30 minutes, the precipitate was centrifuged, washed with 3 times 15 ml of water, and 5.01 g of a brown solid substance was obtained. (26.5 mmol, 88.3%) was obtained. Melting point: 197 ° C. ¹ H-NMR (DMSO- d ₆ + CDCl ₃ ) δ ppm: 6.34 (d, J = 9.6
Hz, 3-H, 1H), 6.96 (d, J = 8.0 Hz, 5-H, 1H), 7.33 (d,
J = 8.0 Hz, 6-H, 1H), 7.62 (d, J = 9.6 Hz, 4-H, 1H),
7.76 (s, 8-H, 1H), 9.82 (s, 7-OH, 1H), 17.71 (s, 2
-OH, 1H) MS (Ei, 20 eV): 189 m / z (M ⁺ )

(3) 3-Methyl-9'-hydroxy-spiro [benzoselenazoline-2,3 '-(3'H) naphtho- [2,1-b] -1,4-oxazine] (II) Synthesis of

[0029]

[Chemical 5]

2,3-Dimethylbenzoselenazolenium iodide 57 obtained in (1) above under a nitrogen stream in the dark.
0.4 mg (1.7 mmol) was dissolved in 50 ml of methanol under heating, and 317 mg (1.7 mmol) of 1-nitroso-2,7-dihydroxynaphthalene obtained in the above (2) was added to methanol 2
After dissolving by heating in 60 ml and allowing to cool, both solutions were mixed with stirring and ice-cooled. Triethylamine 2 was added to this mixed solution.
A solution of 10 mg (2.1 ml) in 17 ml of methanol was added dropwise over 45 minutes. The reaction solution gradually changed from brown to green. After the dropwise addition, the mixture was stirred at room temperature for 18 hours, the solvent was removed, and 1.02 g of a green title solid (III) was obtained. Melting point: 87-93 ° C.

The resulting spironaphthoxazine compound (II) was identified by NMR, MS and UV · V. ¹ H-NMR (400 MHz, CDCl ₃ ) δ ppm: 3.77 (s, N-CH ₃ , 3,
H), 6.92 (s, 2'-H, 1H), 6.40 ~ 7.81 (m, aromatic, 9
H), 10.2 (br, 9'-OH, 1H) MS (Ei, 20 eV): 384 m / z (M ⁺ ) UV ・ V:

[0032]

[Table 1]

Ε _max is measured by cooling the methanol solution to 0 ° C.
It was obtained by calculation with a spectrometer immediately after irradiation with ultraviolet rays.

(4) Photochromic property The spironaphthoxazine compound (II) obtained above showed forward / reverse photochromism depending on the polarity of the solvent used.

In methanol, it is colored in yellowish green, and it is exposed to ultraviolet rays (ultra high pressure mercury lamp, filter: U-3).
50) Upon irradiation, the absorbance increased significantly. When the ultraviolet irradiation was stopped, the absorbance gradually decreased and returned to the original yellow-green color (half-life of about 2 minutes).

On the other hand, when this yellow-green solution was irradiated with visible light (filter: Y-50), it immediately became a colorless solution, gradually colored in the dark at room temperature, and returned to the original yellow-green solution.

The visible absorption spectrum of the methanol solution is shown by the curve A in FIGS. On the other hand, the visible absorption spectrum 1 minute after the solution was irradiated with ultraviolet light and visible light was shown in the curve B of FIG. 1 and the curve C of FIG. 2, respectively.

Example 2 (1) 3-Methyl-9'-methacryloyloxy-spiro [benzoselenazoline-2,3 '-(3'H) naphtho- [2,1-b] -1,4-oxazine ] (III) Synthesis

[0039]

[Chemical 6]

3-Methyl-9'-hydroxy-spiro [benzoselenazoline-2,3 'synthesized in Example 1
0.1002 g (0.26 mmol) of (3'H) naphtho- [2,1-b] -1,4-oxazine] (II) was dissolved in 20 ml of dry ethyl acetate in a dark place under a nitrogen stream, and 0.0351 g (0.34 mmol) of methacrylic acid chloride in the solution
Was added and the mixture was cooled with ice. Then, in a nitrogen stream, 0.0306 g (0.30 mmol) of triethylamine was added dropwise over 5 minutes,
Stir for 5 hours. After completion of the reaction, the mixture was centrifuged and the supernatant was washed with 10 ml of a saturated aqueous sodium sulfate solution three times, and then the solution was dried overnight with saturated sodium sulfate. Then, the solvent was distilled off under reduced pressure to give 3-methyl-9'-methacryloyloxy-spiro [benzoselenazoline-2,
0.112 g (0.25 mmol, yield 83) of 3- (3′H) naphtho- [2,1-b] -1,4-oxazine] (III)
%). Melting point: 92-98 ° C.

The spionaphthoxazine compound (IV) thus obtained was identified by IR, NMR, MS and UV · V. IR (KBr), cm ^-1 : 3063 (w, ν _CH ), 2921 (w, ν _CH ),
1735 (vs, ν _{C = O} ) _, 1654 (vs, ν _{C = C} ), 1632 (vs, ν
_{C = N} ), 1463 (vs, benzene), 1120 (vs, ν _CO ), 946 (m, ν
_{pyran ring} ) ¹ H-NMR (400 MHz, CDCl ₃ ) δ ppm: 1.93 (s, C-CH ₃ , 3,
H), 3.52 (s, N-CH ₃ , 3H), 5.63 (s, = CH-H, 1H), 6.19
(s, = CH-H, 1H), 6.7 to 7.9 (m, aromatic, 10H) MS (Ei, 70 eV): 451 m / z (M ⁺ ) UV ・ V:

[0042]

[Table 2]

(2) Photochromic properties The spironaphthoxazine compound (III) obtained above is colored yellow green in ethanol, and changes to blue green by irradiation with ultraviolet rays (ultra high pressure mercury lamp, filter U-350). did. The color gradually disappeared in the dark and returned to the original yellow-green color one hour later. On the other hand, when the blue-green solution was irradiated with visible light (filter: Y-50), it immediately became a colorless solution.
It returned to the original yellow-green solution in about 30 minutes at room temperature in the dark.

The visible absorption spectrum of the ethanol solution is shown by curve A in FIG. On the other hand, the visible absorption spectrum 1 minute after the solution was irradiated with visible light is shown by the curve B in FIG.
It was shown to.

[0045]

INDUSTRIAL APPLICABILITY The spironaphthoxazine compound (I) of the present invention, as a photochromic compound, has excellent color forming performance, good photobleaching and repeating characteristics, and is compatible with other polymerizable monomers. Good copolymerizability and dispersibility in resin. Therefore, the compound of the present invention can be used, for example, for light control plastic lenses, light control materials such as window control light control materials, holographic photosensitive materials, display materials, recording materials, decorative materials or photometers, and LB film techniques. It can be used for various electronic device materials.

[Brief description of drawings]

FIG. 1 shows a visible absorption spectrum (A) of a methanol solution of the compound (II) of Example 1 and a visible absorption spectrum (B) after the solution is irradiated with ultraviolet rays.

FIG. 2 shows a visible absorption spectrum (A) of a methanol solution of the compound (II) of Example 1 and a visible absorption spectrum (C) after the solution is irradiated with visible light.

FIG. 3 shows a visible absorption spectrum (A) of an ethanol solution of the compound (III) of Example 2 and a visible absorption spectrum (B) after the solution is irradiated with visible light.

Claims (1)

[Claims] 1. A spironaphthoxazine compound having Se at the 1-position represented by the following formula (I): [Chemical 1] [In the formula, R ₁ represents a hydrogen atom, an acryloyl group or a methacryloyl group, and R ₂ and R ₃ are the same or different, a hydrogen atom, a lower alkyl group having 1 to 3 carbon atoms, and a carbon number 1
To 3 lower alkoxy groups, halogen atoms, nitro groups or cyano groups, and R ₄ represents an alkyl group having 1 to 18 carbon atoms]