JPH0481998B2 - - Google Patents

Description

[Detailed description of the invention]

[Industrial Application Field] The present invention relates to a novel 3,3-dimethyl-spiro[indolino-2,3'-naphtho[2,1-b]
(1,4) Oxazine] This relates to derivatives. For details, see various recording/memory materials, copying materials,
The present invention relates to a novel compound having photochromic properties that can be used as a printing photoreceptor, a light-sensitive material for lasers, a light-sensitive material for photosetting, an optical filter, a masking material, a photometer, and a display material. [Prior Art] It is known that spironaphthoxazine compounds have photochromic properties that develop or discolor when irradiated with light, and various photochromic light-sensitive materials using them have been proposed. For example, Japanese Patent Publication No. 45-28892 proposes a photochromic material containing a spironaphthoxazine compound as shown in the following formula. (In the formula, R ^a represents a hydrogen atom, a halogen atom, a cyan group, an alkyl group having 1 to 8 carbon atoms, or an alkoxy group.) In addition, in Japanese Patent Publication No. 49-48631, spironaphthoxazines such as the following formula are described. Photochromic light-sensitive materials have been proposed in which a type compound is dispersed in a polymeric substance. (In the formula, R ^b is -(CH ₂ ) - _o COOH, - (CH ₂ ) - _o CN or - (CH ₂ ) - _o COOR (R is an alkyl group having 1 to 5 carbon atoms); R ^c and R ^d is an alkyl group having 1 to 5 carbon atoms; R ^e is a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a halogen atom, a nitro group, a cyano group, an alkoxycarbonyl group having 2 to 6 carbon atoms, or an alkyl group having 1 to 6 carbon atoms; 5 alkoxy groups) Further, in JP-A-55-36284, a photochromic compound as shown in the following formula is proposed. (In the formula, one of R ^f and R ^g is halogen or lower alkoxy and the other is hydrogen, and R ^h and R ⁱ represent hydrogen, lower alkyl, lower alkoxy, or halogen.) A photochromic compound of the following formula has been proposed. (In the formula, one of R ^j and R ^k is halogen or lower alkoxy, the other is hydrogen, and R ^l and R ^m are hydrogen,
It represents lower alkyl, lower alkoxy, or halogen, and R ⁿ represents an alkyl group having 2 to 10 carbon atoms. ) In recent years, interest in organic ultra-thin films has been increasing, and Langmiur films are attracting particular attention as one such thin film. The Langmiur film production method is also called the monomolecular accumulation method, and is a method in which a monomolecular film formed on a water surface is layered one by one on a solid surface to create an ultra-thin film. The fabrication of ultra-thin organic films using Langmiur films is being considered. [Problems with the Prior Art] However, in the case of the conventional spironaphthoxazine compound as described above, even if a film is formed using the above method under ultraviolet irradiation, a sufficient film cannot be obtained. [Means for Solving the Problems] That is, the present invention solves the general formula [] (In the formula, R ¹ represents _{a C 16-24 alkyl} group, R ² ,
R ³ , R ⁴ and R ⁵ represent a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group or an alkoxycarbonyl group. ) 3,3-dimethyl-spiro[indolino 2,3'-naphtho[2,1-b] (1,4)
oxazine] derivatives. The spironaphthoxazine compound of the present invention is represented by the general formula []. In the formula, R ² , R ³ , R ⁴ , and R ⁵ are hydrogen atoms; halogen atoms such as chlorine atoms, bromine atoms, and iodine atoms;
An alkyl group such as a _C1-6 alkyl group; an alkoxy group such as _{a C1-6} alkoxy group; or an alkoxycarbonyl group such as _{a C1-6 alkoxycarbonyl group} . The compound of the present invention can be produced, for example, as follows. In other words, the following general formula [] (In the formula, R ² and R ³ are the same as defined above.) The following general formula [] (In the formula, R ¹ is the same as defined above.) p
-Toluenesulfonic acid esters or alkyl halides represented by ^the following general formula [ ^] Then the following general formula [] It can be produced by reacting a 1-nitroly-2-naphthol derivative represented by the formula (wherein R ⁴ and R ⁵ are the same as defined above). The alkylation reaction using p-toluenesulfonic acid ester or alkyl halide is carried out without a solvent or in a nonpolar solvent such as an aromatic solvent such as chlorobenzene or dichlorobenzene at a reaction temperature of 80 to 200°C. Preferably 130~ without solvent
Can be carried out smoothly at 150℃. Next, the reaction with the 1-nitroso-2-naphthol derivative is carried out in the presence of a basic catalyst such as piperidine, piperazine, or morpholine, using an alcoholic solvent such as methanol, ethanol, propanol, or butanol, or a ketone solvent such as acetone or methyl ethyl ketone. , dichloromethane, trichloroethane, and other halogenated hydrocarbon solvents. The reaction temperature is carried out in the range of 0 to 200°C. Preferably,
in ethanol, methyl ethyl ketone, acetone,
It can be carried out smoothly at 40°C to 120°C in the presence of a piperidine catalyst. The compound of the present invention can also be produced, for example, as follows. In other words, the following general formula [] (In the formula, R ¹ , R ² and R ³ are the same as defined above.) and the following general formula [] It can be produced by reacting a 1-nitroly-2-naphthol derivative represented by the formula (wherein R ⁴ and R ⁵ are the same as defined above). The reaction is usually carried out in the presence of a polar or non-polar solvent such as an alcoholic solvent such as methanol, ethanol, propanol or butanol, a ketone solvent such as acetone or methyl ethyl ketone, or a halogenated hydrocarbon solvent such as dichloromethane or trichloroethane. Ru. The reaction temperature is 0℃~
Conducted in the range of 200°C, preferably 40°C to 120°C
Can be carried out smoothly at ℃. [Function] The spironaphthoxazine compound of the present invention has a long-chain alkyl group (C ₁₆ to C ₂₄ ) as a substituent for N in the above general formula [], so it exhibits good coloring density and has a good color density. By this method, an organic ultra-thin film with excellent film forming properties and good photochromic properties can be produced. [Example] Next, the present invention will be explained in more detail with reference to Examples. Example 1 The following structural formula 21.6g of the compound represented by the following structural formula After adding 7 g of the compound 1-nitroso-2-naphthol and 100 ml of ethanol, and further adding 4 g of triethylamine, the mixture was reacted with stirring under a nitrogen atmosphere for 2 hours. After cooling, the solvent was distilled off and column chromatography (solvent used: benzene: n-
Separated and purified with hexane = 1:1), melting point 64-66
C. colorless crystals were obtained. Elemental analysis results are also shown below.
As shown in the table, the results agreed well with the calculated values.

[Table] Example 2 The following structural formula in Example 1 Instead of 21.6g of the compound represented by the following structural formula Other Example 1 using 20.4 g of the compound represented by
The following compound was obtained in the same manner as above. Example 3 A compound represented by the following general formula [] was synthesized by a method similar to Examples 1 and 2. When irradiated with ultraviolet rays in a toluene solution, each color developed to the color tone λmax shown in Table 2.

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〔effect〕

The compound of the present invention is a novel dye and a compound exhibiting photochromism. That is, this compound develops a color when irradiated with ultraviolet rays, then returns to its original colorless state when irradiated with visible light or heated to 50°C or higher, and this change can be repeated. This compound can be used in various recording/memory materials,
It is used as a copying material, a printing photoreceptor, a light-sensitive material for lasers, a light-sensitive material for phototypesetting, an optical filter, a masking material, a photometer, and a display material.

Claims (1)

[Claims] 1. General formula [] (In the formula, R ¹ represents _{a C 16-24 alkyl} group, R ² ,
R ³ , R ⁴ and R ⁵ represent a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group or an alkoxycarbonyl group. ) 3,3-dimethyl-spiro[indolino 2,3'-naphtho[2,1-b] (1,4)
Oxazine] derivative.