JPH0796553B2 - Spiropyran compound - Google Patents

Description

TECHNICAL FIELD The present invention relates to a novel spiropyran compound, and particularly to a spiropyran compound useful as a photochromic material that repeatedly undergoes color change or decolorization change by the action of light. Is.

[Prior art and its problems]

Photochromism is a phenomenon that has been attracting attention for several years, and when a compound is exposed to sunlight or light containing ultraviolet rays such as the light of a mercury lamp, the color of the compound rapidly changes, and the light is stopped and the light is stopped in the dark. It is a reversible effect of returning to the original color when put on. A compound having this property is called a photochromic compound, and various compounds have been synthesized conventionally, but no special common structure is recognized in the structure. In recent years, among these various photochromic compounds, the following structural formula (II) The 1,3,3-trimethylindolinobenzospiropyran derivative represented by (wherein R ₁ and R ₂ are various substituents) has received the most attention. The above formula (I
The compound of I) changes from colorless in a non-polar solvent such as benzene and toluene to blue rapidly when exposed to sunlight or ultraviolet rays, and returns to the original colorless state when left in the dark or irradiated with visible light. However, when these compounds are dissolved in a polar solvent such as ethyl alcohol, methyl alcohol, acetone, acetonitrile, dimethylformamide, etc., they generally have a red or reddish purple color, and even if this solution is irradiated with ultraviolet rays, notable photochromic Has no effect. Also in the polymer solid matrix,
The compound of the above (II) does not exhibit a remarkable photochromic action, and particularly polymethylmethacrylate, polycarbonate, poly (allyldiglycolcarbonate)
In the polar polymer matrix, it has a red or reddish purple color, and a sufficient photochromic action is not observed even when irradiated with ultraviolet rays. Further, in the polymer matrix as described above, the compound (II) has a drawback that its color-developing structure is stabilized in the matrix, so that the fading speed becomes extremely slow.

Also, US Patent Nos. 3562172, 3578602, and 4215010.
No. 4342668, spiro (indoline) naphthoxazine compounds are not affected by the solvent or polymer matrix as described above, and their fading speed is fast. However, the photochromic action of this spiro (indoline) naphthooxazine compound is remarkable at around 10 to 15 ° C in the solvent or in the polymer matrix, but it is not so remarkable at around room temperature (20 to 30 ° C).

[Means for solving problems]

The present inventor has conducted extensive studies to eliminate the influence of the spiropyran compound in the polymer matrix as described above, to make its photochromic effect remarkable near room temperature, and to improve the photochromic performance regarding color development and fading speed. It was As a result, they have found a novel spiropyran compound represented by the following general formula (I) that satisfies the above characteristics, and have completed the present invention based on this finding. That is, the present invention has the general formula (I) (Here, R ₁ , R ₂ and R ₃ are alkyl groups having 1 to 10 carbon atoms, R ₄ , R ₅ , R ₆ and R ₇ are hydrogen atoms, halogen atoms, alkyl groups having 1 to 5 carbon atoms or Is a spiropyran compound represented by (indicating an alkyl group).

R ₁ , R ₂ and R ₃ represented by the general formula (I) have 1 to 1 carbon atoms.
The same or different alkyl groups of 0 are preferable, and specific examples thereof include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group and a decyl group.

Further, R ₄ , R ₅ , R ₆ and R ₇ represented by the general formula (I) are the same or different hydrogen atom, halogen atom, carbon number 1 to
The alkyl group or alkoxy group of 5 is preferably adopted. As the above halogen atom, chlorine atom, bromine atom,
Iodine atom is used without particular limitation. As the alkyl group, methyl group, ethyl group, propyl group, butyl group,
A lower alkyl group having 1 to 5 carbon atoms of a pentyl group is preferably used. Furthermore, as the alkoxy group, a methoxy group,
A lower alkoxy group having 1 to 5 carbon atoms such as an ethoxy group, a propoxy group, a butoxy group and a pentoxy group is preferable.

The compound represented by the above general formula (I) of the present invention generally exists as a pale yellow solid at room temperature and atmospheric pressure. In addition, it can be confirmed that the compound represented by the general formula (I) of the present invention is generally each compound of the general formula (I) by means of the following (A) to (C).

(B) by measuring the infrared absorption spectrum (IR), absorption by expansion and contraction of the aromatic a -CH the 3100~3000cm ^-1, absorption caused by the expansion and contraction of the ant files ticks of -CH the 3000~2800cm ^-1, 1640 ～1600Cm ^-1 absorption due to stretching of C = N bond, absorption by aromatic of C = C bonds in 1600～1580Cm ^-1, strong absorption due to expansion and contraction of the spiro a C-O bond appears to 990~920cm ^-1.

(B) By measuring the proton nuclear magnetic resonance spectrum ( ¹ H-NMR), the kind and number of protons present in the molecule can be known. Aromatic proton-based peaks around δ7-9.3 ppm, -CH = N-bonded proton-based peaks around δ6.3-δ6.7, δ1.2-
A peak based on a proton of N—R ₁ (wherein R ₁ represents an alkyl group having 1 to 10 carbon atoms) bond near δ3.0 ppm, δ
Around 1.0 to δ2.0ppm (However, R ₂ and R ₃ represent an alkyl group having 1 to 10 carbon atoms)
A peak based on bound protons appears. By comparing the respective peak intensities relatively, the number of protons in each bonding group can be known.

(C) By elemental analysis, each weight% of carbon, hydrogen, nitrogen and halogen can be obtained. Further, the weight% of oxygen can be calculated by subtracting the total weight% of the recognized elements from 100. Therefore, the formula of the corresponding product can be determined.

The compound represented by the above general formula (I) of the present invention is generally soluble in organic solvents such as benzene, toluene, chloroform, carbon tetrachloride, acetonitrile, methyl alcohol, ethyl alcohol and N, N-dimethylformamide.
When the compound represented by the general formula (I) is dissolved in such a solvent, the solution is generally colorless and transparent regardless of the polarity or non-polarity of the solvent, and when irradiated with sunlight or ultraviolet rays, it becomes reddish purple or blue. It changes rapidly, and when it blocks the layer, it exhibits a good reversible photochromic action that immediately returns to the original colorless state. Such a photochromic action in the present invention also occurs in the polymer solid matrix, and the photochromic action of coloring and decoloring is remarkable even at around room temperature (20 to 30 ° C.), and the reversible speed occurs on the order of seconds. The target polymer matrix may be one in which the compound represented by the general formula (I) of the present invention is uniformly dispersed. Optically preferably, for example, polymethyl acrylate, polyethyl acrylate, Examples thereof include polymethylmethacrylate, polyethylmethacrylate, and polycarbonate poly (allyldiglycol carbonate). The compound represented by the general formula (I) can be added to the above-mentioned polymer matrix in an arbitrary ratio depending on the degree of dispersion, but it is generally 0.
001 to 70% by weight is preferable.

The method for producing the compound represented by the above general formula (I) of the present invention is not particularly limited and may be obtained by any method. A typical method that is generally adopted is described below.

2-methylene indoline represented by the general formula (III) (Here, R ₁ , R ₂ and R ₃ are alkyl groups having 1 to 10 carbon atoms, R ₄ and R ₅ are hydrogen atoms, halogen atoms, and 1 to 10 carbon atoms.
5 represents an alkyl group of 5 or a lower alkoxy group such as methoxy and ethoxy) 1-nitroso-2-phenanthrol represented by the general formula (IV) (Wherein R ₆ and R ₇ represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 5 carbon atoms, or a lower alkoxy group such as methoxy and ethoxy) in an equimolar ratio through nitrogen gas in ethyl alcohol. While refluxing, cooling after reaction, brown crystals are precipitated. If this is separated by filtration and recrystallized from ethyl alcohol, a pale yellow compound of the above formula (I) can be obtained with a yield of about 10 to 30%.

〔The invention's effect〕

The photochromic resin obtained by dispersing the thus-obtained spiropyran compound of the general formula (I) in the polymer matrix as shown above is colorless and transparent in any case, and becomes blue by ultraviolet irradiation. Develops color,
It returns to its original color in the order of seconds when ultraviolet rays are removed. It is recognized that the photochromic effect in the present invention is more prominent at around room temperature (20 to 30 ° C.) than that of the above-mentioned spironaphthoxazine compound, and its color density is high.

INDUSTRIAL APPLICABILITY The spiropyran compound of the present invention can be used in a wide range of fields as a photochromic material, for example, various recording memory materials replacing silver salt photosensitive materials, copying materials, printing photoreceptors, cathode ray tube recording materials, laser photosensitive materials, holography. It can be used as various recording materials such as photosensitive materials. In addition, the photochromic material of the present invention can be used as a material for a photochromic lens material, an optical filter material, a display material photometer, a decoration and the like. For example, when it is used for a photochromic lens, it is not particularly limited as long as it is a method capable of obtaining uniform dimming performance, and specifically, the spiropyran compound represented by the general formula (I) is uniformly dispersed. A method of sandwiching a polymer film formed in a lens, or this compound is dissolved in, for example, ethanol, and the lens surface is impregnated with this compound for 10 hours at 70 ° C., for example, and the surface is treated with a curable substance. There is a method of coating and forming a photochromic lens. Furthermore, a method of applying the above-mentioned polymer film to the lens surface and coating the surface with a curable substance to form a photochromic lens can be considered.

As described above, the spiropyran compound represented by the general formula (I) of the present invention is hardly affected by the type of the matrix in the polymer solid matrix and is stable and colorless in a general state. It immediately develops blue color when exposed to light, and returns to original colorlessness on the order of seconds when the irradiation of ultraviolet light is stopped. Its color density is large even near room temperature (20 to 30 ° C), and these discolorations are repeated. is doing.

〔Example〕

Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to these Examples.

Production Example (1) 1,3,3-trimethyl-2-methyleneindoline (8.5 g, 50 mmol), 1-nitroso-2-phenanthol (11.2 g, 50 mmol) and 100 ml of ethanol are dissolved and refluxed for 2 hours while passing nitrogen gas. After the reaction, excess ethanol was distilled off to about 1/4 position, and the mixture was allowed to stand at room temperature to precipitate brown crude crystals. Recrystallization from ethyl alcohol gave 4.7 g of pale yellow crystals. The melting point is 19
It was 5 to 196 ° C. Was measured infrared absorption spectrum, the absorption caused by the expansion and contraction of the C = N bond to 1610 cm ^-1, 950 cm ^-1
Showed strong absorption due to the stretching of the spiro C—O bond.
The elemental analysis values are C 82.74%, H 5.62%, N 7.42%
Therefore, the calculated values for C ₂₆ H ₂₂ N ₂ O (378.26) were in good agreement with C 82.55%, H 5.82%, and N 7.40%. In addition, the proton nuclear magnetic resonance spectrum was measured. As a result, a peak of 12H due to an aromatic proton was observed near δ7 to δ8.3ppm, a peak of 1H due to a proton of -CH = N-bond at δ6.6ppm, and δ2.7ppm. Peak of 3H due to proton of N-CH ₃ bond, δ1.5ppm A peak based on bound protons was shown. From the above results, the isolated product is It was found to be a compound represented by the structural formula: The yield was 24.8%.

Production Example (2) 5-chloro-1,3,3-trimethyl-2-methyleneindoline (10.4 g, 50 mmol) and 1-nitroso-2-phenanthrol (11.2 g, 50 mmol) were reacted, isolated and purified in the same manner as in Production Example 1 to obtain 4.0 g of pale yellow crystals. The melting point was measured and found to be 176 to 179 ° C. When the infrared absorption spectrum was measured, absorption at 1610 cm ^-1 due to expansion and contraction of the -C = N- bond,
It showed strong absorption at 950 cm ^{-1 due} to stretching of the spiro CO bond. The elemental analysis values are C 75.73%, H 5.24%, N
6.96%, which is in very good agreement with the calculated values for C ₂₆ H ₂₁ ClN ₂ O (412.76): C 75.59%, H 5.09%, N 6.78%. In addition, the proton nuclear magnetic resonance spectrum was measured. As a result, the 11H peak based on the aromatic proton was observed at δ7 to δ8.3 ppm, the 1H peak at 6.6 ppm was derived from the -CH = N-bonded proton, and the N peak was observed at δ2.7 ppm. -CH ₃
3H peak due to bound protons, δ1.5ppm A peak based on bound protons was shown. From the above results, the isolated product is It was found to be a compound represented by the structural formula: The yield was 19.4%.

Production Examples (3) to (6) In the same manner as in Production Example 1, reaction, isolation and purification were performed.
The structural formulas, melting points and yields of the reaction starting materials and reaction products are shown in Table 1.

Infrared absorption spectrum, elemental analysis, and proton nuclear magnetic resonance spectrum were used for the structure confirmation.

Application example (1) The compound represented by is dissolved and dispersed in polymethylmethacrylate using benzene, and slide glass (11.2 × 3.7c
m) I made a cast film above. The concentration of the compound contained in this film was adjusted to 1.0 × 10 ⁻⁴ mol / g so that the thickness was 0.1 mm. To this photochromic film, a mercury lamp SHL-100 made by Toshiba Corp.
Irradiation was carried out at a temperature of ± 1 ° C at a distance of 10 cm for 60 seconds to develop the color of the film and measure the photochromic properties. The photochromic characteristics are expressed as follows. The results are shown in Table 2.

Maximum absorption wavelength (lambda _max); from Hitachi, Ltd. made spectrophotometer 220A, was determined lambda _max of the color film.

ε (60 seconds); Absorbance at maximum absorption wavelength of the film after 60 seconds of light irradiation under the above-mentioned conditions.

ε (0 second): Absorbance of the unirradiated film at the maximum absorption wavelength during light irradiation.

Half-life t ^1/2 ; time required for the absorbance of this film to decrease to 1/2 of {ε (60 seconds) −ε (0 seconds)} after irradiation with light for 60 seconds.

Application example (2) Same as application example (1) A photochromic cast film of polymethylmethacrylate of the compound shown by was prepared. Its concentration is 1.
It was 0 × 10 ⁻⁴ mol / g and the thickness was 0.1 mm. Further, the photochromic characteristics of this film were measured in the same manner as in Application Example (1). The results are shown in Table 2.

Comparative Example (1) Application example (1) except for spiropyran shown in
Same as. The results are shown in Table 2.

Comparative example (2) In the same manner as in Application Example (1) except that the spironaphthoxazine represented by The results are shown in Table 2. Application example (3) As a compound The same procedure as in Application Example (1) was carried out except that the compound shown in 1 was used and polycarbonate was used as the film matrix. The results are shown in Table 3.

Application example (4) As a compound The same procedure as in Application Example (3) was performed except that the compound shown in was used. The results are shown in Table 3.

Comparative Example (3) As compound The same procedure as in Application Example (3) was performed except that the compound shown in was used. The results are shown in Table 3.

Comparative Example (4) As compound The same procedure as in Application Example (3) was performed except that the compound shown in was used. The results are shown in Table 3.

Application example (5) As a compound The compound represented by (1) was dissolved in 100 cc of ethanol, and the film surface of poly (allyl diglycol carbonate) having a thickness of 0.1 mm was impregnated at 70 ° C. for 10 hours. The concentration at that time was adjusted to 1.0 × 10 ⁻⁴ mol / g. The photochromic properties of this film were measured in the same manner as in Application Example (1). The results are shown in Table 3.

Comparative example (5) Application example (5) was repeated except that the compound shown in was used. The results are shown in Table 3.

From the above results, it is clear that when the compound of the present invention is used in a polymer solid matrix, its color density is high near room temperature (25 ° C), and it is colorless in the decolored state, and its reversible speed is fast. Is.

Claims (2)

[Claims] 1. A spiropyran compound represented by the following general formula (I): (Here, R ₁ , R ₂ and R ₃ are each an alkyl group having 1 to 10 carbon atoms, and R ₄ , R ₅ , R ₆ and R ₇ are each a hydrogen atom, a halogen atom, and a carbon number of 1 to 5 Represents an alkyl group or an alkoxy group). 2. A photochromic material containing a spiropyran compound represented by the following general formula (I) as an active ingredient. (Here, R ₁ , R ₂ and R ₃ are each an alkyl group having 1 to 10 carbon atoms, and R ₄ , R ₅ , R ₆ and R ₇ are each a hydrogen atom, a halogen atom, and a carbon number of 1 to 5 Represents an alkyl group or an alkoxy group).