JPH03251587A - Spiroxazine compound and production thereof - Google Patents

Abstract

NEW MATERIAL:The compound of formula I [the group of formula II is (substituted) aromatic hydrocarbon group or (substituted) unsaturated heterocyclic group; R1 and R2 are H, alkyl or together form a ring; R3 is alkoxycarbonylalkyl; R4 to R8 are H, alkyl, aryl, halogen, cyano, trifluoromethyl, alkoxycarbonyl, etc.; at least one of R4 and R5 is cyano, trifluoromethyl or alkoxycarbonyl]. EXAMPLE:The compound of formula III. USE:A photochromic material capable of reversibly changing to a dark-colored state with light containing ultraviolet rays such as solar light and mercury lamp. PREPARATION:An azolium salt of formula IV (R3 is alkoxycarbonylalkyl; A<-> is anion) is reacted with a nitroso compound of formula V in the presence of a base.

Description

Detailed Description of the Invention (Industrial Application Field) The present invention provides an excellent method that changes into a colored or deep-colored form when exposed to sunlight or light containing ultraviolet rays, such as light from a mercury lamp, and that the change is reversible. This invention relates to a novel spirooxazine compound that exhibits durability.

(Prior Art and Problems to be Solved by the Invention) Photochromism is a phenomenon that has attracted attention over the past few years.When a certain compound is irradiated with light containing ultraviolet light, such as sunlight or light from a mercury lamp, photochromism immediately This is a reversible effect in which the color changes and returns to the original color when you stop exposing it to light and place it in a dark place. Compounds having this property are called photochromic compounds, and various compounds have been synthesized to date, but no particular commonality is recognized in their structures.

Japanese Patent Publication No. 49-48631 and Japanese Patent Publication No. 63-304
Publication No. 88 describes spirooxazine compounds. These compounds exhibit photochromic action in solution or in a polymer matrix.

However, the photochromic effect of these spirooxazine compounds in the polymer matrix is 20
Although it is noticeable at temperatures below °C,
C) Furthermore, it is not good at temperatures higher than room temperature.

(Means for Solving the Problem) As a result of extensive research in order to further improve the photochromic properties of the above-mentioned compounds, the present inventors succeeded in synthesizing a new spirooxazine compound, and the spirooxazine It was discovered that the compound exhibits good photochromic action even in a high temperature range (30 to 40°C), and the present invention was completed.

That is, the present invention provides - formula (r) This is a spirooxazine compound represented by

In the above-mentioned formula (I), the group represented by ``-'' is an optionally substituted aromatic hydrocarbon group or an optionally substituted unsaturated heterocyclic group. Specific examples of aromatic hydrocarbon groups include benzene ring, naphthalene ring, phenanthrene ring,
Divalent groups derived from one benzene ring or 2 to 4 condensed rings such as anthracene ring can be mentioned. Also,
Hydroxyl group, nitro group, cyano group, fluoroalkyl group, substituted amino group, halogen atom,
Examples include substituted aromatic hydrocarbon groups substituted with one or more heterocyclic groups such as an alkyl group, an alkoxy group, a phenyl group, a thienyl group, a furyl group, or a pyrrolyl group.

In the above-mentioned formula (I), the optionally substituted unsaturated heterocyclic group represented by -7 Examples include heterocyclic groups.

Specifically, nitrogen-containing heterocycles such as pyridine ring, quinoline ring, pyrrole ring, and indole ring; furan ring.

Oxygen-containing heterocycles such as benzofuran rings; thiophene rings.

Examples include divalent heterocyclic groups derived from sulfur-containing heterocycles such as benzothiophene rings. In particular, benzene ring and 5
In the case of a two-ring condensed heterocycle with a membered ring or a six-membered heterocycle, high coloring density can be obtained.

Furthermore, as the substituent for the unsaturated heterocyclic group, the above-mentioned substituents for the aromatic hydrocarbon group can be employed without any restrictions.

Furthermore, in the above formula (1), R3 and R2 are a hydrogen atom or an alkyl group, and R1 and Rt may be taken together to form a ring. The above alkyl group is not particularly limited, but generally has 1 to 20 carbon atoms, preferably 1 to 20 carbon atoms.
6 is preferable. More specific examples of the alkyl groups mentioned above include methyl, ethyl, and isopropyl groups. In addition, when R and R2 are combined to form a ring, there are no particular limitations, but generally the number of carbon atoms is 5.
-10 cycloalkyl rings, bicycloalkyl rings, and tricycloalkyl rings are preferred. A more specific example of these is a cyclopentyl ring.

Examples include divalent groups derived from a cyclohexyl ring, a cycloheptyl ring, a norbornane ring, and a 5-adamantane ring. Either one of these RI and R2 is an alkyl group having 1 or more carbon atoms and the other is an alkyl group having 2 or more carbon atoms, or a compound in which these are taken together to form a ring is It is preferable because it shows good color density.

In the above formula (I), R1 is an alkoxycarbonylalkyl group. The alkoxy group in the alkoxycarbonylalkyl group is not particularly limited, but generally has 1 carbon number.
-10, preferably 1-4 are suitable. The alkylene group in the alkoxycarbonylalkyl group is not particularly limited, but generally has 1 to 100 carbon atoms, preferably 1 to 100 carbon atoms.
4 is preferred. More specific examples of the alkoxycarbonylalkyl group include a methoxycarbonylmethyl group, a methoxycarbonylethyl group, a methoxycarbonylpropyl group, an ethoxycarbonylmethyl group, an ethoxycarbonylethyl group, an ethoxycarbonylbutyl group, a butoxycarbonylethyl group, and the like.

In the formula (I) above, Ra, Rs, Rh, Rt and R3 are hydrogen atoms, alkyl groups, and aryl groups.

It is an aralkyl group, an alkoxy group, a halogen atom, a cyano group, a trifluoromethyl group, or an alkoxycarbonyl group, and at least one of R4 and R3 is a cyano group, a trifluoromethyl group, or a carboxycarbonyl group.

The alkyl group and alkoxy group mentioned above are not particularly limited, but generally have 1 to 10 carbon atoms, preferably 1 to 4 carbon atoms. More specific examples of this alkyl group include a methyl group, an ethyl group, an isopropyl group, and the like, and examples of the alkoxy group include a methoxy group, an ethoxy group, and an isopropyloxy group. Further, the above aryl group preferably has 6 to 10 carbon atoms, specific examples include phenyl group, naphthyl group, etc., and the aralkyl group preferably has 7 to 14 carbon atoms, and specific examples include phenyl group, naphthyl group, etc. Examples include benzyl group, phenylethyl group, phenylpropyl group, and naphthylmethyl group. Fluorine and chlorine are halogen atoms.

Bromine, etc. The alkoxycarbonyl group is not particularly limited, but generally has 1 to 5 carbon atoms, preferably 1 to 3 carbon atoms. More specific examples of this alkoxycarbonyl group include a methoxycarbonyl group and an ethoxycarbonyl group.

-i In formula (I), at least one of R4 and R2 must be a cyano group, a trifluoromethyl group, or an alkoxycarbonyl group. By selecting these groups, the spirooxazine of the present invention The compound shows good photochromic action even at high temperatures.

The compound represented by the above general formula (I) of the present invention generally exists as a colorless or pale yellow solid or viscous liquid at room temperature and pressure, and can be prepared by the following means (a) to (c). You can check it here.

(a) Proton nuclear magnetic resonance spectrum (H'-NMR
), it is possible to know the type and number of protons present in the molecule.

That is, there is a peak based on aromatic protons around 66.5 to 9 ppm, and a peak at 51.2 to 2.5 ppm.
A peak based on the proton of the alkyl group of R and R2 is near, a peak based on the proton of the carbon to which the nitrogen of R8 is bonded is around 63 to 4 ppm, and when R4 is an alkoxycarbonyl group, it is around 62.5 to 4 ppm. The peak based on the proton of carbon bonded to carbonyl and 63.5 to 4
A peak based on carbon protons bonded to oxygen appears near ppm+. Furthermore, by relatively comparing the respective δ peak intensities, it is possible to know the number of protons of each bonding group.

(b) The weight percentages of carbon, hydrogen, nitrogen, sulfur, and halogen can be determined by elemental analysis.

Furthermore, the weight percent of oxygen can be calculated by subtracting the sum of the recognized weight percent of each element from 100. The composition of the corresponding product can therefore be determined.

(c) ISc-Nuclear Magnetic Resonance Spectrum ("C-NMR
), it is possible to know the type of carbon present in the molecule.

Peaks based on primary and secondary carbons near δ20-50ppm, peaks based on carbons of aromatic hydrocarbon groups or unsaturated heterocyclic groups near δ110-150ppa+, 610
Peak based on spiro carbon near 0 ppm, 6170
A peak based on carbonyl carbon appears near ppm.

The method for producing the compound represented by the general formula (1) of the present invention is as follows:
It is not particularly limited and may be obtained by any synthesis method. Representative methods that are generally suitably adopted will be explained below.

This is a method in which an azolium salt represented by the following formula (II) and a nitroso compound represented by the formula (DI) are reacted in the presence of a base.

Above - Compound represented by formula (n) and general formula (I[I)
The reaction with the compound represented by is carried out as follows. The reaction ratio of these two types of compounds is adopted from a wide range, but -g is 1:10 to 10:1 (molar ratio).
selected from the range.

The reaction temperature is generally preferably 0 to 200°C, and the solvent is a polar solvent such as methyl alcohol.

Ethyl alcohol, N-methylpyrrolidone, dimethylformamide, tetrahydrofuran, etc. are used. This reaction is performed using known bases such as tertiary amines such as triethylamine, amines such as secondary amines such as diethylamine, piperidine, pyrrolidine, and morpholine; and inorganic bases such as alkali metal hydroxides or alkali metal carbonates. done in the presence of The amount used is usually preferably in the range of 0.1 to 10 mol per 1 mol of the compound of formula (II) above.

The spirooxazine compound represented by formula (I) of the present invention dissolves well in common organic solvents such as toluene, chloroform, and tetrahydrofuran. When the spirooxazine compound represented by general formula (I) is dissolved in such a solvent, the solution is generally almost colorless and transparent, but when irradiated with sunlight or ultraviolet rays, it rapidly changes color or darkens, and does not absorb light. It exhibits a good reversible photochromic effect that quickly returns to its original colorless state when blocked. Such photochromic action in compounds of formula (1) also occurs in solid polymer matrices, and the reversible speed is on the order of seconds. The target polymer matrix may be one in which the spirooxazine compound represented by the general formula (1) of the present invention is uniformly dispersed, and optically preferably, for example, polymethyl acrylate, polyacrylic acid, etc. Ethyl, polymethyl methacrylate, polyethyl methacrylate, polystyrene, polyacrylonitrile, polyvinyl alcohol, polyacrylamide, poly(
2-hydroxyethyl methacrylate), polydimethylsiloxane, polycarbonate, poly(allyl diglycol carbonate), or polymers formed by copolymerizing the monomers forming these polymers with each other or with other monomers. Suitably used.

The spirooxazine compound of the present invention can be widely used as a photochromic material, such as various storage materials in place of silver salt photosensitive materials, copying materials, photoreceptors for printing, recording materials for cathode ray tubes, photosensitive materials for lasers, and holography. It can be used as various recording materials such as photosensitive materials. In addition, the photochromic material using the spirooxazine compound of the present invention can also be used as a material for photochromic lens materials, optical filter materials, display materials, photometers, decorations, and the like. For example, when used in a photochromic lens, there is no particular restriction as long as the method provides uniform light control performance.A specific example is a polymer film formed by uniformly dispersing the photochromic material of the present invention. How to sandwich it into a lens, or
For example, by dissolving this compound in silicone oil,
There is a method in which the lens surface is impregnated at 0 to 200° C. for 10 to 60 minutes, and then the surface is further coated with a curable substance to form a photochromic lens. Furthermore, a method of applying the polymer film to the lens surface and coating the surface with a curable substance to form a photochromic lens is also considered.

(Effect) The spirooxazine compound of the present invention exhibits remarkable effects in a polymer solid matrix not only near room temperature (20 to 30°C) but also at higher temperatures than room temperature (30 to 40°C). Shows photochromic action.

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

Example 1 A compound of the following formula CHzCOOCH+ 2.01 g (0,0057 mol), a compound O of the following formula 1.4 g (0,0057 eaol), and pyrrolidine 0.01 g (0,0057 mol).
41g (0,0058mol) of 50% ethyl alcohol
ml and heated under reflux for 2 hours.

After the reaction, the solvent was removed and the mixture was purified by chromatography on silica gel to obtain a spirooxazine compound 200 of the following formula.

The elemental analysis values of this compound are C65,12%, H4,9
0%, N 8.51%, O9.74%, F
It is 11.73% and Cz? Calculated values for HtaNzOJs: C65.45%, H4,88%, N
8.48%, 09.69%F, 11.50%, which agreed very well. In addition, when proton nuclear magnetic resonance spectra were measured, a <9H peak based on protons of the quinoline ring, protons of the indoline ring, and protons of the oxazine ring was observed at around 66.5 to 9 ppm, and a peak of <9H, δ4 PPIII
A peak of <2H based on the proton of the 1; N-co, -c- bond near 1; a peak of <3H based on the proton of the 10-CH bond near 63.7 ppm, a peak of <3H based on the proton of the bond, 61.3 to 2. A broad 10H peak based on the proton of the cyclohexane ring was observed around 1 ppm. Furthermore, when we measured the 15C-nuclear magnetic resonance spectrum (Figure 1), we found a peak based on carbonyl carbon at around 170 ppm, and a peak at 6100 to 160 ppm.
Peaks based on the carbons of the benzene ring, quinoline ring, and oxazine ring of indoline near pm, a peak based on the trifluoromethyl group near 6125 ppm, 699 ppm
and a peak based on spiro carbon around 652 ppm, 6
A peak based on methyl group and methylene chain carbon was observed around 20 to 50 ppm.

From the above results, it was confirmed that the isolated product was a compound represented by the above structural formula (1).

Example 2 Compound C) IzCHzCOOCHs 2,0 g (0,0057 mol), compound O 1,4 g (0,00575 oot), and pyrrolidine 0
．． 41 g (0,0057 mol) was dissolved in ethyl alcohol and heated under reflux for 2 hours. After the reaction, the solvent was removed and the mixture was purified by chromatography on silica gel to obtain a spirooxazine compound 150m of the following formula.

CH.

OOCR1 The elemental analysis values of this compound are C 65.23%, H5,
21%. N 8.56%, O 9.71%.
F 11.29%, CzqHzhN,OsFs
C65, which is the calculated value for 18%. H 5.2
7%, N 8.45%, 0 9.93%.

It was in very good agreement with F 11.46%. In addition, when proton nuclear magnetic resonance spectra were measured, 66,5~
A peak based on aromatic protons near 9 ppm, δ1. A peak based on the methyl proton of the ethyl group near Opp-, a peak based on the methylene proton of the ethyl group near 62 ppm, and a peak near 63,5 ppm]
Peaks based on protons of N-CHzCHzCOOCHz are shown. In addition, when C-NMR was measured, there was a peak based on carbonyl carbon near δ170ppa+, aromatic carbon near 6100-160 ppm, a peak based on carbon of oxazine ring and carbon of trifluoromethyl group, and 699 ppm. Peak based on spiro carbon near 650 ppm, peak based on methylene carbon bonded to nitrogen, 620-40 ppm
A peak based on the carbon of the methyl group and methylene group bonded to carbon was shown near m. From the above results, it was confirmed that the isolated product was a compound represented by the above structural formula (2).

Examples 3-15 The chromene derivatives shown in Table 1 were synthesized in the same manner as in Examples 1-2.

As a result of structural analysis of the obtained product using the same structural confirmation method as in Example 1, it was confirmed that it was a compound represented by the structural formula shown in Table 1.

Further, Table 2 shows the elemental analysis values of this compound and the calculated values obtained from the structural formula of each compound.

Examples 18 to 34 and Comparative Examples 1 to 2 The compound represented by the following formula obtained in Example 1 was dissolved and dispersed in polymethyl methacrylate using benzene.
A cast film was made on 3.7 cm). The concentration of the above compound contained in this film is 1. OX
The thickness was adjusted to 10-'+wol/g, and the thickness was 0.1 m. This photochromic film was irradiated with a mercury lamp 5HL-100 manufactured by Toshiba ■ at 35 ± 1°C at a distance of 10 cm for 60 seconds to develop color.
The photochromic properties were measured. The photochromic properties were expressed as follows. The results are shown in Table 3 as Example 18.

Maximum absorption wavelength (λax); ■The λ theory aX of this coloring film was determined using a spectrophotometer 22OA manufactured by Hitachi.

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

ε (0 seconds); at the maximum absorption wavelength at maximum irradiation,
Absorbance of unirradiated film.

Half-life tl/2: The time required for the absorbance of this film to decrease to 172 (ε(60 seconds)−ε(0 seconds)) after irradiation with light for 60 seconds.

In addition, a photochromic film was obtained in the same manner as in Example 1 above, except that the compounds obtained in Examples 2 to 17 were used as spirooxazine compounds, and the properties are shown in Table 3 as Examples 19 to 34. Indicated.

Furthermore, for comparison, the same procedure as in Example 18 was carried out except that spirooxazine represented by the following formula and spirooxazine represented by the following formula were used, and the results are also listed in Table 3 as Comparative Examples 1 and 2. .

CH co Table 3

[Brief explanation of drawings]

FIG. 1 is a chart of the 13C-nuclear magnetic resonance spectrum of the spirooxazine compound obtained in Example 1.

Claims (3)

[Claims] (1) The following general formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [However, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ is an optionally substituted aromatic hydrocarbon group or an optionally substituted unsaturated group. It is a heterocyclic group, R_1 and R_2 are hydrogen atoms or alkyl groups, R_1 and R_2 may be taken together to form a ring, R_3 is an alkoxycarbonyl alkyl group, R_4, R_5, R_6, R_7 and R_8 are
A hydrogen atom, an alkyl group, an aryl group, an aralkyl group, an alkoxy group, a halogen atom, a cyano group, a trifluoromethyl group, or an alkoxycarbonyl group, and at least one of R_4 and R_5 is a cyano group, a trifluoromethyl group, or an alkoxycarbonyl group. It is. ] A spirooxazine compound represented by: (2) The following general formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [However, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ is an optionally substituted aromatic hydrocarbon group or an optionally substituted unsaturated group. It is a heterocyclic group, R_1 and R_2 are hydrogen atoms or alkyl groups, R_1 and R_2 may be combined to form a ring, R_3 is an alkoxycarbonyl alkyl group, and A^■ is an anion. It is. ] There are azolium salts and general formulas ▲ mathematical formulas, chemical formulas, tables, etc. ▼ [However, R^4, R^5, R^6, R^7 and R^8 are hydrogen atoms, alkyl groups, aryl groups , an aralkyl group, an alkoxy group, a halogen atom, a cyano group, a trifluoromethyl group, or an alkoxycarbonyl group, and at least one of R^4 and R^5 is a cyano group, a trifluoromethyl group, or an alkoxycarbonyl group. ] The method for producing a spirooxazine compound according to claim (1), characterized in that the nitroso compound represented by these is reacted in the presence of a base. (3) A photochromic material comprising a spirooxazine compound according to claim (1).