JPH0586955B2 - - Google Patents

Description

[Detailed description of the invention]

[Industrial Field of Application] The present invention relates to a novel spirooxazine compound, and in particular provides a spirooxazine compound useful as a photochromic material that repeatedly changes color or discoloration under the action of light. [Prior art and problems to be solved by the invention] Photochromism is a phenomenon that has attracted attention over the past few years. Photochromism is a phenomenon that occurs when a certain compound is irradiated with light containing ultraviolet light, such as sunlight or light from a mercury lamp. This is a reversible effect in which the color changes quickly and returns to the original color when the light is removed and placed in a dark place. Compounds having this property are called photochromic compounds, and various compounds have been synthesized in the past. In recent years, among these various photochromic compounds, US Pat.
Spiro(indoline) naphthoxazine compounds such as those described in Patent No. 3578602, No. 4215010, and No. 4342668 are attracting particular attention. This compound contains ethyl alcohol, acetone,
It exhibits photochromic action in solvents such as acetonitrile, dimethylformamide, and benzene, and in polymers such as polymethyl methacrylate, polycarbonate, and poly(allyl diglycol carbonate). However, although the photochromic effect of this spiro(indoline) naphthoxazine compound in a polymer matrix is remarkable at temperatures below 15°C, it is
Furthermore, it is not good at temperatures higher than room temperature (30 to 40°C). Further, the color tone of this spiro(indoline) naphthoxazine compound is only blue in any solvent or polymer matrix, and the color tone cannot be freely controlled. In addition, some of the spiro(indoline) naphthoxazine compounds described in JP-A No. 61-501145 can control the color tone to reddish-purple or blue, even at around room temperature (20 to 30°C). There are some compounds that have remarkable photochromic effects, but
This effect is hardly observed at temperatures higher than room temperature (30-40°C). [Means for Solving the Problems] In view of the above-described drawbacks of the conventional spiro(indoline)naphthoxazine compounds, the present inventors have discovered that spiro(indoline)naphthoxazine compounds can be used not only at around room temperature but also at higher temperatures than room temperature in a polymer matrix. It shows good photochromic effect even at 30 to 40℃, and by selecting the type of substituent, the color tone can be changed from red to red.
We have continued to develop spirooxazine compounds that can be changed over a wide range of colors, such as blue. the result,
The present inventors have discovered a spirooxazine compound that not only satisfies the above properties but also exhibits rapid color development and fading, thereby completing the present invention. That is, the present invention is based on the following general formula ()

[Chemical formula] (However, R ₁ , R ₂ and R ₃ are the same or different hydrogen atoms, alkyl groups or aralkyl groups, respectively, R ₄ is an amino group or a substituted amino group, R ₅ ,
R ₆ , R ₇ and R ₈ are the same or different hydrogen atoms, respectively;
halogen atom, nitro group, cyano group, amino group,
an alkyl group or an alkoxy group,

[Formula] is a substituted or unsubstituted aromatic hydrocarbon group, or a substituted or unsubstituted unsaturated heterocyclic group. ) is a spirooxazine compound represented by R ₁ , R ₂ and R ₃ shown in the above general formula () are:
They are the same or different hydrogen atoms, alkyl groups, or aralkyl groups. Although the alkyl group is not particularly limited, generally an alkyl group having 1 to 10 carbon atoms, preferably 1 to 6 carbon atoms is suitably used. Also,
The alkyl group in the above aralkyl group generally has 1 to 6 carbon atoms, preferably 1 to 4 carbon atoms, and the aryl group in the aralkyl group is preferably a phenyl group, xylyl group, triyl group, naphthyl group, etc. It is. Specific examples of the alkyl group and aralkyl group include methyl group, ethyl group, propyl group, butyl group, pentyl group, decyl group, benzyl group, phenylethyl group, phenylpropyl group, phenylbutyl group, and the like. Further, R ₄ shown in the general formula () is an amino group or a substituted amino group. These groups have the general formula

[Formula] or

It is shown by [Formula]. The above R ₉ and R ₁₀ are preferably the same or different hydrogen atoms, alkyl groups, aralkyl groups, or aryl groups, respectively. The alkyl group and aralkyl group are preferably the same as those shown for R ₁ , R ₂ and R ₃ above, and the aryl group is preferably an aryl group such as a phenyl group, tolyl group, or xylyl group. be. Furthermore, R ₄
The general formula

When shown in [Formula], R ₁₁ is an alkylene group such as a tetramethylene group or a pentamethylene group;

[Formula] − CH ₂ OCH ₂ CH ₂ −, −CH ₂ CH ₂ OCH ₂ CH ₂ −, −
Oxyalkylene groups such as CH ₂ O(CH ₂ ) _{3 ---}
CH ₂ SCH ₂ CH ₂ −, −CH ₂ S(CH ₂ ) ₃ --- ₃ , −
Thioalkylene groups such as CH ₂ CH ₂ SCH ₂ CH ₂ −;

【formula】

【formula】

Azoalkyle such as [formula] It is preferable that it is a group such as a carbon group. Furthermore, it is shown by the general formula ()

[Formula] is a substituted or unsubstituted aromatic hydrocarbon group or a substituted or unsubstituted unsaturated heterocyclic group. More specific examples of aromatic hydrocarbon groups include unsubstituted aromatic hydrocarbon groups consisting of one benzene ring or 2 to 4 condensed rings, such as a phenylene group, a naphthalene group, and a phenanthrene group; Also,
Examples include substituted aromatic hydrocarbon groups in which the above-mentioned aromatic hydrocarbon groups are substituted with an alkyl group, an alkoxy group, a nitro group, a cyano group, an amino group, or one or more halogen atoms. Further, examples of the above-mentioned unsaturated heterocyclic group include a 5-membered ring, a 6-membered ring containing oxygen, sulfur, and nitrogen atoms, or an unsaturated heterocyclic group in which a benzene ring is fused to these rings.
Specifically, nitrogen-containing unsaturated heterocyclic groups such as pyridine group and quinoline group; oxygen-containing unsaturated heterocyclic groups such as furylene group and benzofrylene group; sulfur-containing unsaturated heterocyclic groups such as thienylene group and benzothienylene group, etc. be. Further, substituted unsaturated heterocyclic groups in which these unsaturated heterocyclic groups are substituted with the substituents described in the description of the aromatic hydrocarbon group described above are also employed without any limitations in the present invention. In addition, R ₅ , R ₆ , R ₇ and
R ₈ is the same or different hydrogen atom, halogen atom, nitro group, cyano group, amino group, alkyl group, or alkoxy group, respectively. As the above-mentioned halogen atom, chlorine atom, bromine atom, and iodine atom can be used without particular limitation. In addition, as the alkyl group, methyl group, ethyl group, propyl group,
Lower alkyl groups having 1 to 5 carbon atoms such as butyl and pentyl groups are preferably used. Furthermore, as the alkoxy group, lower alkoxy groups having 1 to 5 carbon atoms such as methoxy group, ethoxy group, propoxy group, butoxy group, and pentoxy group are suitable. Among the spirooxazine compounds represented by the general formula (), compounds in which R ₄ is a substituted amino group are preferred in consideration of color development in a higher temperature range than room temperature. Furthermore, the substituted amino group represented by R ₄ is

[Formula] (However, R ₉ and R ₁₀ are the same or different alkyl groups, respectively.) or

The _present invention provides a spirooxazine compound having the formula: Particularly preferred. The compound represented by the above general formula () of the present invention generally exists as a pale yellow solid at room temperature and pressure. Further, the compounds represented by the above general formula () of the present invention can generally be confirmed to be each compound of the general formula () by the following methods (a) to (c). (b) By measuring the infrared absorption spectrum ( ^IR ), aromatic −
Absorption due to expansion and contraction of CH, 3000 to 2800 cm ^-1 - Absorption due to expansion and contraction of CH, 1640
Absorption due to expansion and contraction of C=N bonds at ~1600 cm ^-
Absorption due to aromatic C=C bond at 1600-1580 cm ^-1 , C- of spiro structure at 990-920 cm ^-1
Strong absorption appears due to stretching and contraction of O bonds. Also
Absorption due to stretching and contraction of C--N bonds appears at 1200 to 1050 cm ^-1 . (b) Proton nuclear magnetic resonance spectrum ( ¹ H−
By measuring NMR, we can determine the type and number of protons present in a molecule. Aromatic proton-based peaks near δ7 to δ9.3ppm, R ₁ , R ₂ , R ₃ , R ₄ , R ₅ ,
When R ₆ , R ₇ , and R ₈ are alkyl groups or groups containing an alkyl group, a peak derived from an alkyl proton appears around δ1.2 to δ3.0 ppm. Furthermore, by relatively comparing the respective peak intensities, the number of protons in each bonding group can be determined. (c) The weight percentages of carbon, hydrogen, nitrogen, and halogen can be determined by elemental analysis. moreover,
The weight percent of oxygen can be calculated by subtracting the sum of the weight percent of each recognized element from 100. The formula of the corresponding product can therefore be determined. In addition, by measuring the melting point, carbon nuclear magnetic resonance spectrum, and mass spectrometry, we have determined that the general formula ()
It is possible to determine and identify the structure of The compound represented by the above general formula () of the present invention is
Benzene, toluene, chloroform, carbon tetrachloride, acetonitrile, tetrahydrofuran, N,
Soluble in common organic solvents such as N-dimethylformamide. In such a solvent, the general formula ()
When the compound of the present invention is dissolved, regardless of the polarity or non-polarity of the solvent, the solution is generally almost colorless and transparent, and when irradiated with sunlight or ultraviolet light, the color changes to reddish-purple or in the range of red to blue. It changes rapidly and exhibits a good reversible photochromic effect, quickly returning to its original colorless state when light is blocked. The photochromic effect of the present invention occurs even in polymer matrices, and is noticeable near room temperature (20 to 30°C) and even at higher temperatures than room temperature (30 to 40°C), and the speed of color development and fading is within seconds. It is an order. Such a polymer matrix may be one in which the compound represented by the above general formula () of the present invention is uniformly dispersed, and optically preferably, for example, polymethyl acrylate, polyethyl acrylate, Acrylic resins such as polymethyl methacrylate and polyethyl methacrylate; polycarbonate resins such as polycarbonate and poly(allyl diglycol carbonate); and the like. The compound represented by the general formula () can be added to the polymer matrix in any proportion depending on the degree of dispersion, but 0.001 to 70% by weight is generally preferred. The method for producing the compound represented by the above-mentioned general formula () of the present invention is not particularly limited and may be obtained by any method. Representative methods that are generally suitably employed will be explained below. (Method A) The following general formula ()

[Formula, R ₁ , R ₂ and R ₃ are each the same or different hydrogen atom, alkyl group or aralkyl group,

[Formula] is a substituted or unsubstituted aromatic hydrocarbon group or a substituted or unsubstituted unsaturated heterocyclic group, and A is an anion. ) and the following general formula ()

[Chemical formula] (However, R ₅ , R ₆ , R ₇ and R ₈ are the same or different hydrogen atoms, halogen atoms, nitro groups, cyano groups, amino groups, alkyl groups or alkoxy groups, respectively.) By reacting a nitroso compound and an amine compound, a spirooxazine compound represented by the above general formula () can be obtained. In the general formula (), examples of the anion represented by A include halogen ions such as chlorine, bromine, and iodine; and sulfonic acid ions such as para-toluenesulfonic acid. The amine compound used as a raw material is preferably one in which nitrogen is directly bonded to at least one hydrogen atom. Specifically, the following formula ()

[Formula] or

[Formula] (However, R ₉ and R ₁₀ are the same or different hydrogen atoms, alkyl groups, aryl groups, or aralkyl groups, respectively, and R ₁₁ is an alkylene group, oxyalkylene group, thioalkylene group, or azoalkylene group. ) The amine compounds shown below are suitable. The molar ratio of the azolium salt represented by the general formula (), the nitroso compound represented by the general formula (), and the amine compound, which are the above-mentioned raw materials, is selected from a wide range, but in general, the molar ratio is selected from a wide range. The amount of the nitroso compound represented by the general formula () is preferably 0.5 to 2 moles and the amount of the amine compound is preferably 2 to 8 moles per mole of the azolium salt. These raw materials are dissolved in a suitable solvent, such as alcohols such as methanol and ethanol; ethers such as dimethyl ether, diethyl ether, and tetrahydrofuran; and aromatic hydrocarbons such as benzene and toluene, and then passed through nitrogen gas. The reaction is carried out while The reaction takes place at a temperature range of 20-120℃.
It is preferable to carry out the treatment for 30 minutes to 5 hours. When cooled after the reaction, brown crystals are precipitated, which are filtered and recrystallized using an appropriate solvent to obtain the spirooxazine compound represented by the general formula (). . (Method B)

[C] (However, R ₁ , R ₂ , R ₃ ,

〔effect〕

The spirooxazine compound of the present invention exhibits a remarkable photochromic effect in a polymer matrix not only near room temperature (20 to 30°C) but also at a higher temperature than room temperature (30 to 40°C).Moreover, The solution of the spirooxazine compound of the present invention dissolved in a solvent or the resin exhibiting a photochromic effect dispersed in a polymer matrix is colorless and transparent for any spirooxazine compound;
By irradiating with ultraviolet rays, a color ranging from red to reddish purple to blue can be developed, and the color tone can be freely selected by changing the type of substituent of the spirooxazine compound.
Furthermore, when ultraviolet rays are removed, it returns to its original colorless state within seconds. The spirooxazine compound of the present invention can be used in a wide range of fields as a photochromic material, such as various recording storage materials in place of silver salt photosensitive materials, copying materials, photoreceptors for printing, recording materials for cathode ray tubes, photosensitive materials for lasers, It can be used as a variety of recording materials such as photosensitive materials for holography. In addition, the photochromic material of the present invention can also be used as a material for photochromic lenses, 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 it provides uniform dimming performance.For example, the spirooxazine compound represented by the general formula () above can be uniformly applied. Sandwiching the dispersed polymer film into the lens, or dissolving the compound in, for example, ethanol,
There is a method of impregnating the lens surface with this compound for 10 hours at ℃, and then coating the surface with a curable substance to make 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 make a photochromic lens may also be considered. [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 An example of production by (method A) is shown. 5-chloro-1.2,3.3-tetramethylindolenium iodide

[Chemical] (1.7g, 50mmol), 1-nitroso-2-phenanthole (11.2g, 50mmol) and piperidine (2.1
g, 250 mmol) was dissolved in 50 ml of ethyl alcohol and heated under reflux for 3 hours. After reaction, remove 1/4 of the solvent
When the mixture was concentrated and left at room temperature, brown crude crystals were precipitated. Recrystallization from isopropyl alcohol gave 0.8 g of pale yellow needle crystals. The melting point of the product was 286-287°C. When the infrared absorption spectrum was measured, absorption due to the C=N bond was observed at 1610 cm ^-1 and strong absorption due to stretching and contraction of the C-O bond in the spiro structure was observed at 950 cm ^-1 . In addition, its elemental analysis values are C75.21%, H6.03%, N8.43%, _Cl7.18 %, and _the measured value for _C31H30N3Cl is C75.10.
%, H6.05%, N8.47%, and Cl7.15%. In addition, when we measured the proton nuclear magnetic resonance spectrum, we found that there was a 11H peak based on aromatic protons around δ6.4-8.6ppm,
δ1.5ppm

6H peak based on [Formula], based on proton of N-CH ₃ bond at δ2.7ppm
A 3H peak and a 10H peak based on the piperidine ring were shown at δ1.7 and δ2.9ppm. From the above results, the isolated product is

It was determined to be a compound represented by the structural formula:
The infrared absorption spectrum of this substance is shown in Figure 1. ¹ H
-NMR spectrum is shown in Figure 2. Example 2 An example of production by (method B) is shown. 1-isopropyl-2-dimethylaminomethyl-3.3-dimethylindolium bromide (1.7g,
50 mmol), 1-nitroso-2-phenanthole (11.2 g, 50 mmol) and triethylamine (0.5 g,
50 mmol) and ethyl alcohol under nitrogen atmosphere
The mixture was heated under reflux in 30 ml for 3 hours. After cooling, the precipitated crystals were collected and recrystallized from isopropyl alcohol to obtain 0.4 g of pale yellow crystals. The melting point of the formation is
The temperature was 226-228℃. When an infrared absorption spectrum was measured, absorption due to stretching and contraction of C=N bonds was observed at 1605 cm ^-1 and absorption due to C-N bonds was observed at 1180 cm ^-1 . In addition, when we measured the nuclear magnetic resonance spectrum, we found that there was a 10H peak based on aromatic protons at δ6.4 to δ8.6ppm, δ1.3ppm and δ2.7ppm.
Doublet and septet peaks based on N-CH( _CH3 ) ₂ groups, 6H peak _based on _{CCH3CH3CH3CH3} at _δ1.4ppm , -N( ^CH3 ) at _δ2.6ppm The 6H peak derived from ₂ is shown. In addition, the elemental analysis value is
C80.20%, H6.88%, N9.32%,
C80.18%, _which is the calculated value _{for C30H31N30} ,
It matched extremely well with H6.90% and N9.35%. From the above results, the isolated product is

It was found to be a compound represented by the structural formula: Examples 3 to 12 Reactions, isolation, and purification were performed in the same manner as in Example 1. The structural formulas, melting points, and yields of the reaction starting materials and reaction products are shown in Table 1. In the table, ph is an abbreviation for phenyl group. The structure was confirmed by infrared absorption spectrum, nuclear magnetic resonance spectrum, and elemental analysis.

【table】

[Table] Examples 13-14 Reaction, isolation, and purification were performed in the same manner as in Example 2. The structural formulas, melting points, and yields of the reaction starting materials and reaction products are shown in Table 2. In the table, ph is an abbreviation for phenyl group. The structure was confirmed using infrared absorption spectroscopy, elemental analysis, and proton nuclear magnetic resonance spectroscopy.

【table】 Examples 15-28 and Comparative Examples 1-2 The following formula obtained in Example 1

The compound represented by the formula was dissolved and dispersed in polymethyl methacrylate using benzene, and a cast film was made on slad glass (11.2 x 3.7 cm). The concentration of the above compound contained in this film was adjusted to 1.0×10 ⁻⁴ mol/g, and the thickness was adjusted to 0.1 mm. A mercury lamp SHL-100 manufactured by Toshiba Corporation was placed on this photochromic film at 35℃±1℃.
The film was irradiated for 60 seconds at a distance of 10 cm to develop color, and its photochromic properties were measured. The photochromic characteristics were expressed as follows. The results are shown in Table 3 as Example 15. Maximum absorption wavelength (λ _nax ): The λ _nax of this coloring film was determined using a spectrophotometer 220A manufactured by Hitachi, Ltd. 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); Absorbance of unirradiated film at the maximum absorption wavelength during light irradiation. Half-life t1/2: After 60 seconds of light irradiation, the absorbance of this film is (ε(60
sec) - the time required to drop to 1/2 of ε(0 sec)). In addition, Example 2 as a spirooxazine compound
Photochromic films were obtained in the same manner as in Example 15 above, except that the compounds obtained in Steps 1 to 14 were used, and their properties are shown in Table 3 as Examples 16 to 28. Furthermore, for comparison, the following formula

【formula】 Spironaphthoxazine represented by and the following formula

The same procedure as in Example 15 was carried out except that spironaphthoxazine represented by [Formula] was used, and the results were compared to Comparative Example 1.
and 2 are also listed in Table 3.

【table】

[Table] Examples 29 to 30 and Comparative Examples 3 to 4 Example 15 except that the spirooxazine compounds produced in Examples 6 and 7 were used, and polycarbonate was used as the film matrix.
I did the same thing. The results are shown in Table 4 as Examples 29-30. In addition, for comparison, the following formula is used as a spirooxazine compound.

[expression] and

The same procedure as in Example 29 was carried out except that each compound represented by the formula was used. The results are shown in Table 4 as Comparative Examples 3 and 4. Example 31 and Comparative Examples 5-6

The compound represented by the formula was dissolved in 100 c.c. of ethanol and impregnated onto the surface of a 1 mm thick poly(allyl diglycol carbonate) film at 70° C. for 10 hours. The concentration at that time is 1.0×10 ^-4 mol/g
It was prepared so that The photochromic properties of this film were measured in the same manner as in Example 15.
The results are shown in Table 4. Also, for comparison, as a spirooxazine compound

[expression] and

The same procedure as in Example 31 was carried out except that each compound represented by the formula was used. The results are shown in Table 4 as Comparative Examples 5 and 6.

【table】

[Table] From the above results, when the spirooxazine compound of the present invention is used dispersed in a polymer matrix, the coloring density is greater in the high temperature range (35°C) than room temperature (20 to 30°C), and It is obvious that the color tone can be freely controlled to red, reddish-purple, or blue, and that it is colorless in the decolorized state and that the color fades quickly.

[Brief explanation of the drawing]

1 and 2 show the infrared absorption spectrum and nuclear magnetic resonance spectrum of the spirooxazine compound of the present invention obtained in Example 1, respectively.

Claims (1)

[Claims] 1 The following general formula: (However, R ₁ , R ₂ and R ₃ are the same or different hydrogen atoms, alkyl groups or aralkyl groups, respectively,
R ₄ is an amino group or a substituted amino group, R ₅ , R ₆ ,
R ₇ and R ₈ are the same or different hydrogen atoms, halogen atoms, nitro groups, cyano groups, amino groups, alkyl groups, or alkoxy groups, and [Formula] is a substituted or unsubstituted aromatic hydrocarbon group, or a substituted or unsubstituted unsaturated heterocyclic group. ) A spirooxazine compound represented by 2 (a) The following general formula: (However, R ₁ , R ₂ and R ₃ are the same or different hydrogen atoms, alkyl groups or aralkyl groups, respectively, and [Formula] is a substituted or unsubstituted aromatic group. a hydrocarbon group or a substituted or unsubstituted unsaturated heterocyclic group, and A is an anion.) Azolium salt (b) represented by the following general formula [Chemical formula] (However, R ₅ , R ₆ , R ₇ and R ₈ are the same or different hydrogen atoms, halogen atoms, nitro groups, cyano groups, amino groups, alkyl groups, or alkoxy groups, respectively. _{Characterized} by _{the following general} formula: _R5 ,
R ₆ , R ₇ and R ₈ are the same or different hydrogen atoms, respectively;
halogen atom, nitro group, cyano group, amino group,
an alkyl group or an alkoxy group,
[Formula] is a substituted or unsubstituted aromatic hydrocarbon group, or a substituted or unsubstituted unsaturated heterocyclic group. ) A method for producing a spirooxazine compound. 3(a) The following general formula: (However, R ₁ , R ₂ and R ₃ are the same or different hydrogen atoms, alkyl groups or aralkyl groups,
R ₄ is an amino group or a substituted amino group,
[Formula] is a substituted or unsubstituted aromatic hydrocarbon group or a substituted or unsubstituted unsaturated heterocyclic group, and A is an anion. ₎ and ( _{b )} the following _general formula _{, an} alkyl group _, or an alkoxy group) in the presence of a base. or a different type of hydrogen atom, alkyl group or aralkyl group, R ₄ is an amino group or a substituted amino group, R ₅ ,
R ₆ , R ₇ and R ₈ are the same or different hydrogen atoms, respectively;
halogen atom, nitro group, cyano group, amino group,
an alkyl group or an alkoxy group,
[Formula] is a substituted or unsubstituted aromatic hydrocarbon group, or a substituted or unsubstituted unsaturated heterocyclic group. ) A method for producing a spirooxazine compound. 4 The following general formula: (However, R ₁ , R ₂ and R ₃ are the same or different hydrogen atoms, alkyl groups or aralkyl groups, respectively, R ₄ is an amino group or a substituted amino group, and R ₅ ,
R ₆ , R ₇ and R ₈ are the same or different hydrogen atoms, respectively;
Halogen atom, nitro group, cyano group, amino group,
an alkyl group or an alkoxy group,
[Formula] is a substituted or unsubstituted aromatic hydrocarbon group, or a substituted or unsubstituted unsaturated heterocyclic group. ) A photochromic material characterized by containing a spirooxazine compound as a main component.