JPS63179879A - Spiroxazine compound and production thereof - Google Patents

Abstract

NEW MATERIAL:A compound expressed by formula I [formula II is (substituted) aromatic hydrocarbon group; R<1> is alkyl or aralkyl; R<2>-R<9> are H or alkyl; R<10> is R<2>-R<9> or (substituted)amino]. EXAMPLE:A compound expressed by formula III. USE:A photochromic material, utilizable as various recording materials, particularly useful for repeating coloring or decoloring change by action of light, capable of exhibiting photochromic action even in polar solvents or polar high polymer matrixes and high speed of fading as well as excellent durability with small deterioration of photochromic action even in exposure for a long period. PREPARATION:A tetrahydropyridinium salt expressed by formula IV (A<-> is anion) is reacted with a nitroso compound expressed by formula V in the presence of a base, e.g. triethylamine, etc., in a solvent, e.g. ethyl alcohol, etc., at 20-120 deg.C in N2 gas atmosphere for 30min-5hr to afford the aimed compound expressed by formula I.

Description

[Detailed Description of the Invention] [Industrial Application Field] 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. It is something to do.

[Prior art and its problems]

Photochromicity is a phenomenon that has attracted attention over the past few years.When a certain compound is exposed to light containing ultraviolet light, such as sunlight or mercury lamp light, it immediately changes color, and when the light irradiation is stopped and it is placed in a dark place. This is a reversible effect that returns to its original color when left alone. Compounds having this property are called photochromic compounds, and various compounds have been synthesized to date, but no particular common structure has been recognized among them.

As such a photochromic compound, JP-A-55-
No. 76883 discloses a spiropyran compound represented by the following formula (V).

(However, each R represents the same or different hydrogen atom, furkyl group, 7ralkyl group, or fulkenyl group, and each R1 represents the same or different alkyl group, aralkyl group, or fulkenyl group. R1 represents an electron acceptor. (X represents CH or a sulfur atom.) However, when these compounds are dissolved in polar solvents such as ethyl alcohol, methyl alcohol, acetone, acetonitrile, and dimethylformamide, they generally turn red to reddish-purple. Therefore, even if this solution is irradiated with ultraviolet rays, it does not exhibit a very significant photochromic effect.

In addition, the above (V) also exists in a polymer solid matrix.
The compounds do not exhibit a very pronounced photochromic effect, and are red to reddish-purple in color, especially in polar polymer matrices such as polymethyl methacrylate, polycarbonate, and poly(7lyl diglycol carbonate).
Even when irradiated with ultraviolet rays, sufficient photochromic effect is not observed. In addition, in the polymer matrix (IJ Lux) as described above, the coloring structure of the compound (v) above is stabilized in the matrix, so there is a drawback that the speed of fading becomes extremely slow. .

Furthermore, the spiropyran compound represented by the formula (V) reversibly changes to colorless and blue, but if it repeatedly develops and decolors due to long-term exposure, etc., it will deteriorate due to light and will no longer exhibit photochromic action. . This is generally referred to as poor durability of the photochromic compound.

[Means for solving problems]

In polar solvents or polar polymeric polymers)
Even in IJ Lux, research has been carried out to find a photochromic compound that has a sufficient photochromic effect, exhibits rapid color development and fading speed, and is highly durable. As a result, it was discovered that a spirooxazine compound having a specific structural formula achieves the above object, and the present invention has been completed.

That is, the present invention is an aromatic hydrocarbon group represented by the following general formula (1), where R1 is a furkyl group or an aralkyl group, and R11, R8, R4°RIt, R6, R? ,
R8 and R9 are the same or different hydrogen atoms or alkyl groups, respectively, and RiO is a hydrogen atom, a furkyl group, or a substituted or unsubstituted amino group. ) is a spirooxazine compound represented by

In the above general formula (1), as the unsubstituted aromatic hydrocarbon group represented by [λ], known groups can be used without any restriction. For example, phenylene group, naphthylene group, phenanthrene group.

One or two benzene fR such as anthracene group
An aromatic hydrocarbon group consisting of four condensed rings can be mentioned. Various groups can be used as substituents for these aromatic hydrocarbon groups, but maid, furkyl, flukoxy, nido a, cyano, amino, halogen, etc. are used in the present invention. Preferably used. One or more of these substituents may be substituted on the aromatic hydrocarbon group.

Next, the furkyl group represented by R in the general formula (1) is not limited to the number of carbon atoms, and various alkyl groups can be employed. Generally, a furkyl group having from 1 to 20 carbon atoms, preferably from 1 to 6 carbon atoms, is suitably used. In addition, the alkyl group contained in the aralkyl group represented by R1 generally has 1 to 6 carbon atoms, preferably 1 to 4 carbon atoms, and the 7-aryl group of the aralkyl group includes a phenyl group,
Xylyl group, triyl group, naphthyl group, etc. are suitable.

More specific examples of the above alkyl groups and 7ralkyl groups include methyl group, ethyl group, propyl group, butyl group,
pentyl group, decyl group.

benzyl group, phenylethyl group, phenylpropyl group,
phenylbutyl group, etc.

Furthermore, in the general formula (1), RF, Ha.

R4, R5, R6, R7, R8 and R9 are the same or different hydrogen atoms or alkyl groups, respectively. As this alkyl group, the alkyl group explained above for R1 can be applied as is.

Further, in the general formula (1), Rlo is a hydrogen atom, a furkyl group, or a substituted or unsubstituted 7-mino group.

Here, as the furkyl group, the furkyl group explained for R above is employed. The substituted or unsubstituted 7-mino group is preferably a general group. The above R11 and R12 are preferably the same or different hydrogen atoms, alkyl groups, 7-ralkyl groups, or aryl groups. The alkyl group and aralkyl group are preferably the same as those shown for R above, and the aryl group is preferably a 7-aryl group such as a phenyl group, tolyl group, or xylyl group. Furthermore, when RIO is a substituted amino group represented by the general formula -N R13, R13 is a tetramethylene group,
Fullylene group such as pentamethylene group; -CM, CHO
CR8-.

H8 -CH,OCH,CH,+, -CH,CH,OCH,
CH,-.

Oxyfulkylene groups such as -CH,O(CH,), -: -CH,SCH,CH,-, -CFI, 5(CH,
) 8-ICH, CH, S CH, CH, -, etc. Thioalkylene -CH, NCH, CH, -, -CH, N (CH
, ), -.

Preferably, it is a 7zoalkylene group such as H8 -CH, CH, NCH, CH, -.

It is preferably a spirooxadi-substituted or unsubstituted phenylene group or a substituted or unsubstituted naphthalene group represented by the general formula (I), and RIO is preferably a hydrogen atom or an alkyl group. Furthermore, from the viewpoint of the coloring density of the coloring species, R11 and R12 are the same or different alkyl groups, respectively. ) or -NR13 (wherein R13 is an alkylene group, oxyalkylene group, thiofulkylene group, or 7zofulkylene group, and is a group that forms a 5- to 7-membered ring together with the nitrogen atom.

) is more preferred.

The compound represented by the above general formula (summer) of the present invention generally exists as a colorless to pale yellow solid at room temperature. Further, the compounds represented by the above general formula (1) of the present invention can generally be confirmed to be each compound of the general formula (1) by the following methods (a) to (c).

(a) Infrared absorption spectrum (IR) Absorption due to stretching of CH with 70% difference between 3100 and 3000c1n, absorption due to stretching and contraction of CH with 7% difference between 3000 and 2800 [-1, 1640-1600
cIRKC=Absorption due to N bond stretching, 1600-15
Absorption due to almatiic C=C bond at 8゜α-1,
Strong absorption due to stretching and contraction of the C-O bond of the spiro structure appears between 990 and 920 ctn. Also, 1200-10
Absorption due to stretching and contraction of the C--N bond appears at 503''.

(b) Proton nuclear magnetic resonance spectrum ('H-NMR)
) You can know the type and number of protons present in a molecule. A peak based on a 70-proton proton is present around δ6.7 to δ9.3 ppm, and a peak based on δ0.8 to δ4. O
Around ppm 1c'R1゜R" + R8+ R' +
Peaks originating from R5+ R6+ R' + R8+ R' and the fulkylic proton of RIO appear. Furthermore, by relatively comparing the respective peak intensities, the number of protons in each bonding group can be determined.

(c) Elemental analysis The weight percentages of carbon, hydrogen, nitrogen, and halogen can be determined. Furthermore, the sum of the weight percent of each recognized element is 10
By subtracting from 0, the weight percent of oxygen can be calculated. The formula of the corresponding product can therefore be determined.

Furthermore, the structure of general formula (1) can be determined and identified by measuring the melting point, carbon number nuclear magnetic resonance spectrum, mass spectrometry, and the like.

The compound represented by the above general formula (1) of the present invention is well soluble in common organic solvents such as benzene, toluene, roform, carbon tetrachloride, acetonitrile, tetrahydrofuran, and N,N-dimethylformamide. When the compound represented by the above general formula (1) is dissolved in such a solvent, the solution is generally almost colorless and transparent, regardless of the polarity or non-polarity of the solvent, and turns red or blue when exposed to sunlight or ultraviolet rays. Change quickly. The color tone of the color can be varied in various ways depending on the substituents. When light is blocked, it quickly returns to its original colorless state and exhibits a good reversible photochromic effect.

Such a photochromic effect in the present invention also occurs in the solid polymer matrix IJ Lux, and its coloring and decoloring are observed. The target polymer matrix may be one in which the compound represented by the above general formula (1) of the present invention is uniformly dispersed (optically preferably, for example, polymethyl acrylate, polyacrylic acid Examples include ethyl, polymethyl methacrylate, polyethyl methacrylate, polycarbonate, and poly(allyl diglycol carbonate). It can be added to the molecular matrix, but generally 0.001 to 70% by weight is preferred.

The method for producing the compound represented by the above-mentioned general formula (1) 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.

(&) The following general formula (I[) (However, R is an alkyl group or a 7-ralkyl group,
Rffi, R8, R4, RIt, R6, R? .

R8 and R9 are the same or different hydrogen atoms or alkyl groups, B is an alkyl group, and Ae is an anion. ) The tetrahydro-pyridinium salt represented by (b) the following general formula (1) (wherein) is a substituted or unsubstituted aromatic hydrocarbon group. ) The spirooxazine compound represented by the general formula (1) can be obtained by reacting the compound represented by the above in the presence of a base.

In the general formula (It), the anion represented by Ae is:
Examples include halogen ions such as chlorine, bromine, and iodine; and sulfonic acid ions such as para-toluenesulfonic acid.

As the base to be present in the reaction system, known compounds can be used without any restrictions. For example, alkali hydroxides such as sodium hydroxide and potassium hydroxide; primary amines, secondary amines.

Amine compounds such as tertiary amines are preferably used.

In the present invention, a spirooxazine compound having a desired substituent can be obtained by selecting the type and amount of the base used as described above. Specifically, when obtaining a spirooxazine compound in which RIO in the general formula (1) is a hydrogen atom or a furkyl group, a tertiary oxazine compound such as triflukyl-7mine or triarylamine is used as a base to be present in the reaction system. The grade amine or alkali hydroxide may be used in an amount of 1 to 10 moles per mole of the tetrahydropyridinium salt. In addition, the amount of primary amine or secondary amine is 0.5 to 1 mol per mole of tetrahydropyridinium salt.
．． It may be used in a range of 2 moles. On the other hand, the general formula (1
), when obtaining a spirooxazine compound in which RIO is a substituted or unsubstituted 7-mino group, the first
The excess amount of primary amine or secondary amine is 2 mol or more, preferably 2 to 8 mol, per 1 mol of tetrahydropyridinium salt.
It may be used within the molar range.

As the primary amine and the secondary amine, the following formula (IV
) (However, R11 and R12 are largely the same or different hydrogen atoms, furkyl group, 7-aryl group, or aralkyl group, and R13 is an alkylene group, oxyfulkylene group,
It is a thioalkylene group or a 7zoflukylene group. ) Compounds represented by these are preferred.

The molar ratio of the above raw materials, the tetrahydropyridinium salt represented by the general formula (I[), and the nitroso compound represented by the general formula (1), is selected from a wide range, but in general, The nitroso compound represented by formula (1) is preferably used in an amount of 0.5 to 2 moles per mole of the tetrahydropyridinium salt shown.

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 takes place while

The reaction is preferably carried out at a temperature in the range of 20 to 120°C for 30 minutes to 5 hours. When the reaction is cooled, brown crystals are precipitated, which are filtered and recrystallized using a suitable solvent to obtain the spirooxazine compound represented by the general formula (1).

The spirooxazine compound of the present invention thus obtained can be used in a wide range of fields as a photochromic material. For example, various recording and memory materials in place of chain photosensitive materials,
Copying materials.

It can be used as a variety of recording materials such as photoreceptors for printing, recording materials for cathode ray tubes, photosensitive materials for lasers, and 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, light intensity needles, decorations, and the like. For example, when used in a photocoumin lens, there is no particular restriction as long as it provides uniform dimming performance. To give a specific example, the above general formula (
A method of sandwiching a polymer film formed by uniformly dispersing the spirooxazine compound shown in 1) into a lens, or dissolving this compound in, for example, ethanol and applying it to the lens surface by heating it in the shade at 70°C for 10 hours. There is a method of impregnating the lens with a compound and then coating the surface with a curable substance to make a photochromine lens. Furthermore, the above polymer film is applied to the lens surface,
Another possible method is to coat the surface with a curable substance to make a photochromic lens.

〔effect〕

The spirooxazine compound of the present invention exhibits good photochromic action even in a polar solvent or a polar polymer matrix.

Furthermore, the spirooxazine compound of the present invention has five characteristics such as rapid discoloration. For example, a photochromic resin in which the spirooxazine compound of the present invention is dispersed in a polar polymer matrix as described above,
In either case, it is colorless and transparent and develops color when irradiated with ultraviolet rays. Then, when ultraviolet rays are removed, it returns to its original colorless state within seconds.

Furthermore, the spirooxazine compound of the present invention exhibits little deterioration of photochromic effect even after long-term exposure.
In other words, it also has the feature of excellent durability.

Further, by selecting various substituents in the general formula (1) described above, it is possible to obtain a desired color tone such as red or blue.

As explained above, the spirooxazine compound of the present invention is an extremely suitable compound as a photochromic material due to its excellent properties.

〔Example〕

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 1,2,3.3-tetramethyl-3,4,5,6 iodide
-titrahydropyridinium (1,3,p:5m and 1-
Nitron-2-naphthol (0,9,9:5 m mo
1) and triethylamine (0,4,9:6 mmoj) were heated under reflux in ethylfurfur 301 under a nitrogen atmosphere for 3 hours. Thereafter, the solvent was distilled off, and colorless crystals o, i 11 were obtained from the initial distillate by silica glubenzene column chromatography. The melting point of the product is 1
The temperature was 08-110°C. When the infrared absorption spectrum was measured, an absorption due to the stretching and contraction of the C=N bond was observed at 1590cm-'', and an absorption based on the C-0 bond of the spiro structure was observed at 950c!n.The 1H-nuclear magnetic resonance spectrum was also measured. As a result, δ6.9 to 8.6 ppm was 71:
<7H peak based on I-q titanic protons, δ2
．． Based on N-CH, <3H peak at 2 ppm, δ0.
85 ppm and δ1.22 ppm showed a peak of 6H based on C(CH3), and a peak of 6H based on methylene hydrogen at δ1.0 to 2.1 ppm. ,23%, )f 7.40%,
N9.15%, C74.48%, H7,24% which is the calculated value for C, H N, O.

It matched extremely well with N 9.14%.

From the above results, it was found that the isolated product was a compound represented by the structural formula. When this product was dissolved in toluene and irradiated with ultraviolet rays at 1-1-30°C, it exhibited a reddish-purple color, and immediately became colorless when the irradiation with light was stopped.

Examples 2 to 6 Reactions, isolation, and purification were performed in the same manner as in Example 1 using various raw materials shown in Table 1.

Table 1 shows the reaction products, their melting points, yields, and color tones when irradiated with ultraviolet light. In the table, ph is an abbreviation for phenyl group.

The structure was confirmed by infrared absorption spectrum, 'H-nuclear magnetic resonance spectrum, and elemental analysis.

Example 7 1,2,3.3-tetramethyl-3,4,5,6 iodide
-titrahydropyridinium (2,7#:t.

mmot) and 1-2) 0 so 2-naphthol (1,7
F: 10mmot) and piperidine (4,3#: 50
mmol) was dissolved in ethyl alcohol 3031/ml and heated under reflux for 3 hours under a nitrogen atmosphere.

Thereafter, the solvent was distilled off, and 0.5 g of colorless crystals were obtained by silica gel-benzene column chromatography.

The melting point of the product was 173-176°C. When the infrared absorption spectrum was measured, 1600 cIn KC-
Absorption due to C-0 condensation and contraction of the spill structure at N bond 975 CII+, absorption based on C-N bond at 1180 cm-'' (
Absorption was observed. In addition, when the 1H-nuclear magnetic resonance spectrum was measured, there was a 6H peak based on 7p multi-inch protons at 86.5 to 8.492 m, δ2.20
<3H peak based on N-CH3 group in ppm, δ0.8
A <6H peak based on K(CH8)B at 7 ppm and δ1.23 ppm, and a 16H peak based on methylene hydrogen at δ1.4 to δ3.2 ppm were observed. In addition, the elemental analysis values are C76.38%, H8.03%, N11
．． 36%, calculated value C for C□H8□N80
76, 36%, H, 8, 28%, and N, 11.14%.

From the above results, the isolated product is H8 It was found to be a compound represented by the structural formula.

Examples 8 to 14 Reactions, isolation, and purification were performed in the same manner as in Example 7 using various raw materials shown in Table 2.

The structural formula, melting point and yield of the reaction product 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.

Example 15 The spirooxazine compounds produced in Examples 1 to 14 were dissolved and dispersed in polymethyl methacrylate using benzene to form a cast film on a slide glass (11.2 x 3.7 crn). The concentration of the above compound contained in this film is 1. The thickness was adjusted to ox1o moll&, and the thickness was set to o and im. This photochromic film has a mercury lamp 5HL-1 manufactured by Toshiba@).
00 was irradiated at -30° C. for 15 seconds at a distance of 10 cm to develop color, and the photochromic properties were measured.

The photochromic properties were expressed as follows. The results are shown in Table 3.

ε (15 seconds): Absorbance of this film at the maximum absorption wavelength after 15 seconds of light irradiation under the above conditions.

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

Table 3 Example 16 A photochromic film was prepared in the same manner as in Example 15 using each of the spirooxazine compounds produced in Examples 1 to 14, and the durability of each photochromic compound was measured using the following procedure. .

One photochromic film was irradiated with xenon light for 20 hours using a long-life xenon fade meter manufactured by Suga Test Instruments@), and then the ε (10 seconds) (A
), and also measured ε (10 seconds) (B) of another photochromic film that was not irradiated with xenon light, and the remaining rate of photochromic film (1o ox (A-
B)/A) was calculated to evaluate durability. In addition, ε
(10 seconds) is the same as in Example 15. The results are shown in Table 4.

For comparison, the same procedure as above was carried out except that the spirupyran compound (A) CH8 and the hisspirobilan compound (B) were used as conventionally known spirubiran compounds. The results are also shown in Table 4.

Table 4 Note: Scraps 15 and 16 are comparative examples.

[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 (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 a substituted or unsubstituted aromatic hydrocarbon group, and R^1 is an alkyl group. or an aralkyl group, R^2, R^3,
R^4, R^5, R^6, R^7, R^8 and R^9 are the same or different hydrogen atoms or alkyl groups, respectively, and R^1^0 is a hydrogen atom, an alkyl group or a substituted or an unsubstituted amino group. ) A spirooxazine compound represented by (2) (a) The following general formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (However, R^1 is an alkyl group or an aralkyl group, R^2, R^3, R^4, R^5, R^6, R^7
, R^8 and R^9 are the same or different hydrogen atoms or alkyl groups, respectively, and B is an alkyl group and is an A^■ anion. Tetrahydropyridinium salt represented by (b) the following general formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (However, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ is a substituted or unsubstituted aromatic hydrocarbon group The following general formula ▲ includes mathematical formulas, chemical formulas, tables, etc. ▼ (However, ▲ includes mathematical formulas, chemical formulas, tables, etc. ▼ or an unsubstituted aromatic hydrocarbon group, R^1 is an alkyl group or an aralkyl group, R^2, R^3,
R^4, R^5, R^6, R^7, R^8 and R^9 are the same or different hydrogen atoms or alkyl groups, respectively, and R^1^0 is a hydrogen atom, an alkyl group or a substituted or an unsubstituted amino group. ) A method for producing a spirooxazine compound represented by (3) The following general formula ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (However, ▲There are mathematical formulas, chemical formulas, tables, etc.▼ is a substituted or unsubstituted aromatic hydrocarbon group, and R^1 is an alkyl group. or an aralkyl group, R^2, R^3,
R^4, R^5, R^6, R^7, R^8 and R^9 are the same or different hydrogen atoms or alkyl groups, respectively, and R^1^0 is a hydrogen atom, an alkyl group or a substituted or an unsubstituted amino group. ) A photochromic material mainly composed of spirooxazine compounds represented by