JPH0368584A - Photochromic compound - Google Patents

Abstract

NEW MATERIAL:A spirooxazine compound expressed by the formula [A' represents 1-24C alkyl, allyl, (substituted) aralkyl, (substituted) aryloxyalkyl, etc.; R<1> to R<8> represent H or alkyl; R<9> represents H, halogen, alkyl, alkoxy, OH or alkoxyalkyl; either of X and Y represents N and the other represents methyne]. EXAMPLE:1,3,3-Trimethylspiro[piperidine-2,3'-(3H)-pyrido(3,4-f)(1,4)be nzoxazine]. USE:Useful as a recording material or a dimming material. PREPARATION:A 5-nitroso-6-quinolinol or 8-nitroso-7-isoquinolinol derivative and a piperidine compound having a desired substituent group are dissolved in a solvent such as ethanol or toluene and refluxed at a boiling point in nitrogen gas atmosphere.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a novel photochromic compound, and more particularly to a photochromic compound useful as various recording materials or light control materials.

[Prior Art] Various photochromic organic compounds have been known in the past, but spirooxazine compounds are known as having relatively good durability over repeated color-forming actions; for example, as disclosed in Japanese Patent Publication No. 45-28892 , Special Public Interest Publication No. 49-4863
Publication No. 1, JP-A-55-36284, JP-A-60
-53586 publication, JP-A-61-53288 publication,
JP-A-61-263982 discloses 1,3,3-trimethylspiro [indoline-2,3''-(3H)-naphtho(2,1-b)(1,4)oxazine] and its derivatives. ing.

In addition, as a response to the demand for color development of colors other than blue, for example, Japanese Patent Application Laid-Open No. 145089/1989, Japanese Patent Application Laid-Open No. 63-1
No. 79879 discloses a photochromic compound that develops a red color.

[Problem to be solved by the invention]

However, the conventional photochromic compounds made of spirooxazine compounds as described above have a problem in that the coloring properties at room temperature or higher temperatures are not necessarily good.

An object of the present invention is to solve the above problems and provide a novel photochromic compound that exhibits good color development even at room temperature or higher temperatures.

[Means to solve problems]

The photochromic compound of the present invention has the following general formula (1):
Alternatively, it is characterized by comprising a spirooxazine compound represented by the general formula (If).

General formula (1) (wherein, AI represents an alkyl group having 1 to 24 carbon atoms, an allyl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted aryloxyalkyl group, or an alkoxyalkyl group, and R1 to R8 represents a hydrogen atom, a linear or branched alkyl group, R3 represents a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, a hydroxyl group, or an alkoxyalkyl group, and one of X and Y represents a nitrogen atom and the other represents a methine group.〉General formula (n) R9 represents a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, a hydroxyl group, or an alkoxyalkyl group, one of X and Y represents a nitrogen atom, and the other represents a methine group .

〉 The present invention will be specifically explained below.

In the present invention, the general formula (1) or the general formula (n
) is used as a photochromic compound.

Among the spirooxazine compounds represented by the general formula (I), those represented by the following general formula (1-A>) are particularly preferred.

General formula (I-A) (wherein A2 represents an alkylene group, an alkylene(polyoxy)alkylene group or an alkylenearylalkylene group, and R'-wR@ represents a hydrogen atom, a straight or branched alkyl group , (wherein A1 is a carbon number of 1 to 24
represents an alkyl group, allyl group, substituted or unsubstituted aralkyl group, substituted or unsubstituted aryloxyalkyl group or alkoxyalkyl group, R1 and R2
represents an alkyl group having 5 or less carbon atoms. ) This general formula (I
Specific examples of the compound represented by -A) include (1) 1,3,3-trimethylspiro[piperidine-2゜3'-(3H)-pyrido(3,4-f) (1
,4>benzoxazine] (2>l-isopropyl-3,3-dimethylspiro[piperidine-2,3°-(3H)-pyrido(3,4-f)
(1,4)benzoxazine] (3) 1-(2-phenoxyethyl)-3,3-dimethylspiro[piperidine-2,3'-(3H)-pyrido(
3,4-f)(1,4)benzoxazine] (4)
1-(p-methoxybenzyl)-3,3-dimethylspiro[piperidine-2,3'-(3H)-pyrido(3,4
-f)(1,4)benzoxazine](5) 1-isopropyl-3-methyl-3-ethylspiro[piperidine-2,3'-(3H)-pyrido(3°4-f)(1,
4) Benzoxazine](6>1-methoxyethyl-3
-Methyl-3-ethylspiro[piperidine-2,3'-
(3H)-pyrido(3,4-f) (1,4)benzoxazine] (7) 1-hexyl-3,3-dimethylspiro[piperidine-2,3″-(3H)-pyrido(
3,4-f)(1,4)benzoxazine] (8) 1-octadecyl-3,3-dimethylspiro[piperidine-2,3″-(3H)-pyrido(3,4-f)
(1,4)benzoxazine] (9) 1-hephthyl-3-methyl-3-ethylspiro[piperidine-2,3°-(3H)-pyrido(3,4
-f) (1,4)benzoxazine] (10) 1
-cyclohexylmethyl-3,3-dimethylspiro[piperidine-2,3'-(3H)-pyrido(3,4-f)
(L4) benzoxazine] and others, but are not limited to these, of course. Moreover, a compound in which a bulky group such as an octadecyl group or a cyclohexylmethyl group is introduced at the 1-position is preferable because a large coloration can be obtained.

In addition to the above, specific examples of spirooxazine compounds represented by general formula (1) include (11) 1,3.3-trimethylspiro[piperidine-
2°3°-(3H)-pyrido(3,2-f)(1,4)
Benzoxazine] (12) 1-isopropyl-3,3-dimethylspiro[piperidine-2,3°-(3H)-pyrido(3,2-
f) (1,4)benzoxazine] (i3) 1-hensyl-3,3-'; methylspiro[piperidine-2,3°-(3H)-pyrido(3,2-
f) (1,4)benzoxazine] (14) 1-(2-phenoxyethyl)-3,3-dimethylspiro[piperidine-2,3°-(3H)-pyrido(3,2-f)(1 , 4) Benzoxazine] (15)
1-(p-methoxybenzyl)-3,3-dimethylspiro[piperidine-2,3″-(3H)-pyrido(3,2
-f)(1,4)benzoxazine](16N-(2
-methoxyethyl)-3,3-dimethylspiro[piperidine-2,3°-(3H)-pyrido(3°2-f)(1
, 4) Benzoxazine] (17N, 3-dimethyl-3
-nitylspiro[piperidine-2,3''-(3H>-pyrido(3,,2-f) (1,4)benzoxazine] (18) 1,3.3.4.5-pentamethylspiro[piperidine -2,3°-(3H)-pyrido(3,2-
f) (1,4>Benzoxazine] (19) 1-isopropyl-3-methyl-3-ethylspiro[piperidine-2,3°-(3H)-pyrido(3
゜2-f) (1,4) Benzoxazine〕(20) 1
, 3.3.4.5-pentamethylspiro[piperidine-2,3'-(3H)-pyrido(3,4-f) (1
,4) Benzoxazine] <21) 1 ,3.3.5-tetramethylspiro[piperidine-2,3"-(3H)-pyrido(3,4-f)
(1,4)benzoxazine] (22) 1-hexyl-3,3-dimethylspiro[piperidine-2,3°-(3H)-pyrido(3,2-f
) (1,4) Benzoxazine] (23) 1-hexadecyl-3,3-dimethylspiro[piperidine-2,3'-(3H)-pyrido(3,2-
f) (1,4)benzoxazine] (24> 1-octyl-3,5,6-)dimethyl-3
-ethylspiro[piperidine-2,3'-(3H)-pyrido(3,4-f)(1,4)benzoxazine] and others, but are not limited to these, of course.

Among the above compounds, the spirooxazine compound represented by the general formula (1-A) is particularly preferred because it has a large degree of color development and has good color development at room temperature or higher temperatures.

Further, the spirooxazine compound represented by the general formula (II) also has a good degree of color development.

Among the spirooxazine compounds represented by the general formula (n), those represented by the following general formula (n-A) are particularly preferred.

General formula (n-A) (In the formula, A2 represents an alkylene group, an alkylene(polyoxy)alkylene group, or an alkylenearylalkylene group, and R' and R2 represent an alkyl group having 5 or less carbon atoms.) General formula (II Specific examples of the compound represented by -A> include (IN, 1''-(1,5-pentanediyl)bis[3,
3-dimethylspiro[piperidine-2,3°-(3H)
-pyrido(3,4-f') (1,4)benzoxazine]co(2)1.1"-[1,4-phenylenebis(
methylene)]bis[:3,3-dimethylspiro[piperidine-2゜3'-(3H)-pyrido(3,4-f)(1
, 4>benzoxazine]] Others can be mentioned, but of course they are not limited to these.

In addition to the above, specific examples of spirooxazine compounds represented by general formula (II) include (3) 1.1l-(l,5-pentanediyl)bis[3,3-dimethylspiro[piperidine-2,3° −(
3H)-pyrido(3,2-f)(1,4)benzoxazine]](4) 1.1″-(l,6-hexanediyl)bis[5-methyl-3,3-dimethylspiro[piperidine -2゜3″-(3H)-pyrido(3,2-f)
(1,4) Benzoxazine coco (5) 1.1”-(1,10-decanediyl)bis[5-methoxy-3,3-dimethylspiro[piperidine-2,3′-(3H)-pyrido(3 ,4-f)(1,4
) benzoxazine]] (6) 1.1'-[1,4-phenylenebis(methylene)]bis[3-ethyl-3-methylspiro[piperidine-2,3'-(3H)-pyrido(3,2 -f)(1
, 4) Benzoxazine Coco (7) 1.1"=(l,6-hexanediyl)bis[3,3-dimethylspiro[piperidine-2,3'-(
3H)-pyrido(3,2-f)(1,4)benzoxazine] and others, but are not limited to these, of course.

Among the above compounds, the spirooxazine compound represented by the general formula (It-A) is particularly preferred because it has a large degree of color development and has good color development at room temperature or higher temperatures.

The above spirooxazine compound can be synthesized, for example, by reacting a 5-nitroso-6-quinolinol or 8-nitrone-7-yne quinolinol derivative with a piperidine compound having a desired substituent. Specifically, both of them may be dissolved in a suitable solvent such as ethyl alcohol or toluene, and the mixture may be brought to boiling point reflux under a nitrogen gas atmosphere to cause the reaction to occur.

A piperidinium salt compound having a desired substituent may be used instead of the piperidine compound described above. In these reactions, a base such as triethylamine can also be added as a catalyst. Furthermore, this synthesized spirooxazine compound can be purified by a method such as a recrystallization method, a column separation method, or an activated carbon treatment method, if necessary.

The photochromic compound of the present invention can be embodied as an object having photochromic action by dispersing or dissolving it in a solid medium.

Here, the solid medium is not particularly limited as long as it can contain the photochromic compound alone or together with other necessary additives. Therefore, it may be a simple binder, or it may be a resin that constitutes an article having a unique function by itself, such as a resin that constitutes an optical material.

Specific examples of resins used as the solid medium include polyols (allyl carbonate), acrylic resins, cellulose resins, polyvinyl alcohol, polyvinyl acetate, urethane resins, epoxy resins, silicone resins, polystyrene, polyesters such as polyethylene terephthalate, polyvinyl Mention may be made of butyral, polyamide, polyvinyl chloride, polyvinylidene chloride, and other resins.

The proportion of the spirooxazine compound in the solid medium made of such a resin is not particularly limited, but it is o,oot to 100 parts by weight, preferably 0.01 to 50 parts by weight, based on 100 parts by weight of the solid medium. used in range.

The photochromic compound of the present invention can be used in the same manner as ordinary photochromic substances. Therefore, it can be put to practical use, for example, by using the following method.

(2) A method in which a mixture obtained by mixing the photochromic compound with a binder is used as a material, and the material is shaped into a film, plate, or other desired shape by means such as a casting method or a melting method.

According to this method, it is possible to produce a solid article that itself has a photochromic effect.

■Dissolve the photochromic compound together with a binder in a suitable common solvent and use the resulting solution as a coating solution.
For example, a method of forming a photochromic layer on a substrate by coating it on a substrate made of various optical materials and then removing the solvent.

According to this method, optical materials such as lenses having a photochromic layer can be manufactured.

■Method of casting the solution in the method of ■ above.

According to this method, a photochromic film can be suitably formed.

(2) A method in which a suitable dispersion medium is used instead of the solvent in the method (2) or (2) above, and the photochromic compound is dispersed in the dispersion medium together with a binder to obtain a dispersion liquid.

■A photochromic article formed by using a polymerizable monomer that polymerizes to become a binder in place of part or all of the binder in the methods from ■ to ■ above;
A method of further polymerizing a layer or film, etc.

According to this method, articles, layers, films, etc. made of a polymer having photochromic action can be obtained. Therefore, for example, by adding the above-mentioned photochromic compound to a monomer composition that polymerizes to give an optical material, and filling it into a cast polymerization container and polymerizing it,
Optical materials such as lenses that have a photochromic effect can be directly produced.

In carrying out the above method, an antioxidant,
UV absorber to block unnecessary short wavelength light,
It is also possible to add light stabilizers and other additives.

By using particularly a hindered amine light stabilizer as the light stabilizer, it is possible to improve the weather resistance of the resulting photochromic optical material.

Such light stabilizers include bis(1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, bis(2,2,6,6-tetramethyl-4-piperidyl) sebacate, di( 1,2,2,6,6-pentamethyl-4-piperidyl>-butyl (3°,5°-di-tert-butyl-4-
Hydroxybenzyl) malonate,! -(2-(3-(3,5-di-tert-butyl-4-
Hydroxyphenyl)propionyloxyphethyl)
-4-(3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionyloxygo 2, 2.6.
6-titramethylpiveridine, poly[[6-((1,
1,3,3-tetramethylbutyl)amino)-1,3°5-triazine-2,4-diyl] [l.

6-(2,2,6,6-tetramethyl-4-piperidinyl)aminohexamethylene]), poly([6-(morpholino)-5-triazine-2
,4-diyl] [1,6-(2,2,6,6-tetramethyl-4-piperidyl>amino]hexamethylene)
, 4-hydroxy-2,2,6,6-tetramethyl-1
- Dimethyl succinate polymer with piperidinethanol and other commercially available products can be usefully used.

The light stabilizer is used in an amount of 0.01 to 100 parts by weight of the solid medium.
It is used in proportions ranging from 50 parts by weight, preferably from 0.01 to 30 parts by weight.

In addition, the addition of a heavy ring oxygen quencher suppresses the adverse effect of oxygen on the coloring mechanism of the spirooxazine compound, and therefore improves the repeated durability of the coloring state of the spirooxazine compound. is valid.

Examples of such heavy ring oxygen quenchers include β-carotene, various Schiff base N1(II) complexes, 1.4-
Examples include amine compounds such as diazabicyclo[2,2,2]octane and triethylamine, and phenol compounds. Among these, amine compounds and phenol compounds can be preferably used because they do not have absorption in the visible region, although the -heavy ring oxygen extinction coefficient is somewhat small. The amount of the heavy ring oxygen quencher added is preferably as large as possible, and is used in an amount of 0.1 to 100 parts by weight, preferably 0.5 to 50 parts by weight, based on 100 parts by weight of the solid medium.

〔Effect of the invention〕

Since the photochromic compound of the present invention is composed of a spirooxazine compound having a specific chemical structure, its specificity stabilizes the coloring property, as is clear from the explanation of the examples below. High color density can be obtained, and the color has good repeat durability even at room temperature or higher temperatures.

Therefore, the photochromic compound of the present invention can be used in various displays, memories, etc. by utilizing the above properties.
It can be suitably used for optical materials for optical instruments such as photochromic lenses, photochromic filters, and light meters, and others.

Examples of the present invention will be described below, but the present invention is not limited thereto.

In addition, the measurement of the light transmittance in each Example and Comparative Example was performed using a light beam having a wavelength that caused a maximum change in the light transmittance.

Example 1 [Synthesis example] 1.3.3-)limethylspiro[piperidine-2,3'
-(3H)-pyrido(3,4-f) (1,4)benzoxazine] base 1.3.3-)tumethyl-2-methylenepiperidine 5,
61 g and 8-nitrone-7-isoquinolinol 6,
97 g was dissolved in 200 g of toluene, and the mixture was refluxed at the boiling point for 6 hours under a nitrogen gas atmosphere to react.

After the reaction was completed, the solvent was concentrated, and separation was performed by column chromatography using silica gel as a carrier and a mixed solvent of ethyl acetate and hexane as a developing solvent. After distilling off the developing solvent, the obtained solid was purified by a recrystallization method using a mixed solvent of acetone and hexane to obtain 1.26 g of white powder.

This compound has a nuclear magnetic resonance spectroscopy (NMR) spectrum,
By infrared absorption spectrum and CHN elemental analysis,
1,3.3-)limethylspiro[piperidine-2,3
'-(3H)-pyrido(3,4-f)(1,4)benzoxazine].

The result of elemental analysis is charcoal! 73.17% by weight, hydrogen 7
．． 25% by weight, 14.11% by weight of nitrogen, calculated values of 73.19% by weight of carbon, 7.17% by weight of hydrogen, 14% by weight of nitrogen.
．． 23% by weight, and the NMR spectrum is
0.9-3 in deuterated chloroform. oppm (158)
, 7, 0 to 10.0 ppm (6H).

[Application example]

734.0 parts by weight of 1,3,3-trimethylspiro[piperidine-2,3°-(3H)-pyrido(3,4-f)(1,4)benzoxadi] was added to the epoxy resin precursor "Eponix 81100 Clear". (manufactured by Dainippon Paint) 6
A coating solution was obtained by dissolving 0 parts by weight of N in 100 parts by weight of methyl ethyl ketone.

This coating solution was applied to the surface of a glass slide by dipping, the methyl ethyl ketone was evaporated at 40°C until the coated surface lost its tackiness, and then cured at 80°C for 16 hours to form a slightly red color with a thickness of 10J1111. A photochromic film with a tinge was prepared.

When this film is irradiated with ultraviolet rays, it develops a color, and the change in transmittance of light with a wavelength of 578 nm is 92% at room temperature before irradiation with ultraviolet rays, and decreases to 51% after 5 minutes of irradiation with ultraviolet rays. did.

Thereafter, when the film was placed in a dark place, the light transmittance returned to its original state.

Example 2 [Synthesis 1 & Example] 1.3.3-) Synthesis of Limethylsuviro[piperidine-2,3゛-(3H)-pyrido(3゜2-fHl,4)benzoxazine] 1.3.3-) 2-methyl-2-methylenepiperidine5.
61 g and 6.97 g of 5-nitroso-6-quinolinol.
was dissolved in 200% of toluene, and the mixture was refluxed at the boiling point for 8 hours under a nitrogen gas atmosphere to react.

After completion of the reaction, separation was carried out by column chromatography using I11$1ii as a solvent, silica gel as a carrier, and a mixed solvent of ethyl acetate and hexane as a developing solvent. After distilling off the developing solvent, the obtained solid was purified by a recrystallization method using a mixed solvent of acetone and hexane.
g of white powder was obtained.

This compound was confirmed by NMR spectrum, infrared absorption spectrum and CHN elemental analysis to be 1.3.3-trimethylspiro[piperidine-2,3'-(3H)-pyrido(
3,2-f)(1,4)benzoxazine].

The results of elemental analysis are 73.11% by weight of carbon and 7% by weight of hydrogen.
．． 33% by weight, 14.35% by weight of nitrogen, calculated values of 73.19% by weight of carbon, 7.17% by weight of hydrogen, 14% by weight of nitrogen.
, 23% by weight, and the NMR spectrum is
0.9-3.0 ppm in deuterated chloroform (15)1
), 7.0 to 9.0 ppm (6N).

[Application example]

1.3.3-) Dimethylspiro [1.3.3- in place of 734.0 parts by weight of piperidine-2,3°-(3H)-pyrido(3,4-f)(1,4)benzoxadi) Dimethylspiro[piperidine-2,3'-(3H)-pyrido(3,2-f) (1,4)benzoxadi 734.
A slightly reddish photochromic film having a thickness of 10 layers was produced in exactly the same manner as in Example 1, except that 0 parts by weight was used.

When this film is irradiated with ultraviolet rays, it develops a color, and the change in transmittance of light with a wavelength of 578 nm is 92% at room temperature before irradiation with ultraviolet rays, and decreases to 60% after 5 minutes of irradiation with ultraviolet rays. did.

Thereafter, when the film was placed in a dark place, the light transmittance returned to its original state.

Comparative Example 1 1.3.3-) Dimethylspiro[piperidine-2,3'
-(3H)-pyrido(3,4-f) (1.3.3-) in place of 734.0 parts by weight of (1,4)benzoxadi
Dimethylspiro[piperidine-2,3°-(3H)-naphtho(2,1-b)(1,4)oxasif 34.0 parts by weight was used, but the thickness was prepared in the same manner as in Example 1. A colorless photochromic film of IOJLm was produced.

When this film was irradiated with ultraviolet light, it developed a color, but the wavelength was 5.
The change in transmittance of 78 nm light was 92% at room temperature before UV irradiation, and only decreased to 84% after 5 minutes of UV irradiation.

Example 3 [Common example] 2 ” ”J shi) Lt-3,3-dimethylspiro [
piperidine-2,3'-(3H)-pyrido(3,4-f
)(1,4)Benzoxazine] 5.92 g of 1-benzyl-2,3,3-)limethylbiperidinium bromide, 3.48 g of 8-nitrone-7-inquinolinol, and 4.0 g of triethylamine. was dissolved in 150 r111 of toluene, and the mixture was refluxed at the boiling point for 6 hours under a nitrogen gas atmosphere to react.

After the reaction was completed, the solvent was concentrated, the precipitated yellowish brown crystals were separated and washed with a small amount of ethyl alcohol, and the obtained powder was purified by recrystallization method using ethyl alcohol to obtain 1.1 g of pale yellow powder. Ta.

This compound was found to be 1-benzyl-3,3 by NMR spectrum, infrared absorption spectrum and CHN elemental analysis.
-dimethylspiro[piperidine-2゜3'-(3H)-
It was identified as pyrido(3,4-f)(1,4)benzoxazine].

The results of elemental analysis were 77.58% by weight of carbon and 16% by weight of water.
．． 97% by weight, nitrogen 11.20% by weight, calculated value of carbon 77, 60% by weight hydrogen, 6.78% by weight nitrogen, 11% by weight nitrogen.
．． 31% by weight, and the NMR spectrum is
0.9-3 in deuterated chloroform. OppH1(121(
), 4, 49 layers m (2) 1), 7.0 to 10.0 p
pm (IIH).

[Application example] 26.97 parts by weight of 2-hydroxyethyl methacrylate, 23.03 parts by weight of inphorone diisocyaner), and 50 parts by weight of 2-ethylhexyl methacrylate were mixed with 2,6-dimethylmethacrylate as an antioxidant. tart-butyl-p-
Adding 5 parts by weight of cresol and 0□05 parts by weight of di-n-butyltin dilaurate, which is a urethanization catalyst,
The urethane reaction was carried out at 60°C for 3 hours.

In the urethane monomer composition thus obtained, 1-
Benzyl-3,3-dimethylspiro[piperidine-2,
3'-(3H)-pyrido(3,4-f)(1,4)benzoxazine 30.1 heavy 1815 and the hindered amine light stabilizer 1(2-[:3-(3,5-di ter
t-butyl-4-hydroxyphenyl> propionyloxyphethyl)-4-(3-(3,5-di-tert
-butyl-4-hydroxyphenyl)propionyloxy) -2,2,6,6-titramethylbiperidine (Sanol L S-2626J (manufactured by Sankyo)) was added and mixed, and then polymerized. tert as an initiator
-1 part by weight of butyl baroxypiparate was added to obtain a monomer composition solution containing a photochromic compound.

This monomer composition solution was injected into a glass mold for lens production, and heated at 50°C for 10 hours and at 60°C for 5 hours.
Polymerization was carried out by gradually increasing the polymerization temperature at 100° C. for 2 hours and 1 #7 to produce a slightly reddish lens with a center thickness of 1.3 mm.

When this lens is irradiated with ultraviolet rays, it develops a color, and the resulting change in transmittance of light with a wavelength of 575 nm is as follows at room temperature:
It was 89% before UV irradiation, and decreased to 55% after 5 minutes of UV irradiation.

Thereafter, when the lens was placed in a dark place, the transmittance of the light beam returned to its original state.

Example 4 1-Cyclohexylmethyl-3,3-dimethylspiro [
piperidine-2,3'=(3H)-pyrido(3,4-f
) (1,4) Benzoxazine] 4.43 g of 1-cyclohexylmethyl-3,3-dimethyl-2-methylenepiperidine and 3.48 g of 8-nitroso-7-inquinolinol were dissolved in 100% of toluene. This was reacted by boiling under reflux for 6 hours under a nitrogen gas atmosphere.

After the reaction, the solution was allowed to cool, the insoluble matter was filtered off, and then concentrated to obtain a dark brown viscous liquid. Next, the hexane-soluble component was extracted from this liquid, and after further concentration, it was extracted with acetone. 1.3g purified by recrystallization method using a mixed solvent with hexane
A white powder was obtained.

This compound was confirmed by NMR spectrum, infrared absorption spectrum and CHN elemental analysis to be 1-cyclohexylmethyl-3,3-dimethylspiro[piperidine-2,3°
-(38)-pyrido(3,4-f)(1,4)benzoxazine].

The results of elemental analysis were 76% carbon, 29% by weight, and 8% hydrogen.
．． 51% by weight, 11.02% by weight of nitrogen, calculated value of carbon 76, 35% by weight of hydrogen, 8.28% by weight of hydrogen, 11% by weight of nitrogen.
．． It almost coincides with 13% by weight, and the NMR spectrum is
0.8-3.0ppm (25H) in deuterated chloroform
, 7, 0 to 10.0 ppm (6)1).

[Application example]

1-benzyl-3,3-dimethylspiro[piperidine-
2,3°-(3H)-pyrido(3,4-f)(1,4)
1-cyclohexylmethyl-3,3-dimethylspiro[piperidine-2,3
Example 3 except that 0.05 parts by weight of '-(3H)-pyrido(3,4-fHl,4)benzoxazine was used.
In exactly the same manner as above, a slightly reddish lens with a center thickness of 1.3 mm was manufactured.

When this lens is irradiated with ultraviolet rays, it develops a color, and the change in transmittance of light with a wavelength of 575nrQ is 85% at room temperature before irradiation with ultraviolet rays, and decreases to 31% after 5 minutes of irradiation with ultraviolet rays. did.

Thereafter, when the lens was placed in a dark place, the transmittance of the light beam returned to its original state.

Example 5 [Example] 1.1"-1,6-hexanediyl>bis[3,3-
Dimethylspiro[piperidine-2,3'-(3H)-pyrido(3,4-f)(1,4)benzoxazineCoco base 1.1'-(1,6-hesanodiyl)bis[3 ，
3-dimethyl-2-methylene piperidinoko 3.33 g
and 3.48 g of 8-nitroso-7-isoquinolinol in 100 ml of toluene! This was reacted by boiling under reflux for 8 hours under a nitrogen gas atmosphere.

After the reaction was completed, the solvent was concentrated, and separation was performed by column chromatography using silica gel as a carrier and a mixed solvent of ethyl acetate and Hegyu San as a developing solvent. After distilling off the developing solvent, the obtained solid was purified by a recrystallization method using a mixed solvent of acetone and hexane to obtain 0.55 g of pale yellow powder.

This compound was found to have i, t”-(1,6
-hexanediyl)bis[3,3-dimethylspiro[piperidine-2,3°-(3H)-pyrido(3,4-f)
It was identified as (1,4) benzoxazine fuco.

The results of elemental analysis are 74.45% by weight of carbon and 7% by weight of hydrogen.
．． 68% by weight, 12.95% by weight of nitrogen, calculated values of 74.50% by weight of carbon, 7.50% by weight of hydrogen, 13% by weight of nitrogen.
, 03% by weight, and the NMR spectrum is
0.9-3.0 ppm in deuterated chloroform (32)1
), 3, 2ppm (4)l), 7. O~10. O
ppm(12)1).

[Application example]

1.3.3-)dimethylspiro[piperidine-2,3°-(3H)-pyrido(3,4-f)(1,4) 1.1″-(1 ,6
-hexanediyl)bis[3,3-dimethylspiro[piperidine-2,3'-(3H)-pyrido(3,4-f)
(1,4) Benzoxazine]] A slightly reddish photochromic film having a thickness of 10 mm was prepared in exactly the same manner as in Example 1 except that 4.0 parts by weight of benzoxazine was used.

When this film is irradiated with ultraviolet rays, it develops a color, and the change in transmittance of light with a wavelength of 578 nm is 89% at room temperature before irradiation with ultraviolet rays, and decreases to 44% after 5 minutes of irradiation with ultraviolet rays. did.

Thereafter, when the film was placed in a dark place, the light transmittance returned to its original state.

Claims (1)

[Scope of Claims] (1) A photochromic compound comprising a spirooxazine compound represented by the following general formula (I). General formula (I) ▲ Numerical formulas, chemical formulas, tables, etc. are available▼ (In the formula, A^1 is an alkyl group having 1 to 24 carbon atoms, an allyl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted aryl group, etc.) Roxyalkyl group or alkoxyalkyl group, R^1 to R^6 represent a hydrogen atom, a linear or branched alkyl group, R^9 represents a hydrogen atom,
It represents a halogen atom, an alkyl group, an alkoxy group, a hydroxyl group, or an alkoxyalkyl group, one of X and Y represents a nitrogen atom, and the other represents a methine group. ) (2) The photochromic compound according to claim 1, comprising a spirooxazine compound represented by the following general formula (I-A). General formula (I-A) ▲ Numerical formulas, chemical formulas, tables, etc. represents an aryloxyalkyl group or an alkoxyalkyl group, and R^1 and R^2 represent an alkyl group having 5 or less carbon atoms.) (3) Consisting of a spirooxazine compound represented by the following general formula (II). Characteristic photochromic compounds. General formula (II) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, A^2 represents an alkylene group, an alkylene (polyoxy)alkylene group, or an alkylenearylalkylene group, and R^1 to R^8 are hydrogen atoms. , represents a linear or branched alkyl group, R^9 represents a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, a hydroxyl group, or an alkoxyalkyl group, one of X and Y represents a nitrogen atom, and the other represents a methine atom. (4) The photochromic compound according to claim 3, comprising a spirooxazine compound represented by the following general formula (II-A). General formula (II-A) ▲ Numerical formulas, chemical formulas, tables, etc. (Indicates an alkyl group having 5 or less carbon atoms.)