JP3248768B2 - Spiropyran compounds and photochromic materials - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel dye which changes from colorless to colored or darkened by light containing ultraviolet rays such as sunlight or light from a mercury lamp, and the change is reversible and shows excellent durability. Spiropyran compounds.

[0002]

2. Description of the Related Art Photochromism is a phenomenon that has attracted attention in recent years. When a compound is irradiated with light containing ultraviolet rays such as sunlight or light from a mercury lamp, the color changes rapidly, and the light irradiation is performed. It is a reversible action that returns to the original color when it is stopped and placed in a dark place.

A compound having this property is called a photochromic compound, and various compounds have been conventionally synthesized, but no special common skeleton is recognized in the structure.

JP-A-3-11075 describes a spiropyran compound in which a bicyclo [3.3.1] 9-nonylidene group is bonded to the 2-position of a benzopyran or naphthopyran ring. These spiropyran compounds have a temperature range of room temperature or slightly higher (10 to 10).
(40 ° C.), the compound develops a color from colorless to yellow to orange upon irradiation with ultraviolet light, returns from the colored state to a colorless state in a short time, and has excellent photochromic properties.

[0005]

The present inventors have further studied to further improve the photochromic properties of spiropyran compounds and to synthesize spiropyran compounds having excellent photochromic properties in good yield. As a result, by forming a structure in which a 2-bicyclo [3.3.1] 9-nonenylidene group is bonded to the 2-position of the benzopyran ring or naphthopyran ring of the above spiropyran compound, the coloring density is improved, and the synthesis is further improved. The inventors have found that the yield is improved, and have come to propose the present invention.

[0006]

That is, the present invention provides a compound represented by the general formula (I):

[0007]

Embedded image

[However,

[0009]

Embedded image

Is a substituted or unsubstituted 2-bicyclo [3.3.1] 9-nonenylidene group,

[0011]

Embedded image

Is a substituted or unsubstituted aromatic hydrocarbon group or a substituted or unsubstituted unsaturated heterocyclic group;
₁ and R ₂ are the same or different hydrogen atoms, alkyl groups, aralkyl groups, aryl groups or substituted amino groups, respectively. ] Is a spiropyran compound represented by the formula:

In the above general formula [I],

[0014]

Embedded image

The group represented by the formula is 2-bicyclo [3.3.
1] 9-nonenylidene group

[0016]

Embedded image

Or a 2-bicyclo [3.3.1] 9-nonenylidene group substituted by a substituent. Specific examples of the substituent include, for example, a hydroxy group; a substituted amino group such as a methylamino group and a diethylamino group; and a C1-C1 group such as a methoxy group, an ethoxy group, and a tert-butoxy group.
An alkoxy group having 4 to 7 carbon atoms such as a benzyloxy group;
An aryloxy group having 6 to 14 carbon atoms such as a phenoxy group and 1-naphthoxy group; a lower alkyl group having 1 to 4 carbon atoms such as a methyl group, an ethyl group and a t-butyl group; fluorine, chlorine, A halogen atom such as sulfur; a cyano group; a carboxyl group; an alkoxycarbonyl group having 2 to 10 carbon atoms such as an ethoxycarbonyl group; a halogen-substituted alkyl group having 1 or 2 carbon atoms such as a trifluoromethyl group;
A nitro group; an aryl group such as a phenyl group or a tolyl group; an aralkyl group such as a benzyl group, a phenylethyl group or a phenylpropyl group, and the like. It may be included as a multi-substituted compound having a plurality of substituents having two or more substituents. Further, the substituents in the multi-substituted product may be the same or different without any problem. Can be changed according to the purpose or use.

In the above general formula (I),

[0019]

Embedded image

The group represented by is a substituted or unsubstituted aromatic hydrocarbon group or a substituted or unsubstituted unsaturated heterocyclic group. More specific examples of the aromatic hydrocarbon group include a benzene ring, a naphthalene ring, a phenanthrene ring, one or two to four fused rings of a benzene ring such as an anthracene ring, or toluene substituted with an alkyl group, Examples thereof include a divalent group derived from an aromatic hydrocarbon ring having 6 to 14 carbon atoms such as xylene. Further, the above-mentioned aromatic hydrocarbon group alkoxy group, hydroxyl group, nitro group, cyano group, trifluoromethyl group, substituted amino group,
Examples thereof include a substituted aromatic hydrocarbon group in which one or two or more heterocyclic groups such as a halogen atom, a phenyl group, a furyl group, and a pyrrolyl group are substituted. Also,

[0021]

Embedded image

Examples of the unsaturated heterocyclic group represented by the above include a 5- or 6-membered ring containing oxygen, sulfur and nitrogen atoms or a heterocyclic group having 4 to 10 carbon atoms in which a benzene ring is condensed to these. be able to. Specifically, a pyridine ring,
Examples include divalent groups derived from nitrogen-containing heterocycles such as quinoline ring and pyrroline ring; oxygen-containing heterocycles such as furan and benzofuran rings; and sulfur-containing heterocycles such as thiophene and benzothiophene rings. Further, substituted unsaturated heterocyclic groups obtained by substituting these unsaturated heterocyclic groups with the substituents described in the description of the aromatic hydrocarbon group described above are also employed without limitation in the present invention.

Further, in the general formula (I), R ₁ and R ₂
Are respectively the same or different hydrogen atoms, alkyl groups, aralkyl groups, aryl groups, and substituted amino groups. The alkyl group is not particularly limited, but generally an alkyl group having 1 to 20 carbon atoms, preferably 1 to 6 carbon atoms is suitably used. The alkyl group of the aralkyl group generally has 1 to 10, preferably 1 to 4 carbon atoms. More specific examples of the alkyl group and the aralkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, a benzyl group, a phenylethyl group, a phenylpropyl group, and a phenylbutyl group. As the aryl group, one having 6 to 10 carbon atoms is preferable, and for example, a phenyl group, a tolyl group, a xylyl group, a naphthyl group and the like are preferable.

Further, in the general formula [I], R ₁ and R ₂
The substituted amino group represented by the general formula

[0025]

Embedded image

Or

[0027]

Embedded image

## EQU2 ## Here group represented by R _3, R ₄ are either the other in either one of R ₃ and R ₄ are hydrogen atoms is an alkyl group, or shows the same or different alkyl groups. The alkyl group is not particularly limited, but specifically, the same groups as those described above for the alkyl group can be employed. R ₅ is an alkylene group having 3 to 6 carbon atoms such as a tetramethylene group or a pentamethylene group; An oxyalkylene group having 3 to 6 carbon atoms, such as —CH ₂ O (CH ₂ ) ₃ —; —CH ₂ SCH ₂ CH ₂ —, —CH ₂ S (C
H ₂ ) ₃ —, —CH ₂ CH ₂ SCH ₂ CH ₂ —, etc.
6 to 6 thioalkylene groups; An azoalkylene group having 3 to 6 carbon atoms, such as, for example, is suitably employed.

Specific examples of suitable spiropyran compounds in the present invention include the following compounds.

1) Spiro (2-bicyclo (3.3.1)
Nonene-9,2 '-(2H) benzo (h) chromene) 2) spiro (2-bicyclo (3.3.1) nonene-9,
2 '-(2H) benzo (f) chromene) 3) 4'-methylspiro (2-bicyclo (3.3.1)
Nonene-9,2 '-(2H) benzo (f) chromene) 4) 3'-methylspiro (2-bicyclo (3.3.1)
Nonene-9,2 '-(2H) benzo (f) chromene) 5) 4'-Pyrrolidinospiro (2-bicyclo (3.3.
1) Nonene-9,2 '-(2H) benzochromene 6) 7'-Ethyl-5'-methoxy-4'-morpholinospiro (2-bicyclo (3.3.1) nonene-9,2'
-(2H) benzochromene) 7) 4'-diethylamino-5-dimethylaminospiro (2-bicyclo (3.3.1) nonene-9,2 '-(2
H) Benzo (f) chromene) 8) 5'-chloro-4 '-(1,3-thiazolino) -7
-Methoxyspiro (2-bicyclo (3.3.1) nonene-9,2 '-(2H) benzo (f) chromene) 9) 4'-(4-Methylpiperazino) spiro (2-bicyclo (3.3. 1) Nonene-9,2 '-(2H) isoquino (3,4-e) pyran) 10) 5,8,8-Trimethylspiro (2-bicyclo (3.3.1) nonene-9,2'- (2H) pyrido (3,2-e) pyran) 11) 8'-cyanospiro (2-bicyclo (3.3.
1) Nonene-9,2 '-(2H) chromene) 12) 7'-phenylspiro (2-bicyclo (3.3.
1) Nonene-9,2 '-(2H) benzo (h) chromene 13) 7'-Phenyl-5-chlorospiro (2-bicyclo (3.3.1) nonene-9,2'-(2H) chromene 14) Spiro (2-bicyclo (3.3.1) nonene-
9,2 '-(2H) pyrido (6,5-b) chromene 15) 5,7,7-trimethylspiro (2-bicyclo (3.3.1) nonene-9,2'-(2H) dibenzo (F, h) chromene) 16) 10'-ethoxy-5,7,7-trimethyl-
7'-nitrospiro (2-bicyclo (3.3.1) nonene-9,2 '-(2H) benzo (h) chromene) 17) 5,7,7-trimethyl-7'-trifluoromethyl-10' -Pentylspiro (2-bicyclo (3.
3.1) Nonene-9,2 '-(2H) benzo (h) chromene 18) 5,8'-Diphenylspiro (2-bicyclo (3.3.1) nonene-9,2'-(2H) Benzo (f) chromene) 19) 7-thienylspiro (2-bicyclo (3.3.
1) Nonene-9,2 '-(2H) thienylbenzo (h)
Chromene) 20) 5-trifluoromethyl-10'-n-propoxyspiro (2-bicyclo (3.3.1) nonene-9,
2 '-(2H) pyrido (2,3-h) chromene 21) 5-cyano-7'-furanylspiro (2-bicyclo (3.3.1) nonene-9,2'-(2H) (benzo (h )) Chromene) 22) 5-Butyl-7-fluoro-6'-bromo-8 '
-Hydroxyspiro (2-bicyclo (3.3.1) nonene-9,2 '-(2H) benzo (f) chromene) 23) 7'-dimethylamino-5-benzylspiro (2
-Bicyclo (3.3.1) nonene-9,2 '-(2H)
Benzo (h) chromene) 24) 5-Ethyl-8-ethoxyspiro (2-bicyclo (3.3.1) nonene-9,2 '-(2H) (benzo (b) thieno (3,2-e) Pyran) 25) Spiro (2-bicyclo (3.3.1) nonene-
9,2 '-(2H) methylpyrrolo (3,2-e) pyran) 26) 4'-benzylspiro (2-bicyclo (3.3.
1) Nonene-9,2 '-(2H) quino (4,3-e) pyran) 27) 8'-Cyano-4'-n-butylspiro (2-bicyclo (3.3.1) nonene-9, 2 '-(2H) chromene) 28) 4'-phenylspiro (2-bicyclo (3.3.
1) Nonene-9,2 '-(2H) pyrido (3,2-e)
Pyran) 29) 3'-n-propylspiro (2-bicyclo (3.
3.1) Nonene-9,2 '-(2H) benzo (f) chromene 30) 3'-(2-phenylethyl) spiro (2-bicyclo (3.3.1) nonene-9,2'- (2H) Benzo (f) chromene 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 normal temperature and normal pressure, and has the following (A) ) To (c). (A) Proton nuclear magnetic resonance spectrum (H ¹ -NMR)
By measuring, the type and number of protons present in the molecule can be known. That is, δ7-8.
A peak based on an aromatic proton around 5 ppm, around δ 1.2 to 2.5 ppm and 5.3 to 5.7.
a broad peak around 2 ppm based on a proton derived from a 2-bicyclo [3.3.1] 9-nonenylidene group;
When R ₁ and R ₂ are hydrogen atoms, δ 5.5 to 7.0 p
A peak based on the alkene proton appears near pm. Further, by comparing the respective δ peak intensities, the number of protons of each bonding group can be known.

(B) By elemental analysis, the respective weight percentages of carbon, hydrogen, nitrogen, sulfur and halogen can be determined. Further, the weight% of oxygen can be calculated by subtracting the sum of the recognized weight% of each element from 100. Thus, the composition of the corresponding product can be determined.

(C) ¹³ C nuclear magnetic resonance spectrum ( ¹³ C
-NMR), the type of carbon present in the molecule can be known. A peak derived from the carbon of the 2-bicyclo [3.3.1] 9-nonenylidene group at about δ27 to 52 ppm, and based on the carbon of the alkyl group at about δ15 to 35 ppm when R ₁ and R ₂ are alkyl groups. A peak based on the carbon of the aromatic hydrocarbon group or unsaturated heterocyclic group appears at around δ110 to 150 ppm.

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

The following general formula (II)

[0035]

Embedded image

(Where:

[0037]

Embedded image

Is the same as in the general formula (I). ) And a compound of the general formula (III)

[0039]

Embedded image

(Where:

[0041]

Embedded image

Is a substituted or unsubstituted 2-bicyclo [3.3.1] 9-nonenylidene group. ) In the presence of a primary or secondary amine to give R ₁ or R in the above general formula (I).
_A compound in which ₂ is a hydrogen atom or a substituted amino group and at least one is a substituted amino group can be obtained.

The reaction between the compound represented by the general formula (II) and the compound represented by the general formula (III) is carried out as follows. The reaction ratio of these two mixtures can be employed from a wide range but is generally from 1:10 to 10: 1.
(Molar ratio). The reaction temperature is usually 0
To 200 ° C., and a polar aprotic solvent such as N-methylpyrrolidone, dimethylformamide, toluene, benzene, tetrahydrofuran or the like is used as the solvent. In this reaction, N-ethylamine,
A condensing agent represented by a primary amine such as N-propylamine or a secondary amine such as pyrrolidine, piperidine or morpholine is usually in the range of 0.1 to 10 mol per mol of the compound represented by the general formula (II). The reaction can be completed by removing water generated during the reaction. As a method of removing water, a method of removing water to the outside of the reaction system using a Dean-Stark apparatus, and a method of adding a dehydrating agent such as calcium chloride, calcium oxide, zinc chloride, etc. There is a method of removing water generated in the system by a dehydrating agent, and any method may be adopted.

By this reaction, the following formula (IV)

[0045]

Embedded image

[However,

[0047]

Embedded image

And

[0049]

Embedded image

Is the same as in the general formula (I). Is obtained. When the above reaction is further continued, the following formula (V) in which at least _one of R _{1 and} R ₂ is a substituted amino group in the general formula (I)

[0051]

Embedded image

[However,

[0053]

Embedded image

And

[0055]

Embedded image

Is the same as in the general formula (I), and R ₁ and R ₂ are the same or different hydrogen atoms or substituted amino groups, respectively, and at least one is a substituted amino group. Is obtained.

In the above general formula (I), the compound in which both R ₁ and R ₂ are hydrogen atoms can be obtained by replacing the chromanone compound represented by the above (IV) with sodium borohydride, lithium aluminum hydride or the like. After reacting with a reducing agent, the following formula

[0058]

Embedded image

[However,

[0060]

Embedded image

And

[0062]

Embedded image

Is the same as in the general formula (I). Is obtained, and then dehydrated with a dehydrating agent such as anhydrous copper sulfate to obtain the following formula

[0064]

Embedded image

[However,

[0066]

Embedded image

And

[0068]

Embedded image

Is the same as in the general formula (I). Is obtained.

In the general formula (I), the compound in which R ₁ is an alkyl group, an aralkyl group or an aryl group is obtained by converting the chromanone compound represented by the above formula (IV) to an organic compound such as an alkyl magnesium halide or an alkyl lithium. Reaction with metal compound, the following formula

[0071]

Embedded image

[However,

[0073]

Embedded image

And

[0075]

Embedded image

Is the same as in the general formula (I), and R ₁ is
An alkyl group, an aralkyl group, and an aryl group. Is obtained, and then dehydrated using a dehydrating agent such as anhydrous copper sulfate to obtain the following formula

[0077]

Embedded image

[However,

[0079]

Embedded image

And

[0081]

Embedded image

Is the same as in the general formula (I), and R ₁ is
An alkyl group, an aralkyl group, and an aryl group. Is obtained.

In the general formula (I), the compound in which R ₂ is an alkyl group, an aralkyl group or an aryl group can be obtained by converting the compound represented by the above (IV) into an alkyl halide, an aryl halide or a halogenated aryl. Reaction with aralkyl, the following formula (VI)

[0084]

Embedded image

[However,

[0086]

Embedded image

And

[0088]

Embedded image

Is the same as in the general formula (I), and R ₂ is
An alkyl group, an aralkyl group, and an aryl group. Is obtained, reduced with a reducing agent in the same manner as described above, and further dehydrated with a dehydrating agent, thereby obtaining the following formula

[0090]

Embedded image

[However,

[0092]

Embedded image

And

[0094]

Embedded image

Is the same as in the general formula (I), and R ₂ is
An alkyl group, an aralkyl group, and an aryl group. Is obtained. Further, the chromanone compound represented by the above (VI) is reacted with an organometallic compound such as an alkylmagnesium halide in the same manner as described above, followed by dehydration using a dehydrating agent, whereby the following formula is obtained.

[0096]

Embedded image

[However,

[0098]

Embedded image

And

[0100]

Embedded image

Is the same as in formula (I), and R ₁ and R ₂
Is the same or different alkyl group, aralkyl group and aryl group, respectively. Is obtained.

The spiropyran compound represented by the above general formula (I) of the present invention is well soluble in general organic solvents such as toluene, chloroform and tetrahydrofuran. When a spiropyran compound represented by the general formula (I) is dissolved in such a solvent, the solution is generally almost colorless and transparent, and rapidly changes to a color or a dark color when irradiated with sunlight or ultraviolet light, and when light is blocked. It exhibits a good reversible photochromic action that quickly returns to its original colorless state. Such a photochromic action in the compound of the general formula (I) also occurs in a polymer solid matrix, and the reversible speed occurs on the order of seconds. The target polymer matrix may be any one in which the spiropyran compound represented by the general formula (I) of the present invention is uniformly dispersed. Optically preferred are, for example, polymethyl acrylate and polyethyl acrylate. , Polymethyl methacrylate,
Polymers such as polyethyl methacrylate, polystyrene, polyacrylonitrile, polyvinyl alcohol, polyacrylamide, poly (2-hydroxyethyl methacrylate), polydimethylsiloxane, polycarbonate, poly (allyl diglycol carbonate), or monomers forming these polymers Polymers obtained by copolymerizing the monomers or the monomers and other monomers are preferably used.

The spiropyran compound of the present invention can be widely used as a photochromic material. For example, various memory materials, copying materials, photoreceptors for printing, recording materials for cathode ray tubes, photosensitive materials for lasers, holographic materials, in place of silver salt photosensitive materials. It can be used as various recording materials such as photosensitive materials for use. In addition, the photochromic material using the spiropyran compound of the present invention can be used as a material for a photochromic lens material, an optical filter material, a display material, a light meter, a decoration, and the like. For example, when used in a photochromic lens, there is no particular limitation as long as uniform light control performance can be obtained, and specifically, a polymer film obtained by uniformly dispersing the photochromic material of the present invention. Or a method of sandwiching this in a lens, or dissolving this compound in, for example, silicone oil, impregnating the lens surface at 150 to 200 ° C. for 10 to 60 minutes, and further coating the surface with a curable substance; There is a method of forming a photochromic lens. Further, a method of applying the above polymer film to the lens surface and coating the surface with a curable substance to form a photochromic lens is also conceivable.

When used in such a photochromic lens, a photochromic material that develops a strong color with sunlight at around normal temperature is preferable. Preferred compounds for such a photochromic lens are those represented by the general formula (I):

[0105]

Embedded image

Is a compound which is a divalent group derived from a naphthalene ring, a phenanthrene ring, a pyridine ring and a quinoline ring. In particular, a compound in which both R ₁ and R ₂ are hydrogen atoms has a feature that it develops a particularly deep color and has a high fading speed.

Further, by selecting each substituent of R ₁ or R _{2 in} the general formula (I), the discoloration rate of the compound of the general formula (I) can be changed. For example, R ₁
When R ₂ and R ₂ are an alkyl group, it is likely that the trans-form of the color-developing state is hardly obtained, but a high fading speed can be obtained. When R ₁ is a substituted amino group,
The trans-form in the color-developed state is stabilized by resonance, and a high color-developed density is obtained, but the fading speed tends to be slightly reduced. These substituents of R ₁ and R ₂ can be arbitrarily selected depending on the purpose.

[0108]

The spiropyran compound of the present invention has a 2-bicyclo [3.3.1] 9-nonenylidene group bonded to the 2-position of the benzopyran ring or naphthopyran ring, and thus has a higher effect than conventional compounds. It develops a deep color. Further, also when synthesizing the spiropyran compound of the present invention, the yield is improved as compared with the conventional compounds, which is advantageous in terms of production.

[0109]

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples.

Example 1 10 g of 1-hydroxy-2-acetonaphthone (0.05 g)
4 mol) and 2-bicyclo [3.3.1] nonene-9-
8.16 g (0.06 mol) and 8 g of pyrrolidine
(0.113 mol) was dissolved in 300 cc of toluene to prepare a solution. The mixture was boiled for 10 hours and the water was separated. After the reaction, the toluene was removed under reduced pressure,
The remaining chromanone compound was crystallized from acetone. Next, this chromanone compound was dissolved in 200 cc of methanol, and sodium borohydride was gradually added.
Chromanol compound. This chromanol compound 1
2.8 g of the spiropyran compound represented by the following formula was obtained by heating 2.8 g together with 4.5 g of anhydrous copper sulfate in a stream of carbon dioxide at 150 to 160 ° C. for 10 minutes, and purifying the brown viscous liquid by chromatography on silica gel. 11.2g
I got

[0111]

Embedded image

The elemental analysis value of this compound was C87.34.
%, H 7.04%, O 5.62%, C ₂₁ H ₂₀ O
Calculated values for C 87.46%, H 6.99%,
This was in very good agreement with O 5.55%. When the proton nuclear magnetic resonance spectrum (FIG. 1) was measured, it was found that δ7.
A peak of 6H based on a naphthalene ring proton around 2 to 8.3 ppm, a peak of 4H based on an alkene proton around δ 5.3 to 6.7 ppm, δ 1.2 to 2.5
A broad peak of 10H based on the proton of the 2-bicyclo [3.3.1] 9-nonenylidene group was shown around ppm. Further, when ¹³ C-nuclear magnetic resonance spectrum was measured, 2-bicyclo [3.3.
1] peak based on carbon of 9-nonenylidene group, δ11
A peak based on the carbon of the naphthalene ring appears around 0 to 160 ppm, and a peak based on the carbon of the alkene appears around δ 80 to 140 ppm. From the above results, it was confirmed that the isolated product was the compound represented by the above structural formula (1).

Example 2 10 g of 1-acetyl-2-naphthol (0.054 mol)
l) and 2-bicyclo [3.3.1] nonen-9-one
16 g (0.06 mol) and morpholine 8.7 g (0.
10 mol) was dissolved in 300 cc of toluene to prepare a solution. The mixture was boiled for 5 hours and the water was separated. After completion of the reaction, toluene was removed under reduced pressure, and the remaining chromanone compound was recrystallized from acetone. Next, this chromanone compound was dissolved in 200 cc of methanol, and lithium aluminum hydride was added to obtain a chromanol compound. 11.9 g of this chromanol compound
170 to 180 with anhydrous copper sulfate in a stream of carbon dioxide.
After heating at 10 ° C. for 10 minutes, the brown viscous liquid was purified by chromatography on silica gel to obtain 20.4 g of a spiropyran compound represented by the following formula.

[0114]

Embedded image

The elemental analysis value of this compound was C87.36.
%, H 7.02%, O 5.62%, and C ₂₁ H ₂₀ O
Calculated values for C 87.46%, H 6.99%,
This was in very good agreement with O 5.55%. Also, when the proton nuclear magnetic resonance spectrum was measured, it was found that δ7.2 to 8.8.
A peak of 6H based on a proton of a naphthalene ring is around 3 ppm, a peak of 4H is around 5.5 to 7.0 ppm of a proton of an alkene, and a 2-bicyclo [3.3.1] is around δ 1.2 to 2.5 ppm. It showed a broad peak at 10H based on the proton of the 9-nonenylidene group. Further, when a ¹³ C-nuclear magnetic resonance spectrum was measured, δ
2-Bicyclo [3.3.1] 9 around 27 to 55 ppm
A peak based on the carbon of the nonenylidene group, δ 110-1
A peak based on carbon of the naphthalene ring around 60 ppm,
A peak based on the carbon of the alkene appears around δ80 to 140 ppm. From the above results, it was confirmed that the isolated product was the compound represented by the above structural formula (2).

Example 3 Chromanone compound represented by the following formula obtained in Example 2
06g

[0117]

Embedded image

(0.01 mol) in anhydrous ether 50c
c, cooled to 0 ° C. and freshly prepared Grignard reagent CH ₃ M in 50 cc of anhydrous ether.
gI (0.012 mol) was added dropwise to the solution over about one hour. After the dropwise addition, the mixture was stirred at room temperature for another 2 hours, then the ether solution was gently poured into cold water, the product was extracted with ether, the solution was dried over magnesium sulfate, and the ether was removed under reduced pressure. The compound was changed to a chromanol compound. Then, the chromanol compound was put together with anhydrous copper sulfate in a stream of carbon dioxide at 200 ° C.
For about 10 minutes, and the brown viscous liquid was purified by chromatography on silica gel to obtain 2.59 g of a spiropyran compound of the following formula.

[0119]

Embedded image

As in Example 2, elemental analysis, measurement of proton nuclear magnetic resonance spectrum and measurement of ¹³ C-nuclear magnetic resonance spectrum confirmed that this compound was the compound represented by the above structural formula (3). . Table 2 shows the elemental analysis values of this compound and the calculated values calculated from the composition formula of compound (3).

Example 4 10 g of 1-acetyl-2-naphthol (0.054 mol)
l), 8.16 g (0.06 mol) of 2-bicyclo [3.3.1] nonen-9-one and 8.7 g of morpholine
(0.10 mol) was dissolved in 300 cc of toluene,
Boil for 15 hours and separate water. After the completion of the reaction, toluene was removed under reduced pressure, and the remaining product was recrystallized from acetone to obtain 11.2 g of a compound represented by the following formula.

[0122]

Embedded image

Then, 11.2 g of this compound was dissolved in 100 cc of methanol and reacted with methyl iodide to obtain 9.6 g of a chromanone compound represented by the following formula.
I got

[0124]

Embedded image

Next, the produced chromanone compound was changed to a chromanol compound in the same manner as in Example 2 and a dehydration reaction was carried out. After separation and purification, 8.7 g of a spiropyran compound of the following formula was obtained.

[0126]

Embedded image

As in Example 2, it was confirmed by an elemental analysis, a proton nuclear magnetic resonance spectrum and a ¹³ C-nuclear magnetic resonance spectrum that this compound was the compound represented by the above structural formula (4). . Table 2 shows the elemental analysis values of this compound and the calculated values calculated from the composition formula of compound (4).

Examples 5 to 30 Various spiropyran compounds were synthesized from the raw materials shown in Table 1 in the same manner as in Examples 1 to 4. However, in the table, Examples 5 to 9 are the same as Example 4, Examples 10 to 25 are the same as Example 1, and Examples 26 to 30 are the examples 3 or 4.
The same was done.

The obtained product was subjected to structural analysis using the same means for structure confirmation as in Example 1, and as a result, it was confirmed that the product was a compound represented by the structural formula shown in Table 1. Table 2 shows the elemental analysis values of this compound, the calculated values obtained from the structural formulas of each compound, and the characteristic absorptions of the infrared absorption spectrum.

[0130]

[Table 1]

[0131]

[Table 2]

[0132]

[Table 3]

[0133]

[Table 4]

[0134]

[Table 5]

[0135]

[Table 6]

[0136]

[Table 7]

[0137]

[Table 8]

[0138]

[Table 9]

[0139]

[Table 10]

[0140]

[Table 11]

Example 31 The compound of the following formula synthesized in Example 1 was used

[0142]

Embedded image

The polymethyl methacrylate was dissolved and decomposed using benzene, and the slide glass (11.2 × 3.7) was used.
cm). The concentration of the compound contained in this film was 1.0 × 10 ⁻⁴ mo
1 / g, and the thickness was adjusted to 0.1 mm.
To this photochromic film, a mercury lamp SHL-100 manufactured by Toshiba Corp.
The film was irradiated for 0 seconds to develop color, and the photochromic properties were measured. The photochromic properties were expressed as follows. The results are shown in Table 3.

Maximum absorption wavelength (λmax): λmax of the color-developing film was determined using a spectrophotometer 220A manufactured by Hitachi, Ltd.

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

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

After light irradiation for a half-life t ^1/2 ; 60 seconds, the absorbance of the film is expressed by Δε (60 seconds) −ε
(0 second) The time required to decrease to 1/2 of｝.

Examples 32 to 60 The photochromic properties of the compounds produced in Examples 2 to 30 were measured in the same manner as in Example 31. The results are shown in Table 3.

For comparison, in Example 1, bicyclo [3.3.1] nonan-9-one was replaced with 0-bicyclo [3.3.1] nonen-9-one as a starting material. Except that 06 mol was used, the following formula was obtained in the same manner as in Example 1.

[0150]

Embedded image

A spirobicyclononane compound represented by the formula (1) was synthesized (yield: 6.9 g), and the photochromic properties of this compound were similarly measured by preparing a film and the results are shown in Table 3.

[0152]

[Table 12]

[Brief description of the drawings]

FIG. 1 is a chart of the ¹ H-nuclear magnetic resonance spectrum of the spiropyran compound obtained in Example 1.

──────────────────────────────────────────────────続 き Continuation of front page (51) Int.Cl. ⁷ Identification symbol FI C09K 9/02 C09K 9/02 B (56) References JP-A-3-11075 (JP, A) JP-A-3-115385 ( JP, A) JP-A-3-133988 (JP, A) JP-A-3-252492 (JP, A) JP-A-3-252493 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) C07D 311/96 C07D 409/04 C07D 417/04 C07D 491/052 C07D 495/04 101 C09K 9/02 CA (STN) CAOLD (STN) REGISTRY (STN)

Claims (2)

(57) [Claims] (1) The following formula: [However, Is a substituted or unsubstituted 2-bicyclo [3.3.1]
A 9-nonenylidene group, Is a substituted or unsubstituted aromatic hydrocarbon group or a substituted or unsubstituted unsaturated heterocyclic group, and R ₁ and R ₂ are
These are the same or different hydrogen atoms, alkyl groups, aralkyl groups, aryl groups and substituted amino groups, respectively. And a spiropyran compound represented by the formula: 2. A photochromic material comprising the spiropyran compound according to claim 1.