JPH0311075A - Spiropyran compound and production thereof - Google Patents

Abstract

NEW MATERIAL:A spiropyran compound expressed by formula I [formula II is substituted or unsubstituted bicyclo[3,3,1]9-nonylidene group; formula III is substituted or unsubstituted aromatic hydrocarbon group or substituted or unsubstituted unsaturated heterocyclic group; R1 and R2 each are homologous or heterologous H, alkyl, aralkyl, aryl or substituted amino]. EXAMPLE:A compound expressed by formula IV. USE:Useful as a photochromic material, utilized as recording material, such as various memorizing materials, copying materials or printing photosensitive substances, substitute for silver salt photosensitive materials and usable as a material, such as optical filter or display material. The above-mentioned compound is colorless and transparent and capable of rapidly coloring by irradiation with sunrays or ultraviolet rays and quickly fading by shutting off the rays. PREPARATION:A compound expressed by formula V is reacted with a compound expressed by formula VI in the presence of a primary or secondary amine to afford the compound expressed by formula I.

Description

Detailed Description of the Invention (Industrial Application Field) The present invention is characterized in that it changes from a colorless form to a colored or darkly colored form when exposed to sunlight or light containing ultraviolet rays such as light from a mercury lamp, and the change is reversible. This invention relates to a new spiropyran compound that exhibits excellent durability.

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

JP-A-63-66178 describes spiroadamantane compounds in which an adamantylidene group is present at the 2-position of a benzobylane ring or a naphthopyran ring. These spiroadamancun compounds are produced at around room temperature (
It is a compound that exhibits photochromic properties even at temperatures of 10 to 40°C, and is generally known to change color from colorless to yellow to orange. However, these spiroadamancune compounds are relatively stable in colored form and do not fade very quickly due to ambient temperature, probably due to their bulky adamantylidene groups.

(Means for Solving the Problems) As a result of intensive research to further improve the photochromic properties of the above-mentioned compounds, the present inventors succeeded in synthesizing a novel spiropyran compound. It was discovered that the color fading rate is fast, and the present invention was completed.

That is, the present invention provides - Formula (1) [However, CBn is a substituted or unsubstituted bicyclyl group or a substituted or unsubstituted unsaturated heterocyclic group,
R and R2 are the same or different hydrogen atoms, alkyl groups, aralkyl groups, aryl groups, or substituted amino groups, respectively. ] This is a spiropyran compound represented by

In the above-mentioned formula (1), the group represented by an C represents an ``N----bicyclo(3,3,1)9-nonylidene group 9-nonylidene group. Specific examples of the substituent include, for example,
Hydroxy group; substituted amino groups such as methylamino group and diethylamino group; methoxy group, ethoxy group, tert-
Alkoxy groups with 1 to 4 carbon atoms such as butoxy groups; aralkoxy groups with 7 to 15 carbon atoms such as benzyloxy groups; aryloxy groups with 6 to 14 carbon atoms such as phenoxy groups and ■-naphthoxy groups; methyl groups, ethyl lower alkyl groups having 1 to 4 carbon atoms such as t-butyl groups; halogen atoms such as fluorine, chlorine, and oxaline; cyano groups; carboxyl groups; alkoxycarbonyl groups having 2 to 10 carbon atoms such as ethoxycarbonyl groups; 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; a benzyl group or a phenylethyl group;
Examples include aralkyl groups such as phenylpropyl groups,
Furthermore, these substituents are not only included as single substituents, but may also be included as polysubstituted products having two or more substituents (furthermore, substituents in polysubstituted products may be of the same type). However, there is no problem even if the substituent is of a different type, and the position of the substituent can be changed depending on the preference or use.

It 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 groups consisting of one benzene ring or 2 to 4 condensed rings thereof, such as phenylene group, naphthylene group, phenanthrylene group, tolylene group, and xylylene group. Examples include hydrocarbon groups, and the above aromatic hydrocarbon groups include alkoxy groups, hydroxyl groups, nitro groups,
Lists substituted aromatic hydrocarbon groups substituted with one or more heterocyclic groups such as cyano group, trifluoromethyl group, substituted amino group, halogen atom, phenyl group, or thienyl group, furyl group, or pyrrolyl group. Examples of the unsaturated heterocyclic group include a 5-membered ring or 6-membered ring containing oxygen, sulfur, or nitrogen atoms, or a heterocyclic group in which a benzene ring is fused to these rings. Specifically, they include nitrogen-containing heterocyclic groups such as pyridylene group, quinorylene group, and pyrrolylene group; oxygen-containing heterocyclic groups such as furylene group and pensifrylene group; and sulfur-containing heterocyclic groups such as chenylene group and benzothhenylene group. Furthermore, substituted unsaturated heterocyclic groups in which these unsaturated heterocyclic groups are substituted with the substituents mentioned above in the explanation of the aromatic hydrocarbon group,
In the present invention, it is adopted without any restriction.

Furthermore, in the formula (1) above, the groups represented by R+ and R2 are the same or different hydrogen atoms, alkyl groups, aralkyl groups, aryl groups, or substituted amino groups, respectively.

The alkyl group mentioned above 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 carbon atoms.
．． Preferably, those of 1 to 4 are suitable.

More specific examples of these alkyl groups and aralkyl groups include methyl, ethyl, propyl, methyl, benzyl, phenylethyl, phenylpropyl, and phenylbutyl groups.

- Also, as the aryl group, for example, phenyl group, tolyl group, xylyl group, naphthyl group, etc. are suitable.

Furthermore, in the above-mentioned formula (1), the groups R1 and R2 are:
Either one of R1 and R4 is a hydrogen atom and the other is an alkyl group, or each represents the same or different alkyl group. The alkyl group is not particularly limited, but specifically, the same groups as the above-mentioned examples of the alkyl group can be employed. Furthermore, R3 is an alkylene group having 3 to 6 carbon atoms such as a tetramethylene group or a pentamethylene group; -CHzCHOCHz CHtOC
HtCHz-CB.

CHzCHzOCHzCHz -C)lzo(CH
z) Oxyalkylene group having 3 to 6 carbon atoms such as 3-1; C) lzscHzcHz -CHzS(CHz)
C3-6 thioalkylene group such as z-1CHzGHzSC)IzGHz-; CHJCHzCIb-C)l,
C8゜-CI4zN(CHz)s-CIZCH2NC71□C
Azoalkylene groups having 3 to 6 carbon atoms such as I□- are preferably employed.

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

(a) Proton nuclear magnetic resonance spectrum (II'-NMR)
), it is possible to know the type and number of protons present in the molecule. That is, 67-8.
A peak based on aromatic protons is located around 5 ppm, and a peak based on bicyclo (3
, 3, 1) Broad peak based on protons derived from 9-nonylidene group, 65.5-7. when R+ and Rz are hydrogen atoms. A peak based on alkene protons appears near Oppm. Furthermore, by relatively comparing the respective δ peak intensities, the number of protons of each bonding group can be determined.

(IT) Carbon, hydrogen, nitrogen, sulfur,
Each weight percent of halogen can be determined. Furthermore, by subtracting the sum of the weight percent of each recognized element from 100, the! of oxygen! Amount % can be calculated. Therefore,
The composition of the corresponding product can be determined.

(c) 13C-Nuclear Magnetic Resonance Spectrum C''C-NMR)
By measuring , the type of carbon present in the molecule can be determined. A peak derived from the carbon of the bicyclo(3,3,1)9-nonylidene group near δ227-52pp, 615 to 615 when R3 and R7 are alkyl groups
A peak based on the carbon of the alkyl group near 35 ppm, δ
1) A peak based on carbon of an aromatic hydrocarbon group or an unsaturated heterocyclic group appears around 0 to 150 ppn+.

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

General formula (II) below CH.

The compound represented by the general formula (III) is a (3,3,1)9-nonylidene group. ) in the presence of a primary amine or a secondary amine, R1 or R in formula (1)
A compound can be obtained in which 2 is a hydrogen atom or a substituted amino group, and at least one of them is a substituted amino group.

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

The reaction temperature is usually preferably θ to 200°C, and the solvent used is a polar aprotic solvent such as N-methylpyrrolidone, dimethylformamide, toluene, benzene ζtetrahydrofuran, or the like. In this reaction,
The condensing agent represented by primary amines such as N-ethylamine and N-propylamine or secondary amines such as pyrrolidine, piperidine and morpholine is usually 0.1 to 1 mol per mole of the compound represented by the general formula (If). It is used in an amount of 10 mol, and the reaction can be completed by removing water generated during the reaction. Two ways to remove water are to use a Dean-Stark device to remove water from the reaction system, and to add calcium chloride, calcium oxide, and zinc chloride to the reaction system and use these dehydrating agents to remove water from the reaction system. There are ways to remove the water that forms inside, and any of these methods may be used.

This reaction is similar to the following formula (IV). ] A chromanone compound represented by the following is obtained. Then, if the above reaction is continued further, in the above-mentioned formula (1), R
, or R2 is the same as the following formula (V) in which at least one is a substituted amino group, and R1 and R2 are the same or different hydrogen atoms or substituted amino groups, and at least one of them is a substituted amino group. ] A compound represented by the following is obtained.

The compound in which R+ and R2 are both hydrogen atoms in formula (I) above can be obtained by reacting the chromanone compound represented by (IV) above with a reducing agent such as sodium borohydride or lithium aluminum hydride. The reaction with any organometallic compound of the following formula is the same as the following formula. ] A chromanol compound represented by is obtained and then dehydrated using a dehydrating agent such as anhydrous copper sulfate to obtain the same formula as the following formula. ] A compound represented by the following is obtained.

In the above-mentioned formula (1), the compound in which R1 is an alkyl group, an aralkyl group, or an aryl group is a compound represented by the above-mentioned formula (IV).
The chromanone compound represented by is the same as an alkylmagnesium halide or an alkyllithium halide, and R1 is
These are an alkyl group, an aralkyl group, and an aryl group. ] By obtaining a chromanol compound represented by the following and then dehydrating it using a dehydrating agent such as anhydrous copper sulfate, the following formula is obtained, and R1 is an alkyl group, an aralkyl group, or an aryl group. ] A compound represented by the following is obtained.

Further, in the above-mentioned formula (I), R2 is an alkyl group,
Compounds having an aralkyl group or an aryol group are the above-mentioned (V
) is reacted with a halogenated alkyl, a halogenated aryl, or a halogenated aralkyl to form the following formula (Vl) group, an aryl group. ] A chromanone compound represented by is obtained, reduced with a reducing agent in the same manner as described above, and further dehydrated with a dehydrating agent to obtain the following formula, where R is an alkyl group, an aralkyl group, or an aryl group. It is the basis. ] A compound represented by the following is obtained. Furthermore, by reacting the chromanone compound represented by (Vl) above with an organometallic compound such as alkylmagnesium halide in the same manner as described above, and then dehydrating it using a dehydrating agent, the following formula is obtained, and R2 is Alkyl group and aralkyl are the same, R1 and R2 are respectively the same or different alkyl groups,
They are an aralkyl group and an aryl group. ] A compound represented by the following is obtained.

The spiropyran compound of the present invention represented by the above formula (1) is well soluble in common organic solvents such as toluene, chloroform, and tetrahydrofuran.

When the spiropyran compound represented by the general formula (1) is dissolved in such a solvent, the solution is generally almost colorless and transparent, but when exposed to sunlight or ultraviolet light, it quickly changes color or darkens, and when the light is blocked, the solution becomes almost colorless and transparent. It exhibits a good reversible photochromic effect that quickly returns to its original colorless state. Such a photochroming effect in the compound of formula (1) also occurs in a polymeric solid matrix, and the reversible speed occurs on the order of seconds. As such a target polymer matrix, -a formula (1
) can be uniformly dispersed, and optically preferable examples include polymethyl acrylate, polyethyl acrylate, polymethyl methacrylate, polyethyl methacrylate, polystyrene, polyacrylonitrile, and polyvinyl. Polymers such as alcohol, polyacrylamide, poly(2-hydroxyethyl methacrylate), polydimethylsiloxane, polycarbonate, poly(allyl diglycol carbonate), or the monomers forming these polymers, may be used together or with other monomers. Polymers formed by polymerization are preferably used.

The photochromic action of the spiropyran compound of the present invention is particularly superior in fading speed compared to conventional spiroadamantane compounds.

Therefore, the spiropyran compound of the present invention can be widely used as a photochromic material, such as various storage materials in place of silver salt photosensitive materials, copying materials, photoreceptors for printing, recording materials for cathode ray tubes, photosensitive materials for lasers, etc. It can be used as various recording materials such as photosensitive materials for holography. In addition, the photochromic material using the spiropyran compound 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 the method provides uniform light control performance.A specific example is a polymer film formed by uniformly dispersing the photochromic material of the present invention. How to sandwich it into a lens, or
For example, by dissolving this compound in silicone oil,
There is a method in which the lens surface is impregnated at 0 to 200° C. for 10 to 60 minutes, and the surface is further coated with a curable substance to form a photochromin 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.

When acting on such photochromic lenses, it is preferable to use a photochromic material that develops a deep color when exposed to sunlight at room temperature. Preferred compounds for such photochromic lenses include the general threne group, pyridylene group,
It is a compound that is a quinolylene group. Among others, R, and R2
A compound in which both are hydrogen atoms has the advantage of developing a particularly deep color and fading quickly.

Further, by selecting R2 or each substituent of R2 in the above-described general formula (I), the fading rate of the compound represented by formula (1) can be changed. For example, when R1 and R8 are alkyl groups, a fast color fading rate can be obtained, probably because it becomes difficult to take the trans form of the coloring state. Furthermore, when R1 is a substituted amino group, the trans form in the coloring state is stabilized by resonance, and while a high coloring density can be obtained, the fading rate is a little slow. Each of these substituents of R1 and R2 can be arbitrarily selected depending on the purpose.

〔effect〕

The spiropyran compound represented by the general formula (1) of the present invention is
In a solid polymer matrix, the type of matrix does not affect the color of the matrix; - it is stable and colorless when fishing on a boat, but it immediately develops color when exposed to ultraviolet rays; It has the property of returning to its original colorless state at a fast fading rate of the order of seconds when it is discontinued, and repeating these discolorations with good durability.

〔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 10 g of 1-hydroxy-2-acetonaphthone (0,05
4 mojrito bicyclo(3,3,1)nonan-9-one 8.29 g (0.06 mol) and pyrrolidine 8 g
(0,1)3mol) was dissolved in 300cc of toluene to prepare a solution. The mixture was boiled for 10 hours and the water was separated. After the reaction is complete, toluene is 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.
It was made into a chromanol compound. This chromanol compound 7
．． Spiropyran compound 6 of the following formula was obtained by heating 47 g with 4.5 g of anhydrous copper sulfate at 150-160°C for 10 minutes in a carbon dioxide stream and purifying the brown viscous liquid by chromatography on silica gel. .9g
I got it.

The elemental analysis value of this compound is C86,78% R7,6
4% 05.58%, calculated value for Cz+Hi□O CB 6.90%, R7,59% 05
．． There was a very good agreement of 52%. In addition, when we measured the proton nuclear magnetic resonance spectrum (Fig. 1), we found that δ7.2
A peak of <6H based on the proton of the naphthalene ring around 8.3 ppm, a peak of <2H based on the proton of the alkene around 65.6 to 6.7 ppm, a peak of <2H based on the proton of the alkene around 65.6 to 6.7 ppm, 61.2 to 2.
A broad peak of < 14 H based on the proton of the bicyclo(3,3,1)9-nonylidene group was shown around 5 ppm. Furthermore, when I″C-nuclear magnetic resonance spectrum was measured, bicyclo(3,3,
1) Peak based on carbon of 9-nonylidene group, 61) 0
A peak based on the carbon of the naphthalene ring appears around ~160 ppm, and a peak based on the carbon of the alkene appears around δ80~1)0pp....

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

Example 2 1-acetyl-2-naphthol 10 g (0,054
mol) and bicyclo(3,3,1)nonan-9-one8
．． 29 g (0.06n + ojrito morpholine 8.7
g (0.10 mol) was dissolved in 300 cc of toluene to prepare a solution. Boil this mixture for 5 hours,
Water was separated. After the reaction was completed, toluene was removed under reduced pressure, and the remaining chromanone compound was recrystallized with acetone.
Next, this chromanone compound was mixed with 200 cc of methanol.
by adding lithium aluminum hydride,
It was made into a chromanol compound. This chromanol compound 6
．． 49 g with anhydrous copper sulfate in a stream of carbon dioxide.
After heating at 0-180° C. for 10 minutes, the brown viscous liquid was purified by chromatography on silica gel to obtain 5.8 g of spiropyran compound of the following formula.

The elemental analysis values of this compound are C86,81%, H7,6
2%, 05.57%, and the calculated values for Cz+HzO are C 86.90%, H7, 59%, 05.
There was a very good agreement of 52%. In addition, when proton nuclear magnetic resonance spectra were measured, 67.2 to 8.3 p
<6H peak based on the proton of the naphthalene ring near pm, 66.0~? , <2H peak based on alkene proton near Oppts, δ1.2-2,5 ppm
A broad peak of 14H based on the proton of the bicyclo(3,3,1)9-nonylidene group was shown nearby. moreover,
When 13G-nuclear magnetic resonance spectrum was measured, 62
Peak based on carbon of bicyclo(3,3,1)9-nonylidene group near 7-55ppai, 61) 0-160p
Peak based on carbon of naphthalene ring near pm, 680
~1) A peak based on the carbon of the alkene appears near 0 ppm. From the above results, it was confirmed that the isolated product was a compound represented by the above structural formula (2).

Example 3 Chromanone compound represented by the following formula obtained in Example 2 3.
06 g (dissolve 0.01 mon in 50 cc of anhydrous ether,
Cool the solution to 0 °C and add freshly prepared Grignard reagent CLMgl (0,01
2 moj of water was added dropwise into the solution over a period of about 1 hour.
After the addition was completed, the ether solution was stirred for another 2 hours at room temperature, the ether solution was gently poured into cold water, the product was extracted with ether, the solution was dried over magnesium sulfate, the ether was removed under reduced pressure, and the chromanone The compound was changed to a chromanol compound. This chromanol compound was then heated 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 form a spiropyran compound of the following formula 2.
47g was obtained.

8.48g of the compound represented by the following formula
I got it.

As in Example 2, by elemental analysis, proton nuclear magnetic resonance spectrum, and C-nuclear magnetic resonance spectrum measurements,
This compound was confirmed to be a 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 compositional formula of compound (3).

Example 4 1-acetyl-2-naphthol 10 g (0,054
wo1) and bicyclo(3,3,1)nonan-9-one 8
．． 29 g (0,06++offi) and morpholine 8
．． 7 g (0,10+wo1) was dissolved in 300 cc of toluene, boiled for 15 hours, and water was separated. After the reaction, toluene was removed under reduced pressure, and the remaining product was acetate. Then, 8.48 g of this compound was dissolved in 100 cc of methanol and reacted with methyl iodide to obtain 7.83 g of a chromanone compound represented by the following formula.

Next, the produced chromanone compound was changed into a chromanol compound in the same manner as in Example 2, and a dehydration reaction was carried out. After separation and purification, a spiropyran compound 6.5 of the following formula was obtained.
8 g was obtained.

The elemental analysis value of the compound (4) and the calculated value calculated from the compositional formula of compound (4) are shown.

Examples 5-30 Various spiropyran compounds were synthesized from the raw materials shown in Table 1 in the same manner as in Examples 1-4. However, in Table 1, Examples 5 to 9 were conducted in the same manner as Example 4, Examples 10 to 25 were conducted in the same manner as Example 1, and Examples 26 to 30 were conducted in the same manner as Example 3 or 4. Ta.

As a result of structural analysis of the obtained product using the same structural confirmation method as in Example 1, it was confirmed that it was a compound represented by the structural formula shown in Table 1. Further, Table 2 shows the elemental analysis values of this compound and the calculated values obtained from the structural formula of each compound.

As in Example 2, it was confirmed by elemental analysis, proton nuclear magnetic resonance spectrum, and 13C-nuclear magnetic resonance spectrum that this compound was a compound represented by the above structural formula (4). Table 2 Example 31 The compound of the following formula synthesized in Example 1 was dissolved and decomposed in polymethyl methacrylate using benzene, and the mixture was prepared using a slide glass (Li, 2 x 3.7 cm).
) to make a cast film. The concentration of the above compound contained in this film is 1.0×101)01
/ g, and the thickness was adjusted to 0.1 mm. A mercury lamp 5HL-100 manufactured by Toshiba ■ was placed on this photochromic film at a distance of 10 cm at 25°C ± 1°C.
The film was irradiated for a second to develop color, and its photochromic properties were measured. The photochromic properties were expressed as follows. The results are shown in Table 3.

The maximum absorption wavelength (λ*sx); ■λ□ of this color-forming film was determined using a spectrophotometer 22OA manufactured by Hitachi.

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

ε (0 seconds); at the maximum absorption wavelength during light irradiation”
, absorbance of unirradiated film.

Half-life tI/2B Time required for the absorbance of this film to decrease to (ε (60 seconds) ε (0 seconds)) after light irradiation for 5Q seconds.

Examples 32-60 The photochromic properties of the compounds produced in Examples 2-30 were measured in the same manner as in Example 31, and the results are shown in Table 3. For comparison, a film was similarly prepared and measured for the photochromic properties of the spiroadamancune compound shown in (31) below.

[Brief explanation of drawings]

Figure 1 shows the L of the spiropyran compound obtained in Example 1.
It is a chart of H-nuclear magnetic resonance spectrum.

Claims (4)

[Claims] (1) The following formula ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [However, ▲There are mathematical formulas, chemical formulas, tables, etc.▼ is a substituted or unsubstituted bicyclo[3,3,1]9-nonylidene group, ▲There are mathematical formulas, chemical formulas, tables, etc.▼ is a substituted or unsubstituted aromatic hydrocarbon group or a substituted or unsubstituted unsaturated heterocyclic group, and R_1 and R_2 are the same or different hydrogen atoms, respectively. It is an alkyl group, an aralkyl group, an aryl group or a substituted amino group. ] A spiropyran compound represented by (2) 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 or a substituted or unsubstituted unsaturated heterocycle It is the basis. ] Compounds represented by the general formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [However, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ is substituted or unsubstituted bicyclo[3,3,1]9-nonylidene It is the basis. ] with a primary amine or a secondary amine.
The following formula, which is characterized by reacting in the presence of an amine, includes mathematical formulas, chemical formulas, and tables. 1] 9-nonylidene group, ▲ has a numerical formula, chemical formula, table, etc. ▼ is a substituted or unsubstituted aromatic hydrocarbon group or a substituted or unsubstituted unsaturated heterocyclic group, R_1 and R_2 are, They are the same or different hydrogen atoms or substituted amino groups, respectively, and at least one of them is a substituted amino group. ] A method for producing a spiropyran compound shown by. (3) 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 or a substituted or unsubstituted unsaturated heterocycle It is the basis. ] Compounds represented by the general formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [However, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ is a substituted or unsubstituted bicyclo[3,3,1]9-nonylidene group It is. ] is reacted with the compound shown in the presence of a condensing agent to produce the general formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [However, ▲ There are mathematical formulas, chemical formulas, tables, etc. [3,3,1] is a 9-nonylidene group, and ▲ has a numerical formula, chemical formula, table, etc. ▼ is a substituted or unsubstituted aromatic hydrocarbon group or a substituted or unsubstituted unsaturated heterocyclic group. ] The following formula, which is characterized by obtaining a compound represented by, then reducing this compound, and further dehydrating it ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [However, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ is a substituted or unsubstituted bicyclo[3,3,1]9-nonylidene group, and ▲ has a numerical formula, chemical formula, table, etc. ▼ is a substituted or unsubstituted aromatic hydrocarbon group or a substituted or unsubstituted unsubstituted It is a saturated heterocyclic group, and R_1 and R_2 are hydrogen atoms. ] A method for producing a spiropyran compound shown by. (4) A photochromic material comprising a spiropyran compound according to claim (1).