JPH06220048A - Sulfonated diarylethene-based compound having conjugated double bond chain - Google Patents

Abstract

PURPOSE:To obtain a new compound excellent in thermal stability, moisture resistance and sensitivity and useful as a light recording material, etc., having good repeated durability of coloring and decoloring and photochromic properties. CONSTITUTION:A compound of formula I [n is 2-5; A is formula II (R<1> and R<2> are alkyl; R<3> to R<6> are H, alkyl, dialkylamino or alkoxy); B is formula III (R<7> is alkyl; R<8> to R<15> are H, alkyl, alkoxy, cyano, nitro, etc.)], e.g. l-(5- methoxy-1,2-dimethyl-3-indolyl)-2-(6-(2-(4-methoxyphenyl)-1-ethenyl)-1 ,1-dioxo-2- methyl-3-benzothienyl)-3,3,4,4,5,5-hexafluorocyclopentene. The compound of formula I is obtained by reacting a compound of formula IV (Y is Br or I) with a compound of the formula ALi to afford a halogenated diarylethene-based compound of formula V, substituting the halogen with a metal and formylating the metal to give a formylated diarylethene-based compound of formula VI and subjecting the resultant compound to Wittig reaction with a phosphonium salt.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a novel diarylethene compound, and more particularly to a diarylethene compound having photochromic properties and suitable for optical recording materials and the like.

[0002]

2. Description of the Related Art Hue is reversibly changed by light irradiation,
So-called photochromic compounds have been known for a long time, and various recording / memory materials, copying materials, light control materials, masking materials, photometers, display materials and the like using these have been proposed. As these photochromic compounds, for example, compounds such as benzospiropyrans, naphthoxazines, fulgides, diazo compounds, and diarylethenes have been proposed. In recent years, vigorous studies have been conducted to utilize such photochromic compounds as reversible optical recording materials, but the following basic performances are required for application to optical recording materials. That is, recording stability, repetitive durability,
Semiconductor laser sensitivity, high sensitivity, etc. However, many of the currently known photochromic compounds are thermally unstable in either the colored state or the decolored state and return to a stable state within a few hours even at room temperature. It has a drawback that the stability cannot be secured. Among them, fulgides and diarylethenes are known as compounds whose two states are relatively thermally stable by irradiation with light, but their stability is still insufficient for use as a recording material. It has one of the drawbacks such as poor repetitive durability, poor sensitivity to semiconductor lasers, and low sensitivity (molecular extinction coefficient), and a photochromic compound that satisfies all performances has not yet been obtained. Is the reality.

[0003]

SUMMARY OF THE INVENTION The present invention has been made in view of the above problems, and its object is to obtain thermal stability in a colored state, repeated durability, semiconductor laser sensitivity, sensitivity ( (EN) A novel diarylethene compound having excellent properties as a photochromic material such as a molecular extinction coefficient).

[0004]

The above-mentioned object is achieved by a sulfonated diarylethene compound having a conjugated double bond chain represented by the following general formula (1).

[Chemical 4] (However, in the formula, n, A and B are the same as above.)

Next, the present invention will be described in detail. The diarylethene compound of the present invention is represented by the above general formula (1), n is an integer of 2 to 5, and has a 4- to 7-membered ring cyclic structure in cooperation with a double bond. Among them, a 5- or 6-membered ring structure in which n is 3 or 4 exhibits particularly preferable photochromic properties. A represents an indolyl group represented by the general formula (2). R ¹ and R ² represent an alkyl group, but a lower alkyl group such as methyl, ethyl or propyl group is preferable.
R ^{3 to} R ⁶ represent a hydrogen atom, an alkyl group, a dialkylamino group or an alkoxy group, and in order to extend the absorption wavelength of the compound to the semiconductor laser oscillation wavelength range, R ³
More preferably, at least one of R ⁶ to R ⁶ is an alkoxy group or a dialkylamino group. B represents a benzothienyl group represented by the general formula (3). R ⁷ represents an alkyl group, and R ^{8 to} R ¹⁵ represent a hydrogen atom, an alkyl group, a dialkylamino group, an alkoxy group, a cyano group or a nitro group.

The diarylethene compound of the present invention can be produced by appropriately selecting from known methods. For example, it can be produced by the following method. That is, the following general formula (4)

[Chemical 5] (However, in the formula, n represents an integer of 2 to 5) and a method of simultaneously reacting the aryllithium derivatives ALi and BLi (A and B are the same as above), or the following general formula (5).

[Chemical 6] (However, in the formula, n and B are the same as above.) As a result, only BLi is reacted to obtain a monoarylethene derivative into which one aryl group is introduced, and then another aryllithium derivative ALi is reacted. Or the following general formula (6)

[Chemical 7] (However, in the formula, Y represents a bromine atom or an iodine atom, and R ⁷
~ R ¹⁰ is the same as above. ) And ALi (A is the same as above) are reacted to give the following general formula (7).

[Chemical 8] (However, in the formula, A, n, R ^{7 to} R ¹⁰ , and Y are the same as above.)
After the halogenated diarylethene compound represented by

[Chemical 9] (However, in the formula, A, n, and R ^{7 to} R ¹⁰ are the same as above.) As the formylated diarylethene compound, there may be mentioned a method of performing Wittig reaction with a predetermined phosphonium salt. The third method is preferable in view of the yield and the versatility of the intermediate. The sulfonation is carried out by reacting a sulfur atom of the benzothiophene ring with a peroxide, and the sulfonated monoarylethene derivative obtained by sulfonation of the general formula (5) is added to another aryl lithium. The derivative ALi is reacted with to form a sulfonated diarylethene compound, or the diarylethene compound represented by the general formula (1) is sulfonated to give a sulfonated diarylethene compound.

The following is an example of a preferred manufacturing method. First, the following general formula (9)

[Chemical 10] (However, in the formula, X and Y represent a bromine atom or an iodine atom,
R ^{7 to} R ¹⁰ are the same as above. ), The benzothienyl dihalide derivative represented by the formula (1) is reacted with an alkyllithium or a lithium dialkylamide at a reaction temperature of −45 to −120 ° C., preferably −70 to −110 ° C., and the halogen atom at the 3-position is replaced with lithium. A lithiated benzothiophene derivative.

As the solvent, ether type solvents such as tetrahydrofuran and diethyl ether are preferably used, but in order to prevent solvent coagulation at low temperature, n-hexane and n-hexane are used.
-Lower alkanes such as pentane may be mixed. Examples of alkyllithium and lithium dialkylamide as lithiating agents include n-butyllithium, t-butyllithium,
Methyllithium, phenyllithium, lithium diisopropylamide, lithium dicyclohexylamide and the like can be mentioned, but a hexane solution of n-butyllithium is preferably used. The amount of the lithiating agent is preferably 1.0 to 1.2 times mol based on the total amount of the halogenated benzothiophene derivative. The reaction time is usually 20 minutes to 3 hours, preferably 30 minutes to 2 hours.

Next, the perfluorocycloalkene derivative represented by the above general formula (4) is added to the produced lithiated benzothiophene derivative. The amount of the perfluorocycloalkene derivative used is that of the halogenated benzothiophene derivative. The molar amount is preferably 1.0 to 1.5 times, and it can be added undiluted or diluted with a solvent.
The reaction temperature is −60 to −110 ° C., and the reaction time is 30 minutes to 2
Time is preferred. After the above operation, the following general formula (10)

[Chemical 11] (However, in the formula, Y represents a bromine atom or an iodine atom, and n,
R ^{7 to} R ¹⁰ are the same as above. The monobenzothienyl ethene derivative shown by these is obtained.

Next, the following general formula (11)

[Chemical 12] (However, in the formula, Z represents a bromine atom or an iodine atom, and R ¹
~ R ⁶ is the same as above. ) Is converted into a lithiated indole derivative in the same manner as described above, and the above-mentioned solution of the monobenzothienylethene derivative in terahydrofuran is added thereto. The amount of the monobenzothienylethene derivative used is halogen. It is preferably used in an amount of 1.0 to 1.2 times the molar amount of the indole derivative. At this time, the reaction temperature is preferably −60 to −110 ° C., and the reaction time is preferably 30 minutes to 2 hours.

As the production method, a monobenzothienylethene derivative represented by the general formula (10) is synthesized from the dihalogenated benzothiophene derivative represented by the general formula (9) as described above, and then this and the general formula (11). In contrast to the route for reacting the halogenated indole derivative represented by the formula (1), first, the halogenated indole derivative represented by the general formula (11) is converted to the following general formula (12).

[Chemical 13] (However, in the formula, n and R ^{1 to} R ⁶ are the same as above.) Even after synthesizing the monoindolylethene derivative, it is reacted with the lithiated benzothiophene derivative represented by the general formula (6). Good.

Thus, the halogenated diarylethene compound represented by the general formula (7) is obtained. The halogen atom of the obtained halogenated diarylethene-based compound represented by the general formula (7) sequentially reacts with the organometallic reagent and the formylating agent in this order to give the formylated diarylethene-based compound represented by the general formula (8). can get. This formylated diarylethene compound is subjected to the Wittig reaction to give the following general formula (13):

[Chemical 14] (However, in the formula, A, n, and R ^{7 to} R ¹⁵ are the same as described above.) A diarylethene compound is obtained.

As the sulfonation method, the monoarylethene derivative represented by the general formula (5) or the diarylethene compound represented by the general formula (1) is treated with hydrogen peroxide, peracetic acid, trifluoroperacetic acid, or a perfluoroacetic acid. Benzoic acid, metachloroperbenzoic acid, t-butyl hydroperoxide,
Dimethyldioxirane, Oxone (Du. Pont
Company) or a method of reacting with an oxidizing agent such as potassium permanganate to sulfonate a sulfur atom, and preferably metachloroperbenzoic acid and dimethyldioxirane are preferably used. The amount of peroxide is preferably 2.0 to 5.0 times mol based on the total amount of sulfur atoms. As the solvent, chlorine-based solvents such as dichloromethane and 1,2-dichloroethane are preferably used. The reaction temperature is -70 to 50 ° C, preferably -20 to 30 ° C.
The reaction time is 1 to 72 hours, preferably 4 to 24 hours. The sulfonated monoarylethene derivative is made into a sulfonated diarylethene derivative by reacting with another aryllithium derivative by the above method. In order to obtain the diarylethene compound from the reaction product obtained by the above method, it may be separated and purified by a method such as extraction, column chromatography, recrystallization and the like.

The diarylethene compound of the present invention is, for example, 1- (5-methoxy-1,2-dimethyl-3-indolyl) -2- (2- (6- (4-methoxyphenyl) -1-). Ethenyl) -1,1-dioxo-2-
Methyl-3-benzothienyl) -3,3,4,4,5,5
An example of 5-hexafluorocyclopentene will be described. In an appropriate medium such as an organic solvent or an appropriate resin binder, as shown by the following formula (14),

[Chemical 15] When the opened ring is irradiated with ultraviolet light, it changes to a closed ring and is colored.
When this closed ring is irradiated with visible light, it returns to the original open ring,
Erase.

An optical recording material using a recording medium containing the diarylethene compound of the present invention can be easily obtained by a known method. For example, a method of depositing the diarylethene compound of the present invention on a suitable substrate by a known vapor deposition method, or a method of depositing the diarylethene compound of the present invention in a polyester resin, polyethylene resin, polyvinyl chloride resin, polyvinyl acetate polyvinyl butyral Resin, polymethylmethacrylic acid resin, polycarbonate resin, phenol resin, resin binder such as epoxy resin, benzene, toluene, xylene, hexane, cyclohexane, methyl ethyl ketone, acetone, methanol, ethanol, tetrahydrofuran, dioxane, carbon tetrachloride, chloroform, Dispersing or dissolving it in a solvent such as cellosolve or diglyme and coating it on a suitable substrate, or dissolving the diarylethene compound of the present invention in a solvent as described above and coating it on a suitable substrate. An optical recording material can be obtained by a method or the like.

In such an optical recording material, the diarylethene compound of the present invention has high thermal stability in both a colored state and a decolored state, is stable to moisture, oxygen and the like and changes its structure for a long period of time. It is retained without being used, and has excellent durability against repeated wear and removal of colors. The maximum absorption wavelength in the colored state is 640n.
Since it exceeds m and the absorption edge is 800 nm or more, 6
It is reversible because it has excellent photochromic characteristics such as sensitivity to semiconductor lasers having an oscillation wavelength of 70 nm or 780 nm and high sensitivity in that wavelength region (having a large molecular absorption coefficient). It can be effectively used for optical information recording materials and the like.

[0017]

INDUSTRIAL APPLICABILITY As described above, the diarylethene compound of the present invention has excellent photochromic properties such as thermal stability, repeated durability of color fading and decoloring, sensitivity to semiconductor laser, sensitivity, etc. It can be used for various purposes such as recording materials. Next, the present invention will be specifically described with reference to examples, but the present invention is not limited thereto.

(Example 1) 1- (5-methoxy-1,2-dimethyl-3-indolyl) -2- (6- (2- (4-methoxyphenyl) -1)
-Ethenyl) -1,1-dioxo-2-methyl-3-benzothienyl) -3,3,4,4,5,5-hexafluorocyclopentene

A) Preparation of 3-bromo-6-iodo-2-methylbenzothiophene 17.7 g of iodine in a 300 ml capacity two-necked flask.
(69.8 mmol) 7.11 g (40.4 m) of iodic acid
mol), sulfuric acid 1.17 ml, acetic acid 69.3 ml, water 2
6.1 ml, carbon tetrachloride 34.2 ml and 3-bromo-2
-Methylbenzothiophene 25.1 g (110 mmo
1) was added, and the mixture was heated to 70 to 80 ° C. and stirred for 48 hours. After the reaction, the reaction solution was saturated aqueous solution of sodium thiosulfate 1
Open to 00 ml and extract 3 times with 200 ml of ethyl acetate,
After washing and drying, the solvent was distilled off under reduced pressure. The obtained reaction product was purified by silica gel column chromatography, and 28.4 g (yield 7) of the compound of the following structural formula (Formula 16)
3.0%) was obtained.

[Chemical 16]

Analytical value: Analytical value: 1) ¹ H-NMR (in CDCl ₃ ) δ (ppm) 2.50 (s 1H) 7.15 to 8.21 (m 1H) 2) MS m / e 353 ( M ⁺ )

B) 1- (6-iodo-2-methyl-3-
Preparation of benzothienyl) -2,3,3,4,4,5,5-heptafluorocyclopentene In a 1000 ml capacity two-necked flask, Example 1-a).
21.2 g (60 mmol) of 3-bromo-6-iodo-2-methylbenzothiophene prepared in (4) and 500 ml of tetrahydrofuran were added, and after cooling to -95 ° C under a nitrogen stream, 45.0 ml of n-butyllithium-hexane solution.
(72 mmol) was added dropwise and stirred for 1 hour. Next, 18.8 g (90 mmol) of perfluorocyclopentene
90 ml of a tetrahydrofuran solution of was added dropwise and reacted for 1 hour. After completion of the reaction, 40 ml of methanol was added to stop the reaction, 200 ml of water was further added, and the mixture was extracted 3 times with 400 ml of ethyl acetate. The organic layers were collected, washed and dried, and the solvent was distilled off under reduced pressure. The obtained reaction product was purified by silica gel column chromatography to give 13.7 g of a compound of the following structural formula (Formula 17) (yield 49.0).
%) Was obtained.

[Chemical 17]

Analytical value: 1) ¹ H-NMR (in CDCl ₃ ) δ (ppm) 2.49 (s 1H) 7.20 to 7.80 (m 2H) 7.90 (s 1H) 2) MS m / E 466 (M ⁺ )

C) 1- (5-Methoxy-1,2-dimethyl-3-indolyl) -2- (6-iodo-2-methyl-3-benzothienyl) -3,3,4,4,4 Production of 5,5-hexafluorocyclopentene In a 1000 ml two-necked flask, 3-bromo-5 was added.
-Methoxy-1,2-dimethylindole 7.48 g
(29.2 mmol) and 320 ml of tetrahydrofuran
And then cooled to −95 ° C. under a nitrogen stream, and then 22.0 ml (35.2 mmo of n-butyllithium-hexane solution).
1) was added dropwise and stirred for 1 hour. Then, Example 1-b)
30 ml of a tetrahydrofuran solution containing 13.7 g (29.2 mmol) of 1- (6-iodo-2-methyl-3-benzothienyl) -3,3,4,4,5,5-heptafluorocyclopentene prepared in 1. Then, it was reacted for 1 hour. After the reaction was completed, 50 ml of methanol was added to stop the reaction, 300 ml of water was further added, and then 400 ml of ethyl acetate was added.
Extract 3 times with ml. The organic layers were collected, washed and dried, and then the solvent was distilled off under reduced pressure. The obtained reaction product was purified by silica gel column chromatography to obtain 8.2 g (yield 46.0%) of a compound represented by the following structural formula (Formula 18).

[Chemical 18]

Analytical value: 1) ¹ H-NMR (in CDCl ₃ ) δ (ppm) 1.95 (s 1H) 2.20 (s
1H) 3.50 (s 1H) 3.69 (s 1H) 6.80 to 7.82 (m 2H) 2) MS m / e 621 (M ⁺ ).

D) 1- (5-Methoxy-1,2-dimethyl-3-indolyl) -2- (6-formyl-2-methyl-3-benzothienyl) -3,3,4,4,5,5 5-
Preparation of Hexafluorocyclopentene 1- (5-methoxy-1,2-dimethyl-3) prepared in Example 1-c) was placed in a 500 ml two-necked flask.
-Indolyl) -2- (6-iodo-2-methyl-3-
Benzothienyl) -3,3,4,4,5,5-hexafluorocyclopentene (8.2 g, 13.6 mmol) and tetrahydrofuran (140 ml) were added to the mixture under a nitrogen stream.
After cooling to 95 ° C, n-butyllithium-hexane solution 1
0.0 ml (16.4 mmol) was added dropwise and stirred for 1 hour. Next, 1.2 g of dimethylformamide (16.4
20 ml of a tetrahydrofuran solution of (mmol) was added dropwise and reacted for 1 hour. After the reaction, methanol 20m
1 to stop the reaction, and after adding 300 ml of water,
It was extracted 3 times with 300 ml of ethyl acetate. The organic layers were collected, washed and dried, and then the solvent was distilled off under reduced pressure. The obtained reaction product was purified by silica gel column chromatography to obtain 6.0 g (yield 82.0%) of a compound represented by the following structural formula (Formula 19).

[Chemical 19]

Analytical value: 1) ¹ H-NMR (in CDCl ₃ ) δ (ppm) 1.95 (s 1H) 2.20 (s
1H) 3.50 (s 1H) 3.69 (s 1H) 6.80 to 7.82 (m 2H) 2) MS m / e 523 (M ⁺ ) 3) IR (KBr) ν (cm ⁻¹ ). 1692 (CHO)

E) 1- (5-Methoxy-1,2-dimethyl-3-indolyl) -2- (6- (2- (4-methoxyphenyl) -1-ethenyl) -2-methyl-3-benzo Production of thienyl) -3,3,4,4,5,5-hexafluorocyclopentene A 2-necked flask having a capacity of 50 ml was charged with 2.0 g of 4-methoxybenzyltriphenylphosphonium chloride (6.0 g).
mmol), 1- (5-methoxy-1,2-dimethyl-3-indolyl) -2-prepared in Example 1-d)
(6-formyl-2-methyl-3-benzothienyl-
1.0 g (2.0 mmol) of 3,3,4,4,5,5-hexafluorocyclopentene, sodium carbonate 1.3
g, formamide 0.4 g, 1,4-dioxane 50 m
1 was added and refluxed at 95 ° C. for 24 hours for reaction. After the reaction, the insoluble matter was filtered off, the solvent of the filtrate was distilled off under reduced pressure, diethyl ether was added to the residue, and the insoluble matter was filtered off. The solvent of the filtrate was evaporated under reduced pressure, and the obtained reaction product was purified by silica gel column chromatography to obtain 0.95 g (yield 76.2%) of a compound represented by the following structural formula (Formula 20).

[Chemical 20]

Analytical value: 1) ¹ H-NMR (in CDCl ₃ ) δ (ppm) 1.98 (s 1H) 2.20 (s
1H) 3.50 (s 1H) 3.68 (s 1H) 3.83 (s 1H) 6.80 to 7.82 (m 2H) 2) MS m / e 627 (M ⁺ ).

F) 1- (5-Methoxy-1,2-dimethyl-3-indolyl) -2- (6- (2- (4-methoxyphenyl) -1-ethenyl) -1,1-dioxo-2
-Methyl-3-benzothienyl) -3,3,4,4
Production of 5,5-hexafluorocyclopentene 1- (5-methoxy-1,2-dimethyl-3 produced in Example 1-e) in a 200 ml capacity two-necked flask.
-Indolyl) -2-((6- (4-methoxyphenyl) -1-ethenyl) -2-methyl-3-benzothienyl) -3,3,4,4,5,5-hexafluorocyclopentene 0.95 g (1.5 mmol) was dissolved in 75 ml of dichloromethane, and 1.1 g (4.5 mmol) of 70% metachloroperbenzoic acid was added to dichloromethane 15 under ice cooling.
After dropwise adding ml, the mixture was returned to room temperature and stirred for 12 hours.
After the reaction, the solution was washed with a saturated aqueous solution of sodium hydrogen sulfite, a saturated aqueous solution of sodium hydrogencarbonate and a 1N aqueous sodium hydroxide solution, and then the organic layers were collected, dried and the solvent was distilled off. The obtained reaction product was purified by silica gel column chromatography to obtain 0.61 g (yield 62.0%) of a compound represented by the following structural formula (Formula 21).

[Chemical 21]

Analytical value: 1) ¹ H-NMR (in CDCl ₃ ) δ (ppm) 2.06 (s 1H) 2.07 (s
1H) 3.55 3.60 (s 1H cis, trans isomer) 3.79 3.80 (s 1H cis, trans isomer) 3.83 3.85 (s 1H cis, trans isomer) 6.30 ˜7.61 (m 4H cis, trans isomer) 2) MS m / e 659 (M ⁺ ) 3) IR (KBr) ν (cm ⁻¹ ) 1304 (SO ₂ )

Example 2 1- (5-Methoxy-1,2-dimethyl-3-indolyl) -2- (6- (2- (4-cyanophenyl) -1-)
Ethenyl) -1,1-dioxo-2-methyl-3-benzothienyl) -3,3,4,4,5,5-hexafluorocyclopentene a) 1- (5-methoxy-1,2-dimethyl) -3-Indolyl) -2- (6- (2- (4-cyanophenyl)-
1-ethenyl) -2-methyl-3-benzothienyl)-
Production of 3,3,4,4,5,5-hexafluorocyclopentene In the item e) of Example 1, 4-cyanobenzyltriphenylphosphonium bromide was used instead of 4-methoxybenzyltriphenylphosphonium chloride. Using the same method, a diarylethene compound represented by the following structural formula (Formula 22) was obtained. Yield 0.9 g (Yield 84.0
%).

[Chemical formula 22]

Analytical value: 1) ¹ H-NMR (in CDCl ₃ ) δ (ppm) 1.98 (s 1H) 2.23 (s
1H) 3.51 (s 1H) 3.66 (s 1H) 6.79 to 7.61 (m 4H) 2) MS m / e 622 (M ⁺ ) 3) IR (KBr) ν (cm ⁻¹ ). 2221 (CN)

B) 1- (5-methoxy-1,2-dimethyl-3-indolyl) -2- (6- (2- (4-cyanophenyl) -1-ethenyl) -1,1-dioxo-2 −
Methyl-3-benzothienyl) -3,3,4,4,5,5
Production of 5-hexafluorocyclopentene In the item f) of Example 1, 1- (5-methoxy-1,2)
-Dimethyl-3-indolyl) -2- (6- (2- (4
-Methoxyphenyl) -1-ethenyl) -2-methyl-
3-benzothienyl) -3,3,4,4,5,5-hexafluorocyclopentene instead of a) in Example 2
1- (5-methoxy-1,2-dimethyl-3 produced by
-Indolyl) -2- (6- (2- (4-cyanophenyl) -1-ethenyl) -2-methyl-3-benzothienyl) -3,3,4,4,5,5-hexafluorocyclopentene Using the same method, a diarylethene compound having the following structural formula (Formula 23) was obtained. Yield 0.51g
(Yield 56.2%).

[Chemical formula 23]

Analytical value: 1) ¹ H-NMR (in CDCl ₃ ) δ (ppm) 2.09 (s 1H) 2.13 (s
1H) 3.56 3.58 (s 1H cis, trans isomer) 3.61 3.64 (s 1H cis, trans isomer) 6.57 to 8.00 (m 4H cis, trans isomer) 2) MS m / e 654 (M ⁺ ) 3) IR (KBr) ν (cm ^-1 ) 1125, 1305 (SO ₂ ) 2225
(CN)

(Example 3) 1- (5-methoxy-1,2-dimethyl-3-indolyl) -2- (6- (2- (4-nitrophenyl) -1-)
Ethenyl) -1,1-dioxo-2-methyl-3-benzothienyl) -3,3,4,4,5,5-hexafluorocyclopentene a) 1- (5-methoxy-1,2-dimethyl) -3-Indolyl) -2- (6- (2- (4-nitrophenyl)-
1-ethenyl) -2-methylbenzothienyl) -3,
Production of 3,4,4,5,5-hexafluorocyclopentene In the item e) of Example 1, 4-nitrobenzyltriphenylphosphonium chloride was used instead of 4-methoxybenzyltriphenylphosphonium chloride. A diarylethene compound represented by the following structural formula (Formula 24) was obtained by the same method. Yield 1.2 g (Yield 99.0
%).

[Chemical formula 24]

Analytical value: 1) ¹ H-NMR (in CDCl ₃ ) δ (ppm) 1.99 (s 1H) 2.23 (s
1H) 3.50 3.52 (s 1H cis, trans isomer) 3.67 3.68 (s 1H cis, trans isomer) 6.50-8.21 (m 4H cis, trans isomer) 2) MS m / e 642 (M ⁺ ) 3) IR (KBr) ν (cm ^-1 ) 1341, 1515 (NO ₂ )

B) 1- (5-methoxy-1,2-dimethyl-3-indolyl) -2- (6- (2- (4-nitrophenyl) -1-ethenyl) -1,1-dioxo-2 −
Methyl-3-benzothienyl) -3,3,4,4,5,5
Production of 5-hexafluorocyclopentene In the item f) of Example 1, 1- (5-methoxy-1,2)
-Dimethyl-3-indolyl) -2- (6- (2- (4
-Methoxyphenyl) -1-ethenyl) -2-methyl-
3-benzothienyl) -3,3,4,4,5,5-hexafluorocyclopentene instead of a) in Example 3
1- (5-methoxy-1,2-dimethyl-3 produced by
-Indolyl) -2-((6- (4-nitrophenyl)
-1-Ethenyl) -2-methyl-3-benzothienyl)
Using -3,3,4,4,5,5-hexafluorocyclopentene, a diarylethene compound represented by the following structural formula (Formula 25) was obtained in the same manner. Yield 0.64 g (yield 51.0%).

[Chemical 25]

Analytical value: 1) ¹ H-NMR (in CDCl ₃ ) δ (ppm) 2.09 (s 1H) 2.14 (s
1H) 3.56 3.59 (s 1H cis, trans isomer) 3.77 3.85 (s 1H cis, trans isomer) 6.62-8.29 (m 4H cis, trans isomer) 2) MS m / e 674 (M ⁺ ) 3) IR (KBr) ν (cm ^-1 ) 1126, 1307 (SO ₂ ) 134
4,1519 (NO ₂ )

Example 4 Measurement of Absorption Spectra The compounds obtained in Examples 1, 2 and 3 were added to benzene at 5.5 × 10 ⁻⁵ mol / l and 6.3 × 10 ⁻⁵ mol, respectively.
/ L, 6.2 x 10 ^-5 mol / l to obtain a solution obtained by dissolving, and put into a 1 cm x 1 cm x 4 cm quartz glass cell. Using a 100 W ultra-high pressure mercury lamp equipped with a glass filter, a 365 nm light was emitted while stirring.
After irradiating for 0 minutes to color the solution, the absorption spectrum of the solution in the photo steady state was measured. Example 1,
For the compound obtained in a few steps, at 365 nm light,
The absorption spectra of the saturated colored product and the decolorized product are shown in FIGS. The absorption maximum of the absorption spectrum of the compound obtained in Example 1 in the saturated coloring state with light of 365 nm is 643 nm, the absorption edge reaches 800 nm, and the molecular absorption coefficient of the compound at the maximum absorption position is ε = 1.
It showed a high value of 6,800. Further, this coloration / decoloration reaction could be carried out reversibly. Next, regarding the compounds of Examples 1, 2, and 3, the absorption maximum wavelength (λmax) of the colored body and the molecular absorption coefficient (ε · λmax) of the compound at this maximum wavelength are shown.
) Is shown in Table 1.

[0040]

[Table 1]

As described above, by introducing a methoxy group into the indole ring, and by introducing a conjugated double bond chain and a sulfone structure into the benzothiophene ring, the absorption maximum wavelength of the colored body becomes longer, and the oscillation wavelength is 670 nm, or A semiconductor laser sensitivity of 780 nm was imparted. Furthermore, by introducing a conjugated double bond chain into this benzothiophene ring, the molecular extinction coefficient of the compound could be increased.

[Brief description of drawings]

FIG. 1 is a graph showing changes in absorption spectrum of the compound obtained in Example 1 upon light irradiation in a benzene solution.

FIG. 2 is a graph showing changes in absorption spectrum of the compound obtained in Example 2 upon irradiation with light in a benzene solution.

FIG. 3 is a graph showing a change in absorption spectrum of the compound obtained in Example 3 upon light irradiation in a benzene solution.

Claims (1)

[Claims] 1. A sulfonated diarylethene compound having a conjugated double bond chain represented by the following general formula (1). [Chemical 1] (However, in the formula, n represents an integer of 2 to 5. A is a general formula (2) R ¹ and R ² represent an alkyl group, and R ^{3 to} R ⁶ represent a hydrogen atom, an alkyl group, a dialkylamino group or an alkoxy group. B is represented by the general formula (3): R ⁷ represents an alkyl group, R ^{8 to} R ¹⁵ represent a hydrogen atom, an alkyl group, a dialkylamino group, an alkoxy group,
Represents a cyano group or a nitro group. )