JP2711212B2 - Diarylethene compound having conjugated double bond chain and optical recording / reproducing method for optical recording medium using this diarylethene compound - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a diarylethene compound having photochromic properties and suitable for an optical recording material and the like, and a method for optically recording / reproducing an optical recording medium using the diarylethene compound.

[0002]

2. Description of the Related Art Hue changes reversibly by light irradiation.
So-called photochromic compounds have been known for a long time, and various types of recording / memory materials, copying materials, light control materials, masking materials, photometers, display materials, and the like using these compounds have been proposed. As these photochromic compounds, for example, compounds such as benzospiropyranes, naphthoxazines, fulgides, diazo compounds, and diarylethenes have been proposed. In recent years, research has been energetically made to use such a photochromic compound as a reversible optical recording material. However, application to an optical recording material requires the following basic performance. That is, recording stability, repetition durability,
Semiconductor laser sensitivity, high sensitivity, etc. However, most of the currently known photochromic compounds are thermally unstable in either the colored state or the decolored state, and return to a more stable state within several hours at room temperature. Has the drawback that the stability of the product cannot be ensured. Among these, fulgides and diarylethenes are known as compounds whose two states by light irradiation are relatively thermally stable, but the stability is still insufficient for use as a recording material. It has any of the following drawbacks: poor repetition durability, poor semiconductor laser sensitivity, low sensitivity (molecular extinction coefficient), etc., and a photochromic compound that satisfies all performances has not yet been obtained. That is the fact.

[0003] The principle of optical recording of a photochromic compound is that one of the two structures by photoreaction is set to a recording state and the other is set to an erasing state, and the difference in absorbance at a specific wavelength is read out. Writing and erasing are possible. An optical recording medium using a photochromic compound is easily prepared and has features of excellent mass productivity. However, photochromic compounds usually require two
Since the detection is performed based on the difference in the light absorptivity of the two structures, the structure changes due to light absorption at the time of reproduction, and there is a disadvantage that the recording is lost after performing the reproduction many times.

[0004]

SUMMARY OF THE INVENTION The present invention has been made in view of the above-mentioned problems, and has as its object to provide heat stability of a colored state, repetition durability, semiconductor laser sensitivity, and sensitivity. Another object of the present invention is to provide a novel diarylethene-based compound having excellent performance as a photochromic material such as molecular extinction coefficient. Another object of the present invention is to provide an optical recording / reproducing method for an optical recording medium using a diarylethene compound which can prevent the destruction of recording during reproduction.

[0005]

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

Embedded image (Where n, A, and B are the same as described above ).
Another object is to provide a conjugated double bond represented by the general formula (1).
Method for producing diarylethene compound having combined chain
Is achieved by Still further, the other objectives described above are
A di-substituted compound having a conjugated double bond represented by the general formula (1)
An arylethene compound is used as a recording material, and the recording material is
Evaporation method, dispersed or dissolved in solvent with binder
Optical recording medium obtained by dissolving and applying
More achieved. Still further, the other object described above is the above-mentioned object,
In the optical recording medium, after initialization is performed by irradiating ultraviolet light to change to a colored state, information is recorded by irradiating visible light to change to a colorless state, and the recorded information is written. In an optical recording / reproducing method for reproducing by irradiating visible light, a light using a diarylethene-based compound is characterized in that the temperature of the optical recording medium during reproduction is set at least 40 ° C. lower than the temperature of the optical recording medium during recording. This is achieved by an optical recording / reproducing method of a recording medium.

Next, the present invention will be described in detail. The diarylethene compound of the present invention is represented by the general formula (1), wherein n is an integer of 2 to 5, and has a 4- to 7-membered 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 a benzothienyl group represented by the general formula (2). l represents an integer of 1 or 2, and R ¹ represents an alkyl group, preferably a lower alkyl group such as a methyl, ethyl or propyl group. R ^{2 to} R ⁴ represent a hydrogen atom, an alkyl group, a dialkylamino group, a cyano group, a nitro group, or an alkoxy group. In order to increase the absorption wavelength of the compound to the wavelength of the semiconductor laser oscillation, R ³ to R ⁴ R ⁴
Is more preferably an alkoxy group or a dialkylamino group.

B represents a thienyl group or a benzothienyl group represented by the general formula (3) or (4). m, o
Represents an integer of 1 or 2, and R ^{5 to} R ⁷ represent an alkyl group, preferably a lower alkyl group such as a methyl, ethyl or propyl group. R ^{8 to} R ¹⁰ represent a hydrogen atom, an alkyl group,
Represents a dialkylamino group, a cyano group, a nitro group or an alkoxy group. In general formulas (2) to (4),
P, Q, and T represent an aromatic group or a heterocyclic group. Specifically, examples of the aromatic group include an unsubstituted phenyl group, a tolyl group, a mesityl group, an anisyl group, a dimethylanilino group,
Examples include mono- or polysubstituted phenyl groups such as nitrophenyl groups, and polycyclic aromatic groups such as naphthyl groups, anthracene groups, and phenanthrene groups. Further, as the heterocyclic group, thienyl group, benzothienyl group, pyryl group, indolyl group, furyl group, benzofuryl group, imidazolyl group,
Examples include a pyridyl group, a quinolyl group, a pyrimidyl group, an oxazolyl group, a thiazolyl group, a benzothiazolyl group, and a triazole 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 (5)

Embedded image (Where n is the same as above) and aryl lithium derivatives ALi and BLi (where A and B are the same as above) to obtain a diarylethene-based compound in one step, or the following general formula (6) )

Embedded image (Wherein, n and B are the same as above) as shown in the formula (1), where only BLi is reacted to form a monoarylethene derivative into which one aryl group is introduced, and then the other aryllithium derivative ALi is successively added. Reacting to obtain a diarylethene-based compound in two steps, or as C,
The following general formula (7) or general formula (8)

Embedded image (However, in the formula, p is an integer of 0 or 1, and R ^{1 to} R ⁴ are the same as described above.)

Embedded image (Where q is an integer of 0 or 1 and R ⁵ and R ⁶ are the same as described above), or D as the general formula (2), the general formula (3), or the general formula (7 ) Or the aryl lithium derivative CLi or D represented by the general formula (8)
Li is reacted simultaneously or sequentially, and the following general formula (9)

Embedded image (Where n is the same as described above), and after obtaining a diarylethene-based compound represented by the formula (1), an aromatic halide or a heterocycle such as a substituted benzene halide or a hydrogen atom at the olefin end of the obtained diarylethene-based compound is obtained. A method in which a halide is reacted with a palladium catalyst to exchange a hydrogen atom for an aromatic group or a heterocyclic group such as a substituted phenyl group, or the following general formula (10)

Embedded image (However, where X represents a bromine atom or an iodine atom, R ¹
To R ⁴ is as defined above. ) To give a lithiated benzothiophene derivative represented by the following general formula (11)

Embedded image (Wherein, n, R ^{1 to} R ⁴ and X are the same as described above), and after further substituting a halogen for a metal, the following general formula (12)

Embedded image (Wherein, n and R ^{1 to} R ⁴ are the same as above), for example, a method of subjecting this to a predetermined phosphonium salt and subjecting it to a Wittig reaction with a formylated diarylethene-based compound. Depending on the rate, each method is appropriately selected so that the overall yield is good.

Next, an example of a preferred manufacturing method is as follows. First, AX, BX, CX, DX and the following general formula (13)

Embedded image (Where X and Y represent a bromine atom or an iodine atom,
A, B, C, D and R ^{1 to} R ⁴ are the same as described above. ), A halogenated aryl derivative such as a halogenated benzothiophene derivative, a halogenated thiophene derivative, or a dihalogenated benzothiophene derivative, at a reaction temperature of -45.
Reacting with an alkyl lithium or lithium dialkylamide at -120C, preferably -70 to -110C,
An aryl lithium derivative in which the halogen atom at the 3-position is substituted with lithium.

As the solvent, ether solvents such as tetrahydrofuran and diethyl ether are preferably used. In order to prevent the solvent from coagulating at a low temperature, n-hexane, n-hexane and n-hexane are preferably used.
-Lower alkanes such as pentane may be mixed. Examples of the alkyllithium lithiating agent and lithium dialkylamide include n-butyllithium, t-butyllithium,
Examples thereof include methyllithium, phenyllithium, lithium diisopropylamide, and lithium dicyclohexylamide, and a hexane solution of n-butyllithium is preferably used. The amount of the lithiating agent is preferably 1.0 to 1.2 times the mol of the total amount of the aryl halide derivative, and the reaction time is usually 20 minutes to 3 hours, preferably 30 minutes to 2 hours. is there.

Next, a perfluorocycloalkene represented by the general formula (6) is added to the produced aryllithium derivative. The amount of the perfluorocycloalkene used depends on the purpose of obtaining the monoarylethene derivative. 1.0 to 1.5 times the molar amount of the aryl halide derivative. For the purpose of obtaining a diarylethene-based compound, it is preferable to use 0.5 times the molar amount of the aryl halide derivative. It can be diluted and added. Reaction temperature is -60 to -11
0 ° C. and the reaction time are preferably 30 minutes to 2 hours. In order to make the monoarylethene derivative a diarylethene-based compound, AX, BX, CX, DX, the general formula (13) (however, A, B, C, D, X, and R ^{1 to} R ⁴ are the same as described above). ) Is used as an aryllithium derivative in the same manner as described above,
A solution of the monoarylethene derivative in tetrahydrofuran is added, and the amount of the monoarylethene derivative used is preferably 1.0 to 1.2 times the mole of the aryl halide derivative. At this time, the reaction temperature is preferably -60 to -110 ° C, and the reaction time is preferably 30 minutes to 2 hours.

Among the diarylethene compounds thus obtained, the general formula (9) further comprises reacting a hydrogen atom at an olefin terminal with an aromatic halide or a heterocyclic halide such as a substituted benzene halide using a palladium catalyst, A hydrogen atom is exchanged for an aromatic group or a heterocyclic group such as a substituted phenyl group.However, the amount of an aromatic halide or a heterocyclic halide such as a substituted benzene halide used is determined by the total amount of hydrogen atoms at the olefin terminal. 1.0 for
It is preferably used in a molar amount of up to 2.0 times. As a solvent, sodium bicarbonate, triethylamine or the like is added as a base to acetonitrile, dimethylformamide, hexamethylphosphoric triamide, N-methylpyrrolidone, or triethylamine, tri (n-butyl)
Amines such as amine and tri (isopropyl) amine can be used as both a base and a solvent.
(Butyl) amine is preferably used. Further, tetrahydrofuran may be added to dissolve the raw materials.

As a catalyst, a divalent palladium compound such as palladium acetate or palladium chloride is used as a ligand as a ligand.
A phosphine compound such as triphenylphosphine, tri (orthotolyl) phosphine, or tri (2-methoxyphenyl) phosphine is added.
1.0 to 5.0 based on the amount of hydrogen atoms at the olefin terminal.
Mol%, and the amount of the phosphine compound is 2.0 to 8.0 times the mol of the total amount of the palladium compound. Alternatively, a catalyst in which a phosphine compound is previously coordinated with divalent palladium, for example, 1.0 to 5.0 mol% of bis (tri (orthotolyl) phosphine) palladium dichloride may be used. 1.0 to 2.0 mol% is added to the amount of hydrogen atoms at the olefin end,
Preferably, tri (orthotolyl) phosphine is added in a molar amount of 3.0 to 6.0 times the total amount of the palladium compound. The reaction temperature is 80 to 160 ° C, and the reaction time is 2 hours to 2 hours.
00 hours, preferably 20 hours to 150 hours.

The halogen atom of the halogenated diarylethene compound represented by the above general formula (11) is exchanged for lithium with a lithiating agent or reacted with magnesium to convert it to a Grignard reagent, and then to dimethylformamide. , N-formylpiperidine or the like to obtain a formylated diarylethene compound represented by the general formula (12). The formylated diarylethene-based compound is subjected to a Wittig reaction once or several times with a predetermined phosphonium salt to give the following general formula (14) or (15)

Embedded image (However, in the formula, n, R ^{1 to} R ⁴ and P are the same as described above.)

Embedded image (Where n and R ^{1 to} R ⁴ are the same as described above). The general formula (1
By subjecting the diarylethene compound represented by 5) to a Wittig reaction with a predetermined phosphonium salt,
The following general formula (16)

Embedded image (Wherein, n, R ^{1 to} R ⁴ , and P are the same as described above). In order to obtain a diarylethene-based compound from the reaction product obtained by the above-mentioned method, separation and purification may be performed by a method such as extraction, column chromatography, or recrystallization.

The diarylethene compound of the present invention is exemplified by 1- (6- (2- (4-methoxyphenyl) -1-ethenyl) -2-methyl-3-benzothienyl) -2- (5- (4- (4-dimethylaminophenyl) -1,3-butadienyl) -2,4-dimethyl-3
(Thienyl) -3,3,4,4,5,5-hexafluorocyclopentene will be described. In an appropriate medium such as an organic solvent or an appropriate resin binder, the following formula (17) is obtained. ,

Embedded image Irradiation of ultraviolet light to the ring-opened body changes to a ring-closed body and becomes colored,
When this ring-closed body is irradiated with visible light, it returns to the original ring-opened body,
Decolorize.

The optical recording medium containing the diarylethene compound of the present invention can be easily obtained by a known method. For example, a method of vapor-depositing the diarylethene compound of the present invention on a suitable substrate by a known vapor deposition method, or a diarylethene compound of the present invention, a polyester resin,
Along with a resin binder of polyethylene resin, polyvinyl chloride resin, polyvinyl acetate resin, polyvinyl butyral resin, polymethyl methacrylate resin, poly t-butyl methacrylate resin, polycyclohexyl methacrylate resin, polycarbonate resin, phenol resin, epoxy resin, A method of dispersing or dissolving in a solvent such as benzene, toluene, xylene, hexane, cyclohexane, methyl ethyl ketone, acetone, methanol, ethanol, tetrahydrofuran, dioxane, carbon tetrachloride, chloroform, cellosolve, diglyme, etc., and coating on an appropriate substrate, etc. Thus, an optical recording medium can be obtained.

In such an optical recording medium, the diarylethene compound of the present invention has high thermal stability in both the colored state and the decolored state, is stable against moisture and oxygen, and retains its structure for a long time without change. It is also excellent in the durability of repeated coloration and decoloration. The absorption maximum wavelength in the colored state exceeds 570 nm, and the absorption edge is 800 nm or more.
It has sensitivity to semiconductor lasers having an oscillation wavelength of 780 nm or 780 nm, and has excellent photochromic properties such as high sensitivity (having a large molecular extinction coefficient) in that wavelength range, so that reversible light is emitted. It can be used effectively for information recording media and the like.

Further, using an optical recording medium using the diarylethene compound of the present invention as a recording material, initialization is performed by irradiating ultraviolet light to change to a colored state, and then irradiating visible light to a colorless state. In the optical recording / reproduction in which information is recorded by changing the recording information and the recorded information is reproduced by irradiating it with visible light, the temperature of the optical recording medium at the time of reproduction is 40 ° C. or more than that at the time of recording, preferably When the temperature is lowered by 50 ° C. or more, deterioration during reproduction can be prevented, which is preferable. The decolorization of the diarylethene compound of the present invention by visible light is significantly affected by temperature, for example, 40 ° C.
At 1000 ° C. is more than 1000 times slower than that at 120 ° C. That is, the pulse is not erased unless the pulse of the light intensity that erases the color at 120 ° C. is repeatedly irradiated 1000 times or more at 40 ° C. Therefore, by controlling the temperature of the optical recording medium to the above-described temperature, reproduction can be performed 1,000 times or more. Specifically, the temperature of the optical recording medium is preferably 100 to 200 ° C. during recording and 20 to 70 ° C. during reproduction.

As a method of controlling the temperature of the optical recording medium, a heating source such as a heater, infrared rays, or high frequency may be separately used. However, it is preferable to use a rise in temperature due to absorption of light used for recording and reproduction. This is preferable in terms of simplification of the device. More specifically, when the colored state is an unrecorded area and the decolored state is a recorded area, and the unrecorded area is recorded with a semiconductor laser beam of, for example, 780 nm or 680 nm, a spot having an intensity of 4 to 15 mW is irradiated. Then, the temperature of the optical recording medium rises, and the image can be easily erased and recorded. 0.1-
When reproduction is performed with a weak laser beam of 1 mW, the temperature rise of the optical recording medium is small, the decoloring reaction is significantly suppressed, and recording destruction can be prevented. Therefore, the recording sensitivity and the number of reproducible times can be optimized by appropriately selecting the laser intensity for recording and reproduction depending on the optical recording medium.

[0020]

As described above, the diarylethene-based compound of the present invention has photochromic properties excellent in thermal stability, repetition durability of coloring and erasing, semiconductor laser sensitivity, sensitivity, etc. It can be used for various purposes such as recording materials. Further, according to the optical recording / reproducing method of the present invention, reproduction destruction of recording can be prevented by utilizing the large temperature dependence of the decolorization reaction of the diarylethene-based compound. Therefore, the diarylethene-based compound of the present invention has high thermal stability in both the colored state and the decolored state, is stable to moisture, oxygen, etc., is maintained without change in the structure for a long period of time, and is durable to repeated coloration and decoloration. Because it is also excellent
An inexpensive optical information recording medium capable of reversibly recording and erasing can be provided. Next, the present invention will be specifically described with reference to examples, but the present invention is not limited to these examples.

Example 1 1- (6- (2- (4-methoxyphenyl) -1-ethenyl) -2-methyl-3-benzothienyl) -2- (5
-(4- (4-dimethylaminophenyl) -1,3-butadienyl) -2,4-dimethyl-3-thienyl)-
Production of 3,3,4,4,5,5-hexafluorocyclopentene

A) Production of 3-bromo-6-iodo-2-methylbenzothiophene 23.6 g of iodine was placed in a 400 ml two-necked flask.
(93 mmol) iodic acid 9.48 g (53.8 mmol)
l), sulfuric acid 1.56 ml, acetic acid 92.4 ml, water 34.
8 ml, 45.6 ml of carbon tetrachloride and 16.7 g of 3-bromo-2-methylbenzothiophene (146.8 mmol
1), heated to 70-80 ° C., and stirred for 48 hours. After the reaction, the reaction solution was washed with a saturated aqueous solution of sodium thiosulfate 2
Open to 00 ml, extract three times with 400 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 37.5 g of a compound represented by the following structural formula (Formula 23) was obtained (yield: 7).
3.0%).

Embedded image

Analytical values: 1) ¹ H-NMR (in CDCl ₃ ) δ (ppm) 2.50 (s 1H) 7.15 to 8.
21 (m1H) 2) MS m / e 353 (M ⁺ ).

B) Preparation of 3-bromo-6-formyl-2-methylbenzothiophene Example 1-a) was placed in a two-necked flask having a capacity of 1000 ml.
After adding 21.2 g (60.0 mmol) of 3-bromo-6-iodo-2-methylbenzothiophene and 600 ml of diethyl ether prepared in the above, cooling to −78 ° C. under a nitrogen stream, an n-butyllithium-hexane solution 37.6m
1 (60.1 mmol) was added dropwise and stirred for 1 hour. Next, 5.3 g of dimethylformamide (72.5 mmol
60 ml of a diethyl ether solution of 1) was added dropwise and reacted for 1 hour. After completion of the reaction, the reaction was stopped by adding 20 ml of methanol, and after adding 300 ml of water, the mixture was extracted three times with 500 ml of ethyl acetate. This organic layer is collected, washed,
After drying, the solvent was distilled off under reduced pressure. The obtained reaction product was purified by silica gel column chromatography, and 14.4 g of the compound of the following structural formula (Formula 24) (yield 94.1) was obtained.
%).

Embedded image

Analytical values: 1) ¹ H-NMR (in CDCl ₃ ) δ (ppm) 2.61 (s 3H) 7.88 (s)
2H) 8.26 (s 1H) 10.09 (s 1H) 2) MS m / e 255 (M ⁺ ) 3) IR (KBr) ν (cm ⁻¹ ) 1691 (CHO)

C) Production of 3-bromo-6- (2- (4-methoxyphenyl) -1-ethenyl) -2-methylbenzothiophene 4-methoxybenzyltriphenylphosphonium chloride was placed in a 50 ml two-necked flask. 23.6 g (5
6.3 mmol), 3-bromo-6-formyl-2-methylbenzothiophene prepared in Example 1-b) 7.
2 g (28.2 mmol), sodium carbonate 23.4
g, formamide 5.1 g, 1,4-dioxane 220
Then, the mixture was refluxed at 95 ° C. for 24 hours and reacted. After the reaction, insolubles were filtered off, and the solvent in the filtrate was distilled off under reduced pressure. Diethyl ether was added to the residue, and the insolubles were filtered off. The solvent of the filtrate was distilled off under reduced pressure, and the obtained reaction product was purified by silica gel column chromatography to obtain 8.4 g of the compound of the following structural formula (Formula 25) (yield: 83.4%).

Embedded image

Analytical values: 1) ¹ H-NMR (in CDCl ₃ ) δ (ppm) 2.51 (s 1H) 3.80 (s)
1H) 6.70-7.91 (m3H) 2) MS m / e 359 (M ⁺ ).

D) 1- (6- (2- (4-methoxyphenyl) -1-ethenyl) -2-methyl-3-benzothienyl) -2,3,3,4,4,5,5-hepta Production of Fluorocyclopentene In a 300 ml two-necked flask, 3-bromo-6-
4.2 g (11.7 mmol) of ((4-methoxyphenyl) -1-ethenyl) -2-methylbenzothiophene and 150 ml of tetrahydrofuran were added, and the mixture was added under a nitrogen stream.
After cooling to 95 ° C., 8.8 ml (14.0 mmol) of an n-butyllithium-hexane solution was added dropwise and stirred for 1 hour. Next, 5.0 g of perfluorocyclopentene (2
25 ml of a tetrahydrofuran solution (3.4 mmol) was added dropwise, and reacted for 1 hour. After completion of the reaction, methanol 2
0 ml was added to stop the reaction, 50 ml of water was further added, and the mixture was extracted three times with 200 ml of ethyl acetate. The organic layer was 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, and 5.0 g of a compound of the following structural formula (Formula 26) was obtained.
(90.0% yield).

Embedded image

Analytical values: 1) MS m / e 472 (M ⁺ )

E) Production of 3-iodo-5- (1,3-butadienyl) -2,4-dimethylthiophene In a two-neck flask having a capacity of 300 ml, 7.2 g (18.9 mmol) of 2-propenylphosphonium bromide was added. 75 ml of diethyl ether was added, and ice-cooled under a nitrogen stream.
13.0 ml of n-butyllithium-hexane solution (2
0.8 mmol) was added dropwise and stirred for 2 hours. next,
A solution of 5.0 g (18.9 mmol) of 3-iodo-5-formyl-2,4-dimethylthiophene in 50 ml of tetrahydrofuran was added dropwise and reacted for 3 hours. After completion of the reaction, 10 ml of 1 N hydrochloric acid was added to stop the reaction,
After adding 0 ml, the mixture was extracted three times with 200 ml of ethyl acetate. The organic layer was collected, neutralized with a saturated aqueous solution of sodium hydrogen carbonate, washed and dried, and then the solvent was distilled off under reduced pressure. The obtained reaction product was purified by silica gel column chromatography, and 3.6 g of a compound represented by the following structural formula (Formula 27) was obtained.
(66.0% yield).

Embedded image

Analytical values: 1) ¹ H-NMR (in CDCl ₃ ) δ (ppm) 2.19 (s 3H) 2.37 (s)
3H) 5.00 to 6.55 (m2H) 5.65 to 7.00 (m3H) 2) MS m / e 290 (M ⁺ )

F) 1- (6- (2- (4-methoxyphenyl) -1-ethenyl) -2-methyl-3-benzothienyl) -2- (5- (1,3-butadienyl) -2, 4
-Dimethyl-3-thienyl) -3,3,4,4,5,5
Preparation of hexafluorocyclopentene In a 300 ml two-necked flask, 3-iodo-5- (1,3-butadienyl) prepared in Example 1-e) was prepared.
2.6 g of -2,4-dimethylthiophene (8.9 mmo
l) and 100 ml of tetrahydrofuran were added, and the mixture was cooled to -95 ° C under a nitrogen stream, 6.7 ml (10.7 mmol) of an n-butyllithium-hexane solution was added dropwise, and the mixture was stirred for 1 hour. Next, 1- (6) produced in Example 1-d)
-(2- (4-methoxyphenyl) -1-ethenyl)-
2-methyl-3-benzothienyl) -2,3,3,4
4.3 g of 4,5,5-heptafluorocyclopentene
(8.9 mmol) in 10 ml of tetrahydrofuran solution
Was dropped and reacted for 1 hour. After completion of the reaction, the reaction was stopped by adding 10 ml of methanol, and after adding 100 ml of water, the mixture was extracted three times with 200 ml of ethyl acetate. The organic layer was 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, and 5.0 g of a compound represented by the following structural formula (Formula 28) was obtained.
(91.7% yield).

Embedded image

Analytical values: 1) ¹ H-NMR (in CDCl ₃ ) δ (ppm) 1.91 2.05 2.17 (s 6
H, stereoisomer) 2.48 (s 3H) 3.76 (s 3H) 4.90-8.05 (m 14H) 2) MS m / e 616 (M ⁺ )

G) 1- (6- (2- (4-methoxyphenyl) -1-ethenyl) -2-methyl-3-benzothienyl) -2- (5- (4- (4-dimethylaminophenyl) -1,3-butadienyl) -2,4-dimethyl-3
Preparation of -thienyl) -3,3,4,4,5,5-hexafluorocyclopentene In a 100 ml two-necked flask, 3.2 g (16.2 mmol) of 4-bromodimethylaniline was prepared.
1- (6- (2- (4-methoxyphenyl) -1-ethenyl) -2-methyl-3-benzothienyl) -2- (5- (1,3-butadienyl) -2 prepared in f) , 4
-Dimethyl-3-thienyl) -3,3,4,4,5,5
5.0 g of hexafluorocyclopentene (8.1 mm
ol), 35 mg of palladium acetate (0.16 mmol
l), 0.2 g of tri (orthotolyl) phosphine (0.1 g).
64 mmol), 26 ml of tri (n-butyl) amine,
5 ml of tetrahydrofuran was added, and the mixture was refluxed at 100 ° C. for 120 hours to be reacted. After the reaction, insolubles were filtered off, and the solvent in the filtrate was distilled off under reduced pressure. Diethyl ether was added to the residue, and the insolubles were filtered off. The solvent of the filtrate was distilled off under reduced pressure, and the obtained reaction product was purified by silica gel column chromatography to obtain a compound 2.8 of the following structural formula (Formula 29).
g (46.5% yield).

Embedded image

Analytical values: 1) ¹ H-NMR (in CDCl ₃ ) δ (ppm) 1.86 2.11 2.15 (s 6
H, stereoisomer) 2.37 (s 3H) 2.95 (s 6H) 3.83 (s 3H) 6.40-7.77 (m 17H) 2) MS m / e 735 (M ⁺ )

Example 2 1- (6- (4- (4-methoxyphenyl) -1,3-
(Butadienyl) -2-methyl-3-benzothienyl)-
2- (5- (4- (4-methoxyphenyl) -1,3-
(Butadienyl) -2,4-dimethyl-3-thienyl)-
Production of 3,3,4,4,5,5-hexafluorocyclopentene

A) 3-Bromo-6- (2-formyl-1)
Preparation of -ethenyl) -2-methylbenzothiophene In a 100 ml two-necked flask, 6.4 g (25.0 mmol) of 3-bromo-6-formyl-2-methylbenzothiophene prepared in Example 1-a). ) 7.6 g (25.0 mm) formylmethylenetriphenylphosphorane
ol) and 70 ml of toluene were added and refluxed for 120 hours to cause a reaction. After the reaction, the solvent was distilled off under reduced pressure, and diethyl ether was added to the residue, and the insoluble matter was separated by filtration. The solvent of the filtrate was distilled off under reduced pressure, and the obtained reaction product was purified by silica gel column chromatography.
5.7 g (yield 80.9%) of compound 0) was obtained.

Embedded image

Analytical values: 1) ¹ H-NMR (in CDCl ₃ ) δ (ppm) 2.50 (s 3H) 5.80 to 8.8
2 (m5H) 9.58, 9.79 (w1H) 2) MS m / e 281 (M ⁺ ).

B) Production of 3-bromo- (4- (4-methoxyphenyl) -1,3-butadienyl) -2-methylbenzothiophene 4-methoxybenzyltriphenylphosphonium chloride was placed in a two-neck flask having a capacity of 300 ml. 14.8g (3
5.3 mmol), 3-prepared in Example 2-a)
Bromo-6- (2-formyl-1-ethenyl) -2-methylbenzothiophene 5.0 g (17.7 mmol),
15.1 g of sodium carbonate, 3.3 g of formamide,
120 ml of 1,4-dioxane was added and refluxed for 24 hours to cause a reaction. After the reaction, insolubles were filtered off, and the solvent in the filtrate was distilled off under reduced pressure. Diethyl ether was added to the residue, and the insolubles were filtered off. The solvent of the filtrate was distilled off under reduced pressure, and the obtained reaction product was purified by silica gel column chromatography to obtain 5.3 g of a compound represented by the following structural formula (Formula 31) (yield: 7).
8.5%).

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Analytical values: 1) ¹ H-NMR (in CDCl ₃ ) δ (ppm) 2.54 (s 3H) 2.77 (s)
3H) 6.05-7.90 (m11H) 2) MS m / e 627 (M ⁺ ).

C) 1- (6- (4- (4-methoxyphenyl) -1,3-butadienyl) -2-methyl-3-benzothienyl) -2,3,3,4,4,5,5 Preparation of heptafluorocyclopentene In a 500 ml two-necked flask, 3-bromo- (4- (4-methoxyphenyl) -1,3-butadienyl) -2-methyl, prepared as in Example 2-b). 4.0 g (10.0 mmol) of benzothiophene and 100 ml of tetrahydrofuran were added, and the mixture was cooled to -95 ° C under a nitrogen stream, and then 7.5 ml of an n-butyllithium-hexane solution (1 ml) was added.
2.0 mmol) was added dropwise and stirred for 1 hour. Next, 2.1 g of perfluorocyclopentene (10.0 mmo
10 ml of a tetrahydrofuran solution of 1) was added dropwise and reacted for 1 hour. After completion of the reaction, 10 ml of methanol was added to stop the reaction, 50 ml of water was further added, and the mixture was extracted three times with 200 ml of ethyl acetate. This organic layer is collected, washed,
After drying, the solvent was distilled off under reduced pressure. The obtained reaction product was purified by silica gel column chromatography, and 4.4 g of the compound of the following structural formula (Formula 32) was obtained (yield: 87.5).
%).

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Analytical values: 1) ¹ H-NMR (in CDCl ₃ ) δ (ppm) 2.51 (s 3H) 3.86 (s)
3H) 6.10 to 7.94 (m11H) 2) MS m / e 498 (M ⁺ ).

D) 3-Iodo-5- (2-formyl-1)
Preparation of -ethenyl) -2,4-dimethylthiophene In Example 2, section a), 3-bromo-6-formyl-
Instead of using 2-methylbenzothiophene, 3-iodo-5-formyl-2,4-dimethylthiophene was used, and in a similar manner, 3-iodo- of the following structural formula (Formula 29) was used.
5- (2-Formyl-1-ethenyl) -2,4-dimethylthiophene was obtained. Yield 5.6 g (Yield 77.0)
%).

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Analytical values: 1) ¹ H-NMR (in CDCl ₃ ) δ (ppm) 2.35 (s 3H) 2.41 (s)
3H) 6.84-7.84 (m2H) 9.55 9.69 (w1H) 2) MS m / e 292 (M ⁺ ).

E) Preparation of 3-iodo- (4- (4-methoxyphenyl) -1,3-butadienyl) -2,4-dimethylthiophene In section c) of Example 1, 3-bromo-6 -Formyl-
Instead of using 2-methyl-3-benzothiophene,
3-Iodo-5- (2-formyl-1-ethenyl)-
Using 2,4-dimethylthiophene, 3-iodo- (4- (4-methoxyphenyl) -1,3-butadienyl) -2,4-dimethylthiophene of the following structural formula (Formula 34) is obtained in the same manner. Was. Yield 5.0 g (Yield 97.0)
%).

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Analytical values: 1) ¹ H-NMR (in CDCl ₃ ) δ (ppm) 2.20 (s 3H) 2.37 (s)
3H) 3.77 (s 3H) 6.15-7.60 (m8H) 2) MS m / e 396 (M ⁺ ).

F) 1- (6- (4- (4-methoxyphenyl) -1,3-butadienyl) -2-methyl-3-benzothienyl) -2- (5- (4- (4-methoxyphenyl) ) -1,3-Butadienyl) -2,4-dimethyl-
Preparation of 3-thienyl) -3,3,4,4,5,5-hexafluorocyclopentene In a two-neck flask having a capacity of 200 ml, the 3-iodo- (4- (4 -Methoxyphenyl) -1,3-butadienyl) -2,4-dimethylthiophene (2.0 g, 5.0 mmol) and tetrahydrofuran (50 ml) were added.
3.8 ml of a butyl lithium-hexane solution (6.0 m
mol) was added dropwise and stirred for 1 hour. Next, Example 2-
c) 1- (6- (4- (4-methoxyphenyl) -1,3-butadienyl) -2-methyl-3-benzothienyl) -2,3,3,4,4,5 5 ml of a tetrahydrofuran solution of 2.5 g (5.0 mmol) of 5-heptafluorocyclopentene was added dropwise and reacted for 1 hour. After completion of the reaction, the reaction was stopped by adding 5 ml of methanol, and 50 ml of water was further added.
Extracted three times. After collecting this organic layer, washing and drying,
The solvent was distilled off under reduced pressure. The obtained reaction product was purified by silica gel column chromatography to obtain 3.7 g (yield 97.7%) of a compound represented by the following structural formula (Formula 35).

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Analytical values: 1) ¹ H-NMR (in CDCl ₃ ) δ (ppm) 1.86 2.03 2.11 (s 6
H, stereoisomer) 2.36 (s 3H) 3.60 (s 3H) 3.62 (s 3H) 6.10 to 7.99 (m 19H) 2) MS m / e 748 (M ⁺ )

Example 3 1,2-bis (6- (4- (4-methoxyphenyl)-)
Production of 1,3-butadienyl) -2-methyl-3-benzothienyl) -3,3,4,4,5,5-hexafluorocyclopentene In a 300 ml two-necked flask, Example 2-b) 3.9 g (10.0 mmol) of the prepared 3-bromo- (4- (4-methoxyphenyl) -1,3-butadienyl) -2-methylbenzothiophene and 100 ml of tetrahydrofuran are added, and the mixture is charged at -95 ° C under a nitrogen stream. After cooling to 7.6 ml of n-butyllithium-hexane solution (1
2.1 mmol) was added dropwise and stirred for 1 hour. Next, 1- (6- (4- (4-methoxyphenyl) -1,3-butadienyl) -2-methyl-3-benzothienyl) -2,3,3 prepared in Example 2-c). , 4,4,5,5
5.0 g of heptafluorocyclopentene (10.0 m
mol) in 10 ml of tetrahydrofuran solution,
The reaction was performed for 1 hour. After completion of the reaction, the reaction was stopped by adding 10 ml of methanol, and after adding 100 ml of water, the mixture was extracted three times with 200 ml of ethyl acetate. Collect this organic layer,
After washing and drying, the solvent was distilled off under reduced pressure. The obtained reaction product was purified by silica gel column chromatography, and 7.5 g of a compound represented by the following structural formula (Formula 36) was obtained (yield: 9).
5.2%).

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Analytical values: 1) ¹ H-NMR (in CDCl ₃ ) δ (ppm) 2.25 2.45 (s 3H, stereoisomer) 3.75 (s 3H) 6.05 to 8.32 ( m 11H) 2) MS m / e 784 (M ⁺ )

Example 4 1,2-bis (6- (2- (4-methoxyphenyl)-)
1-ethenyl) -2-methyl-3-benzothienyl)-
Preparation of 3,3,4,4,5,5-hexafluorocyclopentene a) 1,2-bis (6-iodo-2-methyl-3-benzothienyl) -3,3,4,4,5,5 Preparation of hexafluorocyclopentene In a two-necked flask having a capacity of 500 ml, 7.0 g (20.0 mmol) of 3-bromo-6-iodo-2-methylbenzothiophene prepared in Example 1-a) and 200 ml of tetrahydrofuran were added. After cooling to −95 ° C. under a nitrogen stream, 15.0 ml of an n-butyllithium-hexane solution was added.
(24.0 mmol) was added dropwise and stirred for 1 hour. Next, 2.1 g of perfluorocyclopentene (10.0 m
mol) in 10 ml of tetrahydrofuran solution,
The reaction was performed for 1 hour. After completion of the reaction, the reaction was stopped by adding 10 ml of methanol, and 100 ml of water was further added, followed by extraction with 200 ml of ethyl acetate three times. The organic layer was 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 10.9 g (yield: 76.0%) of a compound represented by the following structural formula (Formula 37).

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Analytical values: 1) MS m / e 720 (M ⁺ )

B) 1,2-bis (6-formyl-2-methyl-3-benzothienyl) -3,3,4,4,5,5
Preparation of hexafluorocyclopentene In a 300 ml two-necked flask, the 1,2-bis (6-iodo-2-methyl-3) prepared in Example 4-a) was prepared.
-Benzothienyl) -3,3,4,4,5,5-hexafluorocyclopentene 7.2 g (10.0 mmol)
And 100 ml of diethyl ether under nitrogen flow.
After cooling to 78 ° C, n-butyllithium-hexane solution 1
5.0 ml (24.0 mmol) was added dropwise and stirred for 1 hour. Next, 1.8 g of dimethylformamide (24.0 g)
mmol) in 10 ml of diethyl ether solution,
The reaction was performed for 1 hour. After completion of the reaction, the reaction was stopped by adding 5 ml of methanol, and 50 ml of water was further added, followed by extraction with 300 ml of ethyl acetate three times. The organic layer was 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, and 4.2 g of a compound represented by the following structural formula (Formula 38) was obtained (yield: 8).
4.1%).

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Analytical values: 1) MS m / e 524 (M ⁺ )

C) Production capacity of 1,2-bis (2- (4-methoxyphenyl) -1-ethenyl) -2-methylbenzothiophene) -3,3,4,4,5,5-hexafluorocyclopentene In a 50 ml two-necked flask, 13.3 g of 4-methoxybenzyltriphenylphosphonium chloride (3.
2.0 mmol), 1,2 prepared in Example 4-b).
-Bis (6-formyl-2-methyl-3-benzothiophene) -3,3,4,4,5,5-hexafluorocyclopentene 2.6 g (5.3 mmol), sodium carbonate 6.7 g, formamide 1. 7 g and 140 ml of 1,4-dioxane were added, and the mixture was refluxed at 95 ° C. for 24 hours to be reacted. After the reaction, insolubles were filtered off, and the solvent in the filtrate was distilled off under reduced pressure. Diethyl ether was added to the residue, and the insolubles were filtered off. The solvent of the filtrate was distilled off under reduced pressure, and the obtained reaction product was purified by silica gel column chromatography to obtain 3.5 g of the compound of the following structural formula (Formula 39) (yield: 89.4).
%).

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Analytical values: 1) ¹ H-NMR (in CDCl ₃ ) δ (ppm) 2.21 2.46 (s 1H, stereoisomer) 3.76 (s 1H) 6.40 to 7.95 ( m 3H) 2) MS m / e 732 (M ⁺ )

<Measurement of Absorption Spectra>
Compounds obtained in 3 and 4 were respectively added to benzene 2.1
2.times.10.sup.- ⁵ mol / l, 1.5.times.10.sup.- ⁵ mol / l,
The solution obtained by dissolving so as to have a concentration of 5 × 10 ⁻⁵ mol / l and 2.2 × 10 ⁻⁵ mol / l was put into a 1 cm × 1 cm × 4 cm quartz glass cell. This was stirred for 36 hours using a 100 W ultra-high pressure mercury lamp equipped with an interference filter.
After irradiating the solution with 5 nm light to color the solution, the absorption spectrum of the solution in the photo-steady state was measured. 1 for the compound of Example 1, FIG. 2 for the compound of Example 2, and FIG. 3 for the compound of Example 3.
FIG. 4 shows the absorption spectra of the colored body and the decolored body for the compound of Example 4. Next, Table 1 shows the absorption maximum wavelength (λmax) of the colored body and the molecular extinction coefficient (ε · λmax) of the compound at this maximum wavelength.

[0058]

[Table 1]

As described above, by introducing a methoxy group or a dimethylamino group into the thiophene ring and the benzothiophene ring, and by introducing a conjugated double bond chain, the absorption maximum wavelength of the colored body becomes longer, and the oscillation wavelength becomes 670 nm or 780 nm.
nm laser diode sensitivity. Furthermore, by introducing a conjugated double bond chain into this benzothiophene ring,
The molecular extinction coefficient of the compound could be increased.

Example 5 1- (6- (2- (4-dimethylaminophenyl) -1)
-Ethenyl) -2-methyl-3-benzothienyl) -2
-(5- (2- (4-cyanophenyl) -1-ethenyl) -2,4-dimethyl-3-thienyl) -3,3,3
Production of 4,4,5,5-hexafluorocyclopentene

A) Preparation of 3-bromo-6-iodo-2-methylbenzothiophene 16.1 g of iodine was placed in a 400 ml two-necked flask.
(63.4 mmol) 6.5 g of iodic acid (36.6 mm
ol), sulfuric acid 1.06 ml, acetic acid 62.9 ml, water 2
3.7 ml, carbon tetrachloride 31.1 ml and 3-bromo-2
11.4 g of methylbenzothiophene (100 mmol
1), heated to 70-80 ° C., and stirred for 48 hours. After the reaction, the reaction solution was washed with a saturated aqueous solution of sodium thiosulfate 2
Open to 00 ml, extract three times with 400 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 26.2 g of a compound represented by the following structural formula (Formula 40) was obtained (yield: 7).
4.2%).

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Analytical values: 1) ¹ H-NMR (in CDCl ₃ ) δ (ppm) 2.50 (s 1H) 7.15 to 8.
21 (m1H) 2) MS m / e 353 (M ⁺ ).

B) Preparation of 3-bromo-6-formyl-2-methylbenzothiophene Example 5-a) was placed in a 1000 ml two-necked flask.
After adding 21.2 g (60.0 mmol) of 3-bromo-6-iodo-2-methylbenzothiophene and 600 ml of diethyl ether prepared in the above, cooling to −78 ° C. under a nitrogen stream, an n-butyllithium-hexane solution 37.6m
1 (60.0 mmol) was added dropwise and stirred for 1 hour. Next, 5.3 g of dimethylformamide (72.5 mmol
60 ml of a diethyl ether solution of 1) was added dropwise and reacted for 1 hour. After completion of the reaction, the reaction was stopped by adding 20 ml of methanol, and after adding 300 ml of water, the mixture was extracted three times with 500 ml of ethyl acetate. This organic layer is collected, washed,
After drying, the solvent was distilled off under reduced pressure. The obtained reaction product was purified by silica gel column chromatography, and 13.7 g of the compound of the following structural formula (Formula 41) was obtained (yield: 89.5).
%).

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Analytical values: 1) ¹ H-NMR (in CDCl ₃ ) δ (ppm) 2.61 (s 3H) 7.88 (s)
2H) 8.26 (s 1H) 10.09 (s 1H) 2) MS m / e 255 (M ⁺ ) 3) IR (KBr) ν (cm ⁻¹ ) 1691 (CHO)

C) Production of 3-bromo-6-ethenyl-2-methylbenzothiophene In a two-necked flask having a capacity of 500 ml, 5.4 g (15.0 mmol) of 2-propenylphosphonium bromide and 150 ml of diethyl ether were placed, and nitrogen was added. The mixture was ice-cooled under an air stream, and n-butyllithium-hexane solution (11.3 ml)
(18.1 mmol) was added dropwise and stirred for 2 hours. Next, 2.7 g (10.6 g) of 3-bromo-6-formyl-2-methylbenzothiophene prepared in Example 5-b).
(mmol) in 50 ml of tetrahydrofuran solution, and reacted for 3 hours. After the reaction, 1N hydrochloric acid 10m
The reaction was stopped by adding 1 l of water, and 50 ml of water was further added, followed by extraction with 200 ml of ethyl acetate three times. The organic layer was collected, neutralized with a saturated aqueous solution of sodium hydrogen carbonate, washed and dried, and then the solvent was distilled off under reduced pressure. The obtained reaction product was purified by silica gel column chromatography, and the compound of the following structural formula (Formula 42) 2.1 g (yield 78.3%)
I got

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Analytical values: 1) ¹ H-NMR (in CDCl ₃ ) δ (ppm) 2.56 (s 3H) 5.21 5.40 5.68 5.96 6.61 6.61 6.80 6.92 7 .10 (3H) 7.15-7.92 (m3H) 2) MS m / e 253 (M ⁺ )

D) 1- (6-ethenyl-2-methyl-3)
Preparation of -Benzothienyl) -2,3,3,4,4,5,5-heptafluorocyclopentene 3-bromo-6-ethenyl prepared in Example 5-c) in a 200 ml two-necked flask 2.1 g (8.3 mmol) of 2-methylbenzothiophene and 80 ml of tetrahydrofuran were added, and the mixture was cooled to -95 ° C under a nitrogen stream, and then 6.2 ml of an n-butyllithium-hexane solution (1 ml).
0.0 mmol) was added dropwise and stirred for 1 hour. Next, 3.5 g of perfluorocyclopentene (16.6 mmol)
15 ml of a tetrahydrofuran solution of 1) was added dropwise and reacted for 1 hour. After completion of the reaction, 10 ml of methanol was added to stop the reaction, 50 ml of water was further added, and the mixture was extracted three times with 200 ml of ethyl acetate. This organic layer is collected, washed,
After drying, the solvent was distilled off under reduced pressure. The obtained reaction product was purified by silica gel column chromatography, and 2.7 g of a compound represented by the following structural formula (Formula 43) was obtained (yield: 88.8).
%).

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Analytical values: 1) ¹ H-NMR (in CDCl ₃ ) δ (ppm) 2.51 (s 3H) 5.21 5.40 5.68 5.96 6.61 6.61 6.80 6.92 7 .10 (3H) 7.30-7.90 (m3H) 2) MS m / e 366 (M ⁺ )

E) (5- (2- (4-cyanophenyl)
Preparation of 2--1-ethenyl))-2,4-dimethyl-3-iodothiophene In a 300 ml two-necked flask, 27.6 g (60.0 mmol) of 4-cyanophenylphosphonium bromide was placed.
l), 2,4-dimethyl-5-formyl-3-iodothiophene 8.0 g (30.0 mmol), potassium carbonate 24.8 g (180.0 mmol), formamide
4 g (120.0 mmol), 1,4-dioxane 24
0 ml was added, and the mixture was stirred and refluxed at 95 ° C. for 24 hours to be reacted. After the reaction, the insolubles were separated by filtration, the solvent of the filtrate was distilled off under reduced pressure, diethyl ether was further added to the residue, the insolubles were filtered off, and the solvent of the filtrate was distilled off under reduced pressure. The obtained reaction product was purified by silica gel column chromatography to obtain 10.6 g of a compound represented by the following structural formula (Formula 44) (yield: 9).
6.7%).

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Analytical values: 1) ¹ H-NMR (in CDCl ₃ ) δ (ppm) 2.31 (s 3H) 2.42 (s
3H) 6.50-8.01 (m3H) 2) MS m / e 365 (M ⁺ ).

F) 1- (6-ethenyl-2-methyl-3)
-Benzothienyl) -2-((5- (2- (4-cyanophenyl) -1-ethenyl) -2,4-dimethyl-3-
Preparation of thienyl) -3,3,4,4,5,5-hexafluorocyclopentene In a 300 ml-capacity two-necked flask, the 3-iodo-5- (2- (4 -Cyanophenyl) -1-ethenyl) -2,4-dimethylthiophene (2.7 g, 7.4 mmol) and tetrahydrofuran 10
After cooling to −95 ° C. under a nitrogen stream, 5.6 ml of n-butyllithium-hexane solution (8.9 mmol) was added.
l) was added dropwise and stirred for 1 hour. Next, Example 1-d)
10 ml of a tetrahydrofuran solution of 2.7 g (7.4 mmol) of 1- (6-ethenyl-2-methyl-3-benzothienyl) -2,3,3,4,4,5,5-heptafluorocyclopentene prepared in the above. Was dropped and reacted for 1 hour. After completion of the reaction, 10 ml of methanol was added to stop the reaction, and 100 ml of water was further added.
Extracted three times with 0 ml. The organic layer was 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 3.2 g (yield 74.3%) of a compound represented by the following structural formula (Formula 45).

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Analytical values: 1) ¹ H-NMR (in CDCl ₃ ) δ (ppm) 1.70 1.93 2.16 2.3
5 2.45 (s3H, isomer) 5.27-7.76 (m4H) 2) MS m / e 585 (M ⁺ ).

G) 1- (6- (2- (4-dimethylaminophenyl) -1-ethenyl) -2-methyl-3-benzothienyl) -2-((5- (2- (4-cyanophenyl) ) -1-Ethenyl))-2,4-dimethyl-3-thienyl) -3,3,4,4,5,5-hexafluorocyclopentene 4-bromodimethylaniline was placed in a 100 ml two-necked flask. 1.4 g (7.2 mmol), Example 5-
1- (6-ethenyl-2-methyl-3) prepared in f)
-Benzothienyl) -2- (5- (2- (4-cyanophenyl) -1-ethenyl) -2,4-dimethyl-3-thienyl) -3,3,4,4,5,5-hexafluoro Cyclopentene 2.1 g (3.6 mmol), palladium acetate 16 mg (0.07 mmol), tri (2-methoxyphenyl) phosphine 0.12 g (0.46 mmol)
l), 20 ml of tri (n-butyl) amine and 10 ml of tetrahydrofuran were added, and the mixture was refluxed at 100 ° C. for 120 hours to be reacted. After the reaction, insolubles were filtered off, and the solvent in the filtrate was distilled off under reduced pressure. Diethyl ether was added to the residue, and the insolubles were filtered off. The solvent of the filtrate was distilled off under reduced pressure, and the obtained reaction product was purified by silica gel column chromatography to obtain 1.3 g of a compound represented by the following structural formula (Formula 46) (yield: 5).
0.0%).

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Analytical values: 1) ¹ H-NMR (in CDCl ₃ ) δ (ppm) 1.67 2.07 2.18 2.4
1 (s2H, isomer) 3.01 (s2H) 6.40-8.00 (m5H) 2) MS m / e 704 (M ⁺ ).

3) IR (KBr) ν (cm ⁻¹ ) 2225 (CN) (Example 6) 1- (6- (2- (4-methoxyphenyl) -1-ethenyl) -2-methyl-3- Benzothienyl) -2- (5
-(2- (4-cyanophenyl) -1-ethenyl)-
2,4-dimethyl-3-thienyl) -3,3,4,4
Production of 5,5-hexafluorocyclopentene

A) Preparation of 3-bromo-6- (2- (4-methoxyphenyl) -1-ethenyl) -2-methylbenzothiophene In Example 5, section e), 3-iodo-5- Formyl-
Similar method using 3-bromo-6-formyl-2-methylbenzothiophene instead of 2,4-dimethylthiophene and 4-methoxyphenylphosphonium chloride instead of using 4-cyanophenylphosphonium bromide Thus, 2.9 g of a compound represented by the following structural formula (Formula 47) was obtained. (Yield 82.0%).

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Analytical values: 1) ¹ H-NMR (in CDCl ₃ ) δ (ppm) 2.51 (s 1H) 3.80 (s)
1H) 6.70-7.91 (m2H) 2) MS m / e 359 (M ⁺ ).

B) 1-((6- (2- (4-methoxyphenyl) -1-ethenyl))-2-methyl-3-benzothienyl) -2,3,3,4,4,5,5 Preparation of -Heptafluorocyclopentene In section d) of Example 5, 3-bromo-6-ethenyl-
Instead of using 2-methyl-3-benzothiophene,
3-bromo-6- (2- (4-methoxyphenyl) -1
Using-(ethenyl) -2-methylbenzothiophene, 3.0 g of a compound of the following structural formula (Formula 48) was obtained in the same manner. (Yield 90.5%).

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Analytical values: 1) ¹ H-NMR (in CDCl ₃ ) δ (ppm) 2.55 (s 1H) 2.44 (s
1H) 6.74 to 7.85 (m 3H) 2) MS m / e 472 (M ⁺ ) 3) IR (KBr) ν (cm ⁻¹ ) 2226 (CN)

C) 1- (6- (2- (4-methoxyphenyl) -1-ethenyl) -2-methyl-3-benzothienyl) -2- (5- (2- (4-cyanophenyl)-
1-ethenyl) -2,4-dimethyl-3-thienyl)-
Preparation of 3,3,4,4,5,5-hexafluorocyclopentene In section f) of Example 5, 1- (6-ethenyl-2-methyl-3-benzothienyl) -2,3,3 , 4,4,
Instead of using 5,5-heptafluorocyclopentene, 1- (6- (2-) prepared in section b) of Example 6
(4-methoxyphenyl) -1-ethenyl) -2-methyl-3-benzothienyl) -2,3,3,4,4,5
Using 5-heptafluorocyclopentene, 1.6 g of the compound of the following structural formula (Formula 49) was obtained in the same manner. (Yield 68.8%).

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Analytical values: 1) ¹ H-NMR (in CDCl ₃ ) δ (ppm) 1.71 1.95 2.23 2.4
1 (s1H) 3.64 (s3H) 6.46-7.64 (m5H) 2) MS m / e 691 (M ⁺ ).

Example 7 1- (6- (2- (4-methoxyphenyl) -1-ethenyl) -2-methyl-3-benzothienyl) -2- (5
-(2- (4-methoxyphenyl) -1-ethenyl)-
2,4-dimethyl-3-thienyl) -3,3,4,4
Production of 5,5-hexafluorocyclopentene

A) 2,4-Dimethyl-5- (2- (4-
Preparation of methoxyphenyl) -1-ethenyl) -3-iodothiophene In Example 5, paragraph e), instead of using 4-cyanophenylphosphonium bromide, 4-methoxyphenylphosphonium chloride was used. According to the method, 8.1 g of a compound represented by the following structural formula (Formula 50) was obtained. (Yield 89.0
%).

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Analytical values: 1) ¹ H-NMR (in CDCl ₃ ) δ (ppm) 2.27 (s 1H) 2.41 (s
1H) 3.80 (s1H) 6.40-7.59 (m2H) 2) MS m / e 370 (M ⁺ ).

B) 1- (6- (2- (4-methoxyphenyl) -1-ethenyl) -2-methyl-3-benzothienyl) -2- (5- (2- (4-methoxyphenyl)
-1-ethenyl) -2,4-dimethyl-3-thienyl)
Preparation of -3,3,4,4,5,5-hexafluorocyclopentene In section f) of Example 5, 5- (2- (4-cyanophenyl) -1-ethenyl) -2,4- Dimethyl-3-yo-
Instead of using dothiophene, the 2,4-dimethyl-5- (2- (4-methoxyphenyl) -1-ethenyl) -3-iodothiophene prepared in section a) of Example 7 was used, Prepared in Example 6, paragraph b) instead of using 1- (6-ethenyl-2-methyl-3-benzothienyl) -2,3,3,4,4,5,5-heptafluorocyclopentene 1- (6- (2- (4-methoxyphenyl) -1-ethenyl) -2-methyl-3-benzothienyl-2,3,3,4,4,5,5-heptafluorocyclopentene The following structural formula (Formula 51)
1.4 g of the compound were obtained. (Yield 67.8%).

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Analytical values: 1) ¹ H-NMR (in CDCl ₃ ) δ (ppm) 1.76 1.98 2.10 2.3
8 (s3H, isomer) 3.62 (s2H) 6.23-7.76 (m4H) 2) MS m / e 696 (M ⁺ ).

Example 8 1- (6- (4- (4-methoxyphenyl) -1,3-
(Butadienyl) -2-methyl-3-benzothienyl)-
2- (5- (2- (4-methoxyphenyl) -1-ethenyl) -2,4-dimethyl-3-thienyl) -3,3
Preparation of 4,4,5,5-hexafluorocyclopentene a) 3-bromo-6- (2-formyl-1-ethenyl)
Preparation of 2-methylbenzothiophene In a 100 ml two-necked flask, 3.8 g (15.0 mmol) of 3-bromo-6-formyl-2-methylbenzothiophene prepared in Example 5-a) was added. 4.5 g of methylenetriphenylphosphorane (15.0 m
mol) and 45 ml of toluene, and the mixture was refluxed for 120 hours to react. After the reaction, the solvent was distilled off under reduced pressure, and diethyl ether was added to the residue, and the insoluble matter was separated by filtration. The solvent of the filtrate was distilled off under reduced pressure, and the obtained reaction product was purified by silica gel column chromatography to obtain the following structural formula (Formula 5)
3.3 g (yield 78.3%) of the compound of 2) was obtained.

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Analytical values: 1) ¹ H-NMR (in CDCl ₃ ) δ (ppm) 2.50 (s 3H) 5.80 to 8.8
2 (m5H) 9.58, 9.79 (w1H) 2) MS m / e 281 (M ⁺ ).

B) Production of 3-bromo- (6- (4- (4-methoxyphenyl) -1,3-butadienyl))-2-methylbenzothiophene 4-methoxybenzyl was placed in a two-neck flask having a capacity of 200 ml. 8.6 g of triphenylphosphonium chloride (2
0.0 mmol), prepared in Example 8-a), 3-
2.9 g (10.0 mmol) of bromo-6- (2-formyl-1-ethenyl) -2-methylbenzothiophene,
15.1 g of sodium carbonate, 3.3 g of formamide,
70 ml of 1,4-dioxane was added and refluxed for 24 hours to cause a reaction. After the reaction, insolubles were filtered off, and the solvent in the filtrate was distilled off under reduced pressure. Diethyl ether was added to the residue, and the insolubles were filtered off. The solvent of the filtrate was distilled off under reduced pressure, and the obtained reaction product was purified by silica gel column chromatography to obtain 2.6 g of a compound represented by the following structural formula (Formula 53) (yield: 6).
7.5%).

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Analytical values: 1) ¹ H-NMR (in CDCl ₃ ) δ (ppm) 2.50 (s 3H) 3.30 (s)
3H) 6.02-7.90 (m11H) 2) MS m / e 385 (M ⁺ ).

C) 1- (6- (4- (4-methoxyphenyl) -1,3-butadienyl) -2-methyl-3-benzothienyl) -2,3,3,4,4,5,5 Preparation of -Heptafluorocyclopentene In section b) of Example 6, 3-bromo- (6- (2-
Instead of using (4-methoxyphenyl) -1-ethenyl) -2-methylbenzothiophene, b) of Example 4
Using 3-bromo- (4- (4-methoxyphenyl) -1,3-butadienyl) -2-methylbenzothiophene prepared in the above section, 2.9 g of a compound of the following structural formula (Formula 54) in the same manner. I got (Yield 86.8%).

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Analytical values: 1) ¹ H-NMR (in CDCl ₃ ) δ (ppm) 2.51 (s 3H) 3.86 (s)
3H) 6.10 to 7.94 (m11H) 2) MS m / e 498 (M ⁺ ).

D) 1- (6- (4- (4-methoxyphenyl) -1,3-butadienyl-2-methyl-3-benzothienyl) -2- (5- (2- (4-methoxyphenyl) Preparation of -1-ethenyl) -2,4-dimethyl-3-thienyl) -3,3,4,4,5,5-hexafluorocyclopentene In section f) of Example 5, 1- (6- Ethenyl-2-methyl-3-benzothienyl) -2,3,3,4,4
Instead of using 5,5-heptafluorocyclopentene, 1- (6- (4-) prepared in Example 4, section c).
(4-methoxyphenyl) -1,3-butadienyl-2
-Methyl-3-benzothienyl) -2,3,3,4
Using 4,5,5-heptafluorocyclopentene, 2.6 g of the compound of the following structural formula (Formula 55) was obtained in the same manner. (Yield 71.0%).

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Analytical values: 1) ¹ H-NMR (in CDCl ₃ ) δ (ppm) 1.75 1.96 2.07 2.3
3 (s9H, isomer) 3.61 (s6H) 6.24-7.71 (m17H) 2) MS m / e 722 (M ⁺ ).

Example 9 1- (6- (2- (4-methoxyphenyl) -1-ethenyl) -2-methyl-3-benzothienyl) -2-
(2,4-dimethyl- (5- (4- (4-methoxyphenyl) -1,3-butadienyl))-3-thienyl)-
Preparation of 3,3,4,4,5,5-hexafluorocyclopentene a) Preparation of 2,4-dimethyl- (5- (2-formyl-1-ethenyl))-3-iodothiophene Example 8a )), 3-bromo-6-formyl-
Instead of using 2-methylbenzothiophene,
-Dimethyl-5-formyl-3-iodothiophene and a compound 8.5 of the following structural formula (Formula 56)
g was obtained. (82.0% yield).

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Analytical values: 1) ¹ H-NMR (in CDCl ₃ ) δ (ppm) 2.35 (s 3H) 2.41 (s
3H) 6.84-7.84 (m2H) 9.55 9.69 (d1H) 2) MS m / e 292 (M ⁺ ).

B) Preparation of 2,4-dimethyl- (4- (4-methoxyphenyl) -1,3-butadienyl) -3-iodothiophene As described in Example 8b), 3-bromo-6 Instead of using 2-formyl-1-ethenyl-2-methylbenzothiophene, 2,4-dimethyl-5- (2-formyl-
Using 1-ethenyl) -3-iodothiophene, 10.4 g of a compound of the following structural formula (Formula 57) was obtained in the same manner. (Yield 97.0%).

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Analytical values: 1) ¹ H-NMR (in CDCl ₃ ) δ (ppm) 2.20 (s 3H) 2.37 (s
3H) 3.77 (s 3H) 6.15-7.60 (m8H) 2) MS m / e 396 (M ⁺ ).

C) 1- (6- (2- (4-methoxyphenyl) -1-ethenyl) -2-methyl-3-benzothienyl) -2-((5- (4- (4-methoxyphenyl)
-1,3-butadienyl))-2,4-dimethyl-3-
Preparation of thienyl) -3,3,4,4,5,5-hexafluorocyclopentene In section f) of Example 5, 1- (6-ethenyl-2-methyl-3-benzothienyl) -2, 3,3,4,4,3
Instead of using 5,5-heptafluorocyclopentene, the 1- (6- (2-) prepared in Example 2, section b).
(4-methoxyphenyl) -1-ethenyl) -2-methyl-3-benzothienyl) -2,3,3,4,4,5
Using 5-heptafluorocyclopentene and the same method, 1.6 g of a compound of the following structural formula (Formula 58) was obtained. (Yield 76.1%).

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Analytical values: 1) ¹ H-NMR (in CDCl ₃ ) δ (ppm) 1.87 2.07 2.19 2.3
7 (9H, isomer) 3.63 (s6H) 6.46-7.78 (m17H) 2) MS m / e 722 (M ⁺ ).

<Measurement of Absorption Spectra>
The compounds obtained in 7, 8 and 9 were added to benzene at 2.1 × 10 ⁻⁵ mol / l and 1.5 × 10 ⁻⁵ mol / l, respectively.
1, 1.7 × 10 ⁻⁵ mol / l, 1.2 × 10 ⁻⁵ mol
/ L and a solution obtained by dissolving them to 2.2 × 10 ^-5 mol / l were put into a 1 cm × 1 cm × 4 cm quartz glass cell. The solution was irradiated with light of 365 nm while stirring using a 100 W ultra-high pressure mercury lamp equipped with an interference filter to color the solution, and the absorption spectrum of the solution in the photo-steady state was measured. FIG. 5 shows the compound of Example 5, and FIG. 6 shows the compound of Example 6.
FIG. 7 shows the absorption spectrum of the compound of Example 7, FIG. 8 shows the absorption spectrum of the compound of Example 8, and FIG. . Next, Table 2 shows the absorption maximum wavelength (λmax) of the colored body saturated and generated by the light of 365 nm and the molecular extinction coefficient (ε · λmax) of the compound at this maximum wavelength.

[0102]

[Table 2]

As described above, by introducing a methoxy group, a cyano group or a dimethylamino group into the thiophene ring and the benzothiophene ring, and by introducing a conjugated double bond chain, the absorption maximum wavelength of the colorant of the compound becomes longer, and Wavelength 670n
m or 780 nm semiconductor laser sensitivity was imparted and the molecular extinction coefficient increased.

(Example 10) As the diarylethene-based compound, the compounds prepared in Examples 1, 2, and 9 were used.
An optical recording medium was manufactured. An optical recording medium is manufactured by recording a 3.5-inch polycarbonate disk substrate having a pregroove by mixing a photochromic compound and polystyrene in a one-to-one ratio by a spin coating method (thickness: about 0.1 mm).
5 μm). Next, an aluminum reflective film was formed thereon by a sputtering method. The obtained disk was irradiated with 100 W black light mainly composed of 365-nm ultraviolet light for 20 minutes to color the entire photochromic compound. A recording / reproducing test was performed by irradiating the colored recording surface with 680 nm semiconductor laser light focused to a spot diameter of about 1 μm. Results were recorded at a disk rotation speed of 1200 times / minute (linear velocity: 4.3 m / second), laser intensity of 7 mW, recording frequency of 1 MHz (duty ratio: 50%), and then reproduced at the same rotation speed and laser intensity of 0.2 mW. Are shown in Table 3. The temperature of the optical recording medium during recording is 1
The temperature was 20 ° C. or higher and 40 ° C. or lower during regeneration.

[0105]

[Table 3]

From the results in Table 3, for example, in Test Example 1,
Immediately after recording, the CN ratio was 51 dB (dB).
When the same track was reproduced for 10 minutes (corresponding to 12000 reproductions), the CN ratio was 47 dB (dB), not much different from that immediately after recording, and the reproduction destruction was very small. Similarly, in all of the discs of Test Examples 2 and 3, the recording destruction by reproduction for 10 minutes was very small.

[Brief description of the drawings]

FIG. 1 is a graph showing a change in an absorption spectrum of a compound obtained in Example 1 due to light irradiation in a benzene solution.

FIG. 2 is a graph showing a change in an absorption spectrum of a compound obtained in Example 2 based on light irradiation in a benzene solution.

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

FIG. 4 is a graph showing a change in an absorption spectrum of the compound obtained in Example 4 due to light irradiation in a benzene solution.

FIG. 5 is a graph showing a change in an absorption spectrum of a compound obtained in Example 5 due to light irradiation in a benzene solution.

FIG. 6 is a graph showing a change in an absorption spectrum of the compound obtained in Example 6 due to light irradiation in a benzene solution.

FIG. 7 is a graph showing a change in an absorption spectrum of the compound obtained in Example 7 due to light irradiation in a benzene solution.

FIG. 8 is a graph showing a change in an absorption spectrum of the compound obtained in Example 8 due to light irradiation in a benzene solution.

FIG. 9 is a graph showing a change in an absorption spectrum of the compound obtained in Example 9 due to light irradiation in a benzene solution.

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──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁶ Identification code Agency reference number FI Technical display location G11B 7/24 516 8721-5D G11B 7/24 516 // C07D 333/62 C07D 333/62 (72 Inventor Masahiro Irie 1-29 Kasuga Park, Kasuga-shi, Fukuoka Examiner Koichi Sesita

Claims (4)

(57) [Claims] 1. A diarylethene compound having a conjugated double bond represented by the following general formula (1). Embedded image (Wherein, n represents an integer of 2 to 5. A is a general formula (2). Wherein l is an integer of 1 or 2, R ¹ is an alkyl group, R ²
To R ⁴ are a hydrogen atom, an alkyl group, a dialkylamino group,
P represents a cyano group, a nitro group or an alkoxy group, and P represents an aromatic group or a heterocyclic group. B is a general formula (3) M represents an integer of 1 or 2, R ⁵ and R ⁶ represent an alkyl group, and Q represents an aromatic group or a heterocyclic group. Or the general formula (4): Wherein o is an integer of 1 or 2, R ⁷ is an alkyl group, R ⁸
To R ¹⁰ are a hydrogen atom, an alkyl group, a dialkylamino group,
T represents a cyano group, a nitro group or an alkoxy group, and T represents an aromatic group or a heterocyclic group. ) 2. A conjugated double bond represented by the following general formula (1):
For producing diarylethene compounds having a concatenated chain
Law. Embedded image (Where n represents an integer of 2 to 5. A is a general formula.
(2) [of 6] Wherein l is an integer of 1 or 2, R ¹ is an alkyl group, R ²
To R ⁴ are a hydrogen atom, an alkyl group, a dialkylamino group,
A cyano group, a nitro group or an alkoxy group, and P is an aromatic group or
Represents a heterocyclic group. B is the general formula (3) [of 7] Wherein m is an integer of 1 or 2, and R ⁵ and R ⁶ are alkyl
The group, Q, represents an aromatic group or a heterocyclic group. Or general formula
(4) [of 8] Wherein o is an integer of 1 or 2, R ⁷ is an alkyl group, R ⁸
To R ¹⁰ are a hydrogen atom, an alkyl group, a dialkylamino group,
A cyano group, a nitro group or an alkoxy group, and T represents an aromatic group or
Represents a heterocyclic group. ) 3. A di-containing compound having a conjugated double bond according to claim 1.
An arylethene compound is used as a recording material, and the recording material is
Evaporation method, dispersed or dissolved in solvent with binder
An optical recording medium obtained by a method of disassembling and applying. 4. A method for irradiating an ultraviolet light to change a colored state.
After initialization, the information is recorded by irradiating visible light to change to a colorless state, and the recorded information is reproduced by irradiating the visible light with the optical recording / reproducing method. The temperature of the optical recording medium at the time of recording is set at least 40 ° C. lower than the temperature of the optical recording medium at the time of recording .
The optical recording / reproducing method for an optical recording medium according to claim 3, wherein