JP3228087B2 - 2,3-Diarylquinone and method for producing the same - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a novel 2,3-diarylquinone and a method for producing the same. More specifically, the present invention relates to 2,3-diarylquinones that exhibit both photoreactions and electrochemical reactions and are useful as photo-electrical functional materials, and to a method for producing the same.

[0002]

2. Description of the Related Art Attempts have been made to use a chemical substance whose absorption spectrum changes upon irradiation with light as a photoresponsive dye for optical recording. Photochromic dyes whose absorption spectra are reversibly changed by light are being studied as rewritable optical recording materials, and photoresponsive dyes whose absorption spectra are irreversibly changed by light are also being studied as write-once optical recording materials. For example, as photochromic compounds, there are diarylethenes disclosed in JP-A-61-263935, JP-A-3-135977, and JP-A-3-14538. On the other hand, a chemical substance that shows a redox response by electrical stimulation is called an electrochromic compound, and is an electrically responsive compound used for recording and displaying electrical information. By using a compound having both a light response function and an electric response function for recording and converting information, it is expected to convert an optical signal into an electric signal or an electric signal into an optical signal.

[0003]

Japanese Unexamined Patent Publication (KOKAI) Showa No. 63-68553 discloses electroresponsive anthraquinones having a photoresponsive azo group as a compound exhibiting a photoresponsive function and an electrical response. However, Molecular Crystals and Liquid
As shown in Crystals, 246, 319 (1994), there was a change in the oxidation-reduction potential due to the photoreaction of the azo moiety, but the change was not large, and the function of converting an optical signal to an electrical signal was not sufficient. . Accordingly, an object of the present invention is to provide a compound having both a light response function and an electric response function, and having a sufficiently large change in oxidation-reduction potential due to a light reaction, and a method for producing the same.

[0004]

In order to solve the above-mentioned problems, the present invention provides a 2,3-diarylquinone having two heteroaromatic ring substituents at the 2- and 3-positions of a quinone ring and a method for producing the same. Is what you do. That is, the present invention provides a 2,3-diarylquinone represented by the following formula (I).

[0005]

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R ₁ is a methyl group or —CHCHCH—CH = CH
-May contain a quinone ring double bond to form a naphthoquinone ring. X is a sulfur atom. R ₂ , R ₃ and R ₄ are hydrogen atoms, R ₂ is a methyl group, R ₃ is a trimethylsilyl group, R ₄ is a hydrogen atom, or R ₂ is a methyl group,
R ₃ and R ₄ may be -CH = CH-CH = CH- and contain a 5-membered double bond to form a ring. And, the present invention relates to 2,3-
A method for producing a diarylquinone, comprising the following formula (II)

[0007]

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(R ₁ is a methyl group or —CH = CH
-CH = CH- may contain a double bond at the 5- or 6-position of the quinone ring to form a naphthoquinone ring. Y represents a bromine atom. )
2,3-dibrominated quinone represented by the following formula (III)

[0009]

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(X is a sulfur atom. R ₂ , R ₃ and R ₄
Is a hydrogen atom, R ₂ is a methyl group, R ₃ is a trimethylsilyl group, R ₄ is a hydrogen atom, or R ₂ is a methyl group, R ₃ and R ₄ are -CH = CH-CH = CH -May contain a 5-membered double bond to form a ring. Z represents Sn (n-Bu) ₃ . 2,3) consisting of reacting with an aryl metal compound represented by
-To provide a process for the preparation of diarylquinones.

Formula (II) is dibrominated dimethylbenzoquinone and naphthoquinone, and specific examples thereof are 2,3
-Dibromo-5,6-dimethylbenzoquinone, 2,3-dibromonaphthoquinone. Dihalogenated quinones are described, for example, in J. Am. Chem. Soc., 64, 528 (1942), J. Am.
It is obtained by halogenating quinone by the method shown in Chem. Soc., 66, 1077 (1944).

In the metal compound having a 5-membered hetero ring represented by the formula (III), R ₂ , R ₃ and R ₄ are the same substituents as R ₂ , R ₃ and R ₄ shown in the formula (I) and have a hydrogen atom , Methyl group, trimethylsilyl group,
Represents a cyano group. When X is a sulfur atom, R ₃ and R ₄ are -C
H = CH-CH = CH- may form a ring including a 5-membered double bond. That is, the hetero 5-membered ring, R ₂ , R ₃ , R ₄ is a methyl group,
When it is a trialkylsilyl group or a cyano group, it is a thiophene or pyrrole derivative optionally having these substituents. Further, R ₃ and R ₄ of the hetero 5-membered ring are -CH = CH-CH = CH-
In the case of forming a ring including a 5-membered double bond, it is a benzothiophene derivative which may have a substituent such as a methyl group. Z is an organic metal group, and represents a trialkyltin residue such as tributyltin. These aryl metal compounds are produced by a conventional method from a precursor aryl halide compound. Examples of manufacturing methods include Tetrahedron Le
tters, 35, 2405 (1994).

The 2,3-dibrominated quinone of the formula (II) and the formula (III)
Of the formula (I)
Produce 2,3-diarylquinone. For the reaction, ether solvents such as diethyl ether, tetrahydrofuran, dioxane and dimethoxyethane, aromatic solvents such as toluene and xylene, amide solvents such as dimethylformamide, chlorine solvents such as methylene chloride, chloroform and ethylene dichloride, and nitrile solvents such as acetonitrile Solvents are preferred.

In the reaction, tetrakis (triphenylphosphine) palladium, trisdibenzylideneacetone) dipalladium, carbonyltris (triphenylphosphine) palladium, and bis (isocyanated t-) are used as catalysts.
Good results are often obtained by using palladium compounds such as (butyl) palladium. These catalysts are used with respect to 2,3-dibrominated quinone represented by the formula (II) in an amount of 0.0
It is preferable to add in the range of 1 to 10%.

The reaction temperature is from 20 to 150 ° C., and it is more preferable to carry out the reaction under the reflux condition of the solvent. The reaction time usually ends within 30 minutes to 24 hours. In some cases, the reaction needs to be performed in dry air or an inert gas such as nitrogen, helium, or argon. The reaction solution is concentrated and purified by a usual treatment to obtain a 2,3-diarylquinone compound represented by the general formula (I).

The trialkylsilyl substituent of the 2,3-diarylquinone is replaced by a hydrogen atom by an acid or fluorine compound. Mineral acids such as hydrochloric acid, sulfuric acid and nitric acid, and fluorine compounds such as tributylammonium fluoride are useful.
Acids and fluorine compounds are used in an amount of one equivalent or more, and solvents such as tetrahydrofuran and ethers such as diethyl ether;
Chlorine solvents such as dichloromethane, chloroform and dichloroethane, and aromatic solvents such as toluene and xylene are used. The reaction is performed by cooling or heating,
0 ° C to 120 ° C is preferable, and the reaction time is 10 minutes to
78 hours is normal. When the aryl group is pyrrole, its nitrogen atom may be protected by a tosyl group, but the tosyl group can be replaced with a hydrogen atom by alkali treatment. As the alkali, carbonates such as potassium carbonate and sodium carbonate, and hydroxides such as sodium hydroxide and potassium hydroxide are effective. The alkali is used in an equivalent amount or more, usually in excess, and as the solvent for the alkali treatment, a combination of water and an ether solvent such as dioxane, ethylene glycol diethyl ether, and tetrahydrofuran is useful. The reaction is usually performed with heating and stirring, and the reaction temperature is from room temperature to 120 ° C.
Is preferred, and the reaction time is usually from 30 minutes to 78 hours.

The 2,3-diarylquinone of the present invention is colored and has a light absorption band in the visible region, and an increase or decrease in the absorption band was observed by light irradiation. Fig. 1 shows an example. When the material of the present invention is used for optical recording, the presence or absence of a recording signal can be read out based on a change in absorption intensity before and after light irradiation. A feature of the present invention is that the 2,3-diarylquinone of the present invention exhibits an electrical response derived from redox of a quinone moiety.
The redox is obtained as an electric signal by measuring the redox potential or the redox current in an electrolytic solution, for example. Usually, quinone is reduced by one electron to a quinone radical. In the case of the 2,3-diarylquinones of the present invention, a redox response to one-electron reduction of quinone into quinone radical in the organic electrolyte was observed. The present material can be formed into a thin film by spin coating or vapor deposition, or can be kneaded or dissolved in a transparent polymer material and formed into a thin film.

[0018]

This 2,3-diarylquinone has an absorption in the visible region, but exhibits a photoresponse in which this absorption band increases and decreases by light irradiation. The 2,3-diarylquinone exhibited a redox response derived from the quinone moiety. The oxidation-reduction potential or the oxidation-reduction current was significantly different before and after the light irradiation, and the change due to the light irradiation could be read out as the oxidation-reduction potential or the oxidation-reduction current by an electric signal. For example, as shown in Example 17, 2,3-bis (2-methyl-
In the case of 5-trimethylsilyl-3-thienyl) -5,6-dimethylbenzoquinone, a redox potential shift of 0.06 V was observed before and after light irradiation. That is, the 2,3-diarylquinone of the present invention provides an information recording material and an information conversion material for converting an optical signal into an electric signal.

[0019]

DESCRIPTION OF THE PREFERRED EMBODIMENTS Specific embodiments for carrying out the present invention will be described below with reference to examples.

[0020]

EXAMPLES The chemical structure of the diarylquinone compound of the present invention was determined by mass spectroscopy (MS), nuclear magnetic resonance spectrum ( ¹
H, ¹³ C). Mass spectrometry spectra were measured by the direct introduction method. Nuclear magnetic resonance spectra were measured in CDCl ₃ at 270 MHz using tetramethylsilane as a reference material. A 500 W xenon lamp was used as the light source for photochemical measurement.
Ultraviolet light and visible light were obtained through various glass filters.
In the electrochemical measurement, 2,3-diarylquinone of this example was dissolved in acetonitrile containing tetrabutylammonium tetrafluoroborate (0.1 mol dm ^-3 ) as a supporting electrolysis, and cyclic voltammogram measurement was performed using a platinum electrode. This was performed by measuring the oxidation-reduction potential at the time of the first potential operation. ¹ H-NMR, ¹³ C-NMR, MS, n-
Table 1 shows the absorption maximum at the longest wavelength side in hexane, the first reduction potential (V vs Ag / AgClO ₄ ), and the yield of 2,3-diarylquinone based on 2,3-dihalogenated quinone. The compounds synthesized in Examples 1 to 16 are shown in Synthesis Example 1.

Example 1 Synthesis of 2,3-bis (3-thienyl) naphthoquinone 2,3-dibromonaphthoquinone (252 mg, 0.79 mmol), (3-
Thienyl) tributyltin (650 mg, 1.74 mmol) and trakis (triphenylphosphine) palladium (18 mg, 0.1 mg).
0016 mmol) in anhydrous toluene (24 ml).
Heated to reflux for an hour. The solution was cooled to room temperature, diluted with ether and filtered, and the filtrate was stirred with a 10% aqueous potassium fluoride solution for 1 hour. The precipitated tributyltin fluoride was removed by filtration, concentrated, and purified by column chromatography. The obtained 2,3-bis (3-thienyl) naphthoquinone was a red powder, and its physical properties are shown in Table 1.

Examples 2,3,4,5,6 2,3-bis (2-methyl-5-trimethylsilylthiene-3
-Yl) naphthoquinone (Example 2, compound 2), 2,3-bis
(2-Cyano-1,5-dimethyl-4-pyrrolyl) naphthoquinone (Example 3, compound 3), 2,3-bis (Nt-butyldimethylsilyl-3-indolyl) naphthoquinone (Example 4,
Compound 4), 2,3-bis (N-tosyl-3-indolyl) -naphthoquinone (Example 5, compound 5), 2,3-bis (2-methylbenzothiophen-3-yl) naphthoquinone (Example 6) , Compound 6) was prepared in the same manner as in Example 1 except that (3-thienyl) tributyltin was used, instead of using 2-methyl-5-trimethylsilyl-3- (tributylstannyl) thiophene.
Cyano-1,5-dimethyl-3- (tributylstannyl) pyrrole, N- (t-butyldimethylsilyl) -3- (tributylstannyl) indole, (N-tosyl-3- (tributylstannyl) indole, The compounds were synthesized using 2-methyl-3- (tributylstannyl) benzothiophene, respectively, and various physical properties are shown in Table 1.

Examples 7, 8, 9, 10 2,3-bis (3-thienyl) -5,6-dimethylbenzoquinone
(Example 7, compound 7), 2,3-bis (2-methyl-5-trimethylsilyl-3-thienyl) -5,6-dimethylbenzoquinone (Example 8, compound 8), 2,3-bis (2 −Cyano-1,5
-Dimethyl-4-pyrrolyl) -5,6-dimethylbenzoquinone (Example 9, compound 9), 2,3-bis (Nt-butyldimethylsilyl-3-indolyl) -5,6-dimethylbenzoquinone (imp. Example 10, compound 10) uses 2,3-dibromo-5,6-dimethylbenzoquinone instead of 2,3-dibromonaphthoquinone and further uses (tributylstannyl) thiophene instead of (3-thienyl) tributyltin. 2-methyl-3- (tributylstannyl) -5-trimethylsilylthithiophene, 2-cyano-1,5-dimethyl-
The synthesis was carried out in the same manner as in Example 1 except that the reaction was carried out using 3- (tributylstannyl) pyrrole and N- (t-butyldimethylsilyl) -3- (tributylstannyl) indole, respectively. The physical properties are shown in Table 1.

Example 11 2,3-Bis (2-methyl-benzothiophen-4-yl)-
5,6-Dimethylbenzoquinone (Compound 11) is composed of 2,3-dibromonaphthoquinone (254 mg, 0.8 mmol), 2-methyl-benzothiophen-3-boric acid (334 mg, 1.74 mmol) and trakis (triphenylphosphine) Palladium (18 mg, 0.00
16 mmol) in ethylene glycol dimethyl ether (24 m
l), an aqueous solution of sodium hydrogen carbonate was added, and the mixture was heated under reflux for 6 hours to synthesize. The solution was cooled to 20 ° C., extracted with ether, concentrated, and purified by column chromatography to obtain 2,3-bis (2-methyl-benzothiophen-3-yl).
-5,6-Dimethylbenzoquinone was obtained in 67% yield.

Example 12 2- (2-cyano-1,5-dimethyl-4-pyrrolyl) -3- (2
-Methyl-5-trimethylsilylthiophen-3-yl)
-5,6-Dimethylbenzoquinone (Compound 12) was synthesized by reacting two bromines of 2,3-dibromo-5,6-dimethylbenzoquinone stepwise. First, 2,3-dibromo-5,6
-Dimethylbenzoquinone 151 mg (0.0514 mmol), 2-cyano-1,5-dimethyl-4-tributylstannylpyrrole 21
0 mg (0.514 mmol) and tetrakis (triphenylphosphine) palladium 12 mg (0.01 mmol) in toluene 16 ml
And reacted by heating and stirring at 80 ° C. for 4 hours. After cooling the reaction mixture to 20 ° C., it was diluted with ether, filtered through celite, and treated with a saturated aqueous potassium fluoride solution. After removing the precipitated tributyltin fluoride by filtration, the ether layer was concentrated, and purified by column chromatography to give 3-bromo-2- (2-cyano-1,5-dimethyl-4.
-Pyrrolyl) -5,6-dimethylbenzoquinone 104 mg was obtained.
(62% yield). 3-bromo-2- (2-cyano-1,5-dimethyl-4-pyrrolyl) -5,6-dimethylbenzoquinone 116 mg
(0.498 mmol), 2-methyl-5-trimethylsilyl-3-
232 mg (0.506 mmol) of tributylstannylthiophene,
Tetrakis (triphenylphosphine) palladium 11
A solution of mg (0.01 mol) in anhydrous toluene was heated and stirred at 100 ° C. for 2 days to be reacted. After cooling the reaction mixture to room temperature,
The mixture was diluted with ether, filtered through celite, and treated with a saturated aqueous potassium fluoride solution. After removing the precipitated tributyltin fluoride by filtration, the ether layer was concentrated, and purified by column chromatography to give 2- (2-cyano-1,5.
-Dimethyl-4-pyrrolyl) -3- (2-methyl-5-trimethylsilylthiophen-3-yl) -5,6-dimethylbenzoquinone (184 mg) was obtained (88% yield). The physical properties are shown in Table 1.

Examples 13, 14 2- (2-Methylbenzothiophen-3-yl) -3- (2-cyano-1,5-dimethyl-4-pyrrolyl) -5,6-dimethylbenzoquinone (Example 13) , Compound 13) and 2- (Np-toluenesulfonyl-3-indolyl) -3- (2-cyano-1,5
-Dimethyl-4-pyrrolyl) -5,6-dimethylbenzoquinone (Example 14, compound 14) was synthesized by the stepwise reaction of two bromines of 2,3-dibromo-5,6-dimethylbenzoquinone. Monosubstituted 3-bromo-2- (2-cyano-1,5-
(Dimethyl-4-pyrrolyl) -5,6-dimethylbenzoquinone was synthesized in the same manner as in Example 12, except that 2-methyl-5-trimethylsilyl-3-tributylstannylthiophene was used. In a similar manner, 2-methyl-3-tributylstannylbenzothiophene, N-p-
Compounds 13 and 14 were synthesized by reacting toluenesulfonyl-3-tributylstannyl indole, respectively. The physical properties are shown in Table 1.

Example 15 2,3-Bisindolo-3-ylnaphthoquinone (Compound 1
5) was synthesized by replacing the t-butyldimethylsilyl group of 2,3-bis (Nt-butyldimethylsilyl-3-indolyl) naphthoquinone obtained in Example 4 with a hydrogen atom. 128 mg of 2,3-bis (Nt-butyldimethylsilyl-3-indolyl) naphthoquinone was added to tetrahydrofuran 10
dissolved in 3 ml, and added with 3 equivalents of tetrabutylammonium fluoride and stirred at 0 ° C. for 2 hours to obtain t.
A -butyldimethylsilyl group was replaced by a hydrogen atom. The reaction mixture was concentrated, extracted with ether, and then treated with column chromatography to obtain 2,3-bisindolo-3-ylnaphthoquinone in a yield of 32%. Table 1 shows the physical properties of 2,3-bisindolo-3-ylnaphthoquinone.

Example 16 2,3-Bisindolo-3-ylnaphthoquinone was synthesized by replacing the tosyl group of 2,3-bis (N-tosyl-3-indolyl) naphthoquinone obtained in Example 5 with a hydrogen atom. did. 2,3
-Bis (N-tosyl-3-indolyl) naphthoquinone was dissolved in dioxane, 4 equivalents of a saturated aqueous potassium carbonate solution was added, and the mixture was stirred under reflux for 6 hours to convert the tosyl group into a hydrogen atom. The reaction mixture was concentrated, extracted with ether, and the concentrate was purified by column chromatography to give 2,3-
Bisindolo-3-ylnaphthoquinone was obtained. Got
The physical properties of 2,3-bisindolo-3-ylnaphthoquinone were consistent with those obtained in Example 15.

[0029]

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[0030]

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[0031]

[Table 1]

[0032]

[Table 2]

[0033]

[Table 3]

[0034]

[Table 4]

Example 17 The 2,3-bis (2-methyl-5-trimethylsilyl-3-thienyl) -5,6-dimethylbenzoquinone obtained in Example 8 was dissolved in n-hexane and the absorption spectrum was measured. It showed an absorption maximum with a molar extinction coefficient of 1866 at a wavelength of 424 nm. When this solution was irradiated with light having a wavelength of 450 nm (500 W xenon lamp light is separated by an interference filter) for 10 minutes, 424 nm
Absorption band decreased. The results are shown in FIG. When the oxidation-reduction potential was measured in acetonitrile containing tetrabutylammonium tetrafluoroborate (0.1 moldm ^-3 ) as a supporting electrolyte, quinone radical was converted from quinone to quinone radical.
The first reduction potential for electron reduction is −0.96 V (Reference electrode: Ag
/ AgClO ₄ ). After light irradiation, the potential reduced from quinone to quinone radical changed to -0.90 V, and the reduction current decreased. Table 1 shows the absorption maximum of other 2,3-diarylquinone in a hexane solution and the first reduction potential in acetonitrile. 2,3-Diarylquinone was observed to decrease the absorption in the visible region and the reduction current by light irradiation.

[0036]

According to the present invention, the 2,3-- represented by the general formula (I)
Since diarylquinone is a compound having both a light response function and an electric response function and a change in oxidation-reduction potential caused by a photoreaction is sufficiently large, the present invention can provide a material useful as a photo-electric function material. When the 2,3-diarylquinone of the present invention is immobilized on an electrode, a change in the oxidation-reduction potential due to light irradiation can be extracted as an electric signal. That is,
Converts optical signals to electrical signals. Accordingly, a sensor that converts an optical signal into an electric signal, and a device that operates as a memory or a transducer that inputs by an optical signal and outputs by a light yellow signal are obtained.

[Brief description of the drawings]

FIG. 1 shows a light absorption spectrum of a solution of 2,3-bis (2-methyl-5-trimethylsilyl-3-thienyl) -5,6-dimethylbenzoquinone dissolved in n-hexane before and after irradiation with light having a wavelength of 450 nm. FIG.

────────────────────────────────────────────────── ─── Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI C07D 409/08 C07D 409/08 // C09K 3/00 C09K 3/00 C (56) Reference European Patent Application Publication 560684 (EP, A 1) Bull. Soc. Chim. Bel g. , (1994), Vol. 103, No. 1, p. 31-33 (58) Field surveyed (Int. Cl. ⁷ , DB name) C07D 207/335 C07D 209/12 C07D 333/08 C07D 333/60 C07D 403/08 C07D 409/08 C09K 3/00 CA (STN ) CAOLD (STN) REGISTRY (STN)

Claims (3)

(57) [Claims] 1. A 2,3-diarylquinone represented by the following formula (I). Embedded image (R ₁ may be a methyl group, or may include a double bond of a quinone ring at —CH = CH—CH = CH— to form a naphthoquinone ring.
X is a sulfur atom. R ₂ , R ₃ and R ₄ are hydrogen atoms, R ₂ is a methyl group, R ₃ is a trimethylsilyl group, R ₄ is a hydrogen atom, or R ₂ is a methyl group, and R ₃ and R ₄ are -C
H = CH-CH = CH- and a 5-membered double bond may be contained to form a ring. ) 2. A process for producing a 2,3-diarylquinone according to claim 1, comprising a 2,3-dibrominated quinone represented by the following formula (II) and an aryl represented by the following formula (III): A method for producing 2,3-diarylquinone, which comprises reacting a metal compound with a metal compound. Embedded image (R ₁ may be a methyl group or may form a naphthoquinone ring containing -CH = CH-CH = CH- containing a 5-position or 6-position double bond of a quinone ring. Y represents a bromine atom ). (X is a sulfur atom. R ₂ , R ₃ and R ₄ are hydrogen atoms, R ₂ is a methyl group, R ₃ is a trimethylsilyl group, R ₄ is a hydrogen atom, or R ₂ is methyl Group, R ₃ and R ₄ are -C
H = CH-CH = CH- and a 5-membered double bond may be contained to form a ring. Z represents Sn (n-Bu) ₃ . ) 3. The palladium compound as a catalyst when the 2,3-dibrominated quinone represented by the formula (II) is reacted with the aryl metal compound represented by the formula (III). Production method of 2,3-diarylquinone.