JP2883639B2 - Thieno [3,2-b] thienylidenebisbenzoquinones and method for producing the same - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a functional dye and near-infrared absorption used for an information recording system using light, an energy conversion system, a control system for equipment, and an electrochromic material. The present invention relates to a novel compound suitably used as an agent and a method for producing the same.

More specifically, optical recording media, optical cards, optical tapes,
Organic photoreceptors, light absorbing or external light blocking materials for control mechanisms such as televisions and sound systems, protective materials during laser processing, protective glasses, optical filter materials for controlling the growth of plant microorganisms, dye lasers, etc. The present invention relates to a light emitting material, a compound used in other fields, and a method for producing the compound.

[Prior art and its problems] Research and development of functional dyes used in information recording systems, energy conversion systems, and equipment control systems using light are being actively conducted.

As one of information recording systems using light, there is high-density optical recording using a semiconductor laser. As a method close to practical use, a recording medium is condensed and irradiated with light to convert it into thermal energy, and the heat causes the recording medium to have pits, for example,
There is a method in which a change in the shape of holes, bubbles, and the like is generated and recorded, and the change in the shape is scanned with light that is sufficiently weakened so as not to damage the recording medium layer, and a change in the reflected light is detected to reproduce a signal. .

Therefore, the role of the functional dye and the near-infrared absorber used in this recording medium plays an important role in efficiently absorbing the light of the semiconductor laser and converting it into heat.

Compounds that can be used as a recording medium of such a type, for example, "Dyes and Chemicals" Vol. 30, No. 11, 308
Pp. 318 describe that an intramolecular charge transfer complex represented by the formula (3) is used.

Equation (3) Further, as a near-infrared absorbing agent, a cyanine dye (JP-A No.
56-46221, JP-A-58-112790); phthalocyanine dye (JP-A-58-36490); naphthoquinone dye (JP-A-60-1)
5458); anthraquinone dyes (JP-A-61-291651); and dithiol complexes (JP-A-58-175693) are known.

However, anthraquinone and naphthoquinone dyes have drawbacks such as a small molar absorption coefficient of about tens of thousands, and dithiol complexes have insufficient thermal stability and insufficient molar absorption coefficient.

[Detailed Disclosure of the Invention] The present inventors have intensively studied and studied a specific cross-conjugated compound that solves the above-mentioned drawbacks. As a result, a novel compound having a long-wavelength portion light absorption ability, thieno [ 3,2
-B] Thienylidenebisbenzoquinones were discovered, and the present invention was completed.

That is, the present invention relates to thieno [3,2-b] thienylidenebisbenzoquinones represented by the following general formula (1): [In the formula (1), R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , and R ₆ each independently represent a hydrogen atom or a linear or branched alkyl group having 1 to 8 carbon atoms. . The following general formula (2) [In the formula (1), R ₁ , R ₂ , R ₃ , R ₄ and R ₅ , R ₆ have the same meaning as described above. [3,2-b]
A method for producing a thieno [3,2-b] thienylidenebisbenzoquinone represented by the above general formula (1), which comprises oxidizing a thiophene bisphenol. [In the formula (2), R ₁ , R ₂ , R ₃ , R ₄ and R ₅ , R ₆ have the same meaning as described above. Thieno [3,2-b]
Thiophene bisphenols.

 Hereinafter, the present invention will be described in detail.

Thieno [3, represented by the following general formula (1) of the present invention:
2-b] thienylidenebisbenzoquinones [In the formula (1), R ₁ , R ₂ , R ₃ , R ₄ and R ₅ , R ₆ have the same meaning as described above. ] Is not particularly limited, but can be produced, for example, as follows.

That is, equation (4) Wherein (4), R _1, R ₂ means R _1, R ₂ the same group in the formula (1). The thieno [3,2-b] thiophene compound represented by the formula
Reacting with butyllithium and further reacting with zinc chloride to synthesize a thieno [3,2-b] thiophene zinc chloride represented by the formula (5), Wherein (5), R _1, R ₂ means R _1, R ₂ the same group in the formula (1). This and equation (6) Wherein (6), R _3, R ₄ means a R _3, R ₄ the same group in the formula (1). And reacting with a trimethylsiloxybenzene iodide compound represented by the following formula (7): [In the formula (7), R ₁ , R ₂ , R ₃ , and R ₄ are the same as R ₁ ,
It means the same group as R ₂ , R ₃ and R ₄ . A thieno [3,2-b] thienylbenzene compound represented by the following formula is synthesized.

Further, after converting the obtained compound into thieno [3,2-b] thienylbenzene zinc chloride represented by the formula (8), [In the formula (8), R ₁ , R ₂ , R ₃ and R ₄ are the same as R ₁ ,
It means the same group as R ₂ , R ₃ and R ₄ . Again reacting the trimethylsiloxybenzene iodide compound represented by (9), Wherein (9), R _5, R ₆ means a R _5, R ₆ the same group in the formula (1). Expression (10) [In the formula (10), R ₁ , R ₂ , R ₃ , R ₄ and R ₅ , R ₆ are the same as R ₁ , R ₂ , R ₃ , R ₄ and R ₅ , It means the same group as R _6. ] The compound shown by these is synthesize | combined. This is hydrolyzed to obtain a thieno [3,2-b] thiophenebisphenol compound represented by the general formula (2), [In the formula (2), R ₁ , R ₂ , R ₃ , R ₄ and R ₅ , R ₆ are the same as R ₁ , R ₂ , R ₃ , R ₄ , R ₅ and R _{6 in the} formula (1). And the same group. By oxidizing this, thieno [3,2-b] thienylidenebisbenzoquinones, which are cross-conjugated compounds represented by the general formula (1), are produced.

As the oxidation reaction in the present invention, a conventionally generally known method of oxidizing phenols to quinones is applied, for example, the Chemical Society of Japan, "New Experimental Chemistry Course, Vol. 15,
Oxidation and reduction 1, 2 "and the like. The conditions of the oxidation reaction may vary depending on the used reactant, oxidation catalyst and the like, but usually the temperature is from room temperature to 200 ° C. and the reaction time is from about 10 minutes to 24 hours.

In the present invention, as the oxidizing agent used in the oxidation reaction, a catalyst known per se for oxidizing phenol to quinone is used, for example, potassium permanganate, manganese dioxide, chromic acid, potassium dichromate, dichromium Inorganic oxidants such as inorganic oxidants such as sodium silicate, lead tetraacetate, potassium ferricyanide, and ferric chloride; oxidants such as oxygen and hydrogen peroxide; and oxidizing systems by coexisting with them and organic oxidation such as dicyanodichlorobenzoquinone and chloranil Any of these agents may be used, but potassium ferricyanide is preferred from the viewpoint of cost or industrial use.

The reaction may be suspended in water, suspended in an organic solvent, or
The reaction may be carried out as a water-organic solvent two-phase system or any reaction system. Particularly, in the case of using a water-benzene two-phase system, the yield is good.

Further, the compound represented by the general formula (1) has a light absorption wavelength in the visible region, and can be usefully used as a light blocking effect in a wavelength range from the visible region to the near infrared region, that is, various filters. For example, electrical products, especially remote control devices such as televisions, radios, stereos, and various sound systems, distance measurement such as cameras, light receiving elements in game machines and automatic doors, etc. It can be suitably used as a protective material at the time, protective glasses, an optical filter material for plants and microorganisms, and growth control.

EXAMPLES Hereinafter, the present invention will be specifically described with reference to Examples. The structural formulas of the compounds used in the examples are summarized on pages 26 to 27.

[2- (3,5-di-t-butyl-4-trimethylsiloxyphenyl) thieno [3,2-b] thiophene (formula (1
Synthesis of 3))] To a solution of thieno [3,2-b] thiophene (2.00 g, 14.26 mmol) dissolved in ether (19 ml), a solution of t-butyllithium in n-pentane (14.26 mmol) was added to perform monolithiation. I do.

This lithiated product was treated with zinc chloride (1.94 g, 14.26 mmol) in THF.
(19 ml) By adding to the solution at 0 ° C., a product represented by the compound (formula (11)) was obtained.

On the other hand, PdCl ₂ (PPh ₃ ) ₂ (385 mg, 0.546 mmol), THF (18 m
l), and 1 M / 1 DIBAH in n-hexane (1.097 mmol)
l) Compound (Formula (12)) (5.76 g, 14.26 mm
ol) in THF (25 ml), and further added at room temperature for 10 minutes.
Stirred.

Next, the compound (formula (11)) prepared above was added thereto.
The THF solution was added at room temperature, and the reaction was further performed for 1 hour.

Water and then 1N HCl (10 mmol) were added to the reaction mixture, and ether was added and extracted. The ether layer was washed with water and saturated saline, and then dried over anhydrous sodium sulfate.
The solvent was removed, and the residue was purified by silica gel chromatography (n-hexane) to obtain 3.58 g of the compound (formula (13)) (yield: 60.3%) as white crystals having a melting point of 127 to 130 ° C.

In the compound (formula (13)), a molecular ion appears as a base peak at m / e416 in a mass spectrum, and 0.4
The trimethylsilyl group and t-
A signal based on a butyl group appears, and a signal due to a six-membered proton appears at 7.514 ppm, and 7.285 ppm, 7.220 ppm, and 7.29 ppm.
At 0 ppm, a signal due to the thienothiophene ring proton appeared, confirming the structure.

[2,5-bis (3,5-di-t-butyl-4-trimethylsiloxyphenyl) thieno [3,2-b] thiophene (formula (1
Synthesis of 5))] 2- (3,5-Di-t-butyl-4-trimethylsiloxyphenyl) thieno [3,2-b] thiophene (Formula (13)
To a solution of (1.00 g, 2.40 mmol) in ether (10 ml) was added -butyllithium solution of n-pentane (2.40 mmol) at -78 ° C to produce a lithiated compound of formula (13).

In this, zinc chloride (372.1 mg, 2.40 mmol) in THF (3 ml)
The solution is added to prepare a THF solution of the compound (Formula (14)).

On the other hand, PdCl ₂ (PPh ₃ ) ₂ (84.2 mg, 0.120 mmol), THF (3 m
l) and 0.24ml of 1M / 1 concentration DIBAH in n-hexane
(0.24 mmol) was added thereto, and a solution of the compound (formula (12)) (970 mg, 2.40 mmol) in THF (3 ml) was added thereto.
Stir at room temperature for 10 minutes. A THF solution of the compound (formula (14)) prepared above was added thereto at room temperature, and reacted for 1 hour.

Water and 2N HCl (1.4 mmol) were added to the reaction mixture, and then ether was added and extracted. The ether layer was washed with water, washed with saturated saline, dried, and the solvent was removed. The residue was subjected to silica gel chromatography. After elution with chloroform, recrystallization from n-hexane gave mp256-258.
Compound (formula (15)) as white needles at 98 ° C
(59%) obtained.

The compound (Formula (15)) shows a molecular ion peak at m / e692 in the mass spectrum, and 0.44 and 1.46 in the 1H NMR spectrum.
A signal based on a trimethylsilyl group and a t-butyl group is shown at 1 ppm, a signal based on a 6-membered ring proton at 7.513 ppm, and a signal based on a thieno [3,2-b] thiophene ring proton at 7.327 ppm. Was done.

[2,5-bis (3,5-di-t-butyl-4-trimethylsiloxyphenyl) thieno [3,2-b] thiophene (formula (1
6))] 2,5-bis (3,5-di-t-butyl-4-trimethylsiloxyphenyl) thieno [3,2-b] thiophene (formula (1)
5) 12N HCl (3 ml) is added to a solution of (313 mg, 0.451 mmol) in THF (33 ml), and the mixture is stirred at room temperature for 15 hours.

Ice was added to the reaction mixture, and the mixture was extracted with ether. The ether layer was washed with saturated saline and dried over anhydrous sodium sulfate.

The solvent was removed and the residue was chromatographed on silica gel,
Elution with a mixed solvent of n-hexane: ether = 1: 1,
Purification yielded 206 mg (83% yield) of compound (Formula (16)) as white crystals, mp 259-260 ° C.

The compound (formula (16)) shows a molecular ion peak at m / e548 in a mass spectrum, shows an absorption due to an -OH group at 3660 cm ^-1 in an IR spectrum, and shows a t-butyl group at 5.49 ppm and a 5.30 ppm in a 1H NMR spectrum. The signal based on the -OH group was shown in ppm, the signal based on the 6-membered ring proton was obtained at 7.434 ppm, and the signal based on the thieno [3,2-b] thiophene ring ring proton was obtained at 7.301 ppm, confirming the structure.

Synthesis of Thieno [3,2-b] thienylidenebisbenzoquinone (Formula (17)) 2,5-bis (3,5-di-t-butyl-4-hydroxyphenyl) thieno [3,2-b] Thiophene (Formula (16) (35.
2mg, 0.064mmol) in benzene (17ml)
0.1N KOH aqueous solution (35ml) and potassium ferricyanide (23
8 mg, 0.721 mmol) and vigorously stir at room temperature for 1 hour.

Ice was added to the reaction mixture, and the mixture was extracted with ether. The ether layer was washed with saturated saline and dried over anhydrous sodium sulfate.

The solvent was removed and the residue was chromatographed on silica gel,
Purification with n-hexane: chloroform = 1: 1 yielded 27.3 mg (78% yield) of dark blue crystals.

The physical properties of the obtained compound are shown below. From these physical properties, it was confirmed that the target substance was thieno [3,2-b] thienylidenebisbenzoquinone (formula (17)).

1. Dark blue crystal with a melting point of 275-276 ° C 2. Electronic spectrum (in acetonitrile solution) Absorption maximum wavelength logε, 26nm sh 4.16 260nm 3.94 375nm 3.69 397nm 3.70 510nm sh 4.14 549nm 4.74 594nm 5.24 where ε indicates the molecular absorption coefficient. sh indicates the shoulder of the spectrum.

3. Infrared spectra (IR) KBr method 2970-2870cm ^-1, 1590cm ^-1 (carbonyl group) 1492cm ^-1 136
^{5cm -1, 1260cm -1 1242cm -1 1090cm} -1 1033cm -1, 995cm -1, 892
^{cm -1, 822cm -1, 805cm -1} , 750cm -1, 710cm -1 4. Mass spectrum (EI-MS) m / e ( attribution, intensity) 548 (M + 2,37%) , 547 (M + 1,45.5% ), 546 (M +, 10
0%) (molecular ion peak) 5. ¹ H-NMR spectrum (200 MHz, in CDCl ₃₎ [delta] value (integrated value, multiplicity, J value, attribution) 1.363ppm (36H, S, t- butyl group protons) 7.205 ppm (2H, d, J = 2.4Hz, 6 membered ring proton at H-6,6 "position) 7.415ppm (2H, d, J = 2.4Hz, H-2,2" position 6 membered ring proton) 7.416ppm (2H, S, H-3 ' thieno [3,2-b] thiophene ring ring protons) 6. ¹³ C-NMR spectrum (50.3MHz, in CDCl ₃₎ δ value (attribution) 20.696 (-C (C H _{3 ) 3), 35.703 (-C (} C H 3) 3), 126.983
(C-1 position), 118.252 (C-2 position), 149.744 (C-3
), 185.605 (C-4th), 147.876 (C-5), 127.4
88 (C-6 position), 152.006 (C-2 'position), 125.389 (C-
3 'position), 156.111 (C-3'a position)

──────────────────────────────────────────────────続 き Continued on the front page (56) References Angew. Chem. vol. 100, No. 4 (1988) p. 597-599 (58) Field surveyed (Int. Cl. ⁶ , DB name) C07D 495/04 G02F 1/17 CA (STN) REGISTRY (STN)

Claims (3)

(57) [Claims] 1. A thieno [3, represented by the following general formula (1):
2-b] Thienylidenebisbenzoquinones. [In the formula (1), R ₁ , R ₂ , R ₃ , R ₄ , R ₅ and R ₆ each independently represent a hydrogen atom or a linear or branched alkyl group having 1 to 8 carbon atoms. ] 2. The following general formula (2) [In the formula (2), R ₁ , R ₂ , R ₃ , R ₄ , R ₅ and R ₆ each independently represent a hydrogen atom or a linear or branched alkyl group having 1 to 8 carbon atoms. A method for producing a thieno [3,2-b] thienylidenebisbenzoquinone represented by the general formula (1), characterized by oxidizing a thieno [3,2-b] thiophenebisphenol represented by the following formula: 3. The following general formula (2) [In the formula (2), R ₁ , R ₂ , R ₃ , R ₄ , R ₅ and R ₆ each independently represent a hydrogen atom or a linear or branched alkyl group having 1 to 8 carbon atoms. ] Thieno [3,2-b] thiophene bisphenols represented by the formula: