JPH0348686A - Thieno(3,2-b)thienylidenebisbenzoquinones and its production - Google Patents

Abstract

NEW MATERIAL:A compound expressed by formula I (R1 to R6 represent H,1-8C alkyl or substituted phenyl). EXAMPLE:A compound expressed by formula II. USE:Useful as various optical filter materials due to light-shuttering effects ranging from visible ray to near infrared ray wave-length region, for example, optical recording medium, optical card, optical tape, organic photosensitive material, light absorbing or external light-shielding material for controlling mechanism of such as TV, protecting material for laser processing work, protective glass and light-emitting material for dye laser. PREPARATION:Thieno[3,2-b]thiophenebisphenols expressed by formula III is oxidized.

Description

Detailed Description of the Invention [Field of Industrial Application] The present invention relates to functional dyes and near-infrared absorbing materials used in information recording systems, energy conversion systems, equipment control systems, and electrochromic materials that utilize light. The present invention relates to a novel compound suitably used as a drug and a method for producing the same.

More specifically, optical recording media, optical cards, optical tapes, organic photoreceptors, light absorption or external light blocking materials for control mechanisms such as televisions and sound systems, protective materials for laser processing, safety glasses, plants and microorganisms. The present invention relates to optical filter materials for growth control, luminescent materials for dye lasers, and compounds used in other fields and their production methods.

[Prior Art and its Section B] Research and development of functional dyes used in information recording systems, energy conversion systems, and equipment control systems that utilize light are actively being carried out.

One of the information recording systems that utilize light is high-density optical recording using semiconductor lasers.

As a method that is close to practical application, the recording medium is irradiated with focused light and converted into thermal energy, and the heat causes shape changes such as pits, holes, bubbles, etc. on the recording medium to be recorded. There is a method in which the recording medium layer is scanned with light that is sufficiently weakened so as not to damage the recording medium layer, and the signal is reproduced by detecting changes in the reflected light.

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

Examples of compounds that can be used as recording media of this type include "Dye and Medicine" Vol. 30, No. 11, 3.
On pages 08 to 318, it is described that an intramolecular charge transfer complex as shown by formula (3) is used.

In addition, as a near-infrared absorber, cyanine dye (Unexamined Japanese Patent Publication No. 5
6-46221, JP-A-58-112790); phthalocyanine dyes (JP-A-58-36490); naphthoquinone dyes (JP-A-6O-15458); anthraquinone dyes (JP-A-6L-291651); 175693 (1973), etc. are known.

However, anthraquinone and naphthoquinone dyes have comparatively small molar extinction coefficients (and dithiol complexes also have drawbacks such as insufficient thermal stability and molar extinction coefficients).

[Detailed Disclosure of the Invention] As a result of extensive research into specific cross-conjugated compounds that solve the above-mentioned drawbacks, the present inventors have discovered Cheno, a novel compound that has the ability to absorb light in the long wavelength range. [3,2
-bl chenylidene bisbenzoquinones were discovered and the present invention was completed.

That is, the present invention provides cheno[3,2-b]chenylidene bisbenzoquinones represented by the following general formula (1) [in formula (1),
R1, Rt, Rs, R4 and R, R, each independently represent a hydrogen atom, a linear or branched alkyl group having 1 to 8 carbon atoms, or a substituted phenyl group; General formula (2) R1 and R6 each independently represent a hydrogen atom, a linear or branched alkyl group having 1 to 8 carbon atoms, or a substituted phenyl group; -b
] Cheno[3,2-
b] A method for producing chenylidene bisbenzoquinones, and also has the following general formula (2) [In formula (1), R1, R8, R3, R4 and [Formula (
2), R3, R2, R3, R4 and R, R, each independently represent a hydrogen atom, a linear or branched alkyl group having 1 to 8 carbon atoms, or a substituted phenyl group, ] The gist is cheno[3,2-b]thiophene bisphenols shown in the following.

The present invention will be explained in detail below.

Cheno[3,
2-bl chenylidene bisbenzoquinones, that is, formula (4) [In formula (1), R3, Rx, Rs, R4 and R1,
R4 is each independently a hydrogen atom or a carbon number of 1 to 8
represents a linear or branched alkyl group or a substituted phenyl group] is not particularly limited, but can be produced, for example, as follows.

[In formula (4), R1 and R1 are R1 and Rx in formula (1)
means the same group as . ] Cheno[3,2-bl thiophene compound represented by t
-Cheno[3,2-b] represented by the formula (5) by reacting with butyllithium and further reacting with zinc chloride.

] A thiophene zinc chloride compound is synthesized, and 1 2 [In formula (5), R3, R, is R1, RR in formula (1)
means the same group as .

This and formula (6) ] [In formula (6), R3 and R4 are R3 and R4 in formula (1)
means the same group as . ] The following formula (7) [In formula (7), R1, Rt, Rs, R4 are RI, Rx, R3 in formula (1), It means the same group as R4. ] The cheno[3,2-b]thienylbenzene compound shown is synthesized.

Furthermore, after converting the obtained compound into cheno[3,2-bl thienylbenzenzinc chloride represented by formula (8), [in formula (8), R1, R2, R3, and R4 are It means the same group as RI, RR, and RゎR1. ) Again, the iodized trimethylsiloxybenzene compound represented by (9) is reacted, and 6 3, R4 and R3 and R4 mean the same group. ] Synthesize the compound shown below. By hydrolyzing this, a cheno[3,2-b]thiophene bisphenol compound represented by general formula (2) is obtained, [in formula (9), R55
R, means the same group as R2 and Rh in formula (1). ] Formula (10) (10) [In formula (10), R3, R3, R5, R4 and R
s, Rh are R3, R2, R in formula (1) [In formula (2), R3, R2, R1, R4 and R3, Rh are the formula (
It means the same groups as R3, R2, R1, R4, R%s and R6 in 1).

] By oxidizing this, cheno[3°2-b]chenylidenebisbenzoquinones, which are cross-conjugated compounds represented by the above general formula (1), are produced.

For the oxidation reaction in the present invention, a conventional method of oxidizing phenols to quinones, which is known in boat fishing, is applied.
It can be carried out according to the method described in "Oxidation and Reduction 1.2". Although the conditions for the oxidation reaction may vary depending on the reactants, oxidation catalyst, etc. used, the temperature is usually room temperature to 200° C. and the reaction time is about 10 minutes to 24 hours.

In the present invention, the oxidizing agent used in the oxidation reaction is a catalyst known per se for oxidizing phenol to quinone, such as potassium permanganate, manganese dioxide, chromic acid, potassium dichromate, dichromate, etc. Inorganic oxidizing agents such as sodium chloride, lead tetrachloride, potassium ferricyanide, and ferric chloride; oxidizing systems such as oxidizing agents alone such as oxygen and hydrogen peroxide, and oxidizing systems in the coexistence of oxidizing agents and catalysts; organic oxidizing agents such as dicyanodichlorobenzoquinone and chloranil Any oxidizing agent may be used, but potassium ferricyanide is preferable from the viewpoint of cost or industrial use.The reaction can be carried out by suspension in water, suspension in an organic solvent, or a two-phase system of water and organic solvent. Although it may be carried out as a reaction system, the yield is particularly good when a two-phase system of water and benzene is used.

In addition, the compound represented by the above general formula (1) has a light absorption wavelength that extends into the visible range, and has a light blocking effect for wavelengths from the visible range to the near-infrared range, that is, it can be usefully used as various filters. Products, especially remote control equipment for televisions, radios, stereos, various sound systems, etc.
Distance measurement for cameras, etc., light-receiving elements for game consoles, automatic doors, etc., external light blocking materials for preventing malfunction, protective materials for laser processing, safety glasses, optical filter materials for controlling the growth of plants and microorganisms, etc. It can be suitably used for.

[Example] Hereinafter, the present invention will be specifically explained 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)cheno[3,2-b]thiophene (formula (
1% formula%] mmol) in ether (19 ml).
- Butyllithium n-pentane solution (14,26 mm
ol) to monolithiate.

This lithium compound was mixed with zinc chloride (1.94 g, 14.26
mm.

By adding 1) to a solution of 1) in THF (19 ml) at O'C, the product of the compound (formula (1,1)) was obtained.

On the other hand, PdCl2(PPhz)z (385 mg, 0.
549 mmol), T) IF (18 ml), and L
M/1 n-hexane solution of DIRAI (1,097
The compound (formula (1% formula %)) was added to the mixture of meal) and further stirred at room temperature for 10 minutes.

Then, a THP solution of the compound (formula (11)) prepared previously was added to this at room temperature, and the reaction was further allowed to proceed for 1 hour.

Water was added to the reaction mixture, followed by IN HCI (10 mmol
), ether was added and extracted, and the ether layer was washed with water and saturated brine, and then dried over anhydrous sodium sulfate. The solvent was removed and the residue was purified by silica gel chromatography (n-hexane), melting point 127-130.
3.58 g of the compound (formula (13)) as white crystals of G
, (Yield 60.3m) was obtained.

The compound (formula (13)) has m/e416 in mass spectrum.
The molecular ion appears as a base peak at IH-N)'
In IR, signals based on trimethylsilyl group and t-butyl group appear at 0.438 ppm and 1.455 ppm, respectively, a signal due to a 6-membered ring proton appears at 7.514 ppm, 7.285 ppm, 7.220
A signal due to the chenothiophene ring proton appeared at 7.290 ppm, and the structure was recognized.

[Synthesis of 2,5-bis(3,5-di-t-butyl-4-trimethylsiloxyphenyl)cheno[3,2-blthiophene (formula (15))] 2-(3,5-di-t-butyl)cheno[3,2-blthiophene (formula (15))] -butyl-4-trimethylsiloxyphenyl)cheno[3,2-b]thiophene (formula 13
) (1,00 g + 2.401111101) in ether (10 ml) was added a solution of t-butyllithium in n-pentane (2,40 mmol) at 78°C to form a lithiated product of the compound (formula (13)). let

In this, zinc chloride (372.1 mg, 2.40 mm
Add a THF (>3 ml) solution of the compound (formula (14)) to prepare the rHFt'ij solution.

On the other hand, PdC1z(PPhs)z (84,21gg+
0.120 mmol).

THF (3 ml) and DIR at IM/1 concentration
n-hexane solution of AII 0.24+1 (0.24 mm
A mixture is prepared by adding the compound (formula (12)
)) TH of (970I1g+2.40 anol)
Add tI solution (3 ml) and stir at room temperature for 10 minutes. In this, T of the previously prepared compound (formula (14))
The I(F solution was added at room temperature and allowed to react for 1 hour.

Water and 2N 1 (CI (1,4-ol)) were added to the reaction mixture, then ether was added and extracted. The ether layer was washed with water, washed with saturated brine, and dried. The solvent was removed and the remaining By subjecting the substance to silica gel chromatography, eluting with chloroform, and recrystallizing with n-hexane,
981 mg (59χ) of the compound (formula (15)) was obtained as white needle crystals with a mp of 256-258°C.

The compound (formula (15)) has mle692 in mass spectrum.
The 01 NMR spectrum shows signals based on trimethylsilyl group and t-butyl group at 0.44 and 1.461 ppm, respectively, and ? ,
513 pp-6-membered ring proton, 7.327
A signal based on the cheno[3,2-bl thiophene ring proton was obtained at ppm, and the structure was confirmed.

[2,5-bis(3,5-di-t-butyl-4-hydroxyphenyl)cheno[3,2-b]thiophene (formula
(% formula %)] (Formula (15)) (313l1g, 0.451 mm
ol) in T)IF (33rin1).
Add 12 N HCI (3 ml) and stir at room temperature for 15 hours.

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

The solvent was removed and the residue was chromatographed on silica gel, n
- Elute with a mixed solvent of hexane:ether = 1:1,
When purified, 206 mg of the compound (formula (16)) was obtained as white crystals at 259-260°C (yield: 83χ).
Obtained.

The compound (formula (16)) has −/e54 in the mass spectrum
The molecular ion peak is shown at 8, and 366 in the IR spectrum.
It shows absorption due to -OH group at 0 cm-', and III
The NMR spectrum shows a signal based on a t-butyl group at 1.491) pH, a 10H group at 5.30 ppm, a 6-membered ring broton at 7°434 ppm, and a 7
．． A signal based on the cheno[3,2-bl thiophene ring proton was obtained at 301 ppm, and the structure was confirmed.

[Synthesis of cheno[3,2-bl chenylidene bisbenzoquinone (formula (17))] 2.5. Bis(3,5-di-t-butyl-4-hydroxyphenyl)cheno[3,2-b]thiophene (formula (
% Formula % (17 ml) and add 0.0% to this. OH aqueous solution (3
5 ml) and potassium ferricyanide (238 mg, 0
．． 721 mmol) and stirred vigorously at room temperature for 1 hour.

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

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

The physical property values of the obtained compound are shown below. From these physical property values, it was confirmed that it was the target compound, cheno[3,2-bl chenylidene bisbenzoquinone (formula (17)).

1. Melting point 275-276°ci4 blue crystal 2.1i
Child spectrum (in acetonitrile solution) absorption maximum wavelength
logε 226 nm sh 4.16260
nm 3.94375 nm
3.69397 nm
3.70510 nm sh 4
．． 14549 ni 4.7459
4 nm 5.24 However, ε indicates the molecular extinction coefficient, and sh indicates the shoulder of the spectrum.

3. Infrared spectrum (rR) KBr method 2970-2
870 cm+-', 1590 cm-' (carbonyl group) 1492 cm-' 1365 cm-',
1260 cm-' 1242 cm-1090 cm-
'1033 cm-', 995 cm-'
, 892 cm-'822 C11l-1,80
5Cm-', 150 cm-', 710 crg-
'4, Mass spectrum (E I -MS) + w/e (
Attribution, strength) 548 (M+2.37χ), 547 (A+1.4
5.5χ).

546 (formerly 1100χ) (molecular ion beak) 5,
'H-NMR spectrum (200MHz, in CD
Ch) δ value (integral value, multiplicity, J value, assignment) 1.363 ppm (36H, S, t-) thyl group proton) 7.205 99m (2H, d, J=
2.4 Hz, H-6,6'' position 6-membered ring ring proton) 7.4151)I)II (211,d, J-2,4
Hz, H-2,2'' position) 6-membered ring ring proton) 7.416 ppm (2L S, 11-3'' Cheno[3,2-bl thiophene ring ring proton 6.13C-
NMR spectrum (50,3 MHz, in CDC1x) δ value (return rI
A) 29.696 (-C(CIri3), 35.703
(-C(CHi)s).

126.983 (C-1 position), 118.252 (
C-2nd place).

149.744 (C-3 position L 185.605 (C-
4th place).

147, 816 (C-5 position), 127.488 (
C-6th place).

152.006 (C-2' position), 125.389 (
C-3°).

156, 111 (C-3°a position) (J1) (I2) ()3) (14)

Claims (3)

[Claims] (1) Thieno[3,2-
b] Thienylidene bisbenzoquinones. ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (1) [In formula (1), R_1, R_2, R_3, R_4 and R_5, R_6 are each independently a hydrogen atom or a straight chain having 1 to 8 carbon atoms. , or a branched alkyl group, or a substituted phenyl group. ] (2) The following general formula (2) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (2) [In formula (1), R_1, R_2, R_3, R_4, R_5, and R_6 are each independently a hydrogen atom, or It represents a straight chain or branched alkyl group having 1 to 8 carbon atoms, or a substituted phenyl group. ] Chieno [3,
2-b] Thieno[3,2-
b] Method for producing thienylidene bisbenzoquinones. (3) General formula (2) below ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (2) [In formula (2), R_1, R_2, R_3, R_4, R_5, and R_6 are each independently a hydrogen atom, or It represents a straight chain or branched alkyl group having 1 to 8 carbon atoms, or a substituted phenyl group. ] Chieno [3,
2-b] Thiophene bisphenols.