JP2002234892A - Pyran derivative - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an organic compound having absorption maximum in visible region, emitting visible light in red color area by exciting the compound and useful as a luminous agent and a light absorbent in organic electroluminescent element or the like. SOLUTION: This purpose is attained by providing a pyran derivative having a specific structure, a luminous agent, a light absorbent and an organic electroluminescent element each containing the pyran derivative and a method for producing pyran derivative through a step for reacting 4-(dicyanomethylene)-2,6-dimethyl-4H-pyran with a coumarin compound having julolidine skeleton in the molecule, in which aldehyde group and hydrocarbon group are each bound at the 3-position and the 4-position.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a pyran derivative, and more particularly to a pyran derivative having a coumarin skeleton and a julolidine skeleton in a molecule, which is useful as a light absorbing agent and a luminescent agent.

[0002]

2. Description of the Related Art In the field of information display, organic electroluminescent devices (hereinafter abbreviated as "organic EL devices") have been spotlighted as next-generation display devices. At present, cathode ray tubes are mainly used in relatively large information display devices such as computer terminals and television receivers. However, since the CRT is large in volume and weight and has a high operating voltage, it is not suitable for consumer devices and small devices that emphasize portability. There is a need for smaller devices that are thinner, lighter, flat, have lower operating voltages, and consume less power. At present, a liquid crystal element has a low operating voltage and a relatively low power consumption, and is frequently used in various fields. However, an information display device using a liquid crystal element changes contrast depending on the viewing angle, so that a clear display cannot be obtained unless the image is read within a certain angle range, and a backlight is usually required. There is a problem that it does not become so small. An organic EL element has emerged as a display element that solves these problems.

[0003] An organic EL device usually has a light-emitting layer containing a light-emitting compound interposed between an anode and a cathode, and a direct-current voltage is applied between the anode and the cathode to form holes in the light-emitting layer. A light-emitting element that uses light emission such as fluorescence or phosphorescence emitted when the excited state returns to the ground state by creating an excited state of the luminescent compound by injecting electrons and recombining them with each other. is there. Organic EL elements
In forming the light-emitting layer, a characteristic feature is that the color tone of light emission can be appropriately changed by selecting an appropriate organic compound as a host compound and changing a guest compound (dopant) combined with the host compound. is there. Further, depending on the combination of the host compound and the guest compound, there is a possibility that the luminance and the lifetime of light emission can be significantly improved. In the first place, since organic EL elements emit light by themselves, information display devices using them have the advantage of not having a viewing angle dependency, and have the advantage that power consumption can be reduced because a backlight is not required. Is said to be.

However, in organic EL devices that emit light in the green range, improvements in luminous efficiency and emission spectrum by the addition of a guest compound have been reported. However, organic EL devices that emit light in the red range have not been reported. Since no effective guest compound has been found, not only the color purity and luminance but also the durability and the reliability are still insufficient. For example, JP-A-10-
The organic EL devices disclosed in US Pat. No. 60427 and US Pat. No. 4,749,292 have low luminance,
Since the emission is not pure red, there is still a problem in realizing full color.

[0005]

SUMMARY OF THE INVENTION In view of such circumstances, an object of the present invention is to provide a light-emitting agent and a light-emitting element for an organic EL device or the like which have an absorption maximum in the visible region and emit red light when excited. It is to provide an organic compound useful as an absorbent.

[0006]

Means for Solving the Problems In order to solve this problem,
The present inventors have focused on pyran derivatives having a coumarin skeleton and a julolidine skeleton in the molecule, and have light absorption properties, emission properties,
A wide variety of pyran derivatives were extensively searched based on their thermal characteristics, amorphous properties in the solid phase, and ease of preparation. As a result, 4- (dicyanomethylene) -2,6
-A group of pyran derivatives which can be prepared relatively easily by reacting -dimethyl-4H-pyran with a coumarin compound having an aldehyde group at the 3-position, a relatively bulky substituent at the 4-position, In particular, the present inventors have found that a pyran derivative having a hydrocarbon group bonded thereto has an absorption maximum in a visible region, and efficiently emits visible light in a red region when excited. Moreover, such a pyran derivative is excellent in amorphousness in a thin film state and has high heat resistance, and thus is extremely useful in an organic EL device or the like as an organic material that absorbs visible light or emits visible light in a red region. It has been found.

[0007]

That is, the present invention solves the above-mentioned problem by providing a pyran derivative having a coumarin skeleton and a urolidine skeleton in a molecule and a hydrocarbon group bonded to the 4-position in the coumarin skeleton. Is to solve the problem.

Further, the present invention solves the above-mentioned problems by providing a luminescent agent containing such a pyran derivative.

Further, the present invention solves the above-mentioned problems by providing an organic EL device containing such a pyran derivative.

Further, the present invention solves the above-mentioned problems by providing a light absorber containing such a pyran derivative.

Further, the present invention solves the above-mentioned problem by 4-
A step of reacting (dicyanomethylene) -2,6-dimethyl-4H-pyran with a coumarin compound having a urolidine skeleton in the molecule and having an aldehyde group and a hydrocarbon group bonded to the 3- and 4-positions, respectively. The problem is solved by providing a method for producing a pyran derivative via the method.

[0012]

BEST MODE FOR CARRYING OUT THE INVENTION As described above, the present invention relates to a pyran derivative having a coumarin skeleton and a urolidine skeleton in a molecule and a hydrocarbon group bonded to the 4-position in the coumarin skeleton, It relates to a pyran derivative represented by the formula 1.

[0013]

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In the general formula 1, R is a hydrocarbon group, and the hydrocarbon group may have one or more substituents. Examples of the hydrocarbon group for R include those having up to 8 carbon atoms, for example, methyl, ethyl, ethynyl, propyl, cyclopropyl, isopropenyl, 1-propenyl, 1-propynyl, 2- Propenyl group, butyl group, isobutyl group, sec-butyl group, tert-
Butyl group, 1,3-butadienyl group, 2-butenyl group,
Pentyl group, isopentyl group, neopentyl group, ter
t-pentyl, 1-methylpentyl, 2-methylpentyl, 2-pentenyl, 2-penten-4-ynyl, hexyl, isohexyl, 5-methylhexyl, heptyl, octyl, etc. Aliphatic hydrocarbon groups, up to 8 carbon atoms, for example, cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloaliphatic hydrocarbon groups such as cyclohexenyl group, and further,
Examples thereof include a monocyclic or polycyclic aromatic hydrocarbon group having a benzene ring as a basic skeleton, such as a phenyl group and a naphthyl group.

Examples of the substituent bonded to the hydrocarbon group include a methyl group, an ethyl group, a propyl group, a butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, a pentyl group, an isopentyl group and a neopentyl group. Aliphatic hydrocarbon group such as a group, methoxy group, ethoxy group, propoxy group, isopropoxy group, butoxy group, isobutoxy group, sec-butoxy group, tert-butoxy group, pentyloxy group, isopentyloxy group, phenoxy group, Ether groups such as benzyloxy group, methoxycarbonyl group, ethoxycarbonyl group, propoxycarbonyl group, pentyloxycarbonyl group, acetoxy group, ester group such as benzoyloxy group, phenyl group, o-
Tolyl group, m-tolyl group, p-tolyl group, xylyl group,
Aromatic hydrocarbon groups such as mesityl group, o-cumenyl group, m-cumenyl group, p-cumenyl group, biphenylyl group, furyl group, thienyl group, pyrrolyl group, pyridyl group, piperidino group, morpholino group, quinolyl group, etc. Examples include a heterocyclic group, a halogen group such as a fluoro group, a chloro group, a bromo group, and an iodo group, as well as a hydroxy group, a carboxy group, a cyano group, and a nitro group. Depending on the application, such a substituent may have one or more of its hydrogen atoms replaced by a halogen group such as, for example, a fluoro group, a chloro group, a bromo group, and an iodo group.

Specific examples of the pyran derivative according to the present invention include those represented by Chemical Formulas 1 to 9. All of these have an absorption maximum in the visible region, especially at a wavelength of 480 to 580 nm, and when excited, emit light in the red region, especially at a wavelength of 620 to 650 nm.
Can be used as a light absorbing agent and / or a luminous agent, alone or in combination with other organic compounds.

[0017]

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[0018]

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[0019]

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[0020]

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[0021]

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[0022]

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[0023]

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[0024]

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[0025]

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The pyran derivative of the present invention can be prepared by various methods.
And a 4- (dicyanomethylene) -2,6-dimethyl-4H-pyran represented by the formula:
How 3-position to the aldehyde group through a step of reacting a coumarin compound comprising bonded are preferred. According to this method, 4- (dicyanomethylene) -2,6-
Dimethyl -4H- pyran, by reacting a compound represented by the general formula 2 with corresponding R in formula 1, pyran derivatives of the present invention is produced in good yield.

[0027]

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[0028]

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That is, 4- (dicyanomethylene) -2,6-dimethyl-4H-pyran and a compound represented by the general formula 2 are respectively put in appropriate amounts in a reaction vessel, and if necessary,
Dissolve appropriately in a solvent, for example, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, sodium acetate, ammonia, triethylamine, piperidine, pyridine, pyrrolidine, aniline,
Basic compounds such as N, N-dimethylaniline and N, N-diethylaniline; hydrochloric acid, sulfuric acid, nitric acid, methanesulfonic acid, p-toluenesulfonic acid, acetic acid, trifluoroacetic acid, trifluoromethanesulfonic acid, acetic anhydride and the like. After the addition of an acidic compound, a Lewis acidic compound such as aluminum chloride, zinc chloride, tin tetrachloride, titanium tetrachloride, etc., the reaction is carried out at ambient or above ambient temperature with stirring.

Examples of the solvent include pentane, hexane, cyclohexane, octane, benzene, toluene,
Hydrocarbons such as xylene, carbon tetrachloride, chloroform, 1,2-dichloroethane, 1,2-dibromoethane, trichloroethylene, tetrachloroethylene, chlorobenzene, bromobenzene, halides such as α-dichlorobenzene, methanol, ethanol, 1- Propanol, 2-propanol, 1-butanol, 2-butanol, isobutyl alcohol, isopentyl alcohol, cyclohexanol, ethylene glycol, propylene glycol, 2-methoxyethanol, 2-ethoxyethanol, phenol, benzyl alcohol, cresol, diethylene glycol, triethylene Alcohols such as ethylene glycol and glycerin and phenols, diethyl ether, diisopropyl ether, tetrahydrofuran, tetra Doropiran, 1,4-dioxane, anisole, 1,2-dimethoxyethane, diethylene glycol dimethyl ether, dicyclohexyl -
Ethers such as 18-crown-6, methyl carbitol, ethyl carbitol, acetic acid, acetic anhydride, trichloroacetic acid, trifluoroacetic acid, propionic anhydride, ethyl acetate, butyl carbonate, ethylene carbonate, propylene carbonate, formamide, N- Acids and acid derivatives such as methylformamide, N, N-dimethylformamide, N-methylacetamide, N, N-dimethylacetamide, hexamethylphosphoric triamide, trimethyl phosphate, acetonitrile,
Examples thereof include nitriles such as propionitrile, succinonitrile, and benzonitrile; nitro compounds such as nitromethane and nitrobenzene; sulfur-containing compounds such as dimethylsulfoxide; water; and the like, if necessary.

In the case of using a solvent, the efficiency of the reaction generally decreases as the amount of the solvent increases, whereas when the amount of the solvent decreases, it becomes difficult to uniformly heat and stir, or a side reaction easily occurs. Accordingly, it is desirable that the amount of the solvent be 100 times, usually 5 to 50 times, the weight of the whole starting compound. Also, 4- (dicyanomethylene) -2,6-
If the amount of the compound represented by the general formula 2 is large relative to dimethyl-4H-pyran, the generation of by-products reaches a level that cannot be ignored, and the yield of the intended pyran derivative is reduced or purification is difficult. On the contrary, when the amount is small, the efficiency of the reaction is reduced. Therefore, 4- (dicyanomethylene) -2,6- is added to the compound represented by the general formula 2.
Dimethyl-4H-pyran is charged in excess, and the molar ratio of 4- (dicyanomethylene) -2,6-dimethyl-4H-pyran to the compound represented by the general formula 2 is not more than equimolar, usually,
1: 0.2 to 1: 0.5, preferably 1: 0.3 to 1: 0.4. Further, when the reaction temperature is high, side reactions are likely to occur, and when the reaction temperature is low, the efficiency of the reaction is reduced.
A temperature not exceeding 140 ° C., preferably 60 to 100
Set in the range of ° C. The reaction is completed within 10 hours, usually 0.5 to 5 hours, depending on the type of the starting compound and the reaction conditions. The progress of the reaction can be monitored by a general-purpose method such as thin-layer chromatography, gas chromatography, and high-performance liquid chromatography. The pyran derivative represented by any one of Chemical Formulas 1 to 9 can be produced in a desired amount by this method.

Incidentally, 4- (dicyanomethylene)-
2,6-Dimethyl-4H-pyran can be prepared by a known method, and if there is a commercially available product, it may be used. On the other hand, the compound represented by the general formula 2 is described in, for example, Japanese Patent Publication No. 60-2336, Eugen R.
R corresponding to the general formula 1 obtained according to the method described in Bissel et al., The Journal of Organic Chemistry, No. 45, 2,283 to 2,287 (1980), etc. The third position of the coumarin derivative represented by the general formula 3 is described in, for example, "New Experimental Chemistry Course" edited by The Chemical Society of Japan, 1977, published by Maruzen Co., Ltd., Vol. 14, (II), pages 688 to 699. Can be prepared by formylation by the Vilsmeier reaction described in (1).

[0033]

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The pyran derivative thus obtained may be used as a reaction mixture depending on the application, but is usually used as a reaction mixture.
Prior to use, for example, purify related compounds such as dissolution, extraction, separation, gradient, filtration, concentration, thin-layer chromatography, column chromatography, gas chromatography, high-performance liquid chromatography, distillation, sublimation, crystallization, etc. Purification is performed by a general-purpose method, and these methods are applied in combination as necessary. When the pyran derivative of the present invention is used for, for example, an organic EL device or a dye laser, it is desirable that the pyran derivative be highly purified before use, for example, by a method such as distillation, crystallization and / or sublimation. Of these, sublimation is particularly excellent because high-purity crystals can be easily obtained in a single operation, and the loss of the pyran derivative due to the operation is small, and the solvent is not taken into the crystals. I have. The sublimation method to be applied may be a normal pressure sublimation method or a reduced pressure sublimation method, but usually the latter reduced pressure sublimation method is employed. In order to sublimate the pyran derivative of the present invention under reduced pressure, for example, an appropriate amount of the pyran derivative is charged into a sublimation purification apparatus, and the inside of the apparatus is 10 ^-2.
Heating is performed at a temperature as low as possible below the melting point, while maintaining the reduced pressure below Torr, specifically, 10 ^-3 Torr or less, so that the pyran derivative is not decomposed. When the purity of the pyran derivative to be subjected to sublimation purification is relatively low, the sublimation rate is suppressed by adjusting the degree of vacuum or heating temperature so that impurities are not mixed, and when the pyran derivative is difficult to sublimate, an inert gas such as rare gas into the sublimation purification apparatus to facilitate sublimation by bubbling. The size of the crystals obtained by sublimation can be adjusted by adjusting the temperature of the condensing surface in the sublimation refining apparatus. Crystals are obtained.

The use of the pyran derivative according to the present invention will be described. As described above, the pyran derivative according to the present invention has an absorption maximum in the visible region and emits visible light in the red region when excited. It is extremely useful in the field of optoelectronics, which requires an organic compound, such as an organic EL device and a dye laser. In particular, the pyran derivative according to the present invention not only has excellent amorphous properties in a thin film state, but also has a melting point and a decomposition point that can be distinguished from each other, and has a decomposition point as high as 350 ° C. or higher. Since it has high heat resistance in the solid phase, it is extremely useful as a material for a light emitting layer of an organic EL device.

The organic EL device of the present invention is essentially an organic EL device using such a pyran derivative, and usually has an anode for applying a positive voltage, a cathode for applying a negative voltage, a hole and an electron. A light emitting layer for recombining and extracting light emission,
If necessary, a hole injection / transport layer for injecting and transporting holes from the anode, an electron injection / transport layer for injecting and transporting electrons from the cathode, and an electron injection / transport layer for emitting holes from the light emitting layer. Single-layer and stacked organic EL elements provided with a hole block layer that suppresses migration to an organic EL element are important applications. The pyran derivative according to the present invention not only forms a stable thin film in a glassy state but also forms an organic E using a host compound.
Since the property of shifting the emission of the organic EL element to the red region in the L element is remarkable, it is extremely useful as a guest compound of the organic EL element aiming at red emission with good color purity. In the organic EL device of the present invention, the host compound and / or the guest compound have a hole injecting / transporting ability and / or an electron injecting / transporting ability, or a material for the hole injecting / transporting layer and the electron injecting / transporting. When one of the layer materials has the other function, the electron injection / transport layer and / or the hole injection / transport layer can be omitted.

As described above, the organic EL device of the present invention can be configured as a single layer type or a stacked type. The operation of an organic EL element is essentially a process of injecting electrons and holes from an electrode, a process of moving electrons and holes through a solid,
Electrons and holes are recombined to generate a singlet exciton or a triplet exciton, and the exciton emits light. These processes are a single-layer organic EL device and a stacked organic EL device. There is essentially no difference in any of the elements. However, in the single-layer organic EL device, the characteristics of the above four steps can be improved only by changing the molecular structure of the light-emitting compound, whereas in the stacked organic EL element, it is required in each step. In general, since functions can be shared among multiple materials and each material can be optimized independently,
It is easier to achieve the desired performance in the case of the laminated type than in the case of the single-layer type.

Therefore, the organic EL device of the present invention
To further explain, taking a stacked organic EL element as an example, FIG. 1 is a schematic view of a stacked organic EL element according to the present invention, in which 1 is a substrate, usually soda glass, barium silicate glass, Glass such as aluminosilicate glass, polyester, polycarbonate, polysulfone, polymethyl methacrylate, polypropylene,
Plastics such as polyethylene, quartz, general-purpose substrate materials including ceramics such as ceramics are used in the form of a plate, sheet or film, and if necessary,
These are appropriately laminated and used. Preferred substrate materials are transparent glass and plastic, and opaque ceramics such as silicon are used in combination with transparent electrodes. When it is necessary to adjust the chromaticity of light emission,
Chromaticity adjusting means such as a filter film, a chromaticity conversion film, and a dielectric reflection film are provided at appropriate places.

Reference numeral 2 denotes an anode, which is one of a metal and a conductive compound which is electrically low in resistivity and has a high light transmittance over the entire visible region, and is formed by vacuum deposition, sputtering, or chemical vapor deposition. It is brought into close contact with one side of the substrate 1 by a method such as vapor deposition (CVD), atomic layer epitaxy (ALE), coating, or dipping, and the resistivity at the anode 2 is 1 kΩ / □ or less, preferably 5 to 50Ω / □. To a thickness of 10 to 1,000 nm, preferably 50 to 500 nm.
It is formed by forming a film into a single layer or a multilayer of nm. Examples of the conductive material for the anode 2 include gold,
Metals such as platinum, silver, copper, cobalt, nickel, palladium, vanadium, tungsten and aluminum, zinc oxide, tin oxide, indium oxide, and a mixed system of tin oxide and indium oxide (hereinafter abbreviated as "ITO") And metal oxides such as aniline, thiophene, pyrrole and the like as a repeating unit. Among them, ITO has a feature that a material having a low resistivity can be easily obtained, and a fine pattern can be easily formed by etching with an acid or the like.

Reference numeral 3 denotes a hole injection / transport layer, which is usually an anode
2 in the same manner as in 2,
The hole injection / transport layer material is manufactured to a thickness of 1 to 1,000 nm.
It is formed by forming a film. Material for hole injection / transport layer
The hole injection and transport from the anode 2
In order to minimize the ionization potential, ⁴
To 10⁶Under an electric field of V / cm, at least 1
0^-6cm²/ V · s that exhibit hole mobility
Good. The material for each hole injection / transport layer is organic E
Commonly used in L devices, for example, arylamine
Conductor, imidazole derivative, oxadiazole derivative,
Oxazole derivative, triazole derivative, chalcone
Conductor, styryl anthracene derivative, stilbene derivative
Body, tetraarylethene derivative, triarylamine
Derivatives, triarylethene derivatives, triarylmeta
Derivatives, phthalocyanine derivatives, fluorenone derivatives
, Hydrazone derivative, N-vinylcarbazole derivative
Body, pyrazoline derivative, pyrazolone derivative, phenyla
Anthracene derivative, phenylenediamine derivative, polya
Reel alkane derivative, polysilane derivative, polyphenylene
Lenvinylene derivatives and the like.
They are used in appropriate combination.

Reference numeral 4 denotes a light-emitting layer which is usually brought into close contact with the hole injecting / transporting layer 3 in the same manner as in the anode 2, and one or more pyran derivatives according to the present invention and, if necessary, And a single layer or a multi-layer, and each is formed into a film having a thickness of 10 to 1,000 nm, preferably 10 to 200 nm. When used in combination with a host compound, the pyran derivative according to the present invention is used in an amount of 0.05 to 50% by weight, preferably 0.1 to 30% by weight, based on the host compound.

When the pyran derivative according to the present invention is used as a guest compound, another luminescent compound to be combined with the pyran derivative according to the present invention, that is, as a host compound, a quinolinol metal complex commonly used in organic EL devices, for example, Condensed polycyclic aromatic hydrocarbons such as anthracene, chrysene, coronene, triphenylene, naphthacene, naphthalene, phenanthrene, picene, pyrene, fluorene, perylene, benzopyrene and derivatives thereof, quarter phenyl, 1,4-diphenyl butadiene, terphenyl , Stilbene, tetraphenylbutadiene, ring-assembled hydrocarbons such as biphenyl and their derivatives, heterocyclic compounds such as carbazole and their derivatives, quinacridone, rubrene, and further styryl-based polymethine dyes And the like.

A preferred host compound is a quinolinol metal complex. The quinolinol metal complex referred to in the present invention has a pyridine residue and a hydroxy group in the molecule.
For example, 8-quinolinols, benzoquinoline-10-
Quinolinols as ligands such as ols, and the formation of a coordination bond with the ligand by donating an electron pair from the nitrogen atom in the pyridine residue, as a central atom, for example, lithium, beryllium, Group 1, Group 2, Group 12, or Group 13 in the periodic table of magnesium, calcium, zinc, aluminum, gallium, indium, etc.
It generally means a complex comprising a metal belonging to the group or an oxide thereof. When the ligand is any of 8-quinolinols or benzoquinolin-10-ols, they may have one or more substituents, for example, the 8- or 10-position to which a hydroxy group is bonded. To a carbon other than carbon fluoro group, chloro group, bromo group, halogen group such as iodine group, methyl group, trifluoromethyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group,
sec-butyl group, tert-butyl group, pentyl group,
Aliphatic hydrocarbon groups such as isopentyl group and neopentyl group, methoxy group, trifluoromethoxy group, ethoxy group, propoxy group, isopropoxy group, butoxy group, isobutoxy group, sec-butoxy group, tert-butoxy group, pentyloxy group , Isopentyloxy group, phenoxy group, ether group such as benzyloxy group, acetoxy group, trifluoroacetoxy group, benzoyloxy group, methoxycarbonyl group, trifluoromethoxycarbonyl group, ethoxycarbonyl group, ester group such as propoxycarbonyl group Further, it does not prevent one or more substituents such as a cyano group, a nitro group and a sulfo group from binding.

Examples of the individual quinolinol metal complexes include, for example, aluminum tris (8-quinolinolate), aluminum tris (3,4-dimethyl-8-quinolinolate), aluminum tris (4-methyl-8-quinolinolate), aluminum tris (4 -Methoxy-8-quinolinolate) aluminum, tris (4,5-dimethyl-8-quinolinolate) aluminum, tris (4,6-dimethyl-8-quinolinolate) aluminum, tris (5-
Chloro-8-quinolinolato) aluminum, tris (5-bromo-8-quinolinolato) aluminum, tris (5,7-dichloro-8-quinolinolato) aluminum, tris (5-cyano-8-quinolinolato) aluminum, tris (5 Aluminum complexes such as sulfonyl-8-quinolinolate) aluminum, tris (7-propyl-8-quinolinolate) aluminum, bis (2-methyl-8-quinolinolate) aluminum oxide, bis (8-quinolinolate) zinc, bis (2-
Methyl-8-quinolinolate) zinc, bis (2,4-dimethyl-8-quinolinolate) zinc, bis (2-methyl-5-chloro-8-quinolinolate) zinc, bis (2-
Methyl-5-cyano-8-quinolinolate) zinc, bis (3,4-dimethyl-8-quinolinolate) zinc, bis (4,6-dimethyl-8-quinolinolate) zinc, bis (5-chloro-8-quinolinolate) Zinc, screw (5
Zinc complexes such as 7-dichloro-8-quinolinolate) zinc, bis (8-quinolinolate) beryllium, bis (2
-Methyl-8-quinolinolate) beryllium, bis (2,4-dimethyl-8-quinolinolate) beryllium, bis (2-methyl-5-chloro-8-quinolinolate) beryllium, bis (2-methyl-5-cyano-8) −
Quinolinolate) beryllium, bis (3,4-dimethyl-8-quinolinolate) beryllium, bis (4,6-dimethyl-8-quinolinolate) beryllium, bis (5-
Chloro-8-quinolinolate) beryllium, bis (5,
Beryllium complexes such as 7-dichloro-8-quinolinolate) beryllium, bis (10-hydroxybenzo [h] quinolinolate) beryllium, bis (8-quinolinolate) magnesium, bis (2-methyl-8-quinolinolate) magnesium, bis (2 , 4-Dimethyl-8-quinolinolate) magnesium, bis (2-methyl-5-
Chloro-8-quinolinolate) magnesium, bis (2
-Methyl-5-cyano-8-quinolinolate) magnesium, bis (3,4-dimethyl-8-quinolinolate)
Magnesium, bis (4,6-dimethyl-8-quinolinolate) magnesium, bis (5-chloro-8-quinolinolate) magnesium, bis (5,7-dichloro-8)
-Quinolinolato) magnesium complex such as magnesium, indium complex such as tris (8-quinolinolato) indium, gallium complex such as tris (5-chloro-8-quinolinolato) gallium, bis (5-chloro-
Examples thereof include calcium complexes such as 8-quinolinolate) calcium, and these may be used in an appropriate combination as necessary. The host compounds described above are merely examples, and the host compounds used in the present invention should not be limited to these. When the quinolinol metal complex has two or more ligands in the molecule, those ligands may be the same or different.

Reference numeral 5 denotes an electron injecting / transporting layer, which is usually brought into close contact with the light emitting layer 4 in the same manner as in the anode 2 to form an organic compound having a high electron affinity or a cyclic compound such as benzoquinone, anthraquinone, or fluorenone. One or more of a conductive oligomer or a conductive polymer having a repeating unit of a ketone or a derivative thereof, a silazane derivative, and aniline, thiophene, pyrrole, or the like, has a thickness of 1 or more.
It is formed by forming a film with a thickness of 0 to 500 nm.
When a plurality of materials for the electron injection / transport layer are used, even if the plurality of materials for the electron injection / transport layers are uniformly mixed and formed into a single layer, each material for the electron injection / transport layer is mixed without mixing. It may be formed in a plurality of adjacent layers. When the hole blocking layer is provided, prior to the formation of the electron injection / transport layer 5, the hole blocking layer is brought into close contact with the light emitting layer 4 in the same manner as in the anode 2, for example, 2-biphenyl-4-yl-5-
(4-tert-butyl-phenyl)-[1,3,4]
Oxadiazole, 2,2-bis [5- (4-biphenyl) -1,3,4-oxadiazol-2-yl-1,
4-phenylene] hexafluoropropane, 1,3,5
-Tris- (2-naphthalen-1-yl- [1,3,
4] A thin film is formed using a hole blocking material including an oxadiazole-based compound such as oxadiazol-5-yl) benzene. The thickness of the hole blocking layer is 1 to 100 nm, usually 10 to 50, while taking into consideration the thickness of the electron injection / transport layer 5 and the operating characteristics of the organic EL device.
Set in the range of nm.

Reference numeral 6 denotes a cathode which is usually in close contact with the electron injecting / transporting layer 5 and has a work function lower than that of the compound used in the electron injecting / transporting layer 5 (usually 6 eV or less), for example, lithium, magnesium, It is formed by vapor deposition of a metal or metal oxide such as calcium, sodium, lithium, silver, copper, aluminum and indium, or a conductive compound alone or in combination. The thickness of the cathode 6 is not particularly limited, and is usually 10 nm or more so that the resistivity is 1 kΩ / □ or less, while taking into account the conductivity, the manufacturing cost, the thickness of the entire element, light transmittance, and the like.
Preferably, it is set to 50 to 500 nm. In addition,
If necessary, for example, an aromatic diamine compound, a quinacridone compound, a naphthacene compound, an organosilicon compound, or an organic compound, in order to enhance adhesion between the cathode 6 and the electron injection / transport layer 5 containing an organic compound. An interface layer containing a phosphorus compound may be provided.

[0047] In this way, the organic EL element of the present invention,
An anode 2, a light-emitting layer 4, a cathode 6, and, if necessary, a hole injection / transport layer 3, an electron injection / transport layer 5, and / or a hole blocking layer are adhered to an adjacent layer on the substrate 1 with an adjacent layer. It can be obtained by integrally forming while making. In forming each layer, in order to minimize oxidation and decomposition of organic compounds, and adsorption of oxygen and moisture, etc.,
It is desirable to work partly under a high vacuum, specifically at 10 ⁻⁵ Torr or less. In forming the light-emitting layer, the host compound and the guest compound are mixed in advance at a predetermined ratio, or by controlling the heating rates of the two in vacuum evaporation independently of each other. The mixing ratio of the two to be deposited on the light emitting layer is adjusted. The organic EL device thus constructed is partially or entirely replaced with a part, for example, in order to minimize deterioration in the use environment.
It is desirable to seal with a sealing glass or a metal cap in an inert gas atmosphere, or to cover with a protective film of an ultraviolet curable resin or the like.

The method of using the organic EL device according to the present invention will be described. The organic EL device according to the present invention may be configured to intermittently apply a relatively high voltage pulse or to generate a relatively low voltage depending on the application. Driving is performed by continuously applying a non-pulse voltage (usually 3 to 50 V). The organic EL device of the present invention emits light only when the potential of the anode is higher than the potential of the cathode. Therefore, the organic E of the present invention
The voltage applied to the L element may be direct current or alternating current, and the waveform and period of the applied voltage may be appropriate. When an alternating current is applied, the organic EL device of the present invention:
In principle, the luminance repeatedly increases and decreases or blinks repeatedly according to the waveform and cycle of the applied alternating current. In the case of the organic EL device shown in FIG. 1, when a voltage is applied between the anode 2 and the cathode 6, the anode 2
From the cathode 6 reach the light emitting layer 4 via the hole injecting / transporting layer 3, and electrons injected from the cathode 6 reach the light emitting layer 4 via the electron injecting / transporting layer 5. as a result,
In the light emitting layer 4, recombination of holes and electrons occurs, and the desired red light is emitted from the excited pyran derivative through the anode 2 and the substrate 1. The organic EL device of the present invention usually has a wavelength of 6 although it depends on the host compound and the pyran derivative used in combination.
00 to 670 nm, preferably 620 to 660 n
m has a light emission maximum in the red region. In addition, the light emission, x
In diagram y chromaticity, typically, x is from 0.50 to 0.72
In the range of, also, y is in the range of 0.20 to 0.36.

Since the organic EL device of the present invention has good color purity of light emission in the red region and excellent light emission efficiency and durability, it can be used in a variety of light emitting devices and information display devices for visually displaying information. Has a variety of uses. Since the light-emitting body using the organic EL element of the present invention as a light source has low power consumption and can be formed into a light-weight flat plate, in addition to a light source for general illumination, for example, a liquid crystal element, a copying apparatus,
Printing equipment, electrophotographic equipment, computers and their applied equipment, industrial control equipment, electronic measuring instruments, analytical instruments, general instruments, communication equipment, medical electronic measuring equipment, equipment mounted on automobiles, ships, aircraft, spacecraft, etc. Aircraft control equipment,
It is useful as an energy-saving and space-saving light source for interiors, signs and signs. When the organic EL device of the present invention is used for an information display device such as a computer, a television, a video, a game, a clock, a telephone, a car navigation, an oscilloscope, a radar, and a sonar, the organic EL device may be used alone or in green. Area and / or
Alternatively, the driving is performed by applying a general-purpose simple matrix system or an active matrix system as needed, in combination with an organic EL element that emits light in the blue region.

When the pyran derivative of the present invention is used as a laser substance, it is purified and dissolved in a solvent as necessary in the case of constructing a known dye laser oscillator, and the pH of the solution is adjusted as necessary. After adjusting to a level, it is sealed in a dye cell in a laser oscillation device. Pyran derivatives of the present invention, compared with known pyran derivatives,
In the visible region, not only an amplification gain can be obtained in an extremely wide wavelength range, but also light resistance is high, and it is hard to deteriorate even when used for a long time.

Further, since the pyran derivative of the present invention has an absorption maximum in the visible region and substantially absorbs visible light, a material for polymerizing a polymerizable compound by exposing it to visible light, a solar cell Sensitizing material, chromaticity adjusting material in optical filter,
It has a wide variety of uses as a material for dyeing various types of clothing. In particular, many of the pyran derivatives of the present invention have an absorption maximum wavelength, for example, an argon ion laser, a gas laser such as a krypton ion laser,
This is because it is close to an oscillation line (wavelength 450 to 550 nm) of a general-purpose laser such as a semiconductor laser such as a CdS laser or a solid-state laser such as a distributed feedback or distributed Bragg reflection type Nd-YAG laser. By compounding the photopolymerizable composition with a laser as an exposure light source as a photosensitizer, facsimile, copiers, information recording fields such as printers, flexographic plate making, gravure plate making and other printing fields, and more.
It can be used very advantageously in the field of printed circuits such as photoresists.

The pyran derivative of the present invention may be used, if necessary, together with one or more other materials that absorb light in the ultraviolet, visible, and / or infrared regions, in general clothing,
Other than clothing, for example, drapes, laces, casements, prints, venetian blinds, roll screens, shutters, goodwill, blankets, futons, duvets, duvet covers, duvet cotton, sheets, cushions, pillows, pillowcases, cushions, Mats, carpets, sleeping bags, tents, car interior materials, window glazing, window glazing, etc., disposable diapers, diaper covers, eyeglasses, monocles, lownets and other health supplies, shoe insoles, shoe linings Ground, luggage, furoshiki,
Filters, panels, and screens for umbrellas, umbrellas, stuffed animals, lighting devices, and information display devices such as television receivers and personal computers using, for example, CRT displays, liquid crystal displays, electroluminescent displays, plasma displays, etc. ,
Sunglasses, sunroofs, PET bottles, storages, greenhouses, cold gauze, optical fibers, prepaid cards, microwave ovens, viewing windows such as ovens, and further, packaging materials for packaging, filling or storing these items,
Filling timber, when using such the container is not only capable of reducing or preventing the disorder or inconvenience due to environmental light such as natural light or artificial light in an organism or an article, or trimmed color of the article, tone, texture and the like, There is a benefit in that light reflected or transmitted from an article can be adjusted to a desired color balance.

Hereinafter, embodiments of the present invention will be described based on examples.

[0054]

[Example 1] <Pyran derivative> 320 m of acetic acid was placed in a reaction vessel.
l, the phenol derivative 13 represented by the chemical formula 11
0 g and 83 g of ethyl acetoacetate.
After heating and stirring for a period of time to react, water 1
000 ml was added and the resulting oil was decanted,
Allowed to solidify. The obtained crude crystal was crushed and recrystallized from ethanol, whereby 109 g of a coumarin compound crystal represented by Chemical Formula 12 was obtained.

[0055]

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[0056]

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Separately, dimethylformamide 2 was added to the reaction vessel.
Take 80 ml and add 105 ml of phosphorus oxychloride while cooling with ice.
Was added dropwise, and the mixture was stirred for 30 minutes at ambient temperature, it had been dissolved in dimethylformamide 700ml Formula 1
70 g of the coumarin compound represented by No. 2 was added dropwise and reacted for 1 hour at ambient temperature with stirring. The reaction mixture was neutralized by adding an appropriate amount of an aqueous sodium hydroxide solution, and the precipitated crystals were collected by filtration and washed with diisopropyl ether to obtain 57 g of a coumarin compound crystal represented by Chemical Formula 13.

[0058]

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Next, dimethylformamide 3 was added to the reaction vessel.
Take 0 ml, 3.1 g of the coumarin compound represented by the chemical formula 13 obtained above and 4- (dicyanomethylene)-
After adding 3.0 g of 2,6-dimethyl-4H-pyran and heating at 80 ° C. for a while while stirring,
2.3 ml of piperidine are added and at the same temperature an additional 1.5 ml.
The reaction was carried out by heating for hours. The reaction mixture was ice-cooled, and the precipitated crude crystals were recrystallized using a mixed solution of chloroform / ethanol to obtain 0.65 g of a dark purple crystal of the pyran derivative of the present invention represented by Chemical Formula 1. A part of the crystal was taken and a ¹ H-nuclear magnetic resonance spectrum (hereinafter referred to as “ ¹ H-NMR spectrum”) in a chloroform-d solution was measured. As a result, a chemical shift δ (ppm, TM
S) is 1.34 (6H, s), 1.57 (6H, s),
1.75 to 1.84 (4H, m), 2.40 (3H,
s), 2.54 (3H, s), 3.28 (2H, t),
3.37 (2H, t), 6.45 (1H, s), 6.6
3 (1H, s), 7.38 (1H, s) and 7.56
A peak was observed at the position (2H, s).

Thereafter, the light absorption characteristics and the light emission characteristics were examined according to a conventional method.
As shown in the visible absorption spectrum (solid line) and the fluorescence spectrum (broken line), the methylene chloride solution had an absorption maximum in the visible region at a wavelength of 510 nm, and when excited, emitted visible light in the red region at a wavelength of 629 nm. When the thermal properties were examined by ordinary thermogravimetric analysis and differential thermal analysis, the pyran derivative of this example had melting points and decomposition points at 351 ° C. and 361 ° C., respectively, which were distinguishable from each other. Furthermore, when the pyran derivative of this example was deposited on a glass substrate according to a conventional method, a thin film having excellent amorphous properties and high heat resistance was formed. For comparison,
An analogous compound having a hydrogen atom at the 4-position of the coumarin skeleton was prepared by a known method and tested in the same manner. As a result, the analogous compound had a decomposition point near 365 to 370 ° C., which was difficult to determine the melting point. compared to pyran derivatives, the heat resistance in a thin film state was significantly poorer.

It has an absorption maximum in the visible region, and when excited,
The pyran derivative of this example, which emits visible light in the red region and has excellent amorphous properties and heat resistance in a thin film state,
It has a wide variety of uses as light absorbers and luminescent agents.

[0062]

Example 2 <Pyran derivative> An appropriate amount of ethanol was placed in a reaction vessel, and 44.8 g of a phenol derivative represented by the chemical formula 11, 37.1 g of ethyl 4,4,4-trifluoroacetoacetate and anhydrous zinc chloride were added. Add 30.6g,
The reaction was carried out by heating under reflux for 10 hours. An appropriate amount of 0.1N hydrochloric acid was added to the reaction mixture, and the mixture was stirred, and the precipitated crude crystals were collected and recrystallized using hexane to obtain 55.8 g of brown crystals of a coumarin compound represented by Chemical Formula 14. Was done.

[0063]

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Separately, dimethylformamide 2 was added to the reaction vessel.
Take 10 ml, add dropwise 70 ml of phosphorus oxychloride while cooling with ice, stir at ambient temperature for 30 minutes, and then dissolve in 330 ml of dimethylformamide.
55 g of a coumarin compound represented by the formula was added dropwise, and the mixture was reacted at 60 to 80 ° C. for 2 hours with stirring. The reaction mixture was neutralized by adding an appropriate amount of an aqueous sodium hydroxide solution, and the precipitated crystals were collected by filtration and washed with diisopropyl ether to obtain 45.1 g of crystals of a coumarin compound represented by Chemical Formula 15.

[0065]

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Next, dimethylformamide 3 was added to the reaction vessel.
0 ml, and 1.5 g of the coumarin compound represented by the chemical formula 15 obtained above and 4- (dicyanomethylene)-
1.4 g of 2,6-dimethyl-4H-pyran was added, and the mixture was heated at 90 ° C. for a while with stirring, and then with stirring.
0.16 ml of piperidine is added and at the same temperature an additional 1.
The reaction was performed by heating for 5 hours. The reaction mixture was ice-cooled, and the precipitated crude crystals were recrystallized using a mixed solution of chloroform / ethanol to obtain 0.3 g of crystals of the pyran derivative of the present invention represented by Chemical Formula 2. Take a part of the crystal,
When the ¹ H-NMR spectrum of the chloroform-d solution was measured, the chemical shift δ (ppm, TMS) was 1.31 (6H, s), 1.55 (6H, s), 1.7.
5 to 1.85 (4H, m), 2.39 (3H, s),
3.31 (2H, t), 6.53 (1H, s), 6.7
1 (1H, s) and 7.48 to 7.76 (3H, m)
A peak was observed at the position.

[0067] Then, were examined light absorption and emission properties according to a conventional method, pyran derivative of the present example, the methylene chloride solution has an absorption maximum in the visible region of wavelength 534 nm, when excited, wavelength 648nm and emit visible light in the red band. Furthermore, when the thermal characteristics were examined by ordinary thermogravimetric analysis and differential thermal analysis, the pyran derivative of this example had a melting point and a decomposition point at 353 ° C. and 369 ° C., respectively, which were distinguishable from each other. . Conventional method was deposited pyran derivative of the present example on a glass substrate in accordance with, excellent amorphous thin film is large heat resistance was formed.

[0068] in the visible region has an absorption maximum, when excited,
The pyran derivative of this example, which emits visible light in the red region and has excellent amorphous properties and heat resistance in a thin film state,
It has a wide variety of uses as light absorbers and luminescent agents.

[0069]

Example 3 <Pyran derivative> A coumarin derivative represented by the chemical formula 16 was obtained in the same manner as in Example 1 except that methyl propionyl acetate was used instead of ethyl acetoacetate. The coumarin compound was formylated in the same manner as in Example 1 and then 4- (dicyanomethylene)
By reacting with -2,6-dimethyl-4H-pyran, a pyran derivative represented by Chemical Formula 4 was obtained.

[0070]

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Having an absorption maximum in the visible region, when excited,
The pyran derivative of this example, which emits visible light in the red region and has excellent amorphous properties and heat resistance in a thin film state,
It has a wide variety of uses as light absorbers and luminescent agents.

[0072]

Example 4 <Pyran derivative> A coumarin compound represented by the chemical formula 17 was obtained in the same manner as in Example 1 except that ethyl 4,4-dimethyl-3-oxovalerate was used in place of ethyl acetoacetate. Was. This coumarin compound was formylated in the same manner as in Example 1 and then reacted with 4- (dicyanomethylene) -2,6-dimethyl-4H-pyran to obtain a pyran derivative represented by the formula (8).

[0073]

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It has an absorption maximum in the visible region, and when excited,
To emit visible light of red region, moreover, pyran derivatives of the present embodiment is excellent in amorphous property and heat resistance in a thin film state,
It has a wide variety of uses as light absorbers and luminescent agents.

[0075]

Example 5 <Pyran derivative> One of the four types of pyran derivatives obtained by the methods of Examples 1 to 4 was charged into a water-cooled sublimation purification apparatus, and the inside of the apparatus was kept under reduced pressure according to a conventional method. Sublimation purification was performed by heating while heating.

The highly pure pyran derivative of the present example was obtained from organic E
It is extremely useful in the field of organic electronics such as L elements and dye lasers.

In the pyran derivative according to the present invention, although there are some differences in the charging conditions and the yield depending on the structure,
For example, desired methods can be prepared by the methods of Examples 1 to 5 or those according to those methods, including those represented by Chemical Formulas 1 to 9 other than the above.

[0078]

Embodiment 6 <Organic EL Device> A glass substrate having a transparent ITO electrode having a thickness of 100 nm patterned with steam is washed with a neutral detergent, pure water and isopropyl alcohol by ultrasonic cleaning, and then boiled from isopropyl alcohol. After being pulled up, dried, and washed with ultraviolet ozone, it was fixed to a vapor deposition device, and the pressure was reduced to 10 -7 Torr. Then, N to a plane having an ITO electrode as an anode in the glass substrate, N'- bis (3-methylphenyl) -
N, N'-diphenyl- [1,1'-biphenyl]-
4,4′-diamine was deposited to a thickness of 50 nm to form a hole injection / transport layer. Thereafter, while monitoring with a film thickness sensor, tris (8-quinolinolato) aluminum (hereinafter abbreviated as “Alq3”) as a host compound, and chemical formulas 1 and 4 obtained by the methods of Examples 1 to 4. 2. A luminescent layer is formed by co-evaporating a pyran derivative represented by any one of Chemical Formulas 4 and 8 to a thickness of 15 nm to 1.5 mol% with respect to Alq3 to form a light-emitting layer. The oxadiazole derivative and Alq3 represented by thicknesses of 20 nm and 25 nm, respectively.
Then, magnesium and silver were co-deposited at a weight ratio of 10: 1 to a thickness of 200 nm to form a cathode. Then, under a nitrogen atmosphere,
The entire device was sealed with a glass plate and an ultraviolet curable resin to obtain an organic EL device.

[0079]

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At the same time, a control organic EL device was prepared in the same manner as described above except that a known pyran derivative having a hydrogen atom at the 4-position of the coumarin skeleton was used instead of the pyran derivative represented by the chemical formula 1. Produced.

In any of the organic EL devices of this example, when the anode is set at a higher potential than the cathode, the wavelength is 600 to 670 nm.
m, specifically, red light having an emission maximum near a wavelength of 650 nm. When DC is applied, 4V
Light emission was confirmed from before and after, and reached the maximum luminance around 18 V. According to a conventional method, it was found that the light emission of the organic EL element of this example was such that x was not more than 0 on the xy chromaticity diagram.
Y was in the range of 50 to 0.72 and y was in the range of 0.20 to 0.36. Light emission stably continued, and no partial dark spot (dark spot) was observed even after 1,000 hours from the start of light emission. On the other hand, the control organic EL device had low luminance and a significantly short emission life.

[0082]

The present invention is based on the creation of a novel pyran derivative. The pyran derivative of the present invention has an absorption maximum in the visible region and emits visible light in the red region when excited, so that a luminescent agent and a light absorber require an organic compound having such properties. For example, it can be used very advantageously in the fields of organic EL devices, dye lasers, photochemical polymerization, solar cells, optical filters, and dyeing.

The organic EL device of the present invention using such a pyran derivative has excellent luminous efficiency and durability in addition to good color purity of light emission in the red region, and therefore, emits light as a light source in general illumination. It can be used very advantageously in a wide variety of information display devices that visually display the body and information.

Such useful pyran derivatives are 4- (dicyanomethylene) -2,6-dimethyl-4H-pyran,
A desired amount can be obtained by the production method of the present invention via a step of reacting with a coumarin compound having a urolidine skeleton in the molecule and having an aldehyde group and a hydrocarbon group bonded to the 3- and 4-positions, respectively. .

[Brief description of the drawings]

FIG. 1 is a schematic view of an organic EL device according to the present invention.

FIG. 2 shows a visible absorption spectrum (solid line) and a fluorescence spectrum (dashed line) of a pyran derivative according to the present invention.

[Explanation of symbols]

 1 substrate 2 anode 3 hole injection / transport layer 4 the light-emitting layer 5 electron injecting / transporting layer 6 cathode

Continued on the front page (72) Inventor Sadaharu Suga 1-2-3, Shimoishii, Okayama-shi, Okayama Pref. Hayashibara Biochemical Laboratory Co., Ltd. (72) Inventor Akio Taniguchi 3- 14-2, Chuo, Ueda-shi, Nagano F Terms (reference) 3K007 AB00 AB03 AB04 BB06 CA01 CA02 CA05 CA06 CB01 DA00 DB03 EB00 FA01 4C064 AA11 CC01 DD02 EE04 FF01 GG07

Claims (19)

[Claims] 1. A pyran derivative represented by the general formula 1. Embedded image In the general formula 1, R represents a hydrocarbon group, and the hydrocarbon group may have a substituent. 2. The pyran derivative according to claim 1, wherein R in the general formula 1 is a hydrocarbon group having up to 8 carbon atoms. 3. The composition according to claim 1, which has a melting point and a decomposition point that can be distinguished from each other, and has a decomposition point of 350 ° C. or more.
The pyran derivative according to the above. 4. The pyran derivative according to claim 1, which has an absorption maximum in a visible region and emits visible light in a red region when excited. 5. A luminescent agent comprising the pyran derivative according to claim 1. 6. The luminescent agent according to claim 5, which is used as a material for a luminescent layer of an organic electroluminescent device. 7. The luminescent agent according to claim 5, comprising one or more other luminescent compounds together with the pyran derivative according to any one of claims 1 to 4. 8. The luminescent agent according to claim 7, wherein the other luminescent compound is a host compound. 9. The luminescent agent according to claim 5, which emits red light when excited in a thin film state. 10. A light absorber comprising the pyran derivative according to any one of claims 1 to 4. 11. An absorption maximum in a visible region.
The light absorber according to the above. 12. An organic electroluminescent device comprising the pyran derivative according to claim 1. Description: 13. The organic electroluminescent device according to claim 12, wherein the light-emitting layer comprises the pyran derivative according to claim 1 and one or more other light-emitting compounds. 14. The organic electroluminescent device according to claim 13, wherein the other luminescent compound is a host compound. 15. The organic electroluminescent device according to claim 13, wherein the other luminescent compound is a quinolinol metal complex. 16. The organic electric field according to claim 12, further comprising a hole injection / transport layer, an electron injection / transport layer and / or a hole block layer together with the anode, the light emitting layer and the cathode. Light emitting element. 17. The light emitting device according to claim 12, which emits light in a red region.
17. The organic electroluminescent device according to 4, 15, or 16. 18. A process comprising reacting 4- (dicyanomethylene) -2,6-dimethyl-4H-pyran with a compound represented by the general formula 2 having R corresponding to the general formula 1. 5. The method for producing a pyran derivative according to any one of 1 to 4. Embedded image (19) a compound represented by the general formula (2):
The method for producing a pyran derivative according to claim 18, wherein-(dicyanomethylene) -2,6-dimethyl-4H-pyran is excessively reacted.