JP2002212114A - Aromatic methylidene compound, aromatic aldehyde compound and methylstyryl compound for producing the same, and method for producing the compounds - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a new organic compound which is used for the charge transport materials of electrophotographic photoreceptors, the charge transport materials and light-emitting materials of organic electroluminescent elements, or various kinds of organic semiconductor elements. SOLUTION: The new aromatic methylidene compound of general formula 1 [R11 and R21 are each an alkyl, an alkoxy, a halogen, cyano or nitro; (n11) is an integer of 0 to 6; (n12) is an integer of 0 to 4; R31 and R41 are each H, an alkyl, a cycloalkyl, an aromatic group, or an aromatic heterocyclic group; R31 and R41 may together form a non-substituted/substituted aromatic ring or an aromatic heterocyclic ring-condensed ring] is provided.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a functional material for an electrophotographic photosensitive member, a functional material such as a charge transporting material or a luminescent material in an organic electroluminescent device, or a functional material used for various other organic semiconductor devices. The present invention relates to a useful novel aromatic methylidene compound, an aromatic aldehyde compound and a methylstyryl compound useful for producing the same, and a method for producing them.

[0002]

2. Description of the Related Art An electroluminescent device utilizing the electroluminescent phenomenon of a substance is of a self-luminous type as compared with a liquid crystal device, so that it has high visibility and can display a clear image when used for a display or the like. Further, since it is a completely solid element, it has characteristics such as excellent impact resistance, and is expected to be widely used in thin displays, backlights of liquid crystal displays, or flat light sources in the future.

At present, there is a distributed electroluminescent element using an inorganic material such as zinc sulfide as an electroluminescent element which has been put into practical use. However, this dispersed electroluminescent element requires a relatively high AC voltage for its driving. Therefore, there are problems such as a complicated driving circuit and low luminance, and the actual situation is that it is not widely used for practical use.

On the other hand, an organic electroluminescent device using an organic material has been disclosed in 1987 by CWTang et al. In Japanese Patent Application Laid-Open No. 63-264629, which discloses an organic fluorescent material having an electron transporting property and a hole transporting property. The proposed organic EL device has a laminated structure in which both organic and electron carriers are injected into the fluorescent material layer to emit light, and has been in the limelight. In this device, it was reported that light emission of 1000 cd / m ² or more was obtained at a driving voltage of 10 V or less, and thereafter, with this proposal as a starting point, active research on the surrounding area has been conducted. At present, various materials and element configurations have been proposed, and research and development for practical use are being actively conducted.

[0005]

On the other hand, it is a fact that there are still various problems and problems in the organic electroluminescent device using the materials proposed so far. In some cases, the function of the element can be degraded just by saving, irrespective of the driving state or non-driving state, and the light emission luminance may decrease. Occurs and grows or grows,
Eventually, there is a phenomenon in which the element is short-circuited and breakage occurs.

[0006] Such a phenomenon can be said to have a substantial problem of the material used therein, and at present, it is hard to say that the life is practically sufficient. Therefore, in practical use of the element, it can be said that it is necessary to limit the device to a device that can be used with a relatively short life.

Further, in consideration of the colorization of the element, at present, a method and a light-emitting material which can cope with the problem are not sufficiently prepared. In any case, in order to solve these problems and problems and aim for the widespread practical use of organic electroluminescent devices,
Therefore, development of new materials such as new high-performance light-emitting materials and charge transport materials used therefor is expected.

The present invention has been made in view of the actual state of such an organic electroluminescent device, and is particularly useful as a luminescent material in order to realize an organic electroluminescent device having low voltage, high luminance, and excellent durability. An object of the present invention is to provide a novel aromatic methylidene compound, an aromatic aldehyde compound and a methylstyryl compound for producing the same, and a method for producing them. This is intended to contribute to the realization of a highly durable organic electroluminescent device with high luminance emission.

[0009]

Means for Solving the Problems In order to achieve the above object, first, means for solving the problems in the present invention are compounds represented by the following general formula (1).

[0010]

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[However, in the above formula, R¹¹And R^{twenty one}Is unsubstituted
Or substituted alkyl group, unsubstituted or substituted alkoxy
Represents a group, a halogen group, a cyano group or a nitro group; n¹¹
Represents an integer of 0, 1, 2, 3, 4, 5 or 6, and n^{twenty one}Is 0, 1,
Represents an integer of 2, 3 or 4. n¹¹, N ^{twenty one}Is an integer greater than or equal to 2
Come, R¹¹, R^{twenty one}Each consist of a plurality of the same substituents
Case, or when consisting of multiple different substituents
There may be. Also R³¹And R⁴¹Is hydrogen (where R³¹You
And R⁴¹Are hydrogen at the same time), unsubstituted
Or a substituted alkyl group (provided that R³¹And R⁴¹But at the same time
Unsubstituted or substituted cycloalkyl)
Alkyl group (however, R³¹And R⁴¹Are simultaneously cycloalkyl groups
), An unsubstituted or substituted aromatic group, or
Represents an unsubstituted or substituted aromatic heterocyclic group;³¹And
And R⁴¹Are different substituents even if they are the same substituent
It may be. Also, R³¹And R⁴¹Is jointly, unsubstituted
Or fused or unsubstituted or substituted aromatic ring
May form a condensed ring of a substituted aromatic heterocycle
No. Or a compound represented by the following general formula (2).

[0012]

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[However, in the above formula, R¹²And R^{twenty two}Is unsubstituted
Or substituted alkyl group, unsubstituted or substituted alkoxy
Represents a group, a halogen group, a cyano group or a nitro group; n¹²
Represents an integer of 0, 1, 2, 3, 4, 5 or 6, and n^{twenty two}Is 0, 1,
Represents an integer of 2, 3 or 4. n¹², N ^{twenty two}Is an integer greater than or equal to 2
Come, R¹², R^{twenty two}Each consist of a plurality of the same substituents
Case, or when consisting of multiple different substituents
There may be. Or a compound represented by the following general formula (3).

[0014]

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[However, in the above formula, R¹³And R^{twenty three}Is unsubstituted
Or substituted alkyl group, unsubstituted or substituted alkoxy
Represents a group, a halogen group, a cyano group or a nitro group; n¹³
Represents an integer of 0, 1, 2, 3, 4, 5 or 6, and n^{twenty three}Is 0, 1,
Represents an integer of 2, 3 or 4. n¹³, N ^{twenty three}Is an integer greater than or equal to 2
Come, R¹³, R^{twenty three}Each consist of a plurality of the same substituents
Case, or when consisting of multiple different substituents
There may be. Or a compound represented by the following general formula (4)
Reacting with the compound represented by (5).
A process for producing the compound represented by the general formula (1).
You.

[0016]

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Wherein R ¹⁴ represents an unsubstituted or substituted alkyl group, an unsubstituted or substituted alkoxy group, a halogen group, a cyano group or a nitro group, and n ¹⁴ represents 0, 1,
Represents an integer of 2, 3, 4, 5 or 6. When n ¹⁴ is an integer of 2 or more, R ¹⁴ may be either a case where it is composed of a plurality of the same substituents or a case where it is composed of a plurality of different substituents.
R represents an unsubstituted or substituted alkyl group. ]

[0018]

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Wherein R ²⁴ represents an unsubstituted or substituted alkyl group, an unsubstituted or substituted alkoxy group, a halogen group, a cyano group or a nitro group, and n ²⁴ represents 0, 1,
Represents an integer of 2, 3 or 4. When n ²⁴ is an integer of 2 or more, R ²⁴
May be either a case where it is composed of a plurality of the same substituents or a case where it is composed of a plurality of different substituents. Also R ^{3 2}
And R ⁴² are hydrogen (except when R ³² and R ⁴² are simultaneously hydrogen), an unsubstituted or substituted alkyl group (except when R ³² and R ⁴² are both an alkyl group), unsubstituted or Substituted cycloalkyl group (provided that R ³²
And R ⁴² are simultaneously a cycloalkyl group), an unsubstituted or substituted aromatic group, or an unsubstituted or substituted aromatic heterocyclic group, wherein R ³² and R ⁴² are the same substituents. Or different substituents.
Further, R ³² and R ⁴² may jointly form a condensed ring of an unsubstituted or substituted aromatic ring or a condensed ring of an unsubstituted or substituted heteroaromatic ring. Or a compound represented by the general formula (2) and a compound represented by the following general formula:
A method for producing a compound represented by the general formula (1), which comprises reacting the compound represented by the formula (6).

[0020]

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Wherein R ³³ and R ⁴³ are hydrogen (except when R ³³ and R ⁴³ are simultaneously hydrogen);
An unsubstituted or substituted alkyl group (except when R ³³ and R ⁴³ are simultaneously an alkyl group), an unsubstituted or substituted cycloalkyl group (except when R ³³ and R ⁴³ are simultaneously a cycloalkyl group), Represents an unsubstituted or substituted aromatic group, or an unsubstituted or substituted aromatic heterocyclic group, wherein R ³³ and R ⁴³ may be the same or different from each other; Further, R ³³ and R ⁴³ may jointly form a condensed ring of an unsubstituted or substituted aromatic ring or a condensed ring of an unsubstituted or substituted heteroaromatic ring. R represents an unsubstituted or substituted alkyl group. Or a compound represented by the following general formula (7):
A process for producing a compound represented by the general formula (1), which comprises reacting the compound represented by the formula (8).

[0022]

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Wherein R ¹⁵ represents an unsubstituted or substituted alkyl group, an unsubstituted or substituted alkoxy group, a halogen group, a cyano group or a nitro group, and n ¹⁵ represents 0, 1,
Represents an integer of 2, 3, 4, 5 or 6. When n ¹⁵ is an integer of 2 or more, R ¹⁵ may be either a case where it is composed of a plurality of the same substituents or a case where it is composed of a plurality of different substituents. ]

[0024]

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Wherein R ²⁵ represents an unsubstituted or substituted alkyl group, an unsubstituted or substituted alkoxy group, a halogen group, a cyano group or a nitro group, and n ²⁵ represents 0, 1,
Represents an integer of 2, 3 or 4. When n ²⁵ is an integer of 2 or more, R ²⁵
May be either a case where it is composed of a plurality of the same substituents or a case where it is composed of a plurality of different substituents. Also R ^{3 4}
And R ⁴⁴ are hydrogen (except when R ³⁴ and R ⁴⁴ are simultaneously hydrogen), an unsubstituted or substituted alkyl group (except when R ³⁴ and R ⁴⁴ are simultaneously an alkyl group), unsubstituted or Substituted cycloalkyl group (provided that R ³⁴
And R ⁴⁴ are simultaneously a cycloalkyl group), an unsubstituted or substituted aromatic group, or an unsubstituted or substituted aromatic heterocyclic group, wherein R ³⁴ and R ⁴⁴ are the same substituents. Or different substituents.
R ³⁴ and R ⁴⁴ may together form a condensed ring of an unsubstituted or substituted aromatic ring or a condensed ring of an unsubstituted or substituted heteroaromatic ring. R represents an unsubstituted or substituted alkyl group. Or a compound represented by the following general formula (9):
A process for producing a compound represented by the general formula (1), which comprises reacting the compound represented by the formula (10).

[0026]

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[However, in the above formula, R¹⁶And R²⁶Is unsubstituted
Or substituted alkyl group, unsubstituted or substituted alkoxy
Represents a group, a halogen group, a cyano group or a nitro group; n¹⁶
Represents an integer of 0, 1, 2, 3, 4, 5 or 6, and n²⁶Is 0, 1,
Represents an integer of 2, 3 or 4. n¹⁶, N ²⁶Is an integer greater than or equal to 2
Come, R¹⁶, R²⁶Each consist of a plurality of the same substituents
Case, or when consisting of multiple different substituents
There may be. R is an unsubstituted or substituted alkyl group
Represents ]

[0028]

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Wherein R ³⁵ and R ⁴⁵ are hydrogen (except when R ³⁵ and R ⁴⁵ are simultaneously hydrogen);
An unsubstituted or substituted alkyl group (except when R ³⁵ and R ⁴⁵ are simultaneously an alkyl group), an unsubstituted or substituted cycloalkyl group (except when R ³⁵ and R ⁴⁵ are simultaneously a cycloalkyl group), Represents an unsubstituted or substituted aromatic group or an unsubstituted or substituted aromatic heterocyclic group, wherein R ³⁵ and R ⁴⁵ may be the same or different substituents; Further, R ³⁵ and R ⁴⁵ may jointly form a condensed ring of an unsubstituted or substituted aromatic ring or a condensed ring of an unsubstituted or substituted heteroaromatic ring. Or a compound represented by the general formula (4) and a compound represented by the following general formula:
A method for producing a compound represented by the general formula (2), comprising reacting the compound represented by (11) to obtain an acetal compound, and then deriving the acetal compound into an aldehyde compound. .

[0030]

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Wherein R ²⁷ represents an unsubstituted or substituted alkyl group, an unsubstituted or substituted alkoxy group, a halogen group, a cyano group or a nitro group, and n ²⁷ represents 0, 1,
Represents an integer of 2, 3 or 4. When n ²⁷ is an integer of 2 or more, R ²⁷
May be either a case where it is composed of a plurality of the same substituents or a case where it is composed of a plurality of different substituents. Also R
Represents an unsubstituted or substituted alkyl group. Or a compound represented by the general formula (4) and a compound represented by the following general formula:
A method for producing a compound represented by the general formula (2), characterized by reacting the compound represented by the formula (12).

[0032]

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[Wherein, R ²⁸ represents an unsubstituted or substituted alkyl group, an unsubstituted or substituted alkoxy group, a halogen group, a cyano group or a nitro group, and n ²⁸ represents 0, 1,
Represents an integer of 2, 3 or 4. When n ²⁸ is an integer of 2 or more, R ²⁸
May be either a case where it is composed of a plurality of the same substituents or a case where it is composed of a plurality of different substituents. Or a compound represented by the general formula (4) and a compound represented by the following general formula:
A process for producing a compound represented by the general formula (3), which comprises reacting the compound represented by the formula (13).

[0034]

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Wherein R ²⁹ represents an unsubstituted or substituted alkyl group, an unsubstituted or substituted alkoxy group, a halogen group, a cyano group or a nitro group, and n ²⁹ represents 0, 1, or
Represents an integer of 2, 3 or 4. When n ²⁹ is an integer of 2 or more, R ²⁹
May be either a case where it is composed of a plurality of the same substituents or a case where it is composed of a plurality of different substituents. Or a compound represented by the general formula (7) and a compound represented by the following general formula:
A method for producing a compound represented by the general formula (3), which comprises reacting the compound represented by the formula (14).

[0036]

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[Wherein, R ²⁰ represents an unsubstituted or substituted alkyl group, an unsubstituted or substituted alkoxy group, a halogen group, a cyano group or a nitro group, and n ²⁰ represents 0, 1, or
Represents an integer of 2, 3 or 4. When n ²⁰ is an integer of 2 or more, R ²⁰
May be either a case where it is composed of a plurality of the same substituents or a case where it is composed of a plurality of different substituents. Also R
Represents an unsubstituted or substituted alkyl group. The compound represented by the general formula (1) according to the present invention is useful as a constituent material of an organic electroluminescent device, and is particularly excellent as a luminescent material. The compounds represented by the general formulas (2) and (3) are useful intermediates for producing the compound represented by the general formula (1). The compounds and their production methods provided by the present invention greatly contribute to the realization of a highly durable and highly durable organic electroluminescent device.

[0038]

BEST MODE FOR CARRYING OUT THE INVENTION The compound represented by the general formula (1) of the present invention can be roughly classified into four synthetic routes, that is, the general formula
Reaction of bismethylphosphonic ester derivative represented by (4) with stilbene aldehyde derivative represented by general formula (5), bis (4-formylstyryl) naphthalene derivative represented by general formula (2) and general formula Reaction with a methylphosphonate derivative represented by (6), reaction between a phthalaldehyde derivative represented by the general formula (7) and a methylphosphonate derivative represented by the general formula (8), general formula (9) A bismethylphosphonic ester derivative represented by the general formula (1
It can be produced by reaction with a ketone derivative represented by the formula (0).

In addition, in each of the above synthetic routes, it is also possible to use the corresponding methyltriarylphosphonium salt instead of the methylphosphonate derivative used therein.

Each of these reactions is a reaction between an aldehyde and active methylene, and is usually performed using a base in an organic solvent. Reaction solvents include water or alcohols such as methanol, ethanol, butanol, and amyl alcohol; aromatic hydrocarbons such as benzene, toluene, xylene, mesitylene, chlorobenzene, and nitrobenzene; ethers such as diethyl ether, tetrahydrofuran, and dioxane; and chloroform. , Dichloromethane, halogenated hydrocarbons such as dichloroethane, pyridine, heterocyclic aromatic hydrocarbons such as quinoline, and other N, N-dimethylformamide, dimethyl sulfoxide and the like,
Usually, all common organic solvents can be used.

The base used in the reaction includes inorganic bases such as potassium carbonate, sodium carbonate, potassium hydroxide and sodium hydroxide, organic bases such as triethylamine, triethanolamine, pyridine and hexamethylenetetramine, sodium methoxide and sodium Examples include alkali metal salts of alcohols such as ethoxide and potassium butoxide, and other sodium amides. The amount of the base to be used may be from a catalytic amount to a chemical equivalent or more, if necessary. The reaction is carried out at a temperature of about −10 ° C. to about 150 ° C., preferably about 0 ° C. to about 80 ° C. The reaction time generally depends on the relationship with the reaction temperature,
Usually, it is about 30 minutes to 100 hours, but it should be appropriately selected depending on the combination of each raw material.

After completion of the reaction, to obtain the desired product from the reaction mixture, the crude product is taken out by concentration, dilution with a poor solvent, etc., preferably after removing inorganic components by washing with water or the like, and then column chromatography, recrystallization or A pure target product can be obtained by a general purification method such as sublimation purification.

Next, the compound represented by formula (2) of the present invention will be described.

The compound represented by the general formula (2) is
After obtaining an acetal compound of the general formula (2) by reacting a bismethylphosphonic ester derivative represented by and a monodialkyl acetal of a terephthalaldehyde derivative represented by the general formula (11), It can also be obtained directly by a derivation method or by a reaction with a terephthalaldehyde derivative represented by the general formula (12) instead of the monodialkyl acetal of the terephthalaldehyde derivative.

Further, the compound represented by formula (3) of the present invention will be described.

The compound represented by the general formula (3) is
Reaction of a bismethylphosphonate derivative represented by the formula with a tolualdehyde derivative represented by the general formula (12), or a phthalaldehyde derivative represented by the general formula (7) and a methylphosphon represented by the general formula (14) It can be obtained by reaction with an acid ester derivative.

The synthesis reaction of the general formulas (2) and (3) is also a reaction between aldehyde and active methylene similarly to the synthesis reaction of the general formula (1), and is usually carried out using a base in an organic solvent. Done. As the reaction solvent and the base used here, those similar to those described in the synthesis route of the above general formula (1) can be used. The same applies to the reaction conditions.

The compound represented by the general formula (3) is a bismethylphosphonate derivative represented by the general formula (9), which is useful as a raw material for obtaining the compound of the general formula (1). This is important as one of the intermediates to obtain. That is, by deriving the compound represented by the general formula (3) into a halomethyl form represented by the following general formula (15), and then reacting with a trialkyl phosphite, the general formula
The bismethylphosphonate derivative represented by (9) can be conveniently obtained.

[0049]

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[Wherein, R ′ and R ″ in the above formula represent a substituent, and X represents a halogen.] Next, specific examples of the compound represented by the general formula (1) of the present invention (Table 1) ) To (Table 5), specific examples of the compound represented by the general formula (2) are shown in (Table 6), and specific examples of the compound represented by the general formula (3) are shown in (Table 7). However, the present invention is not limited to this.

[0051]

[Table 1]

[0052]

[Table 2]

[0053]

[Table 3]

[0054]

[Table 4]

[0055]

[Table 5]

[0056]

[Table 6]

[0057]

[Table 7]

As mentioned above, the general formula according to the present invention
The compound represented by (1) is useful as a constituent material of an organic electroluminescent device, and is particularly excellent as a luminescent material. The compounds represented by the general formulas (2) and (3) are useful intermediates for producing the compound represented by the general formula (1). The compounds provided by the present invention and the methods for producing these compounds greatly contribute to the realization of a highly durable and highly durable organic electroluminescent device. Hereinafter, the present invention will be described in more detail with reference to Examples.

[0059]

Next, specific examples of the present invention will be described.

Example 1 [Production Example of Compound No. 1-22 (Part 1)] Tetraethyl 1,4-dimethylnaphthalene-α, α′-diyldiphosphonate 0.857
g, 4'-formyl-α-phenylstilbene 1.14 g to N, N-
It was dissolved in 12 ml of dimethylformamide, and 0.520 g of potassium tert-butoxide was added in small portions over 10 minutes at 5-10 ° C. Then, after stirring at room temperature for 20 hours, about 30 ml of ethanol was added, and the precipitate was collected by filtration, washed with ethanol,
After washing with water and drying, 1.21 g of yellow crystals were obtained.

Next, this yellow crystal was subjected to stationary phase silica gel,
Column chromatography was performed with toluene as a mobile phase to obtain yellow-orange crystal yellow. Then, the mixture was recrystallized from a mixed solvent of toluene and hexane, and dried in vacuo at 120 ° C. to obtain 1.15 g (83% yield) of orange-yellow crystals having strong fluorescence (melting point: 209.0-2)
10.0 ° C). The elemental analysis value thereof was 94.09% for carbon (94.15% calculated as compound No. 1-22), and 5.66% for hydrogen (5.85% calculated for compound No. 1-22). As shown in FIG. 1, in the infrared absorption spectrum (KBr tablet method), stretching vibration caused by the aromatic ring was observed at around 1590 cm ⁻¹ . In the proton nuclear magnetic resonance spectrum (solvent CDCl ₃ , internal standard TMS), aromatic ring protons and alkene protons were δ = 7.0 to 8.2 p
pm (40H).

In the mass spectrum, a molecular ion peak m / z = 688 was observed. From the above, it was confirmed that the compound obtained above was Compound No. 1-02.

Example 2 [Production Example of Compound No. 1-02 (Part 2)] 3.04 g of diethyl diphenylmethylphosphonate, 1.94 g of 1,4-bis (4-formylstyryl) naphthalene (Compound No. 2-01) Is dissolved in 30 ml of N, N-dimethylformamide, and potassium tert-
1.30 g of butoxide was added in small portions over 10 minutes.
After stirring at room temperature for 20 hours, ethanol 100m
The precipitate was collected by filtration, washed with ethanol, washed with water, and dried to obtain 2.55 g of orange-yellow crystals.

Next, the orange-yellow crystals were subjected to column chromatography in the same manner as in Example 1 using silica gel as a stationary phase and toluene as a mobile phase to obtain orange-yellow crystals. Then, the product was recrystallized from a mixed solvent of toluene and hexane, and dried in vacuo at 120 ° C. to obtain 2.34 g (68% yield) of orange-yellow crystals having strong fluorescence (melting point: 209.0 to 210.0 ° C.). The elemental analysis of this is
94.00% carbon (94.15% calculated as compound number 1-22),
The amount of hydrogen was 5.73% (the calculated value as compound number 1-22 was 5.85%).

The infrared absorption spectrum, proton nuclear magnetic resonance spectrum and mass spectrum were identical with those of the compound obtained in (Example 1), and it was confirmed that both were the same substance and compound No. 1-22.

Example 3 [Production Example of Compound No. 1-22 (No. 3)] 0.921 g of 1,4-naphthalenedicarbaldehyde, 4.06 g of diethyl 4- (2,2′-diphenylvinyl) benzylphosphonate Was dissolved in 30 ml of N, N-dimethylformamide, and 1.30 g of potassium tert-butoxide was added in small portions at 5-10 ° C. over 10 minutes. afterwards,
After stirring at room temperature for 20 hours, 100 ml of ethanol was added, and the precipitate was collected by filtration, washed with ethanol, washed with water, and dried to obtain 2.08 g of orange-yellow crystals.

Next, the orange-yellow crystals were subjected to column chromatography using silica gel as a stationary phase and toluene as a mobile phase in the same manner as in Example 1 to obtain orange-yellow crystals. Then, the product was recrystallized from a mixed solvent of toluene and hexane and dried under vacuum at 120 ° C to obtain 1.78 g (yield: 52%) of orange-yellow crystals having strong fluorescence (melting point: 209.0 to 210.0 ° C). The elemental analysis of this is
94.09% carbon (94.15% calculated as compound number 1-22),
The hydrogen content was 5.62% (the calculated value as Compound No. 1-22 was 5.85%).

Further, the infrared absorption spectrum, proton nuclear magnetic resonance spectrum and mass spectrum were identical with those of the compound obtained in (Example 1), and it was confirmed that both were the same substance and were compound No. 1-22.

Example 4 [Production Example of Compound No. 1-02 (Part 4)] Benzophenone 1.8
2 g, 3.16 g of tetraethyl 1,4-bis (4-methylstyryl) naphthalene-α, α′-diyldiphosphonate were dissolved in 30 ml of N, N-dimethylformamide, and 1.30 g of potassium tert-butoxide was added at 5-10 ° C. Added in small portions over minutes. After stirring at room temperature for 20 hours, 100 ml of ethanol was added, and the precipitate was collected by filtration, washed with ethanol, washed with water and dried to obtain 2.45 g of orange-yellow crystals.

Next, the orange-yellow crystals were subjected to column chromatography using silica gel as a stationary phase and toluene as a mobile phase in the same manner as in Example 1 to obtain orange-yellow crystals. Then, recrystallized from a mixed solvent of toluene and hexane and dried in vacuo at 120 ° C. to obtain 1.92 g (yield: 56%) of orange-yellow crystals having strong fluorescence (melting point: 209.0 to 210.0 ° C.). The elemental analysis value thereof was 94.12% for carbon (94.15% calculated as compound number 1-22) and 5.77% for hydrogen (5.85% calculated for compound number 1-22).

The infrared absorption spectrum, proton nuclear magnetic resonance spectrum and mass spectrum were identical with those of the compound obtained in (Example 1), and it was confirmed that both were the same substance and compound No. 1-02.

Example 5 Production Example of Compound No. 2-01 (Part 1) Tetraethyl 1,4-dimethylnaphthalene-α, α′-diyldiphosphonate 8.57
g, terephthalaldehyde monodiethyl acetal 8.75
g was dissolved in N, N-dimethylformamide (80 ml) and potassium tert-butoxide (5.67 g) was added in small portions at 5-10 ° C. over 10 minutes. Then, after stirring at room temperature for 25 hours,
38.5 ml of 36% hydrochloric acid was added, and the mixture was further stirred at a bath temperature of 80 to 85 ° C. for 30 minutes. After cooling, about 150 ml of water was added, and the precipitated crystals were collected by filtration, washed with water, and dried in vacuo at 60 ° C. to obtain 7.01 g of yellow crystals.

The obtained yellow crystals were recrystallized from toluene and then dried in vacuum at 80 ° C. to obtain 6.77 g (yield 87%) of yellow crystals. Its elemental analysis value was 86.31% of carbon (calculated value of 86.57% as compound number 2-01), and 4.99% of hydrogen (calculated value of 5.19% as compound number 2-01). Further, the compound No. 2-01 was analyzed by infrared absorption spectrum, proton nuclear magnetic resonance spectrum and mass spectrum in the same manner as in the above Examples.
Was confirmed.

Example 6 [Production Example of Compound No. 2-01 (Part 2)] Tetraethyl 1,4-dimethylnaphthalene-α, α'-diyldiphosphonate 8.57
g, 13.41 g of terephthalaldehyde was dissolved in 160 ml of N, N-dimethylformamide, and 5.67 g of potassium tert-butoxide was added in small portions at 5 to 10 ° C. over 10 minutes. Then, after stirring at room temperature for 20 hours, about 300 ml of water was added,
The crystals were collected by filtration, washed with water, and further washed with 200 ml of ethanol under heat to obtain 7.04 g of a yellow powder.

The obtained yellow powder was repeatedly recrystallized from toluene and dried in vacuum at 80 ° C. to obtain 1.55 g (yield 20%) of yellow crystals. Its elemental analysis value was as follows: carbon: 86.48% (calculated value as compound number 2-01: 86.57%), and hydrogen: 5.11% (calculated value as compound number 2-01: 5.19%).

Further, the infrared absorption spectrum, proton nuclear magnetic resonance spectrum and mass spectrum were identical with those of the compound obtained in (Example 5), and it was confirmed that both were the same substance and compound No. 2-01.

Example 7 [Production Example of Compound No. 3-01 (Part 1)] Tetraethyl 1,4-dimethylnaphthalene-α, α′-diyldiphosphonate 4.28
g, 4-methylbenzaldehyde (2.64 g) was dissolved in N, N-dimethylformamide (60 ml), and potassium tert-butoxide (2.60 g) was added in small portions at 5 to 10 ° C. over 10 minutes. Then, after stirring at room temperature for 20 hours, about 150 ml of water was added,
The precipitated crystals are collected by filtration, washed with water and dried to give a tan powder.
3.26 g was obtained.

Next, this powder was recrystallized from N, N-dimethylformamide to obtain 3.03 g (yield: 84%) of yellow crystals. Its elemental analysis value was 93.14% of carbon (93.29% of the calculated value as Compound No. 3-01), and 6.52% of hydrogen (the calculated value of 6.71% as Compound No. 3-01). Further, the compound was identified as Compound No. 3-01 by an infrared absorption spectrum, a proton nuclear magnetic resonance spectrum and a mass spectrum in the same manner as in the above Example.

Example 8 [Production Example of Compound No. 3-01 (No. 2)] 1.84 g of 1,4-naphthalenedicarbaldehyde and 4.85 g of diethyl 4-methylbenzylphosphonate were added to 60 ml of N, N-dimethylformamide. And 2.60 g of potassium tert-butoxide were added in small portions over 10 minutes at 5-10 ° C. After stirring at room temperature for 20 hours, about 150 ml of water was added, and the precipitated crystals were collected by filtration, washed with water, and dried to obtain 3.12 g of a tan powder.

Next, this powder was recrystallized from N, N-dimethylformamide to obtain 2.97 g (83% yield) of yellow crystals. The elemental analysis value thereof was 93.14% for carbon (93.29% calculated as compound No. 3-01) and 6.64% for hydrogen (6.71% calculated for compound No. 3-01). In addition, the infrared absorption spectrum, the proton nuclear magnetic resonance spectrum, and the mass spectrum were consistent with the compound obtained in (Example 7), and it was confirmed that both were the same substance and were Compound No. 3-01.

Example 9 As a positive electrode, a hole transport layer was formed on an electrode of a glass substrate (ITO glass substrate) on which a thin film of indium tin oxide (ITO) as a transparent electrode had been formed in advance.
Aluminum / lithium (Al / Li) electrodes were sequentially formed by vapor deposition as a light emitting layer, an electron transporting layer, and a cathode to produce an organic electroluminescent device of the present invention.

Specifically, first, an ITO glass substrate, N, N'-diphenyl-N, N'-bis (3-methylphenyl) benzidine (TPD) as a hole transport material, and the compound of the present invention as a luminescent material No. 1-02 aromatic methylidene compound, tris (8-hydroxyquinolino) aluminum (Alq) as electron transport material
^Was set in a vacuum evaporation apparatus and evacuated to 10 ^-4 Pa. next
TPD, which is a hole transport material, is placed on an electrode of an ITO glass substrate by 0.1%.
Vapor deposition was performed at a vapor deposition rate of 0.5 nm / sec to form a hole transport layer of 50 nm.

Next, Compound No. 1-02, which is a luminescent material, was added to a light emitting material.
Evaporation was performed at an evaporation rate of 1 to 0.5 nm / sec to form a light emitting layer of 50 nm. Subsequently, an electron transporting material, Alq, was deposited at a rate of 0.1 nm / sec to form an electron transporting layer having a thickness of 10 nm. More Li
Al was simultaneously deposited at a deposition rate of 0.01 to 0.02 nm / sec and a deposition rate of 1 to 2 nm / sec to form an Al / Li electrode. Its thickness was 150 nm.

Each of these depositions was performed continuously without breaking vacuum, and the film thickness was controlled by monitoring with a quartz oscillator. Immediately after the device was produced, the electrodes were taken out in dry nitrogen to produce an organic electroluminescent device.

When a voltage was applied to the device thus fabricated, uniform green light emission was obtained. 100mA / cm ²
When the driving voltage and the emission luminance when the current was applied were measured, the driving voltage was 7.0 V, and the emission luminance was 2500 cd / m ^2.
Met.

[0086]

As described above, the organic electroluminescent device of the present invention using the aromatic methylidene compound according to the present invention is
It is a long-life element with excellent light-emitting characteristics and excellent stability. Therefore, it can be said that the compounds of the present invention and methods for producing them are industrially extremely important.

[Brief description of the drawings]

FIG. 1 shows an infrared absorption spectrum of Compound No. 1-22 of the present invention.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) H05B 33/14 H05B 33/14 B

Claims (11)

[Claims] 1. A compound represented by the following general formula (1). Embedded image[However, in the above formula, R¹¹And R^{twenty one}Is unsubstituted or substituted
Alkyl group, unsubstituted or substituted alkoxy group, halogen
, A cyano group or a nitro group; n¹¹Is 0, 1, 2,
Represents an integer of 3, 4, 5, or 6, and n^{twenty one}Is an integer of 0, 1, 2, 3, or 4.
Represents a number. n¹¹, N ^{twenty one}Is an integer of 2 or more, R¹¹, R
^{twenty one}Are each composed of a plurality of the same substituents, or
Any of a plurality of different substituents
No. Also R³¹And R⁴¹Is hydrogen (where R³¹And R⁴¹Is the same
Sometimes hydrogen)), unsubstituted or substituted
Kill group (however, R³¹And R⁴¹Are simultaneously alkyl groups
Unsubstituted or substituted cycloalkyl group (however,
Shi R³¹And R⁴¹Are simultaneously cycloalkyl groups
Ex), unsubstituted or substituted aromatic groups, or unsubstituted
Or a substituted aromatic heterocyclic group,³¹And R⁴¹Are each other
May be the same or different.
No. Also, R³¹And R⁴¹Are jointly unsubstituted or substituted
Fused or unsubstituted or substituted aromatic compound of aromatic ring
A condensed ring of elementary rings may be formed. ] 2. A compound represented by the following general formula (2). Embedded image[However, in the above formula, R¹²And R^{twenty two}Is unsubstituted or substituted
Alkyl group, unsubstituted or substituted alkoxy group, halogen
, A cyano group or a nitro group; n¹²Is 0, 1, 2,
Represents an integer of 3, 4, 5, or 6, and n^{twenty two}Is an integer of 0, 1, 2, 3, or 4.
Represents a number. n¹², N ^{twenty two}Is an integer of 2 or more, R¹², R
^{twenty two}Are each composed of a plurality of the same substituents, or
Any of a plurality of different substituents
No. ] 3. A compound represented by the following general formula (3). Embedded image[However, in the above formula, R¹³And R^{twenty three}Is unsubstituted or substituted
Alkyl group, unsubstituted or substituted alkoxy group, halogen
, A cyano group or a nitro group; n¹³Is 0, 1, 2,
Represents an integer of 3, 4, 5, or 6, and n^{twenty three}Is an integer of 0, 1, 2, 3, or 4.
Represents a number. n¹³, N ^{twenty three}Is an integer of 2 or more, R¹³, R
^{twenty three}Are each composed of a plurality of the same substituents, or
Any of a plurality of different substituents
No. ] 4. The method according to claim 1, wherein the compound represented by the following general formula (4) is reacted with a compound represented by the following general formula (5). Embedded image [However, in the above formula, R ¹⁴ represents an unsubstituted or substituted alkyl group, an unsubstituted or substituted alkoxy group, a halogen group, a cyano group or a nitro group, and n ¹⁴ represents 0, 1, 2, 3, ⁴ , 5, or Represents an integer of 6. When n ¹⁴ is an integer of 2 or more, R ¹⁴ may be either a case where it is composed of a plurality of the same substituents or a case where it is composed of a plurality of different substituents. R represents an unsubstituted or substituted alkyl group. ] Wherein R ²⁴ represents an unsubstituted or substituted alkyl group, an unsubstituted or substituted alkoxy group, a halogen group, a cyano group or a nitro group, and n ²⁴ represents an integer of 0, 1, 2, 3 or 4. Represent. When n ²⁴ is an integer of 2 or more, R ²⁴ may be either a case where it is composed of a plurality of the same substituents or a case where it is composed of a plurality of different substituents. The R ^{3 2} and R ^42,
Hydrogen (unless R ³² and R ⁴² are simultaneously hydrogen), unsubstituted or substituted alkyl groups (provided that R ³² and R ^42
An unsubstituted or substituted cycloalkyl group (unless R ³² and R ⁴² are simultaneously a cycloalkyl group), an unsubstituted or substituted aromatic group, or an unsubstituted or substituted aromatic group; Represents a substituted aromatic heterocyclic group, wherein R ³² and R ⁴² may be the same or different from each other. Further, R ³² and R ⁴² may jointly form a condensed ring of an unsubstituted or substituted aromatic ring or a condensed ring of an unsubstituted or substituted heteroaromatic ring. ] 5. The production of the compound according to claim 1, wherein the compound represented by the general formula (2) according to claim 2 is reacted with a compound represented by the following general formula (6). Method. Embedded image Wherein R ³³ and R ⁴³ are hydrogen (except when R ³³ and R ⁴³ are simultaneously hydrogen), an unsubstituted or substituted alkyl group (where R ³³ and R ⁴³ are simultaneously an alkyl group Unsubstituted or substituted cycloalkyl group (unless R ³³ and R ⁴³ are simultaneously a cycloalkyl group), an unsubstituted or substituted aromatic group, or an unsubstituted or substituted aromatic heterocyclic group. Represents, R ³³ and R
⁴³ may be the same or different substituents. Further, R ³³ and R ⁴³ may jointly form a condensed ring of an unsubstituted or substituted aromatic ring or a condensed ring of an unsubstituted or substituted aromatic heterocycle. Also
R represents an unsubstituted or substituted alkyl group. ] 6. The method for producing a compound according to claim 1, wherein the compound represented by the following general formula (7) is reacted with a compound represented by the following general formula (8). Embedded image [However, in the above formula, R ¹⁵ represents an unsubstituted or substituted alkyl group, an unsubstituted or substituted alkoxy group, a halogen group, a cyano group or a nitro group, and n ¹⁵ represents 0, 1, 2, 3, 4, 5, or Represents an integer of 6. When n ¹⁵ is an integer of 2 or more, R ¹⁵ may be either a case where it is composed of a plurality of the same substituents or a case where it is composed of a plurality of different substituents. Embedded image Wherein R ²⁵ represents an unsubstituted or substituted alkyl group, an unsubstituted or substituted alkoxy group, a halogen group, a cyano group or a nitro group, and n ²⁵ represents an integer of 0, 1, 2, 3 or 4. Represent. When n ²⁵ is an integer of 2 or more, R ²⁵ may be either a case where it is composed of a plurality of the same substituents or a case where it is composed of a plurality of different substituents. The R ^{3 4} and R ^44,
Hydrogen (unless R ³⁴ and R ⁴⁴ are simultaneously hydrogen), an unsubstituted or substituted alkyl group (provided that R ³⁴ and R ^44
44 is simultaneously an alkyl group), an unsubstituted or substituted cycloalkyl group (unless R ³⁴ and R ⁴⁴ are simultaneously a cycloalkyl group), an unsubstituted or substituted aromatic group, or an unsubstituted or substituted Represents a substituted aromatic heterocyclic group, wherein R ³⁴ and R ⁴⁴ may be the same or different substituents. R ³⁴ and R ⁴⁴ may together form a condensed ring of an unsubstituted or substituted aromatic ring or a condensed ring of an unsubstituted or substituted heteroaromatic ring. R represents an unsubstituted or substituted alkyl group. ] 7. A compound represented by the following general formula (9):
Reacting with the compound represented by the general formula (10).
A method for producing the compound according to claim 1, characterized in that: Embedded image[However, in the above formula, R¹⁶And R²⁶Is unsubstituted or substituted
Alkyl group, unsubstituted or substituted alkoxy group, halogen
, A cyano group or a nitro group; n¹⁶Is 0, 1, 2,
Represents an integer of 3, 4, 5, or 6, and n²⁶Is an integer of 0, 1, 2, 3, or 4.
Represents a number. n¹⁶, N ²⁶Is an integer of 2 or more, R¹⁶, R
²⁶Are each composed of a plurality of the same substituents, or
Any of a plurality of different substituents
No. R represents an unsubstituted or substituted alkyl group. ][However, in the above formula, R³⁵And R⁴⁵Is hydrogen (where R³⁵And
And R⁴⁵Are simultaneously hydrogen), unsubstituted or
Is a substituted alkyl group (provided that R³⁵And R⁴⁵Are simultaneously alkyl
Group)), unsubstituted or substituted cycloal
Kill group (however, R³⁵And R⁴⁵Is simultaneously a cycloalkyl group
Except in certain cases), unsubstituted or substituted aromatic groups, or
Represents an unsubstituted or substituted aromatic heterocyclic group, R³⁵And R
⁴⁵Are the same or different substituents
You may. Also, R³⁵And R⁴⁵Are joint, unsubstituted
Or substituted or unsubstituted or substituted substituted aromatic rings
A condensed ring of an aromatic heterocycle may be formed. ] 8. An acetal compound obtained by reacting a compound represented by the formula (4) with a compound represented by the following general formula (11), and then deriving the acetal compound into an aldehyde compound. 2. A method for producing the compound according to 2. Embedded image Wherein R ²⁷ represents an unsubstituted or substituted alkyl group, an unsubstituted or substituted alkoxy group, a halogen group, a cyano group or a nitro group, and n ²⁷ represents an integer of 0, 1, 2, 3 or 4. Represent. When n ²⁷ is an integer of 2 or more, R ²⁷ may be either a case where it is composed of a plurality of the same substituents or a case where it is composed of a plurality of different substituents. R represents an unsubstituted or substituted alkyl group. ] 9. The method according to claim 2, wherein the compound represented by the formula (4) is reacted with a compound represented by the following general formula (12). Embedded image Wherein R ²⁸ represents an unsubstituted or substituted alkyl group, an unsubstituted or substituted alkoxy group, a halogen group, a cyano group or a nitro group, and n ²⁸ represents an integer of 0, 1, 2, 3 or 4. Represent. When n ²⁸ is an integer of 2 or more, R ²⁸ may be either a case where it is composed of a plurality of the same substituents or a case where it is composed of a plurality of different substituents. ] 10. The method for producing a compound according to claim 3, wherein the compound represented by the formula (4) is reacted with a compound represented by the following general formula (13). Embedded image Wherein R ²⁹ represents an unsubstituted or substituted alkyl group, an unsubstituted or substituted alkoxy group, a halogen group, a cyano group or a nitro group, and n ²⁹ represents an integer of 0, 1, 2, 3 or 4. Represent. When n ²⁹ is an integer of 2 or more, R ²⁹ may be either a case where it is composed of a plurality of the same substituents or a case where it is composed of a plurality of different substituents. ] 11. The method for producing a compound according to claim 3, wherein the compound represented by the general formula (14) is reacted with a compound represented by the following general formula (14). Embedded image Wherein R ²⁰ represents an unsubstituted or substituted alkyl group, an unsubstituted or substituted alkoxy group, a halogen group, a cyano group or a nitro group, and n ²⁰ represents an integer of 0, 1, 2, 3 or 4. Represent. When n ²⁰ is an integer of 2 or more, R ²⁰ may be either a case where it is composed of a plurality of the same substituents or a case where it is composed of a plurality of different substituents. R represents an unsubstituted or substituted alkyl group. ]