JP2000159698A - Aromatic methylidene compound, aromatic aldehyde compound for producing the same and their production - Google Patents

Abstract

PROBLEM TO BE SOLVED: To produce a new compound capable of manifesting light emission at a high luminance under a low voltage and useful especially as a luminous material in order to realize an organic electroluminescent element excellent in durability. SOLUTION: This compound is represented by the formula (R21 is an alkyl, a halogen, cyano or the like; n21 is 0-4; R31 and R41 are each H, an aromatic group, an aromatic heterocyclic group or the like, with the proviso that R31 and R41 are not simultaneously H). The compound represented by formula is obtained by reacting, e.g. diethyl α-phenylstilben-4'-ylmethylphosphonate with 1,2,4,5-tetraformylbenzene in the presence of potassium tert-butoxide in N,N- dimethylformamide at room temperature for 20 h under stirring or reacting octaethyl 1,2,4,5-tetramethylbenzene-α,α',α",α"'-tetrayltetraphosphonate with 4'-formyl-α-phenylstilbene.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a novel aromatic methylidene compound useful as a charge transport material for an electrophotographic photoreceptor, a charge transport material or a luminescent material for an organic electroluminescent device, or a material used for various organic semiconductor devices. And an aromatic aldehyde compound 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 provide a clear display 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.

[0003] The electroluminescent devices currently in practical use include:
There is a dispersion type electroluminescent element using an inorganic material such as zinc sulfide, but since this dispersion type electroluminescent element requires a relatively high AC voltage for driving, a driving circuit becomes complicated, or There is a problem such as low brightness, and the reality is that it is not widely used.

On the other hand, an organic electroluminescent device using an organic material was developed in 1987 by C.I. W. Tang et al. Have proposed a device having a stacked structure in which an organic fluorescent substance having an electron transporting property and an organic substance having a hole transporting property are laminated, and both carriers of electrons and holes are injected into the fluorescent substance layer to emit light. Since then, it has been in the spotlight. (CWTang and SAVAN
Slyke, Appl. Phys. Lett., Vol. 51, pp. 913-915 (1987);
JP-A-63-264629). In this element, 1
It is said that light emission of 1000 cd / m 2 or more can be obtained at a drive voltage of 0 V or less, and thereafter, with this proposal as a starting point, vigorous research on the periphery has been performed. At present, various materials and element configurations have been proposed, and research and development for practical use are being actively conducted.

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. To name a few, irrespective of the driving state or the non-driving state, the element function is deteriorated just by saving, and the emission luminance is reduced,
Further, there is a phenomenon in which a region called a dark spot, which does not emit light, occurs or grows when the device is driven or not driven, and degradation occurs, and eventually, the device is short-circuited and destroyed.

It can be said that such a phenomenon is considered to be an essential problem of the material used therein. However, at present, it is difficult to say that the life is sufficiently long. There is a situation where devices are limited to those that can be used with a relatively short life. In addition, when considering colorization of the element, there is a method that can cope with such a case, a light emitting material is not sufficiently prepared, and the like.
In any case, in order to solve these problems and problems and aim at widespread practical use of organic electroluminescent devices, the development of new materials such as new high-performance light-emitting materials and charge transport materials used in them will be required. Long awaited.

[0007]

SUMMARY OF THE INVENTION The present invention has been made in view of the actual situation of such an organic electroluminescent device, and is intended to realize an organic electroluminescent device which emits light at a low voltage, has high luminance, and has excellent durability. In particular, novel compounds useful as luminescent materials,
An object of the present invention is to provide an aromatic aldehyde compound for producing the compound and a method for producing the compound. Thereby, it is possible to contribute to realizing a highly durable organic electroluminescent device with high luminance emission.

[0008]

In order to achieve the above-mentioned object, the present invention provides a compound represented by the following formula (1):
In Chemical Formula 1, R21 represents an unsubstituted or substituted alkyl group, an unsubstituted or substituted alkoxy group, a halogen group, a cyano group and a nitro group, and n21 represents an integer of 0, 1, 2, 3, and 4.
When n21 is an integer of 2, 3, or 4, R21 may be any of a case where it is composed of a plurality of the same substituents and a case where it is composed of a plurality of different substituents. R31 and R41 represent hydrogen (except when R31 and R41 are simultaneously hydrogen), unsubstituted or substituted alkyl group (except when R31 and R41 are simultaneously an alkyl group), unsubstituted or substituted cycloalkyl A group (except when R31 and R41 are simultaneously a cycloalkyl group), an unsubstituted or substituted aromatic group, an unsubstituted or substituted aromatic heterocyclic group, and R31 and R41 are the same substituents; Or different substituents. A compound represented by the following formula:
R22 represents an unsubstituted or substituted alkyl group, an unsubstituted or substituted alkoxy group, a halogen group, a cyano group and a nitro group, and n22 represents an integer of 0, 1, 2, 3, or 4. n22 is 2,
When it is an integer of 3 or 4, R22 may be any of a case where it is composed of a plurality of the same substituents and a case where it is composed of a plurality of different substituents. A method for producing a compound represented by the formula (1), which comprises reacting a compound represented by the formula (3) with a compound represented by the formula (4); )During
R23 represents an unsubstituted or substituted alkyl group, an unsubstituted or substituted alkoxy group, a halogen group, a cyano group and a nitro group, and n23 represents an integer of 0, 1, 2, 3, or 4. n23 is 2,
When it is an integer of 3 or 4, R23 may be any of a case where it is composed of a plurality of the same substituents and a case where it is composed of a plurality of different substituents. R33 and R43 are hydrogen (however, R33 and R43
An unsubstituted or substituted alkyl group (except when R33 and R43 are simultaneously an alkyl group), an unsubstituted or substituted cycloalkyl group (where R33 and R43 are simultaneously a cycloalkyl group) Represents an unsubstituted or substituted aromatic group, an unsubstituted or substituted aromatic heterocyclic group, and R33 and R43 may be the same or different substituents. R1
0 represents an alkyl group. A method for producing a compound represented by the formula (1), characterized by reacting a compound represented by the formula (5) with a compound represented by the formula (6), R20 represents an alkyl group. Wherein R24 represents an unsubstituted or substituted alkyl group, an unsubstituted or substituted alkoxy group, a halogen group, a cyano group and a nitro group, and n24 represents an integer of 0, 1, 2, 3, or 4. Represent. n24
Is an integer of 2, 3, or 4, R24 may be any of the case where it is composed of a plurality of the same substituents and the case where it is composed of a plurality of different substituents. R34 and R44 are hydrogen (except when R34 and R44 are simultaneously hydrogen), unsubstituted or substituted alkyl group (except when R34 and R44 are simultaneously an alkyl group), unsubstituted or substituted cycloalkyl A group (except when R34 and R44 are simultaneously a cycloalkyl group), an unsubstituted or substituted aromatic group, an unsubstituted or substituted aromatic heterocyclic group, wherein R34 and R44 are the same substituents; Or different substituents. A method for producing a compound represented by the formula (2), characterized by reacting a compound represented by the formula (5) with a compound represented by the formula (7); ) Medium R25
Represents an unsubstituted or substituted alkyl group, an unsubstituted or substituted alkoxy group, a halogen group, a cyano group and a nitro group, and n25 represents an integer of 0, 1, 2, 3, or 4. When n25 is an integer of 2, 3, or 4, when R25 comprises a plurality of the same substituents,
Any of a plurality of different substituents may be used. After reacting the compound represented by the formula (5) with the compound represented by the formula (8) to obtain an acetal compound represented by the formula (9), the acetal compound is derived into an aldehyde compound. 3. The method for producing a compound according to claim 2, wherein R26 represents an unsubstituted or substituted alkyl group, an unsubstituted or substituted alkoxy group, a halogen group, a cyano group and a nitro group. , N26 is 0, 1, 2,
Represents an integer of 3 or 4. When n26 is an integer of 2, 3, or 4, R26
May be composed of a plurality of the same substituents or composed of a plurality of different substituents. R30 represents an alkyl group. Wherein R27 represents an unsubstituted or substituted alkyl group, an unsubstituted or substituted alkoxy group, a halogen group, a cyano group or a nitro group, and n27 is an integer of 0, 1, 2, 3, or 4. Represents When n27 is an integer of 2, 3, or 4, R27 may be either of a plurality of the same substituents or a plurality of different substituents. R40 represents an alkyl group. And a compound represented by the following formula:
A method for producing a compound represented by the general formula (1), which comprises reacting the compound represented by the general formula (1).

Wherein R35 and R45 are
Hydrogen (unless R35 and R45 are simultaneously hydrogen), an unsubstituted or substituted alkyl group (provided that R35 and R45
Are simultaneously an alkyl group), an unsubstituted or substituted cycloalkyl group (except when R35 and R45 are simultaneously a cycloalkyl group), an unsubstituted or substituted aromatic group, an unsubstituted or substituted aromatic heterocycle Represents a ring group, R35
And R45 may be the same or different substituents. R50 represents an alkyl group. ]
The compound represented by Chemical 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 compound represented by the formula (2) is a useful intermediate for producing the compound represented by the 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.

[0010]

BEST MODE FOR CARRYING OUT THE INVENTION The compound represented by the formula (1) of the present invention can be roughly classified into three synthetic routes, ie, the formula (3)
Reaction of an aldehyde derivative represented by the formula with a methylphosphonate derivative represented by the chemical formula 4, and a reaction between a methylphosphonate derivative represented by the chemical formula 5 and a benzaldehyde derivative represented by the chemical formula 6 It can be produced by a reaction, a reaction between an aldehyde derivative represented by (Chemical Formula 2) and a methylphosphonic ester derivative represented by (Chemical Formula 10). In addition, in each of the above synthetic routes, the corresponding methyltriarylphosphonium salt can be used instead of the methylphosphonate derivative used therein.

Each of these reactions is a reaction between an aldehyde and active methylene, and is usually carried out using a base in an organic solvent. Examples of the reaction solvent 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 ethyl ether, tetrahydrofuran, and dioxane; Examples include halogenated hydrocarbons such as chloroform, dichloromethane, dichloroethane, and the like, heterocyclic aromatic hydrocarbons such as pyridine and quinoline, and other N, N-dimethylformamide, dimethylsulfoxide, and the like. is there.

The base used in the reaction may be an inorganic base such as potassium carbonate, sodium carbonate, potassium hydroxide or sodium hydroxide; an organic base such as triethylamine, triethanolamine, pyridine or hexamethylenetetramine; sodium methoxide; 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 and is usually about 30 minutes to 100 hours, but should be appropriately selected depending on the combination of the respective raw materials.

After completion of the reaction, in order to obtain the desired product from the reaction mixture, the crude product is taken out by concentration or dilution with a poor solvent, etc., and preferably the inorganic components are removed by washing with water and the like, followed by column chromatography, recrystallization, etc. A pure target product can be obtained by a commonly used purification method.

Next, another compound of the present invention represented by the following chemical formula (2) will be described. The compound represented by the chemical formula (2) is obtained by reacting the methylphosphonate derivative represented by the chemical formula (5) with the terephthalaldehyde derivative represented by the chemical formula (7), or replacing the terephthalaldehyde derivative. Using a monodialkyl acetal of a terephthalaldehyde derivative represented by the following formula 8,
After obtaining the obtained acetal compound of Chemical formula 9, the acetal compound can be obtained by deriving the acetal compound into an aldehyde compound.

These reactions are also reactions of aldehydes with active methylene, as in the above synthesis reaction (Chem. 1), and are usually carried out in an organic solvent using a base. As the reaction solvent and the base used here, those similar to those described in the synthesis route of the above (Chemical Formula 1) can be used. The same applies to the reaction conditions.

Next, specific examples of the compound represented by the formula (1) of the present invention are shown in (Table 1) to (Table 10), but the present invention is not limited thereto. In addition, in exemplifying the compounds, in (Table 1) to (Table 8), the basic structure is represented as a general formula at the beginning of each table, and subsequently, only the partial structure or the substituent of each compound is represented. (Table 9)
In (Table 10), the entire chemical structure of each compound is shown, but common parts are indicated by parentheses and their numbers are abbreviated.

[0017]

[Table 1]

[0018]

[Table 2]

[0019]

[Table 3]

[0020]

[Table 4]

[0021]

[Table 5]

[0022]

[Table 6]

[0023]

[Table 7]

[0024]

[Table 8]

[0025]

[Table 9]

[0026]

[Table 10]

As described above, the compound represented by the 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 compound represented by the formula (2) is a useful intermediate for producing the compound represented by the 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.

The compounds represented by the formula (11) of the present invention can be roughly classified into three synthetic routes,
Reaction between the aldehyde derivative represented by 3) and the methylphosphonate derivative represented by formula 14;
5) a methylphosphonate derivative represented by the formula:
A reaction with a benzaldehyde derivative represented by (Chem. 16), an aldehyde derivative represented by (Chem. 12), and (Chem. 2)
It can be produced by a reaction with a methylphosphonic ester derivative represented by the formula (1).

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. Examples of the reaction solvent 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 ethyl ether, tetrahydrofuran, and dioxane; Examples include halogenated hydrocarbons such as chloroform, dichloromethane, dichloroethane, and the like, heterocyclic aromatic hydrocarbons such as pyridine and quinoline, and other N, N-dimethylformamide, dimethylsulfoxide, and the like. is there. As the base used in the reaction, an inorganic base such as potassium carbonate, sodium carbonate, potassium hydroxide or sodium hydroxide, an organic base such as triethylamine, triethanolamine, pyridine or hexamethylenetetramine, sodium methoxide, sodium ethoxide, Examples thereof include alkali metal salts of alcohols such as 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, usually about 0 ° C to about 80 ° C.
It is preferably performed at ° C. The reaction time generally depends on the relationship with the reaction temperature, and is usually 30 minutes to 100 minutes.
Although it is about time, it should be appropriately selected depending on the combination of the respective raw materials.

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

Next, another substance of the present invention (Formula 12)
The compound represented by is described. The compound represented by the chemical formula (12) is obtained by reacting the methylphosphonate derivative represented by the chemical formula (15) with the terephthalaldehyde derivative represented by the chemical formula (17), or replacing the terephthalaldehyde derivative. Then, using the monodialkyl acetal of the terephthalaldehyde derivative represented by the chemical formula (18), the obtained acetal compound of the chemical formula (19) is obtained, and then the acetal compound is also converted to an aldehyde compound. I can do it.

These reactions are also reactions of aldehydes with active methylene, as in the above synthesis reaction (Chemical formula 11).
Usually, the reaction is performed using a base in an organic solvent. As the reaction solvent and the base used here, those similar to those described in the synthesis route of the above (Chemical Formula 11) can be used. The same applies to the reaction conditions.

Next, specific examples of the compound represented by the formula (11) of the present invention are shown in (Table 11) to (Table 20), but the present invention is not limited thereto. In addition, in exemplifying the compounds, in (Table 11) to (Table 18), the basic structure is represented by a general formula at the beginning of each table, and subsequently, only the partial structure or the substituent of each compound is represented.
(Table 19) and (Table 20) show the entire chemical structure of each compound, but common parts are indicated by parentheses and their numbers are abbreviated.

[0036]

[Table 11]

[0037]

[Table 12]

[0038]

[Table 13]

[0039]

[Table 14]

[0040]

[Table 15]

[0041]

[Table 16]

[0042]

[Table 17]

[0043]

[Table 18]

[0044]

[Table 19]

[0045]

[Table 20]

As described above, 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.

Further, the compound represented by the formula (12) is a useful intermediate for producing the compound represented by the formula (11). The compounds provided by the present invention, and the methods for producing them, greatly contribute to the realization of a highly durable, highly durable organic electroluminescent device. The present invention will be described in more detail below with reference to examples. I do.

Next, a specific example of the present invention will be described. Example 1 Production Example of Compound No. 1-1 in Table 1 (1) 16.26 g of diethyl α-phenylstilbene-4′-ylmethylphosphonate and 1,2,4,5-tetraformylbenzene 90 g of N, N-dimethylformamide 10
0 g, potassium tert-butoxide 5.6.
7g was added at 5-10 ° C over 10 minutes.

After stirring at room temperature for 20 hours,
300 ml of methanol was added, and the precipitated crystals were collected by filtration, washed with water and dried to obtain 11.18 g of a crude product. Next, the crude product was recrystallized from methylnaphthalene to obtain 9.27 g of a purified product as yellow crystals. Melting point 300 ° C or more. The elemental analysis value thereof was 93.94% for carbon (94.12% calculated as compound number 1-1) and 5.74% for hydrogen (5.88% calculated as compound number 1-1). Was.

Example 2 Production Example of Compound No. 1-1 in Table 1 (2) 1,2,4,5-Tetramethylbenzene-α, α ′, α ″,
3.39 g of octaethyl α ″ ′-tetrayltetraphosphonate, 5.69 g of 4′-formyl-α-phenylstilbene, are dissolved in 60 g of N, N-dimethylformamide, and 28% methanol of NaOCH 3 at 5 to 10 ° C. 5.79 g of the solution was added dropwise over 10 minutes.

After stirring at room temperature for 7 hours, about 300 ml of methanol was added, and the precipitated crystals were collected by filtration, washed with water and dried to obtain 5.96 g of a crude product. Next, the crude product was recrystallized from methylnaphthalene to obtain 5.10 g of a purified product as yellow crystals. Melting point 300 ° C or more. The elemental analysis value thereof was 93.9% of carbon (Table 1).
94.12% calculated as 1), 5.84% hydrogen
(Calculated value 5.88 as compound number 1-1 in (Table 1)
%)Met.

(Example 3) Preparation example of the compound according to claim 2 (1) 10.73 g of terephthalaldehyde and 1,2,4,5-tetramethylbenzene-α, α ', α'',α''' 6.79 g of octaethyl-tetrayltetraphosphonate was added to N, N-
It was dissolved in 60 g of dimethylformamide, and 14.19 g of potassium tert-butoxide was added in small portions at 5 to 10 ° C. over 30 minutes.

Thereafter, the reaction was carried out with stirring at room temperature for 30 hours, and about 150 ml of cold water was added, and the precipitate was collected by filtration, washed with water and dried. Next, this crude product was N, N-dimethylformamide,
Recrystallization from chlorobenzene gave 1.25 g of orange crystals. 253.0-255.0 ° C. Its elemental analysis values were as follows: 84.13% of carbon (calculated value as the compound according to claim 2 84.26%) and 4.86% of hydrogen (claim 3).
(Calculated value of the described compound: 5.05%).

(Example 4) Production example of the compound according to claim 2 (2) Terephthalaldehyde monodiethyl acetal 8.3
3g and 1,2,4,5-tetramethylbenzene-α, α ',
6.79 g of α '', α '''-tetrayltetraphosphonic acid octaethyl was added to N, N-dimethylformamide 60.
and 5.67 g of potassium tert-butoxide was added in small portions over 30 minutes at 5-10 ° C. Thereafter, the reaction was allowed to proceed with stirring at room temperature for 20 hours, 45.4 g of concentrated hydrochloric acid was added, and the mixture was stirred at 80 to 85 ° C for 1 hour, and about 150 ml of cold water was added.

Next, the precipitated crystals were collected by filtration, washed with water and dried to obtain 5.07 g of a crude product as yellow-orange crystals. Then, the product was recrystallized from chlorobenzene to obtain 4.38 g of a purified product. 253.0-255.0 ° C. Its elemental analysis values were as follows: 84.00% of carbon (calculated value as the compound according to claim 2 84.26%), and 5.01% of hydrogen (claim 3).
(Calculated value of the described compound: 5.05%).

Example 5 Preparation Example of Compound No. 1-1 in Table 1 (3) 12.17 g of diethyl diphenylmethylphosphonate and Examples 5 and 6 show the preparation examples. 5.99 g of the compound was dissolved in 100 g of N, N-dimethylformamide, and 5.67 g of potassium tert-butoxide was added at 5 to 10 ° C over 10 minutes.

After stirring at room temperature for 20 hours,
About 200 ml of methanol was added, and the precipitated crystals were collected by filtration, washed with water,
Drying gave 10.41 g of crude product. Next, the crude product was recrystallized from methylnaphthalene to obtain 9.12 g of a purified product as yellow crystals. Melting point 300 ° C or more. Its elemental analysis values were as follows: carbon 94.05% (calculated as compound number 1-1 in Table 1 94.12%), hydrogen 5.77%
(Calculated value 5.88 as compound number 1-1 in (Table 1)
%)Met.

Example 6 A hole transport layer, a light emitting layer, and an electron transport layer were 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 was formed in advance as an anode. An aluminum / lithium (Al / Li) electrode was sequentially formed as a layer and a cathode by vapor deposition to produce an organic electroluminescent device of the present invention. Specifically, first, an ITO glass substrate, N, N 'as a hole transport material
-Diphenyl-N, N'-bis (3-methylphenyl) benzidine (TPD), an aromatic methylidene compound of Compound No. 1-1 of Table 1 of the present invention (Table 1) as a luminescent material, and tris (8- (Hydroxyquinolino) aluminum (Alq) was set in a vacuum evaporation apparatus and evacuated to 10-4 Pa.

Next, TPD as a hole transporting material was deposited on the electrode of the ITO glass substrate at a deposition rate of 0.1 to 0.5 nm / sec to form a hole transporting layer of 50 nm. Next, the compound number 1-1 of the light emitting material (Table 1) was 0.1 to 0.1.
Vapor deposition was performed at a vapor deposition rate of 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.

Further, Li is added at 0.01 to 0.02 nm /
Second, Al is simultaneously deposited at a deposition rate of 1-2 nm / second,
An Al / Li electrode was formed. 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 yellow luminescence was obtained.

Example 7 Production Example of Compound No. 1-1 in Table 11 (1) 12.19 g of diethyl α-phenylstilbene-4′-ylmethylphosphonate and 1,3,5-triformylbenzene 1 0.62 g was dissolved in 75 g of N, N-dimethylformamide and 4.25 g of potassium tert-butoxide were added at 5-10 ° C. over 10 minutes. afterwards,
After stirring at room temperature for 20 hours, 300 ml of methanol was added, and the precipitated crystals were collected by filtration, washed with water and dried to obtain 8.21 crude product.
g was obtained.

Next, the crude product was subjected to column chromatography using a stationary phase silica gel and a mobile phase as a mixed solvent of toluene and hexane at a volume ratio of 1: 1 to separate a pale yellow component. After dissolving the obtained pale yellow resinous material in a small amount of tetrahydrofuran, it was poured into ethanol to precipitate again,
6.91 g of a slightly yellowish white powder were obtained. 235.5-238.0 ° C. The elemental analysis value thereof was 93.97% of carbon (Table 11).
Calculated as 94.08%), hydrogen 5.84% (calculated as compound number 1-1 in (Table 11) 5.92%)
Met.

Example 8 Production Example of Compound No. 1-1 in Table 11 (2) 2.64 g of hexaethyl 1,3,5-trimethylbenzene-α, α ′, α ″ -triyltriphosphonate 4.27 g of 4'-formyl-α-phenylstilbene was dissolved in 60 g of N, N-dimethylformamide, and NaO was added at 5 to 10 ° C.
4.34 g of a 28% solution of CH3 in methanol was added dropwise over 10 minutes.

Then, after stirring at room temperature for 20 hours,
About 200 ml of methanol was added, and the precipitated crystals were collected by filtration, washed with water,
Drying yielded 4.26 g of crude product. Next, this crude product was purified by column chromatography in the same manner as in Example 1, and 3.
85 g of purified product was obtained. 235.5-238.0 °
C. The elemental analysis value of this was 93.88% for carbon (Table 11). The calculated value as compound number 1-1 was 94.08.
%), 5.86% hydrogen ((Table 11), compound No. 1-1)
Calculated as 5.92%).

Example 9 Preparation Example of the compound as defined in claim 12 (1) 8.05 g of terephthalaldehyde and hexaethyl 1,3,5-trimethylbenzene-α, α ′, α ″,-triyltriphosphonate 5 .28 g in N, N-dimethylformamide (45 g) and potassium tert.
4.25 g of butoxide were added in portions over 30 minutes. Thereafter, the reaction was allowed to proceed with stirring at room temperature for 30 hours, and about 150 ml of cold water was added, and the precipitate was collected by filtration, washed with water, and dried.

Next, this crude product was recrystallized from N, N-dimethylformamide and chlorobenzene to give orange-yellow crystals 1.13.
g was obtained. Mp 293.0-295.0 ° C. The elemental analysis value thereof was 84.33% for carbon (calculated value as the compound according to claim 12 84.59%), and 4.96% for hydrogen.
(Calculated value 5.16% as compound according to claim 13).

(Example 10) Production example of the compound according to claim 12 (2) Terephthalaldehyde monodiethyl acetal 6.2
5 g and 5.28 g of hexaethyl 1,3,5-trimethylbenzene-α, α ′, α ″ -triyltriphosphonate were added to N, N
-Dissolved in 45 g of dimethylformamide, 5-10 ° C
Then, 4.25 g of potassium tert-butoxide was added in small portions over 30 minutes.

Thereafter, the reaction was allowed to proceed with stirring at room temperature for 20 hours, and 34.1 g of concentrated hydrochloric acid was added.
After stirring for an hour, about 150 ml of cold water was added. Next, the precipitated crystals were collected by filtration, washed with water and dried to obtain a crude product. Mp 293.0-295.0 ° C. Its elemental analysis value was 84.40% for carbon (calculated value for the compound according to claim 12: 84.59%) and 5.00% for hydrogen (calculated value for the compound according to claim 13: 5.16%). Was.

Example 11 Preparation Example of Compound No. 1-1 in Table 11 (3) 9.13 g of diethyl diphenylmethylphosphonate and Examples 5 and 6 show the preparation examples.
4.69 g of the described compound was dissolved in 75 g of N, N-dimethylformamide, and potassium tert-butoxide was dissolved.
25 g was added at 5-10 ° C over 10 minutes.

After stirring at room temperature for 20 hours,
About 200 ml of methanol was added, and the precipitated crystals were collected by filtration, washed with water,
Drying yielded 8.23 g of crude product. Next, this crude product was purified by column chromatography in the same manner as in Example 1, and 3.
85 g of purified product was obtained. 235.5-238.0 °
C. The elemental analysis value thereof was 93.95% of carbon (calculated as compound number 1-1 of (Table 11) 94.08).
%), 5.90% of hydrogen ((Table 11), Compound No. 1-1)
Calculated as 5.92%).

Example 12 As a positive electrode, a hole transport layer, a light emitting layer, and an electron transport layer were 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 was formed in advance. An aluminum / lithium (Al / Li) electrode was sequentially formed as a layer and a cathode by vapor deposition to produce an organic electroluminescent device of the present invention. Specifically, first, an ITO glass substrate, N, as a hole transport material,
N'-diphenyl-N, N'-bis (3-methylphenyl) benzidine (TPD), the present invention as a luminescent material (Table 11)
An aromatic methylidene compound of Compound No. 1-1 and tris (8-hydroxyquinolino) aluminum (Alq) as an electron transport material were set in a vacuum evaporation apparatus, and 10-4P
It exhausted to a.

Next, TPD as a hole transporting material was deposited on the electrode of the ITO glass substrate at a deposition rate of 0.1 to 0.5 nm / sec to form a hole transporting layer having a thickness of 50 nm. Next, Compound No. 1-1 as a light emitting material was deposited at a deposition rate of 0.1 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.

Further, Li was added at 0.01 to 0.02 nm /
Second, Al is simultaneously deposited at a deposition rate of 1-2 nm / second,
An Al / Li electrode was formed. 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-yellow light emission was obtained.

[0074]

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 is a diagram showing an infrared absorption spectrum of Compound No. 1-1 of (Table 1) of the present invention.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification code FI Theme coat ゛ (Reference) C07C 43/205 C07C 43/205 Z 45/61 45/61 49/796 49/796 205/06 205/06 255/50 255/50 C07D 333/08 C07D 333/08 333/18 333/18 H05B 33/14 H05B 33/14 B // C09K 11/06 615 C09K 11/06 615 625 625 625 635 635 F Term (Reference) 3K007 AB01 AB11 CA01 CB01 DA01 DB03 EB00 FA01 4H006 AA01 AA02 AC22 AC45 BA53 BM71 BM72 BP30 BU26 FC52 FC54 FE74 FE75

Claims (14)

[Claims] A compound represented by the formula (1). Embedded image Wherein R21 represents an unsubstituted or substituted alkyl group, an unsubstituted or substituted alkoxy group, a halogen group, a cyano group and a nitro group, and n21 represents an integer of 0, 1, 2, 3, or 4. When n21 is an integer of 2, 3, or 4, R21 may be any of a case where it is composed of a plurality of the same substituents and a case where it is composed of a plurality of different substituents. R31 and R41 are hydrogen (except when R31 and R41 are simultaneously hydrogen);
Unsubstituted or substituted alkyl group (except when R31 and R41 are simultaneously an alkyl group), unsubstituted or substituted cycloalkyl group (except when R31 and R41 are simultaneously a cycloalkyl group), unsubstituted or substituted Represents an aromatic group, an unsubstituted or substituted aromatic heterocyclic group, and R31 and R41 may be the same or different from each other. ] A compound represented by the formula (2). Embedded image Wherein R22 represents an unsubstituted or substituted alkyl group, an unsubstituted or substituted alkoxy group, a halogen group, a cyano group or a nitro group, and n22 represents an integer of 0, 1, 2, 3, or 4. When n22 is an integer of 2, 3, or 4, R22 may be any of a case where it is composed of a plurality of the same substituents and a case where it is composed of a plurality of different substituents. ] 3. The method for producing a compound according to claim 1, wherein the compound represented by the formula (3) is reacted with the compound represented by the formula (4). Embedded image Embedded image [However, in the above formula, R23 represents an unsubstituted or substituted alkyl group, an unsubstituted or substituted alkoxy group, a halogen group, a cyano group and a nitro group, and n23 represents an integer of 0, 1, 2, 3, and 4. When n23 is an integer of 2, 3, or 4, R23 may be either of a plurality of the same substituents or a plurality of different substituents. R33 and R43 are hydrogen (except when R33 and R43 are simultaneously hydrogen);
Unsubstituted or substituted alkyl group (except when R33 and R43 are simultaneously an alkyl group), unsubstituted or substituted cycloalkyl group (except when R33 and R43 are simultaneously a cycloalkyl group), unsubstituted or substituted Represents an aromatic group, an unsubstituted or substituted aromatic heterocyclic group, and R33 and R43 may be the same or different from each other. R10 represents an alkyl group. ] 4. A method for producing a compound according to claim 1, wherein the compound represented by the formula (5) is reacted with the compound represented by the formula (6). [However, in the above formula, R20 represents an alkyl group. ] [However, in the above formula, R24 represents an unsubstituted or substituted alkyl group, an unsubstituted or substituted alkoxy group, a halogen group, a cyano group, and a nitro group, and n24 represents an integer of 0, 1, 2, 3, and 4. When n24 is an integer of 2, 3, or 4, R24 may be any of a case where it is composed of a plurality of the same substituents and a case where it is composed of a plurality of different substituents. R34 and R44 are hydrogen (except when R34 and R44 are simultaneously hydrogen);
Unsubstituted or substituted alkyl group (except when R34 and R44 are simultaneously an alkyl group), unsubstituted or substituted cycloalkyl group (except when R34 and R44 are simultaneously a cycloalkyl group), unsubstituted or substituted Represents an aromatic group, an unsubstituted or substituted aromatic heterocyclic group, and R34 and R44 may be the same or different substituents; ] 5. The method according to claim 2, wherein the compound represented by the formula (5) is reacted with the compound represented by the formula (7). Embedded image Wherein R25 represents an unsubstituted or substituted alkyl group, an unsubstituted or substituted alkoxy group, a halogen group, a cyano group or a nitro group, and n25 represents an integer of 0, 1, 2, 3, or 4. When n25 is an integer of 2, 3, or 4, R25 may be any of a case where it is composed of a plurality of the same substituents and a case where it is composed of a plurality of different substituents. ] 6. A compound represented by the following formula (5) is reacted with a compound represented by the following formula (8) to obtain an acetal compound represented by the following formula (9). The method for producing a compound according to claim 2, wherein the compound is derived. Embedded image [However, in the above formula, R26 represents an unsubstituted or substituted alkyl group, an unsubstituted or substituted alkoxy group, a halogen group, a cyano group, and a nitro group, and n26 represents an integer of 0, 1, 2, 3, and 4. When n26 is an integer of 2, 3, or 4, R26 may be either of a plurality of the same substituents or a plurality of different substituents. R30 represents an alkyl group. ] [However, in the above formula, R27 represents an unsubstituted or substituted alkyl group, an unsubstituted or substituted alkoxy group, a halogen group, a cyano group, and a nitro group, and n27 represents an integer of 0, 1, 2, 3, and 4. When n27 is an integer of 2, 3, or 4, R27 may be either of a plurality of the same substituents or a plurality of different substituents. R40 represents an alkyl group. ] 7. A compound represented by the formula (2):
The method for producing a compound according to claim 1, wherein the compound is reacted with a compound represented by the formula: Embedded image [However, R35 and R45 are hydrogen (except when R35 and R45 are simultaneously hydrogen), unsubstituted or substituted alkyl group (except when R35 and R45 are simultaneously an alkyl group), unsubstituted or substituted Cycloalkyl group (however, R3
5 and R45 are cycloalkyl groups at the same time), an unsubstituted or substituted aromatic group, an unsubstituted or substituted aromatic heterocyclic group, and R35 and R45 are different even if they are the same substituent. It may be a substituent. Also R50
Represents an alkyl group. ] 8. A compound represented by the formula (11). Embedded image Wherein R21 represents an unsubstituted or substituted alkyl group, an unsubstituted or substituted alkoxy group, a halogen group, a cyano group and a nitro group, and n21 represents an integer of 0, 1, 2, 3, or 4. When n21 is an integer of 2, 3, or 4, R21 may be any of a case where it is composed of a plurality of the same substituents and a case where it is composed of a plurality of different substituents. R31 and R41 are hydrogen (except when R31 and R41 are simultaneously hydrogen);
Unsubstituted or substituted alkyl group (except when R31 and R41 are simultaneously an alkyl group), unsubstituted or substituted cycloalkyl group (except when R31 and R41 are simultaneously a cycloalkyl group), unsubstituted or substituted Represents an aromatic group, an unsubstituted or substituted aromatic heterocyclic group, and R31 and R41 may be the same or different from each other. ] 9. A compound represented by the formula (12). Embedded image Wherein R22 represents an unsubstituted or substituted alkyl group, an unsubstituted or substituted alkoxy group, a halogen group, a cyano group or a nitro group, and n22 represents an integer of 0, 1, 2, 3, or 4. When n22 is an integer of 2, 3, or 4, R22 may be any of a case where it is composed of a plurality of the same substituents and a case where it is composed of a plurality of different substituents. ] 10. A compound represented by the formula (13),
The method for producing a compound according to claim 1, wherein the compound is reacted with the compound represented by 4). Embedded image Embedded image [However, in the above formula, R23 represents an unsubstituted or substituted alkyl group, an unsubstituted or substituted alkoxy group, a halogen group, a cyano group and a nitro group, and n23 represents an integer of 0, 1, 2, 3, and 4. When n23 is an integer of 2, 3, or 4, R23 may be either of a plurality of the same substituents or a plurality of different substituents. R33 and R43 are hydrogen (except when R33 and R43 are simultaneously hydrogen);
Unsubstituted or substituted alkyl group (except when R33 and R43 are simultaneously an alkyl group), unsubstituted or substituted cycloalkyl group (except when R33 and R43 are simultaneously a cycloalkyl group), unsubstituted or substituted Represents an aromatic group, an unsubstituted or substituted aromatic heterocyclic group, and R33 and R43 may be the same or different from each other. R10 represents an alkyl group. ] 11. A compound represented by the formula (15), and a compound represented by the formula (1)
6. The method for producing a compound according to claim 1, wherein the compound is reacted with the compound represented by 6). [However, in the above formula, R20 represents an alkyl group. ] [However, in the above formula, R24 represents an unsubstituted or substituted alkyl group, an unsubstituted or substituted alkoxy group, a halogen group, a cyano group, and a nitro group, and n24 represents an integer of 0, 1, 2, 3, and 4. When n24 is an integer of 2, 3, or 4, R24 may be any of a case where it is composed of a plurality of the same substituents and a case where it is composed of a plurality of different substituents. R34 and R44 are hydrogen (except when R34 and R44 are simultaneously hydrogen);
Unsubstituted or substituted alkyl group (except when R34 and R44 are simultaneously an alkyl group), unsubstituted or substituted cycloalkyl group (except when R34 and R44 are simultaneously a cycloalkyl group), unsubstituted or substituted Represents an aromatic group, an unsubstituted or substituted aromatic heterocyclic group, and R34 and R44 may be the same or different substituents; ] A compound represented by the formula (15), and a compound represented by the formula (1)
3. The method for producing a compound according to claim 2, wherein the compound is reacted with the compound represented by 7). Embedded image Wherein R25 represents an unsubstituted or substituted alkyl group, an unsubstituted or substituted alkoxy group, a halogen group, a cyano group or a nitro group, and n25 represents an integer of 0, 1, 2, 3, or 4. When n25 is an integer of 2, 3, or 4, R25 may be any of a case where it is composed of a plurality of the same substituents and a case where it is composed of a plurality of different substituents. ] 13. A compound represented by the formula (15),
The method for producing a compound according to claim 2, wherein the compound represented by the formula (8) is reacted to obtain an acetal compound represented by the formula (19), and then the acetal compound is derived into an aldehyde compound. . Embedded image [However, in the above formula, R26 represents an unsubstituted or substituted alkyl group, an unsubstituted or substituted alkoxy group, a halogen group, a cyano group and a nitro group, and n26 represents an integer of 0, 1, 2, 3, and 4. When n26 is an integer of 2, 3, or 4, R26 may be either of a plurality of the same substituents or a plurality of different substituents. R30 represents an alkyl group. Embedded image [However, in the above formula, R27 represents an unsubstituted or substituted alkyl group, an unsubstituted or substituted alkoxy group, a halogen group, a cyano group, and a nitro group, and n27 represents an integer of 0, 1, 2, 3, and 4. When n27 is an integer of 2, 3, or 4, R27 may be any of a case where it is composed of a plurality of the same substituents and a case where it is composed of a plurality of different substituents. R40 represents an alkyl group. ] 14. A compound represented by the formula (12):
The method for producing a compound according to claim 1, wherein the compound is reacted with the compound represented by the formula (1). Embedded image [However, R35 and R45 are hydrogen (except when R35 and R45 are simultaneously hydrogen), unsubstituted or substituted alkyl group (except when R35 and R45 are simultaneously an alkyl group), unsubstituted or substituted Cycloalkyl group (however, R3
5 and R45 are cycloalkyl groups at the same time), an unsubstituted or substituted aromatic group, an unsubstituted or substituted aromatic heterocyclic group, and R35 and R45 are different even if they are the same substituent. It may be a substituent. Also R50
Represents an alkyl group. ]