JP2003073313A - Aromatic methylidene compound, aromatic aldehyde compound and methylstyryl compound for producing the same, and method for producing these compounds - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a new aromatic compound usable for a charge transfer material of an electrophotographic photosensitive material, a charge transfer material or a luminescent material of an organic electroluminescent device, or organic semiconductor devices of various kinds, and to provide a method for producing these compounds. SOLUTION: This aromatic compound comprises a new aromatic methylidene compound of the general formula (1) [R11 is an unsubstituted or substituted alkyl, an unsubstituted or substituted alkoxy, a halogen, cyano or nitro; R21 and R31 are each H (provided that R21 and R31 are not allowed to be H at the same time), an unsubstituted or substituted alkyl (provided that R21 and R31 are not allowed to be the alkyl at the same time), an unsubstituted or substituted cycloalkyl (provided that R21 and R31 are not allowed to be the cycloalkyl at the same time), an unsubstituted or substituted aromatic group or an unsubstituted or substituted aromatic heterocyclic group, or R21 and R31 jointly form a condensed ring of unsubstituted or substituted aromatic rings or a condensed ring of unsubstituted or substituted aromatic heterocyclic rings; and n11 is an integer of 0-4]. An aromatic aldehyde compound and a methylstyryl compound for producing the methylidene compound, and the method for producing these compounds are provided.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a functional material for an electrophotographic photoreceptor, a functional material such as a charge transport material or a light emitting material in an organic electroluminescent element, or a functional material used for other various organic semiconductor elements. The present invention relates to a useful novel aromatic methylidene compound, an aromatic aldehyde compound useful for producing the same, a methylstyryl compound, and a method for producing them.

[0002]

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

At present, there is a dispersion type electroluminescent element using an inorganic material such as zinc sulfide as an electroluminescent element which has been put into practical use. However, this dispersion type electroluminescent element requires a relatively high AC voltage for driving. Therefore, there is a problem that the driving circuit is complicated and the brightness is low, and it is not widely used in practice.

On the other hand, in an organic electroluminescent device using an organic material, an organic fluorescent material having an electron transporting property and an organic material having a hole transporting property were laminated by CW Tang et al. A device having a laminated structure was proposed, in which the phosphor was injected into a fluorescent material layer to emit light, and it was in the spotlight. (CWTang and SAVAN Slyke, Appl.Phys.L
ett., vol.51, pp.913-915 (1987); JP-A-63-264629). With this device, 1000 cd / m ² at a drive voltage of 10 V or less
It is said that the above-mentioned luminescence was obtained, and then, with this proposal as a starting point, active research on the surrounding area has been conducted. At present, various materials and device configurations have been proposed, and research and development for practical use are being actively conducted.

On the other hand, it is also true that the organic electroluminescent elements using the materials proposed so far still have various problems and problems. To give some examples, regardless of whether it is in a driving state or a non-driving state, the function of the element is deteriorated and the light emission luminance is reduced only by saving, or a dark spot called a dark spot during driving or non-driving. There is a phenomenon in which deterioration occurs such as occurrence and growth of the element, and finally the element is short-circuited and destroyed. It can be said that such a phenomenon causes a substantial problem in the material used therein, and it is difficult to say that the life is practically sufficient under the present circumstances. Therefore, in practical use of the element, it can be said that there is no choice but to limit to devices that can be used with a relatively short life. Further, in consideration of colorization of the element, at present, there are not sufficiently prepared methods and light-emitting materials capable of coping with it. In any case, in order to solve these problems / problems and aim for widespread practical application of organic electroluminescent devices, new high-performance light-emitting materials used therefor,
The development of new materials such as charge transport materials is highly anticipated.

[0006]

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 having a low voltage, high luminance, and excellent durability. Another object of the present invention is to provide an aromatic methylidene compound which is particularly useful as a light emitting material, an aromatic aldehyde compound for producing the same, a methylstyryl compound, and a method for producing them. This is intended to contribute to the realization of an organic electroluminescence device having high brightness and high durability.

[0007]

According to the present invention, a compound represented by the following general formula (1) is provided.

[Chemical 15] [Wherein R ₁₁ 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 ₁₁ represents 0, 1, 2, 3 or 4
Represents the integer. When n ₁₁ is an integer of 2 or more, R ₁₁ is composed of a plurality of identical substituents or a plurality of different substituents. R ₂₁ and R ₃₁ are the same or different groups and are hydrogen (provided that R ₂₁ and R ₃₁ are simultaneously hydrogen), an unsubstituted or substituted alkyl group (provided that R ₂₁ and R ₃₁ are simultaneously alkyl). A group), an unsubstituted or substituted cycloalkyl group (provided that R ₂₁ and R ₃₁ are simultaneously a cycloalkyl group), an unsubstituted or substituted aromatic group, or an unsubstituted or substituted aromatic hetero group Representing a ring group, or R ₂₁ and R ₃₁ together are a fused ring of an unsubstituted or substituted aromatic ring, or a fused ring of an unsubstituted or substituted aromatic heterocycle. Further, according to the present invention, there is provided an intermediate compound represented by the following general formula (2) for producing the compound of the above formula (1).

[Chemical 16] [Wherein R ₁₂ 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 ₁₂ represents 0, 1, 2, 3 or 4
Represents the integer. When n ₁₂ is an integer of 2 or more, R ₁₂ is composed of a plurality of identical substituents or a plurality of different substituents. Further, according to the present invention, represented by the following general formula (3),
There is provided an intermediate compound for preparing the compound of formula (1).

[Chemical 17] [Wherein R ₁₃ 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 ₁₃ is 0, 1, 2, 3 or 4
Represents the integer. n ₁₃ Is an integer greater than or equal to 2, R ₁₃ Is composed of a plurality of identical substituents or a plurality of different substituents. Furthermore, according to the present invention, a compound represented by the following general formula (4) is reacted with a compound represented by the following general formula (5), in the above general formula (1) Methods of making the represented compounds are provided.

[Chemical 18] [However, each Z in the above formula is the same or different group.
-PO (OR)₂Or-PA ₃ ⁺Where R is unsubstituted or
Represents a substituted alkyl group, A is an unsubstituted or substituted aryl group
Represents ]

[Chemical 19] [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, 2, 3 or 4
Represents the integer. When n ₁₄ is an integer of 2 or more, R ₁₄ is composed of a plurality of identical substituents or a plurality of different substituents. R ₂₂ and R ₃₂ are the same or different groups and are hydrogen (provided that R ₂₂ and R ₃₂ are simultaneously hydrogen), an unsubstituted or substituted alkyl group (provided that R ₂₂ and R ₃₂ are simultaneously alkyl). A group), an unsubstituted or substituted cycloalkyl group (provided that R ₂₂ and R ₃₂ are simultaneously a cycloalkyl group), an unsubstituted or substituted aromatic group, or an unsubstituted or substituted aromatic hetero group Or represents a ring group or R ₂₂ and R ₃₂ together are a fused ring of an unsubstituted or substituted aromatic ring or a fused ring of an unsubstituted or substituted aromatic heterocycle. Furthermore, according to the present invention, the compound represented by the general formula (2) is reacted with a compound represented by the following general formula (6), in the general formula (1) Methods of making the represented compounds are provided.

[Chemical 20] [Wherein R ₂₃ and R ₃₃ are the same or different groups, and are hydrogen (provided that R ₂₃ and R ₃₃ are simultaneously hydrogen), an unsubstituted or substituted alkyl group (provided that R ₂₃
And R ₃₃ are alkyl groups at the same time), an unsubstituted or substituted cycloalkyl group (provided that R ₂₃ and R ₃₃ are simultaneously cycloalkyl groups), an unsubstituted or substituted aromatic group, or Represents a substituted or substituted aromatic heterocyclic group, or R ₂₃ and R ₃₃ together are an unsubstituted or substituted aromatic ring fused or an unsubstituted or substituted aromatic heterocyclic fused ring. Z is -PO (O
R) ₂ or —PA ₃ ⁺ , R represents an unsubstituted or substituted alkyl group, and A represents an unsubstituted or substituted aryl group. Further, according to the present invention, the compound represented by the general formula (1) is characterized by reacting a compound represented by the following formula (7) with a compound represented by the following general formula (8). A method for producing the compound is provided.

[Chemical 21]

[Chemical 22] [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 is 0, 1, 2, 3 or 4
Represents the integer. When n ₁₅ is an integer of 2 or more, R ₁₅ is composed of a plurality of identical substituents or a plurality of different substituents. R ₂₄ and R ₃₄ are the same or different groups and are hydrogen (provided that R ₂₄ and R ₃₄ are simultaneously hydrogen), an unsubstituted or substituted alkyl group (provided that R ₂₄ and R ₃₄ are simultaneously alkyl). Group), an unsubstituted or substituted cycloalkyl group (provided that R ₂₄ and R ₃₄ are simultaneously a cycloalkyl group), an unsubstituted or substituted aromatic group, or an unsubstituted or substituted aromatic hetero group. Representing a ring group, or R ₂₄ and R ₃₄ together are a fused ring of an unsubstituted or substituted aromatic ring or a fused ring of an unsubstituted or substituted aromatic heterocycle. Z is -PO (OR) ₂
Or represents -PA ₃ ⁺ , R represents an unsubstituted or substituted alkyl group, and A represents an unsubstituted or substituted aryl group. Furthermore, according to the present invention, a compound represented by the following general formula (9) is reacted with a compound represented by the following general formula (10), in the above general formula (1) Methods of making the represented compounds are provided.

[Chemical 23] [Wherein R ₁₆ 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 ₁₆ is 0, 1, 2, 3 or 4
Represents the integer. When n ₁₆ is an integer of 2 or more, R ₁₆ is composed of a plurality of identical substituents or a plurality of different substituents. Further, each Z is the same or different group,
Represents PO (OR) ₂ or —PA ₃ ⁺ , R represents an unsubstituted or substituted alkyl group, and A represents an unsubstituted or substituted aryl group. ]

[Chemical 24] [Wherein R ₂₅ and R ₃₅ in the above formula are the same or different, and are hydrogen (provided that R ₂₅ and R ₃₅ are not simultaneously hydrogen), an unsubstituted or substituted alkyl group (provided that R ₂₅
And R ₃₅ are simultaneously an alkyl group), an unsubstituted or substituted cycloalkyl group (provided that R ₂₅ and R ₃₅ are simultaneously a cycloalkyl group), an unsubstituted or substituted aromatic group, or Represents a substituted or substituted aromatic heterocyclic group, or R ₂₅ and R ₃₅ together are a fused of an unsubstituted or substituted aromatic ring or a fused ring of an unsubstituted or substituted aromatic heterocycle. Further, according to the present invention, the compound represented by the general formula (4) is reacted with the compound represented by the following general formula (11) to obtain an acetal compound, and the acetal compound is converted to an aldehyde. There is provided a method for producing the compound represented by the general formula (2), which is characterized in that the compound is derived.

[Chemical 25] [Wherein R ₁₇ 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 ₁₇ is 0, 1, 2, 3 or 4
Represents the integer. When n ₁₇ is an integer of 2 or more, R ₁₇ is composed of a plurality of identical substituents or a plurality of different substituents. R represents an unsubstituted or substituted alkyl group. Further, according to the present invention, a compound represented by the general formula (4) is reacted with a compound represented by the following general formula (12), in the general formula (2) Methods of making the represented compounds are provided.

[Chemical 26] [Wherein R ₁₈ 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 ₁₈ represents 0, 1, 2, 3 or 4
Represents the integer. When n ₁₈ is an integer of 2 or more, R ₁₈ is composed of a plurality of identical substituents or a plurality of different substituents. Furthermore, according to the present invention, the compound represented by the general formula (4) is reacted with a compound represented by the following general formula (13), Methods of making the represented compounds are provided.

[Chemical 27] [Wherein R ₁₉ 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 ₁₉ represents 0, 1, 2, 3 or 4
Represents the integer. When n ₁₉ is an integer of 2 or more, R ₁₉ is composed of a plurality of identical substituents or a plurality of different substituents. Furthermore, according to the present invention, a compound represented by the general formula (7) is reacted with a compound represented by the following general formula (14), the general formula (3) Methods of making the represented compounds are provided.

[Chemical 28] [Wherein, R ₁₀ 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 ₁₀ represents 0, 1, 2, 3 or 4
Represents the integer. When n ₁₀ is an integer of 2 or more, R ₁₀ is composed of a plurality of identical substituents or a plurality of different substituents. Z represents -PO (OR) ₂ or -PA ₃ ⁺ , and R is
It represents an unsubstituted or substituted alkyl group, and A represents an unsubstituted or substituted aryl 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 light emitting material. Further, the compounds represented by the general formula (2) and the general formula (3) are useful intermediates for producing the compound represented by the general formula (1). The compounds provided by the present invention and the method for producing the compounds greatly contribute to the realization of an organic electroluminescence device having high brightness and high durability.

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION The first compound of the present invention has the general formula
It is a compound represented by (1).

In the general formula (1), R ₁₁ represents an unsubstituted or substituted alkyl group, an unsubstituted or substituted alkoxy group, a halogen group, a cyano group or a nitro group. Here, examples of the unsubstituted or substituted alkyl group include those having 1 to 12 carbon atoms. Examples of the unsubstituted or substituted alkoxy group include those having 1 to 12 carbon atoms. Examples of the halogen group include -F, -Cl, -Br and -I. Also, n ₁₁ is 0, 1, 2,
Represents an integer of 3 or 4. When n ₁₁ is an integer of 2 or more, R
₁₁ may consist of a plurality of the same substituents or a plurality of different substituents. In addition, general formula (2) ~
R ₁₀ and R _{12 to} R ₁₉ in (14) may be the same as R _11, and n ₁₀ and n _{12 to} n ₁₉ may be the same number as n ₁₁ .

In the general formula (1), R ₂₁ and R ₃₁ are (i) the same or different groups and are hydrogen (except when R ₂₁ and R ₃₁ are simultaneously hydrogen), unsubstituted or substituted. Alkyl group (provided that R ₂₁ and R ₃₁ are not simultaneously alkyl groups), unsubstituted or substituted cycloalkyl group (provided that R ₂₁
And R ₃₁ simultaneously represent a cycloalkyl group), an unsubstituted or substituted aromatic group, or an unsubstituted or substituted aromatic heterocyclic group, or (ii) jointly, an unsubstituted or substituted aromatic group It is a ring condensed with an aromatic ring or condensed with an unsubstituted or substituted aromatic heterocycle. In the case of (i), at least one of R ₂₁ and R ₃₁ is preferably an unsubstituted or substituted aromatic group or an unsubstituted or substituted aromatic heterocyclic group. The unsubstituted or substituted alkyl group preferably has 1 to 12 carbon atoms, and the unsubstituted or substituted cycloalkyl group has 3 to 8 carbon atoms.
Are preferred. Examples of the unsubstituted or substituted aromatic group include a phenyl group, a naphthyl group, a phenanthryl group, an anthryl group, a pyrenyl group, and the like, as well as one or more methyl groups, t-butyl groups, trifluoromethyl groups, halogen atoms, Examples thereof include groups substituted with a phenyl group, a methoxy group, a nitro group, a benzyl group, a cyclohexyl group, a cyano group, and the like, and the unsubstituted or substituted aromatic heterocyclic group includes a thienyl group, a pyridyl group, a quinolyl group. Etc. can be mentioned. In the case of (ii), examples of the condensed ring which R ₂₁ and R ₃₁ may jointly form include a dibenzocycloheptenylidene group and a dibenzocycloheptanylidene group. R in the general formulas (5), (6), (8) and (10)
_{22 to} R ₂₅ and R _{32 to} R ₃₅ can be the same as R ₂₁ and R ₃₁ , respectively.

The compound represented by the general formula (1) of the present invention is
Broadly divided into four synthetic routes, namely, the reaction of the compound represented by the general formula (4) with the stilbene aldehyde derivative represented by the general formula (5), 1,2-represented by the general formula (2) Screw (4
-Formylstyryl) -4-naphthylbenzene derivative with a compound represented by the general formula (6), a phthalaldehyde derivative represented by the general formula (7) and a compound represented by the general formula (8) Reaction, or the compound represented by the general formula (9) and the general formula
It can be produced by a reaction with a ketone derivative represented by (10). In the general formulas (4), (6), (8) and (9), Z
Represents —PO (OR) ₂ or —PA ₃ ⁺ , and R is an unsubstituted or substituted alkyl group, preferably an unsubstituted or substituted alkyl group having 1 to 4 carbon atoms. A represents an unsubstituted or substituted aryl group, preferably a phenyl group, a tolyl group or a naphthyl group. When there are plural Zs in the formula, these may be the same or different. Also, when Z is -PA ₃ ⁺ , a salt of this group with a suitable base can be subjected to the reaction. Examples of the base include fluorine, chlorine, bromine,
Ions of halogen atoms such as iodine can be mentioned.

All of these reactions are reactions of aldehydes or ketones with active methylene and the like, and are usually carried out in an organic solvent using a base. As the reaction solvent, 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, chloroform. , Halogenated hydrocarbons such as dichloromethane, dichloroethane,
Heterocyclic aromatic hydrocarbons such as pyridine and quinoline, and other organic solvents such as N, N-dimethylformamide and dimethylsulfoxide can be used, and generally, all common organic solvents can be used. As the base used in the reaction, inorganic bases such as potassium carbonate, sodium carbonate, potassium hydroxide or sodium hydroxide, organic bases such as triethylamine, triethanolamine, pyridine or hexamethylenetetramine, sodium methoxide, sodium ethoxide, Examples thereof include alkali metal salts of alcohols such as potassium butoxide, and sodium amide. The amount of the base used may be from a catalytic amount to a chemical equivalent or more, if necessary.

The reaction temperature is about -10 ° C to about 15 ° C.
Can be done at 0 ° C, but usually about 0 ° C to about 80 °
It is preferable to carry out at C. The reaction time generally depends on the reaction temperature and is usually about 30 minutes to 100 hours, but it should be appropriately selected depending on the combination of the raw materials.

After the 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, etc., and preferably inorganic components are removed by washing with water, followed by column chromatography, recrystallization, or A pure target product can be obtained by a general purification method such as sublimation purification.

The second compound of the present invention is a compound represented by the general formula (2).

The compound represented by the general formula (2) is represented by the general formula (4)
After obtaining an acetal compound of the compound of the general formula (2) by reacting a bismethylphosphonate derivative represented by and a monodialkyl acetal of a terephthalaldehyde derivative represented by the general formula (11), the acetal is converted to an aldehyde. A method of obtaining a compound of the general formula (2) by derivation, or instead of the monodialkyl acetal of the terephthalaldehyde derivative, the terephthalaldehyde derivative represented by the general formula (12) is represented by the bismethylphosphone represented by the general formula (4). It can be produced by a method such as directly obtaining it by reacting with an acid ester derivative. In the general formula (11), R is an unsubstituted or substituted alkyl group, preferably an unsubstituted or substituted alkyl group having 1 to 4 carbon atoms.

The compound represented by the general formula (4) and the general formula (1
The reaction with the compound represented by 1) or (12) is carried out by the above general formula.
Similar to the synthetic reaction of the compound represented by (1), it is a reaction between an aldehyde and active methylene, and is usually performed using a base in an organic solvent. The reaction solvent, base and reaction conditions used here may be the same as those described in the synthetic route of the compound represented by the above general formula (1). Further, the reaction of inducing an aldehyde acetal compound obtained by the reaction of the compound represented by the general formula (4) and the compound represented by the general formula (11), water, methanol, alcohols such as ethanol, acetone, Ketones such as methyl ethyl ketone, tetrahydrofuran,
In the solvent such as ethers such as dioxane, dimethyl sulfoxide or N, N-dimethylformamide, the acetal compound is mixed with acids such as acetic acid, hydrochloric acid and sulfuric acid at a temperature of about 0 ° C to 100 ° C for 5 minutes or It can be easily performed by allowing it to act for about 5 hours.

The third compound of the present invention is a compound represented by the general formula (3).

The compound represented by the general formula (3) is represented by the general formula (4)
Reaction of the bismethylphosphonate derivative represented by the formula with the tolualdehyde derivative represented by the general formula (13), or the phthalaldehyde derivative represented by the general formula (7) and the methylphosphone represented by the general formula (14) It can be obtained by a reaction with an acid ester derivative. In the general formula (14), Z represents -PO (OR) ₂ or -PA ₃ ⁺ , R is an unsubstituted or substituted alkyl group, preferably an unsubstituted or substituted alkyl group having 1 to 4 carbon atoms. is there. A represents an unsubstituted or substituted aryl group, preferably a phenyl group, a tolyl group or a naphthyl group. Also, when Z is -PA ₃ ⁺ , a salt of this group with a suitable base can be subjected to the reaction. Examples of the base include fluorine, chlorine, bromine,
Ions of halogen atoms such as iodine can be mentioned.

The synthetic reaction of the compound represented by the general formula (3) is a reaction between an aldehyde and active methylene, similar to the synthetic reaction of the compound represented by the general formula (1). Is performed using. The reaction solvent, base, and reaction conditions used here are the same as those in the above
The same compounds as those described in the synthetic route of the compound represented by (1) can be used.

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). It can be used as one of the intermediates for obtaining. That is, by deriving a compound represented by the general formula (3) into a halomethyl derivative represented by the following general formula (15), and then allowing a trialkyl phosphite to act, the general formula
The bismethylphosphonate derivative represented by (9) can be conveniently obtained.

[0023]

[Chemical 29]

[In the above formula, R'represents the same group as R ₁₁ , n'represents the same number as n _11, and X represents halogen. ]

Derivation of the compound represented by the general formula (3) into the halomethyl derivative represented by the general formula (15) is carried out by using a compound containing a halogen species in an organic solvent such as carbon tetrachloride or carbon disulfide. Acting on the compound represented by the general formula (3) at 30 ° C to 100 ° C for about 30 minutes to 10 hours under irradiation with light and / or with a radical generator such as benzoyl peroxide or azobisisobutyronitrile. It can be easily done by urging. As the compound containing a halogen species, a compound containing a bromine atom is preferable, and bromine, N-bromosuccinimide or the like can be used. Further, a method for converting the obtained halomethyl compound represented by the general formula (15) into a compound represented by the general formula (9) is to add a phosphite triester to the halomethyl compound at 50 ° C to 150 ° C for about 10 minutes. To a method for obtaining a bismethylphosphonate derivative by acting for about 10 hours,
Alternatively, a method of reacting a halomethyl compound with a triarylphosphine compound such as triphenylphosphine to obtain a bismethyltriarylphosphonium compound can be mentioned.

Next, specific examples of the compound represented by the general formula (1) of the present invention are shown in Tables 1 to 5, specific examples of the compound represented by the general formula (2) are shown in Table 6, and generally. Specific examples of the compound represented by the formula (3) are shown in Table 7, but the present invention is not limited thereto.

[0027]

[Table 1]

[0028]

[Table 2]

[0029]

[Table 3]

[0030]

[Table 4]

[0031]

[Table 5]

[0032]

[Table 6]

[0033]

[Table 7]

As mentioned above, according to the present invention, the general formula
The compound represented by (1) is useful as a constituent material of an organic electroluminescent device, and is particularly excellent as a light emitting material. Further, the compounds represented by the general formula (2) and the general formula (3) are useful intermediates for producing the compound represented by the general formula (1). The compounds provided by the present invention and the method for producing these compounds make a great contribution to the realization of an organic electroluminescence device having high brightness and high durability.

[0035]

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited thereto.

Example 1 Production Example of Compound No. 1-02 (Part 1) Tetraethyl 4- (1-naphthyl) -1,2-xylylenediphosphonate 2.02 g, 4'-formyl-α-phenylstilbene 2.27
g was dissolved in 24 ml of N, N-dimethylformamide, 5-10 ° C
At 1.04 g of potassium tert-butoxide was added portionwise over 10 minutes. Then, after stirring at room temperature for 20 hours, the reaction mixture was poured into 200 ml of ethanol, the precipitate was collected by filtration, washed with ethanol, washed with water and dried to obtain 1.44 g of a crude product as a yellow powder.

Next, the crude product of the yellow powder was subjected to column chromatography using a stationary phase silica gel and a mixed solvent of toluene and hexane (volume ratio 1: 1) as a mobile phase to obtain a yellow glassy substance. . Then, it was recrystallized with a mixed solvent of toluene and hexane and vacuum dried at 100 ° C. to obtain 0.920 g (yield 30%) of yellow crystals having strong fluorescence. Melting point 130
~ 150 ° C. The elemental analysis values of this product were as follows: carbon 94.12% (calculated value as compound number 1-02 94.20%), hydrogen 5.75% (calculated value as compound number 1-02 5.80%). Infrared absorption spectrum (KBr tablet method) showed stretching vibration due to aromatic ring at around 1600 cm ^-1 , and proton nuclear magnetic resonance spectrum (solvent CDCl ₃ , internal standard TMS) showed aromatic ring ring proton and alkene proton δ = 6.8. It was confirmed at ~ 8.0ppm (44H). In addition, a molecular ion peak m / z = 764 was observed in the mass spectrum, and it was confirmed from the above that the compound obtained above was compound number 1-02.

Example 2 Production Example of Compound No. 1-02 (Part 2) Diethyldiphenylmethylphosphonate 3.04 g, 1,2-bis
2.32 g of (4-formylstyryl) -4- (1-naphthyl) benzene (Compound No. 2-01) was dissolved in 30 ml of N, N-dimethylformamide, and 10 g of 1.30 g of potassium tert-butoxide was added at 5-10 ° C.
Added portionwise over minutes. Then, after stirring at room temperature for 20 hours, the reaction mixture was poured into 200 ml of ethanol, the precipitate was collected by filtration, washed with ethanol, washed with water and dried to obtain a crude product. Treated in the same manner as 1 to obtain compound number 1-02.

Example 3 Preparation Example of Compound No. 1-02 (Part 3) 1.40 g of 4- (1-naphthyl) phthalaldehyde and 4.06 g of diethyl 4- (2,2'-diphenylvinyl) benzylphosphonate N, N-
It was dissolved in 30 ml of dimethylformamide and 1.30 g of potassium tert-butoxide were added in portions over 10 minutes at 5-10 ° C. Then, after stirring at room temperature for 20 hours, the reaction mixture was poured into 200 ml of ethanol, the precipitate was collected by filtration, washed with ethanol, washed with water and dried to obtain a crude product, which was the same as in Example 1. Compound No. 1-02 was obtained.

Example 4 Production Example of Compound No. 1-02 (Part 4) 1,2-bis (4-methylstyryl) -4- (1-naphthyl) benzene
A mixture consisting of 8.73 g, N-bromosuccinimide 7.12 g, 25% hydrous benzoyl peroxide 0.5 g and carbon tetrachloride 80 ml,
The mixture was heated under reflux for 10 hours. After cooling, 200 ml of diethyl ether
The precipitated crystals were filtered off, and the filtrate was concentrated to obtain a bromomethyl derivative. To this bromomethyl derivative, 13.29 g of triethyl phosphite was added and heated at 120 ° C for 5 hours. After completion of the reaction, the produced ethyl bromide and excess triethyl phosphite were distilled off under reduced pressure, and 1,2-bis (4-methylstyryl) -4-
Tetraethyl (1-naphthyl) benzene-α, α′-diyldiphosphonate was obtained.

1.82 g of benzophenone and 3.54 g of tetraethyl 1,2-bis (4-methylstyryl) -4- (1-naphthyl) benzene-α, α'-diyldiphosphonate obtained as described above
It was dissolved in 30 ml of N, N-dimethylformamide and 1.30 g of potassium tert-butoxide were added portionwise over 10 minutes at 5-10 ° C. Then, after stirring at room temperature for 20 hours, the reaction mixture was poured into 200 ml of ethanol, and the precipitate was collected by filtration,
After washing with ethanol, washing with water and drying to obtain a crude product, which was treated in the same manner as in Example 1, Compound No. 1-02
Got

Example 5 Production Example of Compound No. 2-01 (No. 1) Tetraethyl 4- (1-naphthyl) -1,2-xylylenediphosphonate 10.09 g, terephthalaldehyde monodiethyl acetal 8.75 g in N, It was dissolved in 80 ml of N-dimethylformamide and 5.67 g of potassium tert-butoxide were added in small portions over 10 minutes at 5-10 ° C. Then, the mixture was stirred at room temperature for 25 hours, 36% hydrochloric acid (38.5 ml) was added, and the mixture was further stirred at a bath temperature of 80-85 ° C for 30 minutes. After cooling, about 150 ml of water was added, the precipitate was collected by filtration, washed with water, and dried to obtain a yellowish brown powder. Then, it was recrystallized from a mixed solvent of toluene and ethanol and then vacuum dried at 80 ° C. to obtain 4.92 g (yield 53%) of yellow crystals. The elemental analysis values of this product were as follows: carbon 87.66% (calculated value as compound number 2-01 87.90%), hydrogen 5.13% (compound number 2
The calculated value as -01 was 5.21%). In the infrared absorption spectrum (KBr tablet method), the stretching vibration due to aldehyde was around 1690 cm ^-1 , and the stretching vibration due to aromatic ring was 1600 cm ^-1.
Observed near ^-1 , and mass spectrum shows molecular ion peak
m / z = 464 was observed, and it was confirmed from the above that the compound obtained above was Compound No. 2-01.

Example 6 Production Example of Compound No. 2-01 (Part 2) Tetraethyl 4- (1-naphthyl) -1,2-xylylenediphosphonate 10.09 g and terephthalaldehyde 13.41 g were added to N, N-dimethyl. Dissolve in 160 ml of formamide and add potassium t at 5-10 ° C.
5.67 g of ert-butoxide was added in small portions over 10 minutes. Then, stir at room temperature for 20 hours, and then about 300 ml of water
Was added, and the precipitate was collected by filtration, washed with water, further washed with ethanol, and dried to obtain a pale yellowish brown powder. This light tan powder was repeatedly recrystallized from a mixed solvent of toluene and ethanol to obtain Compound No. 2-01 in the same manner as in Example 5.

Example 7 Production Example of Compound No. 3-01 (Part 1) Tetraethyl 4- (1-naphthyl) -1,2-xylylenediphosphonate 5.04 g and 4-methylbenzaldehyde 2.64 g were added to N, N -Dissolve in 60 ml of dimethylformamide, potassium at 5-10 ° C
2.60 g of tert-butoxide are added portionwise over 10 minutes. Then, after stirring at room temperature for 20 hours, water about 150m
l was added, and the precipitate was collected by filtration, washed with water, and dried to obtain a light brown powder. Next, this powder was recrystallized from a mixed solvent of toluene and ethanol to obtain 2.22 g (yield 51%) of yellow crystals.
The elemental analysis value of this product was 93.40% carbon (Compound No. 3-01
Calculated as 93.54%) and hydrogen 6.51% (calculated as compound No. 3-01 6.46%). Infrared absorption spectrum (K
In the Br tablet method, the stretching vibration caused by the aromatic ring is 1600 cm ^-1.
Admitted near. In the mass spectrum, the molecular ion peak
m / z = 436 was observed. From the above, it was confirmed that the compound obtained above was compound number 3-01.

Example 8 Production Example of Compound No. 3-01 (Part 2) 2.60 g of 4- (1-naphthyl) phthalaldehyde and 4.85 g of diethyl 4-methylbenzylphosphonate in 60 ml of N, N-dimethylformamide. Once dissolved, potassium tert-butoxide (2.60 g) was added portionwise over 10 minutes at 5-10 ° C. afterwards,
After stirring at room temperature for 20 hours, about 150 ml of water was added, and the precipitate was collected by filtration, washed with water and dried to obtain a light brown powder. This was treated in the same manner as in Example 7 to obtain compound number 3-01.

(Example 9) 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 transparent thin film of indium tin oxide (ITO) was formed in advance. A layer and an aluminum / lithium (Al / Li) electrode as a cathode are sequentially formed by vapor deposition,
An organic electroluminescent device containing the compound of the present invention was produced. Specifically, first, as an ITO glass substrate, a hole transport material
N, N'-diphenyl-N, N'-bis (3-methylphenyl) benzidine (TPD), the aromatic methylidene compound of Compound No. 1-02 of the present invention as a light emitting material, and tris (8- Hydroxyquinolino) aluminum (Alq) was set in a vacuum vapor deposition apparatus and evacuated to 10 ⁻⁴ Pa. Next, TPD, which is a hole transport material, is deposited on the ITO glass substrate electrode in a thickness of 0.1 to 0.5 nm.
Vapor deposition was performed at a vapor deposition rate of / sec to form a hole transport layer having a thickness of 50 nm.
Next, Compound No. 1-02, which is a light emitting material, was vapor-deposited at a vapor deposition rate of 0.1 to 0.5 nm / sec to form a light emitting layer having a thickness of 50 nm. Subsequently, electron transporting material Alq was vapor-deposited at a rate of 0.1 nm / sec.
An electron transport layer of 0 nm was formed. Further, Li is 0.01 to 0.02 nm /
Second, Al was simultaneously deposited at a deposition rate of 1 to 2 nm / sec to form an Al / Li electrode. Its thickness was 150 nm. All of these vapor depositions were continuously performed without breaking the vacuum, and the film thickness was controlled by monitoring with a crystal oscillator. Immediately after manufacturing the element, take out the electrode in dry nitrogen,
An organic electroluminescent device was created. When a voltage was applied to the device thus produced, uniform blue light emission was obtained.

[0047]

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 device that has excellent light emitting characteristics and stability. Therefore, it can be said that the compounds of the present invention and the method for producing them are industrially extremely important.

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification code FI theme code (reference) H05B 33/14 H05B 33/14 B // G03G 5/06 313 G03G 5/06 313 314 314

Claims (11)

[Claims] 1. A compound represented by the following general formula (1): [Chemical 1] [Wherein R ₁₁ 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 ₁₁ represents 0, 1, 2, 3 or 4
Represents the integer. When n ₁₁ is an integer of 2 or more, R ₁₁ is composed of a plurality of identical substituents or a plurality of different substituents. R ₂₁ and R ₃₁ are the same or different groups and are hydrogen (provided that R ₂₁ and R ₃₁ are simultaneously hydrogen), an unsubstituted or substituted alkyl group (provided that R ₂₁ and R ₃₁ are simultaneously alkyl). A group), an unsubstituted or substituted cycloalkyl group (provided that R ₂₁ and R ₃₁ are simultaneously a cycloalkyl group), an unsubstituted or substituted aromatic group, or an unsubstituted or substituted aromatic hetero group Representing a ring group, or R ₂₁ and R ₃₁ together are a fused ring of an unsubstituted or substituted aromatic ring, or a fused ring of an unsubstituted or substituted aromatic heterocycle. ] 2. An intermediate compound for producing the compound of claim 1, which is represented by the following general formula (2). [Chemical 2] [Wherein R ₁₂ 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 ₁₂ represents 0, 1, 2, 3 or 4
Represents the integer. When n ₁₂ is an integer of 2 or more, R ₁₂ is composed of a plurality of identical substituents or a plurality of different substituents. ] 3. An intermediate compound for producing the compound of claim 1, which is represented by the following general formula (3). [Chemical 3] [Wherein R ₁₃ 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 ₁₃ is 0, 1, 2, 3 or 4
Represents the integer. n ₁₃ Is an integer greater than or equal to 2, R ₁₃ Is composed of a plurality of identical substituents or a plurality of different substituents. ] 4. A compound represented by the following general formula (4):
Characterized by reacting with a compound represented by the general formula (5)
The method for producing the compound according to claim 1. [Chemical 4] [However, each Z in the above formula is the same or different group.
-PO (OR)₂Or-PA ₃ ⁺Where R is unsubstituted or
Represents a substituted alkyl group, A is an unsubstituted or substituted aryl group
Represents ] [Chemical 5] [However, in the above formula, R₁₄Is an unsubstituted or substituted alkyl
Groups, unsubstituted or substituted alkoxy groups, halogen groups, sia
Group or nitro group, n₁₄Is 0, 1, 2, 3 or 4
Represents the integer. n₁₄Is an integer greater than or equal to 2, R₁₄Is multiple
Of the same substituent or different substituents?
Consists of Also R_{twenty two}And R₃₂Are the same or different groups
Hydrogen (however, R_{twenty two}And R₃₂Are simultaneously hydrogen
, Or an unsubstituted or substituted alkyl group (provided that R_{twenty two}And
And R₃₂Except when is an alkyl group at the same time), unsubstituted
Or a substituted cycloalkyl group (provided that R_{twenty two}And R₃₂At the same time
Is a cycloalkyl group), unsubstituted or
Substituted aromatic group, or unsubstituted or substituted aromatic heterocyclic group
Represents or R_{twenty two}And R₃₂Jointly, non-replaced or
Is a fused, unsubstituted or substituted substituted aromatic ring
It is a condensed ring of aromatic heterocycles. ] 5. The production of the compound according to claim 1, which comprises reacting the compound represented by the general formula (2) according to claim 2 with a compound represented by the following general formula (6). Method. [Chemical 6] [Wherein R ₂₃ and R ₃₃ are the same or different groups, and are hydrogen (provided that R ₂₃ and R ₃₃ are simultaneously hydrogen), an unsubstituted or substituted alkyl group (provided that R ₂₃
And R ₃₃ are alkyl groups at the same time), an unsubstituted or substituted cycloalkyl group (provided that R ₂₃ and R ₃₃ are simultaneously cycloalkyl groups), an unsubstituted or substituted aromatic group, or Represents a substituted or substituted aromatic heterocyclic group, or R ₂₃ and R ₃₃ together are an unsubstituted or substituted aromatic ring fused or an unsubstituted or substituted aromatic heterocyclic fused ring. Z is -PO (O
R) ₂ or —PA ₃ ⁺ , R represents an unsubstituted or substituted alkyl group, and A represents an unsubstituted or substituted aryl group. ] 6. The method for producing a compound according to claim 1, which comprises reacting a compound represented by the following formula (7) with a compound represented by the following general formula (8). [Chemical 7] [Chemical 8] [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 is 0, 1, 2, 3 or 4
Represents the integer. When n ₁₅ is an integer of 2 or more, R ₁₅ is composed of a plurality of identical substituents or a plurality of different substituents. R ₂₄ and R ₃₄ are the same or different groups and are hydrogen (provided that R ₂₄ and R ₃₄ are simultaneously hydrogen), an unsubstituted or substituted alkyl group (provided that R ₂₄ and R ₃₄ are simultaneously alkyl). Group), an unsubstituted or substituted cycloalkyl group (provided that R ₂₄ and R ₃₄ are simultaneously a cycloalkyl group), an unsubstituted or substituted aromatic group, or an unsubstituted or substituted aromatic hetero group. Representing a ring group, or R ₂₄ and R ₃₄ together are a fused ring of an unsubstituted or substituted aromatic ring or a fused ring of an unsubstituted or substituted aromatic heterocycle. Z is -PO (OR) ₂
Or represents -PA ₃ ⁺ , R represents an unsubstituted or substituted alkyl group, and A represents an unsubstituted or substituted aryl group. ] 7. The method for producing the compound according to claim 1, which comprises reacting a compound represented by the following general formula (9) with a compound represented by the following general formula (10). [Chemical 9] [Wherein R ₁₆ 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 ₁₆ is 0, 1, 2, 3 or 4
Represents the integer. When n ₁₆ is an integer of 2 or more, R ₁₆ is composed of a plurality of identical substituents or a plurality of different substituents. Further, each Z is the same or different group,
Represents PO (OR) ₂ or —PA ₃ ⁺ , R represents an unsubstituted or substituted alkyl group, and A represents an unsubstituted or substituted aryl group. ] [Chemical 10] [Wherein R ₂₅ and R ₃₅ in the above formula are the same or different, and are hydrogen (provided that R ₂₅ and R ₃₅ are not simultaneously hydrogen), an unsubstituted or substituted alkyl group (provided that R ₂₅
And R ₃₅ are simultaneously an alkyl group), an unsubstituted or substituted cycloalkyl group (provided that R ₂₅ and R ₃₅ are simultaneously a cycloalkyl group), an unsubstituted or substituted aromatic group, or Represents a substituted or substituted aromatic heterocyclic group, or R ₂₅ and R ₃₅ together are a fused of an unsubstituted or substituted aromatic ring or a fused ring of an unsubstituted or substituted aromatic heterocycle. ] 8. A compound represented by the general formula (4) is reacted with a compound represented by the following general formula (11) to obtain an acetal compound, and then the acetal compound is derived into an aldehyde compound. 3. The method for producing the compound according to claim 2, characterized in that [Chemical 11] [Wherein R ₁₇ 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 ₁₇ is 0, 1, 2, 3 or 4
Represents the integer. When n ₁₇ is an integer of 2 or more, R ₁₇ is composed of a plurality of identical substituents or a plurality of different substituents. R represents an unsubstituted or substituted alkyl group. ] 9. The method for producing a compound according to claim 2, wherein the compound represented by the general formula (4) is reacted with a compound represented by the following general formula (12). [Chemical 12] [Wherein R ₁₈ 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 ₁₈ represents 0, 1, 2, 3 or 4
Represents the integer. When n ₁₈ is an integer of 2 or more, R ₁₈ is composed of a plurality of identical substituents or a plurality of different substituents. ] 10. The method for producing a compound according to claim 3, wherein the compound represented by the general formula (4) is reacted with a compound represented by the following general formula (13). [Chemical 13] [Wherein R ₁₉ 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 ₁₉ represents 0, 1, 2, 3 or 4
Represents the integer. When n ₁₉ is an integer of 2 or more, R ₁₉ is composed of a plurality of identical substituents or a plurality of different substituents. ] 11. The method for producing a compound according to claim 3, wherein the compound represented by the general formula (7) is reacted with a compound represented by the following general formula (14). [Chemical 14] [Wherein, R ₁₀ 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 ₁₀ represents 0, 1, 2, 3 or 4
Represents the integer. When n ₁₀ is an integer of 2 or more, R ₁₀ is composed of a plurality of identical substituents or a plurality of different substituents. Z represents -PO (OR) ₂ or -PA ₃ ⁺ , and R is
It represents an unsubstituted or substituted alkyl group, and A represents an unsubstituted or substituted aryl group. ]