CN101407492A - Nitrogen-containing heterocyclic derivative and organic electroluminescent device using the same - Google Patents

Abstract

The invention provides a nitrogen-containing heterocyclic derivative with a specific structure, an organic electroluminescent element material containing the nitrogen-containing heterocyclic derivative, and an organic electroluminescent element. The organic electroluminescent element is sandwiched between a cathode and an anode. An organic thin film layer formed of one or more layers including at least a light-emitting layer, at least one layer of which contains the above-mentioned nitrogen-containing heterocyclic derivative alone or as a component of a mixture, which can achieve high brightness, high luminous efficiency and high efficiency. Improved adhesion to electrodes for long life.

Description

Nitrogen-containing heterocyclic derivative and organic electroluminescent device using the same

This application is an invention patent with the application number 03826096.4 (PCT/JP2003/012322), the application date is September 26, 2003, and the invention title is "Nitrogen-containing heterocyclic derivatives and organic electroluminescent elements using the derivatives" Divisional application of the application.

technical field

The present invention relates to a novel nitrogen-containing heterocyclic derivative and an organic electroluminescent device (hereinafter referred to as an organic EL device) containing the nitrogen-containing heterocyclic derivative. More specifically, the present invention relates to a nitrogen-containing heterocyclic derivative useful as a constituent of an organic EL element; and by using the nitrogen-containing heterocyclic derivative in at least one layer of organic compound layers, low drive can be realized High voltage, high brightness, high luminous efficiency, and long-term stable organic EL elements due to improved adhesion to electrodes.

Background technique

The organic electroluminescent element is a self-luminous element that utilizes the principle that a fluorescent substance emits light through the recombination energy of holes injected from the anode and electrons injected from the cathode when an electric field is applied. Since C.W.Tang et al. of ィ-ストマン・コダツク company reported a low-voltage drive organic EL element obtained by a laminated element (C.W.Tang, S.A.Vanslyke, Applied Physics Letters, Volume 51, Page 913, 1987, etc.), about Research on organic EL elements using organic materials as constituent materials is in the ascendant. Tang et al. used tris(8-quinolinol)aluminum as the light-emitting layer and triphenylenediamine derivatives as the hole transport layer. The advantages of the laminated structure are: it can improve the hole injection efficiency into the light-emitting layer; it can improve the generation efficiency of excitons generated by blocking and recombining electrons injected from the cathode; it can seal the excitons generated in the light-emitting layer, etc. . As shown in this example, the element structure of the known organic EL element is: a hole transport (injection) layer, an electron transport light-emitting layer two-layer type; or a hole transport (injection) layer, a light-emitting layer, an electron transport injection layer. 3-layer type etc. In such a multilayer structure device, in order to increase the recombination efficiency of injected holes and electrons, it is necessary to improve the device structure, formation method, and the like.

Conventionally, attempts have been made to provide electron injection/transport layers in organic EL devices in order to improve luminous efficiency. In this case, it can be seen that an excited state complex is formed, and although high-intensity light emission can be obtained, it has the disadvantage of short light emission lifetime. In addition, when electricity is applied for a long time, the metal electrode and the organic compound layer will peel off, the organic compound layer and the electrode will crystallize, become cloudy, and the luminous brightness will decrease. It is necessary to prevent the occurrence of the above phenomenon.

Examples of using nitrogen-containing heterocyclic compounds such as pyrazine compounds, quinoline compounds, and quinoxaline compounds as constituents of organic EL devices include 2,3,5,6-tetraphenylene compounds described in US Patent No. 5,077,142. ylpyrazine, 2,3,4-triphenylquinoline, 2,3-diphenylquinoxaline. However, these compounds have problems such as low melting point, immediate crystallization when used as an amorphous thin film layer of an organic EL device, and almost no light emission. In addition, there is a disadvantage that the above-mentioned peeling occurs after energization, and the life is shortened.

Japanese Patent Application Laid-Open No. 2001-6877 discloses a blue light-emitting element using a nitrogen-containing heterocyclic compound; Organic EL element. The invention of Japanese Patent Laid-Open No. 2001-6877 can obtain blue light emission having a peak wavelength at 430-480 nm. In the invention of Japanese Patent Application Laid-Open No. 2001-35664, when nitrogen-containing heterocyclic compounds are used as hole injection materials, a luminous brightness of about 500 cd/m can be obtained at a voltage of ^6V ; when used as a light-emitting material, at 12V Under the voltage, the luminescence with a luminous brightness of about 2300cd/m ² can be obtained, but the voltage is too high and the practical performance is poor. People need further organic EL elements with low driving voltage and high luminous efficiency.

Contents of the invention

The object of the present invention is to provide a novel nitrogen-containing heterocyclic derivative that can be used as a constituent component of an organic EL element; and to provide an organic EL element in which the above-mentioned nitrogen-containing heterocyclic derivative is used in an organic compound layer. At least one layer of it, high luminance, high luminous efficiency, and long life due to improved adhesion to electrodes can be achieved.

The present inventors have carried out in-depth research to achieve the above object, and found that: nitrogen-containing heterocyclic derivatives with a specific structure are novel compounds, by using the compound in at least one layer of organic compounds in organic EL elements (especially electrons) injection layer) to achieve high brightness, high luminous efficiency, and long life due to improved adhesion to electrodes. The present invention has been accomplished based on the knowledge.

That is, the present invention provides nitrogen-containing heterocyclic derivatives represented by any of the general formulas (1), (1')-(3').

HAr-L-Ar ¹ -Ar ² (1)

(wherein, HAr is a nitrogen-containing heterocyclic ring with 3-40 carbon atoms that may have substituents,

L is a single bond, an optionally substituted arylene group with 6 to 60 carbon atoms, an optionally substituted heteroarylene group with 3 to 60 carbon atoms, or an optionally substituted fluorenylene group,

Ar ¹ is a divalent aromatic hydrocarbon group with 6-60 carbon atoms that may have a substituent,

Ar ² is an aryl group with 6-60 carbon atoms that may have substituents or a heteroaryl group with 3-60 carbon atoms that may have substituents);

(wherein, A ¹ -A ³ are each independently a nitrogen atom or a carbon atom;

Ar ¹ ' is an aryl group with 6-60 carbon atoms in a substituted or unsubstituted ring, or a heteroaryl group with 3-60 carbon atoms in a substituted or unsubstituted ring; Ar ² ' is a hydrogen atom, substituted Or an unsubstituted aryl group with 6-60 carbon atoms in the ring, a substituted or unsubstituted heteroaryl group with 3-60 carbon atoms in the ring, a substituted or unsubstituted alkane with 1-20 carbon atoms group, or a substituted or unsubstituted alkoxy group with 1-20 carbon atoms; one of Ar ¹ ' and Ar ² ' is a substituted or unsubstituted condensed ring group with 10-60 carbon atoms , or a substituted or unsubstituted monoheterofused ring group with 3-60 carbon atoms in the ring;

L ¹ and L ² are each independently a single bond, a substituted or unsubstituted arylene group with 6-60 carbon atoms in the ring, or a substituted or unsubstituted heteroarylene group with 3-60 carbon atoms in the ring A group, or a substituted or unsubstituted fluorenylene group;

R is a hydrogen atom, a substituted or unsubstituted aryl group with 6-60 carbon atoms in the ring, a substituted or unsubstituted heteroaryl group with 3-60 carbon atoms in the ring, substituted or unsubstituted carbon atoms It is an alkyl group of 1-20, or a substituted or unsubstituted alkoxy group with a carbon number of 1-20; n is an integer of 0-5, and when n is more than 2, multiple Rs can be the same or different, corresponding to Multiple adjacent R groups can combine with each other to form a carbocyclic alicyclic ring or a carbocyclic aromatic ring);

(wherein, A ¹ -A ³ are each independently a nitrogen atom or a carbon atom;

Ar ¹ ' is an aryl group with 6-60 carbon atoms in a substituted or unsubstituted ring, or a heteroaryl group with 3-60 carbon atoms in a substituted or unsubstituted ring; Ar ² ' is a hydrogen atom, substituted Or an unsubstituted aryl group with 6-60 carbon atoms in the ring, a substituted or unsubstituted heteroaryl group with 3-60 carbon atoms in the ring, a substituted or unsubstituted alkane with 1-20 carbon atoms group, or a substituted or unsubstituted alkoxy group with 1-20 carbon atoms; one of Ar ¹ ' and Ar ² ' is a substituted or unsubstituted condensed ring group with 10-60 carbon atoms , or a substituted or unsubstituted monoheterofused ring group with 3-60 carbon atoms in the ring;

^L1 and ^L2 are each independently a single bond, a substituted or unsubstituted arylene group with 6-60 carbon atoms in the ring, a substituted or unsubstituted heteroarylene group with 3-60 carbon atoms in the ring , or substituted or unsubstituted fluorenylene;

R' is a hydrogen atom, a substituted or unsubstituted aryl group with 6-60 carbon atoms in the ring, a substituted or unsubstituted heteroaryl group with 3-60 carbon atoms in the ring, or a substituted or unsubstituted carbon atom An alkyl group with a number of 1-20, or a substituted or unsubstituted alkoxy group with a number of carbon atoms of 1-20);

(wherein, A ¹ -A ² are each independently a nitrogen atom or a carbon atom;

Ar ¹ ' is an aryl group with 6-60 carbon atoms in a substituted or unsubstituted ring, or a heteroaryl group with 3-60 carbon atoms in a substituted or unsubstituted ring; Ar ² ' is a hydrogen atom, substituted Or an unsubstituted aryl group with 6-60 carbon atoms in the ring, a substituted or unsubstituted heteroaryl group with 3-60 carbon atoms in the ring, a substituted or unsubstituted alkane with 1-20 carbon atoms group, or a substituted or unsubstituted alkoxy group with 1-20 carbon atoms; one of Ar ¹ ' and Ar ² ' is a substituted or unsubstituted condensed ring group with 10-60 carbon atoms , or a substituted or unsubstituted monoheterofused ring group with 3-60 carbon atoms in the ring;

^L1 and ^L2 are each independently a single bond, a substituted or unsubstituted arylene group with 6-60 carbon atoms in the ring, a substituted or unsubstituted heteroarylene group with 3-60 carbon atoms in the ring , or substituted or unsubstituted fluorenylene;

R' and R" are independently hydrogen atom, substituted or unsubstituted aryl group with 6-60 carbon atoms in the ring, substituted or unsubstituted heteroaryl group with 3-60 carbon atoms in the ring, substituted or an unsubstituted alkyl group with 1-20 carbon atoms, or a substituted or unsubstituted alkoxy group with 1-20 carbon atoms, R' and R" can be the same or different).

The present invention also provides a material for an organic EL element formed from the above nitrogen-containing heterocyclic derivative.

The present invention further provides an organic EL element having at least one organic compound layer including a light-emitting layer sandwiched between a pair of electrodes, wherein at least one of the organic compound layers contains the nitrogen-containing heterocycle of the present invention. derivative.

The best way to practice the invention

The nitrogen-containing heterocyclic derivative of the present invention (hereinafter may be referred to as the compound of the present invention) is represented by any of the above general formulas (1), (1')-(3').

First, the nitrogen-containing heterocyclic derivative represented by the general formula (1) of the present invention will be described.

In the general formula (1), HAr is a nitrogen-containing heterocyclic group having 3 to 40 carbon atoms which may have a substituent. The nitrogen-containing heterocyclic group with 3-40 carbon atoms is not particularly limited, as long as it is a cyclic group containing at least one nitrogen atom as a constituent element of the ring, it can be a monocyclic group or a polycyclic group. A polycyclic group formed by fused rings. For example, pyridine, pyrimidine, pyrazine, pyridazine, triazine, quinoline, quinoxaline, acridine, imidazo[1,2-a]pyridine, imidazo[1,2-a]pyrimidine and the like. Substituents of the nitrogen-containing heterocyclic group include groups corresponding to R ¹ -R ¹⁰² in Ar ¹ described later.

Preferably HAr is selected from general formulas (2)-(36):

In the general formula (2)-(36), the carbon atoms in each heterocyclic ring can be combined with an aryl group with a carbon number of 6-60 that may have a substituent, a heteroaryl group with a carbon number of 3-60 that may have a substituent group, an alkyl group with 1-20 carbon atoms that may have a substituent, or an alkoxy group with a carbon number of 1-20 that may have a substituent, and when there are multiple bonding groups, the The bonding groups may be the same or different from each other.

In the above general formulas (8)-(36), the solid lines representing the bonding positions of HAr and L respectively run through all the rings constituting the polycyclic ring, which means that the bonding position of HAr and L can be any position of the polycyclic ring of HAr .

基、芘基、联苯基、三联苯基、甲苯基、叔丁基苯基、(2-苯基丙基)苯基、荧蒽基、芴基、含有螺二芴的1价基团、全氟苯基、全氟萘基、全氟蒽基、全氟联苯基、含有9-苯基蒽的1价基团、含有9-(1’-萘基)蒽的1价基团、含有9-(2’-萘基)蒽的1价基团、含有6-苯基

的1价基团、含有9-[4-(二苯基氨基)苯基]蒽的1价基团等，优选苯基、萘基、联苯基、三联苯基、9-(10-苯基)蒽基、9-[10-(1’-萘基)]蒽基、9-[10-(2’-萘基)]蒽基等。The aryl group with 6-60 carbon atoms is preferably an aryl group with 6-40 carbon atoms, more preferably an aryl group with 6-20 carbon atoms, specifically: phenyl, naphthyl, anthracenyl, phenanthrenyl, naphthacene base,

Base, pyrenyl, biphenyl, terphenyl, tolyl, tert-butylphenyl, (2-phenylpropyl)phenyl, fluoranthene, fluorenyl, monovalent groups containing spirobifluorene, Perfluorophenyl, perfluoronaphthyl, perfluoroanthracenyl, perfluorobiphenyl, monovalent groups containing 9-phenylanthracene, monovalent groups containing 9-(1'-naphthyl)anthracene, Monovalent group containing 9-(2'-naphthyl)anthracene, containing 6-phenyl

1-valent groups, 1-valent groups containing 9-[4-(diphenylamino)phenyl]anthracene, etc., preferably phenyl, naphthyl, biphenyl, terphenyl, 9-(10-benzene base) anthracenyl, 9-[10-(1'-naphthyl)]anthracenyl, 9-[10-(2'-naphthyl)]anthracenyl, etc.

The heteroaryl group with 3-60 carbon atoms is preferably a heteroaryl group with 3-40 carbon atoms, more preferably a heteroaryl group with 3-20 carbon atoms, specifically: pyrrolyl, furyl, thienyl, Silolyl (silolyl), pyridyl, quinolinyl, isoquinolyl, benzofuryl, imidazolyl, pyrimidinyl, carbazolyl, phenylselenyl, oxadiazolyl, triazolyl, etc., preferably pyridine base, quinolinyl, isoquinolyl.

An alkyl group with 1-20 carbon atoms is preferably an alkyl group with 1-6 carbon atoms, specifically methyl, ethyl, propyl, butyl, pentyl, hexyl, etc., and an alkyl group with 3 or more carbon atoms The group may be a linear, cyclic or branched alkyl group.

An alkoxy group with 1-20 carbon atoms is preferably an alkoxy group with 1-6 carbon atoms, specifically methoxy, ethoxy, propoxy, butoxy, pentyloxy, hexyloxy, etc. , the alkyl group having 3 or more carbon atoms may be a linear, cyclic, or branched alkyl group.

More preferably HAr is selected from the following formulae:

In the general formula (1), L is a single bond, an arylene group having 6 to 60 carbon atoms which may have a substituent, a heteroarylene group having 3 to 60 carbon atoms which may have a substituent, or an arylene group which may have a substituent The fluorenylene group.

The arylene group with a carbon number of 6-60 is preferably an arylene group with a carbon number of 6-40, and more preferably an arylene group with a carbon number of 6-20, specifically: A divalent group formed by removing a hydrogen atom from an aryl group.

The heteroarylene group with 3-60 carbon atoms is preferably a heteroarylene group with 3-40 carbon atoms, more preferably a heteroarylene group with 3-20 carbon atoms, specifically: from the above-mentioned bonding group A divalent group formed by removing one hydrogen atom from the heteroaryl group described in the group.

The substituents of the above-mentioned arylene group with 6-60 carbon atoms or heteroarylene group with 6-60 carbon atoms include: halogen atoms, alkyl groups with 1-20 carbon atoms that may have substituents, and may have An alkoxy group with 1 to 20 carbon atoms in the substituent, an aryloxy group with 6 to 40 carbon atoms that may have a substituent, an aryl group with 6 to 40 carbon atoms that may have a substituent, or an optional substituent A heteroaryl group having 3 to 40 carbon atoms, etc.

L is also preferably selected from the following formulae:

In the general formula (1), Ar ¹ is a divalent aromatic hydrocarbon group having 6 to 60 carbon atoms which may have a substituent. The divalent aromatic hydrocarbon group with 6-60 carbon atoms is preferably a group with 6-40 carbon atoms, more preferably a group with 6-20 carbon atoms, specifically: the specific examples of the aryl group from the above-mentioned HAr A divalent group obtained by further removing a hydrogen atom from the compound.

Particularly preferred Ar ¹ may be a group represented by any of the following general formulas (43) to (54).

In the formula, R ¹ -R ¹⁰² are each independently, and may be combined with a halogen atom, an alkyl group with 1-20 carbon atoms that may have a substituent, an alkoxy group with 1-20 carbon atoms that may have a substituent, and may have An aryloxy group having 6 to 40 carbon atoms in the substituent, a diarylamino group having 12 to 80 carbon atoms that may have a substituent, an aryl group having 6 to 40 carbon atoms that may have a substituent, and a substituent The bonding group of a heteroaryl group with 3-40 carbon atoms or a diarylaminoaryl group with 18-120 carbon atoms that may have a substituent, when there are multiple bonding groups, the bonding The groups can be the same or different from each other;

L' is a single bond, or selected from

group.

In the general formula (1), Ar ² is an optionally substituted aryl group having 6 to 60 carbon atoms or an optionally substituted heteroaryl group having 3 to 60 carbon atoms.

The aryl group having 6 to 60 carbon atoms and the heteroaryl group having 3 to 60 carbon atoms are the same as those described above for the bonding group, and the substituents of these groups include: halogen atoms, carbon atoms that may have substituents Alkyl group having 1 to 20 atoms, alkoxy group having 1 to 20 carbon atoms which may have substituent, aryloxy group having 6 to 40 carbon atoms which may have substituent, 6 carbon atoms which may have substituent An aryl group having -40 or a heteroaryl group having 3 to 40 carbon atoms which may have a substituent, and the preferred substituent is an alkyl group having 1 to 6 carbon atoms. Preferably, the aforementioned arylene group having 6 to 60 carbon atoms or heteroarylene group having 3 to 60 carbon atoms is unsubstituted.

Preferably Ar ² is selected from

Groups, more preferably selected from

group.

In the above general formula (1), the nitrogen-containing heterocyclic derivatives of ① are preferred, wherein L is an arylene group with 6-60 carbon atoms that may have a substituent, and an arylene group with 3-60 carbon atoms that may have a substituent. A heteroaryl group or a fluorenylene group that may have a substituent, Ar ¹ is a divalent condensed aromatic hydrocarbon group with 10-60 carbon atoms that may have a substituent; or the nitrogen-containing heterocyclic derivative of ②, wherein L is a single Bond, Ar ¹ is a divalent condensed aromatic hydrocarbon group with 11-60 carbon atoms which may have substituents.

In the case of ① above, Ar ^is preferably any group selected from the fused ring groups shown in the following general formulas (37)-(42):

In the formula, each condensed ring may be combined with a halogen atom, an alkyl group with 1-20 carbon atoms that may have a substituent, an alkoxy group with 1-20 carbon atoms that may have a substituent, a carbon atom that may have a substituent A bonding group of an aryloxy group having 6 to 40 carbon atoms, an aryl group having 6 to 40 carbon atoms which may have a substituent, or a heteroaryl group having 3 to 40 carbon atoms which may have a substituent. When there are multiple bonding groups, the bonding groups can be the same or different;

L' is a single bond or selected from

group.

Halogen atoms include fluorine, chlorine, bromine, and iodine.

An alkyl group with 1-20 carbon atoms is preferably an alkyl group with 1-6 carbon atoms, specifically methyl, ethyl, propyl, butyl, pentyl, hexyl, etc., and an alkyl group with 3 or more carbon atoms The group is a linear, cyclic or branched alkyl group.

An alkoxy group with 1-20 carbon atoms is preferably an alkoxy group with 1-6 carbon atoms, specifically: methoxy, ethoxy, propoxy, butoxy, pentyloxy, hexyloxy etc., the alkoxy group having 3 or more carbon atoms is a linear, cyclic or branched alkoxy group.

The aryloxy group with 6-40 carbon atoms is preferably an aryloxy group with 6-20 carbon atoms, specifically phenoxy, biphenyloxy and the like.

The aryl group having 6 to 40 carbon atoms and the heteroaryl group having 3 to 40 carbon atoms are the same as those described above for the bonding group.

The substituents of these groups include: a halogen atom, an alkyl group with 1 to 20 carbon atoms that may have a substituent, an alkoxy group with 1 to 20 carbon atoms that may have a substituent, and a carbon number with 1 to 20 carbon atoms that may have a substituent. 6-40 aryloxy group, optionally substituted aryl group having 6-40 carbon atoms, or optionally substituted heteroaryl group having 3-40 carbon atoms, and the like.

In the case of ② above, Ar ^is preferably any group selected from the condensed ring groups shown in the following general formulas (37)-(41):

In the formula, each condensed ring may be combined with a halogen atom, an alkyl group with 1-20 carbon atoms that may have a substituent, an alkoxy group with 1-20 carbon atoms that may have a substituent, a carbon atom that may have a substituent A bonding group of an aryloxy group having 6 to 40 carbon atoms, an aryl group having 6 to 40 carbon atoms which may have a substituent, or a heteroaryl group having 3 to 40 carbon atoms which may have a substituent. When there are plural bonding groups, the bonding groups may be the same as or different from each other. L' is the same as above.

The preferred number of carbon atoms, specific examples, and substituents of these groups are the same as in the case of ①.

The nitrogen-containing heterocyclic derivative represented by the general formula (1) of the present invention can be produced by a known method.

For example, HAr-L-Ar ¹ -X or HAr-LX can be prepared by Suzuki reaction with (HO) ₂ B-Ar ² or (HO) ₂ B-Ar ¹ -Ar ² .

Specific examples of the nitrogen-containing heterocyclic derivatives represented by the general formula (1) of the present invention are as follows, but the present invention is not limited to these exemplified compounds.

HAr-L-Ar ¹ -Ar ²

HAr-Ar ¹ -Ar ²

Among the above specific examples, (1-1), (1-3), (1-4), (1-10), (1-11), (2-3), (2-4), (3-3), (3-4), (3-10), (3-11), (4-3), (4-4), (5-11), (5-4), (5 -18), (8-4), (9-11), (10-18), (13-11), (13-14), (13-15), (13-16), (14-1 ), (14-2), (14-6), (14-7), (14-9), (15-1), (15-3), (15-4), (15-5), (16-3), (19-1), (19-5), (26-8).

Next, nitrogen-containing heterocyclic derivatives represented by the general formulas (1') to (3') of the present invention will be described.

In the general formula (1'), A ¹ -A ³ are each independently a nitrogen atom or a carbon atom.

In the general formula (1'), Ar ¹ ' is an aryl group with 6-60 carbon atoms in the ring (preferably 6-40 carbon atoms in the ring), or a substituted or unsubstituted ring A heteroaryl group having 3-60 carbon atoms (preferably 3-40 carbon atoms in the ring).

基、2-

基、6-

基、1-芘基、2-芘基、4-芘基、2-联苯基、3-联苯基、4-联苯基、对三联苯-4-基、对三联苯-3-基、对三联苯-2-基、间三联苯-4-基、间三联苯-3-基、间三联苯-2-基、邻甲苯基、间甲苯基、对甲苯基、对叔丁基苯基、对(2-苯基丙基)苯基、3-甲基-2-萘基、4-甲基-1-萘基、4-甲基-1-蒽基、4’-甲基联苯基、4”-叔丁基-对三联苯-4-基、荧蒽基、芴基、含有螺二芴的1价基团、全氟苯基、全氟萘基、全氟蒽基、全氟联苯基、含有9-苯基蒽的1价基团、含有9-(1’-萘基)蒽的1价基团、含有9-(2’-萘基)蒽的1价基团、含有6-苯基

的1价基团、含有9-[4-(二苯基氨基)苯基]蒽的1价基团等，优选苯基、萘基、联苯基、三联苯基、9-(10-苯基)蒽基、9-[10-(1’-萘基)]蒽基、9-[10-(2’-萘基)]蒽基等。Examples of substituted or unsubstituted aryl groups of Ar ¹ ' are preferred: phenyl, 1-naphthyl, 2-naphthyl, 1-anthracenyl, 2-anthracenyl, 9-anthracenyl, 1-phenanthrenyl, 2- phenanthrenyl, 3-phenanthrenyl, 4-phenanthrenyl, 9-phenanthrenyl, 1-naphthalenyl, 2-naphthalenyl, 9-naphthalenyl, 1-

Base, 2-

Base, 6-

Base, 1-pyrenyl, 2-pyrenyl, 4-pyrenyl, 2-biphenyl, 3-biphenyl, 4-biphenyl, p-terphenyl-4-yl, p-terphenyl-3-yl , p-terphenyl-2-yl, m-terphenyl-4-yl, m-terphenyl-3-yl, m-terphenyl-2-yl, o-tolyl, m-tolyl, p-tolyl, p-tert-butylbenzene Base, p-(2-phenylpropyl)phenyl, 3-methyl-2-naphthyl, 4-methyl-1-naphthyl, 4-methyl-1-anthracenyl, 4'-methylbi Phenyl, 4"-tert-butyl-p-terphenyl-4-yl, fluoranthenyl, fluorenyl, monovalent group containing spirobifluorene, perfluorophenyl, perfluoronaphthyl, perfluoroanthracenyl, Perfluorobiphenyl, monovalent group containing 9-phenylanthracene, monovalent group containing 9-(1'-naphthyl)anthracene, monovalent group containing 9-(2'-naphthyl)anthracene group, containing 6-phenyl

1-valent groups, 1-valent groups containing 9-[4-(diphenylamino)phenyl]anthracene, etc., preferably phenyl, naphthyl, biphenyl, terphenyl, 9-(10-benzene base) anthracenyl, 9-[10-(1'-naphthyl)]anthracenyl, 9-[10-(2'-naphthyl)]anthracenyl, etc.

Examples of substituted or unsubstituted heteroaryl groups of Ar ¹ ' are preferred: pyrrolyl, furyl, thienyl, thialyl, pyridyl, quinolinyl, isoquinolyl, benzofuryl, imidazolyl, pyrimidine Carbazolyl, phenylselenyl, oxadiazolyl, triazolyl, etc., preferably pyridyl, quinolinyl, isoquinolyl.

In general formula (1'), Ar ² ' is a hydrogen atom, a substituted or unsubstituted aryl group with 6-60 carbon atoms in the ring (preferably 6-40 carbon atoms in the ring), substituted or unsubstituted Heteroaryl with 3-60 carbon atoms in the ring (preferably 3-40 carbon atoms in the ring), substituted or unsubstituted alkane with 1-20 carbon atoms (preferably 1-6 carbon atoms) group, or a substituted or unsubstituted alkoxy group having 1-20 carbon atoms (preferably 1-6 carbon atoms).

Examples of the substituted or unsubstituted aryl group for Ar ² ' include the same aryl groups as those for Ar ¹ ' above.

Examples of the substituted or unsubstituted heteroaryl group for Ar ² ' include the same aryl groups as those for Ar ¹ ' above.

Examples of substituted or unsubstituted alkyl groups for Ar ² ' are: methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, n-pentyl, n-hexyl , n-heptyl, n-octyl, hydroxymethyl, 1-hydroxyethyl, 2-hydroxyethyl, 2-hydroxyisobutyl, 1,2-dihydroxyethyl, 1,3-dihydroxyisopropyl , 2,3-dihydroxy tert-butyl, 1,2,3-trihydroxypropyl, chloromethyl, 1-chloroethyl, 2-chloroethyl, 2-chloroisobutyl, 1,2-di Chloroethyl, 1,3-dichloroisopropyl, 2,3-dichloro-tert-butyl, 1,2,3-trichloropropyl, bromomethyl, 1-bromoethyl, 2-bromoethyl , 2-bromoisobutyl, 1,2-dibromoethyl, 1,3-dibromoisopropyl, 2,3-dibromo-tert-butyl, 1,2,3-tribromopropyl, iodine Methyl, 1-iodoethyl, 2-iodoethyl, 2-iodoisobutyl, 1,2-diiodoethyl, 1,3-diiodoisopropyl, 2,3-diiodo-tert-butyl , 1,2,3-triiodopropyl, aminomethyl, 1-aminoethyl, 2-aminoethyl, 2-aminoisobutyl, 1,2-diaminoethyl, 1,3-diamino Isopropyl, 2,3-diaminotert-butyl, 1,2,3-triaminopropyl, cyanomethyl, 1-cyanoethyl, 2-cyanoethyl, 2-cyanoisobutyl Base, 1,2-dicyanoethyl, 1,3-dicyanoisopropyl, 2,3-dicyano-tert-butyl, 1,2,3-tricyanopropyl, nitromethyl Base, 1-nitroethyl, 2-nitroethyl, 2-nitroisobutyl, 1,2-dinitroethyl, 1,3-dinitroisopropyl, 2,3-di Nitro-tert-butyl, 1,2,3-trinitropropyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, 4-methylcyclohexyl, 1-adamantyl, 2-adamantyl Alkyl, 1-norbornyl, 2-norbornyl, etc., preferably methyl, ethyl, tert-butyl.

The substituted or unsubstituted alkoxy group of Ar ² ' is a group represented by -OY. Examples of Y include: methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, isobutyl , tert-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, hydroxymethyl, 1-hydroxyethyl, 2-hydroxyethyl, 2-hydroxyisobutyl, 1,2-dihydroxyethyl Base, 1,3-dihydroxyisopropyl, 2,3-dihydroxy-tert-butyl, 1,2,3-trihydroxypropyl, chloromethyl, 1-chloroethyl, 2-chloroethyl, 2 -Chloroisobutyl, 1,2-dichloroethyl, 1,3-dichloroisopropyl, 2,3-dichloro-tert-butyl, 1,2,3-trichloropropyl, bromomethyl , 1-bromoethyl, 2-bromoethyl, 2-bromoisobutyl, 1,2-dibromoethyl, 1,3-dibromoisopropyl, 2,3-dibromo-tert-butyl, 1,2,3-Tribromopropyl, iodomethyl, 1-iodoethyl, 2-iodoethyl, 2-iodoisobutyl, 1,2-diiodoethyl, 1,3-diiodoiso Propyl, 2,3-diiodo-tert-butyl, 1,2,3-triiodopropyl, aminomethyl, 1-aminoethyl, 2-aminoethyl, 2-aminoisobutyl, 1,2 -Diaminoethyl, 1,3-diaminoisopropyl, 2,3-diamino-tert-butyl, 1,2,3-triaminopropyl, cyanomethyl, 1-cyanoethyl, 2-cyanoethyl, 2-cyanoisobutyl, 1,2-dicyanoethyl, 1,3-dicyanoisopropyl, 2,3-dicyano-tert-butyl, 1,2 , 3-tricyanopropyl, nitromethyl, 1-nitroethyl, 2-nitroethyl, 2-nitroisobutyl, 1,2-dinitroethyl, 1,3- Dinitroisopropyl, 2,3-dinitro-tert-butyl, 1,2,3-trinitropropyl, etc., preferably methyl, ethyl, or tert-butyl.

In the general formula (1'), any one of Ar ¹ ' and Ar ² ' is a fused ring group with 10-60 carbon atoms in a substituted or unsubstituted ring, or a substituted or unsubstituted ring with carbon atoms of 3-60 monoheterofused ring group.

L ¹ and L ² of the general formula (1′) are each independently a single bond, a substituted or unsubstituted arylene group with 6-60 carbon atoms in the ring (preferably 6-40 carbon atoms in the ring), A substituted or unsubstituted heteroarylene group having 3-60 carbon atoms in the ring (preferably having 3-40 carbon atoms in the ring), or a substituted or unsubstituted fluorenylene group.

Examples of substituted or unsubstituted arylene groups for L ¹ and L ² include divalent groups obtained by removing a hydrogen atom from the same aryl group as Ar ¹ ' above.

Examples of substituted or unsubstituted heteroarylene groups for L ¹ and L ² include divalent groups obtained by removing a hydrogen atom from the same heteroaryl group as Ar ¹ ' above.

In general formula (1'), preferably L ¹ and/or L ² are selected from

group. The same applies to the following general formulas (2')-(3').

In the general formula (1'), it is preferable that Ar ¹ ' is a group represented by any of the following general formulas (4') to (13'). The same applies to the following general formulas (2')-(3').

(wherein, R ¹ 'R ⁹² ' are each independently a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group with 1-20 carbon atoms, a substituted or unsubstituted alkane with 1-20 carbon atoms Oxygen, substituted or unsubstituted aryloxy with 6-40 carbon atoms in the ring, substituted or unsubstituted diarylamino with 12-80 carbon atoms in the ring, substituted or unsubstituted ring carbon Aryl with 6-40 atoms, substituted or unsubstituted heteroaryl with 3-40 carbon atoms in the ring, or diarylaminoaryl with 18-120 carbon atoms in the substituted or unsubstituted ring base; L ³ is a single bond and is selected from the following formula:

group).

R in the general formula (1') is a hydrogen atom, an aryl group with 6-60 carbon atoms in a substituted or unsubstituted ring, a heteroaryl group with 3-60 carbon atoms in a substituted or unsubstituted ring, a substituted Or an unsubstituted alkyl group with 1-20 carbon atoms, or a substituted or unsubstituted alkoxy group with 1-20 carbon atoms.

Examples of the substituted or unsubstituted aryl group for R are the same as the above Ar ¹ ′.

Examples of the substituted or unsubstituted heteroaryl group for R are the same as the above-mentioned Ar ¹ ′.

Examples of the substituted or unsubstituted alkyl group for R are the same as the above-mentioned Ar ² ′.

Examples of the substituted or unsubstituted alkoxy group for R are the same as the above-mentioned Ar ² ′.

n is an integer of 0-5, preferably 0-3, when n is more than 2, a plurality of R groups can be the same or different, in addition, a plurality of adjacent R groups can be combined with each other to form a carbocyclic alicyclic ring or Carbocyclic aromatic ring.

Carbocyclic alicyclic rings include rings such as cyclopentane and cyclohexane.

Carbocyclic aromatic rings include rings such as benzene, naphthalene, phenanthrene, and anthracene.

In the general formula (2'), A ¹ -A ³ are each independent, the same as above.

In the general formula (2'), Ar ¹ ' and Ar ² ' are independently independent, and the same as above, any one of Ar ¹ ' and Ar ² ' is a fused ring with 10-60 carbon atoms in a substituted or unsubstituted ring group, or a substituted or unsubstituted monoheterocondensed ring group with 3-60 carbon atoms in the ring.

In the general formula (2'), L ¹ and L ² are each independent, as described above.

In the general formula (2'), R' is the same as R in the general formula (1').

In the general formula (3'), A ¹ -A ² are each independent, the same as above.

In the general formula (3'), Ar ¹ ' and Ar ² ' are independent, and the same as above, any one of Ar ¹ ' and Ar ² ' is a fused ring with 10-60 carbon atoms in a substituted or unsubstituted ring group, or a substituted or unsubstituted monoheterocondensed ring group with 3-60 carbon atoms in the ring.

In the general formula (3'), L ¹ and L ² are each independent, as described above.

In the general formula (3'), R' and R" are each independent, and like R in the general formula (1'), R' and R" may be the same or different.

Specific examples of nitrogen-containing heterocyclic derivatives represented by the general formulas (1') to (3') of the present invention are shown below, but are not limited to these examples.

In the following table, "\" indicates a single key.

(基础骨架)

(basic skeleton)

(基础骨架)

(basic skeleton)

(基础骨架)

(basic skeleton)

(basic skeleton)

The nitrogen-containing heterocyclic derivatives represented by any of these general formulas (1), (1')-(3') have high electron injection and transport properties, and are preferably used as organic EL element materials.

By using the compound of the present invention in at least one layer of the organic compound layer in the organic EL element, higher luminance and high-efficiency light emission than before can be obtained, and the adhesion between the organic compound layer and the electrode can be improved, and long-term stability can be achieved. Therefore, The life of the organic EL element can be extended.

The compounds of the present invention are preferably used in the light-emitting band region, light-emitting layer and/or electron-transport layer of organic EL elements. Particular preference is given to using the compounds according to the invention as electron-injecting and/or electron-transporting materials. It is also preferred that the layer containing the electron injection material and/or the electron transport material contains a reducing dopant.

Here, the light-emitting region refers to the entire portion including a light-emitting material that emits light when an electric field is applied to the organic EL element. At present, organic EL elements generally have a structure in which thin films are laminated. The thin films are formed of materials with different functions and roles. Most of the light-emitting materials are contained only in the organic thin film layer called the light-emitting layer. In this case, the light-emitting layer corresponds to a light-emitting band. The light emitting layer, electron transport layer, and electron injection material will be described later.

Next, the device configuration of the organic EL device of the present invention will be described.

The organic EL element of the present invention has at least one organic compound layer including a light-emitting layer sandwiched between a pair of electrodes, and is characterized in that at least one of the organic compound layers contains the above-mentioned general formula (1) of the present invention, A nitrogen-containing heterocyclic derivative represented by any of the formulas (1')-(3').

A representative element composition of the organic EL element of the present invention has the following structure:

(1) anode/luminescent layer/cathode

(2) Anode/hole injection layer/luminescent layer/cathode

(3) anode/luminescent layer/electron injection layer/cathode

(4) Anode/hole injection layer/light emitting layer/electron injection layer/cathode

(5) anode/organic semiconductor layer/light-emitting layer/cathode

(6) anode/organic semiconductor layer/electron blocking layer/light-emitting layer/cathode

(7) Anode/organic semiconductor layer/emissive layer/improved adhesion layer/cathode

(8) Anode/hole injection layer/hole transport layer/light emitting layer/electron injection layer/cathode

(9) anode/insulating layer/luminescent layer/insulating layer/cathode

(10) Anode/inorganic semiconductor layer/insulating layer/luminescent layer/insulating layer/cathode

(11) Anode/organic semiconductor layer/insulating layer/luminescent layer/insulating layer/cathode

(12) Anode / insulating layer / hole injection layer / hole transport layer / light emitting layer / insulating layer / cathode

(13) Anode/insulating layer/hole injection layer/hole transport layer/light emitting layer/electron injection layer/cathode, etc.

Among them, the configuration of (8) is usually preferably used, but of course, it is not limited to these.

In the organic EL device of the present invention, it is preferable to use the compound of the present invention as a material constituting the light emitting layer and/or the electron injection layer. In the element constitution, a hole injection layer or an electron injection layer is not essential, but an element having these layers has an advantage that light emitting performance is improved. In addition, the above-mentioned hole injection layer, light emitting layer, and electron injection layer may be sandwiched between a pair of electrodes in a mixed form. In order to stabilize each component, a binder such as a polymer compound may be used to form a mixed layer.

Here, the organic EL device of the present invention will be described by taking the anode/hole injection layer/light emitting layer/electron injection layer/cathode type as an example. The organic EL element of the present invention is preferably supported by a substrate. The substrate is not particularly limited, and may be a substrate commonly used in organic EL elements, for example, a substrate made of glass, transparent plastic, quartz, or the like. Regarding the light transmittance thereof, a substrate having a light transmittance of 50% or more in the visible region of 400 to 700 nm is preferable, and a smooth substrate is more preferably used.

As the anode in this organic EL element, it is preferable to use a metal, an alloy, a conductive compound, or a mixture thereof as an electrode substance having a large work function (4 eV or more). Specific examples of the electrode substance include metals such as Au, conductive transparent materials such as CuI, ITO, SnO ₂ , and ZnO. The anode can be produced by forming a thin film of these electrode substances by methods such as vapor deposition or sputtering. When light is emitted from the anode side, the transmittance is preferably greater than 10%, and the sheet resistance of the electrode is preferably several hundred Ω/□ or less. In addition, the film thickness of the anode varies depending on the material, but is usually selected within the range of 10 nm to 1 μm, preferably 10 to 200 nm.

As the cathode, metals, alloys, conductive compounds and mixtures thereof having a small work function (4 eV or less) are preferably used as electrode substances. Specific examples of the electrode substance include sodium, sodium-potassium alloy, magnesium, magnesium-silver alloy, lithium, magnesium/copper mixture, magnesium-indium alloy, Al/Al ₂ O ₃ , indium, aluminum-lithium alloy, and the like. The cathode can be produced by forming a thin film of these electrode substances by methods such as vapor deposition or sputtering. The sheet resistance of the electrode is preferably several hundred Ω/□ or less. The film thickness can usually be selected within the range of 10nm-500nm, preferably 50-200nm. In order to transmit luminescence, it is preferable that either the anode or the cathode of the organic EL element be transparent or semitransparent, since the luminous efficiency is improved.

In the organic EL device of the present invention, a chalcogenide layer, a metal halide layer, or a metal oxide layer (hereinafter referred to as a surface layer) is preferably disposed on at least one surface of the pair of electrodes produced as above. Specifically, a chalcogenide (including oxide) layer of metals such as silicon and aluminum may be disposed on the anode surface on the light emitting layer side, and a metal halide layer or metal oxide layer may be disposed on the cathode surface on the light emitting layer side. Stability of the drive can thus be achieved.

Preferred examples of the above-mentioned chalcogenides include: SiOx (1≤X≤2), AlOx (1≤X≤1.5), SiON, SiAlON, etc. Preferred examples of metal halides include: LiF, MgF ₂ , CaF ₂ , fluoride Preferable examples of rare earth metals and metal oxides include Cs ₂ O, Li ₂ O, MgO, SrO, BaO, CaO, and the like.

In the organic EL device of the present invention, it is preferable that a mixed region of an electron injection/transport material and a reducing dopant or a hole injection/transport material and an oxidative dopant be disposed on at least one surface of the pair of electrodes produced as above. mixed zone. In this way, the electron injection/transport material is reduced to an anion, and the mixed region is more likely to inject and transfer electrons to the light emitting layer. In addition, the hole injecting/transporting material is oxidized into cations, and the mixed region is more likely to inject and transport holes into the light emitting layer. Preferred oxidative dopants include various Lewis acids, acceptor compounds. Preferred reducing dopants are those mentioned above.

In the organic EL element of the present invention, the light-emitting layer has:

①Injection function: When an electric field is applied, holes can be injected from the anode or hole injection layer, and electrons can be injected from the cathode or electron injection layer

②Transport function: The function of moving the injected charge (electron or hole) by the force of the electric field

③Light-emitting function: It provides a place for electrons and holes to recombine and connects it with light emission.

苝骨架的稠环发光物质，含有约8个稠环的其他稠环发光物质等。具体来说，可以使用1，1，4，4-四苯基-1，3-丁二烯、4，4’-(2，2-二苯基乙烯基)联苯等。该发光层可以由含有1种或多种这些发光材料的1层构成，或者层合含有与该发光层不同的化合物的发光层。As the light-emitting material constituting the light-emitting layer in the organic EL device of the present invention, the compound of the present invention described above is preferably used. When using the compound of the present invention as a luminescent material, the compound of the present invention may be used alone or in combination with a known luminescent material. When the compound of the present invention is used in a light-emitting layer other than the light-emitting layer, the light-emitting material of the light-emitting layer is not particularly limited, and any material can be selected from conventionally known light-emitting materials. Such luminescent materials can be used, for example, polycyclic fused aromatic compounds, fluorescent whitening agents such as benzoxazole series, benzothiazole series, and benzimidazole series, metal chelated oxanoid compounds, and distyrylbenzene series compounds. And other good film-forming compounds. Here, the above-mentioned polycyclic condensed aromatic compounds include, for example: anthracene, naphthalene, phenanthrene, pyrene,

Condensed-ring luminescent substances with a perylene skeleton, other fused-ring luminescent substances containing about 8 fused rings, etc. Specifically, 1,1,4,4-tetraphenyl-1,3-butadiene, 4,4'-(2,2-diphenylvinyl)biphenyl, and the like can be used. The light-emitting layer may be composed of a single layer containing one or more of these light-emitting materials, or a light-emitting layer containing a compound different from that of the light-emitting layer may be laminated.

As a method for forming the light emitting layer, known methods such as vapor deposition, spin coating, and LB method can be used, for example. The light-emitting layer is particularly preferably a molecular deposition film. Here, the molecular stacking film is a thin film formed by deposition of a material compound in a gas phase state, or a thin film formed by solidification of a material compound in a solution state or a liquid phase state. Usually, the molecular stacking film can be formed by different condensation structures, higher-order structures, or the resulting The resulting difference in function distinguishes it from thin films (molecular accumulation films) formed by the LB method.

As disclosed in Japanese Patent Application Laid-Open No. 57-51781, the light-emitting layer can also be formed by dissolving a binder such as a resin and a material compound in a solvent to make a solution, and then forming a thin film by spin coating or the like. .

The hole injection layer in the organic EL element of the present invention contains a hole transport compound and has the function of transporting holes injected from the anode to the light emitting layer. By placing the hole injection layer between the anode and the light emitting layer, more A low electric field will also cause a lot of holes to be injected into the light-emitting layer. In addition, the electrons injected into the light-emitting layer from the cathode or the electron injection layer are blocked by the electrons existing at the interface between the light-emitting layer and the hole injection layer, and are accumulated in the interface in the light-emitting layer, so that an element with excellent light-emitting performance such as improved luminous efficiency can be obtained. The hole transport compound used in the hole injection layer is a compound that is placed between two electrodes to which an electric field is applied, and when holes are injected from the anode, can properly transport holes to the light-emitting layer. For example, it is preferable to apply 10 ⁴ - A hole-transporting compound having a hole mobility of at least 10 ^-6 cm ² /V·sec in an electric field of 10 ⁶ V/cm. The hole-transporting compound is not particularly limited as long as it has the above-mentioned preferred properties, and it can be used from compounds commonly used as hole charge injection/transport materials in current photoconductive materials, or hole injection layers of organic EL devices. Selected and used from known compounds.

The above-mentioned hole transfer compounds include, for example: copper phthalocyanine, N,N,N',N'-tetraphenyl-4,4'-diaminophenyl, N,N'-diphenyl-N,N'- Bis(3-methylphenyl)-4,4'-diaminobiphenyl (TPDA), 2,2-bis(4-di-p-tolylaminophenyl)propane, 1,1-bis(4- Di-p-tolylaminophenyl)cyclohexane, N,N,N',N'-tetra-p-tolyl-4,4'-diaminobiphenyl, etc. Crystalline and amorphous materials of inorganic semiconductors such as Si, SiC, and CdS can also be used. The hole injection layer may consist of a single layer containing one or more of the above hole injection materials, or a hole injection layer containing a different compound from the above hole injection layer may be laminated.

When forming the hole injection/transport layer, the hole injection/transport material can be formed into a thin film by known methods such as vacuum evaporation, spin coating, casting, and LB method. At this time, the film thickness of the hole injection/transport layer is not particularly limited, but is usually 5 nm to 5 μm.

The electron injection layer in the organic EL device of the present invention contains an electron injection material and has a function of transferring electrons injected from the cathode to the light emitting layer. In the organic EL device of the present invention, it is preferable to use the above-mentioned compound of the present invention as an electron injection material. When the compound of the present invention is used other than the electron injection layer, the electron injection material is not particularly limited, and any compound can be selected from conventionally known electron injection material compounds for use.

A preferred embodiment of the organic EL element of the present invention is that an element containing a reducing dopant is present in the region for transporting electrons or the interface region between the cathode and the organic compound layer. In the present invention, an organic EL device in which a reducing dopant is contained in the compound of the present invention is preferable. Here, the reductive dopant is defined as a substance capable of reducing an electron-transporting compound. Therefore, any substance can be used as long as it has a certain reducing property. At least one of alkaline earth metal halides, rare earth metal oxides, rare earth metal halides, alkali metal organic complexes, alkaline earth metal organic complexes, and rare earth metal organic complexes.

Alkali metals include: Na (work function: 2.36eV), K (work function: 2.28eV), Rb (work function: 2.16eV), Cs (work function: 1.95eV), and the like.

Alkaline earth metals include: Ca (work function: 2.9eV), Sr (work function: 2.0-2.5eV), Ba (work function: 2.52eV) and the like.

Rare earth metals include: Sc, Y, Eu, Tb, Ce, etc.

Oxides of alkali metals include: Li ₂ O, LiO, NaO and the like.

Alkali metal halides: LiF, NaF, KF, LiCl, KCl, NaCl, etc.

Oxides of alkaline earth metals include: CaO, BaO, SrO, BeO, etc.

Halides of alkaline earth metals include fluorides such as CaF ₂ , BaF ₂ , SrF ₂ , MgF ₂ , BeF ₂ , and halides other than fluorides.

The preferred reductive dopant preferably has a work function below 2.9eV, and more specific examples include one or more selected from Na (work function: 2.36eV), K (work function: 2.28eV), Rb ( Work function: 2.16eV) and alkali metals of Cs (work function: 1.95eV), one or more selected from Ca (work function: 2.9eV), Sr (work function: 2.0-2.5eV) and Ba (work function : 2.52eV) alkaline earth metal. Among them, the more preferred reductive dopant is one or more alkali metals selected from K, Rb, and Cs, more preferably Rb or Cs, and most preferably Cs. The reduction ability of these alkali metals is particularly high, and adding a small amount to the electron injection region can improve the luminance of the organic EL element or increase the lifespan. It is preferable to combine two or more of the above-mentioned alkali metals as a reductive dopant with a work function of 2.9 eV or less, particularly preferably a combination containing Cs, such as Cs and Na, Cs and K, Cs and Rb, or Cs and Na and K. combination. By containing Cs in combination, the reduction ability can be effectively exhibited, and by adding to the electron injection region, it is possible to improve the luminance of the organic EL element or increase the lifespan. In addition, in addition to alkali metals, one or more metal compounds selected from alkali metal chalcogenides, alkaline earth metal chalcogenides, alkali metal halides, and alkaline earth metal halides can also be used to obtain the same Effect, the same effect can be obtained by using alkali metal organic complexes and alkaline earth metal organic complexes.

In the organic EL element of the present invention, an electron injection layer made of an insulator, a semiconductor, or an inorganic compound may be further provided between the cathode and the organic layer. By providing the electron injection layer, the current leakage can be effectively prevented and the electron injection property can be improved. The insulator preferably uses one or more metal compounds selected from the group consisting of alkali metal chalcogenides, alkaline earth metal chalcogenides, alkali metal halides, and alkaline earth metal halides. When the electron injection layer is composed of these metal compounds, the electron injection property can be further improved, which is preferable. Specifically, preferred alkali metal chalcogenides include, for example, Li ₂ O, LiO, Na ₂ S, Na ₂ Se, and NaO. Preferred alkaline earth metal chalcogenides are, for example: CaO, BaO, SrO, BeO, BaS and CaSe. Preferred alkali metal halides include, for example, LiF, NaF, KF, LiCl, KCl, NaCl and the like. Preferable alkaline earth metal halides include, for example, fluorides such as CaF ₂ , BaF ₂ , SrF ₂ , MgF ₂ , and BeF ₂ , or halides other than fluorides.

The semiconductors constituting the electron injection layer are: one or more kinds containing one or more kinds selected from Ba, Ca, Sr, Yb, Al, Ga, In, Li, Na, Cd, Mg, Si, Ta, Sb and Zn A combination of oxides, nitrides, or oxynitrides of elements. The inorganic compound constituting the electron injection layer is preferably a microcrystalline or amorphous insulating thin film. If the electron injection layer is composed of these inorganic compounds, a more uniform thin film can be formed, so pixel defects such as black spots can be reduced. The inorganic compounds include: the above-mentioned alkali metal chalcogenides, alkaline earth metal chalcogenides, alkali metal halides, alkaline earth metal halides, and the like.

The electron injection layer in the organic EL device of the present invention can be formed by forming a film from the compound of the present invention or other electron injection materials by known thin film forming methods such as vacuum evaporation, spin coating, casting, and LB. The film thickness of the electron injection layer is not particularly limited, but is usually 5 nm to 5 μm. The electron injection layer may be composed of a single layer containing one or more of the above-mentioned electron injection materials, or two or more electron injection layers containing other kinds of compounds may be laminated. Inorganic p-type-Si, p-type-SiC hole injection materials, n-type α-Si, n-type α-SiC electron injection materials can also be used as the electron injection material constituting the electron injection layer. Specific examples include inorganic semiconductors disclosed in International Patent Publication No. WO90/05998 and the like.

Next, a method for producing the organic EL element of the present invention will be described. As a preferable example, a method for producing the aforementioned anode/hole injection layer/light emitting layer/electron injection layer/cathode type organic EL element will be described. First, form a desired electrode substance, such as a thin film containing an anode substance, on a suitable substrate by methods such as evaporation or sputtering, and make the film thickness less than 1 μm, preferably in the range of 10-200 nm, to serve as the anode. Next, by forming a thin film containing each constituent material, a hole injection layer, a light emitting layer, and an electron injection layer, which are constituent elements of an EL element, are sequentially laminated on the anode. The thin film forming methods used here include the above-mentioned spin coating method, casting method, vapor deposition method, etc., and the vacuum vapor deposition method is preferable from the viewpoints that a uniform film is easily obtained and pinholes are not easily formed. When forming a thin film using a vacuum evaporation method, the evaporation conditions vary depending on the type of compound used, the crystal structure of the target molecular accumulation film, the association structure, etc., and it is usually preferable to use a channel heating temperature of 50-400°C in a vacuum. The temperature is 10 ^-6 -10 ^-3 Pa, the vapor deposition rate is 0.01-50nm/sec, the substrate temperature is -50 to 300°C, and the film thickness is 5nm-5μm. After forming these layers, for example, by evaporation or sputtering, a thin film containing cathode material with a film thickness of 1 μm or less, preferably in the range of 50-200 nm, can be formed on it as the cathode, so that the desired organic EL can be obtained. element. In the production of the organic EL element, the production order may be reversed, and the order of the cathode, the electron injection layer, the light emitting layer, the hole injection (transport) layer, and the anode may be produced.

In the fabrication of the above organic EL element, it is preferable to fabricate continuously from the anode to the cathode by vacuum suction once.

When a hole injection layer, a light emitting layer, and an electron injection layer are sandwiched between a pair of electrodes in a mixed form, the method of manufacturing an organic EL element of the anode/light emitting layer/cathode type may be, for example, by placing the Form a film containing an anode substance, and coat a solution containing a hole injection material, a luminescent material, an electron injection material, and a binder such as polyvinylcarbazole, polycarbonate, polyacrylate, polyester, and polyether, or A thin film can be formed from this solution by a dip coating method as a light-emitting layer (or light-emitting band), and a thin film containing a cathode substance can be formed thereon. Here, an element material as a material for the light emitting layer or the electron injection layer is vacuum-deposited on the produced light emitting layer, and then a thin film containing a cathode substance is formed thereon.

When a DC voltage is applied to the organic EL element obtained above, with the anode as + and the cathode as - polarity, and about 3-50 V is applied, light emission can be observed. Also, when a voltage is applied with the opposite polarity, there is no current and no light is emitted at all. When an AC voltage is applied, it emits light only when the anode is + and the cathode is -. The waveform of the applied alternating current may be arbitrary.

In the organic EL device of the present invention, the adhesion between the organic compound layer containing the compound of the present invention and the electrode (especially the cathode) can be improved by using the nitrogen-containing heterocyclic derivative of the present invention for the organic compound layer, especially the electron injection layer sex.

According to the organic EL element of the present invention prepared as described above, high luminance and high luminous efficiency can be realized.

Hereinafter, the present invention will be more specifically described through synthesis examples and examples, but the present invention is not limited by these examples.

Synthesis Example 1 : Synthesis of Compound (1-1)

(1) Synthesis of 3-anthracene-9-yl-1-phenyl-propenone

Dissolve 25g (0.12mol) of anthracene-9-carbaldehyde in 800ml of ethanol, add 15g (0.12mol) of acetophenone, 23g (0.12mol) of 28% sodium methoxide in methanol, and stir at room temperature for 4 hours. After the reaction, the precipitated solid was collected by filtration and washed with methanol to obtain 34.0 g of 3-anthracen-9-yl-1-phenyl-propenone (91% yield).

(2) Synthesis of 4-anthracene-9-yl-2,6-diphenyl-pyrimidine

20g (65mmol) of 3-anthracene-9-yl-1-phenyl-propenone obtained in (1) was dissolved in 200 ml of ethanol, and 10g (65mmol) of benzamidine hydrochloride, 5.4g (0.13mol) Sodium hydroxide, heated to reflux for 25 hours. After the reaction was finished, it was cooled to room temperature, and the precipitated crystals were collected by filtration, washed with water and methanol to obtain 19.1 g of 4-anthracene-9-yl-2,6-diphenyl-pyrimidine (yield 72%).

(3) Synthesis of 4-(10-bromo-anthracen-9-yl)-2,6-diphenyl-pyrimidine

19g (47mmol) of 4-anthracene-9-yl-2,6-diphenyl-pyrimidine obtained in (2) was dissolved in 200 ml of N,N-dimethylformamide, and 9.2g (52mmol) of N- Bromosuccinimide, stirred at room temperature for 8 hours. After the reaction, the precipitated solid was collected by filtration, washed with water and methanol to obtain 14.9 g of 4-(10-bromo-anthracen-9-yl)-2,6-diphenyl-pyrimidine (66% yield).

(4) Synthesis of 2,4-diphenyl-6-(10-phenyl-anthracene-9-yl)-pyrimidine (compound 1-1)

2.0g (4.1mmol) of 4-(10-bromo-anthracene-9-yl)-2,6-diphenyl-pyrimidine obtained in (3), 0.60g (4.9mmol) of phenylboronic acid, 0.10g of tetra (Triphenylphosphine) palladium was dissolved in 20 ml of 1,2-dimethoxyethane, 8 ml of 2.0 M sodium carbonate aqueous solution was added, and heated to reflux for 7 hours. After the reaction, the precipitated solid was dissolved in dichloromethane, washed with water, and dried over anhydrous sodium sulfate. The solvent was distilled off, and the obtained product was washed with methanol to obtain 1.8 g of a yellow-white solid (91% yield). When analyzed by mass spectrometry (MS), it was the target compound (Compound 1-1) with a molecular weight of 484.19 and m/e=484.

Synthesis Example 2 : Synthesis of 4-(10-naphthalene-1-yl-anthracene-9-yl)-2,6-diphenyl-pyrimidine (compound 1-3)

Except having used the corresponding boronic acid instead of phenylboronic acid, it carried out similarly to the said synthesis example 1, and obtained the target compound (compound 1-3).

(Compound 1-3) (yield 86%). According to mass spectrometry (MS) analysis, the molecular weight is 534.21, m/e=534.

Synthesis Example 3 : Synthesis of 4-(10-naphthalene-2-yl-anthracene-9-yl)-2,6-diphenyl-pyrimidine (compound 1-4)

Except having used the corresponding boronic acid instead of phenylboronic acid, it carried out similarly to the said synthesis example 1, and obtained the target compound (compound 1-4).

(Compound 1-4) (99% yield). According to mass spectrometry (MS) analysis, the molecular weight is 534.21, m/e=534.

Synthesis Example 4 : Synthesis of Compound (1-10)

(1) Synthesis of 3-anthracene-9-yl-1-naphthalen-1-yl-propenone

Dissolve 10 g (48 mmol) of anthracene-9-carbaldehyde in 300 ml of ethanol, add 8.3 g (49 mmol) of 1-acetylnaphthalene, and 9.4 g (49 mmol) of 28% sodium methoxide in methanol, and stir at room temperature for 4 hours. After the reaction, the precipitated solid was collected by filtration and washed with methanol to obtain 16.6 g of 3-anthracene-9-yl-1-naphthalene-1-yl-propenone (95% yield).

(2) Synthesis of 4-anthracene-9-yl-6-naphthalene-1-yl-2-phenyl-pyrimidine

10g (28mmol) of 3-anthracene-9-yl-1-naphthalene-1-yl-propenone obtained in (1) was dissolved in 100 ml of ethanol, and 4.4g (28mmol) of benzamidine hydrochloride, 2.3g (57mmol) sodium hydroxide, heated to reflux for 25 hours. After the reaction was finished, cool to room temperature, filter the precipitated crystals, wash with water and methanol to obtain 8.5g 4-anthracene-9-yl-6-naphthalene-1-yl-2-phenyl-pyrimidine (67% yield) .

(3) Synthesis of 4-(10-bromo-anthracene-9-yl)-6-naphthalene-1-yl-2-phenyl-pyrimidine

8.5g (19mmol) of 4-anthracene-9-yl-6-naphthalene-1-yl-2-phenyl-pyrimidine obtained in (2) was dissolved in 100 ml of N,N-dimethylformamide, and 3.6 g (20 mmol) N-bromosuccinimide, stirred at room temperature for 8 hours. After the reaction finished, the precipitated solid was collected by filtration, washed with water and methanol to obtain 7.2g 4-(10-bromo-anthracen-9-yl)-6-naphthalene-1-yl-2-phenyl-pyrimidine (yield 73 %).

(4) Synthesis of 4-naphthalene-1-yl-6-(10-naphthalene-1-yl-anthracen-9-yl)-2-phenyl-pyrimidine (compound 1-10)

2.2g (4.1mmol) of 4-(10-bromo-anthracene-9-yl)-6-naphthalene-1-yl-2-phenyl-pyrimidine obtained in (3), 0.85g (5.1mmol) of 1- Naphthalene boronic acid and 0.11 g of tetrakis(triphenylphosphine) palladium were dissolved in 20 ml of 1,2-dimethoxyethane, 8 ml of 2.0 M sodium carbonate aqueous solution was added, and heated to reflux for 8 hours. After the reaction, the precipitated solid was dissolved in dichloromethane, washed with water, and dried over anhydrous sodium sulfate. The solvent was distilled off, and the obtained product was washed with methanol to obtain 2.33 g of a yellow-white solid (97% yield). This was analyzed by mass spectrometry (MS), and it was the target compound (compound 1-10) with a molecular weight of 584.23 and m/e=584.

Synthesis Example 5: Synthesis of 4-naphthalene-1-yl-6-(10-naphthalene-2-yl-anthracene-9-yl)-2-phenyl-pyrimidine (compound 1-11)

Except having used the corresponding boronic acid instead of 1-naphthylboronic acid, it carried out similarly to the said synthesis example 4, and obtained the target compound (compound 1-11).

(Compound 1-11) (97% yield). According to mass spectrometry (MS) analysis, the molecular weight is 584.23, m/e=584.

Synthesis Example 6 : Synthesis of Compound (2-4)

(1) Synthesis of 3-(4-bromo-phenyl)-1-phenyl-propenone

Dissolve 15g (81mmol) of 4-bromobenzaldehyde in 300ml of ethanol, add 10g (83mmol) of acetophenone, 15g (81mmol) of 28% sodium methoxide in methanol, and stir at room temperature for 7 hours. After the reaction was finished, the precipitated solid was collected by filtration and washed with methanol to obtain 19.4 g of 3-(4-bromo-phenyl)-1-phenyl-propenone (83% yield).

(2) Synthesis of 4-(4-bromo-phenyl)-2,6-diphenyl-pyrimidine

19g (67mmol) of 3-(4-bromo-phenyl)-1-phenyl-propenone obtained in (1) was dissolved in 150 ml of ethanol, and 10.6g (69mmol) of benzamidine hydrochloride, 5.5g (138mmol) sodium hydroxide, heated to reflux for 12 hours. After the reaction was completed, it was cooled to room temperature, and the precipitated crystals were collected by filtration, washed with water and methanol to obtain 15.9 g of 4-(4-bromo-phenyl)-2,6-diphenyl-pyrimidine (yield 61%).

(3) Synthesis of 4-[4-(10-naphthalene-2-yl-anthracene-9-yl)-phenyl]-2,6-diphenyl-pyrimidine (compound 2-4)

1.8g (4.6mmol) of 4-(4-bromo-phenyl)-2,6-diphenyl-pyrimidine, 1.6g (4.6mmol) of 10-naphthalene-2-yl-anthracene- 9-boronic acid and 0.11 g of tetrakis(triphenylphosphine) palladium were dissolved in 20 ml of 1,2-dimethoxyethane, 7 ml of 2.0 M sodium carbonate aqueous solution was added, and the mixture was heated to reflux for 6 hours. After the reaction, the precipitated solid was dissolved in dichloromethane, washed with water, and dried over anhydrous sodium sulfate. The solvent was distilled off, and the obtained product was washed with methanol to obtain 2.1 g of a yellow-white solid (yield 74%). This was analyzed by mass spectrometry (MS), and it was the target compound (Compound 2-4) with a molecular weight of 610.24 and m/e=610.

Synthesis Example 7 : Synthesis of Compound (3-3)

(1) Synthesis of 3-anthracene-9-yl-1-pyridin-2-yl-propenone

Dissolve 10 g (48 mmol) of anthracene-9-carbaldehyde in 300 ml of ethanol, add 5.9 g (49 mmol) of 2-acetylpyridine, and 9.4 g (49 mmol) of 28% sodium methoxide in methanol, and stir at room temperature for 4 hours. After the reaction, the precipitated solid was collected by filtration and washed with methanol to obtain 14.2 g of 3-anthracene-9-yl-1-pyridin-2-yl-propenone (95% yield).

(2) Synthesis of 4-anthracene-9-yl-2-phenyl-6-pyrimidin-2-yl-pyrimidine

10g (32mmol) of 3-anthracene-9-yl-1-pyridin-2-yl-propenone obtained in (1) was dissolved in 100 ml of ethanol, and 5.1g (33mmol) of benzamidine hydrochloride, 2.6g (65mmol) sodium hydroxide, heated to reflux for 25 hours. After the reaction was finished, cool to room temperature, filter the precipitated crystals, wash with water and methanol to obtain 12.4g 4-anthracene-9-yl-2-phenyl-6-pyridin-2-yl-pyrimidine (94% yield) .

(3) Synthesis of 4-(10-bromo-anthracen-9-yl)-2-phenyl-6-pyridin-2-yl-pyrimidine

12g (30mmol) of 4-anthracen-9-yl-2-phenyl-6-pyridin-2-yl-pyrimidine obtained in (2) was dissolved in 100 ml of N,N-dimethylformamide, and 5.9g (33 mmol) N-bromosuccinimide, stirred at room temperature for 8 hours. After the reaction finished, the precipitated solid was collected by filtration, washed with water and methanol to obtain 10.8g 4-(10-bromo-anthracen-9-yl)-2-phenyl-6-pyridin-2-yl-pyrimidine (yield 73 %).

(4) Synthesis of 4-(10-naphthalene-1-yl-anthracene-9-yl)-2-phenyl-6-pyridin-2-yl-pyrimidine (compound 3-3)

2.2g (4.5mmol) of 4-(10-bromo-anthracen-9-yl)-2-phenyl-6-pyridin-2-yl-pyrimidine obtained in (2), 0.88g (5.1mmol) of 1- Naphthalene boronic acid and 0.11 g of tetrakis(triphenylphosphine) palladium were dissolved in 20 ml of 1,2-dimethoxyethane, 8 ml of 2.0 M sodium carbonate aqueous solution was added, and heated to reflux for 8 hours. After the reaction, the precipitated solid was dissolved in dichloromethane, washed with water, and dried over anhydrous sodium sulfate. The solvent was distilled off, and the obtained product was washed with methanol to obtain 2.5 g of a yellow-white solid (99% yield). When analyzed by mass spectrometry (MS), it was the target compound (compound 3-3) with a molecular weight of 535.20 and m/e=535.

Synthesis Example 8 : Synthesis of 4-(10-naphthalene-2-yl-anthracene-9-yl)-2-phenyl-6-pyridin-2-yl-pyrimidine (compound 3-4)

Except having used the corresponding boronic acid instead of 1-naphthylboronic acid, the same operation as the said synthesis example 7 was performed, and the target compound (compound 3-4) was obtained.

(Compound 3-4) (yield 92%). According to mass spectrometry (MS) analysis, the molecular weight is 535.20, m/e=535.

Synthesis Example 9 : Synthesis of 4'-(10-naphthalene-2-yl-anthracene-9-yl)-[2,2';6',2"]terpyridine (compound 5-4)

1.8g (6.7mmol) 4'-chloro-[2,2'; 6',2"] terpyridine, 2.0g (5.7mmol) 10-naphthalene-2-yl-anthracene-9-boronic acid, 0.14g tetra (Triphenylphosphine) palladium was dissolved in 20 milliliters of 1,2-dimethoxyethane, added 9 milliliters of 2.0M sodium carbonate aqueous solution, and heated to reflux for 7 hours. After the reaction finished, the precipitated solid was dissolved in dichloromethane, Wash with water and dry with anhydrous sodium sulfate. The solvent is distilled off, and the product obtained is washed with methanol to obtain 2.33g yellow-white solid (yield 84%).It is analyzed by mass spectrometry (MS), and the result is the target object (compound 5 -4), the molecular weight is 535.20, m/e=535.

Synthesis Example 10 : Synthesis of Compound (6-18)

(1) Synthesis of 6-(4-bromo-phenyl)-3-phenyl-[1,2,4]triazine

Dissolve 5.0g (18mmol) of 2,4'-dibromoacetophenone and 4.9g (36mmol) of benzohydrazide in 20ml of acetic acid, add 1.5g of sodium acetate, and heat to reflux for 10 hours. After the reaction, water was added and extracted with dichloromethane. The organic layer was washed with aqueous sodium bicarbonate solution and brine, and dried over anhydrous sodium sulfate. The solvent was distilled off, and the obtained product was washed with methanol to obtain 1.6 g of 6-(4-bromo-phenyl)-3-phenyl[1,2,4]triazine (yield 29%).

(2) Synthesis of 6-[4-(10-naphthalene-2-yl-anthracene-9-yl)-phenyl]-3-phenyl-[1,2,4]triazine (compound 6-18)

1.6g (5.1mmol) of 6-(4-bromo-phenyl)-3-phenyl[1,2,4]triazine obtained in (1), 1.8g (5.2mmol) of 10-naphthalene-2- Base-anthracene-9-boronic acid and 0.10 g of tetrakis(triphenylphosphine) palladium were dissolved in 20 ml of 1,2-dimethoxyethane, and 10 ml of 2.0 M sodium carbonate aqueous solution was added, and heated to reflux for 6 hours. After the reaction, the precipitated solid was dissolved in dichloromethane, washed with water, and dried over anhydrous sodium sulfate. The solvent was distilled off, and the obtained product was washed with methanol to obtain 1.17 g of a yellow-white solid (yield 43%). This was analyzed by mass spectrometry (MS), and it was the target compound (compound 6-18) with a molecular weight of 535.20 and m/e=535.

Synthesis Example 11 : Synthesis of Compound (8-4)

(1) Synthesis of 2-(4-bromo-phenyl)-quinoxaline

10 g (36 mmol) of 2,4'-dibromoacetophenone and 4.0 g (37 mmol) of 1,2-phenylenediamine were dissolved in 20 ml of ethanol, and heated to reflux for 3.5 hours. After the reaction was over, the resulting crystals were collected by filtration and washed with ethanol to obtain 4.2g of 2-(4-bromo-phenyl)-quinoxaline (yield 41%).

(2) Synthesis of 2-(4-anthracene-9-yl-phenyl)-quinoxaline

Dissolve 2.0g (7.0mmol) of 2-(4-bromo-phenyl)-quinoxaline, 1.7g (7.7mmol) of 9-anthracenboronic acid, and 0.16g of tetrakis(triphenylphosphine)palladium obtained in (1) To 20 ml of 1,2-dimethoxyethane was added 12 ml of 2.0M aqueous sodium carbonate solution, and the mixture was heated to reflux for 6 hours. After the reaction, the precipitated solid was dissolved in dichloromethane, washed with water, and dried over anhydrous sodium sulfate. The solvent was distilled off, and the resulting product was washed with methanol to obtain 2.37 g of 2-(4-anthracene-9-yl-phenyl)-quinoxaline (yield 88%).

(3) Synthesis of 2-[4-(10-bromo-anthracene-9-yl)-phenyl]-quinoxaline

2.37g (6.2mmol) 2-(4-anthracene-9-yl-phenyl)-quinoxaline obtained in (2) was dissolved in 20 milliliters of N,N-dimethylformamide, and 1.2g (6.7 mmol) N-bromosuccinimide, stirred at room temperature for 8 hours. After the reaction, the precipitated solid was collected by filtration, washed with water and methanol to obtain 2.24 g of 2-[4-(10-bromo-anthracen-9-yl)-phenyl]-quinoxaline (yield 78%).

(4) Synthesis of 2-[4-(10-naphthalene-2-yl-anthracene-9-yl)-phenyl]-quinoxaline (compound 8-4)

2.2g (4.8mmol) 2-[4-(10-bromo-anthracene-9-yl)-phenyl]-quinoxaline, 0.98g (5.7mmol) 2-naphthylboronic acid, 0.11 g of tetrakis(triphenylphosphine)palladium was dissolved in 20 ml of 1,2-dimethoxyethane, and 8 ml of 2.0M aqueous sodium carbonate solution was added, and heated to reflux for 6 hours. After the reaction, the precipitated solid was dissolved in dichloromethane, washed with water, and dried over anhydrous sodium sulfate. The solvent was distilled off, and the obtained product was washed with methanol to obtain 2.4 g of a yellow-white solid (99% yield). This was analyzed by mass spectrometry (MS), and it was the target compound (Compound 8-4) with a molecular weight of 508.19 and m/e=508.

Synthesis Example 12 : Synthesis of Compound (10-18)

(1) Synthesis of 2-(4-bromo-phenyl)-4-phenyl-quinoline

Dissolve 5.0 g (25 mmol) of 4-bromoacetophenone and 5.0 g (25 mmol) of 2-aminobenzophenone in 50 ml of ethanol, add 3.1 g of sodium hydroxide, and heat to reflux for 7 hours. After the reaction was finished, it was collected by filtration, and the obtained crystals were washed with water and ethanol to obtain 5.56g 2-(4-bromo-phenyl)-4-phenyl-quinoline (yield 61%).

(2) Synthesis of 2-[4-(10-naphthalene-2-yl-anthracene-9-yl)-phenyl]-4-phenyl-quinoline (compound 10-18)

2.0 g (5.6 mmol) of 2-(4-bromo-phenyl)-4-phenyl-quinoline, 2.0 g (5.7 mmol) of 10-naphthalene-2-yl-anthracene-9- Boric acid and 0.10 g of tetrakis(triphenylphosphine) palladium were dissolved in 20 ml of 1,2-dimethoxyethane, and 8 ml of 2.0 M sodium carbonate aqueous solution was added, and heated to reflux for 6 hours. After the reaction, the precipitated solid was dissolved in dichloromethane, washed with water, and dried over anhydrous sodium sulfate. The solvent was distilled off, and the obtained product was washed with methanol to obtain 2.07 g of a yellow-white solid (yield 64%). When analyzed by mass spectrometry (MS), it was the target compound (compound 10-18) with a molecular weight of 583.23 and m/e=583.

Synthesis Example 13 : Synthesis of Compound (14-7)

(1) Synthesis of 2-(4-bromo-phenyl)-imidazo[1,2-a]pyridine

Dissolve 15g (54mmol) of 2,4'-dibromoacetophenone and 5.2g (55mmol) of 2-aminopyridine in 100ml of ethanol, add 7.0g of sodium bicarbonate, and heat to reflux for 6 hours. After the reaction was over, the resulting crystals were collected by filtration, washed with water and ethanol to obtain 12.5 g of 2-(4-bromo-phenyl)-imidazo[1,2-a]pyridine (yield 85%).

(2) Synthesis of 2-[4-(10-naphthalene-2-yl-anthracene-9-yl)-phenyl]-imidazo[1,2-a]pyridine (compound 14-7)

1.5g (5.5mmol) of 2-(4-bromo-phenyl)-imidazo[1,2-a]pyridine obtained in (1), 2.0g (5.78mmol) of 10-naphthalene-2-yl-anthracene -9-boronic acid and 0.13 g of tetrakis(triphenylphosphine)palladium were dissolved in 30 ml of 1,2-dimethoxyethane, and 8.6 ml of 2.0 M sodium carbonate aqueous solution was added, and heated to reflux for 6 hours. After the reaction, the precipitated solid was dissolved in dichloromethane, washed with water, and dried over anhydrous sodium sulfate. The solvent was distilled off, and the obtained product was washed with methanol to obtain 1.2 g of a yellow-white solid (yield 45%). When analyzed by mass spectrometry (MS), it was the target compound (compound 14-7) with a molecular weight of 496.19 and m/e=496.

Synthesis Example 14 : Synthesis of 9-(10-naphthalene-2-yl-anthracene-9-yl)-acridine (compound 13-4)

Dissolve 1.3g (6.1mmol) of 9-chloro-acridine, 2.0g (5.7mmol) of 10-naphthalene-2-yl-anthracene-9-boronic acid, and 0.10g of tetrakis(triphenylphosphine)palladium in 20ml of 1, To 2-dimethoxyethane, add 8 ml of 2.0M aqueous sodium carbonate solution, and heat to reflux for 6 hours. After the reaction, the precipitated solid was dissolved in dichloromethane, washed with water, and dried over anhydrous sodium sulfate. The solvent was distilled off, and the obtained product was washed with methanol to obtain 2.16 g of a yellow-white solid (yield 74%). When analyzed by mass spectrometry (MS), it was the target compound (compound 13-4) with a molecular weight of 481.18 and m/e=481.

Synthesis Example 15 : Synthesis of 9-[4-(10-naphthalene-2-yl-anthracene-9-yl)-phenyl]-acridine (compound 13-11)

1.6g (4.8mmol) 9-(4-bromo-phenyl)-acridine, 1.6g (4..6mmol) 10-naphthalene-2-yl-anthracene-9-boronic acid, 0.11g tetrakis(triphenylphosphine ) and palladium were dissolved in 20 milliliters of 1,2-dimethoxyethane, and 7 milliliters of 2.0 M sodium carbonate aqueous solution was added, and heated to reflux for 6 hours. After the reaction, the precipitated solid was dissolved in dichloromethane, washed with water, and dried over anhydrous sodium sulfate. The solvent was distilled off, and the obtained product was washed with methanol to obtain 1.98 g of a yellow-white solid (yield 74%). When analyzed by mass spectrometry (MS), it was the target compound (compound 13-11) with a molecular weight of 557.21 and m/e=557.

Synthesis Example 16 : Synthesis of 2-[4-(10-phenylanthracene-9-yl)-phenyl]-imidazo[1,2-a]pyridine (compound 14-1)

In (2) of Synthesis Example 13, except that 10-phenylanthracene-9-boronic acid was used instead of 10-naphthalene-2-yl-anthracene-9-boronic acid, the same operation was performed to obtain 3.4 g of a yellow-white solid (Yield 78%). When analyzed by mass spectrometry (MS), it was the target compound (compound 14-1) with a molecular weight of 446.18 and m/e=446.

Synthesis Example 17 : Synthesis of 2-[4-(10-biphenyl-2-yl-anthracen-9-yl)-phenyl]-imidazo[1,2-a]pyridine (compound 14-2)

In (2) of Synthesis Example 13, except that 10-biphenyl-2-yl-anthracene-9-boronic acid was used instead of 10-naphthalene-2-yl-anthracene-9-boronic acid, the same operation was performed to obtain 3.4 g of off-white solid (yield 81%). When analyzed by mass spectrometry (MS), it was the target compound (Compound 14-2) with a molecular weight of 522.21 and m/e=522.

Synthesis Example 18 : Synthesis of 2-[4-(10-naphthalene-1-yl-anthracen-9-yl)-phenyl]-imidazo[1,2-a]pyridine (compound 14-6)

In (2) of Synthesis Example 13, except that 10-naphthalene-1-yl-anthracene-9-boronic acid was used instead of 10-naphthalene-2-yl-anthracene-9-boronic acid, the same operation was performed to obtain 2.6 g yellow-white solid (yield 72%). This was analyzed by mass spectrometry (MS), and it was the target compound (compound 14-6) with a molecular weight of 496.19 and m/e=496.

Synthesis Example 19 : Synthesis of (Compound 14-5)

(1) Synthesis of 2-[4-(10-bromo-anthracene-9-yl)-phenyl]-imidazo[1,2-a]pyridine

20g (81mmol) of 4'-iodoacetophenone was dissolved in 200ml of acetic acid, 12.8g (81mmol) of bromine was added under ice cooling, and stirred at 15°C for 3 hours. After the color of bromine disappeared, water was added, and the precipitated solid was filtered to obtain 27 g of crude 2-bromo-4'-iodoacetophenone.

The resulting 27g (83mmol) of crude 2-bromo-4'-iodoacetophenone and 8.0g (85mmol) of 2-aminopyridine were dissolved in 200ml of ethanol, 10g of sodium bicarbonate was added, and heated to reflux for 6 hours. After the reaction was finished, it was filtered, and the obtained crystals were washed with water and ethanol to obtain 21 g of 2-(4-iodophenyl)-imidazo[1,2-a]pyridine (yield 82%).

10.6g (33mmol) 2-(4-iodophenyl)-imidazo[1,2-a]pyridine, 10g (33mol) 10-bromoanthracene-9-boronic acid, 0.77g tetrakis(triphenylphosphine)palladium Dissolve in 100 ml of 1,2-dimethoxyethane, add 50 ml of 2.0M aqueous sodium carbonate solution, and heat to reflux for 7 hours. Filter after reaction finishes, gained crystal is washed with water, methanol, obtains 11.7g 2-[4-(10-bromo-anthracene-9-yl)-phenyl]-imidazo[1,2-a]pyridine (yield 78%).

(2) 2-[4-(10-[1,1'; 3',1"]terphenyl-5'-yl-anthracene-9-yl)-phenyl]-imidazo[1,2-a Synthesis of ]pyridine (compound 14-5)

2.5g (5.5mmol) 2-[4-(10-bromo-anthracen-9-yl)-phenyl]-imidazo[1,2-a]pyridine, 1.6g (5.8mmol)[1,1' ; 3', 1 "] terphenyl-5'-boronic acid, 0.13g tetrakis (triphenylphosphine) palladium was dissolved in 20 milliliters of 1,2-dimethoxyethane, and 9 milliliters of 2.0M sodium carbonate aqueous solution was added, Heated to reflux for 8 hours.Filter after the reaction finishes, the gained crystal is washed with water and methanol to obtain 2.4g yellowish-white solid (yield 71%).It is analyzed by mass spectrometry (MS), and the result is target object, molecular weight is 598.24, m /e=598.

Synthesis Example 20 : Synthesis of 2-[4-(10-phenanthrene-9-yl-anthracene-9-yl)-phenyl]-imidazo[1,2-a]pyridine (compound 14-8)

In Synthesis Example 19, 9-phenanthrene boronic acid was used instead of [1,1'; 3', 1 "] terphenyl-5'-boronic acid, except that, the same operation was carried out to obtain 2.4 g of yellow-white solid (yield The yield was 78%). It was analyzed by mass spectrometry (MS), and the result was the target compound (compound 14-8), with a molecular weight of 446.18 and m/e=446.

Synthesis Example 21 : Synthesis of 2-[4-(10-fluoranthene-3-yl-anthracen-9-yl)-phenyl]-imidazo[1,2-a]pyridine (compound 14-9)

In synthesis example 19, use 3-fluoranthene boronic acid instead of [1,1'; 3', 1 "] terphenyl-5'-boronic acid, except that, carry out the same operation, obtain 2.5g yellow-white solid ( Yield 93%). It was analyzed by mass spectrometry (MS), and the result was the target compound (compound 14-9), with a molecular weight of 570.21 and m/e=570.

Synthesis Example 22 : Synthesis of (Compound 15-1)

(1) Synthesis of 2-(4-bromo-phenyl)-3-methyl-imidazo[1,2-a]pyridine

5.0 g (23 mmol) of 4'-bromopropionophenone was dissolved in 50 ml of acetic acid, 3.7 g (23 mmol) of bromine was added under ice-cooling, and the mixture was stirred at 10°C for 3 hours. After the color of bromine disappeared, water was added and extracted with dichloromethane. The organic layer was washed with water and dried over sodium sulfate. The solvent was distilled off, and the obtained crystals were washed with hexane to obtain 4.3 g of 2,4'-dibromopropionylphenone (yield 63%).

The resulting 4.3g (15mmol) 2,4'-dibromopropionophenone and 1.4g (15mmol) 2-aminopyridine were dissolved in 50ml of ethanol, 1.9g of sodium bicarbonate was added, and heated to reflux for 6 hours. After the reaction, water was added and extracted with dichloromethane. The organic layer was washed with water and dried over sodium sulfate. The solvent was distilled off, and the resulting slurry was purified by silica gel column chromatography to obtain 1.6g 2-(4-bromo-phenyl)-3-methyl-imidazo[1,2-a]pyridine (yield 37% ).

(2) 2-[4-(10-naphthalene-2-yl-anthracene-9-yl)-phenyl]-3-methyl-imidazo[1,2-a]pyridine (compound 15-1) synthesis

In (2) of Synthesis Example 13, use 2-(4-bromo-phenyl)-3-methyl-imidazo[1,2-a]pyridine instead of 2-(4-bromo-phenyl)-imidazole Except for do[1,2-a]pyridine, the same operation was carried out to obtain 1.9 g of a yellow-white solid (yield 70%). When analyzed by mass spectrometry (MS), it was the target compound (compound 15-1) with a molecular weight of 510.23 and m/e=510.

Synthesis Example 23: Synthesis of (Compound 15-3)

(1) Synthesis of 2-(4-bromo-phenyl)-6-methyl-imidazo[1,2-a]pyridine

Dissolve 5g (18mmol) of 2,4'-dibromoacetophenone and 2.0g (19mmol) of 2-amino-5-picoline in 30ml of ethanol, add 2.9g of sodium bicarbonate, and heat to reflux for 6 hours. After the reaction was completed, it was filtered, and the obtained crystals were washed with water and ethanol to obtain 4.2g of 2-(4-bromo-phenyl)-6-methyl-imidazo[1,2-a]pyridine (yield 81%).

(2) 2-[4-(10-naphthalene-2-yl-anthracene-9-yl)-phenyl]-6-methyl-imidazo[1,2-a]pyridine (compound 15-3) synthesis

In (2) of Synthesis Example 13, use 2-(4-bromo-phenyl)-6-methyl-imidazo[1,2-a]pyridine instead of 2-(4-bromo-phenyl)-imidazole Except for do[1,2-a]pyridine, the same operation was carried out to obtain 1.6 g of a yellow-white solid (yield 55%). When analyzed by mass spectrometry (MS), it was the target compound (compound 15-3) with a molecular weight of 510.23 and m/e=510.

Synthesis Example 24 : Synthesis of (Compound 15-4)

(1) Synthesis of 2-(4-bromo-phenyl)-7-methyl-imidazo[1,2-a]pyridine

In (1) of Synthesis Example 23, 2.8 g of 2-(4-bromo- Phenyl)-7-methyl-imidazo[1,2-a]pyridine (54% yield).

(2) 2-[4-(10-naphthalene-2-yl-anthracene-9-yl)-phenyl]-7-methyl-imidazo[1,2-a]pyridine (compound 15-4) synthesis

In (2) of Synthesis Example 13, 2-(4-bromo-phenyl)-7-methyl-imidazo[1,2-a]pyridine was used instead of 2-(4-bromo-phenyl)-imidazole Except for do[1,2-a]pyridine, the same operation was carried out to obtain 1.6 g of a yellow-white solid (yield 57%). When analyzed by mass spectrometry (MS), it was the target compound (compound 15-4) with a molecular weight of 510.21 and m/e=510.

Synthesis Example 25 : Synthesis of (Compound 15-5)

(1) Synthesis of 2-(4-bromo-phenyl)-8-methyl-imidazo[1,2-a]pyridine

In (1) of Synthesis Example 23, except that 2-amino-3-picoline was used instead of 2-amino-5-picoline, the same operation was performed to obtain 3.5 g of 2-(4-bromo- Phenyl)-8-methyl-imidazo[1,2-a]pyridine (68% yield).

(2) 2-[4-(10-naphthalene-2-yl-anthracene-9-yl)-phenyl]-8-methyl-imidazo[1,2-a]pyridine (compound 15-5) synthesis

In (2) of Synthesis Example 13, use 2-(4-bromo-phenyl)-8-methyl-imidazo[1,2-a]pyridine instead of 2-(4-bromo-phenyl)-imidazole Except for do[1,2-a]pyridine, the same operation was carried out to obtain 1.8 g of a yellow-white solid (yield 64%). When analyzed by mass spectrometry (MS), it was the target compound (compound 15-5) with a molecular weight of 510.21 and m/e=510.

Synthesis Example 26 : Synthesis of (Compound 16-3)

(1) Synthesis of 2-(4-bromo-phenyl)-imidazo[2,1-a]isoquinoline

In (1) of Synthesis Example 23, except that 1-aminoisoquinoline was used instead of 2-amino-5-picoline, the same operation was carried out to obtain 5.1 g of 2-(4-bromo-phenyl) - imidazo[2,1-a]isoquinoline (yield 88%).

(2) Synthesis of 2-[4-(10-naphthalene-2-yl-anthracene-9-yl)-phenyl]-imidazo[2,1-a]isoquinoline (compound 16-3)

In (2) of Synthesis Example 13, use 2-(4-bromo-phenyl)-imidazo[2,1-a]isoquinoline instead of 2-(4-bromo-phenyl)-imidazo[1 , 2-a] pyridine, except that, the same operation was carried out to obtain 2.2 g of yellow-white solid (yield 72%). When analyzed by mass spectrometry (MS), it was the target compound (compound 16-3) with a molecular weight of 546.21 and m/e=546.

Synthesis Example 27 : Synthesis of (Compound 16-7)

(1) Synthesis of 2-(4-bromo-phenyl)-imidazo[1,2-a]pyrimidine

In (1) of Synthesis Example 23, except that 2-aminopyrimidine was used instead of 2-amino-5-picoline, the same operation was performed to obtain 4.1 g of 2-(4-bromo-phenyl)-imidazole And[1,2-a]pyrimidine (yield 83%).

(2) Synthesis of 2-[4-(10-naphthalene-2-yl-anthracene-9-yl)-phenyl]-imidazo[1,2-a]pyrimidine (compound 16-7)

In (2) of Synthesis Example 13, use 2-(4-bromo-phenyl)-imidazo[1,2-a]pyrimidine instead of 2-(4-bromo-phenyl)-imidazo[1,2 -a] Except for pyridine, the same operation was carried out to obtain 1.7 g of a yellow-white solid (yield 62%). When analyzed by mass spectrometry (MS), it was the target compound (compound 16-7) with a molecular weight of 497.19 and m/e=497.

Synthesis Example 28 : Synthesis of (Compound 19-1)

(1) Synthesis of 2-(3-bromo-phenyl)-imidazo[1,2-a]pyridine

Dissolve 10g (50mmol) of 3'-bromoacetophenone in 20ml of acetic acid, add 7.0g (44mmol) of bromine at about 5-10°C, and stir for 4 hours at about 5-10°C until the color of bromine disappears. After the reaction, water was added and extracted with dichloromethane. Then washed with water and dried over sodium sulfate. The solvent was distilled off, the obtained crude 2,3'-dibromoacetophenone was dissolved in 30 ml of ethanol, 5.0 g (53 mmol) of 2-aminopyridine and 7.0 g of sodium bicarbonate were added, and the mixture was heated to reflux for 8 hours. After the reaction was completed, it was filtered, and the obtained crystals were washed with water and methanol to obtain 3.5 g of 2-(3-bromo-phenyl)-imidazo[1,2-a]pyridine (yield 26%).

(2) Synthesis of 2-[3-(10-naphthalene-2-yl-anthracene-9-yl)-phenyl]-imidazo[1,2-a]pyridine (compound 19-1)

In (2) of Synthesis Example 13, use 2-(3-bromo-phenyl)-imidazo[1,2-a]pyridine instead of 2-(4-bromo-phenyl)-imidazo[1,2 -a] Except for pyridine, the same operation was carried out to obtain 3.3 g of a yellow-white solid (yield 91%). When analyzed by mass spectrometry (MS), it was the target compound (Compound 19-1) with a molecular weight of 496.19 and m/e=496.

Synthesis Example 29 : Synthesis of (Compound 19-5)

(1) Synthesis of 2-(4'-bromo-biphenyl-4-yl)-imidazo[1,2-a]pyridine

4.3g (32mmol) of aluminum chloride was added to 30ml of 1,2-dichloroethane, 2.0g (25mmol) of acetyl chloride was added under ice cooling, followed by 5.0g (21mmol) of 4-bromobiphenyl dissolved in 20 Form a solution in ml 1,2-dichloroethane. As it was, the mixture was stirred for 4 hours under ice cooling. After the reaction, water was added and extracted with dichloromethane. Then washed with water and dried over sodium sulfate. The solvent was distilled off to obtain 5.9 g of crude 1-(4'-bromo-biphenyl-4-yl)ethanone.

The resulting 1-(4'-bromo-biphenyl-4-yl)-ethanone was dissolved in 20 milliliters of acetic acid and 10 milliliters of carbon tetrachloride, and 3.0 g (19 mmol) of bromine was added at about 5° C. Stir at -10°C for 3 hours. Leave overnight. After the reaction, water was added and extracted with dichloromethane. Then washed with water and dried over sodium sulfate. The solvent was distilled off to obtain 6.7 g of 2-bromo-1-(4'-bromo-biphenyl-4-yl)-ethanone as white crystals (yield 89%).

Dissolve 6.7g (19mmol) of 2-bromo-1-(4'-bromo-biphenyl-4-yl)-ethanone in 50ml of ethanol, add 2.1g (22mmol) of 2-aminopyridine, 5.0g of sodium bicarbonate , heated to reflux for 7 hours. After reaction finishes, filter, gained crystal is washed with water, methanol, obtains the 2-(4'-bromo-biphenyl-4-yl)-imidazo[1,2-a]pyridine that obtains 5.5g as yellow crystal (yield 84%).

(2) Synthesis of 2-[4'-(10-naphthalene-2-yl-anthracene-9-yl)biphenyl-4-yl]-imidazo[1,2-a]pyridine (compound 19-5)

In (2) of Synthesis Example 13, 2-(4'-bromo-biphenyl-4-yl)-imidazo[1,2-a]pyridine was used instead of 2-(4-bromo-phenyl)-imidazole Except for do[1,2-a]pyridine, the same operation was carried out to obtain 2.6 g of a yellow-white solid (yield 63%). When analyzed by mass spectrometry (MS), it was the target compound (compound 19-5) with a molecular weight of 572.23 and m/e=572.

Synthesis Example 30 : Synthesis of (Compound 26-8)

(1) Synthesis of 6-bromo-2-phenyl-imidazo[1,2-a]pyridine

Dissolve 5.8g (29mmol) of phenacyl bromide and 5.0g (29mmol) of 2-amino-5-bromopyridine in 50ml of ethanol, add 3.6g of sodium bicarbonate, and heat to reflux for 6 hours. After the reaction was finished, it was filtered, and the obtained crystals were washed with water and ethanol to obtain 6.4 g of 6-bromo-2-phenyl-imidazo[1,2-a]pyridine (yield 81%).

(2) Synthesis of 6-(10-naphthalene-2-yl-anthracene-9-yl)-2-phenyl-imidazo[1,2-a]pyridine (compound 26-8)

2.0g (7.3mmol) 6-bromo-2-phenyl-imidazo[1,2-a]pyridine, 2.5g (11mmol) 10-naphthalene-2-yl-anthracene-9-boronic acid, 0.17g tetrakis( Triphenylphosphine) palladium was dissolved in 20 ml of 1,2-dimethoxyethane, 11 ml of 2.0 M sodium carbonate aqueous solution was added, and heated to reflux for 7 hours. After the reaction was completed, it was filtered, and the obtained crystals were washed with water and methanol to obtain 2.7 g of a yellow-white solid (yield 75%). When analyzed by mass spectrometry (MS), it was the target substance with a molecular weight of 496.19 and m/e=496.

Synthesis Example 31 : (Synthesis of Compound 2-7')

(1) Synthesis of 2-(4-bromo-phenyl)-6-phenyl-imidazo[1,2-a]pyridine

Dissolve 5.0g (29mmol) of 2-amino-5-bromopyridine, 3.6g (30mmol) of phenylboronic acid, and 0.67g of tetrakis(triphenylphosphine)palladium in 90ml of 1,2-dimethoxyethane, and add 45 ml of 2.0M aqueous sodium carbonate solution was heated to reflux for 6 hours. After the reaction, it was dissolved in ethyl acetate, filtered, washed with water, and dried over sodium sulfate. The solvent was distilled off to obtain 4.0 g of crude 5-phenyl-2-amino-pyridine.

The resulting crude 5-phenyl-2-amino-pyridine and 6.5g (23mmol) of 2,4'-dibromoacetophenone were dissolved in 50ml of ethanol, 3.7g of sodium bicarbonate was added, and heated to reflux for 6 hours. After the reaction was completed, it was filtered, and the obtained crystals were washed with water and methanol to obtain 3.1 g of 2-(4-bromo-phenyl)-6-phenyl-imidazo[1,2-a]pyridine (yield 31%).

(2) 2-[4-(10-naphthalene-2-yl-anthracene-9-yl)-phenyl]-6-phenyl-imidazo[1,2-a]pyridine (compound 2-7') Synthesis

4.0g (11mmol) 2-(4-bromo-phenyl)-6-phenyl-imidazo[1,2-a]pyridine, 4.0g (11mmol) 10-naphthalene-2-yl-anthracene-9- Boric acid and 0.27 g of tetrakis(triphenylphosphine) palladium were dissolved in 40 ml of 1,2-dimethoxyethane, 18 ml of 2.0 M sodium carbonate aqueous solution was added, and the mixture was heated to reflux for 7 hours. After the reaction was completed, it was filtered, and the obtained crystals were washed with water and methanol to obtain 4.9 g of a yellow-white solid (yield 76%). When analyzed by mass spectrometry (MS), it was the target substance with a molecular weight of 572.23 and m/e=572.

Synthesis Example 32 : Synthesis of (Compound 3-3')

(1) Synthesis of 2-(4-bromo-phenyl)-6-biphenyl-2-yl-imidazo[1,2-a]pyridine

In (1) of Synthesis Example 31, except that 2-biphenylboronic acid was used instead of phenylboronic acid, the same operation was performed to obtain 4.0 g of 2-(4-bromo-phenyl)-6-biphenyl- 2-yl-imidazo[1,2-a]pyridine (54% yield).

(2) 2-[4-(10-naphthalene-2-yl-anthracene-9-yl)-phenyl]-6-biphenyl-2-yl-imidazo[1,2-a]pyridine (compound 3 -3') synthesis

In (2) of Synthesis Example 31, 2-(4-bromo-phenyl)-6-biphenyl-2-yl-imidazo[1,2-a]pyridine was used instead of 2-(4-bromo-phenyl yl)-6-phenyl-imidazo[1,2-a]pyridine, the same operation was carried out to obtain 3.7 g of a yellow-white solid (yield 91%). When analyzed by mass spectrometry (MS), it was the target substance with a molecular weight of 648.26 and m/e=648.

Synthesis example 33 : (synthesis of compound 3-4')

(1) Synthesis of 2-(4-bromo-phenyl)-6-[1,1'; 3',1"]terphenyl-5'-yl-imidazo[1,2-a]pyridine

In (1) of Synthesis Example 31, except that [1,1'; 3',1"]terphenylboronic acid was used instead of phenylboronic acid, the same operation was performed to obtain 6.3 g of 2-(4-bromo -phenyl)-6-[1,1';3',1"]terphenyl-5'-yl-imidazo[1,2-a]pyridine (73% yield).

(2) 2-[4-(10-naphthalene-2-yl-anthracene-9-yl)-phenyl]-6-[1,1'; 3',1"]terphenyl-5'-yl- Synthesis of imidazo[1,2-a]pyridine (compound 3-4')

In (2) of Synthesis Example 31, 2-(4-bromo-phenyl)-6-[1,1'; 3',1"]terphenyl-5'-yl-imidazo[1,2 -a] pyridine instead of 2-(4-bromo-phenyl)-6-phenyl-imidazo[1,2-a]pyridine, except that, the same operation was carried out to obtain 2.8g yellowish white solid (yield 69%). It was analyzed by mass spectrometry (MS), and the result was the target object with a molecular weight of 724.29 and m/e=724.

Synthesis example 34 : (synthesis of compound 3-5')

(1) Synthesis of 2-(4-bromo-phenyl)-6-naphthalen-1-yl-imidazo[1,2-a]pyridine

In (1) of Synthesis Example 31, 9.2 g of 2-(4-bromo-phenyl)-6-naphthalene-1-yl was obtained in the same manner except that 1-naphthaleneboronic acid was used instead of phenylboronic acid. - imidazo[1,2-a]pyridine (yield 80%).

(2) 2-[4-(10-naphthalene-2-yl-anthracene-9-yl)-phenyl]-6-naphthalene-1-yl-imidazo[1,2-a]pyridine (compound 3- 5') Synthesis

In (2) of Synthesis Example 31, use 2-(4-bromo-phenyl)-6-naphthalen-1-yl-imidazo[1,2-a]pyridine instead of 2-(4-bromo-phenyl )-6-Phenyl-imidazo[1,2-a]pyridine, except that the same operation was carried out to obtain 4.3 g of a yellow-white solid (yield 90%). This was analyzed by mass spectrometry (MS), and it was the target substance with a molecular weight of 622.24 and m/e=622.

Synthesis example 35 : (synthesis of compound 3-6')

(1) Synthesis of 2-(4-bromo-phenyl)-6-naphthalene-2-yl-imidazo[1,2-a]pyridine

In (1) of Synthesis Example 31, except that 2-naphthylboronic acid was used instead of phenylboronic acid, the same operation was performed to obtain 9.9 g of 2-(4-bromo-phenyl)-6-naphthalene-2-yl - imidazo[1,2-a]pyridine (yield 86%).

(2) 2-[4-(10-naphthalene-2-yl-anthracene-9-yl)-phenyl]-6-naphthalene-2-yl-imidazo[1,2-a]pyridine (compound 3- 6') Synthesis

In (2) of Synthesis Example 31, use 2-(4-bromo-phenyl)-6-naphthalen-2-yl-imidazo[1,2-a]pyridine instead of 2-(4-bromo-phenyl )-6-Phenyl-imidazo[1,2-a]pyridine, except that the same operation was carried out to obtain 3.6 g of a yellow-white solid (yield 83%). When analyzed by mass spectrometry (MS), it was the target substance with a molecular weight of 622.24 and m/e=622.

Synthesis example 36 : (synthesis of compound 3-7')

(1) Synthesis of 2-(4-bromo-phenyl)-6-phenanthrene-9-yl-imidazo[1,2-a]pyridine

In (1) of Synthesis Example 31, except that 9-phenanthreneboronic acid was used instead of phenylboronic acid, the same operation was performed to obtain 7.3 g of 2-(4-bromo-phenyl)-6-phenanthrene-9-yl - imidazo[1,2-a]pyridine (95% yield).

(2) 2-[4-(10-naphthalene-2-yl-anthracene-9-yl)-phenyl]-6-phenanthrene-9-yl-imidazo[1,2-a]pyridine (compound 3- 7') Synthesis

In (2) of Synthesis Example 31, use 2-(4-bromo-phenyl)-6-phenanthrene-9-yl-imidazo[1,2-a]pyridine instead of 2-(4-bromo-phenyl )-6-Phenyl-imidazo[1,2-a]pyridine, except that the same operation was carried out to obtain 2.7 g of a yellow-white solid (yield 73%). This was analyzed by mass spectrometry (MS), and it was the target substance with a molecular weight of 672.26 and m/e=672.

Synthesis example 37 : (synthesis of compound 7-8')

(1) Synthesis of 2-(4-bromo-phenyl)-6,8-diphenyl-imidazo[1,2-a]pyridine

Dissolve 5.0g (20mmol) of 2-amino-3,5-dibromopyridine, 5.0g (41mmol) of phenylboronic acid, and 0.92g of tetrakis(triphenylphosphine)palladium in 130ml of 1,2-dimethoxyethyl Alkanes, add 62 ml of 2.0M aqueous sodium carbonate solution, and heat to reflux for 6 hours. After the reaction, it was dissolved in ethyl acetate, filtered, washed with water, and dried over sodium sulfate. The solvent was distilled off to obtain 8.9 g of crude 3,5-diphenyl-2-amino-pyridine.

The resulting crude 3,5-diphenyl-2-amino-pyridine and 5.5 g (20 mmol) of 2,4'-dibromoacetophenone were dissolved in 80 ml of ethanol, 3.0 g of sodium bicarbonate was added, and heated to reflux for 7 hours. After the reaction was completed, it was filtered, and the obtained crystals were washed with water and methanol to obtain 6.9 g of 2-(4-bromo-phenyl)-6-phenyl-imidazo[1,2-a]pyridine (yield 82%).

(2) 2-[4-(10-naphthalene-2-yl-anthracene-9-yl)-phenyl]-6,8-diphenyl-imidazo[1,2-a]pyridine (compound 7- 8') Synthesis

In (2) of Synthesis Example 31, use 2-(4-bromo-phenyl)-6,8-diphenyl-imidazo[1,2-a]pyridine instead of 2-(4-bromo-phenyl )-6-Phenyl-imidazo[1,2-a]pyridine, except that the same operation was carried out to obtain 3.2 g of a yellow-white solid (yield 86%). When analyzed by mass spectrometry (MS), it was the target substance with a molecular weight of 648.26 and m/e=648.

Synthesis example 38 : (synthesis of compound 9-7')

(1) Synthesis of 2-(4-bromo-phenyl)-6-phenyl-imidazo[1,2-a]pyrimidine

Dissolve 5.5g (32mmol) of 2-amino-5-bromopyridine, 4.3g (35mmol) of phenylboronic acid, and 0.80g of tetrakis(triphenylphosphine)palladium in 100ml of 1,2-dimethoxyethane, and add 50 ml of 2.0M aqueous sodium carbonate solution was heated to reflux for 8 hours. After the reaction was completed, it was filtered, and the organic layer was washed with water and dried over sodium sulfate. The solvent was distilled off to obtain 6.2 g of crude 5-phenyl-2-amino-pyrimidine.

The resulting crude 5-phenyl-2-amino-pyrimidine and 8.0 g (29 mmol) of 2,4'-dibromoacetophenone were dissolved in 100 ml of ethanol, 3.7 g of sodium bicarbonate was added, and heated to reflux for 3 hours. After the reaction was completed, it was filtered, and the obtained crystals were washed with water and methanol to obtain 5.4 g of 2-(4-bromo-phenyl)-6-phenyl-imidazo[1,2-a]pyrimidine (yield 49%).

(2) 2-[4-(10-naphthalene-2-yl-anthracene-9-yl)-phenyl]-6-phenyl-imidazo[1,2-a]pyrimidine (compound 9-7') Synthesis

3.0g (8.6mmol) 2-(4-bromo-phenyl)-6-phenyl-imidazo[1,2-a]pyrimidine, 3.0g (8.6mmol) 10-naphthalene-2-yl-anthracene- 9-boronic acid and 0.20 g of tetrakis(triphenylphosphine)palladium were dissolved in 30 ml of 1,2-dimethoxyethane, 13 ml of 2.0M aqueous sodium carbonate solution was added, and the mixture was heated to reflux for 7 hours. After the reaction was completed, it was filtered, and the obtained crystals were washed with water, methanol, and toluene to obtain 3.0 g of a yellow-white solid (yield 62%). When analyzed by mass spectrometry (MS), it was the target substance with a molecular weight of 573.22 and m/e=573.

Example 1 (Fabrication of an organic EL element using the compound of the present invention as a dry electron injection layer)

/秒:1

/分钟的成膜速度，形成膜厚为10nm的电子注入层(或阴极)。在该化合物(1-3)：Li膜上蒸镀金属Al，形成膜厚130nm的金属阴极，得到有机EL元件。A 25 mm x 75 mm x 1.1 mm thick glass substrate with an ITO transparent electrode (Jicai Mattik Co., Ltd.) was ultrasonically cleaned in isopropanol for 5 minutes, and then washed with UV ozone for 30 minutes. Set the washed glass substrate with transparent electrode lines on the substrate frame of the vacuum evaporation device, firstly, on the surface of the side where the transparent electrode lines are formed, the N, N' with a film thickness of 60nm is formed by resistive evaporation. - Membranes of bis(N,N'-diphenyl-4-aminophenyl)-N,N-diphenyl-4,4'-diamino-1,1'-biphenyl (hereinafter referred to as "TPD232 film"), so that the thin film covers the above-mentioned transparent electrodes. This TPD232 film functions as a first hole injection layer (hole transport layer). After the TPD232 film is formed, a film of 4,4'-bis[N-(1-naphthyl)-N-phenylamino]biphenyl with a film thickness of 20 nm is formed on the TPD232 film by resistance plus evaporation. (hereinafter referred to simply as "NPD film"). This NPD film functions as a second hole injection layer (hole transport layer). After forming the NPD film, then on the NPD film, add evaporation by resistance to form a film thickness of 4', 4 "-two (2,2-diphenylvinyl)-9,10-diphenylanthracene ( Hereinafter abbreviated as "DPVDPAN") film. The DPVDPAN film functions as a luminescent film. After the DPVDPAN film is formed, the compound (1-3) of the present invention is formed on the DPVDPAN film by resistive evaporation to form a film thickness of 10 nm. The film. This compound (1-3) acts as an electron injection layer. Then binary evaporation Li (Li source: サェゲゲツタ-Company) is used to compound (1-3): Li film=1.6

/sec:1

/min film formation speed, an electron injection layer (or cathode) with a film thickness of 10 nm is formed. Metal Al was vapor-deposited on the compound (1-3): Li film to form a metal cathode with a film thickness of 130 nm to obtain an organic EL element.

Example 2-15

An organic EL device was fabricated in the same manner except that the compound in Table 1 was used instead of the compound (1-3) in Example 1.

Comparative example 1

An organic EL device was produced in the same manner except that Alq (an aluminum complex of 8-hydroxyquinoline) was used instead of the compound (1-3) in Example 1.

(Evaluation of organic EL elements)

For the organic EL elements obtained in Examples 1-15 and Comparative Example 1 above, the emission luminance and emission efficiency were measured under the conditions of applying the DC voltage described in Table 1 below. The evaluation results are shown in Table 1.

Table 1

The compound of the electron injection layer Voltage (V) Current density (mA/cm ² ) Luminous brightness (nit) Luminous efficiency (cd/A) Example 1 Compound 1-3 7.5 3.09 119 3.85 Example 2 Compound 1-4 6.0 4.39 237 5.40 Example 3 Compound 14-7 3.7 7.74 532 6.87 Example 4 Compound 14-1 3.0 2.00 127 6.40 Example 5 Compound 14-2 3.0 2.10 146 7.10 Example 6 Compound 14-6 3.3 1.90 139 7.30 Example 7 Compound 14-9 4.2 2.60 150 5.80 Example 8 Compound 15-1 3.0 1.40 93 6.80 Example 9 Compound 15-3 3.5 3.30 242 7.40 Example 10 Compound 15-4 3.5 4.60 330 7.20 Example 11 Compound 15-5 3.5 3.00 222 7.40 Example 12 Compound 16-3 3.5 2.70 200 7.50 Example 13 Compound 19-1 3.0 1.70 123 7.30 Example 14 Compound 19-5 4.0 2.20 137 6.20 Example 15 Compound 26-8 4.8 3.40 178 5.30 Comparative example 1 Alq 6.0 5.20 190 3.75

From the results in Table 1 above, it can be known that using the above-mentioned compounds as electron injection materials can produce devices with extremely high luminous efficiency.

Example 16 (Manufacture of organic EL element using the compound of the present invention for the light-emitting layer)

/秒:1

/分钟的成膜速度，形成膜厚为20nm的电子注入层(阴极)。在该化合物(14-7)：Li膜上蒸镀金属Al，形成膜厚130nm的金属阴极，得到有机EL发光元件。该元件的直流电压为4.6V，发光亮度为1030cd/m²，可得到3.05cd/A的蓝色发光。A 25 mm x 75 mm x 1.1 mm thick glass substrate with an ITO transparent electrode (Jicai Mattik Co., Ltd.) was ultrasonically cleaned in isopropanol for 5 minutes, and then washed with UV ozone for 30 minutes. The glass substrate with the transparent electrode line after washing is arranged on the substrate frame of the vacuum evaporation device, firstly, a TPD232 film with a film thickness of 60 nm is formed by resistive evaporation on the surface of the side where the transparent electrode line is formed. A thin film covers the above-mentioned transparent electrodes. This TPD232 film functions as a first hole injection layer (hole transport layer). After the TPD232 film was formed, an NPD film with a thickness of 20 nm was formed on the TPD232 film by resistive vapor deposition. This NPD film functions as a second hole injection layer (hole transport layer). After the NPD film was formed, a film of the compound (14-7) of the present invention with a film thickness of 40 nm was formed on the NPD film by resistive vapor deposition. This compound (14-7) film functions as a light-emitting layer. Then binary evaporation Li (Li source: サェゲツツタ-company), with compound (14-7): Li film=1.6

/sec:1

/min, an electron injection layer (cathode) with a film thickness of 20 nm was formed. Metal Al was vapor-deposited on the compound (14-7): Li film to form a metal cathode with a film thickness of 130 nm, and an organic EL light-emitting element was obtained. The DC voltage of this element is 4.6V, the luminous brightness is 1030cd/m ² , and the blue luminescence of 3.05cd/A can be obtained.

Example 17

In Example 16, an organic EL device was produced using the compound (1-3) obtained in the synthesis example instead of the compound (14-7).

(Evaluation of organic EL elements)

For the organic EL elements obtained in Examples 16 and 17 above, the emission luminance, emission efficiency, and chromaticity were measured under the conditions of applying the DC voltage described in Table 2 below. The evaluation results are shown in Table 2.

Table 2

Compounds of the luminescent layer Voltage (V) Current density (mA/cm ² ) Luminous brightness (nit) Luminous efficiency (cd/A) Chroma Example 16 Compound 14-7 4.6 33.80 1030 3.05 (0.186, 0.212) Example 17 Compound 1-3 6.5 4.80 103 2.15 (0.229, 0.325)

From the results in Table 2 above, it can be seen that the use of the above compound as a light-emitting layer exhibits a sufficient effect.

Example 18

/分钟的成膜速度，形成膜厚10nm，作为电子注入层或阴极，除此之外同样地制作有机EL元件。In Example 1, use compound (2-7') instead of compound (1-3), with compound (2-7'): Li film=1.5 /sec:1

The organic EL element was fabricated in the same manner as the electron injection layer or cathode except that the film was formed at a film forming rate of 10 nm per minute.

For the obtained organic EL element, the luminous brightness, luminous efficiency, and chromaticity were measured by the voltage and current density in Table 3, and the results and luminous color are shown in Table 3.

Examples 19-21 (Manufacture of an organic EL element using the compound of the present invention for an electron injection layer)

In Example 18, an organic EL device was produced in the same manner except that the compounds in Table 3 were used instead of the compound (2-7').

According to the voltage and current density in Table 3, the luminous brightness, luminous efficiency, and chromaticity of the obtained organic EL element were measured, and the results and luminous color are shown in Table 3.

Comparative Example 2 (Preparation of Organic EL Element)

In Example 18, an organic EL device was produced in the same manner except that the aluminum complex (Alq) of 8-hydroxyquinoline was used instead of the compound (2-7').

According to the voltage and current density in Table 3, the luminous brightness, luminous efficiency, and chromaticity were measured for the obtained organic EL element, and the results and luminous color are shown in Table 3.

Comparative Example 3 (Preparation of Organic EL Element)

In Example 18, an organic EL device was produced in the same manner except that the following compound A described in JP-A-2001-6887 was used instead of the compound (2-7').

According to the voltage and current density in Table 3, the luminous brightness, luminous efficiency, and chromaticity of the obtained organic EL element were measured, and the results and luminous color are shown in Table 3.

Compound A

table 3

Types of Electron Injection Materials Voltage (V) Current density (mA/cm ² ) Luminous brightness (nit) Luminous efficiency (cd/A) Chroma Luminous color Example 18 Compound 2-7' 3.8 2.8 192 6.8 (0.146, 0.157) blue Example 19 Compound 3-5' 3.8 3.1 208 6.6 (0.144, 0.152) blue Example 20 Compound 3-6' 4.0 2.5 150 6.1 (0.147, 0.161) blue Example 21 Compound 7-8' 3.3 2.2 167 7.4 (0.150, 0.170) blue Comparative example 2 Alq 6.0 5.2 190 3.8 (0.149, 0.164) blue Comparative example 3 Compound A 7.0 3.2 135 4.2 (0.144, 0.144) blue

Table 3 shows that compared with Comparative Examples 2 and 3, the organic EL elements of Examples 8-21 using the nitrogen-containing heterocyclic derivatives of the present invention as electron injection materials have lower driving voltage and higher luminous brightness and luminous efficiency. .

Industrial applicability

The present invention provides an organic EL element capable of achieving high luminance, low driving voltage, and High luminous efficiency and long-term stability through improved adhesion to electrodes to increase lifetime.

Claims (11)

1. Nitrogen-containing heterocyclic derivatives shown in general formula (1): HAr-L-Ar ¹ -Ar ² (1) In the formula, HAr is any group selected from the nitrogen-containing heterocyclic group shown in the following general formulas (2) and (4)-(36): Wherein the carbon atom of the nitrogen-containing heterocyclic group is optionally substituted by a group selected from the following groups: an aryl group with 6-60 carbon atoms, a heteroaryl group with 3-60 carbon atoms, a heteroaryl group with 1 carbon atom -20 alkyl and alkoxy with 1-20 carbon atoms; L is a single bond, phenylene, biphenylene, pyridylene, naphthylene or anthracenediyl, these groups are respectively optionally substituted by alkyl, aryl or heteroaryl, the alkyl is selected from Methyl, ethyl, propyl, butyl, pentyl and hexyl; said aryl is selected from phenyl, naphthyl, anthracenyl, phenanthrenyl, naphthacene, Base, pyrenyl, biphenyl, terphenyl, tolyl, tert-butylphenyl, (2-phenylpropyl)phenyl, fluoranthene, fluorenyl, monovalent groups containing spirobifluorene, Perfluorophenyl, perfluoronaphthyl, perfluoroanthracenyl, perfluorobiphenyl, monovalent groups containing 9-phenylanthracene, monovalent groups containing 9-(1'-naphthyl)anthracene, Monovalent group containing 9-(2'-naphthyl)anthracene, containing 6-phenyl

The 1-valent group and the 1-valent group containing 9-[4-(diphenylamino)phenyl]anthracene; the heteroaryl group is selected from pyrrolyl, furyl, thienyl, silyl, pyridyl , quinolinyl, isoquinolyl, benzofuryl, imidazolyl, pyrimidinyl, carbazolyl, phenylselenyl, oxadiazolyl and triazolyl; Ar ¹ is 9,10-anthracenediyl or 2,7-anthracendiyl, which are optionally substituted by alkyl, aryl or heteroaryl respectively, and said alkyl is selected from methyl, ethyl, propyl, Butyl, pentyl and hexyl; The aryl is selected from phenyl, naphthyl, anthracenyl, phenanthrenyl, naphthacene,

Base, pyrenyl, biphenyl, terphenyl, tolyl, tert-butylphenyl, (2-phenylpropyl)phenyl, fluoranthene, fluorenyl, monovalent groups containing spirobifluorene, Perfluorophenyl, perfluoronaphthyl, perfluoroanthracenyl, perfluorobiphenyl, monovalent groups containing 9-phenylanthracene, monovalent groups containing 9-(1'-naphthyl)anthracene, Monovalent group containing 9-(2'-naphthyl)anthracene, containing 6-phenyl

The 1-valent group and the 1-valent group containing 9-[4-(diphenylamino)phenyl]anthracene; the heteroaryl group is selected from pyrrolyl, furyl, thienyl, silyl, pyridyl , quinolinyl, isoquinolyl, benzofuryl, imidazolyl, pyrimidinyl, carbazolyl, phenylselenyl, oxadiazolyl and triazolyl; Ar ² is any one group selected from the following formula:

These groups are optionally substituted by alkyl, aryl or heteroaryl respectively, the alkyl is selected from methyl, ethyl, propyl, butyl, pentyl and hexyl; the aryl is selected from phenyl, Naphthyl, anthracenyl, phenanthrenyl, naphthacene,

Base, pyrenyl, biphenyl, terphenyl, tolyl, tert-butylphenyl, (2-phenylpropyl)phenyl, fluoranthene, fluorenyl, monovalent groups containing spirobifluorene, Perfluorophenyl, perfluoronaphthyl, perfluoroanthracenyl, perfluorobiphenyl, monovalent groups containing 9-phenylanthracene, monovalent groups containing 9-(1'-naphthyl)anthracene, Monovalent group containing 9-(2'-naphthyl)anthracene, containing 6-phenyl

The 1-valent group and the 1-valent group containing 9-[4-(diphenylamino)phenyl]anthracene; the heteroaryl group is selected from pyrrolyl, furyl, thienyl, silyl, pyridyl , quinolinyl, isoquinolyl, benzofuryl, imidazolyl, pyrimidinyl, carbazolyl, phenylselenyl, oxadiazolyl and triazolyl. 2. The nitrogen-containing heterocyclic derivative of claim 1, wherein the carbon atom of the nitrogen-containing heterocyclic group is optionally substituted by a group selected from: phenyl, naphthyl, anthracenyl, phenanthrenyl, tetracene base,

Base, pyrenyl, biphenyl, terphenyl, tolyl, tert-butylphenyl, (2-phenylpropyl)phenyl, fluoranthene, fluorenyl, monovalent groups containing spirobifluorene, Perfluorophenyl, perfluoronaphthyl, perfluoroanthracenyl, perfluorobiphenyl, monovalent groups containing 9-phenylanthracene, monovalent groups containing 9-(1'-naphthyl)anthracene, Monovalent group containing 9-(2'-naphthyl)anthracene, containing 6-phenyl

Monovalent groups containing 9-[4-(diphenylamino)phenyl]anthracene, pyrrolyl, furyl, thienyl, thialyl, pyridyl, quinolinyl, isoquinolyl Linyl, benzofuryl, imidazolyl, pyrimidinyl, carbazolyl, phenylselenyl, oxadiazolyl, triazolyl, methyl, ethyl, propyl, butyl, pentyl, hexyl, methoxy ethoxy, propoxy, butoxy, pentyloxy and hexyloxy. 3. the nitrogen-containing heterocyclic derivative of claim 1, wherein, HAr is a group selected from the following formula:

4. the nitrogen-containing heterocyclic derivative of claim 1, wherein, L is a group selected from the following formula:

5. A material for an organic electroluminescence device, which contains the nitrogen-containing heterocyclic derivative according to any one of claims 1-4. 6. An organic electroluminescence element, which has at least one organic compound layer sandwiched by a pair of electrodes and comprising a light-emitting layer, and contains any one of claims 1-4 in at least one of the organic compound layers. Nitrogen-containing heterocyclic derivatives. 7. The organic electroluminescent device according to claim 6, wherein said nitrogen-containing heterocyclic derivative is contained in a light-emitting band region. 8. The organic electroluminescent device according to claim 6, wherein the nitrogen-containing heterocyclic derivative is contained in the light-emitting layer. 9. The organic electroluminescent device according to claim 6, wherein the nitrogen-containing heterocyclic derivative is used as an electron injection material and/or an electron transport material. 10. The organic electroluminescent device according to claim 9, wherein the layer containing the above-mentioned electron injection material and/or electron transport material contains a reducing dopant. 11. The organic electroluminescent element according to claim 10, wherein the above-mentioned reductive dopant is at least one selected from the oxides of alkali metals, alkaline earth metals, rare earth metals, alkali metals, halides of alkali metals, and oxides of alkaline earth metals. substances, halides of alkaline earth metals, oxides of rare earth metals, halides of rare earth metals, organic complexes of alkali metals, organic complexes of alkaline earth metals and organic complexes of rare earth metals.