KR20160034230A

KR20160034230A - Multicyclic compound including nitrogen and organic electronic device using the same

Info

Publication number: KR20160034230A
Application number: KR1020150132692A
Authority: KR
Inventors: 하재승; 곽지원
Original assignee: 주식회사 엘지화학
Priority date: 2014-09-19
Filing date: 2015-09-18
Publication date: 2016-03-29
Also published as: KR101778371B1

Abstract

The present invention relates to a nitrogen-containing polycyclic compound, and an organic electronic device comprising the same. One embodiment of the present invention provides a compound represented by chemical formula 1. Lifespan properties of the device can be improved by thermal stability of the compound, when the compound the used in the organic electronic device.

Description

TECHNICAL FIELD [0001] The present invention relates to a nitrogen-containing polycyclic compound and an organic electronic device using the same. BACKGROUND ART < RTI ID = 0.0 >

TECHNICAL FIELD The present invention relates to an organic electronic device material and an organic electronic device including the same. This application claims the benefit of the filing date of Korean Patent Application No. 10-2014-0125287 filed on September 19, 2014 to the Korean Intellectual Property Office, the entire contents of which are incorporated herein by reference.

An organic electronic device means an element requiring charge exchange between an electrode and an organic material using holes and / or electrons. The organic electronic device can be roughly classified into two types according to the operating principle as described below. First, an exciton is formed in an organic material layer by a photon introduced into an element from an external light source. The exciton is separated into an electron and a hole, and the electrons and holes are transferred to different electrodes to be used as a current source Type electric device. The second type is an electronic device that injects holes and / or electrons into an organic semiconductor that interfaces with an electrode by applying a voltage or current to two or more electrodes, and operates by injected electrons and holes.

Examples of the organic electronic device include an organic light emitting device, an organic solar cell, an organic photoconductor (OPC), an organic transistor, and the like. These devices may be used as a hole injecting or transporting material, an electron injecting or transporting material, need. Hereinafter, the organic light emitting device will be described in detail. However, in the organic electronic devices, hole injecting or transporting materials, electron injecting or transporting materials, or light emitting materials act on a similar principle.

In general, organic light emission phenomenon refers to a phenomenon in which an organic material is used to convert electric energy into light energy. An organic light emitting device using an organic light emitting phenomenon generally has a structure including an anode, a cathode, and an organic material layer therebetween. Here, in order to increase the efficiency and stability of the organic light emitting device, the organic material layer may have a multi-layer structure composed of different materials and may include a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, and an electron injection layer. When a voltage is applied between the two electrodes in the structure of such an organic light emitting device, holes are injected in the anode, electrons are injected into the organic layer in the cathode, excitons are formed when injected holes and electrons meet, When it falls back to the ground state, the light comes out. Such an organic light emitting device is known to have characteristics such as self-emission, high luminance, high efficiency, low driving voltage, wide viewing angle, high contrast, and high speed response.

Materials used as an organic material layer in an organic light emitting device can be classified into a light emitting material and a charge transporting material such as a hole injecting material, a hole transporting material, an electron transporting material, and an electron injecting material depending on functions. In addition, the luminescent material can be classified into blue, green and red luminescent materials and yellow and orange luminescent materials necessary for realizing a better natural color depending on the luminescent color. On the other hand, when only one material is used as the light emitting material, there arises a problem that the maximum light emitting wavelength shifts to a long wavelength due to intermolecular interaction, the color purity drops, or the efficiency of the device decreases due to the light emission attenuating effect. A host / dopant system may be used as a light emitting material in order to increase the efficiency of light emission through the light emitting layer.

In order for the organic luminescent device to sufficiently exhibit the above-described excellent characteristics, a material constituting the organic material layer in the device, such as a hole injecting material, a hole transporting material, a luminescent material, an electron transporting material and an electron injecting material is supported by a stable and efficient material However, development of a stable and efficient organic material layer material for an organic light emitting device has not been sufficiently developed yet. Therefore, development of new materials is continuously required, and the necessity of developing such materials is the same in other organic electronic devices described above.

Korean Patent Publication No. 2000-0051826

The present invention provides a nitrogen-containing polycyclic compound and an organic light-emitting device comprising the same.

One embodiment of the present disclosure provides compounds represented by Formula 1:

[Chemical Formula 1]

In Formula 1,

X is represented by the following formula (2)

(2)

At least one of R ₁ to R ₂ is - (L1) p- (Y) q, wherein p is from 0 to 10, q is an integer from 1 to 10,

L1 is a substituted or unsubstituted arylene group; A substituted or unsubstituted heteroarylene group,

Y is a substituted or unsubstituted aryl group; A substituted or unsubstituted heteroaryl group; Or -N (Z < 1 >) (Z < 2 &

Z 1 and Z 2 are the same or different and are each independently a substituted or unsubstituted alkyl group; A substituted or unsubstituted cycloalkyl group; A substituted or unsubstituted alkenyl group; A substituted or unsubstituted aryl group; Or a substituted or unsubstituted heteroaryl group,

L ₂ is a substituted or unsubstituted arylene group or a substituted or unsubstituted heteroarylene group,

A ₁ to A ₃ are the same or different from each other, and each independently CR 'or N,

Ar ₁ And Ar ₂ are the same or different and each independently represents a substituted or unsubstituted aryl group; Or a substituted or unsubstituted heteroaryl group,

At least one of Ar ₁ and Ar ₂ is a group of two or more rings,

R 'and R ₃ to R ₁₀ are the same or different from each other, and each independently hydrogen; heavy hydrogen; A halogen group; A nitrile group; A nitro group; An amino group; A hydroxy group; A carbonyl group; An ester group; Imide; An amino group; A substituted or unsubstituted silyl group; A substituted or unsubstituted boron group; A substituted or unsubstituted alkyl group; A substituted or unsubstituted cycloalkyl group; A substituted or unsubstituted alkoxy group; A substituted or unsubstituted aryloxy group; A substituted or unsubstituted alkylthio group; A substituted or unsubstituted arylsulfoxy group; A substituted or unsubstituted alkenyl group; A substituted or unsubstituted aryl group; A substituted or unsubstituted aralkyl group; A substituted or unsubstituted aralkenyl group; A substituted or unsubstituted alkylaryl group; A substituted or unsubstituted alkylamine group; A substituted or unsubstituted aralkylamine group; A substituted or unsubstituted heteroarylamine group; A substituted or unsubstituted arylamine group; A substituted or unsubstituted phosphine oxide group; A substituted or unsubstituted arylphosphine group; Or a substituted or unsubstituted heterocyclic group, or two or more groups adjacent to each other may be connected to each other to form a ring.

Also, the present specification discloses a plasma display panel comprising a first electrode; A second electrode facing the first electrode; And at least one organic compound layer provided between the first electrode and the second electrode, wherein at least one of the organic compound layers includes the compound of the formula (1) .

The compound of the present invention can be used as an organic material layer material, particularly a hole injecting material and / or a hole transporting material in an organic electronic device. When the compound is used in an organic electronic device, the driving voltage of the device is lowered, The lifetime characteristics of the device can be improved by the thermal stability of the device.

1 to 5 are cross-sectional views illustrating the structure of an organic electronic device according to the present invention.

Hereinafter, the present invention will be described in more detail.

The present invention provides a compound represented by the above formula (1).

In this specification

Quot; refers to a position at which a substituent is bonded to another substituent.

As used herein, the term " substituted or unsubstituted " A halogen group; A nitrile group; A nitro group; An alkoxy group; An aryloxy group; An alkyloxy group; Arylthioxy group; An alkylsulfoxy group; Arylsulfoxy group; An alkyl group; A cycloalkyl group; An alkenyl group; An aryl group; Aralkyl groups; An aralkenyl group; An alkylaryl group; An alkylamine group; A heteroarylamine group; An arylamine group; Or a heterocyclic group, or that at least two of the substituents exemplified above are substituted or unsubstituted with a substituent to which they are linked. For example, the "substituent group to which two or more substituents are connected" may be a biphenyl group. That is, the biphenyl group may be an aryl group, and may be interpreted as a substituent in which two phenyl groups are connected.

In the present specification, examples of the halogen group include fluorine, chlorine, bromine or iodine.

In the present specification, the carbon number of the carbonyl group is not particularly limited,

40 < / RTI > Specifically, it may be a compound having the following structure,

.

In the present specification, the ester group may be substituted with a straight-chain, branched or cyclic alkyl group having 1 to 25 carbon atoms or an aryl group having 6 to 25 carbon atoms in the ester group. Specifically, it may be a compound of the following structural formula, but is not limited thereto.

In the present specification, the number of carbon atoms of the imide group is not particularly limited, but is preferably 1 to 25 carbon atoms. Specifically, it may be a compound having the following structure, but is not limited thereto.

In the present specification, the silyl group specifically includes a trimethylsilyl group, a triethylsilyl group, a t-butyldimethylsilyl group, a vinyldimethylsilyl group, a propyldimethylsilyl group, a triphenylsilyl group, a diphenylsilyl group, But are not limited thereto.

In the present specification, the boron group specifically includes, but is not limited to, a trimethylboron group, a triethylboron group, a t-butyldimethylboron group, a triphenylboron group, and a phenylboron group.

In the present specification, the alkyl group may be linear or branched, and the number of carbon atoms is not particularly limited, but is preferably 1 to 40. According to one embodiment, the alkyl group has 1 to 20 carbon atoms. According to another embodiment, the alkyl group has 1 to 10 carbon atoms. According to another embodiment, the alkyl group has 1 to 6 carbon atoms. Specific examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, a n-butyl group, an isobutyl group, a tert-butyl group, But are not limited to, pentyl, isopentyl, neopentyl, tert-pentyl, hexyl, n-hexyl, 1-methylpentyl, , n-heptyl, 1-methylhexyl, cyclopentylmethyl, cyclohexylmethyl, octyl, n-octyl, tert-octyl, 1-methylheptyl, But are not limited to, dimethylheptyl, 1-ethyl-propyl, 1,1-dimethyl-propyl, isohexyl, 2-methylhexyl, 4-methylhexyl and 5-methylhexyl.

In the present specification, the alkoxy group may be linear, branched or cyclic. The number of carbon atoms of the alkoxy group is not particularly limited, but is preferably 1 to 20 carbon atoms. Specific examples include methoxy, ethoxy, n-propoxy, isopropoxy, i-propyloxy, n-butoxy, isobutoxy, tert-butoxy, sec-butoxy, n-pentyloxy, neopentyloxy, N-hexyloxy, n-hexyloxy, 3,3-dimethylbutyloxy, 2-ethylbutyloxy, n-octyloxy, n-nonyloxy, n-decyloxy, benzyloxy, But is not limited thereto.

In the present specification, the alkenyl group may be straight-chain or branched, and the number of carbon atoms is not particularly limited, but is preferably 2 to 40. According to one embodiment, the alkenyl group has 2 to 20 carbon atoms. According to another embodiment, the alkenyl group has 2 to 10 carbon atoms. According to another embodiment, the alkenyl group has 2 to 6 carbon atoms. Specific examples include vinyl, 1-propenyl, isopropenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-pentenyl, Butenyl, allyl, 1-phenylvinyl-1-yl, 2-phenylvinyl-1-yl, (Diphenyl-1-yl) vinyl-1-yl, stilbenyl, stilenyl, and the like.

In this specification, the cycloalkyl group is not particularly limited, but preferably has 3 to 60 carbon atoms. According to one embodiment, the cycloalkyl group has 3 to 30 carbon atoms. According to another embodiment, the cycloalkyl group has 3 to 20 carbon atoms. According to another embodiment, the cycloalkyl group has 3 to 6 carbon atoms. Specific examples include cyclopropyl, cyclobutyl, cyclopentyl, 3-methylcyclopentyl, 2,3-dimethylcyclopentyl, cyclohexyl, 3-methylcyclohexyl, 4-methylcyclohexyl, 2,3-dimethylcyclohexyl, 4,5-trimethylcyclohexyl, 4-tert-butylcyclohexyl, cycloheptyl, cyclooctyl, and the like, but are not limited thereto.

In the present specification, examples of the arylamine group include a substituted or unsubstituted monocyclic diarylamine group, a substituted or unsubstituted polycyclic diarylamine group, or a substituted or unsubstituted monocyclic and polycyclic diaryl Amine group.

In the present specification, the aryl group is not particularly limited, but preferably has 6 to 60 carbon atoms, and may be a monocyclic aryl group or a polycyclic aryl group. According to one embodiment, the aryl group has 6 to 30 carbon atoms. According to one embodiment, the aryl group has 6 to 20 carbon atoms. The aryl group may be a phenyl group, a biphenyl group, a terphenyl group or the like as the monocyclic aryl group, but is not limited thereto. Examples of the polycyclic aryl group include, but are not limited to, a naphthyl group, an anthracenyl group, a phenanthryl group, a pyrenyl group, a perylenyl group, a klycenyl group and a fluorenyl group.

In the present specification, a fluorenyl group may be substituted, and two substituents may be bonded to each other to form a spiro structure.

When the fluorenyl group is substituted,

,

,

, And

And the like. However, the present invention is not limited thereto.

In the present specification, the heterocyclic group is a heterocyclic group containing at least one of O, N and S as a heteroatom. The number of carbon atoms is not particularly limited, but is preferably 2 to 60 carbon atoms. Examples of the heterocyclic group include a thiophene group, a furan group, a pyrrolyl group, an imidazole group, a thiazole group, an oxazole group, an oxadiazole group, a pyridyl group, a bipyridyl group, a pyrimidyl group, , A pyridazinyl group, a pyrazinyl group, a quinolinyl group, a quinazoline group, a quinoxalinyl group, a phthalazinyl group, a pyridopyrimidinyl group, a pyridopyranyl group, a pyrazinopyranyl group, an isoquinoline group, , A carbazole group, a benzoxazole group, a benzoimidazole group, a benzothiazole group, a benzocarbazole group, a benzothiophene group, a dibenzothiophene group, a benzofuranyl group, a phenanthroline group, a thiazolyl group, Group, an oxadiazolyl group, a thiadiazolyl group, a benzothiazolyl group, a phenothiazinyl group, and a dibenzofuranyl group, but is not limited thereto.

In the present specification, the aryl group in the aralkyl group, the aralkenyl group, the alkylaryl group and the arylamine group is the same as the aforementioned aryl group.

In the present specification, the alkyl group in the aralkyl group, the alkylaryl group, and the alkylamine group is the same as the alkyl group described above.

In the present specification, the heteroaryl group in the heteroarylamine group and the heteroaryl group can be applied to the description of the above-mentioned heterocyclic group.

In the present specification, the alkenyl group in the aralkenyl group is the same as the above-mentioned alkenyl group.

In the present specification, the description of the aryl group described above can be applied except that arylene is a divalent group.

In the present specification, the description of the above-mentioned heterocyclic group can be applied except that the heteroarylene is a divalent group.

In the present specification, the term " two or more adjacent groups bonded to each other to form a ring means an aliphatic hydrocarbon ring which is bonded to an adjacent group to be substituted or unsubstituted; A substituted or unsubstituted aromatic hydrocarbon ring; A substituted or unsubstituted aliphatic heterocycle; Or a substituted or unsubstituted aromatic heterocycle.

In the present specification, the term " forming a ring by bonding to adjacent groups " means forming a ring by bonding to adjacent groups to form a substituted or unsubstituted aliphatic hydrocarbon ring; A substituted or unsubstituted aromatic hydrocarbon ring; A substituted or unsubstituted aliphatic heterocycle; Or a substituted or unsubstituted aromatic heterocycle.

As used herein, the term "adjacent group" means a group in which the substituent is substituted with an atom directly bonded to the atom to which the substituted atom is substituted, a substituent having the closest stereostructure to the substituent, It can mean. For example, two substituents substituted at the ortho position in the benzene ring and two substituents substituted at the same carbon in the aliphatic ring may be interpreted as "adjacent groups ".

In the present specification, an aliphatic hydrocarbon ring means a ring which is a non-aromatic ring and consists only of carbon and hydrogen atoms.

In the present specification, examples of the aromatic hydrocarbon ring include a phenyl group, a naphthyl group, and an anthracenyl group, but are not limited thereto.

As used herein, an aliphatic heterocycle refers to an aliphatic ring containing one or more of the N, O, or S atoms as heteroatoms.

As used herein, an aromatic heterocycle refers to an aromatic ring containing one or more of N, O, or S atoms as heteroatoms.

In the present specification, the aliphatic hydrocarbon ring, the aromatic hydrocarbon ring, the aliphatic heterocyclic ring and the aromatic heterocyclic ring may be monocyclic or polycyclic.

According to one embodiment of the present invention, L1 is a substituted or unsubstituted arylene group having 6 to 30 carbon atoms.

According to one embodiment of the present disclosure, L 1 is a substituted or unsubstituted phenylene group; Substituted or unsubstituted biphenylene group.

In one embodiment of the present specification, L 1 is a substituted or unsubstituted phenylene group.

In one embodiment of the present disclosure, L1 is a phenylene group.

In one embodiment of the present specification, L 1 is a substituted or unsubstituted biphenylene group.

In one embodiment of the present disclosure, L1 is a biphenylene group.

In one embodiment of the present disclosure, L1 is a naphthalene group.

In one embodiment of the present specification, L1 is an anthracene group.

In one embodiment of the present disclosure, L1 is selected from the substituents described in Table 3 below. These substituents may further have a substituent.

In one embodiment of the present specification, Y is a substituted or unsubstituted aryl group.

In one embodiment of the present specification, Y is a substituted or unsubstituted aryl group having 6 to 30 carbon atoms.

In one embodiment of the present specification, Y is a substituted or unsubstituted phenyl group.

In one embodiment of the present specification, Y is a substituted or unsubstituted naphthalene group.

In one embodiment of the present specification, Y is a substituted or unsubstituted carbazole group condensed with one or more substituted or unsubstituted benzenes.

In another embodiment, Y is a substituted or unsubstituted carbazole group having 1, 2 or 3 or more condensed benzene substituted or unsubstituted.

In one embodiment of the present specification, Y is a substituted or unsubstituted carbazole group condensed with 1, 2, 3 or 4 or more substituted or unsubstituted benzenes.

In one embodiment of the present specification, Y is a substituted or unsubstituted carbazole group condensed with 1, 2, 3, 4 or 5 or more of substituted or unsubstituted benzene.

In one embodiment of the present specification, Y is a substituted or unsubstituted carbazole group; A substituted or unsubstituted fluorenyl group; A substituted or unsubstituted benzocarbazole group; A substituted or unsubstituted dibenzocarbazole group; A substituted or unsubstituted dibenzofurane group; A substituted or unsubstituted dibenzothiophene group; Or -N (Z1) (Z2).

In one embodiment of the present specification, Y is a substituted or unsubstituted carbazole group; A substituted or unsubstituted benzocarbazole group; A substituted or unsubstituted dibenzocarbazole group; A substituted or unsubstituted fluorenyl group; Or -N (Z1) (Z2).

According to one embodiment of the present invention, Y in Formula 1 is a substituted or unsubstituted carbazolyl group substituted with an aryl group having 6 to 30 carbon atoms; A substituted or unsubstituted benzocarbazolyl group substituted with an aryl group having 6 to 30 carbon atoms; A substituted or unsubstituted dibenzocarbazole group substituted with an aryl group having 6 to 30 carbon atoms; Or -N (Z1) (Z2).

According to another embodiment, Y in the formula (1) is a substituted or unsubstituted carbazolyl group substituted with an aryl group having 6 to 30 carbon atoms; A substituted or unsubstituted benzocarbazolyl group substituted with an aryl group having 6 to 30 carbon atoms; A dibenzocarbazole group substituted with an aryl group having 6 to 30 carbon atoms; A fluorenyl group substituted with an alkyl group; A substituted or unsubstituted fluorenyl group substituted with an aryl group having 6 to 30 carbon atoms; A substituted or unsubstituted fluorenyl group containing a spiro structure; Or -N (Z1) (Z2).

According to one embodiment of the present invention, Y in Formula 1 is a fluorenyl group substituted with an alkyl group; A substituted or unsubstituted fluorenyl group substituted with an aryl group having 6 to 30 carbon atoms; A substituted or unsubstituted fluorenyl group containing a spiro structure; Or -N (Z1) (Z2).

According to one embodiment of the present invention, Y in Formula 1 is a carbazol group substituted or unsubstituted with a substituted or unsubstituted aryl group.

According to one embodiment of the present invention, Y in Formula 1 is a carbazol group substituted or unsubstituted with a substituted or unsubstituted aryl group having 6 to 30 carbon atoms.

According to another embodiment, Y in the formula (1) is a carbazol group substituted or unsubstituted with a substituted or unsubstituted phenyl group.

According to one embodiment of the present invention, Y in formula (1) is a carbazol group substituted or unsubstituted with a phenyl group.

According to one embodiment of the present invention, Y in the formula (1) is a substituted or unsubstituted carbazole group.

According to one embodiment of the present invention, Y in formula (1) is a carbazole group.

According to one embodiment of the present invention, Y in formula (1) is a dibenzocarbazole group substituted or unsubstituted with a substituted or unsubstituted aryl group.

According to one embodiment of the present invention, Y in Formula 1 is a dibenzocarbazole group substituted or unsubstituted with a substituted or unsubstituted aryl group having 6 to 30 carbon atoms.

According to another embodiment, Y in the formula (1) is a dibenzocarbazole group substituted or unsubstituted with a substituted or unsubstituted phenyl group.

According to one embodiment of the present invention, Y in Formula 1 is a dibenzocarbazole group substituted or unsubstituted with a phenyl group.

According to one embodiment of the present invention, Y in the formula (1) is a substituted or unsubstituted dibenzocarbazole group.

According to one embodiment of the present invention, Y in formula (1) is a dibenzocarbazole group.

According to one embodiment of the present invention, Y in formula (1) is a fluorenyl group substituted or unsubstituted with an alkyl group or an aryl group.

According to one embodiment of the present invention, Y in formula (1) is a fluorenyl group which is substituted or unsubstituted with a substituted or unsubstituted alkyl group.

According to one embodiment of the present invention, Y in formula (1) is a fluorenyl group substituted or unsubstituted with a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms.

According to one embodiment of the present invention, Y in Formula 1 is a fluorenyl group substituted or unsubstituted with a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms.

According to one embodiment of the present invention, Y in Formula 1 is a fluorenyl group substituted or unsubstituted with an aryl group having 1 to 30 carbon atoms.

According to one embodiment of the present invention, Y in formula (1) is a fluorenyl group substituted or unsubstituted with a substituted or unsubstituted phenyl group.

According to another embodiment, Y in formula (1) is a fluorenyl group substituted or unsubstituted with a phenyl group.

According to one embodiment of the present invention, Y in the formula (1) is a substituted or unsubstituted fluorenyl group.

In one embodiment of the present specification, Y is a substituted or unsubstituted fluorenyl group including a spiro structure.

In one embodiment of the present disclosure, Y can be represented by the following formula (A): < RTI ID = 0.0 >

(A)

In the above formula [A]

n is an integer of 1 to 7,

m is an integer of 1 to 3,

p and q are each an integer of 1 to 4,

When n is 2 or more, a plurality of Ra's are the same or different from each other,

When m is 2 or more, a plurality of Rb's are the same or different from each other,

When p is 2 or more, a plurality of Rc's are the same or different from each other,

When q is 2 or more, a plurality of Rd's are the same as or different from each other,

The definitions of Ra to Rd are the same as those of R 'and R ₃ to R _{10 in} the above formula (1).

In one embodiment of the present disclosure, Y is

to be.

In yet another embodiment, Y is

to be.

In another embodiment, Y is < RTI ID = 0.0 >

to be.

According to one embodiment of the present invention, Y in formula (1) is a fluorenyl group.

According to one embodiment of the present invention, Y in the formula (1) is a substituted or unsubstituted dibenzofurane group.

According to one embodiment of the present invention, Y in the formula (1) is a substituted or unsubstituted dibenzothiophene group.

According to another embodiment, Z1 or Z2 in the formula (1) is a substituted or unsubstituted aryl group having 6 to 30 carbon atoms.

According to one embodiment of the present invention, Z1 or Z2 in Formula 1 is a substituted or unsubstituted phenyl group; A substituted or unsubstituted biphenyl group; A substituted or unsubstituted terphenyl group; A substituted or unsubstituted naphthyl group or a substituted or unsubstituted fluorenyl group.

According to one embodiment of the present invention, Z1 or Z2 in Formula 1 is a substituted or unsubstituted phenyl group; A substituted or unsubstituted biphenyl group; Or a substituted or unsubstituted terphenyl group.

According to one embodiment of the present invention, Z1 or Z2 in the formula (1) is a phenyl group substituted or unsubstituted with a substituted or unsubstituted amine group.

According to one embodiment of the present invention, Z 1 or Z 2 in the general formula (1) is a phenyl group substituted or unsubstituted with an amine group substituted or unsubstituted with an aryl group.

According to one embodiment of the present invention, Z1 or Z2 in the general formula (1) is a phenyl group substituted or unsubstituted with an amine group substituted or unsubstituted with an aryl group having 6 to 30 carbon atoms.

According to one embodiment of the present invention, Z1 or Z2 in Formula 1 is a phenyl group substituted or unsubstituted with an amine group substituted with a substituted or unsubstituted phenyl group.

According to one embodiment of the present invention, Z1 or Z2 in Formula 1 is a phenyl group substituted or unsubstituted with an amine group disubstituted with a phenyl group.

According to another embodiment, Z1 or Z2 in Formula 1 is a phenyl group.

According to one embodiment of the present invention, Z1 or Z2 in Formula 1 is a substituted or unsubstituted biphenyl group.

According to one embodiment of the present invention, Z1 or Z2 in Formula 1 is a biphenyl group.

According to one embodiment of the present invention, Z1 or Z2 in Formula 1 is a substituted or unsubstituted terphenyl group.

According to one embodiment of the present invention, Z1 or Z2 in Formula 1 is a terphenyl group.

According to one embodiment of the present invention, Z1 or Z2 in Formula 1 is a substituted or unsubstituted naphthyl group.

According to one embodiment of the present invention, Z1 or Z2 in Formula 1 is a naphthyl group.

According to one embodiment of the present invention, Z1 and Z2 in the above formula (1) are mutually the same.

According to one embodiment of the present invention, Z1 and Z2 in the formula (1) are the same or different and are a substituted or unsubstituted phenyl group; Or a substituted or unsubstituted biphenyl group.

In one embodiment of the present disclosure, R1 or R2 is selected from Table 1 below. These substituents may further have a substituent.

In one embodiment of the present specification, at least one of A ₁ to A ₃ is N or CR "and R" is a halogen group; A nitrile group; A nitro group; An amino group; A hydroxy group; A carbonyl group; An ester group; Imide; An amino group; A substituted or unsubstituted silyl group; A substituted or unsubstituted boron group; A substituted or unsubstituted alkyl group; A substituted or unsubstituted cycloalkyl group; A substituted or unsubstituted alkoxy group; A substituted or unsubstituted aryloxy group; A substituted or unsubstituted alkylthio group; A substituted or unsubstituted arylsulfoxy group; A substituted or unsubstituted alkenyl group; A substituted or unsubstituted aryl group; A substituted or unsubstituted aralkyl group; A substituted or unsubstituted aralkenyl group; A substituted or unsubstituted alkylaryl group; A substituted or unsubstituted alkylamine group; A substituted or unsubstituted aralkylamine group; A substituted or unsubstituted heteroarylamine group; A substituted or unsubstituted arylamine group; A substituted or unsubstituted phosphine oxide group; A substituted or unsubstituted arylphosphine group; Or a substituted or unsubstituted heterocyclic group, or two or more groups adjacent to each other may be connected to each other to form a ring.

In one embodiment of the present disclosure, at least one of A ₁ to A ₃ is N.

In another embodiment, A ₁ to A ₃ are not simultaneously CH.

In another embodiment, X is selected from the following Table 2, but is not limited thereto.

In one embodiment of the present specification, L ₂ is a substituted or unsubstituted arylene group having 6 to 30 carbon atoms.

In one embodiment of the present specification, L ₂ is a substituted or unsubstituted phenylene group; A substituted or unsubstituted biphenylene group; Or a substituted or unsubstituted naphthalene group.

In one embodiment of the present specification, L ₂ is a substituted or unsubstituted phenylene group.

In one embodiment of the present disclosure, L ₂ is a phenylene group.

In one embodiment of the present specification, L ₂ is a substituted or unsubstituted biphenylene group.

In one embodiment of the present specification, L ₂ is a biphenylene group.

In one embodiment of the present specification, L < ₂ > is a substituted or unsubstituted naphthylene group.

In one embodiment of the present disclosure, L ₂ is a naphthylene group.

In one embodiment of the present specification, L < ₂ > can be selected from the substituents described in [Table 3] below, but is not limited thereto. These substituents may further have a substituent.

In another embodiment, Ar ₁ or Ar ₂ is a substituted or unsubstituted aryl group having 6 to 30 carbon atoms.

In one embodiment of the present specification, Ar ₁ or Ar ₂ is a substituted or unsubstituted aryl group having 1 to 4 ring members.

In one embodiment of the present specification, Ar ₁ or Ar ₂ represents a substituted or unsubstituted phenyl group; A substituted or unsubstituted biphenyl group; A substituted or unsubstituted terphenyl group; A substituted or unsubstituted naphthyl group; A substituted or unsubstituted phenanthrene group; Or a substituted or unsubstituted triphenylene group.

In one embodiment of the present specification, Ar ₁ or Ar ₂ is a substituted or unsubstituted phenyl group.

In one embodiment of the present specification, Ar ₁ or Ar ₂ is a phenyl group.

In one embodiment of the present specification, Ar ₁ or Ar ₂ is a substituted or unsubstituted biphenyl group.

In one embodiment of the present disclosure, Ar ₁ Or Ar ₂ is a biphenyl group.

In one embodiment of the present specification, Ar ₁ or Ar ₂ is a substituted or unsubstituted terphenyl group.

In one embodiment of the present specification, Ar ₁ or Ar ₂ is a terphenyl group.

In one embodiment of the present specification, Ar ₁ or Ar ₂ is a substituted or unsubstituted naphthyl group.

In one embodiment of the present specification, Ar ₁ or Ar ₂ is a naphthyl group.

In one embodiment of the present specification, Ar ₁ or Ar ₂ is a substituted or unsubstituted phenanthrene group.

In one embodiment of the present specification, Ar ₁ or Ar ₂ is a phenanthrene group.

In one embodiment of the present disclosure, Ar ₁ Or Ar ₂ is a substituted or unsubstituted triphenylene group.

In one embodiment of the present disclosure, Ar ₁ Or Ar ₂ is a triphenylene group.

In one embodiment of the present specification, Ar ₁ and Ar ₂ are the same.

In one embodiment of the present specification, Ar1 and Ar2 are naphthyl groups which are simultaneously substituted or unsubstituted.

In one embodiment of the present specification, Ar ₁ and Ar ₂ are simultaneously a naphthyl group.

In one embodiment of the present specification, Ar ₁ and Ar ₂ are biphenyl groups substituted or unsubstituted at the same time.

In one embodiment of the present specification, Ar ₁ and Ar ₂ are simultaneously biphenyl groups.

In one embodiment of the present specification, Ar ₁ or Ar ₂ may be selected from the following Table 4, but is not limited thereto. These substituents may further have a substituent.

In one embodiment of the present specification, among R ₁ and R ₂ , the group not substituted with - (L 1) p - (Y) q and R ₃ to R ₁₀ are both hydrogen.

In one embodiment of the present disclosure, the compound of Formula 1 may be selected from the following structural formulas, but is not limited thereto.

The compound represented by the above formula (1) can be produced based on the following production example. According to one embodiment, it can be prepared in the following manner.

[Reaction Scheme 1]

In Scheme 1, the Br of the S1 compound is located in ortho or meta with respect to the amine group and the Br of the S2 and S3 compounds is located ortho or meta with respect to the N.

However, the process for synthesizing the compound of formula (1) is not limited to the reaction conditions of formula (1), and any conditions may be used as long as the reaction conditions are known in the art.

According to one embodiment, the compound represented by Formula 1 may be prepared in the same manner as in Scheme 1-1.

[Reaction Scheme 1-1]

According to one embodiment, the compound represented by Formula 1 may be prepared in the following manner.

[Reaction Scheme 1-2]

In addition, the compound represented by Formula 1 may have various substituents using methods and materials known in the art.

The compounds represented by Formula 1 may have properties suitable for use as organic layers used in organic electronic devices by introducing various substituents into the core structure represented by the formula.

In one embodiment of the present disclosure, the first electrode; A second electrode facing the first electrode; And at least one organic material layer provided between the first electrode and the second electrode, wherein at least one of the organic material layers includes the compound of the formula (1).

The organic electronic device may be selected from the group consisting of an organic light emitting device, an organic solar cell, an organic photoconductor (OPC), and a glass transistor.

The organic material layer of the organic electronic device in this specification may have a single layer structure, but may have a multi-layer structure in which two or more organic material layers are stacked. For example, the organic electronic device of the present invention may have a structure including a hole injecting layer, a hole transporting layer, a light emitting layer, an electron transporting layer, an electron injecting layer, and the like as an organic material layer. However, the structure of the organic electronic device is not limited thereto and may include a smaller number of organic layers.

In one embodiment of the present invention, the organic material layer includes a hole injecting layer, a hole transporting layer, or a layer simultaneously injecting and transporting holes, and the hole injecting layer, the hole transporting layer, (1).

In another embodiment, the organic layer includes a light-emitting layer, and the light-emitting layer includes the compound of the general formula (1).

In another embodiment, the organic material layer includes an electron transporting layer, and the electron transporting layer includes the compound of the above formula (1).

In one embodiment of the present invention, the organic layer includes an electron transporting layer or an electron injecting layer, and the electron transporting layer or the electron injecting layer includes the compound of the above formula (1).

In one embodiment of the present invention, the electron transporting layer, the electron injecting layer, or the layer which simultaneously transports electrons and injects electrons includes the compound of the above formula (1).

In another embodiment, the organic material layer includes a light emitting layer and an electron transporting layer, and the electron transporting layer includes the compound of the above formula (1).

In another embodiment, the organic electronic device may be a normal type organic light emitting device in which an anode, one or more organic layers, and a cathode are sequentially stacked on a substrate.

In another embodiment, the organic electronic device may be an inverted type organic light emitting device in which a cathode, at least one organic layer, and an anode are sequentially stacked on a substrate.

The organic electronic device according to the present invention may have a structure as shown in Figs. 1 to 5, but the present invention is not limited thereto.

1 shows an organic electronic device in which a substrate 1, an anode 2, a hole injecting layer 3, a hole transporting layer 4, a light emitting layer 5, an electron transporting layer 6 and a cathode 7 are sequentially stacked Structure is illustrated.

2 illustrates the structure of an organic electronic device in which a substrate 1, an anode 2, a hole injection layer 3, a hole transport layer 4, a light emitting layer 5, and a cathode 7 are sequentially stacked.

3 illustrates the structure of an organic electronic device in which a substrate 1, an anode 2, a hole transport layer 4, a light emitting layer 5, an electron transport layer 6, and a cathode 7 are sequentially stacked.

4 shows a structure of an organic electronic device in which a substrate 1, an anode 2, a light emitting layer 5, an electron transport layer 6, and a cathode 7 are sequentially laminated.

5 illustrates a structure of an organic electronic device in which a substrate 1, an anode 2, a light emitting layer 5, and a cathode 7 are sequentially laminated.

The organic electronic device of the present invention can be manufactured by materials and methods known in the art, except that one or more of the organic layers includes the compound of the present invention, i.e., the compound of the above formula (1).

When the organic electronic device includes a plurality of organic layers, the organic layers may be formed of the same material or another material.

The organic electronic device of the present invention can be manufactured by materials and methods known in the art, except that one or more of the organic layers include the compound of the above formula (1), that is, the compound represented by the above formula (1).

For example, the organic electronic device of the present specification can be manufactured by sequentially laminating a first electrode, an organic material layer, and a second electrode on a substrate. At this time, a PVD (Physical Vapor Deposition) method such as sputtering or e-beam evaporation is used to deposit a metal or a metal oxide having conductivity or an alloy thereof on a substrate to form a positive electrode Forming an organic material layer including a hole injecting layer, a hole transporting layer, a light emitting layer and an electron transporting layer thereon, and depositing a material usable as a cathode thereon. In addition to such a method, an organic electronic device can be formed by sequentially depositing a negative electrode material, an organic material layer, and a positive electrode material on a substrate.

In addition, the compound of Formula 1 may be formed into an organic material layer by a solution coating method as well as a vacuum evaporation method in the production of an organic electronic device. Here, the solution coating method refers to spin coating, dip coating, doctor blading, inkjet printing, screen printing, spraying, roll coating and the like, but is not limited thereto.

In addition to such a method, an organic electronic device may be fabricated by sequentially depositing an organic material layer and a cathode material on a substrate from a cathode material (International Patent Application Publication No. 2003/012890). However, the manufacturing method is not limited thereto.

In one embodiment of the present invention, the first electrode is an anode and the second electrode is a cathode.

In another embodiment, the first electrode is a cathode and the second electrode is a cathode.

As the anode material, a material having a large work function is preferably used so that hole injection can be smoothly conducted into the organic material layer. Specific examples of the cathode material that can be used in the present invention include metals such as vanadium, chromium, copper, zinc, and gold, or alloys thereof; Metal oxides such as zinc oxide, indium oxide, indium tin oxide (ITO), and indium zinc oxide (IZO); ZnO: Al or SnO _2: a combination of a metal and an oxide such as Sb; Conductive polymers such as poly (3-methylthiophene), poly [3,4- (ethylene-1,2-dioxy) thiophene] (PEDOT), polypyrrole and polyaniline.

The negative electrode material is preferably a material having a small work function to facilitate electron injection into the organic material layer. Specific examples of the negative electrode material include metals such as magnesium, calcium, sodium, potassium, titanium, indium, yttrium, lithium, gadolinium, aluminum, silver, tin and lead or alloys thereof; Layer structure materials such as LiF / Al or LiO ₂ / Al, but are not limited thereto.

The hole injecting material is a layer for injecting holes from the electrode. The hole injecting material has a hole injecting effect, a hole injecting effect in the anode, and an excellent hole injecting effect in the light emitting layer or the light emitting material. A compound which prevents the exciton from migrating to the electron injection layer or the electron injection material and is also excellent in the thin film forming ability is preferable. It is preferable that the highest occupied molecular orbital (HOMO) of the hole injecting material be between the work function of the anode material and the HOMO of the surrounding organic layer. Specific examples of the hole injecting material include metal porphyrin, oligothiophene, arylamine-based organic materials, hexanitrile hexaazatriphenylene-based organic materials, quinacridone-based organic materials, and perylene- , Anthraquinone, polyaniline and polythiophene-based conductive polymers, but the present invention is not limited thereto.

The hole transport layer is a layer that transports holes from the hole injection layer to the light emitting layer. The hole transport material is a material capable of transporting holes from the anode or the hole injection layer to the light emitting layer. The material is suitable. Specific examples include arylamine-based organic materials, conductive polymers, and block copolymers having a conjugated portion and a non-conjugated portion together, but are not limited thereto.

The light emitting material is preferably a material capable of emitting light in the visible light region by transporting and receiving holes and electrons from the hole transporting layer and the electron transporting layer, respectively, and having good quantum efficiency for fluorescence or phosphorescence. Specific examples include 8-hydroxy-quinoline aluminum complex (Alq ₃ ); Carbazole-based compounds; Dimerized styryl compounds; BAlq; 10-hydroxybenzoquinoline-metal compounds; Compounds of the benzoxazole, benzothiazole and benzimidazole series; Polymers of poly (p-phenylenevinylene) (PPV) series; Spiro compounds; Polyfluorene, rubrene, and the like, but are not limited thereto.

The light emitting layer may include a host material and a dopant material. The host material is a condensed aromatic ring derivative or a heterocyclic compound. Specific examples of the condensed aromatic ring derivatives include anthracene derivatives, pyrene derivatives, naphthalene derivatives, pentacene derivatives, phenanthrene compounds, and fluoranthene compounds. Examples of the heterocycle-containing compounds include carbazole derivatives, dibenzofuran derivatives, Furan compounds, pyrimidine derivatives, and the like, but are not limited thereto.

Examples of the dopant material include aromatic amine derivatives, styrylamine compounds, boron complexes, fluoranthene compounds, and metal complexes. Specific examples of the aromatic amine derivatives include condensed aromatic ring derivatives having substituted or unsubstituted arylamino groups, and examples thereof include pyrene, anthracene, chrysene, and peripherrhene having an arylamino group. Examples of the styrylamine compound include substituted or unsubstituted Wherein at least one aryl vinyl group is substituted with at least one aryl vinyl group, and at least one substituent selected from the group consisting of an aryl group, a silyl group, an alkyl group, a cycloalkyl group and an arylamino group is substituted or unsubstituted. Specific examples thereof include, but are not limited to, styrylamine, styryldiamine, styryltriamine, styryltetraamine, and the like. Examples of the metal complex include iridium complex, platinum complex, and the like, but are not limited thereto.

The electron transporting material is a layer that receives electrons from the electron injecting layer and transports electrons to the light emitting layer. The electron transporting material is a material capable of transferring electrons from the cathode well to the light emitting layer. Is suitable. Specific examples include an Al complex of 8-hydroxyquinoline; Complexes containing Alq ₃ ; Organic radical compounds; Hydroxyflavone-metal complexes, and the like, but are not limited thereto. The electron transporting layer can be used with any desired cathode material as used according to the prior art. In particular, an example of a suitable cathode material is a conventional material having a low work function followed by an aluminum layer or a silver layer. Specifically cesium, barium, calcium, ytterbium and samarium, in each case followed by an aluminum layer or a silver layer.

The electron injection layer is a layer for injecting electrons from the electrode. The electron injection layer has the ability to transport electrons, has an electron injection effect from the cathode, and has an excellent electron injection effect with respect to the light emitting layer or the light emitting material. A compound which prevents migration to a layer and is excellent in a thin film forming ability is preferable. Specific examples thereof include fluorenone, anthraquinodimethane, diphenoquinone, thiopyran dioxide, oxazole, oxadiazole, triazole, imidazole, perylene tetracarboxylic acid, preorenylidene methane, A complex compound and a nitrogen-containing five-membered ring derivative, but are not limited thereto.

Examples of the metal complex compound include 8-hydroxyquinolinato lithium, bis (8-hydroxyquinolinato) zinc, bis (8-hydroxyquinolinato) copper, bis (8- Tris (8-hydroxyquinolinato) aluminum, tris (2-methyl-8-hydroxyquinolinato) aluminum, tris (8- hydroxyquinolinato) gallium, bis (10- Quinolinato) beryllium, bis (10-hydroxybenzo [h] quinolinato) zinc, bis (2-methyl-8- quinolinato) chlorogallium, bis (2-methyl-8-quinolinato) (2-naphtholato) gallium, and the like, But is not limited thereto.

The organic electronic device according to the present invention may be a top emission type, a back emission type, or a both-sided emission type, depending on the material used.

In one embodiment of the present invention, the compound of Formula 1 may be included in an organic solar cell or an organic transistor in addition to an organic electronic device.

Hereinafter, the present invention will be described in detail by way of examples with reference to the drawings. However, the embodiments according to the present disclosure can be modified in various other forms, and the scope of the present specification is not construed as being limited to the embodiments described below. Embodiments of the present disclosure are provided to more fully describe the present disclosure to those of ordinary skill in the art.

Example

PREPARATION EXAMPLE 1 Preparation of the following compounds 1-1 to 1-4

Synthesis Example 1-1 Synthesis of Compound 1-1

[Compound 1-1]

The compound 3-bromophenylhydrazine hydrochloride (25 g, 112 mmol) and 1-tetralone (18 g, 112 mmol) were added to ethanol (200 ml) and acetic acid (3 ml), and the mixture was heated with stirring. After 18 hours' reaction, the reaction mixture was cooled to room temperature, and the solvent was distilled off under reduced pressure to precipitate a solid with 30 ml of water. Dissolved in ethyl acetate, washed with water, and layered. After removal of the solvent, the compound 1-1 was recrystallized from ethyl acetate and n-hexane to obtain 11.6 g (yield: 35%) of the compound 1-1.

MS [M + H] < ⁺ > = 299.18

Synthesis Example 1-2 Synthesis of Compound 1-2 below

[Compound 1-2]

Except that 2-bromophenylhydrazine hydrochloride was used instead of the compound 3-bromophenylhydrazine hydrochloride in Synthesis Example 1-1, to thereby prepare Compound 1-2.

MS [M + H] < ⁺ > = 299.18

Synthesis Example 1-3 Synthesis of Compound 1-3 below

[Compound 1-3]

The compound 1-1 (11 g, 36.9 mmol) was added to 100 ml of acetonitrile and then 2,3-dichloro-5,6-dicyanobenzoquinone (9.2 g, 40.6 mmol) was added thereto. The mixture was stirred at room temperature for 1 hour Respectively. The reaction mixture was poured into 300 ml of water saturated with potassium carbonate, filtered, washed with water, dissolved in ethyl acetate, washed with water, and layered. After removal of the solvent, the compound 1-3 (10.3 g, yield: 95%) was prepared by recrystallization from ethyl acetate and n-hexane

MS [M + H] < ⁺ > = 297.18

<Synthesis Example 1-4> Synthesis of the following compounds 1-4

[Compound 1-4]

Compound 1-4 was prepared by the same method except for using Compound 1-2 in place of Compound 1-1 in Synthesis Example 1-3.

MS [M + H] < ⁺ > = 297.18

PREPARATION EXAMPLE 2 Preparation of the following compounds 2-1 to 2-4

Synthesis Example 2-1 Synthesis of the following compound 2-1

[Compound 2-1]

Phosphoryl trichloride (22.1 g, 144.1 mmol) was slowly added to the above compound N, N-dimethyl-1-naphthamide (26.1 g, 131 mmol) and heated to reflux. Then, Z-cyanobenzimideamide 19.01 g, 131 mmol) was slowly added with acetonitrile and the mixture was heated and stirred. The solution was cooled to room temperature, poured into water, filtered, and washed with ethanol. Thus, Compound 2-1 (32 g, yield: 77%) was prepared.

MS [M + H] < ⁺ > = 318.78

Synthesis Example 2-2 Synthesis of the following compound 2-2

[Compound 2-2]

Compound 2-2 was synthesized in the same manner as in Synthesis Example 2-1, except that N, N-dimethyl-2-naphthamide was used in place of N, N-dimethyl-1-naphthamide.

MS [M + H] < ⁺ > = 318.78

<Synthesis Example 2-3> Synthesis of the following compound 2-3

[Compound 2-3]

The compound of Synthesis Example 2-1 was synthesized in the same way except that N, N-dimethylphenanthrene-2-carboxamide was used in place of N, N-dimethyl-1-naphthamide, .

MS [M + H] < ⁺ > = 368.84

Synthesis Example 2-4 Synthesis of the following compound 2-4

[Compound 2-4]

The compound 2-4 was synthesized in the same manner except that N, N-dimethylphenanthrene-9-carboxamide was used instead of the compound N, N-dimethyl-1-naphthamide in Synthesis Example 2-1 .

MS [M + H] < ⁺ > = 368.84

PREPARATION EXAMPLE 3 Preparation of the following compounds 3-1 to 3-8

Synthesis Example 3-1 Synthesis of the following compound 3-1

[Compound 3-1]

To a solution of the compound 2-1 (22 g, 69.12 mmol) and 4-chlorophenylboronic acid (10.83 g, 69.2 mmol) in tetrahydrofuran (250 ml) was added 2M potassium carbonate aqueous solution (120 ml) Triphenylphosphinopalladium (2.4 mg, 2.1 mmol) was added thereto, followed by heating and stirring for 10 hours. After the temperature was lowered to room temperature and the reaction was terminated, the aqueous potassium carbonate solution was removed and the white solid was suspended. The filtered solid was recrystallized from tetrahydrofuran and ethanol to give the above compound 3-1 (22.1 g, yield 81%).

MS [M + H] < ⁺ > = 394.87

Synthesis Example 3-2 Synthesis of the following compound 3-2

[Compound 3-2]

The compound of Synthesis Example 3-1 was synthesized in the same manner except that 3-chlorophenylboronic acid was used in place of 4-chlorophenylboronic acid to prepare Compound 3-2.

MS [M + H] < ⁺ > = 394.87

Synthesis Example 3-3 Synthesis of Compound 3-3 below

[Compound 3-3]

Compound 3-2 was synthesized in the same manner as in Synthesis Example 3-1, except that Compound 2-2 was used instead of Compound 2-1 in Synthesis Example 3-1.

MS [M + H] < ⁺ > = 394.87

Synthesis Example 3-4 Synthesis of Compound 3-4 below

[Compound 3-4]

Compound 3-2 was synthesized by the same method except that 2-2 was used instead of the compound 2-1 in Synthesis Example 3-2.

MS [M + H] < ⁺ > = 394.87

Synthesis Example 3-5 Synthesis of Compound 3-5 below

[Compound 3-5]

Compound 3-5 was synthesized in the same manner as in Synthesis Example 3-1, except that Compound 2-3 was used instead of Compound 2-1.

MS [M + H] < ⁺ > = 444.12

Synthesis Example 3-6 Synthesis of Compound 3-6 below

[Compound 3-6]

Compound 3-6 was synthesized by the same method except that Compound 2-3 was used instead of Compound 2-1 of Synthesis Example 3-2.

MS [M + H] < ⁺ > = 444.12

Synthesis Example 3-7 Synthesis of Compound 3-7

[Compound 3-7]

Compound 3-7 was synthesized by the same method except for using 2-4 instead of Compound 2-1 in Synthesis Example 3-1.

MS [M + H] < ⁺ > = 444.12

Synthesis Example 3-8 Synthesis of the following compound 3-8

[Compound 3-8]

Compound 3-8 was synthesized by the same method except for using 2-4 instead of Compound 2-1 in Synthesis Example 3-2.

MS [M + H] < ⁺ > = 444.12

Preparation Example 4 Preparation of the following compounds 4-1 to 4-5

Synthesis Example 4-1 Synthesis of the following compound 4-1

[Compound 4-1]

Phenyl-9H-carbazol-3-yl-boronic acid instead of 9-bromo-11H-benzo [a] carbazole and 4- The compound 4-1 was synthesized by the same method except that the compound 4-1 was used.

MS [M + H] < ⁺ > = 459.18

Synthesis Example 4-2 Synthesis of the following compound 4-2

[Compound 4-2]

Except that 4- (9H-carbazol-9-yl) phenylboronic acid was used in place of 9-phenyl-9H-carbazol-3-yl-boronic acid in Synthesis Example 4-1, 4-2.

MS [M + H] < ⁺ > = 459.18

<Synthesis Example 4-3> Synthesis of the following compound 4-3

[Compound 4-3]

(Fluorene-9,8'-indolo [3,2,1-de] acridine) -2 (4-fluoro-9H-carbamoyl) -Ylboronic acid, the compound 4-3 was prepared.

MS [M + H] < ⁺ > = 621.23

<Synthesis Example 4-4> Synthesis of the following compound 4-4

[Compound 4-4]

(Fluorene-9,8'-indolo [3,2,1-de] acridine) -3 instead of 9-phenyl-9H-carbazol-3-yl-boronic acid in Synthesis Example 4-1 -Ylboronic acid as a starting material, to give a compound 4-4.

MS [M + H] < ⁺ > = 621.23

<Synthesis Example 4-5> Synthesis of the following compound 4-5

[Compound 4-5]

(Fluorene-9,8'-indolo [3,2,1-de] acridine) -4 (4-phenyl-9H-carbazol- -Ylboronic acid as a starting material, to give a compound 4-4.

MS [M + H] < ⁺ > = 621.23

PREPARATION EXAMPLE 5 Preparation of the following compounds 5-1 to 5-11

Synthesis Example 5-1 Synthesis of the following compound 5-1

[Compound 5-1]

Potassium-tertiary-butoxide (4.4 g, 45.7 mmol) was added to 300 ml of xylene after the addition of the compound 4-1 (15 g, 32.7 mmol) and 3-2 (13.1 g, 33.4 mmol) Pd [P (t-Bu) ₃ ] ₂ ) was added dropwise to the solution under stirring with heating, and bis [(tri- tertiary- butyl) phosphine] palladium (30 mg, 0.588 mmol) was added thereto, followed by heating and stirring for 4 hours. After lowering the temperature to room temperature and terminating the reaction, the white solid was filtered. The filtered white solid was recrystallized from chloroform, ethanol and ethyl acetate to give the above compound 5-1 (15 g, yield 60%).

MS [M + H] < ⁺ > = 816.30

Synthesis Example 5-2 Synthesis of the following compound 5-2

[Compound 5-2]

Except that 4-2 was used instead of 4-1 of Synthesis Example 5-1, and 3-4 was used instead of 3-2, to give Compound 5-2.

MS [M + H] < ⁺ > = 816.30

Synthesis Example 5-3 Synthesis of the following compound 5-3

[Compound 5-3]

The compound 5-3 was synthesized in the same manner as in Synthesis Example 5-1, except that 3-8 was used instead of 3-2 in the above Synthesis Example 5-1.

MS [M + H] < ⁺ > = 865.33

Synthesis Example 5-4 Synthesis of the following compound 5-4

[Compound 5-4]

Except that 4-2 was used instead of 4-1 of Synthesis Example 5-1, and 3-3 was used instead of 3-2, to thereby prepare a compound 5-4.

MS [M + H] < ⁺ > = 816.30

Synthesis Example 5-5 Synthesis of Compound 5-5

[Compound 5-5]

Compound 5-5 was synthesized by the same method except that 4-3 was used instead of 4-1 of Synthesis Example 5-1, and 3-1 was used instead of 3-2.

MS [M + H] < ⁺ > = 978.35

Synthesis Example 5-6 Synthesis of Compound 5-6

[Compound 5-6]

Compound 5-6 was synthesized by the same method except that 4-3 was used instead of 4-1 of Synthesis Example 5-1, and 3-3 was used instead of 3-2.

MS [M + H] < ⁺ > = 978.35

Synthesis Example 5-7 Synthesis of the following compounds 5-7

[Compound 5-7]

Compound 5-7 was synthesized in the same way except that 4-1 was used instead of 4-1 in Synthesis Example 5-1 and 3-1 was used in place of 3-2.

MS [M + H] < ⁺ > = 978.35

Synthesis Example 5-8 Synthesis of the following compounds 5-8

[Compound 5-8]

Compound 5-8 was synthesized by the same method except for using 4-5 instead of 4-1 in Synthesis Example 5-1.

MS [M + H] < ⁺ > = 978.35

Synthesis Example 5-9 Synthesis of the following compounds 5-9

[Compound 5-9]

Compound 5-9 was synthesized by the same method except for using 3-5 instead of 3-2 in Synthesis Example 5-1.

MS [M + H] < ⁺ > = 866.32

Synthesis Example 5-10 Synthesis of the following compounds 5-10

[Compound 5-10]

Compound 5-10 was synthesized in the same manner except that 4-2 was used instead of 4-1 of Synthesis Example 5-1 and 3-6 was used instead of 3-2.

MS [M + H] < ⁺ > = 866.32

Synthesis Example 5-11 Synthesis of the following compound 5-11

[Compound 5-11]

Compound 5-11 was synthesized by the same method except for using 4-2 instead of 4-1 of Synthesis Example 5-1 and 3-7 instead of 3-2.

MS [M + H] < ⁺ > = 866.32

&Lt; Comparative Example 1 &

The glass substrate coated with ITO (indium tin oxide) thin film with a thickness of 1,000 Å was immersed in distilled water containing detergent and washed with ultrasonic waves. In this case, Fischer Co. was used as a detergent, and distilled water filtered by a filter of Millipore Co. was used as distilled water. The ITO was washed for 30 minutes and then washed twice with distilled water and ultrasonically cleaned for 10 minutes. After the distilled water was washed, it was ultrasonically washed with a solvent of isopropyl alcohol, acetone, and methanol, dried, and then transported to a plasma cleaner. Further, the substrate was cleaned using oxygen plasma for 5 minutes, and then the substrate was transported by a vacuum evaporator.

On this ITO transparent electrode, hexanitrile hexaazatriphenylene (HAT) of the following chemical formula was thermally vacuum deposited to a thickness of 500 Å to form a hole injection layer.

[LINE]

N-phenylamino] biphenyl (NPB) (300 Å) was vacuum-deposited on the hole injection layer to form a hole transport layer, which is a material for transporting holes, and the following compound 4-4'-bis [N- (1-naphthyl) Respectively.

[NPB]

Subsequently, the following compound N - ([1,1'-bisphenyl] -4-yl) -N- (4- (11 - ([1,1'-biphenyl] -4 -yl) -11H-benzo [a] carbazole-5-yl) phenyl) - [1,1'-biphenyl] -4-amine (100A) and EB1 were vacuum deposited to form an electron blocking layer.

[EB1]

Subsequently, BH and BD were vacuum deposited on the electron blocking layer to a thickness of 300 ANGSTROM at a weight ratio of 25: 1 to form a light emitting layer.

[BH]

[BD]

[ET1]

[LiQ]

The compound ET1 and the compound LiQ (Lithium Quinolate) were vacuum deposited on the light emitting layer at a weight ratio of 1: 1 to form an electron injection and transport layer having a thickness of 300 Å. Lithium fluoride (LiF) and aluminum were deposited to a thickness of 2000 Å on the electron injecting and transporting layer sequentially to form a cathode.

Was maintained at the deposition rate was 0.4 ~ 0.7Å / sec for organic material in the above process, the lithium fluoride of the cathode was 0.3Å / sec, aluminum is deposited at a rate of 2Å / sec, the degree of vacuum upon deposition ⅹ10 2 ^-7 To 5 x 10 < ^-6 > torr, thereby fabricating an organic light emitting device.

&Lt; Example 1 >

In the same manner as in Comparative Example 1 except that the compound of Formula 5-1 was used instead of ET1.

&Lt; Example 2 >

In the same manner as in Comparative Example 1, except that ET1 was replaced with the compound of Formula 5-2.

&Lt; Example 3 >

In the same manner as in Comparative Example 1, except that ET1 was replaced with the compound of Formula 5-3.

<Example 4>

In the same manner as in Comparative Example 1, except that ET1 was replaced with the compound of Formula 5-4.

&Lt; Example 5 >

In the same manner as in Comparative Example 1, except that ET1 was replaced with the compound of Formula 5-5.

&Lt; Example 6 >

In the same manner as in Comparative Example 1, except that ET1 was used instead of the compound of Formula 5-6.

&Lt; Example 7 >

In the same manner as in Comparative Example 1, except that ET1 was replaced with the compound of Formula 5-7.

&Lt; Example 8 >

In the same manner as in Comparative Example 1 except that ET1 was replaced with the compound of Formula 5-8.

&Lt; Example 9 >

In the same manner as in Comparative Example 1, except that ET1 was replaced with the compound of Formula 5-9.

&Lt; Example 10 >

In the same manner as in Comparative Example 1, except that ET1 was replaced with the compound of Formula 5-10.

&Lt; Example 11 >

In the same manner as in Comparative Example 1, except that ET1 was replaced with the compound of Formula 5-11.

&Lt; Comparative Example 2 &

An organic light emitting device was fabricated in the same manner as in Comparative Example 1, except that the compound of ET2 was used in place of the compound ET1 in Comparative Example 1.

[ET2]

&Lt; Comparative Example 3 &

An organic light emitting device was fabricated in the same manner as in Comparative Example 1, except that the following compound ET3 was used instead of the compound ET1 in Comparative Example 1.

[ET3]

&Lt; Comparative Example 4 &

An organic light emitting device was fabricated in the same manner as in Comparative Example 1, except that the compound of ET4 was used in place of the compound ET1 in Comparative Example 1.

[ET4]

&Lt; Comparative Example 5 &

An organic light emitting device was fabricated in the same manner as in Comparative Example 1 except that the compound of ET5 was used in place of the compound ET1 in Comparative Example 1.

[ET5]

The results shown in Table 5 were obtained when a current was applied to the organic light-emitting device manufactured by Examples 1 to 11 and Comparative Examples 1 to 5.

compound
(Electron injection and transport layer) Voltage
(V @ 10 mA / cm ² ) efficiency
(cd / A @ 10mA / cm 2) Color coordinates
(x, y) Comparative Example 1 ET1 4.11 5.33 (0.138, 0.127) Example 1 5-1 3.94 5.35 (0.139, 0.122) Example 2 5-2 3.86 5.36 (0.138, 0.126) Example 3 5-3 3.85 5.51 (0.138, 0.127) Example 4 5-4 4.03 5.42 (0.137, 0.125) Example 5 5-5 3.83 5.56 (0.136, 0.125) Example 6 5-6 4.03 5.54 (0.136, 0.127) Example 7 5-7 3.94 5.35 (0.136, 0.125) Example 8 5-8 3.86 5.36 (0.137, 0.125) Example 9 5-9 3.85 5.51 (0.138, 0.125) Example 10 5-10 4.00 5.42 (0.136, 0.125) Example 11 5-11 3.84 5.46 (0.137, 0.125) Comparative Example 2 ET2 3.88 5.42 (0.136, 0.125) Comparative Example 3 ET3 3.89 5.36 (0.138, 0.126) Comparative Example 4 ET4 3.81 5.34 (0.137, 0.125) Comparative Example 5 ET5 3.80 5.50 (0.136, 0.127)

The compound represented by the chemical formula according to the present invention can serve as an electron injecting and electron transporting material in an organic electronic device including an organic light emitting device, and the device according to the present invention exhibits excellent characteristics in terms of efficiency, driving voltage, and stability.

1: substrate
2: anode
3: Hole injection layer
4: hole transport layer
5: light emitting layer
6: electron transport layer
7: cathode

Claims

A compound represented by the following formula (1):
[Chemical Formula 1]

In Formula 1,
X is represented by the following formula (2)
(2)

At least one of R ₁ to R ₂ is - (L1) p- (Y) q, wherein p is from 0 to 10, q is an integer from 1 to 10,
L1 is a substituted or unsubstituted arylene group; A substituted or unsubstituted heteroarylene group,
Y is a substituted or unsubstituted aryl group; A substituted or unsubstituted heteroaryl group; Or -N (Z < 1 >) (Z < 2 &
Z 1 and Z 2 are the same or different and are each independently a substituted or unsubstituted alkyl group; A substituted or unsubstituted cycloalkyl group; A substituted or unsubstituted alkenyl group; A substituted or unsubstituted aryl group; Or a substituted or unsubstituted heteroaryl group,
L ₂ is a substituted or unsubstituted arylene group or a substituted or unsubstituted heteroarylene group,
A ₁ to A ₃ are the same or different from each other, and each independently CR 'or N,
Ar ₁ and Ar ₂ are the same or different and each independently represents a substituted or unsubstituted aryl group; Or a substituted or unsubstituted heteroaryl group,
Ar ₁ And at least one of Ar ₂ is a group of two or more rings,
R 'and R ₃ to R ₁₀ are the same or different from each other, and each independently hydrogen; heavy hydrogen; A halogen group; A nitrile group; A nitro group; An amino group; A hydroxy group; A carbonyl group; An ester group; Imide; An amino group; A substituted or unsubstituted silyl group; A substituted or unsubstituted boron group; A substituted or unsubstituted alkyl group; A substituted or unsubstituted cycloalkyl group; A substituted or unsubstituted alkoxy group; A substituted or unsubstituted aryloxy group; A substituted or unsubstituted alkylthio group; A substituted or unsubstituted arylsulfoxy group; A substituted or unsubstituted alkenyl group; A substituted or unsubstituted aryl group; A substituted or unsubstituted aralkyl group; A substituted or unsubstituted aralkenyl group; A substituted or unsubstituted alkylaryl group; A substituted or unsubstituted alkylamine group; A substituted or unsubstituted aralkylamine group; A substituted or unsubstituted heteroarylamine group; A substituted or unsubstituted arylamine group; A substituted or unsubstituted phosphine oxide group; A substituted or unsubstituted arylphosphine group; Or a substituted or unsubstituted heterocyclic group, or two or more groups adjacent to each other may be connected to each other to form a ring.

[3] The compound according to claim 1, wherein at least one of A1 to A3 in Formula 1 is N or CR "
R " represents a halogen group; A nitrile group; A nitro group; An amino group; A hydroxy group; A carbonyl group; An ester group; Imide; An amino group; A substituted or unsubstituted silyl group; A substituted or unsubstituted boron group; A substituted or unsubstituted alkyl group; A substituted or unsubstituted cycloalkyl group; A substituted or unsubstituted alkoxy group; A substituted or unsubstituted aryloxy group; A substituted or unsubstituted alkylthio group; A substituted or unsubstituted arylsulfoxy group; A substituted or unsubstituted alkenyl group; A substituted or unsubstituted aryl group; A substituted or unsubstituted aralkyl group; A substituted or unsubstituted aralkenyl group; A substituted or unsubstituted alkylaryl group; A substituted or unsubstituted alkylamine group; A substituted or unsubstituted aralkylamine group; A substituted or unsubstituted heteroarylamine group; A substituted or unsubstituted arylamine group; A substituted or unsubstituted phosphine oxide group; A substituted or unsubstituted arylphosphine group; Or a substituted or unsubstituted heterocyclic group, or two or more groups adjacent to each other may be connected to each other to form a ring.

The method according to claim 1, at least one of Formula 1, A ₁ to A ₃ is a compound wherein the N.

The compound according to claim 1, wherein L 1 in Formula 1 is a substituted or unsubstituted arylene group having 6 to 30 carbon atoms.

The compound according to claim 1, wherein Y in Formula 1 is a substituted or unsubstituted carbazole group; A substituted or unsubstituted fluorenyl group; A substituted or unsubstituted benzocarbazole group; A substituted or unsubstituted dibenzocarbazole group; Or -N (Z1) (Z2).

The compound according to claim 1, wherein L ₂ in Formula 1 is a substituted or unsubstituted arylene group having 6 to 30 carbon atoms.

The compound according to claim 1, wherein Y in the formula (1) is represented by the following formula [A].
[A]

In the above formula [A]
n is an integer of 1 to 7,
m is an integer of 1 to 3,
p and q are each an integer of 1 to 4,
When n is 2 or more, a plurality of Ra's are the same as or different from each other,
When m is 2 or more, a plurality of Rb's are the same or different from each other,
When p is 2 or more, a plurality of Rc's are the same as or different from each other,
When q is 2 or more, a plurality of Rd's are the same as or different from each other,
The definitions of Ra to Rd are the same as those of R 'and R ₃ to R _{10 in} the above formula (1).

The compound according to claim 1, wherein R ₁ or R ₂ in the formula (1) is selected from the substituents described in the following Table 1:

The compound according to claim 1, wherein X in the formula (1) is selected from the substituents described in the following Table 2:

The compound according to claim 1, wherein L 1 or L 2 in the formula (1) is selected from the substituents described in the following Table 3:

The compound according to claim 1, wherein Ar ₁ or Ar ₂ in Formula 1 is a substituted or unsubstituted aryl group having 6 to 30 carbon atoms.

The compound according to claim 1, wherein Ar ₁ or Ar ₂ in the formula (1) is selected from the substituents described in the following Table 4:

The compound of claim 1, wherein the compound of formula (1) is selected from the following formulas:

A first electrode; A second electrode facing the first electrode; And at least one organic compound layer provided between the first electrode and the second electrode, wherein at least one of the organic compound layers comprises a compound according to any one of claims 1 to 13, device.

The organic electronic device according to claim 14, wherein the organic compound layer including the compound is a light emitting layer.

15. The organic electronic device according to claim 14, wherein the organic compound layer containing the compound is a hole injection layer, a hole transport layer, or a hole injection and transport layer.

The organic electronic device according to claim 14, wherein the organic compound layer containing the compound is an electron injecting layer, an electron transporting layer, or an electron injecting and transporting layer.

15. The organic electronic device according to claim 14, wherein the compound is a phosphorescent host material or a fluorescent host material.