KR101991428B1 - Heterocyclic compound and organic electronic device using the same - Google Patents

Abstract

The present application relates to heterocyclic compounds and organic electronic devices containing them.

Description

TECHNICAL FIELD [0001] The present invention relates to a heterocyclic compound and an organic electronic device including the heterocyclic compound.

The present application relates to heterocyclic compounds and organic electronic devices containing them.

A representative example of the organic electronic device is an organic light emitting device. 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.

Development of new materials for such organic light emitting devices has been continuously required.

International Patent Application Publication No. 2003-012890

The present application provides a heterocyclic compound and an organic electronic device including the heterocyclic compound.

The present application provides a compound represented by the following general formula (1).

[Chemical Formula 1]

In formula (1)

Y is O, S, NR or CRR '

L ₁ and L ₂ are the same or different and are each independently a direct bond; A substituted or unsubstituted arylene group; Or a substituted or unsubstituted heteroarylene group,

Wherein _{one of} Ar ₁ and Ar ₂ is selected from the following Group 1 and the other is selected from the following Group 2,

R, R ', R ₂ and R ₄ to R ₈ are the same or different from each other, and each independently hydrogen; heavy hydrogen; A halogen group; A hydroxy group; A nitro group; Cyano; A substituted or unsubstituted alkyl group; A substituted or unsubstituted alkenyl group; A substituted or unsubstituted alkynyl group; A substituted or unsubstituted cycloalkyl group; A substituted or unsubstituted alkoxy group; A substituted or unsubstituted aryloxy group; A substituted or unsubstituted arylthio group; A substituted or unsubstituted amine group; A substituted or unsubstituted aryl group; Or a substituted or unsubstituted heteroaryl group,

[Group 1]

[Group 2]

In Groups 1 and 2,

X is N or CR ", wherein at least one X is N,

R "and R ₉ to R ₄₅ are the same or different and are each independently hydrogen, heavy hydrogen; halogen; hydroxy group; nitro group; cyano group; a substituted or unsubstituted alkyl group; a substituted or unsubstituted alkenyl group; a substituted or A substituted or unsubstituted alkynyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heteroaryl group,

Ar ₃ and Ar ₄ are the same or different from each other, and each independently hydrogen; heavy hydrogen; Substituted or unsubstituted alkyl; A substituted or unsubstituted aryl group; A substituted or unsubstituted heteroaryl group; Or Ar ₃ and Ar ₄ are connected to each other to form a ring,

a, b, d, l, p, t and o are integers of 0 to 5,

c, h, k, m, n, q and u are integers of 0 to 4,

g, j and r are integers of 0 to 6,

f and w are integers of 0 to 7,

e and v are integers of from 0 to 8,

s is an integer of 0 to 9;

The dotted line (-----) means a site to be bonded to L ₁ or L ₂ .

The present application also includes a 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 above-described compound.

The compound according to one embodiment of the present application is used in organic electroluminescent devices including organic electroluminescent devices to lower the driving voltage of the organic electroluminescent device and to effectively transfer holes and electrons when used as a light emitting layer to improve light efficiency, The thermal stability can be improved to improve the lifetime characteristics of the device.

1 shows an example of an organic light emitting device in which a substrate 1, an anode 2, a light emitting layer 3, and a cathode 4 are sequentially laminated.
2 shows an organic light emitting device in which a substrate 1, an anode 2, a hole injecting layer 5, a hole transporting layer 6, a light emitting layer 3, an electron transporting layer 7 and a cathode 4 are sequentially laminated FIG.
3 is a graph showing the 1 H-NMR spectrum of Compound 15.

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

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

According to one embodiment of the present application, the compound represented by Formula 1 has the core structure, whereby the electron-withdrawing group and the electron-covalent group can be substituted adjacent to each other, and the energy When the substituent is located at such a position, HOMO (Highest Occupied Molecular Orbital) and LUMO (Lowest Unoccupied Molecular Orbital) can be separated to improve stability against electrons and holes.

Examples of substituents herein are described below, but are not limited thereto.

The term "substituted" means that the hydrogen atom bonded to the carbon atom of the compound is replaced with another substituent, and the substituted position is not limited as long as the substituent is a substitutable position, , Two or more substituents may be the same as or different from each other.

As used herein, the term " substituted or unsubstituted " A halogen group; Cyano; A nitro group; A hydroxy group; An alkyl group; A cycloalkyl group; An alkenyl group; An amine group; A phosphoryl group; An aryl group; And a heterocyclic group, or that at least two of the substituents exemplified in the above exemplified substituents are substituted with a connected substituent, or have no substituent. For example, "a substituent to which at least two 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 alkyl group may be linear or branched, and the number of carbon atoms is not particularly limited, but is preferably 1 to 50. Specific examples include methyl, ethyl, propyl, n-propyl, isopropyl, butyl, n-butyl, isobutyl, tert-butyl, sec- N-pentyl, 3-dimethylbutyl, 2-ethylbutyl, heptyl, n-hexyl, Cyclohexylmethyl, octyl, n-octyl, tert-octyl, 1-methylheptyl, 2-ethylhexyl, 2-propylpentyl, n-nonyl, 2,2-dimethyl Heptyl, 1-ethyl-propyl, 1,1-dimethyl-propyl, isohexyl, 2-methylpentyl, 4-methylhexyl, 5-methylhexyl and the like.

In the present specification, the cycloalkyl group is not particularly limited, but preferably has 3 to 60 carbon atoms. Specific examples thereof include cyclopropyl, cyclobutyl, cyclopentyl, 3-methylcyclopentyl, 2,3-dimethylcyclopentyl, But are not limited to, 3-methylcyclohexyl, 4-methylcyclohexyl, 2,3-dimethylcyclohexyl, 3,4,5-trimethylcyclohexyl, 4-tert- butylcyclohexyl, cycloheptyl, Do not.

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. 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 the present specification, when the aryl group is a monocyclic aryl group, the number of carbon atoms is not particularly limited, but is preferably 6 to 25 carbon atoms. Specific examples of the monocyclic aryl group include a phenyl group, a biphenyl group, a terphenyl group, and the like, but are not limited thereto.

When the aryl group is a polycyclic aryl group, the number of carbon atoms is not particularly limited. And preferably has 10 to 24 carbon atoms. Specific examples of the polycyclic aryl group include naphthyl, anthracenyl, phenanthryl, pyrenyl, perylenyl, klychenyl, fluorenyl, and the like.

In the present specification, the fluorenyl group may be substituted, and adjacent substituents may be bonded to each other to form a ring.

,

,

,

,

,

등이 될 수 있으나, 이에 한정되는 것은 아니다.When the fluorenyl group is substituted,

,

,

,

,

,

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

), 피리다지닐기, 피라지닐기, 퀴놀리닐기, 퀴나졸리닐기, 퀴녹살리닐기, 프탈라지닐기, 피리도피리미디닐기, 피리도피라지닐기, 피라지노피라지닐기, 이소퀴놀리닐기, 인돌기, 카바졸릴기, 벤즈옥사졸릴기, 벤즈이미다졸릴기, 벤조티아졸릴기, 벤조카바졸릴기, 디벤조카바졸릴기, 벤조티오페닐기, 디벤조티오페닐기, 벤조퓨라닐기, 디벤조퓨라닐기; 벤조실롤기; 디벤조실롤기; 페난트롤리닐기(phenanthrolinyl group), 티아졸릴기, 이소옥사졸릴기, 옥사디아졸릴기, 티아디아졸릴기, 벤조티아졸릴기, 페노티아지닐기, 페노옥사지닐기, 및 이들의 축합구조 등이 있으나, 이들에만 한정되는 것은 아니다. 이외에도 헤테로고리기의 예로서, 술포닐기를 포함하는 헤테로고리 구조, 예컨대,

,

등이 있다.In the present specification, the heterocyclic group includes at least one non-carbon atom or hetero atom, and specifically, the hetero atom may include at least one atom selected from the group consisting of O, N, Se and S, and the like. The number of carbon atoms of the heterocyclic group is not particularly limited, but is preferably 2 to 60 carbon atoms. Examples of the heterocyclic group include thiophenyl group, furanyl group, pyrrolyl group, imidazolyl group, thiazolyl group, oxazolyl group, oxadiazolyl group, triazolyl group, pyridyl group, bipyridyl group, pyrimidyl group, Group, an acridyl group, a hydroacridyl group (e.g.,

), A pyridazinyl group, a pyrazinyl group, a quinolinyl group, a quinazolinyl group, a quinoxalinyl group, a phthalazinyl group, a pyridopyrimidinyl group, a pyridopyranyl group, a pyrazinopyrazinyl group, an isoquinolinyl group , An indole group, a carbazolyl group, a benzoxazolyl group, a benzimidazolyl group, a benzothiazolyl group, a benzocarbazolyl group, a dibenzocarbazolyl group, a benzothiophenyl group, a dibenzothiophenyl group, a benzofuranyl group, A furanyl group; Benzosyl group; Dibenzosilyl groups; A phenanthrolinyl group, a thiazolyl group, an isoxazolyl group, an oxadiazolyl group, a thiadiazolyl group, a benzothiazolyl group, a phenothiazinyl group, a phenoxazinyl group, and condensation structures thereof , But are not limited thereto. In addition, examples of the heterocyclic group include a heterocyclic structure including a sulfonyl group,

,

.

,

,

등이 될 수 있으나, 이에 한정되는 것은 아니다.In the present specification, the condensed structure may be a structure in which an aromatic carbon-hydrogen ring is condensed with the substituent. For example, as a condensation ring of benzimidazole

,

,

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

As used herein, the term "adjacent" means that the substituent is a substituent substituted on an atom directly connected to the substituted atom, a substituent stereostructically closest to the substituent, or another substituent substituted on the substituted atom . 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 to each other.

In the present specification, the adjacent groups bonded to each other to form a ring means that adjacent groups are bonded to each other to form a 5-membered to 8-membered hydrocarbon ring or a 5-to 8-membered heterocyclic ring as described above , Monocyclic or polycyclic, and may be aliphatic, aromatic, or condensed forms thereof, but is not limited thereto.

According to one embodiment of the present application, Y is O.

According to one embodiment of the present application, Y is S.

According to one embodiment of the present application, Y is NR and R is the same as defined in formula (1).

According to one embodiment of the present application, Y is NR and R is a substituted or unsubstituted aryl group.

According to one embodiment of the present application, Y is NR and R is an aryl group.

According to one embodiment of the present application, Y is NR and R is a phenyl group.

According to one embodiment of the present application, Y is CRR ', and R and R' are the same as defined in formula (1).

According to one embodiment of the present application, Y is CRR ', R and R' are the same or different and each independently hydrogen; heavy hydrogen; A halogen group; A substituted or unsubstituted alkyl group; Or a substituted or unsubstituted aryl group.

According to one embodiment of the present application, Y is CRR ', R and R' are the same or different and each independently hydrogen; heavy hydrogen; Or a substituted or unsubstituted alkyl group.

According to one embodiment of the present application, Y is CRR ', and R and R' are methyl groups.

According to one embodiment of the present application, L < _{1 >} and L < ₂ > are the same or different and are each independently a direct bond; A substituted or unsubstituted phenylene group; A substituted or unsubstituted divalent biphenyllylene group; A substituted or unsubstituted naphthylene group; A substituted or unsubstituted thiophenylene group; A substituted or unsubstituted pyridyl group; A substituted or unsubstituted pyrimidylene group; Or a substituted or unsubstituted triazylene group.

According to one embodiment of the present application, L < ₁ > is a direct bond.

According to one embodiment of the present application, L < ₁ > is a phenylene group.

According to one embodiment of the present application, L < ₁ > is a biphenylene group.

According to one embodiment of the present application, L < ₁ > is a naphthylene group.

According to one embodiment of the present application, L &_lt; ₁ > is a thiophenylene group.

According to one embodiment of the present application, L < ₁ > is a pyridylene group.

According to one embodiment of the present application, L < ₁ > is a pyrimidylene group.

According to one embodiment of the present application, L < ₁ > is a triazylene group.

According to one embodiment of the present application, L < ₂ > is a direct bond.

According to one embodiment of the present application, L < ₂ > is a phenylene group.

According to one embodiment of the present application, L < ₂ > is a biphenylene group.

According to one embodiment of the present application, L < ₂ > is a naphthylene group.

According to one embodiment of the present application, L < ₂ > is a thiophenylene group.

According to one embodiment of the present application, L < ₂ > is a pyridylene group.

According to one embodiment of the present application, L < ₂ > is a pyrimidylene group.

According to one embodiment of the present application, L < ₂ > is a triazylene group.

According to one embodiment of the present application, R ₉ to R ₃₉ are the same or different from each other and each independently hydrogen; heavy hydrogen; A halogen group; A substituted or unsubstituted alkyl group; Or a substituted or unsubstituted aryl group.

According to one embodiment of the present application, R ₉ to R ₃₉ are the same or different from each other and each independently hydrogen; heavy hydrogen; A halogen group; Methyl group; An ethyl group; Propyl group; i-propyl; Butyl group; t-butyl group; A phenyl group; Or a naphthyl group.

According to one embodiment of the present application, R "is hydrogen, deuterium, a halogen group, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aryl group.

According to one embodiment of the present application, R "is hydrogen, deuterium, halogen, methyl, phenyl, biphenyl or naphthyl.

According to one embodiment of the present application, Ar ₃ and Ar ₄ are the same or different and are each independently a substituted or unsubstituted aryl group.

According to one embodiment of the present application, Ar ₃ and Ar ₄ are the same or different and are each independently a substituted or unsubstituted phenyl group; A substituted or unsubstituted biphenyl group; A substituted or unsubstituted naphthyl group; Or a substituted or unsubstituted fluorene group.

According to one embodiment of the present application, Ar ₃ and Ar ₄ are the same or different from each other, and each independently represents a phenyl group; A biphenyl group; Naphthyl group; Or a dimethylfluorene group.

According to one embodiment of the present application, the group 1 is selected from the following structural formulas, and R 9 to R 15 and a to d are the same as defined in the formula (1).

According to one embodiment of the present application, each of R9 to R15 is independently hydrogen, deuterium, or a substituted or unsubstituted aryl group.

According to one embodiment of the present application, each of R9 to R15 is, independently, hydrogen, deuterium, a substituted or unsubstituted phenyl group, a substituted or unsubstituted biphenyl group, or a substituted or unsubstituted fluorenyl group.

According to one embodiment of the present application, each of R9 to R15 independently represents hydrogen, deuterium, a phenyl group, a biphenyl group, or a dimethylfluorenyl group.

According to one embodiment of the present application, R ₂ and R ₄ to R ₈ are the same or different and each independently hydrogen; heavy hydrogen; A halogen group; A C ₁ to C ₁₀ alkyl group; Or a C ₆ to C ₂₀ aryl group.

According to one embodiment of the present application, R ₂ and R ₄ to R ₈ are the same or different and each independently hydrogen; heavy hydrogen; A halogen group; Methyl group; An ethyl group; Propyl group; i-propyl; Butyl group; t-butyl group; A phenyl group; Or a naphthyl group.

According to one embodiment of the present application, R ₂ and R ₄ to R ₈ are hydrogen.

According to one embodiment of the present application, the compound represented by Formula 1 is selected from the following structural formulas.

The compound according to one embodiment of the present application can be produced by a production method described below.

For example, the compound of Formula 1 may be prepared as a core structure as shown in the following reaction formula.

The above reaction scheme is an example of a method of synthesizing the core of Formula 1, but the present invention is not limited thereto, and the type and position of the substituent may be changed if necessary.

Substituent groups may be attached by methods known in the art, and the type, position or number of substituent groups may be varied according to techniques known in the art.

In the above reaction formula, L ₁ , L ₂ , Ar ₁ and Ar ₂ are the same as described above.

A concrete manufacturing method will be described later.

Further, the present invention provides an organic electronic device comprising the above-mentioned compounds.

In one embodiment of the present application, the 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.

When a member is referred to herein as being "on " another member, it includes not only a member in contact with another member but also another member between the two members.

Whenever a component is referred to as "comprising ", it is to be understood that the component may include other components as well, without departing from the scope of the present invention.

The organic material layer of the organic electronic device of the present application 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, as a representative example of the organic electronic device of the present invention, the organic light emitting device 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, etc. 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.

According to one embodiment of the present application, the organic electronic device may be selected from the group consisting of an organic light emitting device, an organic phosphorescent device, an organic solar cell, an organic photoconductor (OPC), and an organic transistor.

Hereinafter, the organic light emitting device will be described.

In one embodiment of the present application, the organic layer includes a light emitting layer, and the light emitting layer includes the compound.

In one embodiment of the present application, the organic layer includes a hole injection layer or a hole transport layer, and the hole injection layer or the hole transport layer includes the compound.

In another embodiment, the organic layer includes a light emitting layer, and the light emitting layer includes the compound.

In one embodiment of the present application, the organic material layer includes an electron transporting layer or an electron injecting layer, and the electron transporting layer or the electron injecting layer includes the above compound.

In one embodiment of the present application, the organic layer includes an electron blocking layer or a hole blocking layer, and the electron blocking layer or the hole blocking layer includes the compound.

In one embodiment of the present application, the organic light emitting element is a hole injecting layer, a hole transporting layer. An electron transport layer, an electron injection layer, an electron blocking layer, and a hole blocking layer.

In one embodiment of the present application, the organic light emitting device includes a first electrode; A second electrode facing the first electrode; And a light emitting layer provided between the first electrode and the second electrode; At least one of the two or more organic layers includes two or more organic layers disposed between the light emitting layer and the first electrode or between the light emitting layer and the second electrode. In one embodiment of the present application, the two or more organic layers may be selected from the group consisting of an electron transport layer, an electron injection layer, a layer that simultaneously transports electrons and electrons, and a hole blocking layer.

In one embodiment of the present application, the organic material layer includes two or more electron transporting layers, and at least one of the two or more electron transporting layers includes the above compound. Specifically, in one embodiment of the present specification, the compound may be contained in one of the two or more electron transporting layers, and may be included in each of two or more electron transporting layers.

In the embodiment of the present application, when the compound is contained in each of the two or more electron transporting layers, the materials other than the above compounds may be the same or different from each other.

In one embodiment of the present application, the organic layer further includes a hole injection layer or a hole transport layer containing a compound containing an arylamino group, a carbazolyl group or a benzocarbazolyl group in addition to the organic compound layer containing the compound.

In one embodiment of the present invention, the light emitting layer comprises a compound of the general formula (1), and further comprises a luminescent dopant.

In another embodiment, the luminescent dopant comprises a phosphorescent dopant.

In another embodiment, the phosphorescent dopant comprises an iridium phosphorescent dopant.

In another embodiment, the phosphorescent dopant material is Ir (ppy) ₃ .

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

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

For example, the structure of an organic light emitting device according to one embodiment of the present application is illustrated in Figs. 1 and 2. Fig.

1 shows a structure of an organic electronic device in which a substrate 1, an anode 2, a light emitting layer 3, and a cathode 4 are sequentially laminated. In such a structure, the compound may be included in the light emitting layer (3).

2 shows an organic electronic device in which a substrate 1, an anode 2, a hole injecting layer 5, a hole transporting layer 6, a light emitting layer 3, an electron transporting layer 7 and a cathode 4 are sequentially stacked Structure is illustrated. In such a structure, the compound may be contained in at least one of the hole injecting layer 5, the hole transporting layer 6, the light emitting layer 3, and the electron transporting layer 7.

In such a structure, the compound may be contained in at least one of the hole injecting layer, the hole transporting layer, the light emitting layer, and the electron transporting layer.

The organic light emitting device of the present application may be manufactured by materials and methods known in the art, except that one or more of the organic layers include the compound of the present application, i.e., the compound.

When the organic light emitting diode includes a plurality of organic layers, the organic layers may be formed of the same material or different materials.

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

For example, the organic light emitting device of the present application can be manufactured by sequentially laminating a first electrode, an organic material layer, and a second electrode on a substrate. At this time, by using a PVD (physical vapor deposition) method such as a sputtering method or an e-beam evaporation method, a metal or a metal oxide having conductivity or an alloy thereof is deposited on the 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 light emitting device can be formed by sequentially depositing a cathode material, an organic material layer, and a cathode 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 light emitting 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 one embodiment of the present application, 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); A combination of a metal and an oxide such as ZnO: Al or SNO2: 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 heterocycle-containing compounds include compounds, dibenzofuran derivatives, ladder furan compounds , Pyrimidine derivatives, 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, perylenetetracarboxylic 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 hole blocking layer prevents holes from reaching the cathode, and may be formed under the same conditions as those of the hole injecting layer. Specific examples thereof include, but are not limited to, oxadiazole derivatives, triazole derivatives, phenanthroline derivatives, BCP, aluminum complexes and the like.

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

In one embodiment of the present application, the compound may be included in an organic solar cell or an organic transistor in addition to the organic light emitting device.

The compound according to the present application may act on a principle similar to that applied to organic light emitting devices in organic electronic devices including organic phosphorescent devices, organic solar cells, organic photoconductors, organic transistors and the like.

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 application is not construed as being limited to the embodiments described below. The embodiments of the present application are provided to enable those skilled in the art to more fully understand the present invention.

< Manufacturing example  1> Synthesis of intermediate 1

(Reaction Example 1-1) Synthesis of 1-1

(0.24 mol) of 2-bromo-4-chlorophenol and 37 g (0.26 mol) of (2-fluorophenyl) boronic acid were dissolved in 600 mL of THF (tetrahydrofuran), 100 g (0.73 mol) Carbonate (200 mL) was added to the reaction solution, followed by heating. 2.8 g (2.4 mmol) of tetrakis (triphenylphosphine) palladium (0) was added thereto under reflux. The mixture was refluxed for 12 hours. After completion of the reaction, the reaction mixture was cooled to room temperature and the water layer was discarded. The organic solvent was concentrated under reduced pressure. The residue was dissolved in chloroform and washed twice with water. The organic layer was separated and treated with anhydrous magnesium sulfate, 53 g (-100%) of 1-1 was obtained.

 (Reaction Example 1-2) Synthesis of 1-2

53 g (0.24 mol) of compound 1-1 in oil were dissolved in 400 mL of N, N-dimethylformamide, and the mixture was cooled to 0 캜. 38 g (0.24 mol) of N-bromosuccinimide was slowly added thereto and stirred. After stirring at the same temperature for 2 hours, the reaction was diluted with 2 L of water and extracted with ethyl acetate. The extracted organic solvent was washed twice with water and then slurried with anhydrous magnesium sulfate, followed by filtration and concentration under reduced pressure to obtain 72 g (~ 100%) of 1-2 compounds in the form of an oil in the form of an oil.

(Reaction Example 1-3) Synthesis of Intermediate 1

72 g of the compound 1-2 in an oil state was diluted in 200 mL of N-methyl-2-pyrrolidone, and 66 g (0.48 mol) of potassium carbonate was added. The mixture was heated to 150 캜 and stirred for about 4 hours. After the reaction was completed, the reaction mixture was cooled to room temperature, and the precipitated solid was filtered and washed with ethanol and water. The filtered solid was dissolved in chloroform, washed twice with water, treated with acidic clay and anhydrous magnesium sulfate, filtered and concentrated. Ethanol and hexane were added to the concentrated compound and the slurry was purified at room temperature. This was filtered to obtain 27 g of a white intermediate compound 1 in a yield of 40%.

< Manufacturing example  2> Synthesis of intermediate 2

(Reaction Example 2-1) Synthesis of 2-1

(50 g, 0.5 mol) and (4-bromo-2-chlorophenyl) hydrazine hydrochloride (160 g, 0.5 mol) were diluted with 500 mL of ethanol in a nitrogen stream and 1.5 mL (0.025 mol ). The mixture was stirred at reflux for 12 hours and cooled to room temperature when the reaction was complete. The reaction was concentrated under reduced pressure and the concentrated compound was dissolved in ethyl acetate and washed again twice with water. The organic layer was separated, treated with anhydrous magnesium sulfate, filtered and concentrated to obtain 93 g (83%) of the desired compound 2-1.

(Reaction Example 2-2) Synthesis of Intermediate 2

100 g (0.35 mol) of Compound 2-1 was diluted in 700 mL of tetrahydrofuran, and 4,5-dichloro-3,6-dioxycyclohexa-1,4-diene-1,2-dicarbonitrile (118 g, 0.525 mol) and stirred at room temperature. After completion of the reaction, the reaction mixture was concentrated under reduced pressure to remove the solvent. The concentrated compound was dissolved again in chloroform and filtered through silica gel. The filtrate was concentrated again and purified by column chromatography under the conditions of hexane and chloroform 10: 1 to obtain 68 g (70%) of the target compound 2 as a white solid.

< Manufacturing example  3> Synthesis of Compound 3

(Reaction Example 3-1) Synthesis of 2- (3- (2-chlorodibenzo [b, d] furan-4-yl) phenyl) -4,6-diphenyl-1,3,5-triazine

(0.035 mol) of 4-bromo-2-chlorodibenzo [b, d] furan and 2,4-diphenyl-6- (3- (4,4,5,5- Dioxaborolan-2-yl) phenyl) -1,3,5-triazine (16.4 g, 0.037 mol) was dissolved in 100 mL of THF (tetrahydrofuran) 20 mL of an aqueous solution containing potassium carbonate was added to the reaction mixture and the mixture was heated. 400 mg (0.35 mmol) of tetrakis (triphenylphosphine) palladium (0) was added thereto under reflux. The mixture was refluxed for 12 hours. After completion of the reaction, the reaction mixture was cooled to room temperature, and the precipitated solid was filtered and washed with water and ethyl acetate. The filtered solid was diluted with ethyl acetate, warmed and slurred for about 1 hour, cooled to room temperature and filtered. 27 g (78%) of a white solid was obtained.

(Reaction Example 3-2) Synthesis of Compound 3

Phenyl-4,6-diphenyl-1,3,5-triazine (10 g, 19.6 mmol) and (9- Phenyl-9H-carbazol-3-yl) boronic acid (5.9 g, 20.6 mmol) was added to 100 mL of dioxane and then 20 mL of an aqueous solution containing 8.3 g (58.8 mmol) of potassium carbonate was added to the reaction mixture. 350 mg (1.23 mmol) of tricyclohexylphosphine and 350 mg (0.61 mmol) of bis (dibenzylidineacetone) palladium (0) were mixed and dissolved in dioxane (5 mL) at reflux and then added to the refluxed mixture. When the reaction was completed, the reaction mixture was cooled to room temperature, extracted with ethyl acetate, washed twice with water, and the organic layer was collected, treated with anhydrous magnesium sulfate and filtered. The filtrate was concentrated under reduced pressure and the precipitated solid was filtered. The filtered solid was redissolved in chloroform, and the solvent was removed under reflux, and recrystallization from ethyl acetate gave 10 g (68%) of the target compound 3 as white. MS: [M + H] &lt; ⁺ &gt; = 717

Compounds 4 to 14 were prepared according to the preparation method of Preparation Example 3.

R1 R3 Compound (Px) Yield
(%) MS
[M + H] &lt; Manufacturing example
4
(Compound 4)

71 717 Manufacturing example
5
(Compound 5)

70 717 Manufacturing example
6
(Compound 6)

73 792 Manufacturing example
7
(Compound 7)

80 792 Production Example 8
(Compound 8)

68 792 Manufacturing example
9
(Compound 9)

73 792 Manufacturing example
10
(Compound 10)

57 792 Manufacturing example
11
(Compound 11)

  45 792 Manufacturing example
12
(Compound 12)

78 717 Manufacturing example
13
(Compound 13)

77 717 Manufacturing example
14
(Compound 14)

38 717

< Manufacturing example  15> Synthesis of Compound 15

(Reaction Example 15-1) Synthesis of 2- (2-chlorodibenzo [b, d] furan-4-yl) -4,4,5,5-tetramethyl-1,3,2-dioxaborolane

15 g (0.05 mol) of Compound 1 was dissolved in 180 mL of 1,4-dioxane, and 16 g (0.06 mol) of bis (pinacolato) diboron was added thereto. 15.6 g (0.16 mol) of potassium acetate was added with stirring and the mixture was warmed to reflux. 900 mg (0.001 mol) of dibenzylidene acetone palladium and 890 mg (0.003 mol) of tricyclohexylphosphine were added under reflux and stirring, and the mixture was stirred under reflux for 24 hours. After completion of the reaction, the reaction mixture was cooled to room temperature, washed with water, and extracted twice with ethyl acetate. The collected organic layer was washed once with water, and water was removed with anhydrous magnesium sulfate, followed by filtration and concentration. The concentrated material was stirred with heating in a mixed solution of ethyl acetate and hexane and filtered to obtain 15.7 g (90%) of the desired compound.

(Reaction Example 15-2) Synthesis of 2- (2-chlorodibenzo [b, d] furan-4-yl) -4,6-diphenyl-1,3,5-triazine

(0.035 mol) of 2- (2-chlorodibenzo [b, d] furan-4-yl) -4,4,5,5-tetramethyl- 10.0 g (0.037 mol) of chloro-4,6-diphenyl-1,3,5-triazine was dissolved in 100 mL of THF (tetrahydrofuran), 20 mL of an aqueous solution containing 14.5 g (0.10 mol) of potassium carbonate Was added to the reaction mixture and the mixture was warmed. 400 mg (0.35 mmol) of tetrakis (triphenylphosphine) palladium (0) was added thereto under reflux. The mixture was refluxed for 12 hours. After completion of the reaction, the reaction mixture was cooled to room temperature, and the precipitated solid was filtered and washed with water and ethyl acetate. The filtered solid was diluted with ethyl acetate, warmed and slurred for about 1 hour, cooled to room temperature and filtered. 11.8 g (78%) of a white solid was obtained.

(Reaction Example 15-3) Synthesis of Compound 15

(10.0 g, 23.0 mmol) and (9-phenyl-9H-benzo [b, d] furan- 3-yl) boronic acid (7.2 g, 25.3 mmol) was added to 100 mL of dioxane, and 20 mL of an aqueous solution containing 9.7 g (68.7 mmol) of potassium carbonate was added to the reaction mixture and the mixture was warmed. 400 mg (1.43 mmol) of tricyclohexylphosphine and 400 mg (0.71 mmol) of bis (dibenzylidineacetone) palladium (0) were mixed and dissolved in dioxane (5 mL) at reflux and then added to the refluxed mixture. When the reaction was completed, the solvent was concentrated under reduced pressure, diluted with chloroform and washed twice with water. The organic layer was collected, treated with anhydrous magnesium sulfate and acidic white clay, and filtered. Ethyl acetate was added and the mixture was recrystallized under reflux to obtain 10.3 g (70%) of the target compound 15 as white. MS: [M + H] &lt; ⁺ &gt; = 641

Compounds 16 to 35 were prepared according to the preparation method of Preparation Example 15.

R1 R3 Compound (Px) Yield
(%) MS
[M + H] &lt; Manufacturing example
16
(Compound 16)

73 641 Manufacturing example
17
(Compound 17)

63 641 Manufacturing example
18
(Compound 18)

85 641 Manufacturing example
19
(Compound 19)

82 641 Manufacturing example
20
(Compound 20)

57 641 Manufacturing example
21
(Compound 21)

76 717 Manufacturing example
22
(Compound 22)

75 717 Manufacturing example
23
(Compound 23)

64 717 Manufacturing example
24
(Compound 24)

74 717 Manufacturing example
25
(Compound 25)

70 717 Manufacturing example
26
(Compound 26)

41 717 Manufacturing example
27
(Compound 27)

68 717 Manufacturing example
28
(Compound 28)

72 717 Manufacturing example
29
(Compound 29)

63 717 Manufacturing example
30
(Compound 30)

72 717 Manufacturing example
31
(Compound 31)

69 717 Manufacturing example
32
(Compound 32)

41 717 Manufacturing example
33
(Compound 33)

78 614 Manufacturing example
34
(Compound 34)

77 690 Manufacturing example
35
(Compound 35)

77 64

< Manufacturing example  36> Synthesis of Compound 36

Reaction Example 36-1 Synthesis of 2- (3- (2-chlorodibenzo [b, d] furan-4-yl) phenyl) -4,6-diphenyl-1,3,5-triazine

(0.035 mol) of 4-bromo-2-chlorodibenzo [b, d] furan was reacted in the same manner as in the preparation of Reaction Example 1 of Preparation Example 3 to obtain the desired compound 2- (3- [b, d] furan-4-yl) phenyl) -4,6-diphenyl-1,3,5-triazine (81%).

Reaction Example 36-2) Synthesis of Compound 33

Phenyl) -4,6-diphenyl-1,3,5-triazine (10 g, 19.6 mmol) and 9H-carbazole The sol (3.6 g, 20.6 mmol) was added to 100 mL of xylene, and 3.8 g (39.2 mmol) of sodium tert-butoxide was added to the reaction mixture and the mixture was warmed. 100 mg (0.2 mmol) of bis (tri-tert-butylphosphine) palladium was added under reflux and stirred for 6 hours. When the reaction was completed, the reaction mixture was cooled to room temperature. The precipitated solid was filtered and washed with ethyl acetate. The solid filtered again was washed with chloroform and washed twice with water. The organic layer was collected and treated with anhydrous magnesium sulfate and acidic white clay. The filtered solution was warmed and recrystallized from ethyl acetate to obtain 9.4 g (75%) of the title compound 33 as a white solid.

Compounds 37 to 41 were prepared according to the preparation method of Preparation 36.

R1 R3 Compound (Px) Yield
(%) MS
[M + H] &lt; Manufacturing example
37
(Compound 37)

69 717 Manufacturing example
38
(Compound 38)

65 717 Manufacturing example
39
(Compound 39)

60 767 Manufacturing example
40
(Compound 40)

70 614 Manufacturing example
41
(Compound 41)

72 614

< Manufacturing example  42> Synthesis of Compound 42

Reaction Example 42-1 Synthesis of 3-chloro-1- (3- (4,6-diphenyl-1,3,5-triazin-2-yl) phenyl) -9H-carbazole

A mixture of 15 g (0.053 mol) of 1-bromo-3-chloro-9H-carbazole and 2,4-diphenyl-6- (3- (4,4,5,5-tetramethyl- Dioxaborolan-2-yl) phenyl) -1,3,5-triazine was dissolved in 150 mL of THF (tetrahydrofuran), 22 g (0.16 mol) of potassium carbonate In 30 mL of water was added to the reaction solution, followed by heating. 620 mg (0.5 mmol) of tetrakis (triphenylphosphine) palladium (0) was added under reflux. The mixture was refluxed for 12 hours. After completion of the reaction, the reaction mixture was cooled to room temperature, and the precipitated solid was filtered and washed with water and ethyl acetate. The filtrate was diluted with ethyl acetate and heated to a slurry for about 1 hour. The mixture was cooled to room temperature and filtered to obtain the objective compound 3-chloro-1- (3- (4,6-diphenyl- 5-triazin-2-yl) phenyl) -9H-carbazole (20 g, 75%).

Reaction Example 42-2 Synthesis of 3-chloro-1- (3- (4,6-diphenyl-1,3,5-triazin-2-yl) phenyl) -9-phenyl-9H-

20 g (39.2 mmol) of 3-chloro-1- (3- (4,6-diphenyl-1,3,5-triazin- (1.5 g, 7.85 mmol) and 1,10-phenanthroline (1.4 g, 7.84 mmol) were added to the refluxed mixture, followed by stirring . After the reaction was completed, the mixture was distilled under reduced pressure to remove residual iodobenzene. The mixture was cooled to room temperature, dissolved in chloroform and washed three times with water. The organic layer was collected, treated with anhydrous magnesium sulfate, filtered and concentrated under reduced pressure. Ethyl acetate was added to the concentrated compound, followed by slurrying and filtration to obtain the desired compound 3-chloro-1- (3- (4,6-diphenyl-1,3,5-triazin- 9-phenyl-9H-carbazole (16.2 g, 71%).

Reaction Example 42-3) Synthesis of Compound 42

9-phenyl-9H-carbazole (15 g, 25.6 mmol) and 9H-pyrazolo [3,4- Carbazole (4.7 g, 28.1 mmol) was added to 150 mL of xylene, and then 5.0 g (51.2 mmol) of sodium tert-butoxide was added to the reaction mixture and the mixture was warmed. 130 mg (0.3 mmol) of bis (tri-tert-butylphosphine) palladium was added under reflux and stirred for 6 hours. When the reaction was completed, the reaction mixture was cooled to room temperature. The precipitated solid was filtered and washed with ethyl acetate. The solid filtered again was washed with chloroform and washed twice with water. The organic layer was collected and treated with anhydrous magnesium sulfate and acidic white clay. The filtered solution was warmed and recrystallized with ethyl acetate to obtain 11.5 g (63%) of the target compound 42 as white

Compounds 43 to 46 were prepared according to the preparation method of Preparation 42.

R1 R3 Compound (Px) Yield
(%) MS
[M + H] &lt; Manufacturing example
43
(Compound 43)

72 792 Manufacturing example
44
(Compound 44)

73 792 Manufacturing example
45
(Compound 45)

69 842 Manufacturing example
46
(Compound 46)

73 716

< Manufacturing example  47> Synthesis of Compound 47

Reaction Example 1) Synthesis of Compound 47

Synthesis of 3-chloro-1- (3- (4,6-diphenyl-1,3,5-triazin-2-yl) phenyl) -9H-carbazole 14 (7.2 g, 25.3 mmol) was added to 120 mL of dioxane, and then 9.7 g (68.7 mmol) of potassium carbonate was added to 30 mL of an aqueous solution The reaction mixture was warmed by adding thereto. 400 mg (1.43 mmol) of tricyclohexylphosphine and 400 mg (0.71 mmol) of bis (dibenzylidineacetone) palladium (0) were mixed and dissolved in dioxane (5 mL) at reflux and then added to the refluxed mixture. When the reaction was completed, the solvent was concentrated under reduced pressure, diluted with chloroform and washed twice with water. The organic layer was collected, treated with anhydrous magnesium sulfate and acidic white clay, and filtered. Ethyl acetate was added and the mixture was recrystallized under reflux to obtain 13.8 g (73%) of the target compound 47 as white.

Compounds 48 to 52 were prepared according to the preparation method of Preparation 47.

R1 R3 Compound (Px) Yield
(%) MS
[M + H] &lt; Manufacturing example
48
(Compound 48)

85 792 Manufacturing example
49
(Compound 49)

75 792 Manufacturing example
50
(Compound 50)

76 792 Manufacturing example
51
(Compound 51)

72 792 Manufacturing example
52
(Compound 52)

72 792

< Manufacturing example  53> Synthesis of Compound 53

Reaction Example 53-1) Synthesis of 3- (2-chlorodibenzo [b, d] furan-4-yl) -9-phenyl-9H-

In the same manner as in Production Example 1 of Production Example 3, 4-diphenyl-6- (3- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan- (9-phenyl-9H-carbazol-3-yl) boronic acid was used in the same manner as the preparation of the objective compound 3- (2-chlorodibenzo [b , d] furan-4-yl) -9-phenyl-9H-carbazole (12.3 g, 79%).

Reaction Example 53-2) Synthesis of Compound 53

A mixture of 10 g (22.5 mmol) of 3- (2-chlorodibenzo [b, d] furan-4-yl) 2-yl) phenyl) -1,3,5-triazine (10.7 g, 24.7 mmol) as starting materials in the same manner as in Production Example 3 Was prepared in the same manner as in Reaction Example 2 to obtain 12.3 g (77%) of the desired compound 53 as white.

Compounds 54 to 58 were prepared according to the preparation method of Preparation 53.

R1 R3 Compound (Px) Yield
(%) MS
[M + H] &lt; Production example 54
(Compound 54)

68 717 Manufacturing example
55
(Compound 55)

65 717 Manufacturing example
56
(Compound 56)

71 717 Manufacturing example
57
(Compound 57)

74 717 Manufacturing example
58
(Compound 58)

72 793

< Manufacturing example  59> Synthesis of Compound 59

Reaction Example 59-1) Synthesis of 1- (4- (9H-carbazol-9-yl) phenyl) -3-chloro-9H-

The compound 1-Bromo-3-chloro-9H-carbazole (15 g, 0.053 mol) and 9- (4- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan- -9-phenyl) -9H-carbazole (21.4 g, 0.058 mol) as a starting material was prepared in the same manner as in Production Example 42, Yl) phenyl) -3-chloro-9H-carbazole (21 g, 89%).

Reaction Example 59-2) 1- (4- (9H-Carbazol-9-yl) phenyl) -3- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan- -Yl) -9H-carbazole &lt; / RTI &gt;

Prepared by the same method as in the reaction example 1 of preparation 15, using the starting material of 1- (4- (9H-carbazol-9-yl) phenyl) -3-chloro-9H-carbazole To give the desired compound 1- (4- (9H-carbazol-9-yl) phenyl) -3- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan- Yl) -9H-carbazole (10.9 g, 91%).

Reaction Example 59-3) Synthesis of 1- (4- (9H-carbazol-9-yl) phenyl) -3- (4,6-diphenyl-1,3,5-triazin- Synthesis of carbazole

(4- (9H-carbazol-9-yl) phenyl) -3- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan- Carbazole (12 g, 22.4 mmol) as a starting material, the objective compound 1- (4- (9H-carbazol-9-yl) phenyl) -3 - (4,6-diphenyl-1,3,5-triazin-2-yl) -9H-carbazole was obtained in an amount of 12.9 g (90%).

 Reaction Example 59-4) Synthesis of Compound 59

The compound 1- (4- (9H-carbazol-9-yl) phenyl) -3- (4,6-diphenyl-1,3,5-triazin- , 24.4 mmol) as a starting material, and 14.7 g (85%) of the target compound 59 as a white compound were obtained.

Compounds 60 to 63 were prepared according to the preparation method of Preparation 59.

R1 R3 Compound (Px) Yield
(%) MS
[M + H] &lt; Manufacturing example
60
(Compound 60)

70 716 Manufacturing example
61
(Compound 61)

65 716 Manufacturing example
62
(Compound 62)

83 716 Manufacturing example
63
(Compound 63)

82 792

< Manufacturing example  64> Synthesis of Compound 64

Reaction Example 64-1) Synthesis of 2-methoxycarbonyl-3'-bromo-5'-chlorobiphenyl

(0.18 mol) of 1,3-dibromo-5-chlorobenzene and 34 g (0.18 mol) of 2- (methoxycarbonyl) phenylboronic acid were dissolved in toluene And methanol were reacted with a solvent to obtain 51 g (86%) of 2-methoxycarbonyl-3'-bromo-5'-chlorobiphenyl as a target compound.

Reaction Example 64-2) Synthesis of 2- (3'-bromo-5'-chlorobiphenyl-2-yl) propan-

50 g (0.15 mol) of 2-methoxycarbonyl-3'-bromo-5'-chlorobiphenyl are dissolved in THF, and 100 ml of methylmagnesium bromide diluted with 3 M in THF is slowly added dropwise. The reaction was warmed to 60 占 폚 and stirred for 12 hours. After completion of the reaction, the reaction mixture was cooled to room temperature, washed with water, extracted with ethyl acetate, dried over anhydrous magnesium sulfate, filtered and concentrated under reduced pressure. The residue was recrystallized from ethyl acetate and hexane to obtain 38 g (76%) of the desired compound 2- (3'-bromo-5'-chlorobiphenyl-2-yl) propan-2-ol.

Reaction Example 64-3) Synthesis of 1-bromo-3-chloro-9,9-dimethyl-9H-fluorene

38 g (0.12 mol) of 2- (3'-bromo-5'-chlorobiphenyl-2-yl) propan-2-ol was dissolved in 200 mL of acetic acid and 50 mL of phosphoric acid, and the mixture was heated to 120 ° C and stirred for 12 hours. When the reaction was completed, the reaction mixture was cooled to room temperature, and the precipitated solid was filtered. The filtered solid was diluted with ethanol, washed with an aqueous solution of NaHCO ₃ and then filtered to obtain the desired compound 1-bromo-3-chloro-9,9- -Fluorene (56%).

Reaction Example 64-4) Synthesis of 2- (3-chloro-9,9-dimethyl-9H-fluoren-1-yl) -4,4,5,5-tetramethyl-1,3,2-dioxaborolane Synthesis of

(0.065 mol) of 1-bromo-3-chloro-9,9-dimethyl-9H-fluorene was reacted in the same manner as in the preparation of Reaction Example 15-1 of Preparation Example 15 to obtain the target compound 2- -9,9-dimethyl-9H-fluoren-1-yl) -4,4,5,5-tetramethyl-1,3,2-dioxaborolane was obtained in an amount of 16.8 g (73%).

Reaction Example 64-5) Synthesis of 2- (3-chloro-9,9-dimethyl-9H-fluoren-1-yl) -4,6-diphenyl-1,3,5-triazine

(3-chloro-9,9-dimethyl-9H-fluoren-1-yl) -4,4,5,5-tetramethyl- (0.042 mol) of 3,2-dioxaborolane and 11.3 g (0.042 mol) of 2-chloro-4,6-diphenyl-1,3,5-triazine were reacted to obtain the desired compound (3-chloro- 9,9-dimethyl-9H-fluoren-1-yl) -4,6-diphenyl-1,3,5-triazine (81%).

 Reaction Example 64-6) Synthesis of Compound 64

(3-chloro-9,9-dimethyl-9H-fluoren-1-yl) -4,6-diphenyl-1,3,5-tri (0.032 mol) of azine and 12.4 g (0.032 mol) of 9-phenyl-2- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan- ) To obtain 15.2 g (70%) of the desired compound 64 as white. MS: [M + H] &lt; ⁺ &gt; = 667.8

< Experimental Example  1>

The glass substrate coated with ITO (indium tin oxide) film with a thickness of 1,500 Å was immersed in distilled water containing detergent and washed with ultrasonic waves. At this time, a Fischer Co. product was used as a detergent, and distilled water, which was filtered with 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.

Hexanitrile hexaazatriphenylene (HAT) of the following chemical formula was thermally vacuum deposited on the prepared ITO transparent electrode to a thickness of 500 Å to form a hole injection layer.

[LINE]

N, N-bis- (1-naphthalenyl) -N, N-bis-phenyl- (1,1- biphenyl) -4,4- diamine compound of the following structure was deposited on the hole injection layer to a thickness of 400 Å The hole transport layer was formed by thermal vacuum deposition.

Next, on the hole transport layer, a compound of Formula 3 prepared in Preparation Example 3 was vacuum deposited at a concentration of 10% with Ir (ppy) _{3 as a} dopant to form a light emitting layer.

The following electron transport material was vacuum deposited on the light emitting layer to a thickness of 200 Å to form an electron injection and transport layer.

[Electron transport material]

Lithium fluoride (LiF) and aluminum were deposited to a thickness of 12 Å on the electron injection and transport layer sequentially to form a cathode.

The deposition rate of the organic material was maintained at 0.4 to 0.7 Å / sec, the lithium fluoride at the cathode was maintained at a deposition rate of 0.3 Å / sec, and the deposition rate of aluminum was maintained at 2 Å / sec. ^-7 to 5 x 10 &lt; ^-8 &gt; torr.

< Experimental Example  2>

In the same manner as in Experimental Example 1, except that the compound of Formula 15 was used instead of the compound of Formula 3.

< Experimental Example  3>

In the same manner as in Experimental Example 1, except that the compound of Formula 24 was used instead of the compound of Formula 3.

< Experimental Example  4>

In the same manner as in Experimental Example 1, except that the compound of Formula 38 was used instead of the compound of Formula 3.

< Experimental Example  5>

In the same manner as in Experimental Example 1, except that the compound of Formula 47 was used instead of the compound of Formula 3.

< Experimental Example  6>

In the same manner as in Experimental Example 1, except that the compound of Formula 53 was used instead of the compound of Formula 3.

< Experimental Example  7>

In the same manner as in Experimental Example 1, except that the compound of Formula 63 was used instead of the compound of Formula 3.

< Comparative Example  1>

In the same manner as in Experimental Example 1, except that the following H1 was used in place of the compound of Formula 3:

< Comparative Example  2>

In the same manner as in Experimental Example 1, except that the following H2 was used in place of the compound of Formula 3:

Table 8 shows the results of devices manufactured using the compounds of Examples 1 to 7 and Comparative Examples 1 and 2 as the light emitting layer.

No. Host Dopant
(Dopant) Doping concentration
(%) The driving voltage (V)
@ 5,000 cd / m ² Luminous efficiency
(Cd / A) Comparative Example 1 H1 Ir (ppy) ₃ 10 5.3 9.5 Comparative Example 2 H2 Ir (ppy) ₃ 10 4.3 44 Experimental Example 1 (3) Ir (ppy) ₃ 10 4.3 48 Experimental Example 2 Formula 15 Ir (ppy) ₃ 10 4.9 53 Experimental Example 3 24 Ir (ppy) ₃ 10 4.5 50 Experimental Example 4 Formula 38 Ir (ppy) ₃ 10 4.4 47 Experimental Example 5 Formula 47 Ir (ppy) ₃ 10 4.2 48 Experimental Example 6 Formula 53 Ir (ppy) ₃ 10 4.5 53 Experimental Example 7 Formula 63 Ir (ppy) ₃ 10 4.7 49

As can be seen from the above Table 1, Examples 1 to 7 show that the compound of the present invention can be used as a host of a green light emitting layer and can exhibit an improved efficiency than Comparative Examples 1 and 2. [

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

Claims (12)

delete delete delete delete delete delete A compound which is any one selected from the following structural 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 the compound according to claim 7. The organic electronic device according to claim 8, wherein the organic layer includes a light emitting layer, and the light emitting layer comprises the compound. The organic electronic device according to claim 8, wherein the organic layer includes an electron transporting layer or an electron injecting layer, and the electron transporting layer or the electron injecting layer comprises the compound. The organic electroluminescent device according to claim 8, wherein the organic electronic device further comprises one or more layers selected from the group consisting of a hole injection layer, a hole transport layer, an electron transport layer, an electron injection layer, an electron blocking layer and a hole blocking layer. Electronic device. The organic electronic device according to claim 8, wherein the organic electronic device is selected from the group consisting of an organic light emitting device, an organic phosphorescent device, an organic solar cell, an organic photoconductor (OPC), and an organic transistor.

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