KR102083923B1 - Organic electro luminescence device - Google Patents

Abstract

The present invention is an anode; cathode; And one or more organic material layers interposed between the anode and the cathode, wherein at least one of the one or more organic material layers includes a first host and a second host.

Description

Organic electroluminescent element {ORGANIC ELECTRO LUMINESCENCE DEVICE}

The present invention relates to an organic electroluminescent device comprising at least one organic material layer.

In the organic electroluminescent device, when a voltage is applied between two electrodes, holes are injected into the organic material layer at the anode, and electrons are injected into the organic material layer at the cathode. When the injected holes and electrons meet, excitons are formed, and when the excitons fall to the ground, they shine. In this case, the material used as the organic material layer may be classified into a light emitting material, a hole injection material, a hole transport material, an electron transport material, an electron injection material and the like according to its function.

In order to increase the luminous efficiency of the organic EL device, color purity and energy transfer are required. For this, a light emitting material mixed with a host material and a dopant material may be used. The dopant material may be divided into a fluorescent dopant using an organic material and a phosphorescent dopant using a metal complex compound containing heavy atoms such as Ir and Pt. At this time, since the phosphor can theoretically improve the luminous efficiency up to four times as compared to the fluorescent material, research on phosphorescent hosts as well as phosphorescent dopants has been conducted. Currently, as a phosphorescent dopant material of the light emitting layer, metal complex compounds including Ir such as Firpic, Ir (ppy) ₃ , and (acac) Ir (btp) ₂ are known, and CBP is known as a phosphorescent host material.

However, the conventional materials do not have a satisfactory level in terms of lifespan in organic electroluminescent devices because of low thermal stability due to low glass transition temperature. Therefore, there is a demand for the development of an organic EL device including a light emitting material having excellent performance.

An object of the present invention is to provide an organic electroluminescent device having improved characteristics such as driving voltage, luminous efficiency and lifespan.

In order to achieve the above object, the present invention is an anode; cathode; And one or more organic material layers interposed between the anode and the cathode, wherein at least one of the one or more organic material layers includes a first host and a second host, wherein the first host is represented by Formula 1 below. It is a compound, wherein the second host provides an organic electroluminescent device, characterized in that the compound represented by the formula (2).

In Chemical Formula 1,

R ₁ to R ₇ are the same as or different from each other, and are each independently hydrogen, deuterium, a substituted or unsubstituted C ₁ to C ₄₀ alkyl group, and a substituted or unsubstituted C ₆ to C ₆₀ aryl group Selected,

a to c are each independently an integer of 0 to 5,

d to g are each independently an integer of 0 to 4,

n and m are each independently integers of 0 to 1, wherein n is 1, f is an integer of 0 to 3, and m is 1, g is an integer of 0 to 3;

In Chemical Formula 2,

L ₁ to L ₃ are the same as or different from each other, and are each independently a single bond, a substituted or unsubstituted C ₆ to C ₁₈ arylene group, or a substituted or unsubstituted heteroarylene group having 5 to 18 nuclear atoms. ,

Ar ₁ to Ar ₃ are the same as or different from each other, and each independently hydrogen, deuterium, a substituted or unsubstituted C ₆ -C ₄₀ aryl group, and a substituted or unsubstituted heteroaryl group having 5 to 40 nuclear atoms Selected from the group consisting of, except that Ar ₁ to Ar ₃ are all the same,

R ₈ to R ₁₀ are the same as or different from each other, and each independently hydrogen, deuterium, a halogen group, a cyano group, a nitro group, an amino group, a substituted or unsubstituted C ₁ to C ₄₀ alkyl group, a substituted or unsubstituted C Alkenyl group of ₂ to C ₄₀ , substituted or unsubstituted alkynyl group of C ₂ to C ₄₀ , cycloalkyl group of substituted or unsubstituted C ₃ to C ₄₀ , heterocyclo substituted or unsubstituted 3 to 40 heteroatoms Alkyl group, substituted or unsubstituted C ₆ to C ₆₀ aryl group, substituted or unsubstituted heteroaryl group having 5 to 60 nuclear atoms, substituted or unsubstituted C ₁ to C ₄₀ alkyloxy group, substituted or unsubstituted Substituted C ₆ ~ C ₆₀ aryloxy group, substituted or unsubstituted C ₁ ~ C ₄₀ alkylsilyl group, substituted or unsubstituted C ₆ ~ C ₆₀ arylsilyl group, substituted or unsubstituted C ₁ ~ a C ₄₀ alkyl boron group, a substituted or unsubstituted C ₆ ~ arylboronic group, a substituted or unsubstituted of C ₆₀ unsubstituted C ₁ ~ C ₄₀ phosphine group, It is selected from the group consisting of a ring or an unsubstituted C ₁ ~ C ₄₀ of the phosphine oxide group, and a substituted or unsubstituted C ₆ ~ C ₆₀ aryl amine,

o to q are each independently an integer of 0 to 1,

h to j are each independently an integer of 0 to 4, where o is 1, h is an integer of 0 to 3, p is 1, i is an integer of 0 to 3, and q is 1, j is 0 to 3 Is an integer of;

In the above L ₁ to L ₃ , R ₁ to R ₁₀ and Ar ₁ to Ar ₃ , an arylene group, heteroarylene group, alkyl group, alkenyl group, alkynyl group, cycloalkyl group, heterocycloalkyl group, aryl group, heteroaryl group, alkyl The oxy group, aryloxy group, alkylsilyl group, arylsilyl group, alkyl boron group, aryl boron group, phosphine group, phosphine oxide group and arylamine group are each independently deuterium, halogen group, cyano group, nitro group, amino group , C ₁ ~ C ₄₀ Alkyl group, C ₂ ~ C ₄₀ Alkenyl group, C ₂ ~ C ₄₀ Alkynyl group, C ₃ ~ C ₄₀ Cycloalkyl group, C ₃ ~ 40 Heterocycloalkyl group, C ₆ ~ C ₄₀ aryl group, nuclear atom 5 to 40 heteroaryl group, C ₁ ~ C ₄₀ alkyloxy group, C ₆ ~ C ₆₀ aryloxy group, C ₁ ~ C ₄₀ alkylsilyl group, C ₆ ~ aryl silyl group of C _60, C ₁ ~ C ₄₀ group of an alkyl boron, C ₆ ~ C group ₆₀ arylboronic of, C ₁ ~ C ₄₀ of the phosphine group, C ₁ ~ C ₄₀ phosphine oxide group, and a C ₆ ~ of of C ₆₀ Ah It may be substituted with at least one member selected from the group consisting of an amine group.

Herein, the organic material layer including the first host and the second host is preferably a phosphorescent layer.

In addition, the light emitting layer preferably includes a metal complex compound dopant.

The organic electroluminescent device of the present invention includes an organic material layer including a first host and a second host, by mixing a compound represented by Formula 1 and a compound represented by Formula 2 as the first host and the second host, respectively. The driving voltage, the luminous efficiency, and the lifetime of the device can be improved. Therefore, when the display panel is manufactured using the organic EL device of the present invention, it is possible to provide a display panel having improved performance and lifespan.

Hereinafter, the present invention will be described.

The organic electroluminescent device of the present invention includes an anode, a cathode and one or more organic material layers interposed between the anode and the cathode, and at least one of the one or more organic material layers includes a first host and a second host. The first host is a compound represented by Formula 1, and the second host is a compound represented by Formula 2 below.

As the first host in the present invention, the compound represented by Formula 1 is 9-phenyl-carbazole (9-phenyl which may be substituted with deuterium, an alkyl group of C ₁ ~ C ₄₀ or an aryl group of C ₆ ~ C ₆₀ -9H-carbazole) is characterized in that it has a structure in which one to three basic skeletons are linked.

In general, the carbazole skeleton has an electron donating group characteristic with high electron donating and hole transporting properties.

In the compound represented by Formula 1, R ₁ to R ₃ are the same as or different from each other, and each independently hydrogen, deuterium, a substituted or unsubstituted C ₁ to C ₄₀ alkyl group, a substituted or unsubstituted C ₆ It is selected from the aryl group of ~ C ₆₀ . More specifically, R ₁ to R ₃ are the same as or different from each other, and each independently may be selected from the group consisting of hydrogen, methyl, ethyl, propyl, iso-propyl, t-butyl, phenyl, biphenyl, naphthyl and the like. have. Alkyl and aryl groups, which are the aforementioned substituents, have electron donating and hole transporting properties to enhance the properties of the electron donating group in the molecule. In the present invention, it is preferable that each of R ₁ to R ₃ is a phenyl group or a biphenyl, wherein the bonding position of the phenyl group and the biphenyl group is not particularly limited and is not limited.

In the general formula (1) according to the present invention, the 9-phenyl-9H-carbazole basic skeleton may be linked to one or more, such as 1 to 3, the binding position is not particularly limited. At this time, it is preferable when binding to the position 3, the main binding site of the carbazole. In addition, when two carbazole skeletons are included in the molecule, the carbazole skeleton has a high hole transporting property, and when the carbazole skeleton is one, the molecular weight is significantly increased to have high thermal stability. In particular, the 3,3'-bonded biscarbazole-type base skeleton is the main binding site of carbazole, and can firmly connect two carbazoles to enhance the thermal and electrical stability of the molecule itself. Therefore, it is more preferable when it is 1 or 3 carbazoles.

Compound represented by the formula (1) of the present invention may be more specific compound group consisting of the following formula (1a) to formula (1c).

* [Formula 1a]

(n=m=0)

(n = m = 0)

[Formula 1b]

(m=0, n=1)

(m = 0, n = 1)

[Formula 1c]

(n=m=1)

(n = m = 1)

In Chemical Formulas 1a to 1c,

R ₁ to R ₇ and a to g are the same as defined in the formula (1).

More specifically, R _{1 To} R _{3 Are} the same as or different from each other, each independently represent a substituted or unsubstituted C ₆ ~ C ₆₀ aryl group,

R ₄ to R ₇ are the same as or different from each other, and each independently hydrogen, deuterium, a substituted or unsubstituted C ₁ to C ₄₀ alkyl group, or a substituted or unsubstituted C ₆ to C ₆₀ aryl group is preferable. .

The compound represented by Chemical Formula 1 of the present invention may be more specific as a compound group consisting of the following C-1 to C-61, but is not particularly limited thereto.

As the second host of the present invention, the compound represented by Formula 2 has a structure in which an aryl group or a heteroaryl group is bonded to a triphenylene basic skeleton.

Since the triphenylene base skeleton has a high triplet energy, the triphenylene base skeleton is suitable for a phosphorescent host, and has an electron donating group characteristic having high electron donating and hole transporting properties.

The compound represented by Formula 2 of the present invention is characterized in that the triphenylene moiety is bipolar because one or more electron withdrawing groups (Electron Withdrawing Group) having high electron transporting and hole donating properties are combined. The bipolar compound combines EDG capable of giving electrons with EWG that attracts electrons at the same time, thereby alleviating the imbalance of exciton recombination caused by the fast mobility of holes without the carrier being biased to one side. Accordingly, when the compound represented by Chemical Formula 2 is used as the second host of the organic material layer of the organic electroluminescent device, it may exhibit excellent properties as a phosphorescent host material of the light emitting layer compared to the conventional CBP.

Compound represented by the formula (2) of the present invention can be more specifically formulated to the formula (2a) to formula (2c).

[Formula 2a]

[Formula 2b]

[Formula 2c]

In Chemical Formulas 2a to 2c, L ₁ to L ₃ and Ar ₁ to Ar ₃ are the same as defined in Chemical Formula 2.

In the compound represented by Formula 2, L ₁ to L ₃ are the same as or different from each other, each independently, a single bond, a substituted or unsubstituted C ₆ ~ C ₆₀ arylene group, and a substituted or unsubstituted nucleus It is selected from the group consisting of a heteroarylene group having 5 to 60 atoms. More specifically, the L ₁ to L ₃ are the same as or different from each other, and each independently selected from a single bond, phenylene, biphenylene, carbazolylene.

Ar ₁ to Ar ₃ are the same as or different from each other, and each independently, hydrogen, deuterium, a substituted or unsubstituted C ₆ -C ₄₀ aryl group, and a substituted or unsubstituted heteroaryl having 5 to 40 nuclear atoms It is selected from the group consisting of groups. In the present invention, at least one of Ar ₁ to Ar ₃ is preferably a heteroaryl group having 5 to 40 nuclear atoms including one or more elements selected from the group consisting of N, O, and S. In this case, the case where Ar ₁ to Ar ₃ are all the same is excluded. More specifically, Ar ₁ is a C ₆ ~ C ₄₀ aryl group, Ar ₃ is more preferably a heteroaryl group having 5 to 40 nuclear atoms.

In consideration of characteristics such as luminous efficiency, driving voltage, and lifespan of the organic EL device, at least one of Ar ₁ to Ar ₃ in Formula 2 used as the second host is preferably a substituent represented by the following Formula 3.

[Formula 3]

In Chemical Formula 3,

L is selected from the group consisting of a single bond, a substituted or unsubstituted C ₆ -C ₁₈ arylene group, and a substituted or unsubstituted heteroarylene group having 5 to 18 nuclear atoms,

Z ₁ to Z ₅ are the same as or different from each other, and each independently N or C (R ₁₁ ), wherein at least one of Z ₁ to Z ₅ is N,

When the plurality of C (R ₁₁ ) is a plurality of R ₁₁ are the same or different from each other, each independently hydrogen, deuterium, halogen, cyano group, nitro group, substituted or unsubstituted C ₁ ~ C ₄₀ Alkyl group, Substituted or unsubstituted C _{2 Through} C ₄₀ Alkenyl group, Substituted or unsubstituted C _{2 Through} C ₄₀ Alkynyl group, Substituted or unsubstituted C _{6 Through} C ₆₀ An aryl group, Substituted or unsubstituted nuclear atoms 5 to 60 heteroaryl groups, substituted or unsubstituted C ₆ to C ₆₀ aryloxy groups, substituted or unsubstituted C ₁ to C ₄₀ alkyloxy groups, substituted or unsubstituted C ₃ to C ₄₀ cyclo An alkyl group, a substituted or unsubstituted heterocycloalkyl group having 3 to 40 nuclear atoms, a substituted or unsubstituted C ₆ to C ₆₀ arylamine group, a substituted or unsubstituted C ₁ to C ₄₀ alkylsilyl group, substituted or Unsubstituted C ₁ ~ C ₄₀ alkyl boron group, C ₆ ~ C ₆₀ aryl boron group, substituted or unsubstituted C ₆ ~ C ₆₀ arylphosphine group, A substituted or unsubstituted C ₆ -C ₆₀ arylphosphine oxide group, and a substituted or unsubstituted C ₆ -C ₆₀ arylsilyl group, wherein they are combined with adjacent groups to form a condensed ring Can and

In the above L and R ₁₁ , arylene group, heteroarylene group, alkyl group, alkenyl group, alkynyl group, aryl group, heteroaryl group, aryloxy group, alkyloxy group, cycloalkyl group, heterocycloalkyl group, arylamine group, alkylsilyl Group, alkyl boron group, aryl boron group, aryl phosphine group, aryl phosphine oxide group and aryl silyl group are each independently deuterium, halogen, cyano group, nitro group, C ₁ ~ C ₄₀ alkyl group, C ₂ ~ C ₄₀ Alkenyl group, C ₂ ~ C ₄₀ Alkynyl group, C ₆ ~ C ₆₀ Aryl group, Nuclear atoms 5 to 60 heteroaryl group, C ₆ ~ C ₆₀ Aryloxy group, C ₁ ~ C ₄₀ Alkyl jade C ₆ -C ₆₀ arylamine group, C ₃ -C ₄₀ cycloalkyl group, nuclear atom 3 to 40 heterocycloalkyl group, C ₁ ~ C ₄₀ alkylsilyl group, C ₁ ~ C ₄₀ alkyl boron group, C ₆ ~ C ₆₀ aryl boron group, C ₆ ~ C ₆₀ aryl phosphine group, C ₆ ~ C ₆₀ aryl phosphine oxide group, and a C ₆ ~ from the group consisting of C ₆₀ arylsilyl of It may be substituted or unsubstituted with one or more substituents selected. In this case, when there are a plurality of substituents, they may be the same or different from each other.

In the substituent represented by Formula 3, L is preferably a single bond, a phenylene group or a biphenylene group.

In addition, * means a part bonded to the formula (2), when two or more of Z ₁ to Z ₅ is C (R ₁₁ ), a plurality of R ₁₁ may be the same or different from each other.

More specifically, the substituent represented by Formula 3 is preferably selected from the group of substituents consisting of the structures represented by A-1 to A-15.

In the above A-1 to A-15,

L and R ₁₁ are the same as defined in Formula 3,

R ₁₂ is hydrogen, deuterium, halogen, cyano group, nitro group, substituted or unsubstituted C ₁ ~ C ₄₀ alkyl group, substituted or unsubstituted C ₂ ~ C ₄₀ alkenyl group, substituted or unsubstituted C ₂ ~ C ₄₀ alkynyl group, substituted or unsubstituted C ₃ to C ₄₀ cycloalkyl group, substituted or unsubstituted heterocycloalkyl group having 3 to 40 nuclear atoms, substituted or unsubstituted C ₆ to C ₆₀ aryl group, Substituted or unsubstituted heteroaryl group having 5 to 60 nuclear atoms, substituted or unsubstituted C ₆ to C ₆₀ aryloxy group, substituted or unsubstituted C ₁ to C ₄₀ alkyloxy group, substituted or unsubstituted C ₆ ~ C ₆₀ arylamine group, substituted or unsubstituted C ₁ ~ C ₄₀ Alkylsilyl group, substituted or unsubstituted C ₁ ~ C ₄₀ Alkyl boron group, substituted or unsubstituted C ₆ ~ C ₆₀ aryl boron group, substituted or unsubstituted C ₆ ~ C ₆₀ aryl phosphine group, substituted or unsubstituted C ₆ ~ C ₆₀ aryl phosphine oxide group, and substituted or Unsubstituted C ₆ ~ C _{60 It} is selected from the group consisting of arylsilyl group, or they may combine with adjacent groups to form a condensed ring,

p is an integer from 1 to 4.

In R ₁₂ , an alkyl group, alkenyl group, alkynyl group, cycloalkyl group, heterocycloalkyl group, aryl group, heteroaryl group, aryloxy group, alkyloxy group, arylamine group, alkylsilyl group, alkyl boron group, aryl boron group , Arylphosphine group, arylphosphine oxide group and arylsilyl group are each independently deuterium, halogen, cyano group, nitro group, C ₁ ~ C ₄₀ alkyl group, C ₂ ~ C ₄₀ alkenyl group, C ₂ ~ C ₄₀ Alkynyl group, C ₆ ~ C ₆₀ Aryl group, Nuclear 5 to 60 heteroaryl group, C ₆ ~ C ₆₀ Aryloxy group, C ₁ ~ C ₄₀ Alkyloxy group, C ₆ ~ C ₆₀ Aryl Amine group, C ₃ to C ₄₀ cycloalkyl group, C ₃ to C ₄₀ heterocycloalkyl group, C ₁ to C ₄₀ alkylsilyl group, C ₁ to C ₄₀ alkylboron group, C ₆ to C ₆₀ aryl boron group, C ₆ ~ C ₆₀ aryl phosphine group, C ₆ ~ C ₆₀ aryl phosphine oxide of the group and a C ₆ ~ value to one or more of the substituents selected from the group consisting of C ₆₀ aryl silyl Or it may be unsubstituted. In this case, when there are a plurality of substituents, they may be the same or different from each other.

In the compound represented by Formula 2 according to the present invention, Ar ₁ to Ar ₃ and R ₈ to R ₁₀ may be each independently selected from the group consisting of hydrogen or the following substituents (functional groups) (S1-S206), but specifically It is not limited.

The compound represented by Formula 2 of the present invention may be embodied in the compound group consisting of the following D-1 to D-34, but is not particularly limited thereto.

Meanwhile, alkyl in the present invention is a monovalent substituent derived from a straight or branched chain saturated hydrocarbon having 1 to 40 carbon atoms, and examples thereof include methyl, ethyl, propyl, isobutyl, sec-butyl, pentyl, iso-amyl and hexyl. Etc. can be mentioned.

Alkenyl in the present invention is a monovalent substituent derived from a straight or branched chain unsaturated hydrocarbon having 2 to 40 carbon atoms having one or more carbon-carbon double bonds. Examples thereof include vinyl and allyl. ), Isopropenyl, 2-butenyl, and the like.

Alkynyl in the present invention is a monovalent substituent derived from a C2-C40 straight or branched chain unsaturated hydrocarbon having at least one carbon-carbon triple bond, examples of which are ethynyl, 2- Propanyl (2-propynyl) etc. are mentioned.

Aryl in the present invention means a monovalent substituent derived from an aromatic hydrocarbon having 6 to 60 carbon atoms combined with a single ring or two or more rings. In addition, a form in which two or more rings are attached to each other (pendant) or condensed may also be included. Examples of such aryls include phenyl, naphthyl, phenanthryl, anthryl and the like.

Heteroaryl in the present invention means a monovalent substituent derived from a monoheterocyclic or polyheterocyclic aromatic hydrocarbon having 5 to 40 nuclear atoms. At least one carbon in the ring, preferably 1 to 3 carbons, is substituted with a heteroatom such as N, O, S or Se. In addition, a form in which two or more rings are pendant or condensed with each other may also be included, and may also include a form condensed with an aryl group. Examples of such heteroaryl include 6-membered monocyclic rings such as pyridyl, pyrazinyl, pyrimidinyl, pyridazinyl, triazinyl, phenoxathienyl, indolinzinyl, indolyl ( polycyclic rings such as indolyl, purinyl, quinolyl, benzothiazole, carbazolyl, 2-furanyl, N-imidazolyl, 2-isoxazolyl , 2-pyridinyl, 2-pyrimidinyl, and the like.

Aryloxy in the present invention is a monovalent substituent represented by RO-, wherein R means aryl having 5 to 60 carbon atoms. Examples of such aryloxy include phenyloxy, naphthyloxy, diphenyloxy and the like.

Alkyloxy in the present invention is a monovalent substituent represented by R'O-, wherein R 'means 1 to 40 alkyl, and includes a linear, branched or cyclic structure It is interpreted as. Examples of such alkyloxy include methoxy, ethoxy, n-propoxy, 1-propoxy, t-butoxy, n-butoxy, pentoxy and the like.

Aryl amine in the present invention means an amine substituted with aryl having 6 to 60 carbon atoms.

Cycloalkyl in the present invention means monovalent substituents derived from monocyclic or polycyclic non-aromatic hydrocarbons having 3 to 40 carbon atoms. Examples of such cycloalkyl include cyclopropyl, cyclopentyl, cyclohexyl, norbornyl, adamantine and the like.

Heterocycloalkyl in the present invention means a monovalent substituent derived from a non-aromatic hydrocarbon having 3 to 40 nuclear atoms, wherein at least one carbon in the ring, preferably 1 to 3 carbons is N, O, S or Substituted with a hetero atom such as Se. Examples of such heterocycloalkyl include morpholine, piperazine and the like.

Alkylsilyl in the present invention is silyl substituted with alkyl having 1 to 40 carbon atoms, and arylsilyl means silyl substituted with aryl having 5 to 40 carbon atoms.

Condensed ring in the present invention means a condensed aliphatic ring, a condensed aromatic ring, a condensed heteroaliphatic ring, a condensed heteroaromatic ring or a combination thereof.

The organic electroluminescent device of the present invention configured as described above may have a long life because at least one of the plurality of organic material layers may balance holes and electrons injected into the device including the first host and the second host. have. Here, although the mixing ratio of the first host and the second host is not particularly limited when the organic layer is manufactured, the first host and the second host may be mixed in a weight ratio of 1:99 to 99: 1.

In the organic electroluminescent device of the present invention, the light emitting layer may be a single light emitting layer, or may have a plurality of light emitting layers to implement a mixed color thereof. More specifically, in the present invention, a plurality of light emitting layers may be sequentially stacked between the hole transport layer and the electron transport layer to implement a mixed color thereof when voltage and current are applied.

The stacked organic electroluminescent device of the present invention having a plurality of light emitting layers including a plurality of light emitting layers or heterogeneous materials in series between the hole transport layer and the electron transport layer as described above may realize a mixed color when voltage and current are applied or a plurality of light emitting layers. The light emission efficiency can be increased by the number of light emitting layers.

On the other hand, the organic material layer of the present invention including the first host and the second host is preferably a light emitting layer, wherein the light emitting layer of the present invention may include a dopant with the first host and the second host. Here, the material that can be used as the dopant included in the light emitting layer may use any conventional dopant component known in the art without limitation, and it is preferable to use a metal complex compound containing iridium (Ir) as an example.

The method of manufacturing the light emitting layer including the first host, the second host, and the dopant described above may be manufactured without particular limitation according to methods known in the art. Hereinafter, two preferable embodiment which manufactures the said light emitting layer is illustrated below. However, this is not particularly limited.

A first method of the above two embodiments is a co-deposition method in which a light emitting layer is formed by placing a first host and a second host in a first heat source and a second heat source, and placing a dopant in a third heat source and applying heat simultaneously.

More specifically, at a vacuum degree of 1 × 10 ⁻⁰⁶ torr or less, a second host having high hole mobility and good hole injection efficiency is positioned in the first heat source, and electron mobility is located in the second heat source. A method of co-depositing at a proper ratio by placing a second host having a high c) and having a high electron injection efficiency and controlling a dopant of a third heat source and an evaporation rate per second. In this case, the number of co-deposited hosts may be two or more depending on the characteristics of the light emitting layer.

The amount of the first host, the second host, and the dopant is not particularly limited. For example, the first host, the second host, and the dopant may be used in the range of 70 to 99 wt% and the dopant in the range of 1 to 30 wt%. More specifically, it is preferable to use 80 to 95 wt% of the first host and the second host, and 5 to 20 wt% of the dopant.

In the second of the two embodiments, in order to reduce the number of heat sources used and to simplify the formation process, the first host and the second host used for forming the light emitting layer are mixed at an appropriate ratio to be placed in one heat source and heat is removed. It is a co-deposition method which adds and forms a light emitting layer.

More specifically, by placing the host (first host + second host) mixed in the first heat source at a vacuum degree of 1 × 10 ^-06 or less, and the dopant is placed in the second heat source at the same time to control the evaporation rate per second It is a method of forming. This second method can reduce the mixing ratio error that occurs when using more than one host, and can form the light emitting layer with a small number of heat sources.

In this case, the amount of the first host, the second host, and the dopant is not particularly limited. For example, the first host, the second host, and the dopant may be used in the range of 70 to 99 wt% and the dopant in the range of 1 to 30 wt%. More specifically, it is preferable to use 80 to 95 wt% of the first host and the second host and 5 to 20 wt% of the dopant.

The material usable as the anode included in the organic electroluminescent device of the present invention is not particularly limited, but non-limiting examples include metals such as vanadium, chromium, copper, zinc, gold or alloys thereof; Metal oxides such as zinc oxide, indium oxide, indium tin oxide (ITO) and indium zinc oxide (IZO); Combinations of metals and oxides such as ZnO: Al and SnO ₂ : Sb; Conductive polymers such as polythiophene, poly (3-methylthiophene), poly [3,4- (ethylene-1,2-dioxy) thiophene] (PEDT), polypyrrole and polyaniline; And carbon black.

The material usable as the cathode included in the organic electroluminescent device of the present invention is not particularly limited, but non-limiting examples include magnesium, calcium, sodium, potassium, titanium, indium, yttrium, lithium, gadolinium, aluminum, silver, tin, lead Metals such as these, alloys thereof, and multilayered structural materials such as LiF / Al and LiO ₂ / Al.

The structure of the organic EL device of the present invention is not particularly limited, and a structure in which a substrate, an anode, an organic material layer (hole injection layer-> hole transport layer-> light emitting layer-> electron transport layer) and a cathode are sequentially stacked is not limited thereto. Can be. In this case, at least one of the hole injection layer, the hole transport layer, the light emitting layer, the electron transport layer and the electron injection layer may include the compound represented by Formula 1 as a first host.

On the other hand, the electron injection layer may be further stacked on the electron transport layer. In addition, the structure of the organic EL device according to the present invention may be a structure in which an insulating layer or an adhesive layer is inserted at the interface between the anode and cathode and the organic material layer.

The organic electroluminescent device of the present invention may be formed using other materials and methods known in the art, except that one or more layers (eg, a light emitting layer) of the organic material layer are formed to include the first host and the second host. The organic material layer can be formed.

The substrate used in manufacturing the organic EL device of the present invention is not particularly limited, but non-limiting examples thereof include silicon wafers, quartz, glass plates, metal plates, plastic films and sheets.

Hereinafter, the present invention will be described in detail with reference to Examples, but the following Examples are merely illustrative of the present invention, and the present invention is not limited by the following Examples.

Preparation Example 1 Synthesis of IIC-1

Step 1 Synthesis of IIC-1

3-Bromo-9H-carbazole (27.8 g, 113 mmol), (9H-carbazol-3-yl) boronic acid (23.8 g, 113 mmol), K ₂ CO ₃ (46.8 g, 339 mmol) and THF under nitrogen stream / H ₂ O (400 ml / 100 ml) was mixed, Pd (PPh ₃ ) ₄ (6.53 g, 5.65 mmol) was added and stirred at 80 ℃ for 12 hours.

After completion of the reaction, the mixture was extracted with methylene chloride and MgSO ₄ was added and filtered. The solvent was removed from the obtained organic layer and purified by column chromatography (Hexane: MC = 5: 1 (v / v)) to obtain IIC-1 (30 g, yield 80%).

¹ H-NMR of IIC-1: δ 7.29-7.50 (m, 5H), 7.94 (d, 1H), 8.01 (s, 1H), 10.1 (s, 1H)

Preparation Example 2 Synthesis of IIC-2

Step 1 Synthesis of IIC-2

3-Bromo-6-phenyl-9H-carbazole (24.9 g, 77.4 mmol), (6-phenyl-9H-carbazol-3-yl) boronic acid (22.2 g, 77.4 mmol), K ₂ CO ₃ ( 32.0 g, 232 mmol) and THF / H ₂ O (400 ml / 100 ml) were mixed, and then Pd (PPh ₃ ) ₄ (4.47 g, 3.86 mmol) was added thereto and stirred at 80 ° C. for 12 hours.

After completion of the reaction, the mixture was extracted with methylene chloride and MgSO ₄ was added and filtered. After removing the solvent from the organic layer obtained was purified by column chromatography (Hexane: MC = 5: 1 (v / v)) to give IIC-2 (30 g, yield 80%).

¹ H-NMR of IIC-2: δ 7.29-7.50 (m, 10H), 7.92 (s, 1H), 8.00 (s, 1H), 10.1 (s, 1H)

Preparation Example 3 Synthesis of IIC-3

Step 1 Synthesis of IIC-3

3-Bromo-9H-carbazole (22.6 g, 91.8 mmol), (9-phenyl-9H-carbazol-3-yl) boronic acid (26.4 g, 91.8 mmol), K ₂ CO ₃ (38.1 g, 275) under nitrogen stream mmol) and THF / H ₂ O (400 ml / 100 ml) were mixed and Pd (PPh ₃ ) ₄ (5.31 g, 4.59 mmol) was added thereto and stirred at 80 ° C. for 12 hours.

After completion of the reaction, the mixture was extracted with methylene chloride and MgSO ₄ was added and filtered. The solvent was removed from the organic layer and purified by column chromatography (Hexane: MC = 5: 1 (v / v)) to obtain IIC-3 (30 g, yield 80%).

¹ H-NMR of IIC-3: δ 7.29-7.50 (m, 15H), 7.92 (d, 1H), 7.94 (d, 1H), 8.00 (s, 1H), 8.03 (s, 1H), 10.1 (s , 1H)

Preparation Example 4 Synthesis of IIC-4

Step 1 Synthesis of 9-([1,1 ': 3', 1 ''-terphenyl] -5'-yl) -3-bromo-9H-carbazole

5'-iodo-1,1 ': 3', 1 ''-terphenyl (39.7 g, 111 mmol), 3-bromo-9H-carbazole (27.4 g, 111 mmol), Pd (OAc) ₂ ( 1.25 g, 5.57 mmol), NaO (t-Bu) (21.4 g, 223 mmol), P (t-Bu) ₃ (50wt%) (4.51 g, 11.1 mmol) and Toluene (100 ml) were mixed and 110 ° C Stir at 12 h. After completion of the reaction, the mixture was extracted with ethyl acetate, followed by removal of water with MgSO ₄ , and purification by column chromatography to obtain the title compound 9-([1,1 ': 3', 1 ''-terphenyl] -5'-yl ) -3-bromo-9H-carbazole (31.7 g, 60%) was obtained.

¹ H-NMR: δ 7.07-7.35 (m, 18 H), 7.92 (d, 1 H), 7.98 (s, 1 H)

Step 2 Synthesis of IIC-4

9-([1,1 ': 3', 1 ''-terphenyl] -5'-yl) -3-bromo-9H-carbazole (31.7 g, 66.9 mmol), (9H-carbazol-3- under nitrogen stream yl) boronic acid (14.1 g, 66.9 mmol), K ₂ CO ₃ (27.7 g, 200 mmol) and THF / H ₂ O (400 ml / 100 ml) were mixed, followed by Pd (PPh ₃ ) ₄ (3.86 g , 3.34 mmol) was added and stirred at 80 ° C. for 12 hours.

After completion of the reaction, the mixture was extracted with methylene chloride and MgSO ₄ was added and filtered. After removing the solvent in the obtained organic layer was purified by column chromatography (Hexane: MC = 5: 1 (v / v)) to give IIC-4 (30 g, yield 80%).

¹ H-NMR: δ 7.05-7.33 (m, 18H), 7.38-7.42 (m, 5H), 7.92 (d, 1H), 7.94 (d, 1H), 8.00 (s, 1H), 8.03 (s, 1H ), 10.1 (s, 1H)

Preparation Example 5 Synthesis of IIC-5

Step 1 Synthesis of 3-bromo-6,9-diphenyl-9H-carbazole

3-bromo-6-phenyl-9H-carbazole (35.9 g, 111 mmol), iodobenzene (22.7 g, 111 mmol), Pd (OAc) ₂ (1.25 g, 5.57 mmol), NaO (t-Bu) under nitrogen stream (21.4 g, 223 mmol), P (t-Bu) ₃ (50 wt%) (4.51 g, 11.1 mmol) and Toluene (100 ml) were mixed and stirred at 110 ° C. for 12 h. After completion of the reaction was extracted with ethyl acetate, water was removed with MgSO ₄ and purified by column chromatography to give the target compound 3-bromo-6,9-diphenyl-9H-carbazole (31.7g, 60%).

¹ H-NMR: δ 7.07-7.35 (m, 14H), 7.92 (s, 1H), 7.98 (s, 1H)

Step 2 Synthesis of IIC-5

3-bromo-6,9-diphenyl-9H-carbazole (26.6 g, 66.9 mmol), (6-phenyl-9H-carbazol-3-yl) boronic acid (19.2 g, 66.9 mmol), K ₂ CO under nitrogen stream ₃ (27.7 g, 200 mmol) and THF / H ₂ O (400 ml / 100 ml) were mixed, and then Pd (PPh ₃ ) ₄ (3.86 g, 3.34 mmol) was added thereto and stirred at 80 ° C. for 12 hours.

After completion of the reaction, the mixture was extracted with methylene chloride and MgSO ₄ was added and filtered. The solvent was removed from the obtained organic layer and purified by column chromatography (Hexane: MC = 5: 1 (v / v)) to obtain IIC-5 (30 g, yield 80%).

¹ H-NMR: δ 7.05-7.33 (m, 15H), 7.38-7.42 (m, 8H), 7.92 (s, 1H), 7.94 (s, 1H), 8.00 (s, 1H), 8.03 (s, 1H ), 10.3 (s, 1 H)

Preparation Example 6 Synthesis of IIC-6

Step 1 Synthesis of IIC-6

3-bromo-6,9-diphenyl-9H-carbazole (30.8 g, 77.4 mmol) under nitrogen stream, (9H-carbazol-3-yl) boronic acid (16.3 g, 77.4 mmol), K ₂ CO ₃ (32.1 g , 232 mmol) and THF / H ₂ O (400 ml / 100 ml) were mixed, and then Pd (PPh ₃ ) ₄ (4.47 g, 3.87 mmol) was added thereto and stirred at 80 ° C. for 12 hours.

After completion of the reaction, the mixture was extracted with methylene chloride and MgSO ₄ was added and filtered. The solvent was removed from the organic layer and purified by column chromatography (Hexane: MC = 5: 1 (v / v)) to obtain IIC-6 (30 g, yield 80%).

¹ H-NMR: δ 7.05-7.33 (m, 10H), 7.38-7.42 (m, 9H), 7.92 (s, 1H), 7.94 (s, 1H), 8.00 (s, 1H), 8.03 (s, 1H ), 10.1 (s, 1H)

Preparation Example 7 Synthesis of IIC-7

Step 1 Synthesis of IIC-7

3-bromo-6-phenyl-9H-carbazole (24.9 g, 77.4 mmol), (9-phenyl-9H-carbazol-3-yl) boronic acid (22.2 g, 77.4 mmol), K ₂ CO ₃ ( 32.1 g, 232 mmol) and THF / H ₂ O (400 ml / 100 ml) were mixed, and then Pd (PPh ₃ ) ₄ (4.47 g, 3.87 mmol) was added thereto and stirred at 80 ° C. for 12 hours.

After completion of the reaction, the mixture was extracted with methylene chloride and MgSO ₄ was added and filtered. The solvent was removed from the organic layer and purified by column chromatography (Hexane: MC = 5: 1 (v / v)) to obtain IIC-7 (30 g, yield 80%).

¹ H-NMR: δ 7.03-7.29 (m, 10H), 7.38-7.42 (m, 9H), 7.94 (s, 1H), 7.96 (s, 1H), 7.98 (s, 1H), 8.01 (s, 1H ), 10.2 (s, 1H)

Preparation Example 8 Synthesis of IIC-8

Step 1 Synthesis of 9- (biphenyl-3-yl) -3-bromo-9H-carbazole

3-iodobiphenyl (39.7 g, 111 mmol), 3-bromo-9H-carbazole (27.4 g, 111 mmol), Pd (OAc) ₂ (1.25 g, 5.57 mmol), NaO (t-Bu) (21.4 under nitrogen stream g, 223 mmol), P (t-Bu) ₃ (50 wt%) (4.51 g, 11.1 mmol) and Toluene (100 ml) were mixed and stirred at 110 ° C. for 12 h. After completion of the reaction, the mixture was extracted with ethyl acetate, and then water was removed with MgSO ₄ , and purified by column chromatography to obtain the target compound 9- (biphenyl-3-yl) -3-bromo-9H-carbazole (26.9g, 61% )

¹ H-NMR: δ 7.25-7.52 (m, 12H), 7.94 (d, 1H), 8.07 (m, 2H), 8.55 (d, 1H)

Step 2 Synthesis of IIC-8

9- (biphenyl-3-yl) -3-bromo-9H-carbazole (26.9g, 67.7mmol), (9H-carbazol-3-yl) boronic acid (14.1 g, 66.9 mmol), K ₂ CO under nitrogen stream ₃ (27.7 g, 200 mmol) and THF / H ₂ O (400 ml / 100 ml) were mixed, and then Pd (PPh ₃ ) ₄ (3.86 g, 3.34 mmol) was added thereto and stirred at 80 ° C. for 12 hours.

After completion of the reaction, the mixture was extracted with methylene chloride and MgSO ₄ was added and filtered. The solvent was removed from the obtained organic layer and purified by column chromatography (Hexane: MC = 5: 1 (v / v)) to obtain IIC-8 (24.6 g, yield 75%).

¹ H-NMR: δ 7.29 (t, 2H), 7.46-7.69 (m, 13H), 7.77 (s, 2H), 7.87-8.18 (m, 6H), 10.1 (s, 1H)

Preparation Example 9 Synthesis of TP-1

Step 1 Synthesis of TP-1

2,7-Dibromotriphenylene (40.3 g, 104 mmol), Phenylboronic acid (12.7 g, 104 mmol), K ₂ CO ₃ (43.3 g, 313 mmol) and THF / H ₂ O (400 ml / 100 ml) under a nitrogen stream After mixing, Pd (PPh ₃ ) ₄ (6.03 g, 5.21 mmol) was added thereto and stirred at 80 ° C. for 12 hours.

After completion of the reaction, the mixture was extracted with methylene chloride and MgSO ₄ was added and filtered. The solvent was removed from the obtained organic layer, and then purified by column chromatography (Hexane: MC = 10: 1 (v / v)) to obtain TP-1 (20 g, yield 50%).

¹ H-NMR of TP-1: δ 7.05-7.24 (m, 13H), 7.35 (m, 2H)

Preparation Example 10 Synthesis of TP-2

<Step 1> Synthesis of 3-Bromo-9-phenyl-6- (triphenylen-2-yl) -9H-carbazole

3,6-Dibromo-9-phenyl-9H-carbazole (48.1 g, 120 mmol), Triphenylen-2-ylboronic acid (32.6 g, 120 mmol), K ₂ CO ₃ (49.7 g, 360 mmol) under a nitrogen stream and THF / H ₂ O (400 ml / 100 ml) was mixed, and then Pd (PPh ₃ ) ₄ (6.93 g, 6.00 mmol) was added thereto and stirred at 80 ° C. for 12 hours.

After completion of the reaction, the mixture was extracted with methylene chloride and MgSO ₄ was added and filtered. The solvent was removed from the obtained organic layer, and then purified by column chromatography (Hexane: MC = 5: 1 (v / v)) to obtain 3-Bromo-9-phenyl-6- (triphenylen-2-yl) -9H-carbazole (32.9 g, yield 50%) was obtained.

¹ H-NMR: δ 7.05-7.24 (m, 16H), 7.35-7.45 (m, 4H), 7.94 (s, 1H), 7.98 (s, 1H)

Step 2 Synthesis of TP-2

3-Bromo-9-phenyl-6- (triphenylen-2-yl) -9H-carbazole (32.9 g, 60.0 mmol), 4,4,4 ', 4', 5,5, 5 ', 5 under nitrogen stream '-octamethyl-2,2'-bi (1,3,2-dioxaborolane) (15.2 g, 60.0 mmol), Pd (dppf) Cl ₂ (4.89 g, 6.00 mmol), KOAc (17.7 g, 180 mmol) and 1,4-Dioxane (400 ml) was mixed and stirred at 120 ° C. for 12 hours.

After the reaction was completed, the mixture was extracted with ethyl acetate, followed by removing moisture with MgSO ₄ , and purified by column chromatography (Hexane: MC = 5: 1 (v / v)) to obtain TP-2 (25.0 g, yield 70%). Got it.

¹ H-NMR of TP-2: δ 1.24 (s, 12H), 7.01-7.20 (m, 16H), 7.30-7.37 (m, 4H), 7.90 (s, 1H), 7.93 (s, 1H)

Preparation Example 11 Synthesis of TP-3

<Step 1> Synthesis of TP-3

3-Bromo-9H-carbazole (23.5 g, 95.3 mmol), Triphenylen-2-ylboronic acid (26 g, 95.3 mmol), K ₂ CO ₃ (39.5 g, 286 mmol) and THF / H ₂ O (under nitrogen stream) 400 ml / 100 ml) was mixed, and then Pd (PPh ₃ ) ₄ (5.51 g, 4.77 mmol) was added thereto and stirred at 80 ° C. for 12 hours.

After completion of the reaction, the mixture was extracted with methylene chloride and MgSO ₄ was added and filtered. The solvent was removed from the organic layer and purified by column chromatography (Hexane: MC = 5: 1 (v / v)) to obtain TP-3 (30 g, yield 80%).

¹ H-NMR of TP-3: δ 7.01-7.20 (m, 11H), 7.30-7.37 (m, 5H), 7.92 (s, 1H), 7.96 (s, 1H), 10.5 (s, 1H)

Preparation Example 12 Synthesis of TP-4

<Step 1> Synthesis of 2- (3,5-Dibromophenyl) triphenylene

1,3-Dibromo-5-iodobenzene (53.9 g, 149 mmol), Triphenylen-2-ylboronic acid (40.5 g, 149 mmol), K ₂ CO ₃ (61.7 g, 447 mmol) and THF / H ₂ under nitrogen stream O (400 ml / 100 ml) was mixed, and then Pd (PPh ₃ ) ₄ (8.60 g, 7.44 mmol) was added thereto and stirred at 80 ° C. for 12 hours.

After completion of the reaction, the mixture was extracted with methylene chloride and MgSO ₄ was added and filtered. The solvent was removed from the organic layer and purified by column chromatography (Hexane: MC = 5: 1 (v / v)) to give 2- (3,5-Dibromophenyl) triphenylene (34.4 g, yield 50%).

¹ H-NMR: δ 7.07-7.23 (m, 11 H), 7.45 (s, 2 H), 7.72 (s, 1 H)

<Step 2> Synthesis of 3- (3-Bromo-5- (triphenylen-2-yl) phenyl) -9-phenyl-9H-carbazole

2- (3,5-Dibromophenyl) triphenylene (34.4 g, 74.4 mmol), (9-phenyl-9H-carbazol-3-yl) boronic acid (21.4 g, 74.4 mmol), K ₂ CO ₃ (30.9) under nitrogen stream g, 224 mmol) and THF / H ₂ O (400 ml / 100 ml) were mixed, and then Pd (PPh ₃ ) ₄ (4.30 g, 3.72 mmol) was added thereto and stirred at 80 ° C. for 12 hours.

After completion of the reaction, the mixture was extracted with methylene chloride and MgSO ₄ was added and filtered. The solvent was removed from the obtained organic layer, and then purified by column chromatography (Hexane: MC = 5: 1 (v / v)) to obtain 3- (3-Bromo-5- (triphenylen-2-yl) phenyl) -9-phenyl- 9H-carbazole (23.2 g, yield 50%) was obtained.

¹ H-NMR: δ 7.02-7.28 (m, 17H), 7.35-7.40 (m, 5H), 7.42 (s, 1H), 7.45 (s, 1H), 7.92 (s, 1H), 7.96 (s, 1H )

Step 3 Synthesis of TP-4

3- (3-Bromo-5- (triphenylen-2-yl) phenyl) -9-phenyl-9H-carbazole (23.2 g, 37.2 mmol), 4,4,4 ', 4', 5,5 under nitrogen stream , 5 ', 5'-octamethyl-2,2'-bi (1,3,2-dioxaborolane) (9.43 g, 37.2 mmol), Pd (dppf) Cl ₂ (3.03 g, 3.72 mmol), KOAc (10.9 g , 112 mmol) and 1,4-Dioxane (300 ml) were mixed and stirred at 120 ° C. for 12 h.

After completion of the reaction, the mixture was extracted with ethyl acetate, followed by removal of water with MgSO ₄ , and purification by column chromatography (Hexane: MC = 5: 1 (v / v)) to obtain TP-4 (20 g, yield 80%). Got it.

¹ H-NMR of TP-4: δ 1.24 (s, 12H), 7.04-7.26 (m, 19H), 7.32-7.39 (m, 5H), 7.93 (s, 1H), 7.95 (s, 1H)

Preparation Example 13 Synthesis of TP-5

<Step 1> Synthesis of 3-Bromo-9-phenyl-6- (3- (triphenylen-2-yl) phenyl) -9H-carbazole

3,6-Dibromo-9-phenyl-9H-carbazole (29.8 g, 74.4 mmol), (3- (Triphenylen-2-yl) phenyl) boronic acid (25.9 g, 74.4 mmol), K ₂ CO ₃ under nitrogen stream (30.9 g, 224 mmol) and THF / H ₂ O (400 ml / 100 ml) were mixed, and then Pd (PPh ₃ ) ₄ (4.30 g, 3.72 mmol) was added thereto and stirred at 80 ° C. for 12 hours.

After completion of the reaction, the mixture was extracted with methylene chloride and MgSO ₄ was added and filtered. The solvent was removed from the obtained organic layer, and then purified by column chromatography (Hexane: MC = 5: 1 (v / v)) to give 3-Bromo-9-phenyl-6- (3- (triphenylen-2-yl) phenyl)- 9H-carbazole (23.2 g, yield 50%) was obtained.

¹ H-NMR: δ 7.02-7.28 (m, 17H), 7.35-7.40 (m, 7H), 7.93 (s, 1H), 7.98 (s, 1H)

Step 2 Synthesis of TP-5

3-Bromo-9-phenyl-6- (3- (triphenylen-2-yl) phenyl) -9H-carbazole (23.2 g, 37.2 mmol), 4,4,4 ', 4', 5,5 under nitrogen stream , 5 ', 5'-octamethyl-2,2'-bi (1,3,2-dioxaborolane) (9.43 g, 37.2 mmol), Pd (dppf) Cl ₂ (3.03 g, 3.72 mmol), KOAc (10.9 g , 112 mmol) and 1,4-Dioxane (300 ml) were mixed and stirred at 120 ° C. for 12 h.

After completion of the reaction, the mixture was extracted with ethyl acetate and then water was removed with MgSO ₄ , and purified by column chromatography (Hexane: MC = 5: 1 (v / v)) to obtain TP-5 (20 g, 80% yield). Got it.

¹ H-NMR of TP-5: δ 1.24 (s, 12H), 7.04-7.26 (m, 17H), 7.32-7.39 (m, 7H), 7.93 (s, 1H), 7.95 (s, 1H)

Preparation 14 Synthesis of TP-6

<Step 1> Synthesis of 3- (3- (triphenylen-2-yl) phenyl) -9H-carbazole

3-bromo-9H-carbazole (18.31 g, 74.4 mmol), (3- (Triphenylen-2-yl) phenyl) boronic acid (25.9 g, 74.4 mmol), K ₂ CO ₃ (30.9 g, 224 mmol) under nitrogen stream ) And THF / H ₂ O (400 ml / 100 ml) were mixed, and then Pd (PPh ₃ ) ₄ (4.30 g, 3.72 mmol) was added thereto and stirred at 80 ° C. for 12 hours.

After completion of the reaction, the mixture was extracted with methylene chloride and MgSO ₄ was added and filtered. The solvent was removed from the organic layer obtained and purified by column chromatography (Hexane: MC = 5: 1 (v / v)) to give 3- (3- (triphenylen-2-yl) phenyl) -9H-carbazole (17.47 g, yield 50%).

¹ H-NMR of TP-6: δ 7.29 (t, 1H), 7.48-7.88 (m, 13H), 8.04-8.18 (m, 5H), 8.93 (d, 2H), 9.15 (s, 1H), 10.1 (s, 1H)

Preparation Example 15 Synthesis of TP-7

<Step 1> Synthesis of 3- (3 '-(triphenylen-2-yl) biphenyl-3-yl) -9H-carbazole

3- (3-bromophenyl) -9H-carbazole (23.88 g, 74.4 mmol), (3- (Triphenylen-2-yl) phenyl) boronic acid (25.9 g, 74.4 mmol), K ₂ CO ₃ (30.9) under nitrogen stream g, 224 mmol) and THF / H ₂ O (400 ml / 100 ml) were mixed, and then Pd (PPh ₃ ) ₄ (4.30 g, 3.72 mmol) was added thereto and stirred at 80 ° C. for 12 hours.

After completion of the reaction, the mixture was extracted with methylene chloride and MgSO ₄ was added and filtered. The solvent was removed from the obtained organic layer, and then purified by column chromatography (Hexane: MC = 5: 1 (v / v)) to obtain 3- (3 '-(triphenylen-2-yl) biphenyl-3-yl) -9H-carbazole (22.18 g, yield 55%) was obtained.

¹ H-NMR of TP-7: δ 7.28 (t, 1H), 7.48-7.88 (m, 17H), 8.04-8.18 (m, 5H), 8.92 (d, 2H), 9.17 (s, 1H), 10.2 (s, 1H)

Synthesis Example 1 Synthesis of C-1

IIC-1 (5 g, 15.0 mmol), 4-bromo-1,1'-biphenyl (7.01 g, 30.1 mmol), Pd (OAc) ₂ (338 mg, 1.50 mmol), NaO (t-Bu) under nitrogen stream ) (5.78 g, 60.2 mmol), P (t-Bu) ₃ (50 wt%) (1.22 g, 3.01 mmol) and Toluene (100 ml) were mixed and stirred at 110 ° C for 12 h. After the reaction was terminated and extracted with ethyl acetate, water was removed with MgSO ₄ and purified by column chromatography to give the target compound C-1 (6.70 g, 70%).

Mass (Theoretical value: 636.78 g / mol, Measured value: 636 g / mol)

Synthesis Example 2 Synthesis of C-2

Except for using 3-bromo-1,1'-biphenyl (7.02 g, 30.1 mmol) instead of 4-bromo-1,1'-biphenyl, the same procedure as in Synthesis Example 1 was carried out to C -2 (6.70 g, yield 70%) was obtained.

Mass (Theoretical value: 636.78 g / mol, Measured value: 636 g / mol)

[ Synthesis Example  3] Synthesis of C-3

Same as Synthesis Example 1, except that 5'-bromo-1,1 ': 3', 1 ''-terphenyl (9.30 g, 30.1 mmol) was used instead of 4-bromo-1,1'-biphenyl. The process was carried out to obtain the title compound C-3 (8.31 g, yield 70%).

Mass (Theoretical value: 788.97 g / mol, Measured value: 788 g / mol)

Synthesis Example 4 Synthesis of C-4

Under nitrogen stream IIC-2 (5 g, 10.3 mmol), Iodobenzene (4.21 g, 20.6 mmol), Pd (OAc) ₂ (232 mg, 1.03 mmol), NaO (t-Bu) (3.96 g, 41.2 mmol), P (t-Bu) ₃ (50 wt%) (836 mg, 2.06 mmol) and Toluene (100 ml) were mixed and stirred at 110 ° C. for 12 h. After the reaction was terminated and extracted with ethyl acetate, water was removed with MgSO ₄ , and purified by column chromatography to give the target compound C-4 (4.60 g, 70%).

Mass (Theoretical value: 636.78 g / mol, Measured value: 636 g / mol)

Synthesis Example 5 Synthesis of C-5

Except for using 4-bromo-1,1'-biphenyl (4.82 g, 20.6 mmol) instead of iodobenzene, the same procedure as in Synthesis Example 4 was carried out to give the target compound C-5 (5.70 g, yield 70% )

Mass (Theoretical value: 788.97 g / mol, Measured value: 788 g / mol)

Synthesis Example 6 Synthesis of C-6

Except for using 3-bromo-1,1'-biphenyl (4.82 g, 20.6 mmol) instead of iodobenzene, the same procedure as in Synthesis Example 4 was carried out to give the target compound C-6 (5.70 g, yield 70% )

Mass (Theoretical value: 788.97 g / mol, Measured value: 788 g / mol)

Synthesis Example 7 Synthesis of C-7

Except for using 5'-bromo-1,1 ': 3', 1 ''-terphenyl (6.38 g, 20.6 mmol) instead of iodobenzene, the same procedure as in Synthesis Example 4 was carried out to obtain C- 7 (5.70 g, yield 70%) was obtained.

Mass (Theoretical value: 941.16 g / mol, Measured value: 941 g / mol)

Synthesis Example 8 Synthesis of C-8

IIC-3 (5 g, 12.2 mmol), 4-bromo-1,1'-biphenyl (2.85 g, 12.2 mmol), Pd (OAc) ₂ (232 mg, 0.612 mmol), NaO (t-Bu) under nitrogen stream ) (2.35 g, 24.5 mmol), P (t-Bu) ₃ (50 wt%) (495 mg, 1.22 mmol) and Toluene (100 ml) were mixed and stirred at 110 ° C. for 12 h. After the reaction was terminated and extracted with ethyl acetate, water was removed with MgSO ₄ and purified by column chromatography to give the target compound C-8 (4.80 g, 70%).

Mass (Theoretical value: 560.69 g / mol, Measured value: 560 g / mol)

Synthesis Example 9 Synthesis of C-9

Except for using 3-bromo-1,1'-biphenyl (2.85 g, 12.2 mmol) instead of 4-bromo-1,1'-biphenyl, the same procedure as in Synthesis Example 8 was carried out to C -9 (4.80 g, yield 70%) was obtained.

Mass (Theoretical value: 560.69 g / mol, Measured value: 560 g / mol)

Synthesis Example 10 Synthesis of C-10

The same as in Synthesis Example 8, except that 5'-bromo-1,1 ': 3', 1 ''-terphenyl (4.82 g, 20.6 mmol) was used instead of 4-bromo-1,1'-biphenyl. The procedure was carried out to obtain the target compound C-10 (5.46 g, yield 70%).

Mass (Theoretical value: 636.78 g / mol, Measured value: 636 g / mol)

Synthesis Example 11 Synthesis of C-11

IIC-4 (5 g, 8.92 mmol), 4-bromo-1,1'-biphenyl (2.08 g, 8.92 mmol), Pd (OAc) ₂ (100 mg, 0.446 mmol), NaO (t-Bu) under nitrogen stream ) (1.71 g, 17.8 mmol), P (t-Bu) ₃ (50 wt%) (361 mg, 0.892 mmol) and Toluene (100 ml) were mixed and stirred at 110 ° C. for 12 h. After the reaction was terminated and extracted with ethyl acetate, water was removed with MgSO ₄ and purified by column chromatography to give the target compound C-11 (4.45 g, 70%).

Mass (Theoretical value: 712.88 g / mol, Measured value: 712 g / mol)

Synthesis Example 12 Synthesis of C-12

Except for using 3-bromo-1,1'-biphenyl (2.08 g, 8.92 mmol) instead of 4-bromo-1,1'-biphenyl, the same procedure as in Synthesis Example 11 was carried out to C -12 (4.45 g, yield 70%) was obtained.

Mass (Theoretical value: 712.88 g / mol, Measured value: 712 g / mol)

Synthesis Example 13 Synthesis of C-13

IIC-5 (5 g, 8.92 mmol), 4-bromo-1,1'-biphenyl (2.08 g, 8.92 mmol), Pd (OAc) ₂ (100 mg, 0.446 mmol), NaO (t-Bu) under nitrogen stream ) (1.71 g, 17.8 mmol), P (t-Bu) ₃ (50 wt%) (361 mg, 0.892 mmol) and Toluene (100 ml) were mixed and stirred at 110 ° C. for 12 h. After the reaction was terminated and extracted with ethyl acetate, water was removed with MgSO ₄ and purified by column chromatography to give the target compound C -13 (4.45 g, 70%).

Mass (Theoretical value: 712.88 g / mol, Measured value: 712 g / mol)

Synthesis Example 14 Synthesis of C-14

Except for using 3-bromo-1,1'-biphenyl (2.08 g, 8.92 mmol) instead of 4-bromo-1,1'-biphenyl, the same procedure as in Synthesis Example 11 was carried out to C -14 (4.45 g, yield 70%) was obtained.

Mass (Theoretical value: 712.88 g / mol, Measured value: 712 g / mol)

Synthesis Example 15 Synthesis of C-15

IIC-6 (5 g, 10.3 mmol), 4-bromo-1,1'-biphenyl (2.41 g, 10.3 mmol), Pd (OAc) ₂ (116 mg, 0.516 mmol), NaO (t-Bu) under nitrogen stream ) (1.98 g, 20.6 mmol), P (t-Bu) ₃ (50 wt%) (418 mg, 1.03 mmol) and Toluene (100 ml) were mixed and stirred at 110 ° C. for 12 h. After the reaction was terminated and extracted with ethyl acetate, water was removed with MgSO ₄ and purified by column chromatography to give the target compound C-15 (4.60 g, 70%).

Mass (Theoretical value: 636.78 g / mol, Measured value: 636 g / mol)

Synthesis Example 16 Synthesis of C-16

Except for using 3-bromo-1,1'-biphenyl (2.41 g, 10.3 mmol) instead of 4-bromo-1,1'-biphenyl, the same procedure as in Synthesis Example 15 was carried out to C -16 (4.60 g, yield 70%) was obtained.

Mass (Theoretical value: 636.78 g / mol, Measured value: 636 g / mol)

Synthesis Example 17 Synthesis of C-17

The same as in Synthesis Example 15, except that 5'-bromo-1,1 ': 3', 1 ''-terphenyl (3.19 g, 10.3 mmol) was used instead of 4-bromo-1,1'-biphenyl. The process was carried out to obtain the title compound C-17 (5.15 g, yield 70%).

Mass (Theoretical value: 712.88 g / mol, Measured value: 712 g / mol)

Synthesis Example 18 Synthesis of C-18

Under nitrogen stream IIC-7 (5 g, 10.3 mmol), Iodobenzene (2.10 g, 10.3 mmol), Pd (OAc) ₂ (116 mg, 0.516 mmol), NaO (t-Bu) (1.98 g, 20.6 mmol), P (t-Bu) ₃ (50 wt%) (418 mg, 1.03 mmol) and Toluene (100 ml) were mixed and stirred at 110 ° C. for 12 h. After the reaction was terminated and extracted with ethyl acetate, water was removed with MgSO ₄ and purified by column chromatography to give the target compound C-18 (4.05 g, 70%).

Mass (Theoretical value: 560.69 g / mol, Measured value: 560 g / mol)

Synthesis Example 19 Synthesis of C-19

Except for using 4-bromo-1,1'-biphenyl (2.41 g, 10.3 mmol) instead of iodobenzene, the same procedure as in Synthesis Example 18 was carried out to give the title compound C-19 (4.60 g, yield 70% )

Mass (Theoretical value: 636.78 g / mol, Measured value: 636 g / mol)

Synthesis Example 20 Synthesis of C-20

Except for using 3-bromo-1,1'-biphenyl (2.41 g, 10.3 mmol) instead of iodobenzene, the same procedure as in Synthesis Example 18 was carried out to give the target compound C-20 (4.60 g, yield 70% )

Mass (Theoretical value: 636.78 g / mol, Measured value: 636 g / mol)

Synthesis Example 21 Synthesis of C-21

Except for using 5'-bromo-1,1 ': 3', 1 ''-terphenyl (3.19 g, 10.3 mmol) instead of iodobenzene, the same procedure as in Synthesis Example 18 was carried out to obtain C- 21 (5.15 g, yield 70%) was obtained.

Mass (Theoretical value: 712.88 g / mol, Measured value: 712 g / mol)

Synthesis Example 22 Synthesis of C-22

IIC-5 (4.31 g, 8.92 mmol), 4-bromo-1,1'-biphenyl (2.08 g, 8.92 mmol), Pd (OAc) ₂ (100 mg, 0.446 mmol), NaO (t-Bu) under nitrogen stream ) (1.71 g, 17.8 mmol), P (t-Bu) ₃ (50 wt%) (361 mg, 0.892 mmol) and Toluene (100 ml) were mixed and stirred at 110 ° C. for 12 h. After the reaction was terminated and extracted with ethyl acetate, water was removed with MgSO ₄ and purified by column chromatography to give the target compound C-7 (3.68 g, yield 65%).

Mass (Theoretical value: 636.78 g / mol, Measured value: 636 g / mol)

Synthesis Example 23 Synthesis of D-1

TP-1 (5 g, 13.0 mmol), (3- (4,6-diphenyl-1,3,5-triazin-2-yl) phenyl) boronic acid (4.61 g, 13.0 mmol), K ₂ under nitrogen stream CO ₃ (5.41 g, 39.1 mmol) and THF / H ₂ O (80 ml / 20 ml) were mixed and Pd (PPh ₃ ) ₄ (754 mg, 0.652 mmol) was added thereto and stirred at 80 ° C. for 12 hours. .

After completion of the reaction, the mixture was extracted with methylene chloride and MgSO ₄ was added and filtered. The solvent was removed from the obtained organic layer, and then purified by column chromatography (Hexane: MC = 5: 1 (v / v)) to give D-1 (6.38 g, yield 80%).

Mass (Theoretical value: 611.73 g / mol, Measured value: 611 g / mol)

Synthesis Example 24 Synthesis of D-2

 (3 '-(4,6-diphenyl-1,3,5-triazin-2-yl) instead of (3- (4,6-diphenyl-1,3,5-triazin-2-yl) phenyl) boronic acid Except for using-[1,1'-biphenyl] -3-yl) boronic acid (5.60 g, 13.0 mmol), the same procedure as in Synthesis Example 1 was carried out to obtain the title compound D-2 (7.18 g , Yield 80%) was obtained.

Mass (Theoretical value: 687.83 g / mol, Measured value: 687 g / mol)

Synthesis Example 25 Synthesis of D-3

 ((4 '-(4,6-diphenyl-1,3,5-triazin-2-yl) instead of (3- (4,6-diphenyl-1,3,5-triazin-2-yl) phenyl) boronic acid )-[1,1'-biphenyl] -3-yl) boronic acid (5.60 g, 13.0 mmol) was carried out in the same manner as in Synthesis Example 1, except that D-3 (7.18) was a target compound. g, yield 80%) was obtained.

Mass (Theoretical value: 687.83 g / mol, Measured value: 687 g / mol)

Synthesis Example 26 Synthesis of D-4

TP-2 (5 g, 8.40 mmol), 2-chloro-4,6-diphenyl-1,3,5-triazine (2.25 g, 8.40 mmol), K ₂ CO ₃ (3.48 g, 25.2 mmol) under nitrogen stream And THF / H ₂ O (80 ml / 20 ml) were mixed, Pd (PPh ₃ ) ₄ (485 mg, 0.420 mmol) was added thereto, and the mixture was stirred at 80 ° C. for 12 hours.

After completion of the reaction, the mixture was extracted with methylene chloride and MgSO ₄ was added and filtered. After removing the solvent in the obtained organic layer was purified by column chromatography (Hexane: MC = 5: 1 (v / v)) to give D-4 (4.71 g, yield 80%).

Mass (Theoretical value: 700.83 g / mol, Measured value: 700 g / mol)

Synthesis Example 27 Synthesis of D-5

The same procedure as in Synthesis Example 4 was repeated except that 2-chloro-4,6-diphenylpyrimidine (2.24 g, 8.40 mmol) was used instead of 2-chloro-4,6-diphenyl-1,3,5-triazine. The target compound D-5 (4.71 g, yield 80%) was obtained.

Mass (Theoretical value: 699.84 g / mol, Measured value: 699 g / mol)

Synthesis Example 28 Synthesis of D-6

The same procedure as in Synthesis Example 4 was repeated except that 4-chloro-2,6-diphenylpyrimidine (2.24 g, 8.40 mmol) was used instead of 2-chloro-4,6-diphenyl-1,3,5-triazine. To give the title compound D-6 (4.71 g, yield 80%).

Mass (Theoretical value: 699.84 g / mol, Measured value: 699 g / mol)

Synthesis Example 29 Synthesis of D-7

The use of 2- (3-chlorophenyl) -4,6-diphenyl-1,3,5-triazine (2.89 g, 8.40 mmol) instead of 2-chloro-4,6-diphenyl-1,3,5-triazine Except that, the same procedure as in Synthesis Example 4 was performed to obtain B-4 (5.22 g, yield 80%) as a target compound.

Mass (Theoretical value: 776.92 g / mol, Measured value: 776 g / mol)

Synthesis Example 30 Synthesis of D-8

Synthesis Example 4 except that 4- (3-chlorophenyl) -2,6-diphenylpyrimidine (2.89 g, 8.40 mmol) was used instead of 2-chloro-4,6-diphenyl-1,3,5-triazine. To obtain the target compound D-8 (5.22 g, yield 80%).

Mass (Theoretical value: 775.93 g / mol, Measured value: 775 g / mol)

Synthesis Example 31 Synthesis of D-9

TP-3 (5 g, 12.7 mmol), 2-chloro-4,6-diphenyl-1,3,5-triazine (3.74 g, 14.0 mmol), Pd (OAc) ₂ (143 mg, 0.635 mmol) under nitrogen stream ), NaO (t-Bu) (2.44 g, 25.4 mmol), P (t-Bu) ₃ (50 wt%) (514 mg, 1.27 mmol) and Toluene (100 ml) were mixed and stirred at 110 ° C. for 12 h. It was. After the reaction was terminated and extracted with ethyl acetate, water was removed with MgSO ₄ and purified by column chromatography to give the target compound D-9 (5.56g, 70%).

Mass (Theoretical value: 624.73 g / mol, Measured value: 624 g / mol)

Synthesis Example 32 Synthesis of D-10

The same procedure as in Synthesis Example 9 was repeated except that 4-chloro-2,6-diphenylpyrimidine (3.74 g, 14.0 mmol) was used instead of 2-chloro-4,6-diphenyl-1,3,5-triazine. To give the title compound D-10 (5.56 g, 70% yield).

Mass (Theoretical value: 623.74 g / mol, Measured value: 623 g / mol)

Synthesis Example 33 Synthesis of D-11

Use of 2- (3-chlorophenyl) -4,6-diphenyl-1,3,5-triazine (4.81 g, 14.0 mmol) instead of 2-chloro-4,6-diphenyl-1,3,5-triazine Except that in the same manner as in Synthesis Example 9 to give the title compound D-11 (6.23 g, yield 70%).

Mass (Theoretical value: 700.83 g / mol, Measured value: 700 g / mol)

Synthesis Example 34 Synthesis of D-12

Synthesis Example 9 except that 4- (3-chlorophenyl) -2,6-diphenylpyrimidine (4.81 g, 14.0 mmol) was used instead of 2-chloro-4,6-diphenyl-1,3,5-triazine. By the same process as in the title compound D-12 (6.23 g, yield 70%) was obtained.

Mass (Theoretical value: 699.84 g / mol, Measured value: 699 g / mol)

Synthesis Example 35 Synthesis of D-13

TP-4 (5 g, 7.44 mmol), 2-chloro-4,6-diphenyl-1,3,5-triazine (1.99 g, 7.44 mmol), K ₂ CO ₃ (3.08 g, 22.3 mmol) under nitrogen stream And THF / H ₂ O (80 ml / 20 ml) were mixed, Pd (PPh ₃ ) ₄ (430 mg, 0.372 mmol) was added thereto, and the mixture was stirred at 80 ° C. for 12 hours.

After completion of the reaction, the mixture was extracted with methylene chloride and MgSO ₄ was added and filtered. After removing the solvent in the organic layer obtained was purified by column chromatography (Hexane: MC = 5: 1 (v / v) to give D-13 (4.63 g, yield 80%).

Mass (Theoretical value: 776.92 g / mol, Measured value: 776 g / mol)

Synthesis Example 36 Synthesis of D-14

The same procedure as in Synthesis Example 13 was repeated except that 4-chloro-2,6-diphenylpyrimidine (1.99 g, 7.44 mmol) was used instead of 2-chloro-4,6-diphenyl-1,3,5-triazine. D-14 (4.63 g, yield 80%) was obtained as the target compound.

Mass (Theoretical value: 775.93 g / mol, Measured value: 775 g / mol)

Synthesis Example 37 Synthesis of D-15

The use of 2- (3-chlorophenyl) -4,6-diphenyl-1,3,5-triazine (2.56 g, 7.44 mmol) instead of 2-chloro-4,6-diphenyl-1,3,5-triazine Except that in the same manner as in Synthesis Example 13 to obtain the target compound D-15 (5.08 g, yield 80%).

Mass (Theoretical value: 853.02 g / mol, Measured value: 853 g / mol)

Synthesis Example 38 Synthesis of D-16

Synthesis Example 13 except that 4- (3-chlorophenyl) -2,6-diphenylpyrimidine (2.56 g, 7.44 mmol) was used instead of 2-chloro-4,6-diphenyl-1,3,5-triazine. The same procedure as in the title compound D-16 (5.08 g, yield 80%) was obtained.

Mass (Theoretical value: 852.03 g / mol, Measured value: 852 g / mol)

Synthesis Example 39 Synthesis of D-17

TP-5 (5 g, 7.44 mmol), 2-chloro-4,6-diphenyl-1,3,5-triazine (1.99 g, 7.44 mmol), K ₂ CO ₃ (3.08 g, 22.3 mmol) under nitrogen stream And THF / H ₂ O (80 ml / 20 ml) were mixed, Pd (PPh ₃ ) ₄ (430 mg, 0.372 mmol) was added thereto, and the mixture was stirred at 80 ° C. for 12 hours.

After completion of the reaction, the mixture was extracted with methylene chloride and MgSO ₄ was added and filtered. After removing the solvent in the obtained organic layer was purified by column chromatography (Hexane: MC = 5: 1 (v / v)) to give D-17 (4.63 g, yield 80%).

Mass (Theoretical value: 776.92 g / mol, Measured value: 776 g / mol)

Synthesis Example 40 Synthesis of D-18

The same procedure as in Synthesis Example 17 was repeated except that 4-chloro-2,6-diphenylpyrimidine (1.99 g, 7.44 mmol) was used instead of 2-chloro-4,6-diphenyl-1,3,5-triazine. To give the title compound D-18 (4.63 g, yield 80%).

Mass (Theoretical value: 775.93 g / mol, Measured value: 775 g / mol)

Synthesis Example 41 Synthesis of D-19

The use of 2- (3-chlorophenyl) -4,6-diphenyl-1,3,5-triazine (2.56 g, 7.44 mmol) instead of 2-chloro-4,6-diphenyl-1,3,5-triazine Except that in the same manner as in Synthesis Example 17 to obtain the target compound D-19 (5.08 g, yield 80%).

Mass (Theoretical value: 853.02 g / mol, Measured value: 853 g / mol)

Synthesis Example 42 Synthesis of D-20

Synthesis Example 17 except that 4- (3-chlorophenyl) -2,6-diphenylpyrimidine (2.56 g, 7.44 mmol) was used instead of 2-chloro-4,6-diphenyl-1,3,5-triazine. To obtain the target compound D-20 (5.08 g, 80% yield) by the same procedure.

Mass (Theoretical value: 852.03 g / mol, Measured value: 852 g / mol)

Synthesis Example 43 Synthesis of D-22

TP-6 (5.96 g, 12.7 mmol), 2-chloro-4,6-diphenyl-1,3,5-triazine (3.74 g, 14.0 mmol), Pd (OAc) ₂ (143 mg, 0.635 mmol) under nitrogen stream ), NaO (t-Bu) (2.44 g, 25.4 mmol), P (t-Bu) ₃ (50 wt%) (514 mg, 1.27 mmol) and Toluene (100 ml) were mixed and stirred at 110 ° C. for 12 h. It was. After the reaction was terminated and extracted with ethyl acetate, water was removed with MgSO ₄ and purified by column chromatography to give the target compound D-22 (5.78g, 65%).

Mass (Theoretical value: 700.83 g / mol, Measured value: 700 g / mol)

Synthesis Example 44 Synthesis of D-25

Use of 2- (3-chlorophenyl) -4,6-diphenyl-1,3,5-triazine (4.81 g, 14.0 mmol) instead of 2-chloro-4,6-diphenyl-1,3,5-triazine Except for the same procedure as in Synthesis Example 43, a target compound D-25 (6.41 g, yield 70%) was obtained.

Mass (Theoretical value: 776.92 g / mol, Measured value: 776 g / mol)

Synthesis Example 45 Synthesis of D-27

TP-7 (6.92 g, 12.7 mmol), 2-chloro-4,6-diphenyl-1,3,5-triazine (3.74 g, 14.0 mmol), Pd (OAc) ₂ (143 mg, 0.635 mmol) under nitrogen stream ), NaO (t-Bu) (2.44 g, 25.4 mmol), P (t-Bu) ₃ (50 wt%) (514 mg, 1.27 mmol) and Toluene (100 ml) were mixed and stirred at 110 ° C. for 12 h. It was. After the reaction was terminated and extracted with ethyl acetate, water was removed with MgSO ₄ and purified by column chromatography to give the target compound D-27 (6.61g, 68%).

Mass (Theoretical value: 776.92 g / mol, Measured value: 776 g / mol)

Synthesis Example 46 Synthesis of D-28

Use of 2- (3-chlorophenyl) -4,6-diphenyl-1,3,5-triazine (4.81 g, 14.0 mmol) instead of 2-chloro-4,6-diphenyl-1,3,5-triazine Except, the same procedure as in Synthesis Example 45 was carried out to obtain D-28 (7.04 g, yield 65%) as a target compound.

Mass (Theoretical value: 853.02 g / mol, Measured value: 853 g / mol)

Synthesis Example 47 Synthesis of D-31

Synthesis Example 43 except that 4- (3-chlorophenyl) -2,6-diphenylpyrimidine (4.81 g, 14.0 mmol) was used instead of 2-chloro-4,6-diphenyl-1,3,5-triazine. The same procedure as in the title compound D-31 (6.41 g, yield 70%) was obtained.

Mass (Theoretical value: 775.93 g / mol, Measured value: 775 g / mol)

Synthesis Example 48 Synthesis of D-32

Synthesis Example 43 except that 2- (3-chlorophenyl) -4,6-diphenylpyrimidine (4.81 g, 14.0 mmol) was used instead of 2-chloro-4,6-diphenyl-1,3,5-triazine. To obtain the target compound D-32 (6.41 g, 70% yield) by the same procedure.

Mass (Theoretical value: 775.93 g / mol, Measured value: 775 g / mol)

Synthesis Example 49 Synthesis of D-33

Synthesis Example 43 except that 2- (3-chlorophenyl) -4,6-diphenylpyridine (4.81 g, 14.0 mmol) was used instead of 2-chloro-4,6-diphenyl-1,3,5-triazine. The same procedure as in the title compound D-33 (6.41 g, yield 70%) was obtained.

Mass (Theoretical value: 774.95 g / mol, Measured value: 774 g / mol)

Synthesis Example 50 Synthesis of D-34

Synthesis Example 45 except for using 2- (3-chlorophenyl) -4,6-diphenylpyrimidine (4.81 g, 14.0 mmol) instead of 2-chloro-4,6-diphenyl-1,3,5-triazine The same procedure as in the title compound D-34 (7.04 g, yield 65%) was obtained.

Mass (Theoretical value: 852.03 g / mol, Measured value: 852 g / mol)

Synthesis Example 51 Synthesis of C-49

<Step 1> Synthesis of 3,6-di (biphenyl-4-yl) -9H-carbazole

10.0 g (30.8 mmol) of 3,6-dibromo-9H-carbazole, 18.3 g (92.3 mmol) of biphenyl-4-ylboronic acid, 6.16 g (154.0 mmol) of NaOH and 200 ml / 100 ml of THF under nitrogen stream / H ₂ O was added and stirred. 1.78 g (5 mol%) of Pd (PPh ₃ ) ₄ was added at 40 ° C. and stirred at 80 ° C. for 12 hours. After completion of the reaction, the mixture was extracted with methylene chloride and MgSO ₄ was added and filtered. After removing the solvent of the filtered organic layer using column chromatography to obtain the target compound 3,6-di (biphenyl-4-yl) -9H-carbazole (10.9 g, 23.1 mmol, yield 75%).

¹ H-NMR (DMSO): δ 7.35 (t, 2H), 7.47 (t, 4H), 7.57 (d, 2H), 7.73 (d, 4H), 7.78 (m, 6H), 7.89 (d, 4H) , 8.66 (s, 2H), 11.42 (s, 1H)

Step 2 Synthesis of C-49

3,6-di (biphenyl-4-yl) -9H-carbazole (7.06 g, 15.0 mmol), 4-bromo-1,1'-biphenyl (9.24 g, 30.1 mmol), Pd (OAc) ₂ under nitrogen stream (338 mg, 1.50 mmol), NaO (t-Bu) (5.78 g, 60.2 mmol), P (t-Bu) ₃ (50wt%) (1.22 g, 3.01 mmol) and Toluene (100 ml) were mixed and 110 Stir at 12 ° C. for 12 h. After the reaction was terminated and extracted with ethyl acetate, water was removed with MgSO ₄ and purified by column chromatography to give the target compound C-49 (7.96 g, 70%).

Mass (Theoretical value: 699.88 g / mol, Measured value: 699 g / mol)

Synthesis Example 52 Synthesis of C-53

3,6-dibromo-9-phenyl-9H-carbazole (3.69 g, 9.18 mmol), 9-phenyl-9H-carbazol-3-ylboronic acid (5.79 g, 20.2 mmol), K ₂ CO ₃ (7.62) under nitrogen stream g, 55.0 mmol) and THF / H ₂ O (40 ml / 10 ml) were mixed, and then Pd (PPh ₃ ) ₄ (1.062 g, 0.918 mmol) was added thereto and stirred at 80 ° C. for 12 hours.

After completion of the reaction, the mixture was extracted with methylene chloride and MgSO ₄ was added and filtered. After removing the solvent in the obtained organic layer was purified by column chromatography (Hexane: MC = 5: 1 (v / v)) to give C-53 (5.32 g, yield 80%).

Mass (Theoretical value: 725.88 g / mol, Measured value: 725 g / mol)

Examples 1 to 28 Fabrication of Organic Electroluminescent Device

ITO (Indium tin oxide) was ultrasonically cleaned with distilled water to a glass substrate coated with a thin film 1500Å. After washing the distilled water, ultrasonic cleaning with a solvent such as isopropyl alcohol, acetone, methanol, dried and transferred to a UV OZONE cleaner (Power sonic 405, Hwasin Tech), and then wash the substrate using UV for 5 minutes The substrate was transferred to a vacuum evaporator.

On the prepared ITO transparent substrate, m-MTDATA (60 nm) / TCTA (80 nm) / was prepared using C-4 as the first host and the compounds of Synthesis Examples 23 to 50 as the second host, respectively. 90% of the first host and the second host + 10% Ir (ppy) ₃ (300nm) / BCP (10 nm) / Alq ₃ (30 nm) / LiF (1 nm) / Al (200 nm) An organic electroluminescent device was produced.

At this time, the structures of m-MTDATA, TCTA, Ir (ppy) ₃ and BCP used are as follows, and the mixing ratio of the first host and the second host is 5: 5.

Examples 29 to 51 Fabrication of Organic Electroluminescent Device

Example 1 On the prepared ITO transparent substrate, m-MTDATA (60) using C-1 to C-22, C-49 and C-53 as the first host and the compound represented by D-25 as the second host were prepared. nm) / TCTA (80 nm) / 90% of the first and second host + 10% Ir (ppy) ₃ (30nm) / BCP (10 nm) / Alq ₃ (30 nm) / LiF (1 nm) / An organic electroluminescent device was manufactured by laminating in order of Al (200 nm).

The structures of m-MTDATA, TCTA, Ir (ppy) ₃ , and BCP were the same as those of Example 1, and the mixing ratio of the first host and the second host was 5: 5.

Examples 52 to 54 Fabrication of Organic Electroluminescent Device

Example 1 On the prepared ITO transparent substrate, m-MTDATA (60 nm) / TCTA (80 nm) / 90% of C-4 as the first host and the compound represented by the D-25 as the second host Organic electroluminescence by stacking the first host and the second host + 10% Ir (ppy) ₃ (300nm) / BCP (10 nm) / Alq ₃ (30 nm) / LiF (1 nm) / Al (200 nm) The device was produced.

At this time, the structure of m-MTDATA, TCTA, Ir (ppy) ₃ , BCP used is the same as in Example 1, the mixing ratio of the first host and the second host was adjusted as shown in Table 1.

Comparative Example 1 Fabrication of Organic Electroluminescent Device

An organic electroluminescent device was manufactured in the same manner as in Example 1, except that 90% CBP + 10% Ir (ppy) ₃ was used to form the emission layer. At this time, the structure of the CBP used is as follows.

Comparative Example 2 Fabrication of Organic Electroluminescent Device

An organic electroluminescent device was manufactured in the same manner as in Example 1, except that 90% of the second host (D-25) + 10% Ir (ppy) ₃ was used to form the emission layer.

Comparative Example 3 Fabrication of Organic Electroluminescent Device

An organic electroluminescent device was manufactured in the same manner as in Example 1, except that 90% of the first host (C-4) + 10% Ir (ppy) ₃ was used to form the emission layer.

Experimental Example

For each of the organic EL devices manufactured in Examples 1 to 54 and Comparative Examples 1 to 3, the driving voltage and the current efficiency at the current density of 10 mA / cm 2 were measured, and the results are shown in Table 1 below.

Sample Host Usage Rate Drive voltage (V) Current efficiency (cd / A) Example 1 50% C-4 + 50% D-1 6.30 42.9 Example 2 50% C-4 + 50% D-2 6.40 41.8 Example 3 50% C-4 + 50% D-3 6.10 43.9 Example 4 50% C-4 + 50% D-4 6.40 42.0 Example 5 50% C-4 + 50% D-5 6.20 42.5 Example 6 50% C-4 + 50% D-6 6.35 42.2 Example 7 50% C-4 + 50% D-7 6.25 42.3 Example 8 50% C-4 + 50% D-8 6.20 42.7 Example 9 50% C-4 + 50% D-9 6.25 43.0 Example 10 50% C-4 + 50% D-10 6.15 42.7 Example 11 50% C-4 + 50% D-11 6.20 42.0 Example 12 50% C-4 + 50% D-12 6.25 41.5 Example 13 50% C-4 + 50% D-13 6.25 43.0 Example 14 50% C-4 + 50% D-14 6.10 42.2 Example 15 50% C-4 + 50% D-15 5.95 42.9 Example 16 50% C-4 + 50% D-16 5.95 43.1 Example 17 50% C-4 + 50% D-17 6.00 43.3 Example 18 50% C-4 + 50% D-18 6.05 43.2 Example 19 50% C-4 + 50% D-19 6.15 42.8 Example 20 50% C-4 + 50% D-20 6.10 42.9 Example 21 50% C-4 + 50% D-22 6.10 42.1 Example 22 50% C-4 + 50% D-25 6.35 43.5 Example 23 50% C-4 + 50% D-27 6.15 43.2 Example 24 50% C-4 + 50% D-28 6.20 42.2 Example 25 50% C-4 + 50% D-31 6.20 42.9 Example 26 50% C-4 + 50% D-32 6.15 42.6 Example 27 50% C-4 + 50% D-33 6.10 41.4 Example 28 50% C-4 + 50% D-34 6.20 42.0 Example 29 50% C-1 + 50% D-25 6.20 42.5 Example 30 50% C-2 + 50% D-25 6.40 41.8 Example 31 50% C-3 + 50% D-25 6.35 41.9 Example 32 50% C-5 + 50% D-25 6.40 42.4 Example 33 50% C-6 + 50% D-25 6.30 42.5 Example 34 50% C-7 + 50% D-25 6.30 42.6 Example 35 50% C-8 + 50% D-25 6.35 42.5 Example 36 50% C-9 + 50% D-25 6.30 42.9 Example 37 50% C-10 + 50% D-25 6.35 43.0 Example 38 50% C-11 + 50% D-25 6.25 42.7 Example 39 50% C-12 + 50% D-25 6.30 42.9 Example 40 50% C-13 + 50% D-25 6.15 42.5 Example 41 50% C-14 + 50% D-25 6.20 43.2 Example 42 50% C-15 + 50% D-25 6.20 43.0 Example 43 50% C-16 + 50% D-25 6.25 42.9 Example 44 50% C-17 + 50% D-25 6.30 43.1 Example 45 50% C-18 + 50% D-25 6.10 42.3 Example 46 50% C-19 + 50% D-25 6.15 43.0 Example 47 50% C-20 + 50% D-25 6.15 42.8 Example 48 50% C-21 + 50% D-25 6.10 42.9 Example 49 50% C-22 + 50% D-25 6.00 43.0 Example 50 50% C-49 + 50% D-25 6.40 40.5 Example 51 50% C-53 + 50% D-25 6.40 40.9 Example 52 80% C-4 + 20% D-25 6.10 43.1 Example 53 60% C-4 + 40% D-25 6.15 42.7 Example 54 40% C-4 + 60% D-25 6.25 42.5 Comparative Example 1 CBP 6.93 38.2 Comparative Example 2 D-25 6.55 40.3 Comparative Example 3 C-4 6.40 35.2

Referring to Table 1, the organic electroluminescent devices (Examples 1 to 54) of the present invention using the light emitting layer including the first host and the second host are conventional CBP or C-4, D-25 as a single host material. It was confirmed that the organic electroluminescent device of Comparative Examples 1 to 3 using the light emitting layer included exhibited superior performance in terms of current efficiency and driving voltage.

Claims (8)

anode; cathode; And one or more organic material layers interposed between the anode and the cathode,
At least one of the one or more organic material layers is a light emitting layer including a first host and a second host,
The first host is a compound represented by the following formula (1),
The second host is an organic electroluminescent device, characterized in that the compound represented by the formula (2b).
[Formula 1]

In Chemical Formula 1,
R ₁ to R ₇ are the same as or different from each other, and are each independently hydrogen or an aryl group of C ₆ to C ₆₀ ,
a to c are each independently an integer of 0 to 5,
d to g are each independently an integer of 0 to 4,
n and m are each independently integers of 0 to 1, where n + m <2, where n is 1, f is an integer of 0 to 3, and if m is 1, g is an integer of 0 to 3;
[Formula 2b]

In Chemical Formula 2b,
L ₁ and L ₂ are the same as or different from each other, and each independently a group consisting of a single bond, an arylene group having ₆ to ₁₈ carbon atoms, and a heteroarylene group having 5 to 18 nuclear atoms including 1 to 3 N atoms; At least one selected from, but L ₁ or L _{2 to} which a substituent of the following formula 3 is linked includes a carbazolylene group,
One of Ar ₁ and Ar ₂ is a substituent represented by the following formula (3),
Ar ₁ or Ar ₂ not having a substituent of Formula 3 is selected from the group consisting of hydrogen, and an aryl group of C ₆ ~ C ₄₀ ,
[Formula 3]

In Chemical Formula 3,
L is a single bond or an arylene group of C ₆ ~ C ₁₈ ,
Z ₁ to Z ₅ are the same as or different from each other, and each independently N or C (R ₁₁ ), wherein Z ₁ to Z ₅ include 2 to 3 N,
When there are a plurality of C (R ₁₁ ), a plurality of R ₁₁ are each independently hydrogen or an alkyl group of C ₁ to C ₄₀ ,
When the arylene group, heteroarylene group, aryl group, and the alkyl group of R ₁₁ is substituted at L ₁ to L ₂ , L, R ₁ to R ₇ and Ar ₁ to Ar ₂ , each independently deuterium, C ₆ to C _It means that it is substituted with at least one member selected from the group consisting of an aryl group of 40 and a heteroaryl group having 5 to 40 nuclear atoms containing 1 to 3 N. The method of claim 1,
The first host is an organic electroluminescent device, characterized in that represented by the formula (1a) or (1b).
[Formula 1a]

[Formula 1b]

In Formula 1a or Formula 1b,
R ₁ , R ₃ to R ₄ , R ₆ to R ₇ and a, c to d, f to g are the same as defined in claim 1. The method of claim 2,
R ₁ or R ₃ are the same as or different from each other, and each independently a C ₆ -C ₆₀ aryl group,
R ₄ , R ₆ to R ₇ are the same as or different from each other, and are each independently hydrogen or an aryl group of C ₆ to C ₆₀ . delete anode; cathode; And one or more organic material layers interposed between the anode and the cathode,
At least one of the one or more organic material layers is a light emitting layer including a first host and a second host,
The first host is a compound represented by the following formula (1b),
The second host is an organic electroluminescent device, characterized in that the compound represented by the formula (2b).
[Formula 1b]

In Chemical Formula 1b,
R ₁ , R ₃ to R ₄ , R ₇ are the same as or different from each other, and are each independently hydrogen or an aryl group of C ₆ to C ₆₀ ,
a and c are each independently an integer of 0 to 5,
d and g are each independently an integer from 0 to 4;
[Formula 2b]

In Chemical Formula 2b,
L ₁ and L ₂ are the same as or different from each other, and each independently a single bond, an arylene group having ₆ to ₁₈ carbon atoms, and a heteroarylene group having 5 to 18 nuclear atoms including 1 to 3 N atoms; At least one selected from, except that L ₁ or L _{2 to} which a substituent of the formula (3) is linked includes a carbazolylene group,
One of Ar ₁ and Ar ₂ is a substituent represented by the following formula (3),
Ar ₁ or Ar ₂ not having a substituent of Formula 3 is selected from hydrogen, and an aryl group of C ₆ ~ C ₄₀ ,
[Formula 3]

In Chemical Formula 3,
L is a single bond or an arylene group of C ₆ to C ₁₈ ,
Z ₁ to Z ₅ are the same as or different from each other, and each independently N or C (R ₁₁ ), wherein Z ₁ to Z ₅ include 2 to 3 N,
When there are a plurality of C (R ₁₁ ), a plurality of R ₁₁ are each independently hydrogen or an alkyl group of C ₁ to C ₄₀ ,
When an arylene group, a heteroarylene group, an aryl group, and an alkyl group of R ₁₁ in L ₁ to L ₂ , L and Ar ₁ to Ar ₂ are substituted, each independently deuterium, an aryl group of C ₆ to C ₄₀ , and It means to be substituted with one or more selected from the group consisting of heteroaryl group having 5 to 40 nuclear atoms containing 1 to 3 N. The method according to claim 1 or 5,
The mixing ratio of the first host and the second host is an organic electroluminescent device, characterized in that 1 ~ 99: 99 ~ 1 weight ratio. The method according to claim 1 or 5,
The organic material layer including the first host and the second host is a phosphorescent light emitting layer. The method according to claim 1 or 5,
The light emitting layer is an organic electroluminescent device, characterized in that it comprises a metal complex compound dopant.