WO2019190271A1

WO2019190271A1 - Novel compound and organic light-emitting device comprising same

Info

Publication number: WO2019190271A1
Application number: PCT/KR2019/003724
Authority: WO
Inventors: 함호완; 안현철; 강경민; 김동준; 한정우; 임동환; 이형진; 안자은; 임대철; 김승호; 권동열
Original assignee: 주식회사 동진쎄미켐
Priority date: 2018-03-30
Filing date: 2019-03-29
Publication date: 2019-10-03
Also published as: CN111936480B; KR102585155B1; CN111936480A; KR20190114635A; TW201942329A

Abstract

The present application relates to a novel compound and an organic light-emitting device comprising same, the novel compound according to one embodiment of the present invention being applied to an organic light-emitting device to allow same to be highly effective, and have extended lifespan, low driving voltage and operational stability.

Description

[Name ^ 11 book]

[Name of invention]

Novel compounds and organic light emitting device comprising the same {NOVEL COMPOUND AND ORGANIC ELECTROLUMINES 姑 NT DIVICE INCLUDING THE SAME}

Technical Field

The present application relates to a novel compound and an organic light emitting device comprising the same. Background Art

The material used as the organic material layer in the organic light emitting diode can be largely classified into light emitting materials, hole injection materials, hole transport materials, electron transport materials, electron injection materials and the like depending on the function. The light emitting material may be classified into a polymer and a low molecule according to a molecular weight, and may be classified into a fluorescent material derived from a singlet excited state of electrons and a phosphorescent material derived from a triplet excited state of electrons according to a light emitting mechanism. The light emitting materials may be classified into blue, green, and red light emitting materials, and yellow and orange light emitting materials required to realize better natural colors, depending on the light emitting colors. In addition, in order to increase luminous efficiency through increase in color purity and energy transfer, a host / dopant system may be used as a light emitting material. The principle is that when a small amount of dopant having a smaller energy band gap than the host constituting the light emitting layer and excellent luminous efficiency is mixed in the light emitting layer, excitons generated from the host are transported to the dopant to produce high efficiency light. At this time, since the wavelength of the host is shifted to the wavelength of the dopant, light having a desired wavelength can be obtained according to the type of dopant and the host used.

To date, various compounds are known as materials used in such organic light emitting devices. 2019/190271

2, the organic light emitting device using a known material is constantly being developed due to the high driving voltage, low efficiency and short life. Therefore, efforts have been made to develop organic light emitting devices having low voltage driving, high brightness and long life using materials having excellent characteristics.

Detailed Description of the Invention

[Technical problem]

The present application provides a novel organic compound, and an organic light emitting device comprising the same. However, the problem to be solved herein is not limited to the problem described above, other problems that are not described will be clearly understood by those skilled in the art from the following description.

Technical Solution

A first aspect of the present application provides a compound represented by Formula 1 below:

[Formula 1]

And are each independently 0 or 2019/190271 1 »（： 1 ^ 1 {2019/003724

Substituted or unsubstituted 06-050 ^ aryl group containing a substituted or unsubstituted aryl group, or a substituted or unsubstituted aryl group containing a 06-013 ¾ substituted or unsubstituted aryl group 0 ₆ -050 £] heteroaryl group of the ring,

The seedlings, ^ to 1-6 are each independently hydrogen, deuterium, halogen, nitro group, nitrile group, substituted or unsubstituted 30 alkyl group, substituted or unsubstituted 0 (urine alkenyl group, substituted or unsubstituted （1: 1 Alkoxy group of 30, substituted or unsubstituted 0 (sulfide group, substituted or unsubstituted 06-030 £ 1 aryl group, or substituted or unsubstituted 05-030 ^ heteroaryl group, and adjacent I? May or may not form

To n3 are each independently a direct bond, a substituted or unsubstituted 06 ~ 030 £] arylene, or a substituted or unsubstituted 05 30 heteroarylene,

1 and (1 are each independently 0 or an integer of 1 to 4,

II, 0, and 13 are each independently 0 or an integer of 1 to 3, wherein 1, 111, II, 0,?, Or (where 1 is 2 or more, 1 to ¾ may be the same or different from each other.

The second aspect of the present application provides an organic light emitting device comprising an organic material layer containing a compound according to the present application between the first electrode and the second electrode.

【Effects of the Invention】

The compound according to one embodiment of the present invention is formed by linking two linearly linked tricyclic condensed ring groups (dibenzofuran, dibenzothiophene or fluorene with dibenzofuran or dibenzothiophene) to nitrogen of arylamine. It is possible to form a deep 볘 ·) level suitable for the transport layer or the light emitting auxiliary layer and to form a high 11 ·), thereby realizing a high efficiency organic light emitting device. 2019/190271 1 »（： 1 ^ 1 {2019/003724

In addition, the compound according to an embodiment of the present invention is introduced by introducing two tricyclic condensed ring group of linear linkage on one side of the arylamine, and dibenzofuran or dibenzothiophene on the other side

It can have an excellent arrangement of molecules when forming a thin film. Accordingly, it is possible to realize a long life organic light emitting device by implementing a low voltage and suppressing the roll-off phenomenon.

In addition, the compound according to an embodiment of the present invention maintains a high 1 _> 1 0 by introducing dibenzofuran or dibenzothiophene having excellent electron resistance to the other side of the arylamine, and at the same time the Durability can be further improved. Accordingly, high efficiency and long lifespan of the organic light emitting device can be realized.

In addition, the compound according to an embodiment of the present invention can maintain a high by introducing a substituent having a high triplet energy of 6 to 13 carbon atoms forming a ring on one side of the arylamine. Accordingly, a high efficiency organic light emitting device can be realized by maximizing the exciton confinement effect in the light emitting battery.

In addition, the compound according to an embodiment of the present invention includes three or more tricyclic condensed ring structure to form a high ₈ to prevent thin film recrystallization, thereby securing the driving stability of the organic light emitting device can do.

【Brief Description of Drawings】

1 shows a schematic view of an organic light emitting device according to an embodiment of the present disclosure.

[Best form for implementation of the invention]

Hereinafter, with reference to the accompanying drawings will be described in detail the embodiments and embodiments of the present application to be easily carried out by those skilled in the art to which the present invention pertains. 2019/190271 1 »（： 1 ^ 1 {2019/003724

5.

As those skilled in the art would realize, the described embodiments may be modified in various different ways, all without departing from the spirit or scope of the present invention. In the drawings, parts irrelevant to the description are omitted in order to clearly describe the present invention, and like reference numerals refer to like parts throughout the specification.

Throughout this specification, when a member is located "on" another member, this includes not only when a member is in contact with another member but also when another member exists between two members.

Throughout this specification, when a part is said to "include" a certain component, it means that it can further include other components, without excluding the other components unless otherwise stated. As used throughout this specification, the terms "about", "substantially", and the like, are used at, or in close proximity to, numerical values when manufacturing and material tolerances inherent in the stated meanings are set forth, and the understandings herein are to be understood. Accurate or absolute figures are used to assist in preventing unscrupulous infringers from using the disclosures unfairly. As used throughout this specification, the term “step” or “step” does not mean “step for”.

Throughout this specification, the term "combination of these" included in the expression of the makushi form means one or more mixtures or combinations selected from the group consisting of the components described in the expression of the makushi form, It means to include one or more selected from the group consisting of components. 2019/190271 1 »（： 1 ^ 1 {2019/003724

6 Throughout this specification, and / or "," 1 or 8, or show and yo "means.

Throughout this specification, the term "aryl" refers to an aromatic hydrocarbon ring group of 05-30, for example phenyl, benzyl, naphthyl, biphenyl, terphenyl, fluorene, phenanthrenyl, triphenylenyl, perylene Meaning that it contains an aromatic ring such as nil, chrysenyl, fluoranthenyl, benzofluorenyl, benzotriphenylenyl, benzo chrysenyl, anthracenyl, stilbenyl, pyrenyl, and the like. As an aromatic ring of 03-30 containing one hetero element, for example, pyrrolyl, pyrazinyl, pyridinyl, indolyl, isoindoleyl, furyl, benzofuranyl, isobenzofuranyl, dibenzofuranyl , Benzothiophenyl, dibenzothiophenyl, quinolyl group, isoquinolyl, quinoxalinyl, carbazolyl, phenanthridinyl, acridinyl, phenanthrolinyl, thienyl, and pyridine ring, pyrazine ring, pyrimi Ring, pyridazine ring, triazine ring, indole ring, quinoline ring, acridine ring, pyrrolidine ring, dioxane ring, piperidine ring, morpholine ring, piperazine ring, carbazole ring, furan ring, Thiophene ring, oxazole ring, oxadiazole ring, benzoxazole ring, thiazole ring, thiadiazole ring, benzothiazole ring, triazole ring, imidazole ring, benzoimidazole ring, pyran ring, dibenzo It may mean containing a heterocyclic group formed from a furan ring, a dibenzothiophene ring.

Throughout this specification, the term "substituted or unsubstituted" refers to deuterium, halogen, amino group, nitrile group, nitro group or （: 1 20 alkyl group, 02-020 ^ alkenyl group, （: 1 20 alkoxy group, 03 ¾） Or substituted with one or more groups selected from the group consisting of a cycloalkyl group of 03 02, a heterocycloalkyl group of 03 02◦, a 06-030 £ 1 aryl group and a heteroaryl group of 03-030 2019/190271 1 »（： 1 ^ 1 {2019/003724

7 can mean not. In addition, the same symbol throughout the present specification may have the same meaning unless specifically noted.

Throughout this specification, the term `` fluorene '' refers to a substituted or unsubstituted -2 () alkyl group, a substituted or unsubstituted 05-30 aryl group substituted with hydrogen bonded to carbon 9, or a substituted or unsubstituted 03- And substituted with 30 heteroaryl groups.

The first aspect of the present application provides a compound represented by the following formula (1).

[Formula 1]

.

X and are each independently 0 or

Is a ring forming carbon number of 06 ~ 013 ¾ substituted or unsubstituted, a substituted or unsubstituted, where the value ring or unsubstituted 06 to 50 aryl group, or a ring forming carbon atoms containing an aryl group include a 06 ~ 013¾ substituted or unsubstituted aryl ₅₀ Is a heteroaryl group,

The seedlings, 요 1 to ¾ each independently represent hydrogen, deuterium, halogen, nitro group, nitrile group, substituted or unsubstituted （: 1-30 alkyl group, substituted or unsubstituted 02-030 £ 1 alkenyl group, substituted or unsubstituted （： 1 30 alkoxy group, substituted or unsubstituted （: 1 30 sulfide group, The heteroaryl groups of the ring or unsubstituted C6 ~ C ₃₀ aryl group, or a substituted or unsubstituted C5 ~ C30, and may not form a ring, or formed of adjacent R and R 'eunseo,

L ₁ to L ₃ are each independently a direct bond, a substituted or unsubstituted C ₆ to C ₃₀ arylene, or a substituted or unsubstituted C 5 to C 3 _G heteroarylene,

1 and d are each independently 0 or an integer of 1 to 4,

m, n, o, and p are each independently 0 or an integer of 1 to 3, and when 1, m, n, o, p, or 2 or more, Ri to R ₆ may be the same or different from each other. The compound according to one embodiment of the present invention is a hole by connecting two linearly linked tricyclic condensed ring groups (dibenzofuran, dibenzothiophene or fluorene and dibenzofuran or dibenzothiophene) to nitrogen of arylamine. It is possible to form a deep HOMO level suitable for the transport layer or the light emitting auxiliary layer and to form a high LUM0, thereby realizing a high efficiency organic light emitting device.

Compounds according to one embodiment of the present invention may form a deep HOMO level may be more suitable for luminescent supplements.

In addition, the compound according to an embodiment of the present invention is a fast hole mobility (Hole Mobil) by introducing two tricyclic condensed ring of linear linkage on one side of the arylamine, and dibenzofuran or dibenzothiophene on the other side It can have the excellent arrangement of molecules when forming a thin film. Accordingly, it is possible to realize a long life organic light emitting device by implementing a low voltage and suppressing the roll-off phenomenon.

In addition, the compound according to an embodiment of the present invention is introduced to the other side of the arylamine by introducing dibenzofuran or dibenzothiophene excellent in electron resistance to maintain a high LUM0 2019/190271 1 »（： 1 ^ 1 {2019/003724

9 At the same time, it is possible to further improve the durability of the compound when blocking electrons from the light emitting layer. Accordingly, high efficiency and long lifespan of the organic light emitting device can be realized.

In addition, the compound according to an embodiment of the present invention can maintain a high II by introducing a substituent having a high triplet energy of 6 to 13 carbon atoms forming a ring on one side of the arylamine. Accordingly, a high efficiency organic light emitting device can be realized by maximizing the exciton confinement effect in the light emitting layer.

In addition, the compound according to an embodiment of the present invention includes three or more tricyclic condensed ring structure to form a high ₈ to prevent the thin film recrystallization, thereby securing the driving stability of the organic light emitting device can do.

According to an embodiment of the present invention, the chemical formula

Carbon number

Beach also comprising substituted polycyclic aryl substituted or unsubstituted, 06-050 ^ aryl group, or a ring forming carbon number of 0 ~ ₆ 013¾1 substituted or unsubstituted aryl group containing a group may be an unsubstituted heteroaryl of 5 _(). ! May include an aryl group having 06-013 carbon atoms to form a ring, the aryl group may be substituted or unsubstituted. Including such an aryl group, the total carbon number of 1 may be from 06 to 050¾.

In one embodiment of the present invention, the compound may be represented by the following formula (2) or (3). 2019/190271 1 »(： 1 ^ 1 {2019/003724

10

[Formula 2]

In Chemical Formulas 2 and 3,

X, \, 1, 1, seedling, seedling, seedlings 1 to 6, 1 _> 1, 1 _> 2 1 _^ 3, 1, 111, II 0, 13, and are the same as defined in the above formula (1).

The compound represented by the formula (2) is a case where 1 _> 1 in the formula (1) is a direct bond, two tricyclic condensed ring groups of one side of the arylamine (tricyclic condensed ring including X and tricyclic condensed ring including) Is directly bonded without a linking group. In such a case, by minimizing the connector, it is possible to form a deep control layer in the high holding power and the light emitting auxiliary layer, which can be effective in improving the light emitting efficiency.

The compound represented by Chemical Formula 3 is a structure in which 1 _{> 2} in Chemical Formula 1 is a direct bond, and the tricyclic condensed ring including is directly bonded to nitrogen. 2019/190271

11 In this case, by minimizing the linking group, it can be advantageous for low voltage driving because it has high II retention and fast hole mobility through direct bonding with nitrogen of arylamine.

In one embodiment of the present invention, the compound may be represented by the following formula (4) or formula (5).

[Formula 4]

, 0, I) and da are as defined in the formula (1).

The compound represented by the formula (4) or (5) is a structure in which ₂ or 4 of the tricyclic condensed ring including in the formula (1) as a bonding position with 1 _{^ 2} . In this case, it is possible to maintain high Na110 at the same time as forming deep ^ 10¾10, which can improve luminous efficiency and is effective in blocking electrons flowing into the hole transport layer from the light emitting layer. 2019/190271 1 »（： 1 ^ 1 {2019/003724

Can be 12.

In addition, the linking position number of the tricyclic condensed ring compound may be as follows.

In one embodiment of the present invention, the compound may be represented by the following formula (6) or formula (7).

[Formula 6]

In Chemical Formulas 6 and 7,

X, 1, 1, yo, I? ^' , ¾ to 1½, 1 _^ 3,1, III, II 0, I) and the same as defined in Formula 1 above. 2019/190271 1 »（： 1 ^ 1 {2019/003724

13 The compound represented by the formula (6) or (7) is in the case where and in the formula (1) is a direct bond, the tricyclic condensed ring containing ¥ is directly bonded to nitrogen, the second or three of the tricyclic condensed ring containing It is a structure having No. 4 as a coupling position. In this case, it is possible to maintain a high 1 ¾ 10 at the same time as the fast hole mobility can be effective in blocking the electrons flowing into the hole transport layer from the low voltage drive and the light emitting layer. According to an embodiment of the present invention, in Formulas 1 to 7 may be independently hydrogen, deuterium, or a phenyl group. Specifically ^

It may be hydrogen.

In addition, according to an embodiment of the present invention, in Formula 1 to Formula 7, X may be 0 or.

In addition, according to an embodiment of the present invention, in Formulas 1 to 7, wherein X, V and are all 0.

Further, according to one embodiment of the present invention, in Formulas 1 to 7, the X and may be all, and the tricyclic condensed ring containing the nitrogen side of the arylamine 2 or 4 in the bonding position Can be connected to.

In addition, according to an embodiment of the present invention, in Formulas 1 to 7, the 11 to 1 _{^ 3} may be each independently selected from the group consisting of a direct bond, phenylene, biphenylene and combinations thereof. have.

In addition, according to an embodiment of the present invention, in Formulas 1 to 7, at least one of the above to 1 _{^ 3} is substituted or unsubstituted 06 ~ 030 £ 1 arylene, or substituted or unsubstituted 05 30 hetero Arylene, specifically phenylene, biphenylene 2019/190271 1 »（： 1 ^ 1 {2019/003724

14 and combinations thereof.

In addition, according to an embodiment of the present invention, in the above Chemical Formulas 1 to 7, the show is phenyl, biphenyl, terphenyl, fluorene, dialkyl fluorene, dibenzofuran, dibenzothiophene and combinations thereof It may be selected from the group consisting of.

According to an embodiment of the present invention, the compound represented by Formula 1 may be any one of the following compounds, and may not be limited thereto:





2019/190271 1 »（： 1 ^ 1 {2019/003724

65

The second aspect of the present application provides an organic light emitting device comprising the compound represented by Formula 1. The organic light emitting device may include one or more organic layer containing a compound according to the present application between the first electrode and the second electrode.

In one embodiment of the present invention, the organic material layer may be a hole injection layer, a hole transport layer and a light emitting auxiliary layer, but may not be limited thereto. In addition, the compounds of the present invention may be used alone or in combination with known compounds when forming the organic layer. In one embodiment of the present invention, the organic light emitting device contains a hole transport material 2019/190271 1 »（： 1 ^ 1 {2019/003724

66 may include an organic material layer and an organic material layer containing the compound represented by Chemical Formula 1, but may not be limited thereto.

The organic light emitting device includes an anode (in a hole injection layer between c110 (16) and a cathode (0 ^ 110 (16)), a hole transport layer 11), a light emitting layer 犯), an electron transport layer example), an electron injection layer (nee, etc.). It may contain at least one organic layer of.

For example, the organic light emitting device can be manufactured as shown in FIG. The organic light emitting device is formed from the bottom of the anode (hole injection electrode 1000) / hole injection layer 200 / hole transport layer 300 / light emitting layer 400 / electron transport layer 500 / electron injection layer 600 / cathode (electron) The injection electrode 2000 may be stacked in this order.

In FIG. 1, the substrate 100 may be a substrate used in an organic light emitting device. In particular, the substrate 100 may be a transparent glass substrate or a flexible plastic substrate having excellent mechanical strength, thermal stability, transparency, surface smoothness, ease of handling, and water resistance. Can be. The hole injection electrode 1000 is used as an anode for hole injection of the organic light emitting device. Indium tin oxide (比 함 ， indum zinc oxide (1å0) ， graphene

It may be formed of the same transparent material.

The hole injection layer material may be deposited on the anode electrode by vacuum deposition, spin coating, casting, or solid (1 11 11 -ratio 0 (night 0), etc.) to form the hole injection layer 200. When the hole injection layer is formed by the vacuum deposition method, the deposition conditions thereof vary depending on the compound used as the material of the hole injection layer 200, the structure and thermal properties of the desired hole injection layer, and the like. X ： Deposition temperature of 10_ ⁸ to 10 ^'3 2019/190271 1 »（： 1 ^ 1 {2019/003724

67) _! The vacuum degree of!, Deposition rate of 0.01 to 100 yaw /%, and increase thickness range of 10 to 5 / L can be appropriately selected.

Next, the hole transport layer material on the hole injection layer 200 is vacuum deposited, spin coated, cast,

The hole transport layer 300 may be formed by deposition by the same method. In the case of forming the hole transport layer by the vacuum deposition method, the deposition conditions vary depending on the compound used, but in general, it is preferable to select it in almost the same conditions as the formation of the hole injection layer.

The hole transport layer 300 may use a compound according to the present invention. As described above, the compound according to the present invention may be used alone or a known compound may be used together. In addition, according to one embodiment of the present invention, the hole transport layer 300 may be one or more layers, and may include a hole transport layer formed only of a known material. In addition, according to the exemplary embodiment of the present invention, an auxiliary light emitting layer may be formed on the hole transport layer 300.

The vapor deposition method, spin coating method, cast method of the light emitting layer material on the hole transport layer 300 or the light emitting auxiliary

It can be deposited by the same method to form the luminescence 400. In the case of forming the light emitting layer by the vacuum deposition method, the deposition conditions vary depending on the compound used, but in general, it is preferable to select the same condition range as the formation of the hole injection layer. In addition, the light emitting layer material may use a known compound as a host or dopant.

In addition, when used with a phosphorescent dopant in the light emitting layer, an additional hole suppression material is added to prevent the triplet exciter or hole from diffusing into the electron transport layer. 2019/190271 1 »（： 1 ^ 1 {2019/003724

68 can be laminated by vacuum deposition or spin coating. The hole suppressing material that can be used at this time is not particularly limited, but any one of the well-known ones used as the hole suppressing material can be selected and used. For example, an oxadiazole derivative, a triazole derivative, a phenanthroline derivative, or the hole-inhibiting material described in Japanese Patent Laid-Open No. 11-329734 (; \ 1), and the like, are typically represented by 8 ^ (1 ( Bis (8-hydroxy-2-methylquinol linolato) -aluminum biphenoxide), phenanthroline ({)] 161 111: 111'01 63) Compounds (e.g. Nassop 敗! ³ ), Etc. can be used.

The electron transport layer 500 is formed on the light emitting layer 400 formed as described above. The electron transport layer may be formed by a vacuum deposition method, a spin coating method, a casting method, or the like. In addition, although the deposition conditions of the electron transport layer are different depending on the compound used, it is generally preferable to select within the same condition range as the formation of the hole injection layer. Subsequently, an electron injection layer 600 may be formed by depositing an electron injection layer material on the electron transport layer 500, wherein the electron transport layer may be formed by vacuum deposition, spin coating, or casting a conventional electron injection layer material. It can form by a method, such as a method.

The hole injection layer (and) 0), the hole transport layer 300, the light emitting layer 400, the total embroidery 500 of the organic light emitting device may use the compound according to the present invention, or may use the following materials, or The compounds according to the invention and known materials can be used together. 2019/190271 1 »（： 1 ^ 1 {2019/003724

69

The cathode 2000 for electron injection is formed on the electron injection insect 600 by a vacuum deposition method or a sputtering method. Various metals may be used as the cathode. Specific examples include aluminum, gold, and silver.

The organic light emitting device of the present invention is not only an organic light emitting device having an anode, a hole injection layer, a hole transporting layer, a light emitting layer, an electron transporting layer, an electron injection layer, a cathode structure, but also a structure of organic light emitting devices having various structures. It is also possible to form one or two intermediate layers.

The thickness of each organic material layer formed according to the present invention as described above can be adjusted according to the required degree, specifically 1 to 1,000, more specifically 2019/190271 1 »（： 1 ^ 1 {2019/003724

70

5 to 200 there.

In addition, the present invention has an advantage that the organic material layer including the compound represented by Formula 1 has a uniform surface and excellent shape stability because the thickness of the organic material layer can be adjusted in molecular units.

For the organic light emitting compound according to the present aspect may be applied to all of the contents described for the first aspect of the present application, but may not be limited thereto. Hereinafter, the embodiments of the present application will be described in more detail, and the scope of the present application is not limited by the present embodiment.

EXAMPLE

Synthesis of Compound Represented by Formula 1

The compound represented by Formula 1 may be synthesized through the following reaction, but is not limited thereto.

Heavy-weight shout

Intermediate ¾ for the synthesis of the desired compound can be synthesized by the following reaction It is not limited thereto.

Synthesis of Heavy Weight

Intermediate I was synthesized in the following manner.

61120 [1], (1) £ 11 to 11_4-711) 01,011 ac ^ (i 20.0 客, 2,8-1) 1 ^* 01110 501 比 0 [1 ₎ , ₍ 1] £ 11 to 11 33.8 was dissolved in 1,4- (510X311 800 1 in 1, 1 (2 (: 03 (21 \ 1)) 140 Mi1 and? ₍ 1 1¾ ₃ ) 43.3 _§ , and stirred at reflux. 11 (： The reaction was terminated after addition of water and the reaction was terminated The organic layer was extracted with, filtered under reduced pressure and recrystallized to give intermediate ¾126.1 £ (67% yield).

Synthesis of Heavy Weight ¾2 and 3

By varying the starting material as shown in Table 1 below, in the same manner as in 1 2019/190271 1 »(： 1/10 公 019/003724

72 to synthesized.

TABLE 1

Chinese Synthesis of Object 11 \ 14

Intermediate 1¾14 was synthesized in the following manner.

? ₍ 1 fish 1¾3) 43.3 yo was added and stirred under reflux. The reaction was confirmed with 11 (：, water was added, and the reaction was terminated. The organic layer was extracted with sodium sulfate, filtered under reduced pressure, and recrystallized to obtain an intermediate «4-1 for 25.3 (yield 65%).

A round bottom flask was used for 11 \ 14-1 25.0, 3 (1 (： 0131; 0) (1 01'011 20 fusion 1,4- 2019/190271

73

It was dissolved in ^ 0X311 450011 and stirred under reflux with 1 (0 ^ 17.0) and (1 ((¾ 뱐 £)) 20.2 for 20.2. The reaction was confirmed with 11 (：), and the reaction was terminated after adding water. The organic layer was extracted with, filtered under reduced pressure and recrystallized to obtain the intermediate 1¾14-2 for 22.3 (yield 80%).

Dissolve 1¾14-2 22.0, 1-1) 1, 01110-4 -0 0 (10 匕 61126116 14.9) into 1, 4- (110X311 550) in a round bottom flask and add ¥ 3 （2 則 70 and 11 （? 1¾3） 4 1. After adding ¾, the mixture was stirred under reflux. The reaction was confirmed with 11 (：), and the reaction was terminated after adding water. The organic layer was extracted with filtrate, filtered under reduced pressure and recrystallized to obtain an intermediate «4 14.0 g (yield 60%).

Synthesis of Heavy Weight ¾5 and 13

By varying the starting material as shown in Table 2, the following 5 to 1¾113 was synthesized in the same manner as 1¾14.

TABLE 2

Synthesis of Intermediates

Intermediate 0 was synthesized in the following manner.

0, [1,1'-!) 1161171] -4- 抑 116 7.8 fusion, 1: -0 10.9 yo, (((¾3) ₃ 2.8g, (1: -¾) 3? 3.½1 The reaction mixture was dissolved in toluene 570 and stirred under reflux. It was done. The organic layer was extracted with water, filtered under reduced pressure and recrystallized.

(Yield 68%) was obtained.

Synthesis of heavy weight （犯 2 to 陳 5

By varying the starting material as shown in Table 3 below, 0 to 2 to 0 to 5 were synthesized in the same manner as above.

TABLE 3

Compound Synthesis

The target compounds 1 to 15 were synthesized using the intermediates 1111 to «13 and 0 to 0 to 5. 2019/190271 1 »(1 ^ 1 {2019/003724

76 Synthesis of Compound 1

For ¾13.0 a round bottom ^{flask, 01) 12.¾八-8110犯1.1} ,戶[12 (此greater) for _three 0.3, (a ¾) was dissolved in toluene 100 ₃ 0.3 was stirred under reflux.

The reaction was confirmed and the reaction was terminated after adding water. The organic layer was extracted with, filtered under reduced pressure, column purified and recrystallized to give compound 13.½ (yield 67%).

Miyoshi: 667.21 (100.0%), 668.22 (52.4%), 669.22 (14.2%), 670.22 (2.6%) Synthesis of Compound 2

Compound 2 was synthesized in the same manner as Compound 1 using ¾2 and 02 instead of 1¾11 and 0. (63% yield)

01 八: 699.17 (100.0%), 700.17 (53.9%), 701.18 (13.4%), 701.16 (9.0%), 702.17 (4.8%), 702.18 (2.6%), 703.17 (1.3%), 701.17 (1.2%) 2019/190271 1 »(： 1 ^ 1 {2019/003724

77 Synthesis of Compound 3

Compound 3 was synthesized in the same manner as Compound 1 using 1¾11 and 0 instead of «3 and 0-2. (Yield 60%)

US: 715.15 (100.0%), 716.15 (54.7%), 717.15 (14.6%), 717.14 (13.6%), 718.15 (7.5%), 718.16 (2.2%), 719.15 (1.8%)

Synthesis of Compound 4

Compound 4 was synthesized in the same manner as Compound 1 using 0-3 instead. (Yield 65%)

111/2: 667.21 (100.0%), 668.22 (52.4%), 669.22 (14.2%), 670.22 (2.6%) Synthesis of Compound 5

Compound 5 was prepared in the same manner as Compound 1 using ml and 0 instead of »4 and 4. 2019/190271 1 »(： 1 ^ 1 {2019/003724

78 synthesized. (Yield 71%)

819.28 (100.0%), 820.28 (65.4%), 821.28 (21.6%), 822.29 (4.4%) Synthesis of Compound 6

Compound 6 was synthesized in the same manner as in compound 1. (Yield 67%)

m / z. 819.28 (100.0%), 820.28 (65.4%), 821.28 (21.6%), 822.29 (4.4%) Synthesis of Compound 7

Compound 7 was synthesized in the same manner as Compound 1 using IM5 and 0P4 instead of IM1 and 0P1. (Yield 65%)

m / z ： 819.28 (100.0%), 820.28 (65.4%), 821.28 (21.6%), 822.29 (4.4%) 2019/190271 1 »（： 1 ^ 1 {2019/003724

79 Synthesis of Compound 8

Compound 8 was synthesized in the same manner as Compound 1 using 1¾16 and 0¾ instead of «1 and 0 ^. (Yield 67%)

111/2: 819.28 (100.0%), 820.28 (65.4%), 821.28 (21.6%), 822.29 (4.4%) Synthesis of Compound 9

Compound 9 was synthesized in the same manner as Compound 1 using II ′ and 0 and 7 and 4 instead. (63% yield)

Mi8: 819.28 (100.0%), 820.28 (65.4%), 821.28 (21.6%), 822.29 (4.4%) Synthesis of Compound 10

Compound 10 was synthesized in the same manner as in compound 1, using 1¾ 18 and 0 mu 4 instead of 1¾ 11 and 01 ^ 1. (66% yield) 2019/190271 1 »(1 ^ 1 {2019/003724

80

111 ^: 835.25 (100.0%), 836.26 (65.4%), 837.26 (22.0%), 838.26 (4.9%),

837.25 (4.8%), 838.25 (3.0%), 836.25 (1.2%), 839.26 (1.0%)

Synthesis of Compound 11

Compound 11 was synthesized in the same manner as Compound 1, using 1 9 and 0-4 instead of 1¾11 and 0. (Yield 65%)

Mio: 835.25 (100.0%), 836.26 (65.4%), 837.26 (22.0%), 838.26 (4.9%),

837.25 (4.8%), 838.25 (3.0%), 836.25 (1.2%), 839.26 (1.0%)

Synthesis of Compound 12

Compound 12 was synthesized in the same manner as Compound 1 using 1¾110 and 0-4 instead of ¾1 and 0. (Yield 60%)

835.25 (100.0%), 836.26 (65.4%), 837.26 (22.0%), 838.26 (4.9%),

837.25 (4.8%), 838.25 (3.0%), 836.25 (1.2%), 839.26 (1.0%) 2019/190271 1 »(： 1 ^ 1 {2019/003724

81 Synthesis of Compound 13

Compound 13 was synthesized in the same manner as Compound 1 using ¾ 11 and 0-4 instead of «1 and 0. (Yield 62%)

Mio: 851.23 (100.0%), 852.24 (65.4%), 853.24 (21.2%), 853.23 (10.3%), 854.23 (6.0%), 854.24 (5.0%), 855.23 (2.0%), 852.23 (2.0%)

Synthesis of Compound 14

Compound 14 was synthesized in the same manner as Compound 1 using ¾ 1 and 4 instead of ¾ 12 and 4. (Yield 60%)

111/2: 835.25 (100.0%), 836.26 (65.4%), 837.26 (22.0%), 838.26 (4.9%), 837.25 (4.8%), 838.25 (3.0%), 836.25 (1.2%), 839.26 (1.0% ) Synthesis of Compound 15

Compound 15 was synthesized in the same manner as Compound 1 using IM1 and 0P4 instead of IM1 and 0P1. (Yield 65%)

m / z ： 845.33 (100.0%), 846.33 (68.6%), 847.34 (23.2%), 848.34 (5.4%)

Example 1

Indium tin oxide (IT0) 1500A thick thin glass substrate was washed with distilled water ultrasonic waves. After washing the distilled water, ultrasonic cleaning with a solvent such as isopropyl alcohol, acetone, methanol, etc., dried, transferred to a plasma cleaner, and then cleaned the substrate using oxygen plasma for 5 minutes, Using a thermal evaporator, a hole injection layer HI01 600 A, HATCN 50 A, a hole transport layer HT01 250 A and a light emitting auxiliary layer were formed into a compound 1 100 A and then the light emitting layer was doped with BH01: BD01 3% to form a 250 A It was. Next, after forming ET01: Liq (l: l) 300 A with an electron transport layer, LiF 10 A and aluminum (Al) 1000 A were formed, and the device was encapsulated in a glove box to produce an organic light emitting device. . Example 2 to Example 15 In the same manner as in Example 1, instead of compound 1, compounds 2 to 15 were manufactured to form an organic light emitting device.

Comparative Example 1 to Comparative Example 7

In the same manner as in Example 1, instead of compound 1, 1 1 to 1 7 was used to prepare a film-produced organic light emitting device.

Performance Evaluation of Organic Light Emitting Diode

When electrons and holes are injected by applying a voltage to the Keithley 2400 source measurement unit and light is emitted using a Konica Minolta spectroradiometer (CS-2000). By measuring the luminance, the performance of the organic light emitting diodes of Examples and Comparative Examples was evaluated by measuring the current density and luminance with respect to the applied voltage under atmospheric pressure conditions, and the results are shown in Table 4 below. 2019/190271 1 »（： 1 ^ 1 {2019/003724

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TABLE 4

As shown in Table 4, Examples 1 to 15 using the compound of the present invention as a hole transport layer can be confirmed that the efficiency and life is increased compared to Comparative Examples 1 to 7.

More specifically, compared with Comparative Example 1, Examples 1 to 15 have a substituent having two tricyclic condensed ring connected to one side of the arylamine can have a fast hole mobility 0 ratio 1, furthermore to low voltage driving It is advantageous. 0 2019/190271 1 »（： 1 ^ 1 {2019/003724

85 In addition, compared with Comparative Examples 2 and 3, Examples 1 to 15 have a substituent in which two tricyclic condensed rings are connected at one side of the arylamine, and further include a tricyclic condensed ring at the other side to form a thin film. Molecular alignment is excellent and hole mobility is improved, and roll-off phenomenon is suppressed to improve lifespan.

In addition, compared with Comparative Examples 4 and 5, Examples 1 to 15 showed that the nitrogen of the arylamine was combined with another dibenzofuran or dibenzothiophene in addition to the two tricyclic condensed rings to maintain a deep 11 (10 and B) can be formed to realize excellent efficiency and long life.

In addition, in comparison with Comparative Examples 6 and 7, Examples 1 to 15 have an aryl group having a carbon number of 13 or less aryl group having a triplet energy of 紅 1, so that it is possible to maximize the exciton confinement effect in the emission layer by maintaining high extinction. The organic light emitting diode may have an organic light emitting diode having a low driving voltage and having greatly improved efficiency and lifespan. The foregoing description of the application is intended for illustration, and it will be understood by those skilled in the art that the present invention may be easily modified in other specific forms without changing the technical spirit or essential features of the present application. Therefore, it should be understood that the embodiments described above are exemplary in all respects and not restrictive. For example, each component described as a single type may be implemented in a distributed manner, and similarly, components described as distributed may be implemented in a combined form.

The scope of the present application is defined by the appended claims rather than the detailed description above. 2019/190271 1 »（： 1 ^ 1 {2019/003724

All changes or modifications derived from the meaning and scope of the claims and their equivalents shall be construed as being included within the scope of this application.

[Explanation of code]

100 ： Board

200 ： Hole injection insect

300 ： hole transport layer

400 ： light emitting layer

500 ： electron transport layer

600 ： electron injection layer

1000 ： Anode

2000 ： cathode

Claims

2019/190271 1 »（： 1 ^ 1 {2019/003724

87

[Range of request]

[Claim 1]

A compound represented by Formula 1;

[Formula 1]

In Chemical Formula 1,

X is 0, 3 or 0,

V and å are each independently 0 or

A substituted or unsubstituted 06-050 ^ 1 aryl group containing a substituted or unsubstituted aryl group having a ring-forming carbon number of ~ ( ₁₃₎ , or a substituted or unsubstituted aryl group having a ring-shaped carbon number of 06-013 3/4 substituted or unsubstituted or Unsubstituted 06-050 ^ 1 heteroaryl group,

Independently hydrogen, deuterium, halogen, nitro group, nitrile group, substituted or unsubstituted LE 30 alkyl group, substituted or unsubstituted 02 30 alkenyl group, substituted or unsubstituted 3 ₀ alkoxy group, substituted or unsubstituted (: 1 30 sulfide group, substituted or unsubstituted 06 ^ 30 aryl group, or substituted or unsubstituted 05 ^ 30 heteroaryl group, adjacent yo and mo 'may or may not form a ring with each other,

匕 1 to 3 are each independently a direct bond, a substituted or unsubstituted 06 ~ 030 £ 1 arylene, 02019/190271 1 »(1 ^ 1 {2019/003724

88 or substituted or unsubstituted 05-030 £ 1 heteroarylene,

1 and (1 are each independently 0 or an integer of 1 to 4,

II, 0, and 13 are each independently 0 or an integer of 1 to 3, and when 1, II, 0, V, or 2 or more, ¾ to ¾ may be the same or different from each other.

[Claim 2]

In that claim,

The compound is a compound represented by the following formula (2) or (3);

[Formula 2]

In Chemical Formulas 2 and 3,

X,, 1, 1, seedlings, seedlings, seedlings 1 to 1¾, 1, 匕 2, 3, 1, 111, II, 0, {3 and others are as defined in the above formula (1). 2019/190271 1 »（： 1 ^ 1 {2019/003724

89

[Claim 3]

The method of claim 1,

The compound is a compound represented by the following formula (4) or (5);

[Formula 4]

0, I? And ₍ ｝ is the same as defined in the above formula.

[Claim 4]

The method of claim 1,

The compound is a compound represented by the following formula (6) or (7); 2019/190271 1 »（1 ^ 1 {2019/003724

90

[Formula 6]

II, 0, I) and c are the same as defined in the formula (1).

[Claim 5]

The method according to any one of claims 1 to 4,

Wherein ¾ to ¾ are each independently hydrogen, deuterium, or a phenyl group. [Claim 6]

The method according to any one of claims 1 to 4,

X is 0 or 3;

[Claim 7] 2019/190271 1 »（： 1 ^ 1 {2019/003724

91 The method according to any one of claims 1 to 4,

Wherein X, and å are all zeros.

[Claim 8]

The method according to any one of claims 1 to 4,

And each independently is a compound selected from the group consisting of direct bonds, phenylene, biphenylene, and combinations thereof.

[Claim 9]

The method according to any one of claims 1 to 4,

At least one of the above to 3 is substituted or unsubstituted 06 ~ 030 £] arylten, or substituted or unsubstituted 0 ₅ ~ 030 £ 1 heteroarylene.

[Claim 10]

The method according to any one of claims 1 to 4,

To the _1> 3 at least one of X is phenyl, biphenylene and a compound selected from the group true lure caught a combination thereof.

[Claim 11]

The method according to any one of claims 1 to 4,

1 is a compound selected from the group consisting of phenyl, biphenyl, terphenyl, fluorene, dialkylfluorene, dibenzofuran, dibenzothiophene, and combinations thereof.

[Claim 12]

The method of claim 1, 2019/190271 1 »（： 1/10 公 019/003724

92

The compound is any one of the following compounds.

105

2019/190271 1 »（： 1 ^ 1 {2019/003724

142

[Claim 13]

An organic light-emitting device comprising an organic layer containing a compound according to any one of claims 1 to 12 between a first electrode and a second electrode.

[Claim 14]

The method of claim 13,

The organic material layer is an organic light emitting device of at least one of a hole injection layer, a hole transport layer and a light emitting auxiliary layer.