KR20180080603A - organic light-emitting diode with High efficiency - Google Patents

Abstract

The present invention relates to an organic light-emitting diode with high efficiency, and more particularly, to an organic light-emitting diode including: a first electrode; a second electrode facing the first electrode; a hole injection layer or a hole transport layer interposed between the first electrode and the second electrode; and a light emitting layer, wherein the hole injection layer or the hole transport layer includes at least one amine compound represented by the following formula (A) or (B), and the light emitting layer includes at least one compound represented by one of the following formulas (D1) to (D5). Formula (A) and (B), and formula (D1) to (D5) are the same as described in the detailed description of the invention.

Description

[0001] The present invention relates to an organic light-emitting diode (OLED)

The present invention relates to an organic electroluminescent device having a high efficiency, and more specifically, to a device using a material having a specific structure as a hole injecting layer material or a hole transporting layer material in an organic light emitting device, To an organic light emitting device exhibiting high efficiency.

The organic light emitting diode (OLED) is a display using a self-luminous phenomenon. The organic light emitting diode (OLED) has a wide viewing angle and is thinner and lighter than a liquid crystal display and has a fast response speed. ) Applications for display or illumination are expected.

In general, organic light emission phenomenon refers to a phenomenon in which an organic material is used to convert electric energy into light energy. An organic light emitting device using an organic light emitting phenomenon generally has a structure including an anode, a cathode, and an organic material layer therebetween.

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

The material used as the organic material layer in the organic light emitting device may be classified into a light emitting material and a charge transporting material such as a hole injecting material, a hole transporting material, an electron transporting material, an electron injecting material, Or a hole blocking layer may be added.

As a conventional technique related to such a hole transporting layer, JP 10-1074193 A (Oct. 14, 2011) discloses an organic light emitting device using a compound having a core structure in which at least one benzene ring is condensed in a carbazole structure as a hole transporting layer compound A light-emitting layer having a HOMO energy level between the HOMO energy level of the hole transporting layer and the HOMO energy level of the light-emitting layer is provided between the hole transporting layer and the light-emitting layer, in Japanese Patent Laid-Open Publication No. 10-1455156 Emitting layer is formed on the substrate.

As an example of a conventional art relating to a dopant compound of a light emitting layer, an organic light emitting device using an arylamine-bonded indenofluorene derivative or the like is disclosed in Patent Document 10-2008-0015865 (2008.02.20) Patent Publication No. 10-2012-0047706 (20012.05.14) discloses that a dibenzofuran or dibenzothiophene is present together with a fluorene in a single molecule, or a structure in which benzofuran or dibenzothiophene is present together with a carbazole An organic light emitting device using a compound is disclosed.

However, although various methods for manufacturing organic light emitting devices have been attempted in the related art including the above-mentioned prior arts, there is a continuing need for development of an organic light emitting device having improved light emitting efficiency to be.

Patent Registration No. 10-1074193 (Published on October 14, 2011)

Patent Registration No. 10-1455156 (Publication date: Oct. 27, 2014)

Published Japanese Patent Application No. 10-2008-0015865 (Feb. 20, 2008)

Published Japanese Patent Application No. 10-2012-0047706 (2012.05.14)

Therefore, the technical problem to be solved by the present invention is to provide a novel organic light emitting device having a high efficiency characteristic by including a hole injection layer material having a specific structure or a hole transporting layer material having a specific structure, (OLED). < / RTI >

According to an aspect of the present invention, there is provided a plasma display panel comprising: a first electrode; A second electrode facing the first electrode; A hole transporting layer or a hole transporting layer interposed between the first electrode and the second electrode, and a light emitting layer, wherein the hole transporting layer or the hole transporting layer comprises a compound represented by the following formula (A) or (B) At least one amine compound to be displayed; Wherein the light emitting layer comprises at least one compound represented by any one of the following formulas (D1) to (D5).

(A)

[Chemical Formula B]

In the above formulas (A) and (B)

A1, A2, E and F are the same or different and independently of one another are a substituted or unsubstituted aromatic hydrocarbon ring having 6 to 50 carbon atoms or a substituted or unsubstituted aromatic heterocycle having 2 to 40 carbon atoms;

Two carbon atoms adjacent to each other in the aromatic ring of A1 and two carbon atoms adjacent to each other in the aromatic ring of A2 form a condensed ring by forming a 5-membered ring with carbon atoms connected to the substituents R1 and R2;

The linking groups L1 to L6 are the same or different from each other and each independently represents a single bond, a substituted or unsubstituted alkylene group having 1 to 60 carbon atoms, a substituted or unsubstituted alkenylene group having 2 to 60 carbon atoms, A substituted or unsubstituted C2-C60 alkynylene group, a substituted or unsubstituted C3-C60 cycloalkylene group, a substituted or unsubstituted C2-C60 heterocycloalkylene group, a substituted or unsubstituted C6-C60 aryl Or a substituted or unsubstituted heteroarylene group having 2 to 60 carbon atoms;

M is any one selected from NR ₃ , CR ₄ R ₅ , SiR ₆ R ₇ , GeR ₈ R ₉ , O, S, Se;

The substituents R 1 to R 9 and Ar 1 to Ar 4 are the same or different from each other and each independently represent hydrogen, deuterium, a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted aryl group having 6 to 50 carbon atoms, Or a substituted or unsubstituted C 2 -C 30 alkenyl group, a substituted or unsubstituted C 2 -C 20 alkynyl group, a substituted or unsubstituted C 3 -C 30 cycloalkyl group, a substituted or unsubstituted C 5 -C 30 cycloalkene A substituted or unsubstituted C2-C30 hetero aryl group, a substituted or unsubstituted C2-C30 heterocycloalkyl group, a substituted or unsubstituted C1-C30 alkoxy group, a substituted or unsubstituted C6- A substituted or unsubstituted C1-C30 alkylthio group, a substituted or unsubstituted C6-C30 arylthio group, a substituted or unsubstituted C1-C30 alkylthio group, a substituted or unsubstituted C6-C30 arylthio group, A substituted or unsubstituted arylamine group having 6 to 30 carbon atoms, a substituted or unsubstituted alkylsilyl group having 1 to 30 carbon atoms, a substituted or unsubstituted arylsilyl group having 6 to 30 carbon atoms , A substituted or unsubstituted alkylgermanium group having 1 to 30 carbon atoms, a substituted or unsubstituted arylgermanium group having 1 to 30 carbon atoms, a cyano group, a nitro group, and a halogen group,

The carbon atoms of the formed alicyclic or aromatic monocyclic or polycyclic ring may be one of N, O, P, Si, S, Ge , Se, and Te;

Each of p1 and p2, r1 and r2, s1 and s2 is an integer of 1 to 3, and when each of them is 2 or more, each of the linking groups L1 to L6 is the same or different from each other,

Ar1 and Ar2 may be linked to each other to form a ring, and Ar3 and Ar4 may be linked to each other to form a ring;

X and y are integers of 0 or 1, provided that x + y = 1,

In the formula (A), two carbon atoms adjacent to each other in the A2 ring are bonded to * in the formula (Q1) to form a condensed ring,

In the formula (B), two carbon atoms adjacent to each other in the A1 ring are bonded to * in the formula (Q2) to form a condensed ring, and two carbon atoms adjacent to each other in the A2 ring are bonded to * in the formula (Q1) .

≪ RTI ID =

In formula (D1), A ₁₁ to A ₁₄ are the same or different and each independently represent a substituted or unsubstituted aryl group having 6 to 24 carbon atoms or a substituted or unsubstituted heteroaryl group having 2 to 24 carbon atoms ,

R ₁₀ represents hydrogen, deuterium, a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 30 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 30 carbon atoms, A substituted or unsubstituted alkoxy group having 1 to 30 carbon atoms, a substituted or unsubstituted aryloxy group having 6 to 30 carbon atoms, a substituted or unsubstituted alkylthio group having 1 to 30 carbon atoms, A substituted or unsubstituted C1 to C30 alkylamine group, a substituted or unsubstituted C6 to C30 arylamine group, a substituted or unsubstituted C6 to C30 aryloxy group, A substituted or unsubstituted aryl group, a substituted or unsubstituted heteroaryl group having 2 to 50 carbon atoms having O, N or S as a hetero atom, a substituted or unsubstituted silicon group, a substituted or unsubstituted boron group, It is a silane group, a carbonyl group, a phosphonium group, an amino group, a nitrile group, a hydroxyl group, a nitro group, any of which is a halogen group, an amide group and selected from the group consisting of a polyester,

n1 is and each R ₁₀ is the same as or different from each other are an integer of 1 to 8, in which the n1 2 or more,

The carbon of the pyrene ring which is not substituted with R10 is bonded to hydrogen or deuterium.

[Chemical formula D2]

In the above formula (D2)

Z ₁ is any of a substituted or unsubstituted aromatic hydrocarbon ring having 6 to 30 carbon atoms, a substituted or unsubstituted aromatic heterocyclic ring having 2 to 20 carbon atoms having O, N or S as a hetero atom,

The substituents R ₁₁ to R ₁₆ are the same or different from each other and independently represent hydrogen, deuterium, a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted aryl group having 6 to 50 carbon atoms, A substituted or unsubstituted C2-C20 alkynyl group, a substituted or unsubstituted C2-C20 alkynyl group, a substituted or unsubstituted C3-C30 cycloalkyl group, a substituted or unsubstituted heteroatom, O, N, S A substituted or unsubstituted C1-C30 alkoxy group, a substituted or unsubstituted C6-C30 aryloxy group, a substituted or unsubstituted C1-C30 alkyl group having 1 to 30 carbon atoms, A substituted or unsubstituted aryloxy group having 6 to 30 carbon atoms, a substituted or unsubstituted alkylamine group having 1 to 30 carbon atoms, a substituted or unsubstituted aryloxy group having 6 to 30 carbon atoms A substituted or unsubstituted alkylsilyl group having 1 to 30 carbon atoms, a substituted or unsubstituted arylsilyl group having 6 to 30 carbon atoms, a cyano group, a nitro group, a hydroxyl group and a halogen group , Any one of the substituents R ₁₃ to R ₁₆ is a single bond to be bonded to the linking group L _{11 to} be connected to the formula Q ₃ ,

Structure Q3 Q3 is connected to the structural formula and the substituents R ₁₃ to 6-membered ring that is associated with R ₁₆ being connected to the Z1 ring are the same or different in each occurrence,

The substituents R ₁₁ and R ₁₂ may be connected to each other to form a ring,

The substituents R ₁₃ to R ₁₆ may be connected to adjacent substituents to form a substituted or aromatic monocyclic or polycyclic ring, and the carbon atoms of the formed alicyclic or aromatic monocyclic or polycyclic ring may be N, S , And O, and R < 2 >

The two carbon atoms adjacent to each other in Z 1 together with the carbon atoms connected to the substituents R 11 and R 12 form a 5-membered ring to form a condensed ring,

A carbon atom not forming a 5-membered ring in the aromatic ring of Z1 is bonded to a linking group L11 in Q3,

The linking group L11 is a single bond or a substituted or unsubstituted alkylene group having 1 to 60 carbon atoms, a substituted or unsubstituted alkenylene group having 2 to 60 carbon atoms, a substituted or unsubstituted alkynylene group having 2 to 60 carbon atoms, a substituted Or a substituted or unsubstituted C2-C60 heterocycloalkylene group, a substituted or unsubstituted C6-C60 arylene group, or a substituted or unsubstituted C2-C60 arylene group, A heteroarylene group of 1 to 6 carbon atoms;

n2 is an integer of 0 to 2, and when n2 is 2, each of the linking groups L11 is the same or different from each other,

The substituents Ar ₁₁ and Ar ₁₂ are the same or different and each independently represents a substituted or unsubstituted aryl group having 6 to 40 carbon atoms, a substituted or unsubstituted heteroaryl group having 2 to 30 carbon atoms, a substituted or unsubstituted carbon number A substituted or unsubstituted alkyl group having 1 to 40 carbon atoms, and a substituted or unsubstituted cycloalkyl group having 3 to 30 carbon atoms.

[Chemical formula D3]

In the above formula (D3)

X is a single bond, any one selected from CR ₁₈ R ₁₉ , NR ₂₈ , O, S and SiR ₂₉ R ₃₀ ,

Z ₂ and Z ₃ are the same or different and each independently represent a substituted or unsubstituted aromatic hydrocarbon ring having 6 to 30 carbon atoms, a substituted or unsubstituted aromatic heteroaromatic having 2 to 20 carbon atoms having O, N or S, A ring, and a ring,

Two carbon atoms adjacent to each other in Z2 and two adjacent carbon atoms in Z3 form a 5-membered ring to form a condensed ring,

The substituents R ₁₈ to R ₃₀ are the same or different and are each independently selected from the group consisting of hydrogen, deuterium, a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted aryl group having 6 to 50 carbon atoms, A substituted or unsubstituted C2-C20 alkynyl group, a substituted or unsubstituted C2-C20 alkynyl group, a substituted or unsubstituted C3-C30 cycloalkyl group, a substituted or unsubstituted heteroatom, O, N, S A substituted or unsubstituted C1-C30 alkoxy group, a substituted or unsubstituted C6-C30 aryloxy group, a substituted or unsubstituted C1-C30 alkyl group having 1 to 30 carbon atoms, A substituted or unsubstituted aryloxy group having 6 to 30 carbon atoms, a substituted or unsubstituted alkylamine group having 1 to 30 carbon atoms, a substituted or unsubstituted aryloxy group having 6 to 30 carbon atoms A substituted or unsubstituted alkylsilyl group having 1 to 30 carbon atoms, a substituted or unsubstituted arylsilyl group having 6 to 30 carbon atoms, a cyano group, a nitro group, a hydroxyl group, and a halogen group ,

The carbon atoms of the alicyclic or aromatic monocyclic or polycyclic ring formed may be N, S, or S, and R < ₂₀ > to R < ₂₇ > O, < / RTI >< RTI ID = 0.0 >

Wherein A21 and A22 are the same or different and independently of each other are represented by the following formula [Q4]

[Structural formula Q4]

In the above formula (Q4)

* Means a binding site in which the linking group L ₁₂ in Q4 is bonded to a carbon atom which does not form a 5-membered ring in the aromatic ring of Z2 or Z3 in the above formula [D3]

The linking group L ₁₂ is a single bond or a substituted or unsubstituted alkylene group having 1 to 60 carbon atoms, a substituted or unsubstituted alkenylene group having 2 to 60 carbon atoms, a substituted or unsubstituted alkynylene group having 2 to 60 carbon atoms, A substituted or unsubstituted cycloalkylene group having 3 to 60 carbon atoms, a substituted or unsubstituted heterocycloalkylene group having 2 to 60 carbon atoms, a substituted or unsubstituted arylene group having 6 to 60 carbon atoms, or a substituted or unsubstituted C2- A heteroarylene group having 1 to 60 carbon atoms;

n3 is an integer from 0 to 2, and n3 if a is 2, each of the linking group L ₁₂ are the same or different from each other,

Wherein said substituting groups Ar ₁₃ and Ar ₁₄ are the same or different and each independently represent a substituted or unsubstituted aryl group having 6 to 40 carbon atoms, a substituted or unsubstituted heteroaryl group having 2 to 30 carbon atoms, a substituted or unsubstituted An alkyl group having 1 to 40 carbon atoms, and a substituted or unsubstituted cycloalkyl group having 3 to 30 carbon atoms.

 [Chemical formula D4]

[Chemical formula D5]

Wherein A ₃₁ , A ₃₂ , E 1 and F 1 are the same or different and each independently represent a substituted or unsubstituted aromatic hydrocarbon ring having 6 to 50 carbon atoms or a substituted or unsubstituted ring An aromatic heterocycle having 2 to 40 carbon atoms;

Two carbon atoms adjacent to each other in the aromatic ring of A ₃₁ and two carbon atoms adjacent to each other in the aromatic ring of A ₃₂ form a 5-membered ring with the carbon atoms connected to the substituents R ₃₁ and R ₃₂ , ≪ / RTI >

The linking groups L ₂₁ to L ₃₂ are the same or different and each independently represents a single bond, a substituted or unsubstituted alkylene group having 1 to 60 carbon atoms, a substituted or unsubstituted alkenylene group having 2 to 60 carbon atoms, A substituted or unsubstituted cycloalkylene group having 3 to 60 carbon atoms, a substituted or unsubstituted heterocycloalkylene group having 2 to 60 carbon atoms, a substituted or unsubstituted C2 to C60 alkynylene group having 6 to 60 carbon atoms, An arylene group or a substituted or unsubstituted heteroarylene group having 2 to 60 carbon atoms;

W is any one selected from NR ₃₃ , CR ₃₄ R ₃₅ , SiR ₃₆ R ₃₇ , GeR ₃₈ R ₃₉ , O, S and Se;

The substituents R ₃₁ to R ₃₉ and Ar ₂₁ to Ar ₂₈ are the same or different and are each independently selected from the group consisting of hydrogen, deuterium, a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted aryl group having 6 to 50 carbon atoms A substituted or unsubstituted C2-C30 alkenyl group, a substituted or unsubstituted C2-C20 alkynyl group, a substituted or unsubstituted C3-C30 cycloalkyl group, a substituted or unsubstituted C2-C30 alkenyl group, A substituted or unsubstituted C2-C30 hetero aryl group, a substituted or unsubstituted C2-C30 heterocycloalkyl group, a substituted or unsubstituted C1-C30 alkoxy group, a substituted or unsubstituted C1-C30 alkoxy group, A substituted or unsubstituted alkylthio group having 1 to 30 carbon atoms, a substituted or unsubstituted arylthioxy group having 5 to 30 carbon atoms, a substituted or unsubstituted arylthio group having 6 to 30 carbon atoms, An alkylamine group having 1 to 30 carbon atoms, a substituted or unsubstituted arylamine group having 5 to 30 carbon atoms, a substituted or unsubstituted alkylsilyl group having 1 to 30 carbon atoms, a substituted or unsubstituted arylsilyl group having 5 to 30 carbon atoms , A substituted or unsubstituted alkylgermanium group having 1 to 30 carbon atoms, a substituted or unsubstituted arylgermanium group having 1 to 30 carbon atoms, a cyano group, a nitro group, and a halogen group,

R ₃₁ and R ₃₂ may be connected to form a single alicyclic or aromatic ring or polycyclic ring, and the carbon atom of the alicyclic or aromatic monocyclic or polycyclic ring may be N, O, P, Si, S , Ge, Se, and Te Which may be substituted with any one or more heteroatoms;

Each of p11 to p14, r11 to r14 and s11 to s14 is an integer of 1 to 3, and when each of them is 2 or more, each of the linking groups L ₂₁ to L ₃₂ is the same or different from each other,

X1 is an integer of 1 or 2, y1 and z1 are the same or different and independently of one another an integer of 0 to 3,

Ar ₂₁ and Ar ₂₂ , Ar ₂₃ and Ar ₂₄ , Ar ₂₅ and Ar _26, and Ar ₂₇ and Ar ₂₈ may be connected to each other to form a ring;

The two carbon atoms adjacent to each other in a ring A ₃₂ in formula D4 in combination with * in the structural formula, and Q ₁₁ form a condensed ring,

The two carbon atoms by the A ₃₁ ring my The two carbon atoms to each other neighbors in combination with * in the structural formula Q ₁₂ to form a condensed ring, in adjacent the A ₃₂ ring in the formula D5 of the formula Q ₁₁ * and To form a condensed ring,

Here, the 'substitution' in the 'substituted or unsubstituted' in the above [Formula A], [Formula B], [Formula D1] to [Formula D5] is a substituent selected from the group consisting of deuterium, cyano, halogen, , An alkyl group having 1 to 24 carbon atoms, a halogenated alkyl group having 1 to 24 carbon atoms, an alkenyl group having 2 to 24 carbon atoms, an alkynyl group having 2 to 24 carbon atoms, a heteroalkyl group having 1 to 24 carbon atoms, an aryl group having 6 to 24 carbon atoms, An arylalkyl group having 7 to 24 carbon atoms, a heteroaryl group having 2 to 24 carbon atoms or a heteroarylalkyl group having 2 to 24 carbon atoms, an alkoxy group having 1 to 24 carbon atoms, an alkylamino group having 1 to 24 carbon atoms, an arylamino group having 6 to 24 carbon atoms, Which is substituted with at least one substituent selected from the group consisting of a heteroarylamino group having 1 to 24 carbon atoms, an alkylsilyl group having 1 to 24 carbon atoms, an arylsilyl group having 6 to 24 carbon atoms, and an aryloxy group having 6 to 24 carbon atoms It means.

The organic light emitting device according to the present invention can exhibit improved efficiency as compared with the organic light emitting device according to the related art.

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

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

An organic light emitting device according to the present invention includes: a first electrode; A second electrode facing the first electrode; A hole transporting layer or a hole transporting layer interposed between the first electrode and the second electrode, and a light emitting layer, wherein the hole transporting layer or the hole transporting layer is represented by Formula (A) or Formula (B) At least one amine compound to be displayed; Wherein the light emitting layer comprises at least one compound represented by any one of the formulas (D1) to (D5).

That is, the organic light emitting device according to the present invention uses the compound represented by any one of the above formulas D1 to D5 as the light emitting layer material, and uses the amine compound represented by the above formula A or B as the hole injection layer material, And can have improved characteristics of high efficiency when used as a transport layer material.

On the other hand, considering the range of the alkyl or aryl group in the above "substituted or unsubstituted alkyl group having 1 to 24 carbon atoms" and "substituted or unsubstituted aryl group having 6 to 24 carbon atoms" And the number of carbon atoms in the aryl group of 6 to 24 carbon atoms means the total number of carbon atoms constituting the alkyl moiety or aryl moiety when it is considered that the substituent is not substituted without considering the substituted moiety. For example, a phenyl group substituted with a butyl group at the para position should be considered to correspond to an aryl group having 6 carbon atoms substituted with a butyl group having a carbon number of 4.

The aryl group, which is a substituent used in the compound of the present invention, is an organic radical derived from an aromatic hydrocarbon by the removal of one hydrogen, and when the aryl group has a substituent, it is fused with neighboring substituents to further form a ring .

Specific examples of the aryl group include a phenyl group, o-biphenyl group, m-biphenyl group, p-biphenyl group, o-terphenyl group, m- terphenyl group, p- terphenyl group, naphthyl group, anthryl group, An aromatic group such as a phenyl group, an indenyl group, a fluorenyl group, a tetrahydronaphthyl group, a perylenyle group, a crycenyl group, a naphthacenyl group and a fluoranthenyl group, and at least one hydrogen atom of the aryl group may be substituted with a deuterium atom, a halogen atom (-NH ₂₎ , -NH (R), -N (R ') (R "), R' and R" are independently of each other an alkyl group having 1 to 10 carbon atoms A hydrazine group, a hydrazone group, a carboxyl group, a sulfonic acid group, a phosphoric acid group, an alkyl group having 1 to 24 carbon atoms, a halogenated alkyl group having 1 to 24 carbon atoms, an alkyl group having 2 to 24 carbon atoms An alkynyl group having 2 to 24 carbon atoms, a heteroalkyl group having 1 to 24 carbon atoms, An aryl group having 6 to 24 carbon atoms, an arylalkyl group having 6 to 24 carbon atoms, a heteroaryl group having 2 to 24 carbon atoms, or a heteroarylalkyl group having 2 to 24 carbon atoms.

The heteroaryl group, which is a substituent used in the compounds of the present invention, refers to a C 2 -C 24 ring aromatic system containing 1, 2 or 3 heteroatoms selected from N, O, P or S and the remaining ring atoms are carbon, The rings may be fused to form a ring. And at least one hydrogen atom of the heteroaryl group may be substituted with the same substituent as the aryl group.

Specific examples of the alkyl group as a substituent used in the present invention include methyl, ethyl, propyl, isobutyl, sec-butyl, tert-butyl, pentyl, iso-amyl, hexyl and the like. The atom may be substituted with the same substituent as in the case of the aryl group.

Specific examples of the alkoxy group used as the substituent in the compound of the present invention include methoxy, ethoxy, propoxy, isobutyloxy, sec-butyloxy, pentyloxy, isoamyloxy, hexyloxy, At least one hydrogen atom in the alkoxy group may be substituted with the same substituent as in the case of the aryl group.

Specific examples of the silyl group used as the substituent in the compound of the present invention include trimethylsilyl, triethylsilyl, triphenylsilyl, trimethoxysilyl, dimethoxyphenylsilyl, diphenylmethylsilyl, diphenylvinylsilyl, methylcyclobutylsilyl , And dimethylpurylsilyl. At least one hydrogen atom of the silyl group may be substituted with the same substituent as the aryl group.

In the organic light emitting device according to the present invention, the amine compound represented by the above formula (A) or (B) has two carbon atoms adjacent to each other in the A2 ring in the formula (A) combined with * in the formula (Q1) to form a condensed ring And two carbon atoms adjacent to each other in the A1 ring form a condensed ring by bonding with * in the formula Q2 in the formula (B), and two carbon atoms adjacent to each other in the A2 ring are bonded to * in the formula (Q1) And has an amine group in only one ring of the A1 ring and the A2 ring in the above formulas (A) and (B), and these can be used for the hole injection layer or the hole transport layer in the organic light emitting device, Can be used for the hole transport layer.

On the other hand, The light emitting layer in the organic light emitting device includes a host and a dopant, and the compound represented by any one of formulas (D1) to (D5) may be used as a dopant.

In one embodiment, A1, A2, E and F in the above formula (A) or (B) may be the same or different and independently of each other, a substituted or unsubstituted aromatic hydrocarbon ring having 6 to 50 carbon atoms.

As described above, when A1, A2, E and F in the formula (A) or the formula (B) are the same or different and independently of each other represent a substituted or unsubstituted aromatic hydrocarbon ring having 6 to 50 carbon atoms, The unsubstituted aromatic hydrocarbon rings having 6 to 50 carbon atoms may be the same or different and independently selected from [Structural Formula 10] to [Structural Formula 21].

[Structural formula 10] [Structural formula 11] [Structural formula 12]

[Structural Formula 13] [Structural Formula 14] [Structural Formula 15]

[Structural formula 16] [Structural formula 17] [Structural formula 18]

[Structural formula 19] [Structural formula 20] [Structural formula 21]

"- *" in the above Structural Formulas 10 to 21 represents a 5-membered ring containing a carbon atom connected to the R1 and R2 or a 5-membered ring including M in the Structural Formulas Q1 and Q2 Means a binding site,

When the aromatic hydrocarbon rings of the above-mentioned structural formulas 10 to 21 are bonded to the structural formula Q1 or the structural formula Q2 while being bonded to the A1 ring or the A2 ring, two adjacent carbon atoms are bonded to * of the above structural formula Q1 Or with a * of formula Q2 to form a condensed ring;

In the above Structural Formulas 10 to 21, R is the same as R1 to R9 defined above, m is an integer of 1 to 8, and when m is 2 or more, or when R is 2 or more, each R is the same Or may be different.

In one embodiment of the present invention, x in formula (A) and formula (B) may be 1 and y may be 0.

In one embodiment of the present invention, the linking groups L1 to L6 in the formulas (A) and (B) are the same or different and independently of each other are a single bond or a group selected from the following formulas And p1 and p2, r1 and r4, s1 and s2 may be 1 or 2, respectively.

[Structural Formula 22] [Structural Formula 23] [Structural Formula 24] [Structural Formula 25]

[Structural Formula 26] [Structural Formula 27] [Structural Formula 28] [Structural Formula 29]

[Structural Formula 30]

The carbon position of the aromatic ring in the linking group may be bonded with hydrogen or deuterium.

In the present invention, Ar11, Ar12, Ar13 and Ar14 in the formulas D2 and D3 are the same or different and independently of each other, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms.

According to an embodiment of the present invention, Z1 to Z3 in the above formulas (D2) and (D3) are the same or different and each independently represents a substituted or unsubstituted aromatic hydrocarbon ring having 6 to 30 carbon atoms have.

In the present invention, Z1 to Z3 in the formulas (D2) and (D3) are the same or different, and independently of each other, a substituted or unsubstituted C6-C30 substituted or unsubstituted C 6 -C 30 aromatic The hydrocarbon ring may be any one selected from the following structural formulas (10) to (21).

[Structural formula 10] [Structural formula 11] [Structural formula 12]

[Structural Formula 13] [Structural Formula 14] [Structural Formula 15]

[Structural formula 16] [Structural formula 17] [Structural formula 18]

[Structural formula 19] [Structural formula 20] [Structural formula 21]

In the above-mentioned structural formulas 10 to 21, "- *" means a bonding site of a carbon atom for forming a 5-membered ring in Z1, Z2 or Z3,

In the above Structural Formulas 10 to 21, R is the same as R11 to R16 or R20 to R27 defined above,

m is an integer of 1 to 8, and when m is 2 or more, or when R is 2 or more, each R may be the same or different from each other.

According to an embodiment of the present invention, the linking groups L11 and L12 in the above formulas (D2) and (D3) are the same or different and independently of each other, or may be a single bond or a group selected from the above formulas It can be one.

On the other hand, may be ₂₁ A, ₂₂ A, E1 and F1 are the same or different and each independently represent a substituted or an aromatic hydrocarbon ring having 6 to 50 carbon atoms in the unsubstituted one another each in formula D4) and (D5 of the present invention.

In the meantime, the preparation of the dopant compounds represented by the above formulas (D4) and (D5) in the present invention is described in WO / 2015/174682 (International Publication Date: Nov. 11, 2015, International Application No. PCT / KR2015 / 004552) Can be prepared as described.

As described above, A ₃₁ , A ₃₂ , E 1 and F 1 in the formulas (D4) and (D5) may be the same or different and are each independently a substituted or unsubstituted aromatic hydrocarbon ring having 6 to 50 carbon atoms.

Here, when A ₃₁ , A ₃₂ , E 1 and F 1 in the formulas (D4) and (D5) are the same or different and independently represent a substituted or unsubstituted aromatic hydrocarbon ring having 6 to 50 carbon atoms, Or an unsubstituted aromatic hydrocarbon ring having 6 to 50 carbon atoms may be the same or different and independently selected from the following Structural Formulas 10 to 21:

[Structural formula 10] [Structural formula 11] [Structural formula 12]

[Structural Formula 13] [Structural Formula 14] [Structural Formula 15]

 [Structural formula 16] [Structural formula 17] [Structural formula 18]

[Structural formula 19] [Structural formula 20] [Structural formula 21]

In the above Structural Formulas 10 to 21, "- *" forms a 5-membered ring containing carbon atoms connected to R31 and R32 in the above formulas D4 and D5, or W To form a 5-membered ring,

When the aromatic hydrocarbon ring of the above structural formulas 10 to 21 is bonded to the structural formula Q11 or Q12 corresponding to the A31 ring or the A32 ring in the above formulas D4 and D5, The carbon atom is bonded to * of the formula Q11 or to a * of the formula Q12 to form a condensed ring,

In the above Structural Formulas 10 to 21, R is the same as R31 to R39, m is an integer of 1 to 8, and when m is 2 or more, or when R is 2 or more, each R is the same Can be different.

In the present invention, the linking groups L21 to L32 in the above formulas (D4) and (D5) are the same or different and independently of one another are a single bond or any one of the formulas (22) to (30) p14, r11 to r14, s11 to s14 may be 1 or 2, respectively.

According to an embodiment of the present invention, x1 and y1 in the above formulas (D4) and (D5) may be 1 and z1 may be 0, respectively.

In the present invention, the amine compound represented by the formula (A) or (B) may be any one selected from the group consisting of the following chemical formulas (1) to (165), but is not limited thereto.

&Lt; Formula 1 > < EMI ID =

&Lt; Formula 4 > < EMI ID =

&Lt; Formula 7 > < EMI ID =

&Lt; Formula 10 > < EMI ID =

&Lt; Formula 13 > < EMI ID =

&Lt; Formula 16 > < EMI ID =

&Lt; Formula 19 > < EMI ID =

&Lt; Formula 22 > < EMI ID =

&Lt; Formula 25 > < EMI ID = 26.0 >

&Lt; Formula 28 > < EMI ID = 29.0 >

&Lt; Formula 31 > < EMI ID =

&Lt; Formula 34 > < EMI ID =

&Lt; Formula 37 > < EMI ID = 38.0 >

&Lt; Formula 40 > < EMI ID =

&Lt; General Formula 43 >

&Lt; Formula 46 > < EMI ID =

&Lt; Formula 50 > < Formula 51 >

&Lt; Formula 52 >

&Lt; Formula 55 > < EMI ID = 56.0 >

<Formula 58> <Formula 59>

&Lt; Formula 61 > < EMI ID =

&Lt; Formula 64 > < EMI ID =

&Lt; Formula 67 >

<Formula 70> <Formula 71> <Formula 72>

&Lt; Formula 73 > < EMI ID =

&Lt; Formula 76 > < EMI ID =

&Lt; Formula 79 > < EMI ID =

<Formula 82> <Formula 83> <Formula 84>

&Lt; Formula 85 > < EMI ID =

&Lt; Formula 88 >

&Lt; Formula 91 > < EMI ID =

&Lt; Formula 94 > < EMI ID =

&Lt; Formula 97 >

&Lt; Formula 100 > < EMI ID =

&Lt; EMI ID = 103.1 >

(Formula 107) < EMI ID = 106.1 >

(110) < Formula (111) >

<Formula 112> <Formula 113> <Formula 114>

&Lt; Formula 115 > < EMI ID = 116.1 >

&Lt; EMI ID = 120.1 >

&Lt; Formula 121 > < EMI ID =

&Lt; Formula 124 > < EMI ID =

&Lt; Formula 127 >

[Formula 130] < EMI ID = 131.0 >

<Formula 133> <Formula 134> <Formula 135>

&Lt; EMI ID = 136.0 >

&Lt; Formula 139 > < EMI ID =

&Lt; Formula 142 > < EMI ID = 143.1 >

&Lt; Formula 145 > < EMI ID =

&Lt; Formula 148 >  &Lt; EMI ID =

<Formula 151> <Formula 152> <Formula 153>

<Formula 154> <Formula 155>

&Lt; Formula 15 >

&Lt; Formula 160 > < EMI ID =

&Lt; Formula 163 > < EMI ID =

In the present invention, the compound represented by the above formula (D1) may be any one selected from the following compounds [101] to [190], but is not limited thereto.

&Lt; Compound 101 > < Compound 102 > < Compound 103 >

&Lt; Compound 104 > < Compound 105 > < Compound 106 >

&Lt; Compound 107 > < Compound 108 > < Compound 109 >

&Lt; Compound 110 > < Compound 111 > < Compound 112 &

&Lt; Compound 113 > < Compound 114 > < Compound 115 &

&Lt; Compound 116 > < Compound 117 > < Compound 118 &

&Lt; Compound 119 > < Compound 120 > < Compound 121 &

&Lt; Compound 122 > < Compound 123 > < Compound 124 >

&Lt; Compound 125 > < Compound 126 > < Compound 127 &

&Lt; Compound 128 > < Compound 129 > < Compound 130 &

&Lt; Compound 131 > < Compound 132 > < Compound 133 >

&Lt; Compound 134 > < Compound 135 > < Compound 136 >

&Lt; Compound 137 > < Compound 138 > < Compound 139 &

&Lt; Compound 140 > < Compound 141 > < Compound 142 >

&Lt; Compound 143 > < Compound 144 > < Compound 145 >

<Compound 146> <Compound 147> <Compound 148>

&Lt; Compound 149 > < Compound 150 > < Compound 151 >

&Lt; Compound 152 > < Compound 153 > < Compound 154 >

&Lt; Compound 155 > < Compound 156 > < Compound 157 >

&Lt; Compound 158 > < Compound 159 > < Compound 160 >

&Lt; Compound 161 > < Compound 162 > < Compound 163 &

&Lt; Compound 164 > < Compound 165 > < Compound 166 &

&Lt; Compound 167 > < Compound 168 > < Compound 169 &

&Lt; Compound 170 > < Compound 171 > < Compound 172 >

<Compound 173> <Compound 174> <Compound 175>

<Compound 176> <Compound 177> <Compound 178>

&Lt; Compound 179 > < Compound 180 > < Compound 181 &

<Compound 182> <Compound 183> <Compound 184>

&Lt; Compound 185 > < Compound 186 > < Compound 187 &

&Lt; Compound 188 > < Compound 189 > < Compound 190 &

In the present invention, the compound represented by the above formula [D2] may be any one selected from the following [compounds 201] to [260], but is not limited thereto.

&Lt; Compound 201 > < Compound 202 > < Compound 203 &

<Compound 204> <Compound 205> <Compound 206>

&Lt; Compound 207 > < Compound 208 > < Compound 209 &

&Lt; Compound 210 > < Compound 211 > < Compound 212 &

&Lt; Compound 213 > < Compound 214 > < Compound 215 &

&Lt; Compound 216 > < Compound 217 > < Compound 218 &

&Lt; Compound 219 > < Compound 220 > < Compound 221 &

&Lt; Compound 222 > < Compound 223 > < Compound 224 &

&Lt; Compound 225 > < Compound 226 > < Compound 227 &

&Lt; Compound 228 > < Compound 229 > < Compound 230 &

&Lt; Compound 231 > < Compound 232 > < Compound 233 &

&Lt; Compound 234 > < Compound 235 > < Compound 236 >

&Lt; Compound 237 > < Compound 238 > < Compound 239 >

&Lt; Compound 240 > < Compound 241 > < Compound 242 &

<Compound 243> <Compound 244> <Compound 245>

<Compound 246> <Compound 247> <Compound 248>

&Lt; Compound 249 > < Compound 250 > < Compound 251 &

&Lt; Compound 252 > < Compound 253 > < Compound 254 &

&Lt; Compound 255 > < Compound 256 > < Compound 257 &

<Compound 258> <Compound 259> <Compound 260>

In the present invention, the compound represented by the above formula [D3] may be any one selected from the following [compounds 261] to [326], but is not limited thereto.

&Lt; Compound 261 > < Compound 262 > < Compound 263 &

&Lt; Compound 264 > < Compound 265 > < Compound 266 &

&Lt; Compound 267 > < Compound 268 > < Compound 269 &

&Lt; Compound 270 > < Compound 271 > < Compound 272 &

&Lt; Compound 273 > < Compound 274 > < Compound 275 >

&Lt; Compound 276 > < Compound 277 > < Compound 278 >

&Lt; Compound 279 > < Compound 280 > < Compound 281 &

&Lt; Compound 282 > < Compound 283 > < Compound 284 >

&Lt; Compound 285 > < Compound 286 > < Compound 287 &

<Compound 288> <Compound 289> <Compound 290>

&Lt; Compound 291 > < Compound 292 > < Compound 293 &

&Lt; Compound 294 > < Compound 295 > < Compound 296 &

&Lt; Compound 297 > < Compound 298 > < Compound 299 &

&Lt; Compound 300 > < Compound 301 > < Compound 302 >

&Lt; Compound 303 > < Compound 304 > < Compound 305 &

&Lt; Compound 306 > < Compound 307 > < Compound 308 &

&Lt; Compound 309 > < Compound 310 > < Compound 311 &

&Lt; Compound 312 > < Compound 313 > < Compound 314 >

&Lt; Compound 315 > < Compound 316 > < Compound 317 >

&Lt; Compound 318 > < Compound 319 > < Compound 320 &

&Lt; Compound 321 > < Compound 322 > < Compound 323 >

&Lt; Compound 324 > < Compound 325 > < Compound 326 >

In the present invention, the compound represented by Formula D4 or Formula D5 may be any compound selected from [Compound 401] to [Compound 639], but is not limited thereto.

&Lt; Compound 401 > < Compound 402 > < Compound 403 &

&Lt; Compound 404 > < Compound 405 > < Compound 406 &

<화합물 407><화합물 408><화합물 409>

&Lt; Compound 407 >< Compound 408 >< Compound 409 >

&Lt; Compound 410 > < Compound 411 > < Compound 412 &

<화합물 413><화합물 414><화합물 415>

&Lt; Compound 413 >< Compound 414 >< Compound 415 >

&Lt; Compound 416 > < Compound 417 > < Compound 418 &

&Lt; Compound 419 > < Compound 420 > < Compound 421 &

&Lt; Compound 422 > < Compound 423 > < Compound 424 >

&Lt; Compound 425 > < Compound 426 > < Compound 427 &

&Lt; Compound 428 > < Compound 429 > < Compound 430 >

<화합물 431><화합물 432><화합물 433>

&Lt; Compound 431 >< Compound 432 >< Compound 433 >

&Lt; Compound 434 > < Compound 435 > < Compound 436 >

&Lt; Compound 437 > < Compound 438 > < Compound 439 >

<화합물 440><화합물 441><화합물 442>

&Lt; Compound 440 >< Compound 441 >< Compound 442 &

<화합물 443><화합물 444><화합물 445>

&Lt; Compound 443 >< Compound 444 >< Compound 445 &

&Lt; Compound 446 > < Compound 447 > < Compound 448 &

<화합물 449><화합물 450><화합물 451>

&Lt; Compound 449 >< Compound 450 >< Compound 451 &

&Lt; Compound 452 > < Compound 453 > < Compound 454 >

&Lt; Compound 455 > < Compound 456 > < Compound 457 >

<화합물 458><화합물 459><화합물 460>

&Lt; Compound 458 >< Compound 459 >< Compound 460 &

&Lt; Compound 461 > < Compound 462 > < Compound 463 &

&Lt; Compound 464 > < Compound 465 > < Compound 466 &

<화합물 467><화합물 468><화합물 469>

&Lt; Compound 467 >< Compound 468 >< Compound 469 &

&Lt; Compound 470 > < Compound 471 > < Compound 472 &

&Lt; Compound 473 > < Compound 474 > < Compound 475 &

&Lt; Compound 476 > < Compound 477 > < Compound 478 &

&Lt; Compound 479 > < Compound 480 > < Compound 481 &

<Compound 482> <Compound 483> <Compound 484>

<Compound 485> <Compound 486> <Compound 487>

<화합물 488><화합물 489><화합물 490>

<Compound 488><Compound489><Compound490>

<화합물 491><화합물 492><화합물 493>

&Lt; Compound 491 >< Compound 492 >< Compound 493 &

&Lt; Compound 494 > < Compound 495 > < Compound 496 &

&Lt; Compound 497 > < Compound 498 > < Compound 499 &

&Lt; Compound 500 > < Compound 501 > < Compound 502 >

&Lt; Compound 503 > < Compound 504 > < Compound 505 >

&Lt; Compound 506 > < Compound 507 > < Compound 508 &

&Lt; Compound 509 > < Compound 510 > < Compound 511 &

&Lt; Compound 512 > < Compound 513 > < Compound 514 &

<Compound 515> <Compound 516> <Compound 517>

<Compound 518> <Compound 519> <Compound 520>

&Lt; Compound 521 > < Compound 522 > < Compound 523 &

<Compound 524> <Compound 525> <Compound 526>

&Lt; Compound 527 > < Compound 528 > < Compound 529 &

&Lt; Compound 530 > < Compound 531 > < Compound 532 &

&Lt; Compound 533 > < Compound 534 > < Compound 535 >

&Lt; Compound 536 > < Compound 537 > < Compound 538 >

&Lt; Compound 539 > < Compound 540 > < Compound 541 >

<Compound 542> <Compound 543> <Compound 544>

<Compound 545> <Compound 546> <Compound 547>

<Compound 548> <Compound 549> <Compound 550>

&Lt; Compound 551 > < Compound 552 > < Compound 553 >

<Compound 554> <Compound 555> <Compound 556>

&Lt; Compound 557 > < Compound 558 > < Compound 559 >

&Lt; Compound 560 > < Compound 561 > < Compound 562 &

<Compound 563> <Compound 564> <Compound 565>

<Compound 566> <Compound 567> <Compound 568>

&Lt; Compound 569 > < Compound 570 > < Compound 571 >

&Lt; Compound 572 > < Compound 573 > < Compound 574 >

&Lt; Compound 575 > < Compound 576 > < Compound 577 >

&Lt; Compound 578 > < Compound 579 > < Compound 580 &

<Compound 581> <Compound 582> <Compound 583>

<Compound 584> <Compound 585> <Compound 586>

&Lt; Compound 587 > < Compound 588 > < Compound 589 &

&Lt; Compound 590 > < Compound 591 > < Compound 592 >

<Compound 593> <Compound 594> <Compound 595>

&Lt; Compound 596 > < Compound 597 > < Compound 598 &

&Lt; Compound 599 > < Compound 600 > < Compound 601 >

&Lt; Compound 602 > < Compound 603 > < Compound 604 >

&Lt; Compound 605 > < Compound 606 > < Compound 607 >

&Lt; Compound 608 > < Compound 609 > < Compound 610 &

&Lt; Compound 611 > < Compound 612 > < Compound 613 &

&Lt; Compound 614 > < Compound 615 > < Compound 616 >

&Lt; Compound 617 > < Compound 618 > < Compound 619 >

&Lt; Compound 620 > < Compound 621 > < Compound 622 &

&Lt; Compound 623 > < Compound 624 > < Compound 625 >

&Lt; Compound 626 > < Compound 627 > < Compound 628 &

&Lt; Compound 629 > < Compound 630 > < Compound 631 &

&Lt; Compound 632 > < Compound 633 > < Compound 634 >

&Lt; Compound 635 > < Compound 636 > < Compound 637 &

&Lt; Compound 638 > < Compound 639 >

In one embodiment of the present invention, the organic light emitting device includes a first electrode as an anode and a second electrode as a cathode. In addition to the light emitting layer, the hole injecting layer and the hole transporting layer, the organic light emitting device includes an electron blocking layer, And an electron injection layer, and a hole injection layer may be interposed between the anode and the hole transport layer, and an electron transport layer and an electron injection layer may be sequentially formed between the emission layer and the cathode.

More preferably, the organic light emitting device of the present invention includes a hole transporting layer and a light emitting layer between the first electrode and the second electrode, and the hole transporting layer contains at least one amine compound represented by the formula (A) or (B) ; The light emitting layer may contain at least one compound represented by any one of Chemical Formulas D1 to D5 as a dopant material.

Herein, "(organic layer) contains at least one organic compound" in the present invention means that one or more organic compounds belonging to the category of the present invention (organic layer) Compound "as used herein.

Also, as a preferred embodiment of the present invention, the organic light emitting device may include an electron blocking layer between the hole transporting layer and the light emitting layer.

In the present invention, at least one layer selected from the hole injecting layer, the hole transporting layer, the light emitting layer, the electron transporting layer, and the electron injecting layer may be formed by a deposition process or a solution process. Here, the deposition process refers to a method of forming a thin film by evaporating a material used as a material for forming each of the layers through heating or the like under a vacuum or a low pressure, Refers to a method of mixing a material used as a material with a solvent and forming the thin film by a method such as inkjet printing, roll-to-roll coating, screen printing, spray coating, dip coating, spin coating or the like.

Further, the organic light emitting device of the present invention may be a flat panel display device; A flexible display device; Monochrome or white flat panel illumination devices; And a single-color or white-colored flexible lighting device.

In the present invention, as the material of the hole transport layer, compounds other than the amine compound represented by the above formula (A) or (B) of the present invention may be used, and electron donor molecules having a low ionization potential are generally used. (3-methylphenyl) -N, N'-diphenyl- [1,1-biphenyl] - (1,1-dimethylphenyl) 4,4'-diamine (TPD) or N, N'-di (naphthalene-1-yl) -N, N'-diphenylbenzidine (a-NPD).

In addition, a hole injection layer (HIL) may be further formed on the lower part of the hole transport layer. In addition to the compound having an amine group represented by the above formula (A) or (B) (4,4 ', 4 "-tri (N-carbazolyl) triphenyl-amine), which is a starburst type amine, is used. (4,4 ', 4 "-tris- (3-methylphenylphenylamino) triphenylamine) may further be used.

Meanwhile, in the present invention, the host used for the light emitting layer may include at least one compound represented by the following formula (H), and various known dopant materials may be used.

[Formula H] &lt;

In the above formula (H)

X ₁ to X ₁₀ are the same or different from each other and each independently represents a hydrogen atom, a deuterium atom, a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 30 carbon atoms, A substituted or unsubstituted cycloalkyl group having 3 to 30 carbon atoms, a substituted or unsubstituted cycloalkenyl group having 5 to 30 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 30 carbon atoms, a substituted or unsubstituted aryloxy group having 6 to 30 carbon atoms, A substituted or unsubstituted alkylthio group having 1 to 30 carbon atoms, a substituted or unsubstituted arylthioxy group having 5 to 30 carbon atoms, a substituted or unsubstituted alkylamine group having 1 to 30 carbon atoms, A substituted or unsubstituted aryl group having 5 to 50 carbon atoms, a substituted or unsubstituted heteroaryl group having 3 to 50 carbon atoms having a hetero atom O, N or S, a substituted or unsubstituted Is a group selected from the group consisting of an unsubstituted silicon group, a substituted or unsubstituted boron group, a substituted or unsubstituted silane group, a carbonyl group, a phosphoryl group, an amino group, a nitrile group, a hydroxyl group, a nitro group, a halogen group, an amide group and an ester group And the groups adjacent to each other may form a condensed ring of an aliphatic, aromatic, aliphatic hetero or aromatic hetero.

More specifically, the host may be represented by any one selected from the group consisting of the following [compounds 701] to [compound 896], but is not limited thereto.

[Compound 701] [Compound 702] [Compound 703] [Compound 704]

[Compound 705] [Compound 706] [Compound 707] [Compound 708]

[Compound 709] [Compound 710] [Compound 711] [Compound 712]

[Compound 713] [Compound 714] [Compound 715] [Compound 716]

[Compound 717] [Compound 718] [Compound 719] [Compound 720]

[Compound 721] [Compound 722] [Compound 723] [Compound 724]

[Compound 725] [Compound 726] [Compound 727] [Compound 728]

[Compound 729] [Compound 730] [Compound 731] [Compound 732]

[Compound 733] [Compound 734] [Compound 735] [Compound 736]

[Compound 737] [Compound 738] [Compound 739] [Compound 740]

[Compound 741] [Compound 742] [Compound 743] [Compound 744]

[Compound 745] [Compound 746] [Compound 747] [Compound 748]

[Compound 749] [Compound 750] [Compound 751] [Compound 752]

[Compound 753] [Compound 754] [Compound 755] [Compound 756]

[Compound 757] [Compound 758] [Compound 759] [Compound 760]

[Compound 761] [Compound 762] [Compound 763] [Compound 764]

[Compound 765] [Compound 766] [Compound 767] [Compound 768]

[Compound 769] [Compound 770] [Compound 771] [Compound 772]

[Compound 773] [Compound 774] [Compound 775] [Compound 776]

[Compound 777] [Compound 778] [Compound 779] [Compound 780]

[Compound 781] [Compound 782] [Compound 783] [Compound 784]

[Compound 785] [Compound 786] [Compound 787] [Compound 788]

[Compound 789] [Compound 790] [Compound 791] [Compound 792]

[Compound 793] [Compound 794] [Compound 795] [Compound 796]

[Compound 797] [Compound 798] [Compound 799] [Compound 800]

[Compound 801] [Compound 802] [Compound 803] [Compound 804]

[Compound 805] [Compound 806] [Compound 807] [Compound 808]

[Compound 809] [Compound 810] [Compound 811] [Compound 812]

[Compound 813] [Compound 814] [Compound 815] [Compound 816]

[Compound 817] [Compound 818] [Compound 819] [Compound 820]

[Compound 821] [Compound 822] [Compound 823] [Compound 824]

[Compound 825] [Compound 826] [Compound 827] [Compound 828]

[Compound 829] [Compound 830] [Compound 831] [Compound 832]

[Compound 833] [Compound 834] [Compound 835] [Compound 836]

[Compound 837] [Compound 838] [Compound 839] [Compound 840]

[Compound 841] [Compound 842] [Compound 843] [Compound 844]

[Compound 845] [Compound 846] [Compound 847] [Compound 848]

[Compound 849] [Compound 850] [Compound 851] [Compound 852]

[Compound 853] [Compound 854] [Compound 855] [Compound 856]

[Compound 857] [Compound 858] [Compound 859] [Compound 860]

[Compound 861] [Compound 862] [Compound 863] [Compound 864]

[Compound 865] [Compound 866] [Compound 867] [Compound 868]

[Compound 869] [Compound 870] [Compound 871] [Compound 872]

[Compound 873] [Compound 874] [Compound 875] [Compound 876]

[Compound 877] [Compound 878] [Compound 879] [Compound 880]

[Compound 881] [Compound 882] [Compound 883] [Compound 884]

[Compound 885] [Compound 886] [Compound 887] [Compound 888]

[Compound 889] [Compound 890] [Compound 891] [Compound 892]

[Compound 893] [Compound 894] [Compound 895] [Compound 896]

The light emitting layer may further include various dopants and various hosts as well as the dopant and the host.

Meanwhile, when the light emitting layer according to the present invention includes a host and a dopant, the dopant may be selected from the range of about 0.01 to about 20 parts by weight based on 100 parts by weight of the host, but is not limited thereto .

In the present invention, as the electron transporting layer material, a known electron transporting material can be used as a material that stably transports electrons injected from an electron injection electrode (cathode). Examples of known electron transport materials include quinoline derivatives, especially tris (8-quinolinolate) aluminum (Alq3), Liq, TAZ, BAlq, beryllium bis (benzoquinolin- 10-olate: Bebq2), compound 901, compound 902, BCP, oxadiazole derivative PBD, BMD, BND, and the like may be used, but the present invention is not limited thereto.

TAZ BAlq

&Lt; Compound 901 > < Compound 902 > BCP

In addition, the electron transporting layer used in the present invention can be used alone or in combination with the electron transporting layer material as the organometallic compound represented by the following formula (F).

[Chemical Formula F]

In the above formula (F)

Y is a moiety selected from C, N, O and S, which is directly bonded to M to form a single bond, and any moiety selected from C, N, O and S is a moiety coordinating to M And is a ligand chelated by coordination bond with the single bond; Wherein M is an alkali metal, an alkaline earth metal, an aluminum (Al), or a boron (B) atom, and OA is a monovalent ligand capable of single bond or coordination bond with M,

O is oxygen,

A represents a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted aryl group having 6 to 50 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 30 carbon atoms, a substituted or unsubstituted C2 to C20 Substituted or unsubstituted cycloalkyl groups having 3 to 30 carbon atoms, substituted or unsubstituted cycloalkenyl groups having 5 to 30 carbon atoms, and substituted or unsubstituted hetero atoms having 2 to 50 carbon atoms having O, N or S, An aryl group,

M is 1 and n is 0 when M is a metal selected from an alkali metal,

M = 1, n = 1, or m = 2 and n = 0 when M is a metal selected from alkaline earth metals,

M is 1 to 3 when M is boron or aluminum, and n is any of 0 to 2 and satisfies m + n = 3.

In the present invention, Y may be the same or different and independently of each other may be any one selected from the following formulas [C1] to [C39], but is not limited thereto.

[Structural formula C1] [Structural formula C2] [Structural formula C3]

[Structural formula C4] [Structural formula C5] [Structural formula C6]

[Structural formula C7] [Structural formula C8] [Structural formula C9] [Structural formula C10]

[Structural formula C11] [Structural formula C12] [Structural formula C13]

[Structural formula C14] [Structural formula C15] [Structural formula C16]

[Structural formula C17] [Structural formula C18] [Structural formula C19] [Structural formula C20]

[Structural formula C21] [Structural formula C22] [Structural formula C23]

[Structural formula C24] [Structural formula C25] [Structural formula C26]

[Structural formula C27] [Structural formula C28] [Structural formula C29] [Structural formula C30]

[Structural formula C31] [Structural formula C32] [Structural formula C33]

[Structural formula C34] [Structural formula C35] [Structural formula C36]

[Structural formula C37] [Structural formula C38] [Structural formula C39]

In the above Structural Formula C1 to Structural Formula C39,

R is the same or different and is each independently selected from the group consisting of hydrogen, deuterium, halogen, cyano, substituted or unsubstituted C1-30 alkyl, substituted or unsubstituted C6-30 aryl, A substituted or unsubstituted C1-C30 alkoxy group, a substituted or unsubstituted C3-C30 cycloalkyl group, a substituted or unsubstituted C2-C30 alkenyl group, a substituted or unsubstituted C1-C30 alkoxy group, A substituted or unsubstituted alkylsilyl group having 1 to 30 carbon atoms, a substituted or unsubstituted arylamino group having 6 to 30 carbon atoms, and a substituted or unsubstituted arylsilyl group having 6 to 30 carbon atoms And may be connected to an adjacent substituent by alkylene or alkenylene to form a spiro ring or a fused ring. Herein, the 'substitution' in the 'substituted or unsubstituted' refers to a substituent selected from the group consisting of deuterium, cyano group, halogen group, hydroxyl group, nitro group, alkyl group, alkoxy group, alkylamino group, arylamino group, heteroarylamino group, An aryl group, a heteroaryl group, germanium, phosphorus, and boron. The term &quot; substituted aryl group &quot;

On the other hand, an electron injection layer (EIL) may be further formed on the electron transport layer to facilitate injection of electrons from the cathode to ultimately improve power efficiency. As long as it is commonly used in the related art, it can be used without any particular limitation. For example, materials such as LiF, NaCl, CsF, Li ₂ O, and BaO can be used.

The thickness of the electron injecting layer may be from about 1 A to about 100 A, and from about 3 A to about 90 A. When the thickness of the electron injection layer satisfies the above-described range, satisfactory electron injection characteristics can be obtained without substantially increasing the driving voltage.

Hereinafter, a method of manufacturing an organic light emitting device of the present invention will be described with reference to FIG.

1 is a cross-sectional view showing a structure of an organic light emitting device of the present invention. The organic light emitting device according to the present invention includes an anode 20, a hole transport layer 40, an organic light emitting layer 50, an electron transport layer 60, and a cathode 80, And may further include an injection layer 70. In addition, one or two intermediate layers may be further formed.

A method of manufacturing an organic light emitting diode according to the present invention will be described with reference to FIG.

First, an anode 20 is formed by coating a material for a cathode electrode on the substrate 10. Here, as the substrate 10, an organic substrate or a transparent plastic substrate which is excellent in transparency, surface smoothness, ease of handling, and waterproofness is used as a substrate used in a conventional organic EL device. As the material for the positive electrode, indium tin oxide (ITO), indium zinc oxide (IZO), tin oxide (SnO ₂ ), zinc oxide (ZnO) or the like which is transparent and excellent in conductivity is used.

A hole injection layer 30 is formed on the anode 20 by vacuum thermal deposition or spin coating. Subsequently, a hole transport layer 40 is formed by vacuum thermal deposition or spin coating on the hole transport layer 30 above the hole injection layer 30.

Then, an electron blocking layer is selectively formed between the hole transport layer and a light emitting layer 50 to be formed later. Then, an organic light emitting layer 50 is stacked on the hole transport layer 40, Alternatively, a thin film can be formed on the upper portion of the substrate 50 as a vacuum deposition method or a spin coating method using a hole blocking layer (not shown). The hole blocking layer has a hole blocking layer When the organic light emitting layer is introduced into the cathode through the organic light emitting layer, the lifetime and the efficiency of the device are reduced. Therefore, the use of a material having a very low HOMO level is used to prevent such a problem. In this case, the hole blocking material to be used is not particularly limited, but it is required to have an ionization potential higher than that of the light emitting compound while having electron transporting ability. Typically, BAlq, BCP, TPBI and the like can be used.

After the electron transport layer 60 is deposited on the hole blocking layer through a vacuum deposition method or a spin coating method, an electron injection layer 70 is formed, and a metal for forming an anode is vacuum-deposited on the electron injection layer 70 To form a cathode (80) electrode, thereby completing the organic EL device. Here, as the metal for forming the negative electrode, lithium, magnesium, aluminum, aluminum-lithium, calcium, Mg-Ag). In order to obtain a top-emitting device, a transmissive cathode using ITO or IZO can be used.

Hereinafter, the present invention will be described in more detail with reference to preferred embodiments. It will be apparent, however, to those skilled in the art that these embodiments are for further explanation of the present invention and that the scope of the present invention is not limited thereby.

(Example)

Production Example of Hole Transporting Compound

Synthesis Example 1: Synthesis of Compound (13)

Synthesis of Synthesis Example 1- (1): [Intermediate 1-a]

                                   [Intermediate 1-a]

To a 500 mL round bottom flask was added methyl 2-iodobenzoate (19.1 g, 73 mmol), 4-dibenzofuranboronic acid (18.7 g, 88 mmol), tetrakis (triphenylphosphine) palladium mmol) and potassium carbonate (20.2 g, 146.7 mmol) were added, and 125 mL of toluene, 125 mL of tetrahydrofuran, and 50 mL of water were added. The temperature of the reactor was raised to 80 캜 and stirred for 10 hours. When the reaction was completed, the temperature of the reactor was lowered to room temperature, extracted with ethyl acetate, and the organic layer was separated. The organic layer was concentrated under reduced pressure and then separated by column chromatography to obtain [intermediate 1-a]. (9.5 g, 43%).

Synthesis of Synthesis Example 1- (2): [Intermediate 1-b]

                                    [Intermediate 1-b]

Bromobenzene (13.2 g, 83.97 mmol) and 250 ml of tetrahydrofuran were placed in a 2 L round bottom flask and stirred in a nitrogen atmosphere at a low temperature. At -78 ° C, about 58 ml of n-butyllithium was slowly added dropwise over 2 hours, and then [intermediate 1-a] (9.4 g, 31.1 mmol) was added. After completion of the reaction, 100 ml of water was added and the mixture was stirred for 30 minutes and extracted to obtain [intermediate 1-b]. (3.2 g, 24%).

Synthesis of Synthesis Example 1- (3): [Intermediate 1-c]

                        [Intermediate 1-c]

[Intermediate 1-b] (55.0 g, 129 mmol), 500 ml of acetic acid and 10 ml of sulfuric acid were placed in a 2 L round-bottomed flask and refluxed for 5 hours. After completion of the reaction, the reaction mixture was cooled to room temperature, and the resulting solid was filtered. After washing with methanol, [Intermediate 1-c] was obtained. (50 g, 95%).

Synthesis of Synthesis Example 1- (4): [Intermediate 1-d]

                     [Intermediate 1-d]

[Intermediate 1-c] (50 g, 122 mmol) and 600 ml of dichloromethane were placed in a 2 L round bottom flask and stirred at room temperature. Bromine (13.7 ml, 85 mmol) was diluted with 50 ml of dichloromethane, and the mixture was stirred for about 3 hours. Recrystallization from methanol gave [Intermediate 1-d]. (45 g, 76%).

Synthesis of Synthesis Example 1- (5): [Formula 13]

                                     [Chemical Formula 13]

4-yl-amine (4.3 g, 0.013 mol), palladium (II) acetate (0.08 g, 0.4 mmol) , Sodium tertiary butoxide (3.4 g, 0.035 mol), triturated butylphosphine (0.07 g, 0.4 mmol) and toluene (60 ml) were added and the mixture was stirred under reflux for 2 hours. After completion of the reaction, the reaction solution was cooled to room temperature. The reaction solution was extracted with dichloromethane and water. The organic layer was separated, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure. The reaction mixture was separated by column chromatography, and recrystallized from dichloromethane and acetone to obtain [Formula 13]. (2.6 g, 40%).

MS (MALDI-TOF): m / z 727.29 [M ^&lt; ⁺ &^gt;].

Synthesis Example 2: Synthesis of Formula 40

Synthesis of Synthesis Example 2- (1): [Intermediate 2-a]

                                   [Intermediate 2-a]

4-dibenzofuranboronic acid (85.0 g, 0.401 mol), bismuth (III) nitrate pentahydrate (99.2 g, 0.20 mol) and 400 ml of toluene were placed in a 1 L round bottom flask under nitrogen atmosphere at 70 ° C for 3 hours Lt; / RTI &gt; After completion of the reaction, the reaction mixture was cooled to room temperature and the resulting solid was filtered. After washing with toluene, [intermediate 2-a] (61.5 g, 72%) was obtained.

Synthesis of Synthesis Example 2- (2): [Intermediate 2-b]

                                       [Intermediate 2-b]

A 2 L round bottom flask was charged with ethyl cyanoacetate (202.9 g, 1.794 mol) and dimethylformamide (500 mL). Potassium hydroxide (67.10 g, 1.196 mol) and potassium cyanide (38.95 g, 0.598 mol) were added, and 200 ml of dimethylformamide was added thereto, followed by stirring at room temperature. [Intermediate 2-a] (127.5 g, 0.737 mol) was gradually added to the reaction solution, which was then stirred at 50 ° C for 72 hours. After completion of the reaction, 200 ml of an aqueous solution of sodium hydroxide (25%) was added and the mixture was stirred under reflux. After stirring for 3 hours, the mixture was cooled to room temperature and extracted with ethyl acetate and water. The organic layer was separated, concentrated under reduced pressure, and then separated by column chromatography to obtain [intermediate 2-b] (20.0 g, 16%).

Synthesis of Synthesis Example 2- (3): [Intermediate 2-c]

                                      [Intermediate 2-c]

170 ml of an aqueous solution of [Intermediate 2-b] (20.0 g, 0.096 mol), ethanol (600 ml) and potassium hydroxide aqueous solution (142.26 g, 2.53 mol) was added to a 2 L round bottom flask and the mixture was refluxed for 12 hours. When the reaction was completed, the reaction solution was cooled to room temperature. The reaction solution was acidified with 400 ml of 6 N hydrochloric acid. The resulting solid was stirred for 20 minutes and then filtered. After washing with ethanol, [intermediate 2-c] (17.0 g, 88.5%) was obtained.

Synthesis Example 2- (4): Synthesis of [intermediate 2-d]

                                          [Intermediate 2-d]

[Intermediate 2-c] (17.0 g, 0.075 mol) and 15 ml of sulfuric acid were placed in a 2 L round bottom flask, and the mixture was refluxed for 72 hours. After completion of the reaction, the reaction mixture was cooled to room temperature and extracted with ethyl acetate and water. The organic layer was separated and washed with aqueous sodium hydrogencarbonate solution. The organic layer was concentrated under reduced pressure and methanol was added in an excess amount, and the resultant solid was filtered to obtain [intermediate 2? D] (14.0 g, 77.6%).

Synthesis of Synthesis Example 2- (5): [Intermediate 2-e]

                                        [Intermediate 2-e]

[Intermediate 2-d] (14.0 g, 0.058 mol), 20 ml of hydrochloric acid and 100 ml of water were placed in a 500 ml round bottom flask, and the mixture was cooled to 0 ° C and stirred for 1 hour. At the same temperature, 50 ml of an aqueous solution of sodium nitrite (7.4 g, 0.116 mol) was added dropwise to the reaction solution, followed by stirring for 1 hour. When 100 ml of an aqueous solution of potassium iodide (30.0 g, 0.180 mol) was added dropwise, the temperature of the reaction solution was dropped so that the temperature did not exceed 5 ° C. After stirring for 5 hours at room temperature, the reaction mixture was washed with an aqueous solution of sodium cyanosulfate and extracted with ethyl acetate and water. The organic layer was separated and concentrated under reduced pressure, followed by column chromatography to obtain [intermediate 2-e] (9.1 g, 48%)

Synthesis of Synthesis Example 2- (6): [Intermediate 2-f]

                                         [Intermediate 2-f]

To a 250 mL round bottom flask was added methyl 5-bromo-2-iodobenzoate (9.3 g, 25 mmol), 4-dibenzoylboronic acid (8.3 g, 28 mmol), tetrakis (triphenylphosphine) palladium 0.6 g, 0.05 mmol) and potassium carbonate (6.7 g, 50 mmol) were added, and 50 mL of toluene, 50 mL of tetrahydrofuran and 20 mL of water were added. The temperature of the reactor was raised to 80 캜 and stirred for 10 hours. When the reaction was completed, the temperature of the reactor was lowered to room temperature, extracted with ethyl acetate, and the organic layer was separated. The organic layer was concentrated under reduced pressure and then separated by column chromatography to obtain [intermediate 2-f] (5.3 g, 52.3%).

Synthesis of Synthesis Example 2- (7): [Intermediate 2-g]

                                     [Intermediate 2-g]

Bromobenzene (25.5 g, 0.163 mol) and 170 ml of tetrahydrofuran were placed in a 500 ml round bottom flask and cooled to -78 캜 in a nitrogen atmosphere. N-Butyl lithium (1.6 M) (95.6 ml, 0.153 mol) was added dropwise to the reaction solution. After stirring at the same temperature for 1 hour, [intermediate 2-f] (20.0 g, 0.051 mol) was added, followed by stirring at room temperature for 3 hours. After completion of the reaction, 50 ml of water was added and stirred for 30 minutes. After extraction with ethyl acetate and water, the organic layer was separated and concentrated under reduced pressure. To the concentrated material were added 200 ml of acetic acid and 1 ml of hydrochloric acid, and the mixture was heated to 80 DEG C and stirred. After completion of the reaction, the reaction mixture was cooled to room temperature and the resulting solid was filtered. After washing with methanol, [intermediate 2-g] (20.0 g, 78%) was obtained.

Synthesis of Synthesis Example 2- (8): [Intermediate 2-h]

                         [Intermediate 2-h]

[Intermediate 2-h] (13.1 g, 50%) was obtained in the same manner as in [Intermediate 2-g] (20.0 g, 0.04 mol) in place of [Intermediate 1-c] in Synthesis Example 1- (4) .

Synthesis Example 2- (9): Synthesis of [Formula 40]

                                         (40)

(4-tert-butylphenyl) amine instead of bis-biphenyl-4-yl-amine was used in place of [Intermediate 1-d] in Synthesis Example 1- (5) Was synthesized in the same manner as above to obtain [Formula 40]. (Yield: 45%)

MS (MALDI-TOF): m / z 777.36 [M ^&lt; ⁺ &^gt;].

Synthesis Example 3: Synthesis of Compound (75)

Synthesis of Synthesis Example 3- (1): [Intermediate 3-a]

                              [Intermediate 3-a]

25 g (80 mmol) of [intermediate 1-a] is added to a round bottom flask containing 250 ml of tetrahydrofuran, and the temperature is lowered to -78 ° C under a nitrogen atmosphere. After 30 minutes, add 210 mL (240 mmol) of 1.0 M methylmagnesium bromide slowly dropwise. After 1 hour, it is slowly added dropwise and then the temperature is raised to room temperature. After stirring for about 2 hours at room temperature, ammonium chloride aqueous solution is added dropwise. After distillation under reduced pressure, the residue was recrystallized from a nucleic acid to obtain 19.4 g (yield: 80%) of [intermediate 3-a].

Synthesis of Synthesis Example 3- (2): [Intermediate 3-b]

                            [Intermediate 3-b]

20 g (66 mmol) of [intermediate 3-a] was added to a round bottom flask containing 300 ml of acetic acid and the mixture was stirred at 0 ° C for 10 minutes. Add 350 mL of phosphoric acid and stir at room temperature for about 1 hour. Neutralized with an aqueous solution of sodium hydroxide, extracted and concentrated under reduced pressure. The resultant product was separated by column chromatography to obtain 13.7 g (yield 73%) of [intermediate 3-b].

Synthesis of Synthesis Example 3- (3): [Intermediate 3-c]

                       [Intermediate 3-c]

[Intermediate 3-c] was obtained in the same manner as in [Intermediate 3-b] instead of [Intermediate 1-c] used in Synthesis Example 1- (4). (Yield: 45%)

Synthesis of Synthesis Example 3- (4): [Intermediate 3-d]

                              [Intermediate 3-d]

Dibenzylideneacetone dipalladium (3.9 g, 4 mmol), 2 (4-bromobenzylideneacetone) dipalladium in a 500 ml round- , 1,2'-bis (diphenylphosphine) -1,1'-binaphthyl (1.2 g, 4 mmol), sodium tertiary butoxide (41.3 g, 43 mmol) and toluene (200 ml) were placed and refluxed. The reaction mixture was cooled to room temperature, washed with methanol, and recrystallized from dichloromethane and methane to obtain [intermediate 3-d]. (50.5 g, 78%)

Synthesis Example 3- (5): Synthesis of [Formula 75]

                                   (75)

Intermediate 3-d was used instead of bis-biphenyl-4-yl-amine in place of [Intermediate 1-d] used in Synthesis Example 1- (5) (75). (Yield 67%)

MS (MALDI-TOF): m / z 583.29 [M ^&lt; ⁺ &^gt;].

Preparation Example of Dopant Compound

Synthesis Example 4: Synthesis of Compound 169

Synthesis of Synthesis Example 4- (1): [Intermediate 4-a]

                      [Intermediate 4-a]

(6.2 g, 0.050 mol), palladium acetate (0.22 g, 1 mmol), 2,2'-bis (trimethylsilyl) benzene (1.3 g, 2 mmol) and sodium tertiarybutoxide (12.2 g, 0.120 mol) were added to 100 mL of toluene and refluxed for 12 hours. After cooling to room temperature, the mixture was extracted with ethyl acetate and then separated by column chromatography to obtain [intermediate 4-a] (10.5 g, 78%).

Synthesis of Synthesis Example 4- (2): [Compound 169]

                                 [Compound 169]

(5.3 g, 0.055 mol), palladium acetate (0.1 g, 0.025 mol), and triethylamine 0.44 mmol) and triethyl tertiophosphine (0.36 g, 1.7 mmol) were added to 50 mL of toluene and refluxed for 24 hours. The mixture was cooled to room temperature, extracted with ethyl acetate, and then separated by column chromatography to obtain [Compound 169] (5.7 g, 70%).

MS (MALDI-TOF): m / z 736.37 [M ^&lt; ⁺ &^gt;].

Synthesis Example 5: Synthesis of Compound 203

Synthesis of Synthesis Example 5- (1): [Compound 203]

                                            [Compound 203]

A round bottom flask was charged with 10.7 g (26.7 mmol) of 5,9-dibromo-7,7-dimethyl-7H-benzofluorene, 5.2 g (26.7 mmol) 4- (phenylamino) benzonitrile, 0.7 g 0.4 g (0.7 mmol) of dibenzylideneacetone dipalladium, 6.5 g (66.9 mmol) of sodium tfutilate and 100 ml of toluene were placed in a nitrogen atmosphere and refluxed for 12 hours. After completion of the reaction, the reaction mixture was subjected to layer separation, and the organic layer was concentrated under reduced pressure, followed by separation by column chromatography to obtain 12.9 g of [Compound 203]. (Yield: 77%)

MS (MALDI-TOF): m / z 628.26 [M] ^&lt; ^{+ &}

Synthesis Example 6: Synthesis of Compound 226

Synthesis Example 6-1. Synthesis of [intermediate 6-a]

                                               [Intermediate 6-a]

24 g (112 mmol) of methyl 2-bromobenzoate, 34.7 g (0.156 mmol) of 9-phenanthreneboronic acid, 2.6 g (2 mmol) of tetrakistriphenylphosphine palladium and 30.9 g 223 mmol), 50 mL of water, 125 mL of toluene and 125 mL of tetrahydrofuran, and refluxed for 12 hours. After completion of the reaction, the reaction product was separated into layers. The organic layer was concentrated under reduced pressure, and then separated by column chromatography to obtain 25 g of [intermediate 6-a] (yield 72%).

Synthesis Example 6-2. [Synthesis of intermediate 6-b]

                               [Intermediate 6-b]

25 g (80 mmol) of [intermediate 6-a] is added to a round bottom flask containing 250 ml of tetrahydrofuran, and the temperature is lowered to -78 ° C under a nitrogen atmosphere. After 30 minutes, add 210 mL (240 mmol) of 1.0 M methylmagnesium bromide slowly dropwise. After 1 hour, it is slowly added dropwise and then the temperature is raised to room temperature. After stirring for about 2 hours at room temperature, ammonium chloride aqueous solution is added dropwise. Extracted, vacuum distilled and recrystallized from a nucleic acid to obtain 27 g (yield: 82%) of [intermediate 6-b].

Synthesis Example 6-3. [Synthesis of intermediate 6-c]

                          [Intermediate 6-c]

Add 29 g (66 mmol) of [intermediate 6-b] to a round bottom flask containing 290 ml of acetic acid. After raising the temperature to 80 ° C, add 1 ~ 2 drops of hydrochloric acid solution to the reaction solution. The reaction solution was refluxed for about 2 hours, the temperature was lowered to room temperature, and the resulting solid was filtered to obtain 26 g of [intermediate 6-c] (yield 93%).

Synthesis Example 6-4. Synthesis of [intermediate 6-d]

[Intermediate 6-d]

[Intermediate 6-c] (16.2 g, 0.055 mol) was added to 250 mL of dimethylformamide and stirred at 0 ° C. En-bromosuccinimide (21.5 g, 0.121 mol) was dissolved in 70 mL of dimethylformamide, and the mixture was stirred for 6 hours. The distilled water was filtered and washed with hexane. Dissolved in dichloromethane, heated and treated with acid clay and activated carbon. Washed with dichloromethane and recrystallized with hexane to obtain 19.1 g of [intermediate 6-d]. (Yield: 77%)

Synthesis Example 6-5. Synthesis of [Compound 226]

[Intermediate 6-d] was used in the place of 5,9-dibromo-7,7-dimethyl-7H-benzofluorene used in Synthesis Example 5-1, and N-phenyl -1-naphthylamine, the compound [226] was obtained. (70% yield)

MS (MALDI-TOF): m / z 728.32 [M] ^&lt; ^{+ &}

Synthesis Example 7: Synthesis of Compound 264

Synthesis Example 7-1. [Synthesis of intermediate 7-a]

                                [Intermediate 7-a]

N-Butyllithium (3.5 g, 12.2 mmol) was added to 50 mL of tetrahydrofuran, n-butyllithium (5.8 mL, 14.6 mmol) was added dropwise at -78 ° C, and the mixture was stirred for about 1 hour . 9-xanthone (2.1 g, 10.8 mmol) in tetrahydrofuran (10 mL) was slowly added dropwise at the same temperature, followed by stirring for 2 hours and then stirring at room temperature for 12 hours. The mixture was extracted with ethyl acetate and then recrystallized from diethyl ether to give 3.2 g (yield 75%) of Intermediate 7-a.

Synthesis Example 7-2. [Synthesis of intermediate 7-b]

                           [Intermediate 7-b]

[Intermediate 7-a] (26.5 g, 66.3 mmol) was added to 300 mL of acetic acid and the temperature was raised to 80 ° C. After 1-2 hours of aqueous hydrochloric acid solution was added, the mixture was refluxed for about 2 hours. The temperature was lowered to room temperature and then filtered to obtain 22.8 g (yield 90%) of Intermediate 7-b.

Synthesis Example 7-3. [Synthesis of intermediate 7-c]

                          [Intermediate 7-c]

[Intermediate 7-b] (21 g, 0.055 mol) was added to 250 mL of dimethylformamide and stirred at 0 ° C. En-bromosuccinimide (21.5 g, 0.121 mol) was dissolved in 70 mL of dimethylformamide, and the mixture was stirred for 6 hours. The distilled water was filtered and washed with hexane. Dissolved in dichloromethane, heated and treated with acid clay and activated carbon. Washed with dichloromethane, and recrystallized from hexane to obtain 17.8 g (yield: 60%) of [Intermediate 7-c].

Synthesis Example 7-4. Synthesis of [Compound 264]

[Intermediate 7-c] was used in the place of 5,9-dibromo-7,7-dimethyl-7H-benzofluorene used in Synthesis Example 5-1, and N-phenyl -4-biphenylamine, the compound [264] was obtained. (70% yield)

MS (MALDI-TOF): m / z 868.35 [M] ^&lt; ^{+ &}

Synthesis Example 8: Synthesis of Compound 281

Synthesis Example 8-1. [Synthesis of intermediate 8-a]

                                     [Intermediate 8-a]

(17.6 g, 0.061 mol), tetrakis (triphenylphosphine) palladium (3.62 g, 0.003 mol), carbonic acid Potassium (16.9 g, 0.122 mol) was added to 150 mL of 1,4-dioxane, 150 mL of toluene and 60 mL of distilled water and refluxed for 12 hours. The mixture was cooled to room temperature, extracted with ethyl acetate, and then separated by column chromatography to obtain 16.7 g (yield 82%) of [intermediate 8-a].

Synthesis Example 8-2. Synthesis of [Intermediate 8-b]

[Intermediate 8-b]

[Intermediate 8-a] was used instead of 1- (2-bromophenyl) naphthalene used in Synthesis Example 7-1 to give [Intermediate 8-b] . (Yield: 52%)

Synthesis Example 8-3. Synthesis of [Compound 281]

[Intermediate 8-b] was used instead of 5,9-dibromo-7,7-dimethyl-7H-benzofluorene used in Synthesis Example 5-1, and 4- Review Compound was synthesized in the same way except t-diphenylamine was used to obtain [Compound 281]. (70% yield)

MS (MALDI-TOF): m / z 878.42 [M] ^&lt; ^{+ &}

Synthesis Example 9: Synthesis of Compound 498

Synthesis Example 9- (1): Synthesis of [Intermediate 9-a]

                                 [Intermediate 9-a]

4-dibenzofuranboronic acid (85.0 g, 0.401 mol), bismuth (III) nitrate pentahydrate (99.2 g, 0.200 mol) and 400 ml of toluene were placed in a 1 L round bottom flask and stirred at 70 ° C for 3 hours. After completion of the reaction, the reaction mixture was cooled to room temperature and the resulting solid was filtered. After washing with toluene, [intermediate 9-a] (61.5 g, 72%) was obtained.

Synthesis Example 9- (2): Synthesis of [Intermediate 9-b]

                                [Intermediate 9-b]

A 2 L round bottom flask was charged with ethyl cyanoacetate (202.9 g, 1.794 mol) and dimethylformamide (500 mL). Potassium hydroxide (67.1 g, 1.196 mol) and potassium cyanide (38.95 g, 0.598 mol) were added, and 200 ml of dimethylformamide was added thereto, followed by stirring at room temperature. [Intermediate 9-a] (127.5 g, 0.737 mol) was gradually added to the reaction solution and stirred at 50 ° C for 72 hours. After completion of the reaction, 200 ml of an aqueous solution of sodium hydroxide (25%) was added and the mixture was stirred under reflux. After stirring for 3 hours, the mixture was cooled to room temperature and extracted with ethyl acetate and water. The organic layer was separated, concentrated under reduced pressure, and separated by column chromatography to obtain [intermediate 9-b] (20.0 g, 16%).

Synthesis Example 9- (3): Synthesis of [Intermediate 9-c]

                               [Intermediate 9-c]

(20.0 g, 0.096 mol), 600 ml of ethanol and 170 ml of an aqueous solution of potassium hydroxide (142.26 g, 2.53 mol) were placed in a 2 L round bottom flask, and the mixture was refluxed and stirred for 12 hours. When the reaction was completed, the reaction solution was cooled to room temperature. To the reaction solution, 400 ml of 6 N hydrochloric acid was added and acidified. The resulting solid was stirred for 20 minutes and then filtered. The solid was washed with ethanol and then [intermediate 9-c] (17.0 g, 88.5%) was obtained.

Synthesis Example 9- (4): Synthesis of [Intermediate 9-d]

                                   [Intermediate 9-d]

[Intermediate 9-c] (17.0 g, 0.075 mol) and 15 ml of sulfuric acid were placed in a 2 L round-bottomed flask and refluxed for 72 hours. After completion of the reaction, the reaction mixture was cooled to room temperature and extracted with ethyl acetate and water. The organic layer was separated and washed with aqueous sodium hydrogencarbonate solution. The organic layer was concentrated under reduced pressure and methanol was added in an excess amount, and the resultant solid was filtered to obtain [intermediate 9-d] (14.0 g, 77.6%).

Synthesis Example 9- (5): Synthesis of [Intermediate 9-e]

                                 [Intermediate 9-e]

[Intermediate 9-d] (14.0 g, 0.058 mol), 20 ml of hydrochloric acid and 100 ml of water were placed in a 500 ml round bottom flask, and the mixture was cooled to 0 ° C and stirred for 1 hour. At the same temperature, 50 ml of an aqueous solution of sodium nitrite (7.4 g, 0.116 mol) was added dropwise to the reaction solution, followed by stirring for 1 hour. When 100 ml of an aqueous solution of potassium iodide (30.0 g, 0.180 mol) was added dropwise, the temperature of the reaction solution was dropped so that the temperature did not exceed 5 ° C. After stirring for 5 hours at room temperature, the reaction mixture was washed with an aqueous solution of sodium cyanosulfate and extracted with ethyl acetate and water. The organic layer was separated and concentrated under reduced pressure, followed by separation by column chromatography to obtain [intermediate 9-e] (9.1 g, 48%)

Synthesis Example 9- (6): Synthesis of [Intermediate 9-f]

                                      [Intermediate 9-f]

(9.3 g, 25 mmol), 1-dibenzofuranboronic acid (8.3 g, 28 mmol) and tetrakis (triphenylphosphine) palladium (0.6 g, 0.05 mmol) were added to a 250 mL round bottom flask. ) And potassium carbonate (6.7 g, 50 mmol) were placed, and 50 mL of toluene, 50 mL of tetrahydrofuran, and 20 mL of water were added. The temperature of the reactor was raised to 80 캜 and stirred for 10 hours. When the reaction was completed, the temperature of the reactor was lowered to room temperature, extracted with ethyl acetate, and the organic layer was separated. The organic layer was concentrated under reduced pressure and then separated by column chromatography to obtain [intermediate 9-f] (5.3 g, 52.3%).

Synthesis Example 9- (7): Synthesis of [Intermediate 9-g]

                         [Intermediate 9-g]

[Intermediate 9-f] (5.3 g, 15 mmol), sodium hydroxide (0.7 g, 17 mmol) and ethanol (50 ml) were placed in a 100 mL round bottom flask and refluxed for 48 hours. The resulting solid, which was acidified by dropwise addition of 2-N hydrochloric acid to the solution cooled to room temperature, was stirred for 30 minutes and then filtered. Recrystallization from dichloromethane and hexane gave [intermediate 9-g] (4.5 g, 88.0%).

Synthesis Example 9- (8): Synthesis of [Intermediate 9-h]

                         [Intermediate 9-h]

[Intermediate 9-g] (4.5 g, 12 mmol) and methanesulfonic acid (30 ml) were placed in a 100 ml round bottom flask, and the mixture was heated to 80 ° C and stirred for 3 hours. After cooling to room temperature, the reaction solution was slowly added dropwise to 50 ml of ice water, followed by stirring for 30 minutes. The resulting solid was filtered and washed with water and methanol to give [intermediate 9-h] (3.8 g, 88.8%).

Synthesis Example 9- (9): Synthesis of [Intermediate 9-i]

                          [Intermediate 9-i]

[Intermediate 9-h] (3.8 g, 11 mmol) and 40 ml of dichloromethane were placed in a 100 mL round-bottomed flask and stirred at room temperature. Bromine (1.1 ml, 22 mmol) was added dropwise to 10 ml of dichloromethane, and the mixture was stirred at room temperature for 8 hours. After completion of the reaction, 20 ml of acetone was added to the reaction vessel and stirred. The resulting solid was filtered and washed with acetone. The solid was recrystallized from monochlorobenzene to give [intermediate 9-i] (3.0 g, 55%).

Synthesis Example 9- (10): Synthesis of [Intermediate 9-j]

                                        [Intermediate 9-j]

2-bromobiphenyl (2.1 g, 0.009 mol) and 30 ml of tetrahydrofuran were placed in a 100 ml round bottom flask and cooled to -78 캜 in a nitrogen atmosphere. N-butyl lithium (4.8 ml, 0.008 mol) was added dropwise at the same temperature to the cooled reaction solution. The reaction solution was stirred for 2 hours, then [Intermediate 9-i] (3.0 g, 0.006 mol) was added little by little and stirred at room temperature. The reaction was completed by adding 10 ml of H 2 O and extracted with ethyl acetate and water. The organic layer was separated, concentrated under reduced pressure, and then recrystallized from acetonitrile to obtain [intermediate 9-j] (2.5 g, 64%).

Synthesis Example 9- (11): Synthesis of [Intermediate 9-k]

                             [Intermediate 9-k]

[Intermediate 9-j] (2.5 g, 0.04 mol), 25 ml of acetic acid and 0.5 ml of sulfuric acid were placed in a 100 ml round-bottomed flask, and the mixture was refluxed with stirring for 5 hours. When a solid was formed, the reaction was terminated by thin film chromatography and then cooled to room temperature. The resulting solid was filtered, washed with H2O and methanol, dissolved in monochlorobenzene, filtered through silica gel, concentrated and then cooled to room temperature to obtain [intermediate 9-k] (2.2 g, 90%).

Synthesis Example 9- (12): Synthesis of [Compound 498]

                                           [Compound 498]

(2.2 g, 0.003 mol), bis (4-tert-butylphenyl) amine (2.3 g, 0.008 mol) and palladium (II) acetate (0.04 g, 0.2 mmol) were added to a 100 ml round- , Sodium tertiary butoxide (1.6 g, 0.016 mol), triturated butyl phosphine (0.04 g, 0.2 mmol) and toluene (30 ml) were added and the mixture was stirred under reflux for 2 hours. After completion of the reaction, the reaction solution was cooled to room temperature. The reaction solution was extracted with dichloromethane and water. The organic layer was separated, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure. After separation by column chromatography, recrystallization from dichloromethane and acetone gave [Compound 498] (1.4 g, 43%).

MS (MALDI-TOF): m / z 1054.54 [M ^&lt; ⁺ &^gt;].

Synthesis Example 10: Synthesis of Compound 631

Synthesis Example 10- (1): Synthesis of [intermediate 10-a]

                                   [Intermediate 10-a]

Bromobenzene (25.5 g, 0.163 mol) and 170 ml of tetrahydrofuran were placed in a 500 ml round bottom flask and cooled to -78 캜 in a nitrogen atmosphere. Butyllithium (1.6 M) (95.6 ml, 0.153 mol) was added dropwise to the cooled reaction solution. After stirring at the same temperature for 1 hour, [intermediate 9-f] (20.0 g, 0.051 mol) was added and stirred at room temperature for 3 hours. After completion of the reaction, 50 ml of water was added and stirred for 30 minutes. After extraction with ethyl acetate and water, the organic layer was separated and concentrated under reduced pressure. Acetic acid (200 ml) and hydrochloric acid (1 ml) were added to the concentrated material, and the mixture was stirred at 80 占 폚. After completion of the reaction, the reaction mixture was filtered at room temperature and washed with methanol to obtain [intermediate 10-a] (20.0 g, 78%).

Synthesis of Synthesis Example 10- (2): [Intermediate 10-b]

                        [Intermediate 10-b]

[Intermediate 10-a] (20 g, 58 mmol) and 40 ml of dichloromethane were placed in a 100 mL round bottom flask, and the mixture was stirred at room temperature. Bromine (5.8 ml, 116 mmol) was added dropwise to 10 ml of dichloromethane, and the mixture was stirred at room temperature for 8 hours. After completion of the reaction, 20 ml of acetone was added to the reaction vessel and stirred. The resulting solid was filtered and washed with acetone. And recrystallized with monochlorobenzene to obtain [intermediate 10-b] (15.8 g, 55%).

Synthesis Example 10- (3): Synthesis of [Compound 631]

                                         [Compound 631]

(4.0 g, 0.006 mol), di-p-tolylamine (3.2 g, 0.016 mol), palladium (II) acetate (0.08 g, 0.4 mmol), sodium tertiary Butoxide (3.2 g, 0.032 mol), triturated butylphosphine (0.08 g, 0.4 mmol) and toluene (50 ml) were added and the mixture was stirred under reflux for 2 hours. After completion of the reaction, the reaction solution was cooled to room temperature. The reaction solution was extracted with dichloromethane and water. The organic layer was separated, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure. The separated and purified by column chromatography, and then recrystallized from dichloromethane and acetone to obtain [Compound 631] (2.1 g, 41%).

MS (MALDI-TOF): m / z 888.37 [M ^&lt; ⁺ &^gt;].

Example of synthesis of hole transport layer compound

Synthesis Example 11 Synthesis of Chemical Formula 2

Synthesis Example 11- (1): Synthesis of [intermediate 11-a]

                                     [Intermediate 11-a]

To a 500 mL round bottom flask was added methyl 2-iodobenzoate (19.1 g, 73 mmol), 4-dibenzofuranboronic acid (18.7 g, 88 mmol), tetrakis (triphenylphosphine) palladium mmol) and potassium carbonate (20.2 g, 146.7 mmol) were added, and 125 mL of toluene, 125 mL of tetrahydrofuran, and 50 mL of water were added. The temperature of the reactor was raised to 80 캜 and stirred for 10 hours. When the reaction was completed, the temperature of the reactor was lowered to room temperature, extracted with ethyl acetate, and the organic layer was separated. The organic layer was concentrated under reduced pressure and then separated by column chromatography to obtain [intermediate 11-a]. (9.5 g, 43%).

Synthesis of Synthesis Example 11- (2): [Intermediate 11-b]

                               [Intermediate 11-b]

[Intermediate 11-a] (13.6 g, 45 mmol), sodium hydroxide (2.14 g, 54 mmol) and ethanol (170 ml) were placed in a 500 mL round bottom flask and refluxed for 48 hours. The reaction was terminated by thin film chromatography and then cooled to room temperature. 2-N HCl was added dropwise to the cooled solution, and the resulting solid was stirred for 30 minutes and filtered. Recrystallization from dichloromethane and n-hexane gave [intermediate 11-b]. (11.4 g, 88%).

Synthesis of Synthesis Example 11- (3): [Intermediate 11-c]

                            [Intermediate 11-c]

[Intermediate 11-b] (11.2 g, 39 mmol) and 145 ml of methanesulfonic acid were placed in a 250 ml round-bottomed flask, and the mixture was heated to 80 ° C and stirred for 3 hours. The reaction was terminated by thin film chromatography and then cooled to room temperature. The reaction solution was slowly added dropwise to 150 ml of ice water and then stirred for 30 minutes. The resulting solid was filtered and washed with water and methanol to give [intermediate 11-c]. (8.7 g, 83%)

Synthesis Example 11- (4): Synthesis of [Intermediate 11-d]

                               [Intermediate 11-d]

[Intermediate 11-c] (8.6 g, 32 mmol) and 300 ml of dichloromethane were placed in a 1 L round bottom flask, and the mixture was stirred at room temperature. Bromine (3.4 ml, 66 mmol) was added dropwise to 50 ml of dichloromethane, and the mixture was stirred at room temperature for 8 hours. After completion of the reaction, 100 ml of acetone was added to the reaction vessel and stirred. The resulting solid was filtered and washed with acetone. The solid was recrystallized from monochlorobenzene to give [intermediate 11-d]. (8.7 g, 78%)

Synthesis Example 11- (5): Synthesis of [Intermediate 11-e]

                                       [Intermediate 11-e]

2-bromobiphenyl (8.4 g, 0.036 mol) and 110 ml of tetrahydrofuran were placed in a 250 ml round bottom flask and cooled to -78 캜 in a nitrogen atmosphere. N-butyl lithium (19.3 ml, 0.031 mol) was added dropwise to the cooled reaction solution at the same temperature. The reaction solution was stirred for 2 hours, then [Intermediate 11-d] (8.4 g, 0.024 mol) was added little by little and stirred at room temperature. When the color of the reaction solution changed, the reaction was terminated by TLC. The reaction was completed by adding 50 ml of water and extracted with ethyl acetate and water. The organic layer was separated, concentrated under reduced pressure, and then recrystallized from acetonitrile to obtain [intermediate 11-e]. (9.9 g, 82%).

Synthesis of Synthesis Example 11- (6): [Intermediate 11-f]

                          [Intermediate 11-f]

[Intermediate 11-e] (9.6 g, 0.019 mol), acetic acid (120 ml) and sulfuric acid (2 ml) were placed in a 250 ml round-bottomed flask and refluxed for 5 hours. When a solid was formed, the reaction was terminated by thin film chromatography and then cooled to room temperature. The resulting solid was filtered, washed with water and methanol, dissolved in monochlorobenzene, filtered through silica gel, concentrated and then cooled to room temperature to obtain [intermediate 11-f]. (8.3 g, 90% &gt;

Synthesis Example 11- (7): Synthesis of [Formula 2]

[Intermediate 11-f] [Chemical Formula 2]

(4.4 g, 0.009 mol), (4-tert-butylphenyl) -phenylamine (4.7 g, 0.021 mol) and palladium (II) acetate (0.08 g, 0.4 mmol) in a 250 ml round bottom flask ), Sodium tertiary butoxide (3.4 g, 0.035 mol), triturated butylphosphine (0.07 g, 0.4 mmol) and toluene (60 ml) were added and the mixture was stirred under reflux for 2 hours. After completion of the reaction, the reaction solution was cooled to room temperature. The reaction solution was extracted with dichloromethane and water. The organic layer was separated, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure. The crude product was purified by column chromatography and then recrystallized from dichloromethane and acetone to obtain the compound of formula (2). (3.3 g, 58%).

MS (MALDI-TOF): m / z 629.27 [M ^&lt; ⁺ &^gt;].

Synthesis Example 12 Synthesis of Compound (87)

Synthesis Example 12- (1): Synthesis of [intermediate 12-a]

[Intermediate 12-a]

(1) and Synthesis Example 3 (2) were repeated using (6-phenyldibenzo [b, d] furan-4-yl) boronic acid instead of 4-dibenzofuranboronic acid used in Synthesis Example 11- - (1) to 3- (3) to obtain [intermediate 12-a]. (Yield: 48%)

Synthesis Example 12- (2). [Synthesis of intermediate 12-b]

Synthesis was conducted in the same manner as in Synthesis Example 3- (4) except that aniline was used in place of 4-tertiary butylaniline and 2-bromo-9,9-dimethylfluorene was used instead of 4-bromobiphenyl [Intermediate 12-b] was obtained. (Yield: 75%)

Synthesis Example 12- (3). Synthesis of [Formula 87]

[Intermediate 12-b] instead of bis-biphenyl-4-yl-amine was used in place of [Intermediate 12-a] used in Synthesis Example 1- (5) (87). (Yield 69%)

MS (MALDI-TOF): m / z 643.29 [M ^&lt; ⁺ &^gt;].

Synthesis Example 13: Synthesis of Formula 146

Synthesis of Synthesis Example 13- (1): [Intermediate 13-a]

[Intermediate 13-a]

Synthesis Example 11- (1), Synthesis Example 1- (1) to 1- (3) and Synthesis Example 11- (1) were repeated using 4-dibenzothiophene boronic acid instead of 4-dibenzofuranboronic acid used in Synthesis Example 11- Synthesis was conducted in the same manner as in [Intermediate 13-a]. (Yield: 68%)

Synthesis Example 13- (2): Synthesis of [Intermediate 13-b]

                                   [Intermediate 13-b]

(10.0 g, 0.035 mol), 4-tertiarybutyl aniline (5.8 g, 0.039 mol), tris (dibenzylideneacetone) di (0.65 g, 0.0007 mol), sodium tertiary butoxide (6.79 g, 0.0706 mol), 2,2'-bis (diphenylphosphino) -1,1'-binaphthalene (0.44 g, 0.0007 mol) mol) toluene (100 ml) was added and the mixture was refluxed and stirred for 3 hours. After completion of the reaction, the reaction mixture was cooled to room temperature and extracted with ethyl acetate and water. The organic layer was separated, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure. The intermediate was separated by column chromatography to obtain [intermediate 13-b] (10 g, 80%).

Synthesis Example 13- (3): Synthesis of [Formula 146]

[Intermediate 13-b] instead of bis-biphenyl-4-yl-amine was used instead of [intermediate 13-a] used in Synthesis Example 1- (5) (146). (Yield: 48%)

MS (MALDI-TOF): m / z 773.31 [M ⁺ ] &^lt;

Examples 1 to 24: Preparation of organic light emitting device

The ITO glass was patterned to have a light emitting area of 2 mm x 2 mm and then cleaned. After mounting the ITO glass in the vacuum chamber base pressure is 1 × 10 ^{- 6} torr and then so that the film formed by the ITO on DNTPD (700 Å), a compound (300 Å) shown in Table 1 in order. Subsequently, a film (250 Å) was formed by mixing [BH] as a host as a luminescent layer and 3 wt% of a compound as a dopant as shown in the following Table 1, and then , as an electron transport layer, [E-1] and [E- (E-1) was deposited to a thickness of 5 Å and Al (1000 Å) in this order to form an organic light emitting device. The characteristics of the organic light emitting device were measured at 0.4 mA.

[DNTPD] [BH]

[Formula E-1] [Formula E-2]

Comparative Examples 1 to 8

In place of the hole transport layer compounds used in Examples 1 to 24, organic light emitting devices were fabricated in the same manner as the organic light emitting devices except that the following <HT> used as a hole transport compound in the prior art was used. The results are shown in Table 1. The structure of <HT> is as follows.

[HT]

division Hole transport compound Dopant CIEx CIEy Cd / A lambda max Example 1 Formula 13 Compound 161 0.1327 0.1189 11.09 459 Example 2 Compound 169 0.1327 0.1191 11.37 460 Example 3 Compound 203 0.1414 0.1195 10.04 450 Example 4 Compound 226 0.1415 0.1194 10.21 450 Example 5 Compound 264 0.1364 0.1292 10.83 457 Example 6 Compound 281 0.1365 0.1295 11.13 457 Example 7 Compound 498 0.1367 0.1117 10.58 456 Example 8 Compound 631 0.1361 0.1093 10.37 456 Example 9 40 Compound 161 0.1327 0.1189 10.98 459 Example 10 Compound 169 0.1326 0.1188 11.12 459 Example 11 Compound 203 0.1414 0.1196 9.98 450 Example 12 Compound 226 0.1413 0.1196 10.18 450 Example 13 Compound 264 0.1363 0.1294 10.76 457 Example 14 Compound 281 0.1365 0.1293 10.88 457 Example 15 Compound 498 0.1366 0.1114 10.46 456 Example 16 Compound 631 0.1361 0.1111 10.35 456 Example 17 75 Compound 161 0.1327 0.1190 11.18 459 Example 18 Compound 169 0.1326 0.1187 11.41 459 Example 19 Compound 203 0.1413 0.1194 10.14 450 Example 20 Compound 226 0.1412 0.1197 10.34 450 Example 21 Compound 264 0.1364 0.1294 11.08 457 Example 22 Compound 281 0.1364 0.1294 11.22 457 Example 23 Compound 498 0.1365 0.1116 10.95 456 Example 24 Compound 631 0.1361 0.1110 10.52 456 Comparative Example 1 HT Compound 161 0.1327 0.1188 9.78 459 Comparative Example 2 Compound 169 0.1326 0.1187 9.83 459 Comparative Example 3 Compound 203 0.1413 0.1195 8.99 450 Comparative Example 4 Compound 226 0.1413 0.1197 9.18 450 Comparative Example 5 Compound 264 0.1363 0.1294 9.99 457 Comparative Example 6 Compound 281 0.1364 0.1294 10.02 457 Comparative Example 7 Compound 498 0.1365 0.1118 9.21 456 Comparative Example 8 Compound 631 0.1358 0.1110 8.66 456

As shown in Table 1, the organic light emitting diode according to the present invention exhibits a higher luminous efficiency than that of HT, which is widely used as a hole transport layer material, and has application potential as an organic light emitting device having improved characteristics.

Claims (21)

A first electrode;
A second electrode facing the first electrode;
A hole injection layer or a hole transport layer interposed between the first electrode and the second electrode; and a light emitting layer,
Wherein the hole injection layer or the hole transport layer comprises at least one amine compound represented by the following formula (A) or (B); Wherein the light emitting layer comprises at least one compound represented by any one of the following formulas (D1) to (D5).
(A)

[Chemical Formula B]

In the above formulas (A) and (B)
A1, A2, E and F are the same or different and independently of one another are a substituted or unsubstituted aromatic hydrocarbon ring having 6 to 50 carbon atoms or a substituted or unsubstituted aromatic heterocycle having 2 to 40 carbon atoms;
Two carbon atoms adjacent to each other in the aromatic ring of A1 and two carbon atoms adjacent to each other in the aromatic ring of A2 form a condensed ring by forming a 5-membered ring with carbon atoms connected to the substituents R1 and R2;
The linking groups L1 to L6 are the same or different from each other and each independently represents a single bond, a substituted or unsubstituted alkylene group having 1 to 60 carbon atoms, a substituted or unsubstituted alkenylene group having 2 to 60 carbon atoms, A substituted or unsubstituted C2-C60 alkynylene group, a substituted or unsubstituted C3-C60 cycloalkylene group, a substituted or unsubstituted C2-C60 heterocycloalkylene group, a substituted or unsubstituted C6-C60 aryl Or a substituted or unsubstituted heteroarylene group having 2 to 60 carbon atoms;
M is any one selected from NR ₃ , CR ₄ R ₅ , SiR ₆ R ₇ , GeR ₈ R ₉ , O, S, Se;
The substituents R 1 to R 9 and Ar 1 to Ar 4 are the same or different from each other and each independently represent hydrogen, deuterium, a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted aryl group having 6 to 50 carbon atoms, Or a substituted or unsubstituted C 2 -C 30 alkenyl group, a substituted or unsubstituted C 2 -C 20 alkynyl group, a substituted or unsubstituted C 3 -C 30 cycloalkyl group, a substituted or unsubstituted C 5 -C 30 cycloalkene A substituted or unsubstituted C2-C30 hetero aryl group, a substituted or unsubstituted C2-C30 heterocycloalkyl group, a substituted or unsubstituted C1-C30 alkoxy group, a substituted or unsubstituted C6- A substituted or unsubstituted C1-C30 alkylthio group, a substituted or unsubstituted C6-C30 arylthio group, a substituted or unsubstituted C1-C30 alkylthio group, a substituted or unsubstituted C6-C30 arylthio group, A substituted or unsubstituted arylamine group having 6 to 30 carbon atoms, a substituted or unsubstituted alkylsilyl group having 1 to 30 carbon atoms, a substituted or unsubstituted arylsilyl group having 6 to 30 carbon atoms , A substituted or unsubstituted alkylgermanium group having 1 to 30 carbon atoms, a substituted or unsubstituted arylgermanium group having 1 to 30 carbon atoms, a cyano group, a nitro group, and a halogen group,
The carbon atoms of the formed alicyclic or aromatic monocyclic or polycyclic ring may be one of N, O, P, Si, S, Ge , Se, and Te;
Each of p1 and p2, r1 and r2, s1 and s2 is an integer of 1 to 3, and when each of them is 2 or more, each of the linking groups L1 to L6 is the same or different from each other,
Ar1 and Ar2 may be linked to each other to form a ring, and Ar3 and Ar4 may be linked to each other to form a ring;
X and y are integers of 0 or 1, provided that x + y = 1,
In the formula (A), two carbon atoms adjacent to each other in the A2 ring are bonded to * in the formula (Q1) to form a condensed ring,
In the formula (B), two carbon atoms adjacent to each other in the A1 ring are bonded to * in the formula (Q2) to form a condensed ring, and two carbon atoms adjacent to each other in the A2 ring are bonded to * in the formula (Q1) .

&Lt; RTI ID =

In formula (D1), A ₁₁ to A ₁₄ are the same or different and each independently represent a substituted or unsubstituted aryl group having 6 to 24 carbon atoms or a substituted or unsubstituted heteroaryl group having 2 to 24 carbon atoms ,
R ₁₀ represents hydrogen, deuterium, a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 30 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 30 carbon atoms, A substituted or unsubstituted alkoxy group having 1 to 30 carbon atoms, a substituted or unsubstituted aryloxy group having 6 to 30 carbon atoms, a substituted or unsubstituted alkylthio group having 1 to 30 carbon atoms, A substituted or unsubstituted C1 to C30 alkylamine group, a substituted or unsubstituted C6 to C30 arylamine group, a substituted or unsubstituted C6 to C30 aryloxy group, A heteroaryl group having 2 to 50 carbon atoms having a substituted or unsubstituted heteroatom, O, N or S, an amino group, a nitrile group, a hydroxyl group, a nitro group and a halogen group Which is selected,
n1 is and each R ₁₀ is the same as or different from each other are an integer of 1 to 8, in which the n1 2 or more,
The carbon of the pyrene ring which is not substituted with R10 is bonded to hydrogen or deuterium.

[Chemical formula D2]

In the above formula (D2)
Z ₁ is any of a substituted or unsubstituted aromatic hydrocarbon ring having 6 to 30 carbon atoms, a substituted or unsubstituted aromatic heterocyclic ring having 2 to 20 carbon atoms having O, N or S as a hetero atom,
The substituents R ₁₁ to R ₁₆ are the same or different from each other and independently represent hydrogen, deuterium, a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted aryl group having 6 to 50 carbon atoms, A substituted or unsubstituted C2-C20 alkynyl group, a substituted or unsubstituted C2-C20 alkynyl group, a substituted or unsubstituted C3-C30 cycloalkyl group, a substituted or unsubstituted heteroatom, O, N, S A substituted or unsubstituted C1-C30 alkoxy group, a substituted or unsubstituted C6-C30 aryloxy group, a substituted or unsubstituted C1-C30 alkyl group having 1 to 30 carbon atoms, A substituted or unsubstituted aryloxy group having 6 to 30 carbon atoms, a substituted or unsubstituted alkylamine group having 1 to 30 carbon atoms, a substituted or unsubstituted aryloxy group having 6 to 30 carbon atoms A substituted or unsubstituted alkylsilyl group having 1 to 30 carbon atoms, a substituted or unsubstituted arylsilyl group having 6 to 30 carbon atoms, a cyano group, a nitro group, a hydroxyl group and a halogen group , Any one of the substituents R ₁₃ to R ₁₆ is a single bond to be bonded to the linking group L _{11 to} be connected to the formula Q ₃ ,
Structure Q3 Q3 is connected to the structural formula and the substituents R ₁₃ to 6-membered ring that is associated with R ₁₆ being connected to the Z1 ring are the same or different in each occurrence,
The substituents R ₁₁ and R ₁₂ may be connected to each other to form a ring,
The substituents R ₁₃ to R ₁₆ may be connected to adjacent substituents to form a substituted or aromatic monocyclic or polycyclic ring, and the carbon atoms of the formed alicyclic or aromatic monocyclic or polycyclic ring may be N, S , And O, and R &lt; 2 &gt;
The two carbon atoms adjacent to each other in Z 1 together with the carbon atoms connected to the substituents R 11 and R 12 form a 5-membered ring to form a condensed ring,
A carbon atom not forming a 5-membered ring in the aromatic ring of Z1 is bonded to a linking group L11 in Q3,
The linking group L11 is a single bond or a substituted or unsubstituted alkylene group having 1 to 60 carbon atoms, a substituted or unsubstituted alkenylene group having 2 to 60 carbon atoms, a substituted or unsubstituted alkynylene group having 2 to 60 carbon atoms, a substituted Or a substituted or unsubstituted C2-C60 heterocycloalkylene group, a substituted or unsubstituted C6-C60 arylene group, or a substituted or unsubstituted C2-C60 arylene group, A heteroarylene group of 1 to 6 carbon atoms;
n2 is an integer of 0 to 2, and when n2 is 2, each of the linking groups L11 is the same or different from each other,
The substituents Ar ₁₁ and Ar ₁₂ are the same or different and each independently represents a substituted or unsubstituted aryl group having 6 to 40 carbon atoms, a substituted or unsubstituted heteroaryl group having 2 to 30 carbon atoms, a substituted or unsubstituted carbon number A substituted or unsubstituted alkyl group having 1 to 40 carbon atoms, and a substituted or unsubstituted cycloalkyl group having 3 to 30 carbon atoms.

[Chemical formula D3]

In the above formula (D3)
X is a single bond, any one selected from CR ₁₈ R ₁₉ , NR ₂₈ , O, S and SiR ₂₉ R ₃₀ ,
Z ₂ and Z ₃ are the same or different and each independently represent a substituted or unsubstituted aromatic hydrocarbon ring having 6 to 30 carbon atoms, a substituted or unsubstituted aromatic heteroaromatic having 2 to 20 carbon atoms having O, N or S, A ring, and a ring,
Two carbon atoms adjacent to each other in Z2 and two adjacent carbon atoms in Z3 form a 5-membered ring to form a condensed ring,
The substituents R ₁₈ to R ₃₀ are the same or different and are each independently selected from the group consisting of hydrogen, deuterium, a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted aryl group having 6 to 50 carbon atoms, A substituted or unsubstituted C2-C20 alkynyl group, a substituted or unsubstituted C2-C20 alkynyl group, a substituted or unsubstituted C3-C30 cycloalkyl group, a substituted or unsubstituted heteroatom, O, N, S A substituted or unsubstituted C1-C30 alkoxy group, a substituted or unsubstituted C6-C30 aryloxy group, a substituted or unsubstituted C1-C30 alkyl group having 1 to 30 carbon atoms, A substituted or unsubstituted aryloxy group having 6 to 30 carbon atoms, a substituted or unsubstituted alkylamine group having 1 to 30 carbon atoms, a substituted or unsubstituted aryloxy group having 6 to 30 carbon atoms A substituted or unsubstituted alkylsilyl group having 1 to 30 carbon atoms, a substituted or unsubstituted arylsilyl group having 6 to 30 carbon atoms, a cyano group, a nitro group, a hydroxyl group, and a halogen group ,
The carbon atoms of the alicyclic or aromatic monocyclic or polycyclic ring formed may be N, S, or S, and R &lt; ₂₀ &gt; to R &lt; ₂₇ &gt; O, &lt; / RTI &gt;&lt; RTI ID = 0.0 &gt;
Wherein A21 and A22 are the same or different and independently of each other are represented by the following formula [Q4]
[Structural formula Q4]

In the above formula (Q4)
* Means a binding site in which the linking group L ₁₂ in Q4 is bonded to a carbon atom which does not form a 5-membered ring in the aromatic ring of Z2 or Z3 in the above formula [D3]
The linking group L ₁₂ is a single bond or a substituted or unsubstituted alkylene group having 1 to 60 carbon atoms, a substituted or unsubstituted alkenylene group having 2 to 60 carbon atoms, a substituted or unsubstituted alkynylene group having 2 to 60 carbon atoms, A substituted or unsubstituted cycloalkylene group having 3 to 60 carbon atoms, a substituted or unsubstituted heterocycloalkylene group having 2 to 60 carbon atoms, a substituted or unsubstituted arylene group having 6 to 60 carbon atoms, or a substituted or unsubstituted C2- A heteroarylene group having 1 to 60 carbon atoms;
n3 is an integer from 0 to 2, and n3 if a is 2, each of the linking group L ₁₂ are the same or different from each other,
Wherein said substituting groups Ar ₁₃ and Ar ₁₄ are the same or different and each independently represent a substituted or unsubstituted aryl group having 6 to 40 carbon atoms, a substituted or unsubstituted heteroaryl group having 2 to 30 carbon atoms, a substituted or unsubstituted An alkyl group having 1 to 40 carbon atoms, and a substituted or unsubstituted cycloalkyl group having 3 to 30 carbon atoms.

[Chemical formula D4]

[Chemical formula D5]

In the above formulas [D4] and [D5]
A ₃₁ , A ₃₂ , E 1 and F 1 are the same or different and each independently represent a substituted or unsubstituted aromatic hydrocarbon ring having 6 to 50 carbon atoms or a substituted or unsubstituted aromatic heterocycle having 2 to 40 carbon atoms;
Two carbon atoms adjacent to each other in the aromatic ring of A ₃₁ and two carbon atoms adjacent to each other in the aromatic ring of A ₃₂ form a 5-membered ring with the carbon atoms connected to the substituents R ₃₁ and R ₃₂ , &Lt; / RTI &gt;
The linking groups L ₂₁ to L ₃₂ are the same or different and each independently represents a single bond, a substituted or unsubstituted alkylene group having 1 to 60 carbon atoms, a substituted or unsubstituted alkenylene group having 2 to 60 carbon atoms, A substituted or unsubstituted cycloalkylene group having 3 to 60 carbon atoms, a substituted or unsubstituted heterocycloalkylene group having 2 to 60 carbon atoms, a substituted or unsubstituted C2 to C60 alkynylene group having 6 to 60 carbon atoms, An arylene group or a substituted or unsubstituted heteroarylene group having 2 to 60 carbon atoms;
W is any one selected from NR ₃₃ , CR ₃₄ R ₃₅ , SiR ₃₆ R ₃₇ , GeR ₃₈ R ₃₉ , O, S and Se;
The substituents R ₃₁ to R ₃₉ and Ar ₂₁ to Ar ₂₈ are the same or different and are each independently selected from the group consisting of hydrogen, deuterium, a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted aryl group having 6 to 50 carbon atoms A substituted or unsubstituted C2-C30 alkenyl group, a substituted or unsubstituted C2-C20 alkynyl group, a substituted or unsubstituted C3-C30 cycloalkyl group, a substituted or unsubstituted C2-C30 alkenyl group, A substituted or unsubstituted C2-C30 hetero aryl group, a substituted or unsubstituted C2-C30 heterocycloalkyl group, a substituted or unsubstituted C1-C30 alkoxy group, a substituted or unsubstituted C1-C30 alkoxy group, A substituted or unsubstituted alkylthio group having 1 to 30 carbon atoms, a substituted or unsubstituted arylthioxy group having 5 to 30 carbon atoms, a substituted or unsubstituted arylthio group having 6 to 30 carbon atoms, An alkylamine group having 1 to 30 carbon atoms, a substituted or unsubstituted arylamine group having 5 to 30 carbon atoms, a substituted or unsubstituted alkylsilyl group having 1 to 30 carbon atoms, a substituted or unsubstituted arylsilyl group having 5 to 30 carbon atoms , A substituted or unsubstituted alkylgermanium group having 1 to 30 carbon atoms, a substituted or unsubstituted arylgermanium group having 1 to 30 carbon atoms, a cyano group, a nitro group, and a halogen group,
R ₃₁ and R ₃₂ may be connected to form a single alicyclic or aromatic ring or polycyclic ring, and the carbon atom of the alicyclic or aromatic monocyclic or polycyclic ring may be N, O, P, Si, S , Ge, Se, and Te Which may be substituted with any one or more heteroatoms;
Each of p11 to p14, r11 to r14 and s11 to s14 is an integer of 1 to 3, and when each of them is 2 or more, each of the linking groups L ₂₁ to L ₃₂ is the same or different from each other,
X1 is an integer of 1 or 2, y1 and z1 are the same or different and independently of one another an integer of 0 to 3,
Ar ₂₁ and Ar ₂₂ , Ar ₂₃ and Ar ₂₄ , Ar ₂₅ and Ar _26, and Ar ₂₇ and Ar ₂₈ may be connected to each other to form a ring;
The two carbon atoms adjacent to each other in a ring A ₃₂ in formula D4 in combination with * in the structural formula, and Q ₁₁ form a condensed ring,
The two carbon atoms by the A ₃₁ ring my The two carbon atoms to each other neighbors in combination with * in the structural formula Q ₁₂ to form a condensed ring, in adjacent the A ₃₂ ring in the formula D5 of the formula Q ₁₁ * and To form a condensed ring,
Here, the 'substitution' in the 'substituted or unsubstituted' in the above [Formula A], [Formula B], [Formula D1] to [Formula D5] is a substituent selected from the group consisting of deuterium, cyano, halogen, , An alkyl group having 1 to 24 carbon atoms, a halogenated alkyl group having 1 to 24 carbon atoms, an alkenyl group having 2 to 24 carbon atoms, an alkynyl group having 2 to 24 carbon atoms, a heteroalkyl group having 1 to 24 carbon atoms, an aryl group having 6 to 24 carbon atoms, An arylalkyl group having 7 to 24 carbon atoms, a heteroaryl group having 2 to 24 carbon atoms or a heteroarylalkyl group having 2 to 24 carbon atoms, an alkoxy group having 1 to 24 carbon atoms, an alkylamino group having 1 to 24 carbon atoms, an arylamino group having 6 to 24 carbon atoms, Which is substituted with at least one substituent selected from the group consisting of a heteroarylamino group having 1 to 24 carbon atoms, an alkylsilyl group having 1 to 24 carbon atoms, an arylsilyl group having 6 to 24 carbon atoms, and an aryloxy group having 6 to 24 carbon atoms It means. The method according to claim 1,
Wherein the light emitting layer comprises a host and a dopant, and the compound represented by any one of Chemical Formulas D1 to D5 is used as a dopant. The method according to claim 1,
A1, A2, E and F in the above-mentioned formulas A and B are the same or different and each independently represent a substituted or unsubstituted aromatic hydrocarbon ring having 6 to 50 carbon atoms,
Wherein A ₃₁ , A ₃₂ , E 1 and F 1 in the formulas (D 4) and (D 5) are the same or different and independently represent a substituted or unsubstituted aromatic hydrocarbon ring having 6 to 50 carbon atoms. The method of claim 3,
The substituted or unsubstituted aromatic hydrocarbon rings of Formula A, Formula B, Formula D4 and Formula D5 are the same or different and independently of each other are any one selected from the group consisting of Structural Formulas 10 to 21 &Lt; / RTI &gt;
[Structural formula 10] [Structural formula 11] [Structural formula 12]

[Structural Formula 13] [Structural Formula 14] [Structural Formula 15]

[Structural formula 16] [Structural formula 17] [Structural formula 18]

[Structural formula 19] [Structural formula 20] [Structural formula 21]

In the above Structural Formulas 10 to 21,
"- *" represents a 5-membered ring containing the carbon atom connected to R1 and R2 in the above formulas (A) and (B), or a binding site for forming a 5-membered ring containing M in the above formula Meaning;
Refers to a bonding site for forming a 5-membered ring including carbon atoms connected to R31 and R32 in the above formulas (D4) and (D5), or for forming a 5-membered ring including W in the above formula (Q11) and (Q12)
When the aromatic hydrocarbon rings of the above-mentioned structural formulas 10 to 21 correspond to the A1 ring or the A2 ring in the above formulas A and B and are bonded to the structural formula Q1 or the structural formula Q2, two adjacent carbon atoms are bonded to each other Bonded to * of formula Q1 or combined with * of formula Q2 to form a condensed ring;
When the aromatic hydrocarbon ring of the above structural formulas 10 to 21 is bonded to the structural formula Q11 or Q12 corresponding to the A31 ring or the A32 ring in the above formulas D4 and D5, The carbon atom is bonded to * of the formula Q11 or to a * of the formula Q12 to form a condensed ring,
In the above Structural Formulas 10 to 21, R is the same as R1 to R9 or R31 to R39 defined in Claim 1, m is an integer of 1 to 8, m is 2 or more, or R is 2 or more Each R may be the same or different from each other. The method according to claim 1,
Wherein x in Formula (A) and Formula (B) is 1. The method according to claim 1,
Wherein x1 and y1 in the general formula (D4) and the general formula (D5) are 1 and z1 is 0, respectively. The method according to claim 1,
Wherein Z1 to Z3 in the formulas (D2) and (D3) are the same or different and independently represent a substituted or unsubstituted aromatic hydrocarbon ring having 6 to 30 carbon atoms. 8. The method of claim 7,
Wherein the substituted or unsubstituted aromatic hydrocarbon ring having 6 to 30 carbon atoms in the above formulas (D2) and (D3) is any one selected from the following Structural Formulas (10) to (21).
[Structural formula 10] [Structural formula 11] [Structural formula 12]

[Structural Formula 13] [Structural Formula 14] [Structural Formula 15]

[Structural formula 16] [Structural formula 17] [Structural formula 18]

[Structural formula 19] [Structural formula 20] [Structural formula 21]

In the above-mentioned structural formulas 10 to 21, "- *" means a bonding site of a carbon atom for forming a 5-membered ring in Z1, Z2 or Z3,
In the above Structural Formulas 10 to 21, R is the same as R11 to R16 or R20 to R27 defined in Claim 1,
m is an integer of 1 to 8, and when m is 2 or more, or when R is 2 or more, each R may be the same or different from each other. The method according to claim 1,
Ar11, Ar12, Ar13 and Ar14 in the formulas (D2) and (D3) are the same or different and independently represent a substituted or unsubstituted aryl group having 6 to 30 carbon atoms. The method according to claim 1,
The linking groups L1 to L6 in the above formulas (A) and (B) are the same or different and independently of each other are a single bond or any one selected from the following formulas (22) to (30)
p1 and p2, r1 and r4, s1 and s2 are 1 or 2, respectively.
[Structural Formula 22] [Structural Formula 23] [Structural Formula 24] [Structural Formula 25]

[Structural Formula 26] [Structural Formula 27] [Structural Formula 28] [Structural Formula 29]

[Structural Formula 30]

The carbon position of the aromatic ring in the linking group may be bonded with hydrogen or deuterium. The method according to claim 1,
Wherein the linking groups L11 and L12 in the above formulas (D2) and (D3) are the same or different and independently of one another, or are selected from the following formulas (22) to (30).
[Structural Formula 22] [Structural Formula 23] [Structural Formula 24] [Structural Formula 25]

[Structural Formula 26] [Structural Formula 27] [Structural Formula 28] [Structural Formula 29]

[Structural Formula 30]

The carbon position of the aromatic ring in the linking group may be bonded with hydrogen or deuterium. The method according to claim 1,
The linking groups L21 to L32 in the above formulas (D4) and (D5) are the same or different and independently of each other are a single bond or any one selected from the following formulas (22) to (30)
p11 to p14, r11 to r14, s11 to s14 each is 1 or 2.
[Structural Formula 22] [Structural Formula 23] [Structural Formula 24] [Structural Formula 25]

[Structural Formula 26] [Structural Formula 27] [Structural Formula 28] [Structural Formula 29]

[Structural Formula 30]

The carbon position of the aromatic ring in the linking group may be bonded with hydrogen or deuterium. The method according to claim 1,
Wherein the amine compound represented by Formula (A) or (B) is any one selected from the group consisting of the following Formulas (1) to (165).
&Lt; Formula 1 >< EMI ID =

&Lt; Formula 4 &gt;&lt; EMI ID =

&Lt; Formula 7 >< EMI ID =

&Lt; Formula 10 &gt;&lt; EMI ID =

&Lt; Formula 13 >< EMI ID =

&Lt; Formula 16 &gt;&lt; EMI ID =

&Lt; Formula 19 >< EMI ID =

&Lt; Formula 22 &gt;&lt; EMI ID =

&Lt; Formula 25 >< EMI ID = 26.0 >

&Lt; Formula 28 >< EMI ID = 29.0 >

&Lt; Formula 31 >< EMI ID =

&Lt; Formula 34 &gt;&lt; EMI ID =

&Lt; Formula 37 >< EMI ID = 38.0 >

&Lt; Formula 40 >< EMI ID =

&Lt; General Formula 43 &gt;

&Lt; Formula 46 &gt;&lt; EMI ID =

&Lt; Formula 50 >< Formula 51 >

&Lt; Formula 52 >

&Lt; Formula 55 >< EMI ID = 56.0 >

<Formula 58><Formula59>

&Lt; Formula 61 >< EMI ID =

&Lt; Formula 64 &gt;&lt; EMI ID =

&Lt; Formula 67 >

<Formula 70><Formula71><Formula72>

&Lt; Formula 73 >< EMI ID =

&Lt; Formula 76 &gt;&lt; EMI ID =

&Lt; Formula 79 >< EMI ID =

<Formula 82><Formula83><Formula84>

&Lt; Formula 85 &gt;&lt; EMI ID =

&Lt; Formula 88 >

&Lt; Formula 91 >< EMI ID =

&Lt; Formula 94 &gt;&lt; EMI ID =

&Lt; Formula 97 >

&Lt; Formula 100 >< EMI ID =

&Lt; EMI ID = 103.1 &gt;

(Formula 107) &lt; EMI ID = 106.1 &gt;

(110) &lt; Formula (111) &gt;

<Formula 112><Formula113><Formula114>

&Lt; Formula 115 &gt;&lt; EMI ID = 116.1 &gt;

&Lt; EMI ID = 120.1 &gt;

&Lt; Formula 121 &gt;&lt; EMI ID =

&Lt; Formula 124 >< EMI ID =

&Lt; Formula 127 &gt;

[Formula 130] &lt; EMI ID = 131.0 &gt;

<Formula 133><Formula134><Formula135>

&Lt; EMI ID = 136.0 &gt;

&Lt; Formula 139 &gt;&lt; EMI ID =

&Lt; Formula 142 >< EMI ID = 143.1 >

&Lt; Formula 145 >< EMI ID =

<Formula 148><Formula149><Formula150>

<Formula 151><Formula152><Formula153>

<Formula 154><Formula155>

&Lt; Formula 15 &gt;

&Lt; Formula 160 &gt;&lt; EMI ID =

&Lt; Formula 163 >< EMI ID =

The method according to claim 1,
Wherein the compound represented by the formula (D1) is any one selected from the group consisting of the following compounds (101) to (190).
&Lt; Compound 101 >< Compound 102 >< Compound 103 >

&Lt; Compound 104 >< Compound 105 >< Compound 106 >

&Lt; Compound 107 >< Compound 108 >< Compound 109 >

&Lt; Compound 110 >< Compound 111 >< Compound 112 &

&Lt; Compound 113 >< Compound 114 >< Compound 115 &

&Lt; Compound 116 >< Compound 117 >< Compound 118 &

&Lt; Compound 119 >< Compound 120 >< Compound 121 &

&Lt; Compound 122 >< Compound 123 >< Compound 124 >

&Lt; Compound 125 >< Compound 126 >< Compound 127 &

&Lt; Compound 128 >< Compound 129 >< Compound 130 &

&Lt; Compound 131 >< Compound 132 >< Compound 133 >

&Lt; Compound 134 >< Compound 135 >< Compound 136 >

&Lt; Compound 137 >< Compound 138 >< Compound 139 &

&Lt; Compound 140 >< Compound 141 >< Compound 142 >

&Lt; Compound 143 >< Compound 144 >< Compound 145 >

<Compound 146><Compound147><Compound148>

&Lt; Compound 149 >< Compound 150 >< Compound 151 >

&Lt; Compound 152 >< Compound 153 >< Compound 154 >

&Lt; Compound 155 >< Compound 156 >< Compound 157 >

&Lt; Compound 158 >< Compound 159 >< Compound 160 >

&Lt; Compound 161 >< Compound 162 >< Compound 163 &

&Lt; Compound 164 >< Compound 165 >< Compound 166 &

&Lt; Compound 167 >< Compound 168 >< Compound 169 &

&Lt; Compound 170 >< Compound 171 >< Compound 172 >

<Compound 173><Compound174><Compound175>

<Compound 176><Compound177><Compound178>

&Lt; Compound 179 >< Compound 180 >< Compound 181 &

<Compound 182><Compound183><Compound184>

&Lt; Compound 185 >< Compound 186 >< Compound 187 &

&Lt; Compound 188 >< Compound 189 >< Compound 190 &

The method according to claim 1,
Wherein the compound represented by the formula (D2) is any one selected from the group consisting of the following compounds (201) to (260).
&Lt; Compound 201 >< Compound 202 >< Compound 203 &

<Compound 204><Compound205><Compound206>

&Lt; Compound 207 >< Compound 208 >< Compound 209 &

&Lt; Compound 210 >< Compound 211 >< Compound 212 &

&Lt; Compound 213 >< Compound 214 >< Compound 215 &

&Lt; Compound 216 >< Compound 217 >< Compound 218 &

&Lt; Compound 219 >< Compound 220 >< Compound 221 &

&Lt; Compound 222 >< Compound 223 >< Compound 224 &

&Lt; Compound 225 >< Compound 226 >< Compound 227 &

&Lt; Compound 228 >< Compound 229 >< Compound 230 &

&Lt; Compound 231 >< Compound 232 >< Compound 233 &

&Lt; Compound 234 >< Compound 235 >< Compound 236 >

&Lt; Compound 237 >< Compound 238 >< Compound 239 >

&Lt; Compound 240 >< Compound 241 >< Compound 242 &

<Compound 243><Compound244><Compound245>

<Compound 246><Compound247><Compound248>

&Lt; Compound 249 >< Compound 250 >< Compound 251 &

&Lt; Compound 252 >< Compound 253 >< Compound 254 &

&Lt; Compound 255 >< Compound 256 >< Compound 257 &

<Compound 258><Compound259><Compound260>

The method according to claim 1,
Wherein the compound represented by the formula (D3) is any one selected from the group consisting of the following compounds (261) to (326).
&Lt; Compound 261 >< Compound 262 >< Compound 263 &

&Lt; Compound 264 >< Compound 265 >< Compound 266 &

&Lt; Compound 267 >< Compound 268 >< Compound 269 &

&Lt; Compound 270 >< Compound 271 >< Compound 272 &

&Lt; Compound 273 >< Compound 274 >< Compound 275 >

&Lt; Compound 276 >< Compound 277 >< Compound 278 >

&Lt; Compound 279 >< Compound 280 >< Compound 281 &

&Lt; Compound 282 >< Compound 283 >< Compound 284 >

&Lt; Compound 285 >< Compound 286 >< Compound 287 &

<Compound 288><Compound289><Compound290>

&Lt; Compound 291 >< Compound 292 >< Compound 293 &

&Lt; Compound 294 >< Compound 295 >< Compound 296 &

&Lt; Compound 297 >< Compound 298 >< Compound 299 &

&Lt; Compound 300 >< Compound 301 >< Compound 302 >

&Lt; Compound 303 >< Compound 304 >< Compound 305 &

&Lt; Compound 306 >< Compound 307 >< Compound 308 &

&Lt; Compound 309 >< Compound 310 >< Compound 311 &

&Lt; Compound 312 >< Compound 313 >< Compound 314 >

&Lt; Compound 315 >< Compound 316 >< Compound 317 >

&Lt; Compound 318 >< Compound 319 >< Compound 320 &

&Lt; Compound 321 >< Compound 322 >< Compound 323 >

&Lt; Compound 324 >< Compound 325 >< Compound 326 >

The method according to claim 1,
Wherein the compound represented by the formula (D4) or (D5) is any one selected from the group consisting of the following compounds (401) to (639).
&Lt; Compound 401 >< Compound 402 >< Compound 403 &

&Lt; Compound 404 >< Compound 405 >< Compound 406 &

&Lt; Compound 407 >< Compound 408 >< Compound 409 >

&Lt; Compound 410 >< Compound 411 >< Compound 412 &

&Lt; Compound 413 >< Compound 414 >< Compound 415 >

&Lt; Compound 416 >< Compound 417 >< Compound 418 &

&Lt; Compound 419 >< Compound 420 >< Compound 421 &

&Lt; Compound 422 >< Compound 423 >< Compound 424 >

&Lt; Compound 425 >< Compound 426 >< Compound 427 &

&Lt; Compound 428 >< Compound 429 >< Compound 430 >

&Lt; Compound 431 >< Compound 432 >< Compound 433 >

&Lt; Compound 434 >< Compound 435 >< Compound 436 >

&Lt; Compound 437 >< Compound 438 >< Compound 439 >

&Lt; Compound 440 >< Compound 441 >< Compound 442 &

&Lt; Compound 443 >< Compound 444 >< Compound 445 &

&Lt; Compound 446 >< Compound 447 >< Compound 448 &

&Lt; Compound 449 >< Compound 450 >< Compound 451 &

&Lt; Compound 452 >< Compound 453 >< Compound 454 >

&Lt; Compound 455 >< Compound 456 >< Compound 457 >

&Lt; Compound 458 >< Compound 459 >< Compound 460 &

&Lt; Compound 461 >< Compound 462 >< Compound 463 &

&Lt; Compound 464 >< Compound 465 >< Compound 466 &

&Lt; Compound 467 >< Compound 468 >< Compound 469 &

&Lt; Compound 470 >< Compound 471 >< Compound 472 &

&Lt; Compound 473 >< Compound 474 >< Compound 475 &

&Lt; Compound 476 >< Compound 477 >< Compound 478 &

&Lt; Compound 479 >< Compound 480 >< Compound 481 &

<Compound 482><Compound483><Compound484>

<Compound 485><Compound486><Compound487>

<Compound 488><Compound489><Compound490>

&Lt; Compound 491 >< Compound 492 >< Compound 493 &

&Lt; Compound 494 >< Compound 495 >< Compound 496 &

&Lt; Compound 497 >< Compound 498 >< Compound 499 &

&Lt; Compound 500 >< Compound 501 >< Compound 502 >

&Lt; Compound 503 >< Compound 504 >< Compound 505 >

&Lt; Compound 506 >< Compound 507 >< Compound 508 &

&Lt; Compound 509 >< Compound 510 >< Compound 511 &

&Lt; Compound 512 >< Compound 513 >< Compound 514 &

<Compound 515><Compound516><Compound517>

<Compound 518><Compound519><Compound520>

&Lt; Compound 521 >< Compound 522 >< Compound 523 &

<Compound 524><Compound525><Compound526>

&Lt; Compound 527 >< Compound 528 >< Compound 529 &

&Lt; Compound 530 >< Compound 531 >< Compound 532 &

&Lt; Compound 533 >< Compound 534 >< Compound 535 >

&Lt; Compound 536 >< Compound 537 >< Compound 538 >

&Lt; Compound 539 >< Compound 540 >< Compound 541 >

<Compound 542><Compound543><Compound544>

<Compound 545><Compound546><Compound547>

<Compound 548><Compound549><Compound550>

&Lt; Compound 551 >< Compound 552 >< Compound 553 >

<Compound 554><Compound555><Compound556>

&Lt; Compound 557 >< Compound 558 >< Compound 559 >

&Lt; Compound 560 >< Compound 561 >< Compound 562 &

<Compound 563><Compound564><Compound565>

<Compound 566><Compound567><Compound568>

&Lt; Compound 569 >< Compound 570 >< Compound 571 >

&Lt; Compound 572 >< Compound 573 >< Compound 574 >

&Lt; Compound 575 >< Compound 576 >< Compound 577 >

&Lt; Compound 578 >< Compound 579 >< Compound 580 &

<Compound 581><Compound582><Compound583>

<Compound 584><Compound585><Compound586>

&Lt; Compound 587 >< Compound 588 >< Compound 589 &

&Lt; Compound 590 >< Compound 591 >< Compound 592 >

<Compound 593><Compound594><Compound595>

&Lt; Compound 596 >< Compound 597 >< Compound 598 &

&Lt; Compound 599 >< Compound 600 >< Compound 601 >

&Lt; Compound 602 >< Compound 603 >< Compound 604 >

&Lt; Compound 605 >< Compound 606 >< Compound 607 >

&Lt; Compound 608 >< Compound 609 >< Compound 610 &

&Lt; Compound 611 >< Compound 612 >< Compound 613 &

&Lt; Compound 614 >< Compound 615 >< Compound 616 >

&Lt; Compound 617 >< Compound 618 >< Compound 619 >

&Lt; Compound 620 >< Compound 621 >< Compound 622 &

&Lt; Compound 623 >< Compound 624 >< Compound 625 >

&Lt; Compound 626 >< Compound 627 >< Compound 628 &

&Lt; Compound 629 >< Compound 630 >< Compound 631 &

&Lt; Compound 632 >< Compound 633 >< Compound 634 >

&Lt; Compound 635 >< Compound 636 >< Compound 637 &

&Lt; Compound 638 >< Compound 639 >

The method according to claim 1,
Wherein the organic light emitting device further comprises at least one of an electron blocking layer, an electron transport layer, and an electron injection layer. 19. The method of claim 18,
Wherein at least one layer selected from the respective layers is formed by a deposition process or a solution process. 19. The method of claim 18,
Wherein the organic light emitting device comprises an electron blocking layer between the hole transporting layer and the light emitting layer. The method according to claim 1,
The organic light emitting device includes a flat panel display device; A flexible display device; Monochrome or white flat panel illumination devices; And a device for flexible illumination of a single color or a white color.

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