KR102125343B1 - organic light-emitting diode with High efficiency - Google Patents

Abstract

The present invention relates to an organic light emitting device having a high efficiency, in more detail the first electrode;
A second electrode opposed to the first electrode; An organic light emitting device including a hole transport layer, an electron blocking layer and a light emitting layer sequentially interposed between the first electrode and the second electrode, wherein the hole transport layer is an amine compound represented by the following [Formula A] or [Formula B] It includes at least one; The electron blocking layer relates to an organic light emitting device comprising at least one amine compound represented by the following [Chemical Formula C] or [Chemical Formula D], wherein [Chemical Formula A] to [Chemical Formula D] are described in the detailed description of the invention. Same as bar

Description

Organic light-emitting diode with high efficiency

The present invention relates to an organic light emitting device having high efficiency, and more specifically, to use a material of a specific structure as a hole transport layer material in the organic light emitting device, and also includes a material of another specific structure in the electron blocking layer to show high efficiency. It relates to an organic light emitting device.

An organic light emitting diode (OLED) is a display using a self-emission phenomenon, and has a large viewing angle and can be lighter and shorter than a liquid crystal display, and has advantages such as a fast response speed and is full-color. ) Application to display or lighting is expected.

In general, the organic light emitting phenomenon refers to a phenomenon that converts electrical energy into light energy using an organic material. An organic light emitting device using an organic light emitting phenomenon usually has a structure including an anode and a cathode and an organic material layer therebetween.

Here, in order to increase the efficiency and stability of the organic light emitting device, the organic material layer is often formed of a multi-layered structure composed of different materials, for example, may be formed of a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, an electron injection layer, and the like. When a voltage is applied between two electrodes in the structure of the organic light emitting device, holes are injected at the anode, and electrons are injected at the cathode, and an exciton is formed when the injected holes meet the electrons. When it falls to the ground again, it glows. It is known that such an organic light emitting device has characteristics such as self-luminescence, high luminance, high efficiency, low driving voltage, wide viewing angle, high contrast, and high-speed response.

Materials used as the organic material layer in the organic light emitting device may be classified into light emitting materials and charge transport materials, such as hole injection materials, hole transport materials, electron transport materials, electron injection materials, etc. Alternatively, a hole blocking layer or the like may be added.

As a prior art for such a hole transport layer, in Patent Registration No. 10-1074193 (announcement date: 2011.10.14), organic light emission using a compound having a core structure in which at least one benzene ring is condensed in a carbazole structure as a hole transport layer compound The device is disclosed, and in Patent Registration No. 10-1455156 (announcement date: 2014.10.27), a light-emitting auxiliary layer having a HOMO level between the hole transport layer HOMO energy level and the HOMO energy level of the light-emitting layer between the hole transport layer and the light emitting layer. A description is given of an organic light-emitting device having formed.

However, in spite of various attempts to produce an organic light emitting device in the prior art including the above-mentioned literature, there is still a need for development of an organic light emitting device having more improved luminous efficiency. to be.

Registered Patent Publication No. 10-1074193 (Publication date: 2011.10.14)

Registered Patent Publication No. 10-1455156 (Notice: 2014.10.27)

Therefore, the technical problem to be achieved by the present invention is to include a hole transport layer material having a specific structure in an organic light emitting device and an electron blocking layer material having another specific structure, and thus a novel organic light emitting device having high efficiency characteristics (organic light) emitting diode, OLED).

The present invention to achieve the above technical problems, the first electrode; A second electrode opposed to the first electrode; An organic light emitting device including a hole transport layer, an electron blocking layer, and a light emitting layer sequentially interposed between the first electrode and the second electrode, wherein the hole transport layer is an amine compound represented by the following [Formula A] or [Formula B] It contains at least 1 type; The electron blocking layer provides an organic light emitting device comprising at least one amine compound represented by the following [Chemical Formula C] or [Chemical Formula D].

[Formula A]

[Formula B]

In the above [Formula A] and [Formula B],

A1, A2, E and F are each the same or different from each other, and are each independently 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 five-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 independently of each other, 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 group, Alkynylene group having 2 to 60 carbon atoms, substituted or unsubstituted cycloalkylene group having 3 to 60 carbon atoms, substituted or unsubstituted heterocycloalkylene group having 2 to 60 carbon atoms, substituted or unsubstituted aryl having 6 to 60 carbon atoms A alkylene group or a substituted or unsubstituted heteroarylene group having 2 to 60 carbon atoms;

The 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 R1 to R9, Ar1 to Ar4 are the same or different from each other, and independently of each other, 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, substituted Or an unsubstituted alkenyl group having 2 to 30 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 30 carbon atoms, a substituted or unsubstituted cycloalke having 5 to 30 carbon atoms Nyl group, substituted or unsubstituted heteroaryl group having 2 to 50 carbon atoms, substituted or unsubstituted heterocycloalkyl group having 2 to 30 carbon atoms, substituted or unsubstituted alkoxy group having 1 to 30 carbon atoms, substituted or unsubstituted carbon number 6 Aryloxy group having 30 to 30, substituted or unsubstituted alkyl thioxy group having 1 to 30 carbon atoms, substituted or unsubstituted arylthio group having 6 to 30 carbon atoms, substituted or unsubstituted alkylamine group having 1 to 30 carbon atoms, substituted Or an 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 1 to 30 carbon atoms An alkyl germanium group, a substituted or unsubstituted aryl germanium group having 1 to 30 carbon atoms, any one selected from a cyano group, a nitro group, and a halogen group,

The R1 and R2 may be connected to each other to form an alicyclic, aromatic monocyclic or polycyclic ring, and the carbon atoms of the formed alicyclic, aromatic monocyclic or polycyclic ring are N, O, P, Si, S, Ge , Se, Te may be substituted with any one or more heteroatoms selected from;

Wherein p1 and p2, r1 and r2, s1 and s2 are integers of 1 to 3, respectively, when each of them is 2 or more, each of the linkers L1 to L6 is the same or different from each other,

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

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

In Formula A, two carbon atoms adjacent to each other in the A2 ring combine with * in the structural formula Q1 to form a condensed ring,

In Formula B, two carbon atoms adjacent to each other in the A1 ring combine with * in the structural formula Q2 to form a condensed ring, and two carbon atoms adjacent to each other in the A2 ring combine with * in the structural formula Q1 to form a condensed ring. To form.

[Formula C]

In the above [Formula C],

The substituents R11 to R13 are the same or different, and each independently hydrogen, deuterium, substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, substituted or unsubstituted aryl group having 6 to 50 carbon atoms, substituted or unsubstituted carbon number 2 to 30 alkenyl groups, substituted or unsubstituted alkynyl groups having 2 to 20 carbon atoms, substituted or unsubstituted cycloalkyl groups having 3 to 30 carbon atoms, substituted or unsubstituted cycloalkenyl groups having 5 to 30 carbon atoms, substituted or unsubstituted Substituted heteroaryl group having 2 to 50 carbon atoms, substituted or unsubstituted heterocycloalkyl group having 2 to 30 carbon atoms, substituted or unsubstituted alkoxy group having 1 to 30 carbon atoms, substituted or unsubstituted aryl oxide having 6 to 30 carbon atoms Timing, substituted or unsubstituted alkyl thioxy group having 1 to 30 carbon atoms, substituted or unsubstituted arylthio group having 6 to 30 carbon atoms, substituted or unsubstituted alkylamine group having 1 to 30 carbon atoms, substituted or unsubstituted carbon number 6 to 30 arylamine groups, substituted or unsubstituted alkylsilyl groups having 1 to 30 carbon atoms, substituted or unsubstituted arylsilyl groups having 6 to 30 carbon atoms, substituted or unsubstituted alkyl germanium groups having 1 to 30 carbon atoms, A substituted or unsubstituted aryl germanium group having 1 to 30 carbon atoms, any one selected from cyano, nitro, and halogen groups,

The substituents Ar5 to Ar8 are the same or different, and are each independently a substituted or unsubstituted aryl group having 6 to 40 carbon atoms, or a substituted or unsubstituted heteroaryl group having 2 to 30 carbon atoms;

Wherein n is an integer of 0 to 4, and when n is 2 or more, each aromatic ring containing the substituent R13 is the same or different from each other,

m1 to m3 are integers from 0 to 4, and when they are 2 or more, each R11, R12, or R13 is the same or different from each other,

The carbon atom of the aromatic ring to which the substituents R11 to R13 are not bonded is bonded to hydrogen or deuterium.

[Formula D]

In the above [Formula D],

The substituents R21 to R23 are the same or different, and independently of each other, 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 carbon number 2 to 30 alkenyl groups, substituted or unsubstituted alkynyl groups having 2 to 20 carbon atoms, substituted or unsubstituted cycloalkyl groups having 3 to 30 carbon atoms, substituted or unsubstituted cycloalkenyl groups having 5 to 30 carbon atoms, substituted or unsubstituted Substituted heteroaryl group having 2 to 50 carbon atoms, substituted or unsubstituted heterocycloalkyl group having 2 to 30 carbon atoms, substituted or unsubstituted alkoxy group having 1 to 30 carbon atoms, substituted or unsubstituted aryl oxide having 6 to 30 carbon atoms Timing, substituted or unsubstituted alkyl thioxy group having 1 to 30 carbon atoms, substituted or unsubstituted arylthio group having 6 to 30 carbon atoms, substituted or unsubstituted alkylamine group having 1 to 30 carbon atoms, substituted or unsubstituted carbon number 6 to 30 arylamine groups, substituted or unsubstituted alkylsilyl groups having 1 to 30 carbon atoms, substituted or unsubstituted arylsilyl groups having 6 to 30 carbon atoms, substituted or unsubstituted alkyl germanium groups having 1 to 30 carbon atoms, A substituted or unsubstituted aryl germanium group having 6 to 30 carbon atoms, any one selected from a cyano group, a nitro group, and a halogen group,

The substituents Ar9 to Ar12 are the same or different, and each independently a substituted or unsubstituted aryl group having 6 to 40 carbon atoms, or a substituted or unsubstituted heteroaryl group having 2 to 30 carbon atoms.

The organic light emitting device according to the present invention can exhibit more improved efficiency than the organic light emitting device according to the prior art.

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

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

The present invention is a first electrode; A second electrode opposed to the first electrode; An organic light emitting device including a hole transport layer, an electron blocking layer, and a light emitting layer sequentially interposed between the first electrode and the second electrode, wherein the hole transport layer is an amine compound represented by the following [Formula A] or [Formula B] It contains at least 1 type; The electron blocking layer provides an organic light emitting device comprising at least one amine compound represented by the following [Chemical Formula C] or [Chemical Formula D].

[Formula A]

[Formula B]

In [Formula A] and [Formula B], A1, A2, E and F are the same or different from each other, and each independently substituted or unsubstituted aromatic hydrocarbon ring having 6 to 50 carbon atoms, or substituted or unsubstituted An 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 five-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 independently of each other, 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 group, Alkynylene group having 2 to 60 carbon atoms, substituted or unsubstituted cycloalkylene group having 3 to 60 carbon atoms, substituted or unsubstituted heterocycloalkylene group having 2 to 60 carbon atoms, substituted or unsubstituted aryl having 6 to 60 carbon atoms A alkylene group or a substituted or unsubstituted heteroarylene group having 2 to 60 carbon atoms;

The 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 R1 to R9, Ar1 to Ar4 are the same or different from each other, and independently of each other, 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, substituted Or an unsubstituted alkenyl group having 2 to 30 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 30 carbon atoms, a substituted or unsubstituted cycloalke having 5 to 30 carbon atoms Nyl group, substituted or unsubstituted heteroaryl group having 2 to 50 carbon atoms, substituted or unsubstituted heterocycloalkyl group having 2 to 30 carbon atoms, substituted or unsubstituted alkoxy group having 1 to 30 carbon atoms, substituted or unsubstituted carbon number 6 Aryloxy group having 30 to 30, substituted or unsubstituted alkyl thioxy group having 1 to 30 carbon atoms, substituted or unsubstituted arylthio group having 6 to 30 carbon atoms, substituted or unsubstituted alkylamine group having 1 to 30 carbon atoms, substituted Or an 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 1 to 30 carbon atoms An alkyl germanium group, a substituted or unsubstituted aryl germanium group having 1 to 30 carbon atoms, any one selected from a cyano group, a nitro group, and a halogen group,

The R1 and R2 may be connected to each other to form an alicyclic, aromatic monocyclic or polycyclic ring, and the carbon atoms of the formed alicyclic, aromatic monocyclic or polycyclic ring are N, O, P, Si, S, Ge , Se, Te may be substituted with any one or more heteroatoms selected from;

Wherein p1 and p2, r1 and r2, s1 and s2 are integers of 1 to 3, respectively, when each of them is 2 or more, each of the linkers L1 to L6 is the same or different from each other,

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

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

In Formula A, two carbon atoms adjacent to each other in the A2 ring combine with * in the structural formula Q1 to form a condensed ring,

In Formula B, two carbon atoms adjacent to each other in the A1 ring combine with * in the structural formula Q2 to form a condensed ring, and two carbon atoms adjacent to each other in the A2 ring combine with * in the structural formula Q1 to form a condensed ring. To form.

[Formula C]

In the above [Formula C],

The substituents R11 to R13 are the same or different, and each independently hydrogen, deuterium, substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, substituted or unsubstituted aryl group having 6 to 50 carbon atoms, substituted or unsubstituted carbon number 2 to 30 alkenyl groups, substituted or unsubstituted alkynyl groups having 2 to 20 carbon atoms, substituted or unsubstituted cycloalkyl groups having 3 to 30 carbon atoms, substituted or unsubstituted cycloalkenyl groups having 5 to 30 carbon atoms, substituted or unsubstituted Substituted heteroaryl group having 2 to 50 carbon atoms, substituted or unsubstituted heterocycloalkyl group having 2 to 30 carbon atoms, substituted or unsubstituted alkoxy group having 1 to 30 carbon atoms, substituted or unsubstituted aryl oxide having 6 to 30 carbon atoms Timing, substituted or unsubstituted alkyl thioxy group having 1 to 30 carbon atoms, substituted or unsubstituted arylthio group having 6 to 30 carbon atoms, substituted or unsubstituted alkylamine group having 1 to 30 carbon atoms, substituted or unsubstituted carbon number 6 to 30 arylamine groups, substituted or unsubstituted alkylsilyl groups having 1 to 30 carbon atoms, substituted or unsubstituted arylsilyl groups having 6 to 30 carbon atoms, substituted or unsubstituted alkyl germanium groups having 1 to 30 carbon atoms, A substituted or unsubstituted aryl germanium group having 1 to 30 carbon atoms, any one selected from cyano, nitro, and halogen groups,

The substituents Ar5 to Ar8 are the same or different, and are each independently a substituted or unsubstituted aryl group having 6 to 40 carbon atoms, or a substituted or unsubstituted heteroaryl group having 2 to 30 carbon atoms;

Wherein n is an integer of 0 to 4, and when n is 2 or more, each aromatic ring containing the substituent R13 is the same or different from each other,

m1 to m3 are integers from 0 to 4, and when they are 2 or more, each R11, R12, or R13 is the same or different from each other,

The carbon atom of the aromatic ring to which the substituents R11 to R13 are not bonded is bonded to hydrogen or deuterium.

[Formula D]

In the above [Formula D],

The substituents R21 to R23 are the same or different, and independently of each other, 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 carbon number 2 to 30 alkenyl groups, substituted or unsubstituted alkynyl groups having 2 to 20 carbon atoms, substituted or unsubstituted cycloalkyl groups having 3 to 30 carbon atoms, substituted or unsubstituted cycloalkenyl groups having 5 to 30 carbon atoms, substituted or unsubstituted Substituted heteroaryl group having 2 to 50 carbon atoms, substituted or unsubstituted heterocycloalkyl group having 2 to 30 carbon atoms, substituted or unsubstituted alkoxy group having 1 to 30 carbon atoms, substituted or unsubstituted aryl oxide having 6 to 30 carbon atoms Timing, substituted or unsubstituted alkyl thioxy group having 1 to 30 carbon atoms, substituted or unsubstituted arylthio group having 6 to 30 carbon atoms, substituted or unsubstituted alkylamine group having 1 to 30 carbon atoms, substituted or unsubstituted carbon number 6 to 30 arylamine groups, substituted or unsubstituted alkylsilyl groups having 1 to 30 carbon atoms, substituted or unsubstituted arylsilyl groups having 6 to 30 carbon atoms, substituted or unsubstituted alkyl germanium groups having 1 to 30 carbon atoms, A substituted or unsubstituted aryl germanium group having 1 to 30 carbon atoms, any one selected from cyano, nitro, and halogen groups,

The substituents Ar9 to Ar12 are the same or different, and each independently substituted or unsubstituted aryl group having 6 to 40 carbon atoms, or a substituted or unsubstituted heteroaryl group having 2 to 30 carbon atoms,

Here, the'substitution' in the'substituted or unsubstituted' in the above [Formula A] to [Formula D] is deuterium, cyano group, halogen group, hydroxy group, nitro group, alkyl group having 1 to 24 carbon atoms, carbon number 1 To 24 halogenated alkyl groups, 2 to 24 alkenyl groups, 2 to 24 alkynyl groups, 1 to 24 carbon heteroalkyl groups, 6 to 24 carbon atoms aryl groups, 7 to 24 carbon atoms arylalkyl groups, 2 to 2 carbon atoms Heteroaryl group of 24 or heteroaryl alkyl group of 2 to 24 carbon atoms, alkoxy group of 1 to 24 carbon atoms, alkylamino group of 1 to 24 carbon atoms, arylamino group of 6 to 24 carbon atoms, heteroarylamino group of 1 to 24 carbon atoms, carbon number 1 It means that it is substituted with one or more substituents selected from the group consisting of an alkylsilyl group having 24 to 24 carbon atoms, an arylsilyl group having 6 to 24 carbon atoms, and an aryloxy group having 6 to 24 carbon atoms.

On the other hand, considering the range of the alkyl group or aryl group in the "substituted or unsubstituted alkyl group having 1 to 24 carbon atoms", "substituted or unsubstituted aryl group having 6 to 24 carbon atoms", the carbon number of 1 to 24 The range of the carbon number of the alkyl group and the aryl group having 6 to 24 carbon atoms means the total number of carbon atoms constituting the alkyl portion or the aryl portion when the substituent is regarded as unsubstituted without considering the substituted portion. For example, the phenyl group substituted with a butyl group in the para position should be regarded as corresponding to an aryl group having 6 carbon atoms substituted with a butyl group having 4 carbon atoms.

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 one hydrogen removal, and when the aryl group has a substituent, it is fused with adjacent substituents to each other to form a ring. Can.

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, phenanthryl group, Aromatic groups such as pyrenyl group, indenyl, fluorenyl group, tetrahydronaphthyl group, peryleneyl, chrysenyl, naphthacenyl, fluoranthenyl, and the like, and at least one hydrogen atom of the aryl group is a deuterium atom, a halogen atom , Hydroxy group, nitro group, cyano group, silyl group, amino group (-NH ₂ , -NH(R), -N(R')(R''), R'and R" independently of each other have 1 to 10 carbon atoms. An alkyl group, in this case referred to as "alkylamino group"), amidino group, hydrazine group, hydrazone group, carboxyl group, sulfonic acid group, phosphoric acid group, alkyl group having 1 to 24 carbon atoms, halogenated alkyl group having 1 to 24 carbon atoms, 2 to 24 carbon atoms Alkenyl group of 2 to 24 carbon atoms, an alkynyl group of 1 to 24 carbon atoms, an aryl group of 6 to 24 carbon atoms, an arylalkyl group of 6 to 24 carbon atoms, a heteroaryl group of 2 to 24 carbon atoms or 2 to 24 carbon atoms It may be substituted with a heteroaryl alkyl group.

The heteroaryl group, which is a substituent used in the compound of the present invention, includes 1, 2 or 3 hetero atoms selected from N, O, P or S, and means a ring aromatic system having 2 to 24 carbon atoms with the remaining ring atoms being carbon, The rings can be fused to form a ring. And one or more hydrogen atoms of the heteroaryl group can be substituted with the same substituents as the aryl group.

Specific examples of the alkyl group which is a substituent used in the present invention include methyl, ethyl, propyl, isobutyl, sec-butyl, tert-butyl, pentyl, iso-amyl, hexyl, and the like, and at least one hydrogen atom in the alkyl group is The atom can be substituted with a substituent similar to that of the aryl group.

Specific examples of the alkoxy group which is a substituent used in the compound of the present invention include methoxy, ethoxy, propoxy, isobutyloxy, sec-butyloxy, pentyloxy, iso-amyloxy, hexyloxy, and the like. One or more hydrogen atoms of the alkoxy group can be substituted with the same substituents as the aryl group.

Specific examples of the silyl group which is a substituent used in the compound of the present invention include trimethylsilyl, triethylsilyl, triphenylsilyl, trimethoxysilyl, dimethoxyphenylsilyl, diphenylmethylsilyl, diphenylvinylsilyl, methylcyclobutylsilyl , Dimethylfurylsilyl, and the like, and one or more hydrogen atoms of the silyl group can be substituted with the same substituents as the aryl group.

The organic light emitting device according to the present invention uses the amine compound represented by the formula (A) or (B) as a hole transport layer material in the organic light emitting device, and the amine derivative compound represented by the formula (C) or (D) between the light emitting layer and the hole transport layer When used as an electron blocking layer material, it may have improved characteristics of high efficiency.

On the other hand, in the organic light emitting device according to the present invention, the amine compound represented by Formula A or Formula B in the formula A has two carbon atoms adjacent to each other in the A2 ring and combines with * of the structural formula Q1 to form a condensed ring. In addition, in Formula B, two carbon atoms adjacent to each other in the A1 ring are combined with * in the structural formula Q2 to form a condensed ring, and two carbon atoms adjacent to each other in the A2 ring are combined with * in the structural formula Q1 It forms a condensed ring, characterized in that it has an amine group in only one of the A1 ring and A2 ring in the formula A and formula B, they can be used in the hole injection layer or hole transport layer in the organic light emitting device, preferably Can be used for the hole transport layer.

As an embodiment of the present invention, A1, A2, E, and F in Chemical Formula A and Chemical Formula B may be the same or different, and may be independently substituted or unsubstituted aromatic hydrocarbon rings having 6 to 50 carbon atoms.

As described above, in the case where A1, A2, E, and F in Formula A or Formula B are the same or different, and each independently represents a substituted or unsubstituted aromatic hydrocarbon ring having 6 to 50 carbon atoms, the substituted or The unsubstituted aromatic hydrocarbon ring 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 [Structural Formulas 10] to [Structural Formula 21], “-*” is used to form a 5-membered ring containing carbon atoms connected to R1 and R2, or to form a 5-membered ring containing M in Structural Formulas Q1 and Q2. Means a binding site,

When the aromatic hydrocarbon rings of [Structural Formulas 10] to [Structural Formula 21] correspond to the A1 ring or A2 ring, and when combined with Structural Formula Q1 or Structural Formula Q2, two adjacent carbon atoms among them combine with * of Structural Formula Q1 Or in combination with * in structural formula Q2 to form a condensed ring;

In [Formula 10] to [Formula 21], R is the same as R1 and R2 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 as each other. Or it may be different.

In addition, as an embodiment according to the present invention, x in Formula A and Formula B may be 1, and y may be 0.

In addition, as an embodiment according to the present invention, in the formulas A and B, the linking groups L1 to L6 are the same or different, and are each independently a single bond or selected from the following [Structural Formulas 22] to [Structural Formula 30] Is any one, 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]

Meanwhile, the amine compound represented by [Chemical Formula C] in the present invention may preferably be a compound represented by the following [Chemical Formula C1] or [Chemical Formula C-2].

[Chemical Formula C1]

In the above [Chemical Formula C1],

The substituents Ar13 to Ar16 are the same or different, and are each independently a substituted or unsubstituted aryl group having 6 to 40 carbon atoms, or a substituted or unsubstituted heteroaryl group having 2 to 30 carbon atoms,

The substituent R24 is the same as R13 defined above,

Wherein n1 is an integer of 2 to 4, in this case, each aromatic ring containing the substituent R24 is the same as or different from each other,

m4 is an integer from 0 to 4, and when m4 is 2 or more, each R24 is the same or different from each other, and the carbon atom of the aromatic ring to which the substituent R24 in parentheses is not bonded is bonded to hydrogen or deuterium.

[Chemical Formula C2]

In the above [Chemical Formula C2],

The substituents Ar17 to Ar20 are the same or different, and are each independently a substituted or unsubstituted aryl group having 6 to 40 carbon atoms, or a substituted or unsubstituted heteroaryl group having 2 to 30 carbon atoms,

The substituents Ar21 to Ar24 are the same or different, and each independently hydrogen, deuterium, a substituted or unsubstituted aryl group having 6 to 40 carbon atoms, or a substituted or unsubstituted heteroaryl group having 2 to 30 carbon atoms, substituted or unsubstituted It is selected from a substituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 30 carbon atoms,

The substituent R25 is the same as R13 defined above,

N2 is an integer from 0 to 2, and when n2 is 2, each aromatic ring including the substituent R25 is the same or different from each other,

m5 is an integer from 0 to 4, and when m5 is 2 or more, each R25 is the same or different from each other, and the carbon atom of the aromatic ring in which the substituent R25 in parentheses is not bonded is bonded to hydrogen or deuterium.

In addition, in the formula C1, the substituent R24 is hydrogen or deuterium, and the substituents Ar13 to Ar16 are the same or different, and each independently substituted or unsubstituted aryl group having 6 to 20 carbon atoms, or substituted or unsubstituted carbon number. It may be a 2 to 20 heteroaryl group.

In addition, the substituent R25 in the formula C2 is hydrogen or deuterium, and the substituents Ar17 to Ar20 are the same or different, and each independently substituted or unsubstituted aryl group having 6 to 20 carbon atoms, or substituted or unsubstituted carbon number 2 It may be a heteroaryl group of 20 to 20.

In addition, the substituents Ar9 to Ar12 in Formula D may be the same or different, and may be independently substituted or unsubstituted aryl groups having 6 to 20 carbon atoms, or substituted or unsubstituted heteroaryl groups having 2 to 20 carbon atoms.

Meanwhile, the amine compound represented by Formula A or Formula B in the present invention may be any one selected from the following Formulas 1 to 165, but is not limited thereto.

<Formula 1> <Formula 2> <Formula 3>

<Formula 4> <Formula 5> <Formula 6>

<Formula 7> <Formula 8> <Formula 9>

<Formula 10> <Formula 11> <Formula 12>

<Formula 13> <Formula 14> <Formula 15>

<Formula 16> <Formula 17> <Formula 18>

<Formula 19> <Formula 20> <Formula 21>

<Formula 22> <Formula 23> <Formula 24>

<Formula 25> <Formula 26> <Formula 27>

<Formula 28> <Formula 29> <Formula 30>

<Formula 31> <Formula 32> <Formula 33>

<Formula 34> <Formula 35> <Formula 36>

<Formula 37> <Formula 38> <Formula 39>

<Formula 40> <Formula 41> <Formula 42>

<Formula 43> <Formula 44> <Formula 45>

<Formula 46> <Formula 47> <Formula 48>

<Formula 49> <Formula 50> <Formula 51>

<Formula 52> <Formula 53> <Formula 54>

<Formula 55> <Formula 56> <Formula 57>

<Formula 58> <Formula 59> <Formula 60>

<Formula 61> <Formula 62> <Formula 63>

<Formula 64> <Formula 65> <Formula 66>

<Formula 67> <Formula 68> <Formula 69>

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

<Formula 73> <Formula 74> <Formula 75>

<Formula 76> <Formula 77> <Formula 78>

<Formula 79> <Formula 80> <Formula 81>

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

<Formula 85> <Formula 86> <Formula 87>

<Formula 88> <Formula 89> <Formula 90>

<Formula 91> <Formula 92> <Formula 93>

<Formula 94> <Formula 95> <Formula 96>

<Formula 97> <Formula 98> <Formula 99>

<Formula 100> <Formula 101> <Formula 102>

<Formula 103> <Formula 104> <Formula 105>

<Formula 106> <Formula 107> <Formula 108>

<Formula 109> <Formula 110> <Formula 111>

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

<Formula 115> <Formula 116> <Formula 117>

<Formula 118> <Formula 119> <Formula 120>

<Formula 121> <Formula 122> <Formula 123>

<Formula 124> <Formula 125> <Formula 126>

<Formula 127> <Formula 128> <Formula 129>

<Formula 130> <Formula 131> <Formula 132>

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

<Formula 136> <Formula 137> <Formula 138>

<Formula 139> <Formula 140> <Formula 141>

<Formula 142> <Formula 143> <Formula 144>

<Formula 145> <Formula 146> <Formula 147>

<Formula 148> <Formula 149> <Formula 150>

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

<Formula 154> <Formula 155> <Formula 156>

<Formula 157> <Formula 158> <Formula 159>

<Formula 160> <Formula 161> <Formula 162>

<Formula 163> <Formula 164> <Formula 165>

Further, in the present invention, the amine compound represented by [Chemical Formula C1] may be any one compound selected from the following [Compound 1-1] to [Compound 1-38], but is not limited thereto.

<Compound 1-1> <Compound 1-2> <Compound 1-3>

<Compound 1-4> <Compound 1-5> <Compound 1-6>

<Compound 1-7> <Compound 1-8> <Compound 1-9>

<Compound 1-10> <Compound 1-11> <Compound 1-12>

<Compound 1-13> <Compound 1-14> <Compound 1-15>

<Compound 1-16> <Compound 1-17> <Compound 1-18>

<Compound 1-19> <Compound 1-20> <Compound 1-21>

<Compound 1-22> <Compound 1-23> <Compound 1-24>

<Compound 1-25> <Compound 1-26> <Compound 1-27>

<Compound 1-28> <Compound 1-29> <Compound 1-30>

<Compound 1-31> <Compound 1-32> <Compound 1-33>

<Compound 1-34> <Compound 1-35> <Compound 1-36>

<Compound 1-37> <Compound 1-38>

Further, in the present invention, the amine compound represented by [Chemical Formula C2] may be any one compound selected from [Compound 3-1] to [Compound 3-43], but is not limited thereto.

<Compound 3-1> <Compound 3-2> <Compound 3-3>

<Compound 3-4> <Compound 3-5> <Compound 3-6>

<Compound 3-7> <Compound 3-8> <Compound 3-9>

<Compound 3-10> <Compound 3-11> <Compound 3-12>

<Compound 3-13> <Compound 3-14> <Compound 3-15>

<Compound 3-16> <Compound 3-17> <Compound 3-18>

<Compound 3-19> <Compound 3-20> <Compound 3-21>

<Compound 3-22> <Compound 3-23> <Compound 3-24>

<Compound 3-25> <Compound 3-26> <Compound 3-27>

<Compound 3-28> <Compound 3-29> <Compound 3-30>

<Compound 3-31> <Compound 3-32> <Compound 3-33>

<Compound 3-34> <Compound 3-35> <Compound 3-36>

<Compound 3-37> <Compound 3-38> <Compound 3-39>

<Compound 3-40> <Compound 3-41> <Compound 3-42>

<Compound 3-43>

Further, in the present invention, the amine compound represented by [Formula D] may be any one compound selected from the following [Compound 2-1] to [Compound 2-159], but is not limited thereto.

<Compound 2-1> <Compound 2-2> <Compound 2-3>

<Compound 2-4> <Compound 2-5> <Compound 2-6>

<Compound 2-7> <Compound 2-8> <Compound 2-9>

<Compound 2-10> <Compound 2-11> <Compound 2-12>

<Compound 2-13> <Compound 2-14> <Compound 2-15>

<Compound 2-16> <Compound 2-17> <Compound 2-18>

<Compound 2-19> <Compound 2-20> <Compound 2-21>

<Compound 2-22> <Compound 2-23> <Compound 2-24>

<Compound 2-25> <Compound 2-26> <Compound 2-27>

<Compound 2-28> <Compound 2-29> <Compound 2-30>

<Compound 2-31> <Compound 2-32> <Compound 2-33>

<Compound 2-34> <Compound 2-35> <Compound 2-36>

<Compound 2-37> <Compound 2-38> <Compound 2-39>

<Compound 2-40> <Compound 2-41> <Compound 2-42>

<Compound 2-43> <Compound 2-44> <Compound 2-45>

<Compound 2-46> <Compound 2-47> <Compound 2-48>

<Compound 2-49> <Compound 2-50> <Compound 2-51>

<Compound 2-52> <Compound 2-53> <Compound 2-54>

<Compound 2-55> <Compound 2-56> <Compound 2-57>

<Compound 2-58> <Compound 2-59> <Compound 2-60>

<Compound 2-61> <Compound 2-62> <Compound 2-63>

<Compound 2-64> <Compound 2-65> <Compound 2-66>

<Compound 2-67> <Compound 2-68> <Compound 2-69>

<Compound 2-70> <Compound 2-71> <Compound 2-72>

<Compound 2-73> <Compound 2-74> <Compound 2-75>

<Compound 2-76> <Compound 2-77> <Compound 2-78>

<Compound 2-79> <Compound 2-80> <Compound 2-81>

<Compound 2-82> <Compound 2-83> <Compound 2-84>

<Compound 2-85> <Compound 2-86> <Compound 2-87>

<Compound 2-88> <Compound 2-89> <Compound 2-90>

<Compound 2-91> <Compound 2-92> <Compound 2-93>

<Compound 2-94> <Compound 2-95> <Compound 2-96>

<Compound 2-97> <Compound 2-98> <Compound 2-99>

<Compound 2-100> <Compound 2-101> <Compound 2-102>

<Compound 2-103> <Compound 2-104> <Compound 2-105>

<Compound 2-106> <Compound 2-107> <Compound 2-108>

<Compound 2-109> <Compound 2-110> <Compound 2-111>

<Compound 2-112> <Compound 2-113> <Compound 2-114>

<Compound 2-115> <Compound 2-116> <Compound 2-117>

<Compound 2-118> <Compound 2-119> <Compound 2-120>

<Compound 2-121> <Compound 2-122> <Compound 2-123>

<Compound 2-124> <Compound 2-125> <Compound 2-126>

<Compound 2-127> <Compound 2-128> <Compound 2-129>

<Compound 2-130> <Compound 2-131> <Compound 2-132>

<Compound 2-133> <Compound 2-134> <Compound 2-135>

<Compound 2-136> <Compound 2-137> <Compound 2-138>

<Compound 2-139> <Compound 2-140> <Compound 2-141>

<Compound 2-142> <Compound 2-143> <Compound 2-144>

<Compound 2-145> <Compound 2-146> <Compound 2-147>

<Compound 2-148> <Compound 2-149> <Compound 2-150>

<Compound 2-151> <Compound 2-152> <Compound 2-153>

<Compound 2-154> <Compound 2-155> <Compound 2-156>

<Compound 2-157> <Compound 2-158> <Compound 2-159>

As a more preferred embodiment of the present invention, in the organic light emitting device according to the present invention, the first electrode is an anode, the second electrode is a cathode, and in addition to the light emitting layer, the hole transport layer and the electron blocking layer, the organic light emitting device has a hole injection layer, At least one of an electron transport layer and an electron injection layer may be additionally included, a hole injection layer may be included between the anode and the hole transport layer, and an electron transport layer and an electron injection layer may be sequentially included between the light emitting layer and the cathode.

More preferably, in the organic light emitting device of the present invention, a hole transport layer, an electron blocking layer and a light emitting layer are sequentially included between the first electrode and the second electrode, and the hole transport layer is represented by Formula A or Formula B. At least one amine compound; The electron blocking layer may include at least one amine compound represented by Chemical Formula C or Chemical Formula D.

In this case, in the present invention, "(organic layer) contains one or more organic compounds" means, "(organic layer) one or more organic compounds belonging to the scope of the present invention or two or more different kinds belonging to the category of the organic compounds. It may include a compound.

In addition, at least one layer selected from the hole injection layer, the hole transport layer, the electron blocking layer, the light emitting layer, the electron transport layer and the electron injection layer in the present invention may be formed by a deposition process or a solution process. Here, the deposition process means a method of forming a thin film by evaporating a material used as a material for forming the respective layers through heating or the like in a vacuum or a low pressure state, and the solution process forms the respective layers. It refers to a method of mixing a material used as a material for a solvent with a solvent and forming a thin film through methods such as inkjet printing, roll-to-roll coating, screen printing, spray coating, dip coating, spin coating, and the like.

In addition, the organic light emitting device in the present invention includes a flat panel display device; Flexible display devices; A monochromatic or white flat panel lighting device; And a monochromatic or white flexible lighting device.

In the present invention, as the material of the hole transport layer, other compounds other than the amine compound represented by Formula A or Formula B of the present invention may be used, and an electron donor molecule having a small ionization potential is usually used, mainly triphenylamine. Diamine, triamine or tetraamine derivatives used as the basic skeleton are often used, for example, N,N'-bis(3-methylphenyl)-N,N'-diphenyl-[1,1-biphenyl]- 4,4'-diamine (TPD) or N,N'-di(naphthalen-1-yl)-N,N'-diphenylbenzidine (a-NPD) or the like can be additionally used.

A hole injection layer (HIL, Hole Injecting Layer) may be additionally stacked on the lower portion of the hole transport layer, and the hole injection layer material is also used in the art in addition to the compound having an amine group represented by Formula A or Formula B of the present invention. As long as it is commonly used, it can be used without particular limitation. -MTDATA(4,4',4"-tris-(3-methylphenylphenyl amino)triphenylamine) may be additionally used.

On the other hand, in the present invention, the light emitting layer may include a dopant and a host, and the dopant may include one or more compounds represented by any one of [Formula I] to [Formula K] below. A dopant material may be used, and preferably, a compound represented by the following [Formula J] or [Formula K] can be used.

[Formula I] [Formula J]

[Formula K]

In the above [Formula I] to [Formula K],

In Formula [I], A is 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 O, N or S as a hetero atom, or a substituted or unsubstituted carbon number. An arylene group having 6 to 60, a substituted or unsubstituted heteroarylene group having 3 to 50 carbon atoms having O, N or S as a hetero atom;

Preferred are anthracene, pyrene, phenanthrene, indenophenanthrene, chrysene, naphthacene, picene, triphenylene, perylene, pentacene.

In [Formula I], X1 and X2 are the same as or different from each other, and each independently selected from unsubstituted or substituted arylene groups having 6 to 30 carbon atoms or single bonds; X1 and X2 may combine with each other;

Y1 to Y2 are the same as or different from each other, and each independently substituted or unsubstituted aryl group having 6 to 24 carbon atoms, substituted or unsubstituted heteroaryl group having 2 to 24 carbon atoms, substituted or unsubstituted carbon having 1 to 24 carbon atoms. Alkyl group, substituted or unsubstituted heteroalkyl group having 1 to 24 carbon atoms, substituted or unsubstituted cycloalkyl group having 3 to 24 carbon atoms, substituted or unsubstituted alkoxy group having 1 to 24 carbon atoms, cyano group, halogen group, substituted or unsubstituted Consisting of a substituted aryloxy group having 6 to 24 carbon atoms, a substituted or unsubstituted alkylsilyl group having 1 to 40 carbon atoms, a substituted or unsubstituted arylsilyl group having 6 to 30 carbon atoms, germanium, phosphorus, boron, deuterium and hydrogen Selected from the group, and may form condensed rings of aliphatic, aromatic, aliphatic heteroaromatic or aromatic groups with adjacent groups;

The l and m are each an integer of 1 to 20, n is an integer of 1 to 4.

Also in [Formula J] and [Formula K],

A1, A2, E and F are each the same or different from each other, and are each independently 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 five-membered ring with carbon atoms connected to the substituents R1 and R2;

The linking groups L1 to L12 are the same as or different from each other, and independently of each other, 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, substituted or unsubstituted Alkynylene group having 2 to 60 carbon atoms, substituted or unsubstituted cycloalkylene group having 3 to 60 carbon atoms, substituted or unsubstituted heterocycloalkylene group having 2 to 60 carbon atoms, substituted or unsubstituted arylene group having 6 to 60 carbon atoms Or a substituted or unsubstituted heteroarylene group having 2 to 60 carbon atoms;

The M is any one selected from N-R3, CR4R5, SiR6R7, GeR8R9, O, S, Se;

The substituents R1 to R9, Ar1 to Ar8 are the same or different from each other, and independently of each other, 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, substituted Or an unsubstituted alkenyl group having 2 to 30 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 30 carbon atoms, a substituted or unsubstituted cycloalke having 5 to 30 carbon atoms Nyl group, substituted or unsubstituted heteroaryl group having 2 to 50 carbon atoms, substituted or unsubstituted heterocycloalkyl group having 2 to 30 carbon atoms, substituted or unsubstituted alkoxy group having 1 to 30 carbon atoms, substituted or unsubstituted carbon number 6 Aryloxy group having 30 to 30, substituted or unsubstituted alkyl thioxy group having 1 to 30 carbon atoms, substituted or unsubstituted arylthio group having 5 to 30 carbon atoms, substituted or unsubstituted alkylamine group having 1 to 30 carbon atoms, substituted Or an 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 carbon atom 1 to 30 An alkyl germanium group, a substituted or unsubstituted aryl germanium group having 1 to 30 carbon atoms, any one selected from a cyano group, a nitro group, and a halogen group,

The R1 and R2 may be connected to each other to form an alicyclic, aromatic monocyclic or polycyclic ring, and the formed alicyclic, aromatic monocyclic or polycyclic carbon atom may be N, O, P, Si, S, Ge , Se, Te may be substituted with any one or more heteroatoms selected from;

Wherein p1 to p4, r1 to r4, s1 to s4 are integers of 1 to 3, but when each of these is 2 or more, each of the linkers L1 to L12 is the same or different from each other,

Wherein x is an integer of 1 or 2, y and z are the same or different, each independently an integer of 0 to 3,

Ar1 and Ar2, Ar3 and Ar4, Ar5 and Ar6, and Ar7 and Ar8 may be connected to each other to form a ring;

In Formula J, two carbon atoms adjacent to each other in the A2 ring combine with * in the structural formula Q1 to form a condensed ring,

In Formula K, two carbon atoms adjacent to each other in the A1 ring are combined with * in the structural formula Q2 to form a condensed ring, and two carbon atoms adjacent to each other in the A2 ring are combined with * in the structural formula Q1 to form a condensed ring. To form.

Preparation of the dopant compound represented by the above [Formula J] or [Formula K] in the present invention is described in WO/2015/174682 (International Publication Date: 2015.11.19, International Application No.: PCT/KR2015/004552) Can be manufactured accordingly.

In addition, the amine group in the compound represented by [Formula I] to [Formula K] may be represented by any one selected from the group represented by the following [Substituent 1] to [Substituent 52], but is not limited thereto.

[Substitution 1] [Substitution 2] [Substitution 3]

[Substitution 4] [Substitution 5] [Substitution 6]

[Substitution 7] [Substitution 8] [Substitution 9]

[Substitution 10] [Substitution 11] [Substitution 12]

[Substitution 13] [Substitution 14] [Substitution 15]

[Substitution 16] [Substitution 17] [Substitution 18]

[Substitution 19] [Substitution 20] [Substitution 21]

[Substitution 22] [Substitution 23] [Substitution 24]

[Substitution 25] [Substitution 26] [Substitution 27]

[Substitution 28] [Substitution 29] [Substitution 30]

[Substitution 31] [Substitution 32] [Substitution 33]

[Substitution 34] [Substitution 35] [Substitution 36]

[Substitution 37] [Substitution 38] [Substitution 39]

[Substitution 40] [Substitution 41] [Substitution 42]

[Substitution 43] [Substitution 44] [Substitution 45]

[Substitution 46] [Substitution 47] [Substitution 48]

[Substitution 49] [Substitution 50] [Substitution 51]

[Substituent 52]

In the above substituents, R is the same or independently of each other, hydrogen, deuterium, halogen atom, hydroxyl group, cyano group, nitro group, amino group, amidino group, hydrazine, hydrazone, carboxyl group or salt thereof, sulfonic acid group or salt thereof, phosphoric acid Or a salt thereof, a substituted or unsubstituted alkyl group having 1 to 60 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 60 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 60 carbon atoms, a substituted or unsubstituted carbon number 1 to 60 alkoxy group, a substituted or unsubstituted alkylthio group having 1 to 60 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 60 carbon atoms, a substituted or unsubstituted aryl group having 6 to 60 carbon atoms, a substituted or Unsubstituted aryl group having 5 to 60 carbon atoms, substituted or unsubstituted arylthio group having 5 to 60 carbon atoms, substituted or unsubstituted heteroaryl group having 2 to 60 carbon atoms, substituted or unsubstituted 1 to 60 carbon atoms (Alkyl) amino group, di(substituted or unsubstituted alkyl having 1 to 60 carbon atoms) amino group, or (substituted or unsubstituted aryl having 6 to 60 carbon atoms) amino group, di (substituted or unsubstituted aryl having 6 to 60 carbon atoms) ) Amino group, substituted or unsubstituted alkylsilyl group having 1 to 40 carbon atoms, substituted or unsubstituted arylsilyl group having 6 to 30 carbon atoms, germanium, phosphorus, may be selected from boron, each of 1 to 12 to be substituted And each substituent may form a condensed ring with adjacent groups.

In addition, the host used in the light emitting layer may include one or more compounds represented by the following [Formula H], in addition to various known host materials may be used.

[Formula H]

In the above [Formula H],

X ₁ to X ₁₀ are the same as or different from each other, and each independently 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, substituted or unsubstituted A 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, Substituted or unsubstituted alkylthio group having 1 to 30 carbon atoms, substituted or unsubstituted arylthiooxy group having 5 to 30 carbon atoms, substituted or unsubstituted alkylamine group having 1 to 30 carbon atoms, substituted or unsubstituted 5 to 5 carbon atoms 30 arylamine group, 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 O, N or S, a substituted or unsubstituted silicone 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 Adjacent groups can form condensed rings of aliphatic, aromatic, aliphatic heteroaromatics.

More specifically, the host may be represented by any one selected from the group represented by the following [Compound 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]

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

Meanwhile, in the present invention, as the electron transport layer material, a known electron transport material may be used as a function of stably transporting electrons injected from an electron injection electrode (Cathode). Examples of known electron transport materials include quinoline derivatives, particularly tris(8-quinolinorate)aluminum (Alq3), Liq, TAZ, BAlq, beryllium bis(benzoquinoline-10-noate) (beryllium bis (benzoquinolin- 10-olate: Bebq2), compound 201, compound 202, BCP, oxadiazole derivatives such as PBD, BMD, BND, or the like may be used, but is not limited thereto.

TAZ BAlq

<Compound 201> <Compound 202> BCP

Further, in the electron transport layer used in the present invention, the organometallic compound represented by the following formula F may be used alone or in combination with the electron transport layer material.

[Formula F]

In the above [Formula F],

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

O is oxygen,

A is 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 2 to 20 carbon atoms Alkynyl group, a substituted or unsubstituted cycloalkyl group having 3 to 30 carbon atoms, a substituted or unsubstituted cycloalkenyl group having 5 to 30 carbon atoms, and a substituted or unsubstituted hetero atom having 2, 50, or 50 carbon atoms with O, N or S Any one selected from aryl groups,

When M is one metal selected from alkali metals, m=1, n=0,

When M is one metal selected from alkaline earth metals, m=1, n=1, or m=2, n=0,

When M is boron or aluminum, m is any one of 1 to 3, and n is one of 0 to 2, and m + n = 3 is satisfied.

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

[Structural Formula C1] [Structural Formula C2] [Structural Formula C3]

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

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

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

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

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

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

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

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

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

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

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

In the above [Structural Formula C1] to [Structural Formula C39],

R is the same or different from each other, and each independently hydrogen, deuterium, halogen, cyano group, substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, substituted or unsubstituted aryl group having 6 to 30 carbon atoms, substituted or unsubstituted Heteroaryl group having 3 to 30 carbon atoms, substituted or unsubstituted alkoxy group having 1 to 30 carbon atoms, substituted or unsubstituted cycloalkyl group having 3 to 30 carbon atoms, substituted or unsubstituted alkenyl group having 2 to 30 carbon atoms, substituted or Unsubstituted alkylamino group having 1 to 30 carbon atoms, substituted or unsubstituted alkylsilyl group having 1 to 30 carbon atoms, substituted or unsubstituted arylamino group having 6 to 30 carbon atoms, and substituted or unsubstituted arylsilyl having 6 to 30 carbon atoms. It is selected from groups, and may be connected to an adjacent substituent by alkylene or alkenylene to form a spiro ring or fused ring. However,'substituted' in the'substituted or unsubstituted' is deuterium, cyano group, halogen group, hydroxy group, nitro group, alkyl group, alkoxy group, alkylamino group, arylamino group, hetero arylamino group, alkylsilyl group, aryl It means substituted with one or more substituents selected from the group consisting of silyl group, aryloxy group, aryl group, heteroaryl group, germanium, phosphorus and boron.

On the other hand, an electron injection layer (EIL, Electron Injecting Layer), which facilitates the injection of electrons from the cathode and ultimately improves power efficiency, may be further stacked on the electron transport layer. It can also be used without particular limitation as long as it is commonly used in the art, for example, LiF, NaCl, CsF, Li ₂ O, BaO and the like can be used.

The thickness of the electron injection layer may be about 1 mm 2 to about 100 mm 2, and about 3 mm 2 to about 90 mm 2. When the thickness of the electron injection layer satisfies the above-described range, satisfactory electron injection characteristics can be obtained without a substantial increase in driving voltage.

Hereinafter, a method of manufacturing the organic light emitting device of the present invention will be described with reference to FIG. 1.

1 is a cross-sectional view showing the 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 electron blocking layer 45, an organic light emitting layer 50, an electron transport layer 60 and a cathode 80, and if necessary, holes The injection layer 30 and the electron injection layer 70 may be further included, and in addition, it is also possible to further form one or two intermediate layers.

Looking at the manufacturing method of the organic light emitting device according to the present invention with reference to FIG.

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

A hole injection layer 30 is formed by vacuum thermal vapor deposition or spin coating a hole injection layer material on the anode 20 electrode. Next, a hole transport layer 40 is formed by vacuum thermally evaporating or spin coating the hole transport layer material on the hole injection layer 30.

Subsequently, an electron blocking layer (EBL, 45) is formed on the hole transport layer.

Here, the electron blocking layer (EBL, 45) has a higher LUMO level than the light emitting layer to block the electrons injected into the light emitting layer from leaking into the hole transport layer (leakage), to function to bind the electrons inside the light emitting layer. Through this, it has an advantage of improving efficiency through exciton generation and density increase in the light emitting layer.

In the present invention, the hole transport layer material represented by Formula A or Formula B is used for the hole transport layer in the organic light emitting device, and by using the electron blocking layer material represented by Formula C or Formula D in the electron blocking layer, , It has the advantage of improving the efficiency of the organic light emitting device.

As a subsequent process, an organic light emitting layer 50 is stacked on the electron blocking layer 45, and a hole blocking layer (not shown) is vacuum-deposited or selectively coated on the organic light emitting layer 50. As a method, a thin film can be formed. The hole blocking layer is a hole When flowing through the organic light emitting layer and flowing into the cathode, the life and efficiency of the device is reduced, and thus serves to prevent this problem by using a material having a very low level of HOMO (Highest Occupied Molecular Orbital). In this case, the hole blocking material used is not particularly limited, but has an electron transporting ability and has a higher ionization potential than the light emitting compound, and typically BAlq, BCP, TPBI, etc. 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 a cathode is vacuum-coated on the electron injection layer 70. The organic EL device is completed by depositing to form the cathode 80 electrode. Here, the metal for forming a negative electrode is lithium (Li), magnesium (Mg), aluminum (Al), aluminum-lithium (Al-Li), calcium (Ca), magnesium-indium (Mg-In), magnesium-silver ( Mg-Ag) and the like, and a transmissive cathode using ITO and IZO can be used to obtain a front light emitting device.

Hereinafter, the present invention will be described in more detail with reference to preferred embodiments. However, these examples are intended to illustrate the present invention in more detail, it will be apparent to those skilled in the art that the scope of the present invention is not limited thereby.

(Example)

Preparation example of hole transport layer compound

Synthesis Example 1: Synthesis of Formula 2

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

[Intermediate 1-a]

In a 500 mL round-bottom flask reactor methyl 2-iodobenzoate (19.1 g, 73 mmol), 4-dibenzofuranboronic acid (18.7 g, 88 mmol), tetrakis (triphenylphosphine)palladium (1.7 g, 0.15 mmol), potassium carbonate (20.2 g, 146.7 mmol) was added, toluene 125 mL, tetrahydrofuran 125 mL, and water 50 mL were added. The temperature of the reactor was raised to 80 degrees 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 separated by column chromatography to obtain [Intermediate 1-a]. (9.5 g, 43%)

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

[Intermediate 1-b]

In a 500 mL round-bottom flask reactor, [Intermediate 1-a] (13.6 g, 45 mmol), sodium hydroxide (2.14 g, 54 mmol) and ethanol 170 ml were added and stirred at reflux for 4 to 8 hours. After completion of the reaction by thin film chromatography, the mixture was cooled to room temperature. 2-Normal hydrochloric acid was added dropwise to the cooled solution, and the resulting solid was filtered after stirring for 30 minutes. Recrystallization with dichloromethane and normal hexane gave [Intermediate 1-b]. (11.4 g, 88%)

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

[Intermediate 1-c]

In a 250 ml round-bottom flask reactor, [Intermediate 1-b] (11.2 g, 39 mmol) and 145 ml of methanesulfonic acid were added and heated to 80 degrees and stirred for 3 hours. After confirming the completion of the reaction by thin film chromatography, the mixture was cooled to room temperature. The reaction solution was slowly added dropwise to 150 ml of ice water and stirred for 30 minutes. The resulting solid was filtered and washed with water and methanol to obtain [Intermediate 1-c]. (8.7 g, 83%)

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

[Intermediate 1-d]

In a 1 L round-bottom flask reactor [Intermediate 1-c] (8.6 g, 32 mmol), dichloromethane 300 ml was added and stirred at room temperature. Bromine (3.4 ml, 66 mmol) was added dropwise diluted in 50 ml of dichloromethane and 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 obtain [Intermediate 1-d]. (8.7 g, 78%)

Synthesis Example 1-(5): Synthesis of [Intermediate 1-e]

[Intermediate 1-e]

In a 250 ml round-bottom flask reactor, 2-bromobiphenyl (8.4 g, 0.036 mol) and tetrahydrofuran 110 ml were added and cooled to -78 degrees in a nitrogen atmosphere. Normal butyl lithium (19.3 ml, 0.031 mol) was added dropwise to the cooled reaction solution at the same temperature. After the reaction solution was stirred for 2 hours, [Intermediate 1-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 completion of the reaction was confirmed by TLC. The reaction was terminated by adding 50 ml of water, and extracted with ethyl acetate and water. The organic layer was separated, concentrated under reduced pressure, and recrystallized with acetonitrile to obtain [Intermediate 1-e]. (9.9 g, 82%)

Synthesis Example 1-(6): Synthesis of [Intermediate 1-f]

[Intermediate 1-f]

In a 250 ml round-bottom flask reactor, [Intermediate 1-e] (9.6 g, 0.019 mol), acetic acid 120 ml, and sulfuric acid 2 ml were added and stirred at reflux for 5 hours. When a solid was formed, the reaction was confirmed 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 cooled to room temperature to obtain [Intermediate 1-f]. (8.3 g, 90%>

Synthesis Example 1-(7): Synthesis of [Formula 2]

[Intermediate 1-f] [Formula 2]

In a 250 ml round bottom flask reactor [Intermediate 1-f] (4.4 g, 0.009 mol), (4-tertiarybutylphenyl)-phenylamine (4.7 g, 0.021 mol), palladium(II) acetate (0.08 g, 0.4 mmol), sodium tertiary butoxide (3.4 g, 0.035 mol), tritertyl butylphosphine (0.07 g, 0.4 mmol), toluene 60 ml was added and stirred at reflux for 2 hours. After the reaction was completed, it was cooled to room temperature. The reaction solution was extracted with dichloromethane and water. The organic layer was separated, anhydrous treated with magnesium sulfate, and concentrated under reduced pressure. After separation and purification by column chromatography, dichloromethane and acetone were recrystallized to obtain [Formula 2]. (3.3 g, 58%)

MS (MALDI-TOF): m/z 629.27 [M ⁺ ]

Synthesis Example 2: Synthesis of Formula 13

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

[Intermediate 2-a]

In a 2 L round-bottom flask reactor, bromobenzene (13.2 g, 83.97 mmol) and 250 ml of tetrahydrofuran were added and stirred in a low-temperature nitrogen environment. About 58 ml of n-butyl lithium was slowly added dropwise over 2 hours at 78 degrees below zero, and [Intermediate 1-a] (9.4 g 31.1 mmol) was added. After completion of the reaction, 100 ml of water was added, stirred for 30 minutes, and extracted to obtain [Intermediate 2-a]. (3.2 g, 24%)

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

[Intermediate 2-b]

[Intermediate 2-a] (55.0 g, 129 mmol), 500 ml of acetic acid and 10 ml of sulfuric acid were added to a 2 L round-bottom flask reactor and stirred at reflux for 5 hours. After the reaction was completed, it was cooled to room temperature, and the resulting solid was filtered. After washing with methanol, [Intermediate 2-b] was obtained. (50 g, 95%)

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

[Intermediate 2-c]

In a 2 L round-bottom flask reactor, [Intermediate 2-b] (50 g, 122 mmol>, 600 ml of dichloromethane was added and stirred at room temperature. Bromine (13.7 ml, 85 mmol) was diluted with 50 ml of dichloromethane and added dropwise. The mixture was stirred for 3 hours, and recrystallized with methanol to obtain [Intermediate 2-c] (45 g, 76%).

Synthesis Example 2-(4): Synthesis of [Formula 13]

[Formula 13]

In a 250 ml round bottom flask reactor [Intermediate 2-c] (4.3 g, 0.009 mol), bis-biphenyl-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), triteryl butylphosphine (0.07 g, 0.4 mmol), toluene 60 ml was added and stirred at reflux for 2 hours. After the reaction was completed, it was cooled to room temperature. The reaction solution was extracted with dichloromethane and water. The organic layer was separated, anhydrous treated with magnesium sulfate, and concentrated under reduced pressure. After separation and purification by column chromatography, dichloromethane and acetone were recrystallized to obtain [Formula 13]. (2.6 g, 40%)

MS (MALDI-TOF): m/z 727.29 [M ⁺ ]

Synthesis Example 3: Synthesis of Formula 35

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

[Intermediate 3-a]

2-bromodibenzofuran (53.1 g, 215 mmol), bis-dibenzylideneacetonedipalladium (3.9 g, 4 mmol), 2,2'- in a 500 ml round bottom flask with aniline (20 g, 215 mmol) Bis(diphenylphosphine)-1,1'-binaphthyl (1.2 g, 4 mmol), sodium tertiary butoxide (41.3 g, 43 mmol), toluene 200 ml was added and refluxed. After cooling to room temperature, washed with methanol and recrystallized from dichloromethane and methane to obtain [Intermediate 3-a]. (40 g, 72%)

Synthesis Example 3-(2): Synthesis of [Formula 35]

[Formula 35]

[Intermediate 3-a] was used instead of the bis-biphenyl-4-yl-amine used in Synthesis Example 2-(4) to obtain [Chemical Formula 35]. (Yield 66%)

MS (MALDI-TOF): m/z 665.24 [M ⁺ ]

Synthesis Example 4: Synthesis of Formula 37

Synthesis Example 4-(1): Synthesis of [Formula 37]

Instead of 4-dibenzofuranboronic acid used in Synthesis Example 1-(1), 1-dibenzofuranboronic acid was used, and bis(4) instead of (4-tertylbutylphenyl)-phenylamine used in 1-(7) -It was synthesized in the same manner as in Synthesis Examples 1-(1) to 1-(7) using tertiarylphenyl)amine to obtain [Chemical Formula 37]. (Yield 55%) MS (MALDI-TOF): m/z 685.33 [M ⁺ ]

Synthesis Example 5: Synthesis of Formula 75

Synthesis Example 5-(1): Synthesis of [Intermediate 5-a]

[Intermediate 5-a]

After adding 25 g (80 mmol) of [Intermediate 1-a] to a round-bottom flask containing 250 ml of tetrahydrofuran, the temperature was lowered to -78 °C under nitrogen. After 30 minutes, 210 ml (240 mmol) of 1.0 M methyl magnesium bromide was slowly added dropwise. After dropping slowly after 1 hour, the temperature is raised to room temperature. After stirring at room temperature for about 2 hours, an aqueous ammonium chloride solution is added dropwise. After extraction, distillation under reduced pressure, and recrystallization with nucleic acid, 19.4 g (yield 80%) of [Intermediate 5-a] was obtained.

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

[Intermediate 5-b]

20 g (66 mmol) of [Intermediate 5-a] was added to a round-bottom flask containing 300 ml of acetic acid and stirred at 0°C for 10 minutes. Add 350 mL of phosphoric acid and stir at room temperature for about 1 hour. After extraction by neutralization with aqueous sodium hydroxide solution, it is concentrated under reduced pressure. Separation by column chromatography gave [Intermediate 5-b] 13.7 g (yield 73%).

Synthesis Example 5-(3): Synthesis of [Intermediate 5-c]

[Intermediate 5-c]

[Intermediate 5-c] was obtained by the same method as [Intermediate 5-b] instead of [Intermediate 2-b] used in Synthesis Example 2-(3). (Yield 45%)

Synthesis Example 5-(4): Synthesis of [Intermediate 5-d]

[Intermediate 5-d]

Synthesis was carried out in the same manner as in Example 3-(1), except that 4-tertiarythyl aniline was used instead of aniline and 4-bromobiphenyl was used instead of 2-bromodibenzofuran [Intermediate 5-d] Got (Yield 78%)

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

[Formula 75]

[Intermediate 5-c] was used instead of [Intermediate 2-c] used in Synthesis Example 2-(4), and [Intermediate 5-d] was used instead of bis-biphenyl-4-yl-amine. [Formula 75] was obtained. (Yield 67%)

MS (MALDI-TOF): m/z 583.29 [M ⁺ ]

Synthesis Example 6: Synthesis of Formula 87

Synthesis Example 6-(1): Synthesis of [Intermediate 6-a]

[Intermediate 6-a] Synthesis Example 1-((6-phenyldibenzo[b,d]furan-4-yl)boronic acid was used instead of 4-dibenzofuranboronic acid used in Synthesis Example 1-(1). 1), Synthesis Example 5-(1) to 5-(3) were synthesized in the same manner to obtain [Intermediate 6-a]. (Yield 48%)

Synthesis Example 6-(2). Synthesis of [Intermediate 6-b]

[Intermediate 6-b] was obtained by synthesizing in the same manner except that 2-bromo-9,9-dimethylfluorene was used instead of 2-bromodibenzofuran used in Synthesis Example 3-(1). (Yield 75%)

Synthesis Example 6-(3). Synthesis of [Formula 87]

[Formula 87]

[Intermediate 6-a] was used instead of [Intermediate 2-c] used in Synthesis Example 2-(4), and [Intermediate 6-b] was used instead of bis-biphenyl-4-yl-amine. [Formula 87] was obtained. (Yield 69%)

MS (MALDI-TOF): m/z 643.29 [M ⁺ ]

Synthesis Example 7: Synthesis of Formula 115

Synthesis Example 7-(1): Synthesis of [Intermediate 7-a]

[Intermediate 7-a]

In a 2 L round-bottom flask reactor, ethyl cyanoacetate (202.9 g, 1.794 mol) and 500 ml of dimethylformamide were added. Potassium hydroxide (67.10 g, 1.196 mol) and potassium cyanide (38.95 g, 0.598 mol) were added, 200 ml of dimethylformamide was added, and the mixture was stirred at room temperature. 4-Nitrodibenzofuran (127. g, 0.737 mol) was added to the reaction solution little by little, followed by stirring at 50°C for 72 hours. After completion of the reaction, 200 ml of aqueous sodium hydroxide solution (25%) was added and stirred under reflux. After stirring for 3 hours, the mixture was cooled to room temperature, and extracted with ether acetate and water. The organic layer was separated, concentrated under reduced pressure, and purified by column chromatography to obtain [Intermediate 7-a]. (20.0 g, 16%)

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

[Intermediate 7-b]

In a 2L round-bottom flask reactor, [Intermediate 7-a] (20.0 g, 96 mmol), ethanol 600 ml, and potassium hydroxide aqueous solution (142.26 g, 2.53 mol) were added and stirred at reflux for 12 hours. When the reaction was completed, it was cooled to room temperature. 400 ml of 6 N hydrochloric acid was added to the reaction solution, acidified, and the resulting solid was stirred for 20 minutes and then filtered. The solid was washed with ethanol to obtain [Intermediate 7-b]. (17.0 g, 88.5%)

Synthesis Example 7-(3): Synthesis of [Intermediate 7-c]

[Intermediate 7-c]

In a 2L round-bottom flask, [Intermediate 7-b] (17.0 g, 75 mmol) and 15 ml of sulfuric acid were added and stirred under reflux for 72 hours. After the reaction was completed, the mixture was cooled to room temperature, and extracted with ethyl acetate and water. The organic layer was separated and washed with an aqueous sodium hydrogen carbonate solution. The organic layer was added with an excessive amount of methanol during concentration under reduced pressure, and the resulting solid was filtered to obtain [Intermediate 7-c]. (14.0 g, 77.6%)

Synthesis Example 7-(4): Synthesis of [Intermediate 7-d]

[Intermediate 7-d]

[Intermediate 7-c] (12 g, 50 mmol), 15 ml of hydrochloric acid and 75 ml of water were added to a 500 mL round-bottom flask reactor, cooled to 0 degrees, and stirred for 1 hour. At the same temperature, 38 ml of sodium nitrite (5.6 g, 81 mmol) aqueous solution was added dropwise to the reaction solution, followed by stirring for 1 hour. When 38 ml of potassium iodide (22.4 g, 135 mmol) aqueous solution was added dropwise, the temperature of the reaction solution was added dropwise, being careful not to exceed 5 degrees. The mixture was stirred at room temperature for 5 hours, and after the reaction was completed, washed with aqueous sodium thiosulfate solution, and extracted with ethyl acetate and water. The organic layer was concentrated under reduced pressure, and separated by column chromatography to obtain [Intermediate 7-d]. (11 g, 91%)

Synthesis Example 7-(5): Synthesis of [Intermediate 7-e]

[Intermediate 7-e]

In the same manner using [Intermediate 7-d] instead of methyl 2-iodobenzoate used in Synthesis Example 1-(1), and 1-dibenzofuranboronic acid instead of 4-dibenzofuranboronic acid [ Intermediate 7-e] was obtained. (10.1 g, 75%)

Synthesis Example 7-(6): Synthesis of [Intermediate 7-f]

[Intermediate 7-f]

In a 500 mL round-bottom flask, [Intermediate 7-e] (10.0 g, 25 mmol), sodium hydroxide (1.1 g, 28 mmol) and 80 ml of ethanol were added and stirred at reflux for 48 hours. After completion of the reaction by thin film chromatography, the mixture was cooled to room temperature. 2-Normal hydrochloric acid was added dropwise to the cooled solution, and the resulting solid was filtered after stirring for 30 minutes. Recrystallization with dichloromethane and hexane gave [Intermediate 7-f]. (7.3 g, 77%)

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

[Intermediate 7-g]

In a 250 ml round bottom flask [Intermediate 7-f] (7 g, 18 mmol), methanesulfonic acid 72 ml was added and stirred at 80°C for 3 hours. After completion of the reaction by thin film chromatography, the mixture was cooled to room temperature. The reaction solution was slowly added dropwise to 75 ml of ice water and stirred for 30 minutes. The resulting solid was filtered and washed with water and methanol to obtain [Intermediate 7-g]. (6.1 g, 94%)

Synthesis Example 7-(8): Synthesis of [Intermediate 7-h]

[Intermediate 7-h]

[Intermediate 7-h] was obtained using the same method, except that [Intermediate 7-g] was used instead of [Intermediate 1-c] in Synthesis Example 1-(4). (4.3 g, 85%)

Synthesis Example 7-(8): Synthesis of [Intermediate 7-i]

[Intermediate 7-i]

In a 250 ml round bottom flask, 2-bromobiphenyl (3.2 g, 13.7 mmol) and 40 ml of tetrahydrofuran were added and cooled to -78 degrees in a nitrogen atmosphere. Normal butyl lithium (8 ml, 12 mmol) was added dropwise at the same temperature. After stirring the reaction solution for 2 hours, [Intermediate 7-h] (4 g, 9.1 mmol) was added little by little and stirred at room temperature. When the color of the reaction solution changed, the completion of the reaction was confirmed by TLC. The reaction was terminated by adding 20 ml of H2O, and extracted with ethyl acetate and water. The organic layer was separated, concentrated under reduced pressure, and recrystallized with acetonitrile to obtain [Intermediate 7-i]. (4 g, 74%)

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

[Intermediate 7-j]

In a 250 ml round-bottom flask, [Intermediate 7-i] (4.0 g, 7 mmol), acetic acid 30 ml and sulfuric acid 1 ml were added and stirred at reflux for 5 hours. When a solid was formed, the reaction was confirmed by thin film chromatography, and then cooled to room temperature. The resulting solid was filtered, washed with H2O, methanol, dissolved in monochlorobenzene, filtered through silica gel, and concentrated to obtain [Intermediate 7-j]. (3.5 g, 86%)

Synthesis Example 7-(10): Synthesis of [Formula 115]

[Formula 115]

[Intermediate 7-j] is used instead of [Intermediate 2-c] used in Synthesis Example 2-(4), and bis(4-tertiarybutylphenyl)amine is used instead of bis-biphenyl-4-yl-amine. By the same method, [Formula 115] was obtained. (Yield 45%)

MS (MALDI-TOF): m/z 775.35 [M ⁺ ]

Synthesis Example 8: Synthesis of Formula 131

Synthesis Example 8-(1): Synthesis of [Intermediate 8-a]

[Intermediate 8-a]

4-bromodibenzofuran (100.0 g, 0.405 mol), ethynyl trimethylsilane (47.7 g, 0.486 mol), [1,1'-bis(diphenylphosphino)ferrocene]dichloropalladium (9.92) in a 2L round bottom flask g, 0.012 mol), copper iodide (2.31 g, 0.012 mol), triphenylphosphine (10.6 g, 0.040 mol), and 700 ml of triethylamine were added and stirred under reflux for 5 hours in a nitrogen atmosphere. After the reaction was completed, the mixture was cooled to room temperature, and 500 ml of heptane was added to terminate the reaction. Celite and silica gel pad were placed and filtered. The filtrate was concentrated under reduced pressure to obtain [Intermediate 8-a]. (130 g, 84%)

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

[Intermediate 8-b]

[Intermediate 8-a] (130 g, 0.492 mol), potassium carbonate (101.9 g, 0.738 mol), 650 ml of methanol and 650 ml of tetrahydrofuran were added to a 2 L round-bottom flask and stirred at room temperature for 2 hours. After the reaction was completed, 500 ml of heptane was added to terminate the reaction. The reaction solution was filtered and the filtrate was extracted with ethyl acetate and water. The organic layer was separated, dried over magnesium sulfate, filtered and concentrated under reduced pressure to obtain [Intermediate 8-b] in the form of an oil. (82 g, 84%)

Synthesis Example 8-(3): Synthesis of [Intermediate 8-c]

[Intermediate 8-c]

2-bromobiphenyl (66.0 g, 0.283 mol), [Intermediate 8-b] (65.3 g, 0.340 mol), [1,1'-bis(diphenylphosphino)ferrocene]dicro in a 2 L round bottom flask Ropalladium (6.94 g, 0.008 mol), copper iodide (1.62 g, 0.008 mol), triphenylphosphine (7.4 g, 0.028 mol) and triethylamine were added and stirred at reflux for 5 hours in a nitrogen atmosphere. After the reaction was completed, the mixture was cooled to room temperature, and 400 ml of heptane was added to terminate the reaction. Celite and silica gel pad were placed and filtered. The filtrate was concentrated under reduced pressure and the resulting solid was filtered to obtain [Intermediate 8-c]. (80 g, 82%)

Synthesis Example 8-(4): Synthesis of [Intermediate 8-d]

[Intermediate 8-d]

[Intermediate 8-c] (80.0 g, 0.232 mol) was dissolved in 960 ml of dichloromethane in a 2 L round-bottom flask and cooled to -78 degrees in a nitrogen atmosphere. Iodine monochloride (278.4 ml, 0.279 mol) was added dropwise to the cooled solution and stirred at room temperature for 12 hours. After the reaction was completed, a saturated aqueous solution of sodium thiosulfate was added and stirred. The organic layer was separated by extraction with dichloromethane and water, and concentrated under reduced pressure. Recrystallization with methanol gave [Intermediate 8-d]. (67 g, 61.3%)

Synthesis Example 8-(5): Synthesis of [Intermediate 8-e]

[Intermediate 8-e]

In a 500 ml round-bottom flask, 150 ml of [Intermediate 4-d] (54.8 g, 0.117 mol) and tetrahydrofuran were dissolved and cooled in a nitrogen atmosphere at -78 degrees. To the cooled solution, 1.6 mol of normal butylium (62.4 ml, 0.1 mol) was added dropwise and stirred at the same temperature for 1 hour. 9-Fluorenone (15.0 g, 0.083 mol) was dissolved in 50 ml of tetrahydrofuran and added dropwise, followed by stirring at room temperature for 8 hours. After completion of the reaction, extraction was performed with ethyl acetate and water. The organic layer was separated, dried over magnesium sulfate, filtered, and concentrated under reduced pressure to obtain [Intermediate 8-e] in the form of an oil. (33.2 g, 76%)

Synthesis Example 8-(6): Synthesis of [Intermediate 8-f]

[Intermediate 8-f]

[Intermediate 8-e] (33.3 g, 0.063 mol), acetic acid 330 ml and sulfuric acid 3 ml were added to a 1 L round-bottom flask size, and the mixture was stirred at reflux for 3 hours. After confirming the completion of the reaction by thin film chromatography, the mixture was cooled to room temperature. The resulting solid was filtered and washed with H2O and methanol to obtain [Intermediate 8-f]. (28.6 g, 88%>

Synthesis Example 8-(7): Synthesis of [Intermediate 8-g]

[Intermediate 8-g]

[Intermediate 8-g] was obtained using the same method, except that [Intermediate 8-f] was used instead of [Intermediate 1-c] in Synthesis Example 1-(4). (6.0 g, 82%)

Synthetic example 8-(8): [Formula 131] synthesis

[Formula 131]

[Intermediate 8-g] is used instead of [Intermediate 2-c] used in Synthesis Example 2-(4), and 4-tertiarybutyl-N-phenylaniline is used instead of bis-biphenyl-4-yl-amine. By the same method, [Formula 131] was obtained. (Yield 45%)

MS (MALDI-TOF): m/z 729.30 [M ⁺ ]

Synthesis Example 9: Synthesis of Formula 42

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

[Intermediate 9-a]

In a 2L round bottom flask, methyl-4-bromo-1-hydroxy-2-naphthoate (50 g, 178 mmol) and dichloromethane were added and stirred. Pyridine (28.1 g, 356 mmol) was added to the reaction solution in a nitrogen atmosphere and stirred at room temperature for 20 minutes. After the reaction solution was cooled to 0 degrees, trifluoromethanesulfonic anhydride (65.24 g, 231 mmol) was added dropwise in a nitrogen atmosphere. After stirring for 3 hours and confirming the completion of the reaction by TLC, 20 ml of water was added and stirred for 10 minutes. The reaction solution was concentrated under reduced pressure and separated by column chromatography to obtain [Intermediate 9-a] (45 g, 61%).

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

[Intermediate 9-b]

In a 1L round-bottom flask [Intermediate 9-a] (45.0 g, 0.109 mol), 4-dibenzofuranboronic acid (25.4 g, 0.120 mol), tetrakis(triphenylphosphine)palladium (2.5 g, 0.22 mmol) , Potassium carbonate (30.1 g, 0.218 mol) was added, and 300 mL of toluene, 130 mL of ethanol, and 90 mL of water were added. The temperature of the reactor was raised to 80 degrees and stirred for 5 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 separated by column chromatography to obtain [Intermediate 9-b] (22.0 g, 46.1%).

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

[Intermediate 9-c]

[Intermediate 9-b] (22.0 g, 0.051 mol) and sodium hydroxide (2.65 g, 0.066 mol) were added to a 1 L round-bottom flask and stirred at reflux for 48 hours. After the reaction was completed, it was cooled to room temperature. 2-Normal hydrochloric acid was added dropwise to the cooled solution, and the resulting solid was filtered after stirring for 30 minutes. Recrystallization with dichloromethane and normal hexane gave [Intermediate 9-c] (17.6 g, 83%).

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

[Intermediate 9-d]

In a 500 ml round bottom flask [Intermediate 9-c] (17.6 g, 0.042 mol), 170 ml of methanesulfonic acid was added and heated to 80 degrees and stirred for 3 hours. After confirming the completion of the reaction by thin film chromatography, the mixture was cooled to room temperature. The reaction solution was slowly added dropwise to 150 ml of ice water and stirred for 30 minutes. The resulting solid was filtered and washed with water and methanol. The solid was dissolved in monochlorobenzene and filtered through a silica gel pad. The filtrate was concentrated by heating and recrystallized with acetone to obtain [Intermediate 9-d] (12 g, 71%).

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

[Intermediate 9-e]

[Intermediate 9-e] (12.0 g, 0.030 mol) and dichloromethane 360 ml were placed in a 1 L round-bottom flask. While stirring at room temperature, bromine (3.1 ml, 0.06 mol) was added dropwise diluted in 40 ml of dichloromethane. The mixture was stirred at room temperature for 12 hours, and after completion of the reaction, 100 ml of methanol was added to filter the resulting solid and washed with methanol. Recrystallization with 1,2-dichlorobenzene and acetone gave [Intermediate 9-e] (10.3 g, 72%).

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

[Intermediate 9-f]

[Intermediate 9-f] was obtained using the same method, except that [Intermediate 9-e] was used instead of [Intermediate 1-d] in Synthesis Example 1-(5). (Yield 73%)

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

[Intermediate 9-g]

[Intermediate 9-g] was obtained using the same method, except that [Intermediate 9-f] was used instead of [Intermediate 1-e] in Synthesis Example 1-(6). (Yield 65%)

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

[Intermediate 9-h]

[Intermediate 9-h] was used in the same manner using [Intermediate 9-g] instead of methyl 2-iodobenzoate used in Synthesis Example 1-(1), and using phenylboronic acid instead of 4-dibenzofuranboronic acid. ]. (Yield 45%)

Synthesis Example 9-(9): Synthesis of [Formula 42]

[Formula 42]

[Intermediate 9-h] is used instead of [Intermediate 2-c] used in Synthesis Example 2-(4), and N-phenyl-4-biphenylamine is used instead of bis-biphenyl-4-yl-amine. [Formula 42] was obtained in the same manner. (Yield 44%)

MS (MALDI-TOF): m/z 775.29 [M ⁺ ]

Synthesis Example 10: Synthesis of Formula 146

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

[Intermediate 10-a]

Instead of 4-dibenzofuranboronic acid used in Synthesis Example 1-(1), 4-dibenzothiophenboronic acid was used to prepare Synthesis Examples 1-(1) and Synthesis Examples 2-(1) to 2-(3). It was synthesized in the same manner to obtain [Intermediate 10-a]. (Yield 68%)

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

[Intermediate 10-b]

1-bromo-4-(2-naphthyl)benzene (10.0 g, 0.035 mol), 4-tertiarybutylaniline (5.8 g, 0.039 mol), tris(dibenzylideneacetone)dipalladium in a 250 ml round bottom flask (0) (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) ) 100 ml of toluene was added and stirred at reflux for 3 hours. After the reaction was completed, the mixture was cooled to room temperature, and extracted with ethyl acetate and water. The organic layer was separated, anhydrous treated with magnesium sulfate, and concentrated under reduced pressure. Separated by column chromatography to obtain [Intermediate 10-b] (10 g, 80%).

Synthesis Example 10-(3): Synthesis of [Formula 146]

[Formula 146]

[Intermediate 10-a] was used instead of [Intermediate 2-c] used in Synthesis Example 2-(4), and [Intermediate 10-b] was used instead of bis-biphenyl-4-yl-amine. [Formula 146] was obtained. (Yield 48%)

MS (MALDI-TOF): m/z 773.31 [M ⁺ ]

Preparation example of electron blocking layer compound

Synthesis Example 11: Synthesis of Compound 1-1

<4,4'''-bis｛(biphenyl-4-yl)-phenylamino}-(1,1':4',1'':4'',1'''-quarter-phenyl)( Synthesis of Compound 1-1)>

In a nitrogen-substituted reaction vessel, N-phenyl-N-{4-(4,4,5,5-tetramethyl-1,3,2-dioxyborolan-2-yl) phenyl}-(1, 1'-biphenyl-4-yl) 18.2 g of amine, 7.5 g of 4,4'-diiodide biphenyl, 46 ml of 2M aqueous potassium carbonate solution, 60 ml of toluene and 15 ml of ethanol were added, and nitrogen gas was vented for 1 hour. 1.1 g of tetrakis(triphenyl phosphine) palladium was added and heated and stirred at 72°C for 10 hours. After cooling to room temperature, 60 ml of methanol was added. The precipitated solid was collected by filtration, washed with 100 ml of a mixed solution of methanol/water (5/1,v/v), and dissolved by adding 100 ml of 1, 2-dichlorobenzene and heating. After removing the insoluble matters by filtration, the mixture was allowed to cool, and a precipitate precipitated by adding 200 ml of methanol was collected by filtration. 4,4'''-bisbis(biphenyl-4-yl)-phenylamino}-(1,1':4',1'':4 by reflux washing using 100 ml of methanol in the preparation. 11.8 g (yield 81%) of a pale yellow powder of'',1'''-quater-phenyl) (Compound 1-1) was obtained.

The structure of the obtained pale yellow powder was confirmed by NMR.

H-NMR (CDCl3): δ (ppm) = 7.66-7.77 (8H), 7.50-7.64 (12H), 7.42-7.50 (4H), 7.28-7.38 (6H), 7.20-7.26 (12H), 7.08 (2H )

Synthesis Example 12: Synthesis of Compound 1-13

<4,4''''-bis｛(biphenyl-4-yl)-phenylamino}-(1,1'：4',1'':4'',1''':4''' Synthesis of ,1''''-Quanqua Phenyl) (Compound 1-13)>

In a nitrogen-substituted reaction vessel, N-phenyl-N-{4-(4,4,5,5-tetramethyl-1,3,2-dioxyborolan-2-yl) phenyl}-(1, 1'-biphenyl-4-yl) amine 16.3g, 4,4'-diiodophenyl 8.0g, 2M potassium carbonate aqueous solution 41ml, toluene 64ml, ethanol 16ml was added, and nitrogen gas was vented for 1 hour. . 1.0 g of tetrakis(triphenylphosphine) palladium was added, heated, and stirred at 72°C for 18 hours. After cooling to room temperature, 60 ml of methanol was added. The precipitated solid was collected by filtration, washed with 100 ml of a mixed solution of methanol/water (5/1, v/v), and then 100 ml of 1, 2-dichlorobenzene was added and dissolved by heating. After removing the insoluble matters by filtration, the mixture was allowed to cool, and a precipitate precipitated by adding 200 ml of methanol was collected by filtration. 4,4''''-bisbis(biphenyl-4-yl)-phenylamino}-(1,1': by reflux washing with 100 ml of methanol in the preparation:

9.8 g (yield 66%) of light yellow powder of 4',1'':4'',1''':4''',1''''-Quanqua Phenyl) (Compound 1-13) was obtained.

The structure of the obtained pale yellow powder was confirmed by NMR.

H-NMR (CDCl3): δ (ppm) = 7.66-7.80 (12H), 7.50-7.64 (12H), 7.42-7.50 (4H), 7.28-7.38 (6H), 7.20-7.26 (12H), 7.08 (2H )

Synthesis Example 13: Synthesis of Compound 1-11

<4,4'''-bis｛(biphenyl-4-yl)-phenylamino}-(1,1':3',1'':3",1'"-quarter-phenyl)( Synthesis of Compound 1-11)>

In Synthesis Example 11, by reacting under the same conditions using 3, 3'-dibromo biphenyl instead of 4,4'-diiod biphenyl, 4,4'''-bisbis Light yellow powder 16.2 of (biphenyl-4-yl)-phenylamino}-(1,1':3',1'':3'',1'''-quater-phenyl) (Compound 1-11) g (yield 91%) was obtained.

The structure of the obtained pale yellow powder was confirmed by NMR.

H-NMR (CDCl3): δ (ppm) = 7.87 (2H), 7.48-7.66 (18H), 7.39-7.48 (4H), 7.29-7.39 (6H), 7.18-7.26 (12H), 7.08 (2H)

Synthesis Example 14: Synthesis of Compound 1-15

<4,4''''-bis｛(biphenyl-4-yl)-phenylamino}-(1,1'：3',1'':2'',1''':3''' Synthesis of ,1''''-Quanqua Phenyl) (Compound 1-15)>

In Synthesis Example 11, 3,3''-dibromo (1,1':2',1''-terphenyl) was used instead of 4,4'-diiodide biphenyl, and the same conditions were used. By reacting with, 4,4''''-bis｛(biphenyl-4-yl)-phenylamino}-(1,1':3',1'':2'',1''' : 17.0 g (yield 92%) of a pale yellow powder of 3''',1''''-quinque phenyl) (Compound 1-15) was obtained.

The structure of the obtained pale yellow powder was confirmed by NMR.

H-NMR (CDCl3): δ (ppm) = 7.00-7.62 (48H),

Synthesis Example 15: Synthesis of Compound 1-17

<4,4''''-bis｛(biphenyl-4-yl)-phenylamino}-(1,1'：3',1'':3'',1''':3''' Synthesis of ,1''''-Quanqua Phenyl) (Compound 1-17)>

In Synthesis Example 11, 3,3''-dibromo (1,1':3',1''-terphenyl) was used instead of 4,4'-diiodide biphenyl, and the same conditions were used. By reacting with, 4,4''''-bis｛(biphenyl-4-yl)-phenylamino}-(1,1'：3',1'':3'',1''' : 10.5 g (yield 57%) of a pale yellow powder of 3''',1''''-quinque phenyl) (Compound 1-17) was obtained.

The structure of the obtained pale yellow powder was confirmed by NMR.

H-NMR (CDCl3): δ (ppm) = 7.93 (1H), 7.87 (2H), 7.40-7.72 (24H), 7.16-7.38 (18H), 7.09 (3H)

Synthesis Example 16: Synthesis of Compound 1-21

<4,4'''-bis｛(biphenyl-4-yl)-phenylamino}-(1,1'：2',1'':2'',1'''-quarter-phenyl)( Synthesis of Compound 1-21)

In Synthesis Example 11, instead of 4,4'-diiod biphenyl, 2, 2'-dibromo biphenyl was used, and the reaction was carried out under the same conditions, whereby 4,4'''-bisbis (Biphenyl-4-yl)-Phenylamino}-(1,1':2',1'':2'',1'''-Quarter-phenyl) (Compound 1-21), pale yellow powder 9.0 g (yield 83%) was obtained.

The structure of the obtained pale yellow powder was confirmed by NMR.

H-NMR (CDCl3): δ (ppm) = 7.45-7.54 (6H), 7.23-7.45 (16H), 7.13-7.22 (4H), 7.05-7.13 (8H), 6.94 (2H), 6.82 (4H), 6.62 (4H)

Synthesis Example 17: Synthesis of Compound 1-22

<4,4'''-bisopen(naphthalen-1-yl)-phenylamino}-(1,1':3',1'':3'',1'''-quater-phenyl) (compound Synthesis of 1-22)

In Synthesis Example 11, instead of 4,4'-diiod biphenyl, 3, 3'-dibromo biphenyl was used, and N-phenyl-N-{4-(4,4,5,5 -Tetramethyl-1,3,2-dioxybororan-2-yl) phenyl}-(1,1'-biphenyl-4-yl) in place of amine, N-phenyl-N-{4- By using (4,4,5,5-tetramethyl-1,3,2-dioxyborolan-2-yl) phenyl}-(naphthalen-1-yl) amine and reacting under the same conditions , 4,4'''-bisopen(naphthalen-1-yl)-phenylamino}-(1,1':3',1'':3'',1'''-quater-phenyl) (compound 1-22) of pale yellow powder 4.00 g (yield 26%) was obtained.

The structure of the obtained pale yellow powder was confirmed by NMR.

H-NMR (CDCl3): δ (ppm) = 7.99 (2H), 7.92 (2H), 7.78-7.85 (4H), 7.35-7.61 (18H), 7.19-7.28 (4H), 7.06-7.15 (8H), 6.98 (2H)

Synthesis Example 18: Synthesis of Compound 1-23

<4,4''''-bis｛(biphenyl-4-yl)-phenylamino}-(1,1'：4',1'':2'',1''':4''' Synthesis of ,1''''-Quanqua Phenyl) (Compound 1-23)>

In Synthesis Example 11, 4,4'-dibromo (1,1':2', 1''-terphenyl) was used in place of 4,4'-diiodide biphenyl, and the same conditions were used. By reacting with, 4,4''''-bis｛(biphenyl-4-yl)-phenylamino}-(1,1':4',1'':2'',1''' 13.8 g (yield 62%) of a pale yellow powder of 4''',1''''-quinque phenyl) (Compound 1-23) was obtained.

The structure of the obtained pale yellow powder was confirmed by NMR.

H-NMR (CDCl3): δ (ppm) = 7.60 (4H), 7.03-7.56 (44H)

Synthesis Example 19: Synthesis of Compound 1-24

<4,4''''-bis｛(biphenyl-4-yl)-phenylamino}-(1,1'：2',1'':3'',1''':2''' Synthesis of ,1''''-Quanqua Phenyl) (Compound 1-24)>

In Synthesis Example 11, 2, 2''-dibromo (1,1':3',1''-terphenyl) was used instead of 4,4'-diiodide biphenyl, and the same conditions were used. By reacting with 4,4''''-bis｛(biphenyl-4-yl)-phenylamino}-(1,1':2',1'':3'',1''' 9.7 g (yield 69%) of a pale yellow powder of 2''',1''''-quinque phenyl) (Compound 1-24) was obtained.

The structure of the obtained pale yellow powder was confirmed by NMR.

H-NMR (CDCl3): δ (ppm) = 7.30-7.56 (20H), 6.91-7.24 (28H),

Synthesis Example 20: Synthesis of Compound 1-25

<4,4''''-bis｛(biphenyl-4-yl)-phenylamino}-(1,1'：4',1'':3'',1''':4''' Synthesis of ,1''''-Quanqua Phenyl) (Compound 1-25)>

In Synthesis Example 11, instead of 4,4'-diiodbiphenyl, 4,4''-dibromo (1,1':3',1''-terphenyl) was used, and the same conditions were used. By reacting with 4,4''''-bis｛(biphenyl-4-yl)-phenylamino}-(1,1':4',1'':3'',1''' : 16.5 g of light yellow powder (4% yield) of 4''',1''''-quinque phenyl) (Compound 1-25) was obtained.

The structure of the obtained pale yellow powder was confirmed by NMR.

H-NMR (CDCl3): δ (ppm) = 7.93 (1H), 7.06-7.80 (47H)

Synthesis Example 21: Synthesis of Compound 1-26

<4,4''''-bis｛(dibenzofuran-1-yl)-phenylamino}-(1,1'：4',1'':2'',1''':4'' Synthesis of',1''''-Quanqua Phenyl) (Compound 1-26)>

In Synthesis Example 11, N-phenyl-N-{4-(4,4,5,5-tetramethyl-1,3,2-dioxyborolan-2-yl) phenyl}-(1,1 '-Biphenyl-4-yl) N-phenyl-N-{4-(4,4,5,5-tetramethyl-1,3,2-dioxyborolan-2-yl instead of amine ) By using phenyl}-(dibenzofuran-1-yl) amine and reacting under the same conditions, 4,4''''bis아미노(dibenzofuran-1-yl)-phenylamino}-( 14.0 g of pale yellow powder (yield 61) of 1,1':4',1'':2'',1''':4''',1''''-Quanqua phenyl) (Compound 1-26) %).

The structure of the obtained pale yellow powder was confirmed by NMR.

H-NMR (CDCl3): δ (ppm) = 7.97 (2H), 7.79 (2H), 7.02-7.55 (40H)

Synthesis Example 22: Synthesis of Compound 1-27

<4,4''''-bis｛(biphenyl-4-yl)-phenylamino}-(1,1'：2',1'':2'',1''':2''' Synthesis of ,1''''-Quanqua Phenyl) (Compound 1-27)>

In Synthesis Example 11, 2, 2''-dibromo (1,1':2',1''-terphenyl) was used instead of 4,4'-diiodide biphenyl, and the same conditions were used. By reacting with 4,4''''-bis｛(biphenyl-4-yl)-phenylamino}-(1,1'：2',1'':2'',1''' 8.5g (yield: 61%) of a pale yellow powder of 2''',1''''-quinque phenyl) (Compound 1-27) was obtained.

The structure of the obtained pale yellow powder was confirmed by NMR.

H-NMR (CDCl3): δ (ppm) = 7.62 (4H), 6.78-7.57 (36H), 6.35 (4H), 6.46 (2H), 6.38 (2H)

Synthesis Example 23: Synthesis of Compound 1-28

<4,4'''-bis｛(biphenyl-4-yl)-d5-phenylamino}-(1,1'：3',1'':3'',1'''-quarter-phenyl ) (Compound 1-28)>

In Synthesis Example 11, instead of 4,4'-diiod biphenyl, 3, 3'-dibromo biphenyl was used, and N-phenyl-N-{4-(4,4,5,5 -Tetramethyl-1,3,2-dioxybororan-2-yl) phenyl}-(1,1'-biphenyl-4-yl) in place of amine, N-(phenyl-d5)-N -{4-(4,4,5,5-tetramethyl-1,3,2-dioxybororan-2-yl) phenyl}-(1,1'-biphenyl-4-yl) amine By using and reacting under the same conditions, 4,4'''-bis｛(biphenyl-4-yl)-d5-phenylamino}-(1,1':3',1'':3' 8.7g (yield 68%) of a pale yellow powder of',1'''-quater-phenyl) (Compound 1-28) was obtained.

The structure of the obtained pale yellow powder was confirmed by NMR.

H-NMR (CDCl3): δ (ppm) = 7.87 (2H), 7.40-7.66 (20H), 7.30-7.38 (4H), 7.19-7.26 (8H)

Synthesis Example 24: Synthesis of Compound 2-1

<Synthesis of N,N-bis(phenyl-4-yl)-N-(6-phenyl biphenyl-3-yl) amine (Compound 2-1)>

(Step 1) In a nitrogen-substituted reaction vessel, 40.5 g of N, N-bis (phenyl-4-yl)amine, 28.0 g of 3-bromophenyl, 13.7 g of t-butoxy sodium, and 400 mL of toluene were added and ultrasonicated for 30 minutes. The nitrogen gas was ventilated while investigating. Subsequently, 0.54 g of palladium acetate and 1.46 g of a 50% (w/v) toluene solution of t-butylphosphine were added, heated and stirred at 95°C for 4 hours. After filtering, the insoluble matter was removed, followed by heating to purify and purify silica gel at 100°C, followed by filtration. The filtrate was cooled to room temperature while stirring, and the precipitated solid was collected by filtration and 50.2 g of a green white solid of N, N-bis(phenyl-4-yl)-N-(biphenyl-3-yl) amine (yield 88 %).

(Second process)

To the nitrogen-substituted reaction vessel, 50.0 g of triaryl amine obtained above and 500 m of dimethyl formamide were added and cooled in an ice bath. Then, 22.1 g of N,N-bromothycinimide was slowly stirred for 4 hours. After this, methanol was added and the precipitated water was collected by filtration. Then, it was backwashed with ethyl acetate, and 40.2 g (yield 69%) of a pink powder of N, N-bis(phenyl-4-yl)-N-(6-bromophenyl-3-yl) amine was obtained.

(3rd process)

N,N-bis(phenyl-4-yl)-N-(6-bromophenyl-3-yl)amine 11.8g, toluene 94mL, phenyl boronic acid 2.7g, obtained in advance in the following nitrogen-substituted reaction vessel An aqueous solution in which 5.9 g of potassium carbonate was dissolved in 36 mL of water was added, and nitrogen gas was ventilated while irradiating ultrasonic waves for 30 minutes.

Thereafter, 0.74 g of tetrakis triphenyl phosphine palladium was added, heated, and stirred at 72° C. for 18 hours. After cooling to room temperature, an organic layer was collected by liquid separation. Washing with water After washing sequentially with saturated brine, the mixture was dried and concentrated using anhydrous magnesium sulfate to obtain a formulation. Then purified by column chromatography, N, N-bis(phenyl-4-yl) 8.4 g (yield 72%) of a white powder of -N-(6-phenyl biphenyl-3-yl) amine was obtained. The structure of the obtained white powder was confirmed by NMR.

H-NMR (CDCl3): δ (ppm) = 7.56-7.68 (7H), 7.45-7.52 (4H), 7.14-7.41 (20H)

Synthesis Example 25: Synthesis of Compound 2-2

<Synthesis of N,N-bis(phenyl-4-yl)-N-{6-(naphthyl-1-yl) phenyl-3-yl} amine (Compound 2-2)> Third step of Synthesis Example 24 N,N-bis(phenyl-4-yl)-N-{6-(naphthyl-) was performed under the same conditions as in Synthesis Example 24, except that phenyl boronic acid used in 1-naphthylboronic acid was used instead. 1-day) phenyl-3-yl} amine White powder 9.2g (yield 61%) was obtained. The structure of the obtained white powder was confirmed by NMR.

H-NMR (CDCl3): δ (ppm) = 7.84-7.87 (3H), 7.67-7.83 (6H), 7.26-7.64 (18H), 7.02-7.04 (6H)

Synthesis Example 26: Synthesis of Compound 2-3

<Synthesis of N, N-bis(phenyl-4-yl)-N- {6-(9,9-dimethyl fluoren-2-yl) phenyl-3-yl} amine (Compound 2-3)>

The reaction was performed under the same conditions as in Synthesis Example 24, except that the phenyl boronic acid used in Synthesis Example 24 was replaced with (9,9-dimethyl fluoren-2-yl) boronic acid, and N,N-bis(phenyl-4- 1) -N-{6-(9,9-dimethyl fluoren-2-yl) phenyl-3-yl} amine White powder 9.0g (yield 57%) was obtained.

The structure was confirmed using NMR for the obtained white powder.

H-NMR (CDCl3): δ (ppm) = 7.56-7.64 (10H), 7.26-7.50 (18H), 7.02-7.16 (5H), 1.26 (6H)

Synthesis Example 27: Synthesis of Compound 2-94

<Synthesis of N,N-bis(6-phenyl biphenyl-3-yl)-N-(biphenyl-4-yl) amine (Compound 2-94)>

(1st process)

In a nitrogen-substituted reaction vessel, 13.0 g of benzamide, 52.5 g of 3-bromophenyl, 44.5 g of potassium carbonate, 3.4 g of sodium hydrogen sulfite, 2.2 g of phenanthrolinyl hydrate, 0.68 g of copper powder, 13 mL of dodecyl benzene, 30 mL of toluene The mixture was heated with stirring and refluxed for 19 hours while excluding toluene. After cooling and adding toluene, insoluble matter was removed by filtration. Washing with water After washing sequentially with saturated brine, dried over anhydrous magnesium sulfate and concentrated to obtain a formulation.

(Second process)

In the reaction vessel, N,N-bis(phenyl-3-yl)benzamide obtained above, 41.7g, isoamyl alcohol 36mL, water 12mL, potassium hydroxide 7.6g obtained by purification by column chromatography, N,N-bis( Phenyl-3-yl) Benzamide Yellow viscous substance 41.7 g (yield 91%) was added, heated with stirring, and refluxed for 48 hours. After cooling to room temperature, water and toluene were added, and an organic layer was collected by a separation operation. Washing with water After washing sequentially with saturated brine, dried over anhydrous magnesium sulfate and concentrated to obtain a formulation. Subsequently, 25.3 g (yield 80%) of a brown viscous substance of N and N-bis(phenyl-3-yl) amine was obtained by purification using column chromatography.

(3rd process)

In a nitrogen-substituted reaction vessel, 25.2 g of N, N-ratio (phenyl-3-yl) amine obtained above, 250 mL of toluene, 20.5 g of 4-bromophenyl, 9.0 g of t-butoxy sodium were added, and ultrasonic waves were irradiated for 30 minutes. While ventilating the nitrogen gas. Then, 0.35 g of palladium acetate and 0.95 g of a 50% (w/v) toluene solution of t-butyl phosphine were added, heated, and stirred at 95° C. for 14 hours. After removing insoluble matters by filtration, washing with water was sequentially performed with saturated brine, dried over anhydrous magnesium sulfate and concentrated to obtain a preparation. Then, 31.6 g (yield 85%) of an off-white powder of N, N-bis(phenyl-3-yl)-N-(biphenyl-4-yl)amine was obtained by purification using column chromatography.

(4th process)

To the nitrogen-substituted reaction vessel, 31.5 g of N, N-bis(phenyl-3-yl)-N-(biphenyl-4-yl)amine obtained above, and 320 mL of dimethyl formamide were added and cooled in an ice bath. Then, 26.0 g of N and N-bromo rosinimide were slowly added and stirred for 5 hours. Water was added and precipitated water was collected by filtration. After washing with methanol, purification by column chromatography, 36.9 g of white powder of N, N-bis(6-bromophenyl-3-yl)-N-(biphenyl-4-yl) amine (yield) 88%).

(The fifth step)

The bis (phenyl-4-yl)-(6-bromo phenyl-3-yl) amine used in the third step of Synthesis Example 24 was obtained above, N, N-bis(6-bromo phenyl-3-yl )-N-(biphenyl-4-yl) N,N-bis(6-phenyl biphenyl-3-yl)-N by reacting in the same manner as in the third step of Synthesis Example 24, except that instead of amine -10.2 g (yield 73%) of a white powder of ((biphenyl-4-yl)) amine was obtained.

The structure was confirmed using NMR for the obtained white powder.

H-NMR (CDCl3): δ (ppm) = 7.57-7.66 (4H), 7.10-7.49 (31H)

Synthesis Example 28: Synthesis of Compound 2-129

<Synthesis of tris(6-phenyl biphenyl-3-yl) amine (Compound 2-129)>

(First process)

In a nitrogen-substituted reaction vessel, 10.4 g of 3-amino phenyl, 250 mL of toluene, 30.0 g of 3-bromophenyl, and 13.1 g of t-butoxy sodium were added, and nitrogen gas was ventilated while irradiating ultrasonic waves for 30 minutes. Then, tris dibenzylidene acetone palladium 2.25g, t-butyl phosphine 50% (w / v), toluene solution 1.50g was added and heated and stirred at 95 ℃ for 3 hours. After filtration, the insoluble water was continuously washed with water, and then washed sequentially with saturated brine, dried over anhydrous magnesium sulfate, and concentrated to obtain a formulation. In addition, 24.6 g of a white powder of tris (phenyl-3-yl) amine (yield 85%) was obtained by purification using column chromatography.

(Second process)

In a nitrogen-substituted reaction vessel, 24.5 g of above tris(phenyl-3-yl)amine and 245 mL of dimethyl formamide were added and cooled in an ice bath. Then, 30.4 g of N and N-bromo rosinimide was slowly added and stirred for 7 hours. Toluene was added, followed by washing with water, followed by washing with saturated brine sequentially, followed by drying with anhydrous magnesium sulfate and concentration to obtain a formulation. By purification using column chromatography, 33.6 g (92% yield) of a white powder of tris (6-bromophenyl-3-yl) amine was obtained.

(3rd process)

The bis(phenyl-4-yl)-(6-bromo phenyl-3-yl) amine used in the third step of Synthesis Example 24 was substituted for the tris(6-bromo phenyl-3-yl) amine obtained above. A reaction was performed in the same manner as in the third step of Synthesis Example 24, except that 11.1 g of tris(6-phenylbiphenyl-3-yl)amine white powder (yield 75%) was obtained.

The structure was confirmed using NMR for the obtained white powder.

H-NMR (CDCl3): δ (ppm) = 7.35-7.42 (6H), 7.15-7.35 (33H)

Synthesis Example 29: Synthesis of Compound 2-4

<Synthesis of N,N-bis(phenyl-4-yl)-N-(6-phenyl-1,1': 4'1''-terphenyl-4-yl)amine (Compound 2-4)>

N,N-bis(phenyl-4-yl)-N- was carried out under the same conditions as in Synthesis Example 24, except that phenyl boronic acid used in the third step of Synthesis Example 24 was substituted for 4-biphenylboronic acid. (6-Phenyl-1,1':4'1''-terphenyl-4-yl) 8.4 g (yield 76%) of a white powder of amine was obtained.

The structure was confirmed using NMR for the obtained white powder.

H-NMR (CDCl3): δ (ppm) = 7.60-7.68 (10H), 7.45-7.50 (9H), 7.30-7.39 (8H), 7.22-7.28 (8H)

Synthesis Example 30: Synthesis of Compound 2-9

<N,N-bis(phenyl-4-yl)-N-(6-phenyl-1,1': 4'1': 4''1'''- quarter phenyl-4-yl) amine (Compound 2 -9) Synthesis>

N,N-bis(phenyl-4-yl) was carried out under the same conditions as in Synthesis Example 24, except that phenyl boronic acid used in the third step of Synthesis Example 24 was substituted for p-terphenyl boronic acid pinacol ester. )-N-(6-phenyl-1,1': 4'1': 4''1'''- quarter phenyl-4-yl) 7.6 g of amine white powder (yield 75%) was obtained.

The structure was confirmed using NMR for the obtained white powder.

H-NMR (CDCl3): δ (ppm) = 7.40-7.55 (20H), 7.30-7.39 (7H), 7.19-7.29 (12H)

Synthesis Example 31: Synthesis of Compound 2-56

<N-4-biphenyl-N-(9,9-dimethyl fluoren-2-yl)-N-(6-phenyl-1,1':4'1''-terphenyl-4-yl) amine Synthesis of (Compound 2-56)>

In the third step of Synthesis Example 24, instead of N,N-bis(phenyl-4-yl)-N-(6-bromo phenyl-3-yl) amine and phenyl boronic acid, N-4-biphenyl- Same as the third step of Synthesis Example 24 except that N-(6-bromophenyl-3-yl)-N-(9,9-dimethyl fluoren-2-yl) amine and 4-biphenyl boronic acid were used. N-4-biphenyl-N-(9,9-dimethyl fluoren-2-yl)-N-(6-phenyl -1,1': 4'1''- terphenyl- 4-day) 17.8 g of amine white powder (yield 89%) was obtained.

The structure was confirmed using NMR for the obtained white powder.

H-NMR (CDCl3): δ (ppm) = 7.57-7.70 (7H), 7.18-7.52 (26H), 1.52 (6H)

Synthesis Example 32: Synthesis of Compound 2-68

<N-4-biphenyl -N-(1,1 '4', 1''-terphenyl-4-yl)-N-(6-phenyl-1,1': 4'1''- terphenyl Synthesis of -4-yl)amine (Compound 2-68)>

N-4-biphenyl- in place of N,N-bis(phenyl-4-yl)-N-(6-bromo phenyl-3-yl) amine and phenyl boronic acid in the third step of Synthesis Example 24 The reaction was performed under the same conditions as in the third step of Synthesis Example 24, except that N-(6-bromophenyl-3-yl)-N-(4-bromophenyl) amine and 4-biphenyl boronic acid were used. N-4-biphenyl-N (1,1 '4', 1''-terphenyl-4-yl)-N-(6-phenyl -1,1': 4'1''- terphenyl -4 -Work) Obtained 6.4 g (yield 55%) of white powder of amine.

The structure was confirmed using NMR for the obtained white powder.

H-NMR (CDCl3): δ (ppm) = 7.58-7.79 (15H), 7.42-7.53 (9H), 7.20-7.40 (15H)

Synthesis Example 33: Synthesis of Compound 2-90

<Synthesis of N,N-bis(phenyl-4-yl)-N-(6-phenyl-1,1': 4'1''-terphenyl-3-yl) amine (Compound 2-90)>

Instead of N,N-bis(phenyl-4-yl)-N-(6-bromo phenyl-3-yl) amine in the third step of Synthesis Example 24, N,N-bis(phenyl-4-yl )-N-(6-bromo-1,1': 4'1''- terphenyl-3-yl) N was conducted by performing the reaction under the same conditions as in the third step of Synthesis Example 24, except that amine was used. 6.8 g (yield 84%) of a white powder of N-bis(phenyl-4-yl)-N-(6-phenyl-1,1':4'1''-terphenyl-3-yl) amine was obtained.

The structure was confirmed using NMR for the obtained white powder.

H-NMR (CDCl3): δ (ppm) = 7.58-7.66 (10H), 7.34-7.48 (17H), 7.20-7.28 (8H)

Synthesis Example 34: Synthesis of Compound 2-92

<Synthesis of N,N-bis(phenyl-4-yl)-N-(6-phenyl-1,1': 2'1''-terphenyl-3-yl) amine (Compound 2-92)>

N, N-bis(phenyl-4-yl)-N-(6-bromo phenyl-3-yl) amine in the third step of Synthesis Example 24, N, N-bis(phenyl-4-yl )-N-(6-bromo- 1,1 '2', 1''-terphenyl-3-yl) amine was reacted under the same conditions as in the third step of Synthesis Example 24 except that amine was used, N, 4.8 g (yield 40%) of a white powder of N-bis(phenyl-4-yl)-N-(6-phenyl-1,1 '2', 1''-terphenyl-3-yl) amine was obtained.

The structure was confirmed using NMR for the obtained white powder.

H-NMR (CDCl3): δ (ppm) = 7.62-7.68 (4H), 7.46-7.58 (8H), 7.09-7.39 (19H), 6.84-6.91 (4H)

Synthesis Example 35: Synthesis of Compound 2-134

<N-4-biphenyl-N-{4-(naphthalen-1-yl) phenyl}-N-(6-phenyl-1,1': 4'1''-terphenyl-4-yl) amine ( Synthesis of Compound 2-134)>

N-4-biphenyl- in place of N,N-bis(phenyl-4-yl)-N-(6-bromo phenyl-3-yl) amine and phenyl boronic acid in the third step of Synthesis Example 24 Same conditions as in the third step of Synthesis Example 24, except that N-(6-bromophenyl-3-yl)-N-{4-(naphthalen-1-yl)phenyl} amine and 4-biphenyl boronic acid were used. The reaction was carried out in N-4-biphenyl-N-{4-(naphthalen-1-yl)phenyl}-N-(6-phenyl-1,1': 4'1''-terphenyl-4- 1) 7.5 g of amine white powder (yield 60%) was obtained.

The structure was confirmed using NMR for the obtained white powder.

H-NMR (CDCl3): δ (ppm) = 8.08-8.12 (1H), 7.86-7.98 (2H), 7.21-7.64 (34H)

Synthesis Example 36: Synthesis of Compound 2-135

<N-4-biphenyl-N-{4-(naphthalen-1-yl)phenyl}-N-(6-phenyl-1,1': 4'1': 4''1'''- quarterphenyl -4-yl) Synthesis of amine (Compound 2-135)>

N-4-biphenyl- in place of N,N-bis(phenyl-4-yl)-N-(6-bromo phenyl-3-yl) amine and phenylboronic acid in the third step of Synthesis Example 24 With the third step of Synthesis Example 24, except that N-(6-bromophenyl-3-yl)-N-{4-(naphthalen-1-yl)phenyl}amine and p-terphenyl boronic acid pinacol ester were used. N-4-biphenyl-N-{4-(naphthalen-1-yl)phenyl}-N-(6-phenyl -1,1': 4'1': 4''1 9.0g of white powder of'''- quarter phenyl-4-yl) amine (yield 56%) was obtained.

The structure was confirmed using NMR for the obtained white powder.

H-NMR (CDCl3): δ (ppm) = 8.08-8.12 (1H), 7.86-7.98 (2H), 7.22-7.71 (38H)

Synthesis Example 37: Synthesis of Compound 2-136

<N,N-bis{4-(naphthalen-1-yl)phenyl}-N-(6-phenyl-1,1': 4'1''-terphenyl-4-yl) amine (Compound 2- 136 ) Synthesis>

N,N-bis(phenyl-4-yl)-N-(6-bromo phenyl-3-yl) amine and phenyl boronic acid in the third step of Synthesis Example 24, N,N-bis{4 -(Naphthalen-1-yl) phenyl}-N-(6-bromo phenyl-3-yl) The reaction was performed under the same conditions as in the third step of Synthesis Example 24, except that amine and 4-biphenyl boronic acid were used. N, N-bis{4-(naphthalen-1-yl)phenyl} -N-(6-phenyl-1,1': 4'1''-terphenyl-4-) 10.6 g of white powder of amine ( Yield 79%).

The structure was confirmed using NMR for the obtained white powder.

H-NMR (CDCl3): δ (ppm) = 8.08-8.14 (2H), 7.88-7.96 (4H), 7.24-7.64 (33H)

Synthesis Example 38: Synthesis of Compound 2-137

Synthesis of <N,N-bis{4-(naphthalen-1-yl)phenyl}-N-{6-phenyl-4'-(naphthalen-1-yl)phenyl-4-yl}amine (Compound 2-137) >

N,N-bis(phenyl-4-yl)-N-(6-bromo phenyl-3-yl) amine and phenyl boronic acid in the third step of Synthesis Example 24, N, N-bis{4 -(Naphthalen-1-yl)phenyl}-N-(6-bromo phenyl-3-yl) amine and 4-(naphthalen-2-yl) phenyl boronic acid except the third step of Synthesis Example 24 and N,N-bis{4-(naphthalen-1-yl)phenyl}-N-{6-phenyl-4'- (naphthalen-1-yl)phenyl-4-yl}amine white 9.7 g of powder (yield 74%) was obtained.

The structure was confirmed using NMR for the obtained white powder.

H-NMR (CDCl3): δ (ppm) = 8.08-8.14 (3H), 7.66-7.97 (8H), 7.28-7.66 (30H)

Synthesis Example 39: Synthesis of Compound 2-138

<N,N-bis{4-(naphthalen-1-yl)phenyl}-N-(6-phenyl-1,1': 4'1': 4''1'''- quarter phenyl-4-yl ) Synthesis of amine (Compound 2-138)>

N,N-bis(phenyl-4-yl)-N-(6-bromo phenyl-3-yl) amine and phenyl boronic acid in the third step of Synthesis Example 24, N, N-bis{4 -(Naphthalen-1-yl) phenyl} -N-(6-bromo phenyl-3-yl) Reaction under the same conditions as in the third step of Synthesis Example 24 except that amine and p-terphenyl boronic acid pinacol ester were used. N, N-bis{4-(naphthalen-1-yl)phenyl}-N-(6-phenyl-1,1': 4'1': 4''1'''- quarter phenyl-4 -Day) 6.2 g of amine was obtained (63% yield).

The structure was confirmed using NMR for the obtained white powder.

H-NMR (CDCl3): δ (ppm) = 8.08-8.14 (3H), 7.89-7.95 (4H), 7.25-7.71 (36H)

Synthesis Example 40: Synthesis of Compound 2-139

<N, N-bis{4-(naphthalen-1-yl) phenyl}-N-(6-phenyl-1,1': 3'1''- terphenyl-4-yl) amine (Compound 2- 139 ) Synthesis>

N, N-bis(phenyl-4-yl)-N-(6-bromo phenyl-3-yl) amine and phenyl boronic acid in the third step of Synthesis Example 24, N, N-bis{4 -(Naphthalen-1-yl)phenyl}-N-(6-bromo phenyl-3-yl) The reaction was carried out under the same conditions as in the third step of Synthesis Example 24, except that amine and 3-phenyl boronic acid were used. N, N-bis{4-(naphthalen-1-yl)phenyl} -N-(6-phenyl-1,1': 3'1''-terphenyl-4-yl) 4.9 g of white powder of amine ( Yield 48%).

The structure was confirmed using NMR for the obtained white powder.

H-NMR (CDCl3): δ (ppm) = 8.08-8.12 (2H), 7.86-7.94 (4H), 7.00-7.57 (29H), 6.63-6.75 (4H)

Synthesis Example 41: Synthesis of Compound 2-140

<N-4-biphenyl-N-{4-(naphthalen-2-yl)phenyl}-N-(6-phenyl-1,1': 4'1''-terphenyl-4-yl) amine ( Synthesis of Compound 2-140)>

N-4-biphenyl- in place of N, N-bis(phenyl-4-yl)-N-(6-bromo phenyl-3-yl) amine and phenyl boronic acid in the third step of Synthesis Example 24 Same conditions as in the third step of Synthesis Example 24 except that N-(6-bromophenyl-3-yl)-N-{4-(naphthalen-2-yl)phenyl} amine and 4-biphenyl boronic acid were used. The reaction was carried out in N-4-biphenyl-N-{4-(naphthalen-2-yl)phenyl}-N-(6-phenyl-1,1': 4'1''-terphenyl-4- 1) 4.9 g of amine white powder (yield 44%) was obtained.

The structure was confirmed using NMR for the obtained white powder.

H-NMR (CDCl3): δ (ppm) = 7.73 (1H), 7.61-7.70 (3H), 7.54-7.58 (1H), 7.19-7.52 (32H)

Synthesis Example 42: Synthesis of Compound 2-141

<N-4-biphenyl-N-{4-(naphthalen-2-yl)phenyl}-N-(6-phenyl-1,1':4'1''-terphenyl-3-yl)amine ( Synthesis of Compound 2-141)>

N-4-biphenyl-N-{4 instead of N, N-bis(phenyl-4-yl)-N-(6-bromo phenyl-3-yl) amine in the third step of Synthesis Example 24 -(Naphthalen-2-yl)phenyl}-N-(6-bromo-1,1': 4'1''- terphenyl-3-yl) except for using amine and the third step of Synthesis Example 24 N-4-biphenyl-N- {4-(naphthalen-2-yl)phenyl}-N-(6-phenyl-1,1': 4'1''- terphenyl- 3-Day) Amine white powder 5.8g (yield 56%) was obtained.

The structure was confirmed using NMR for the obtained white powder.

H-NMR (CDCl3): δ (ppm) = 8.08 (1H), 7.81-7.96 (3H), 7.79-7.81 (1H), 7.21-7.73 (32H)

Synthesis Example 43: Synthesis of Compound 2-142

<N-4-biphenyl-N-{4-(naphthalen-2-yl)phenyl}-N-{6-phenyl-4'-(naphthalen-2-yl) phenyl-3-yl} amine (Compound 2 -Synthesis of 142)

Instead of N, N-bis(phenyl-4-yl)-N-(6-bromo phenyl-3-yl)amine in the third step of Synthesis Example 24, N-4-biphenyl-N-{4 -(Naphthalen-2-yl)phenyl}-N-{6-bromo-4'- (naphthalen-2-yl)phenyl-3-yl}amine except the same conditions as in the third step of Synthesis Example 24 The reaction was carried out in N-4-biphenyl-N- {4-(naphthalen-2-yl)phenyl}-N-{6-phenyl-4'-(naphthalen-2-yl)phenyl-3-yl} 10.0 g of amine white powder (yield 81%) was obtained.

The structure was confirmed using NMR for the obtained white powder.

H-NMR (CDCl3): δ (ppm) = 8.04-8.10 (2H), 7.78-7.96 (8H), 7.24-7.65 (29H)

Synthesis Example 44: Synthesis of Compound 2-143

<Synthesis of N-4-biphenyl-N-(9,9-diphenyl fluoren-2-yl)-N-(6-phenyl biphenyl-3-yl} amine (Compound 2-143)>

Instead of N, N-bis(phenyl-4-yl)-N-(6-bromo phenyl-3-yl) amine in the third step of Synthesis Example 24, N-4-biphenyl-N-(6 -Bromo phenyl-3-yl)-N-(9,9-diphenyl fluoren-2-yl) The reaction was carried out under the same conditions as in the third step of Synthesis Example N, except that amine was used, N-4- Biphenyl-N-(9,9-diphenyl fluoren-2-yl)-N-(6-phenyl biphenyl-3-yl} amine white powder 11.0 g (yield 61%) was obtained.

The structure was confirmed using NMR for the obtained white powder.

H-NMR (CDCl3): δ (ppm) = 7.60-7.74 (4H), 7.14-7.52 (33H), 7.00-7.03 (2H)

Synthesis Example 45: Synthesis of Compound 2-144

<N-4-biphenyl-N-(9,9-diphenyl fluoren-2-yl)-N-(6-phenyl1,1': 4'1''-terphenyl-4-yl} amine Synthesis of (Compound 2-144)>

N-4-biphenyl- in place of N, N-bis(phenyl-4-yl)-N-(6-bromo phenyl-3-yl) amine and phenyl boronic acid in the third step of Synthesis Example 24 With the third step of Synthesis Example 24, except that N-(6-bromophenyl-3-yl)-N-(9,9-diphenyl fluoren-2-yl) amine and 4-biphenyl boronic acid were used. N-4-biphenyl-N-(9,9-diphenyl fluoren-2-yl)-N-(6-phenyl -1,1': 4'1''- ter Phenyl-4-yl) amine white powder 6.5g (yield 71%) was obtained.

The structure was confirmed using NMR for the obtained white powder.

H-NMR (CDCl3): δ (ppm) = 7.61-7.77 (6H), 7.20-7.51 (34H), 7.06-7.11 (3H)

Synthesis Example 46: Synthesis of Compound 2-145

<N-4-biphenyl-N-(9,9-diphenyl fluoren-2-yl)-N-(6-phenyl-1,1': 3'1''- terphenyl-4-yl) Synthesis of amine (Compound 2-145)>

N-4-biphenyl- in place of N, N-bis(phenyl-4-yl)-N-(6-bromo phenyl-3-yl)amine and phenyl boronic acid in the third step of Synthesis Example 24 Same as the third step of Synthesis Example 24, except that N-(6-bromo phenyl-3-yl)-N-(9,9-diphenyl fluoren-2-yl) amine and 3-phenyl boronic acid were used. N-4-biphenyl-N-(9,9-diphenyl fluoren-2-yl)-N-(6-phenyl-1,1': 3'1''- terphenyl -4-yl) 8.0 g of amine white powder (yield 87%) was obtained.

The structure was confirmed using NMR for the obtained white powder.

H-NMR (CDCl3): δ (ppm) = 7.70-7.76 (2H), 7.63-7.65 (2H), 7.18-7.54 (36H), 7.08-7.12 (3H)

Synthesis Example 47: Synthesis of Compound 2-146

<N-4-biphenyl-N-(9,9-diphenyl fluoren-2-yl)-N-(6-phenyl-1,1': 2'1''-terphenyl-4-yl) Synthesis of amine (Compound 2-146)>

N-4-biphenyl- in place of N, N-bis(phenyl-4-yl)-N-(6-bromo phenyl-3-yl) amine and phenyl boronic acid in the third step of Synthesis Example 24 Same as the third step of Synthesis Example 24, except that N-(6-bromophenyl-3-yl)-N-(9,9-diphenyl fluoren-2-yl) amine and 2-phenyl boronic acid were used. N-4-biphenyl-N-(9,9-diphenyl fluoren-2-yl)-N-(6-phenyl-1,1': 2'1''- terphenyl -4-yl) 5.2 g of amine white powder (yield 57%) was obtained.

The structure was confirmed using NMR for the obtained white powder.

H-NMR (CDCl3): δ (ppm) = 7.60-7.74 (4H), 7.95-7.49 (35H), 6.68-6.71 (2H), 6.54-6.57 (2H)

Synthesis Example 48: Synthesis of Compound 2-147

<Synthesis of N, N-bis(phenyl-4-yl)-N-{6-phenyl-4'-(naphthalen-1-yl)phenyl-3-yl} amine (Compound 2-147)>

Instead of N, N-bis(phenyl-4-yl)-N-(6-bromo phenyl-3-yl) amine in the third step of Synthesis Example 24, N, N-bis(phenyl-4-yl )-N-{6-Bromo-4'-(naphthalen-1-yl)phenyl-3-yl} N, N- was reacted under the same conditions as in the third step of Synthesis Example 24 except that amine was used. Bis(phenyl-4-yl)-N- {6-phenyl-4'- (naphthalen-1-yl)phenyl-3-yl}amine White powder 5.4 g (yield 33%) was obtained.

The structure was confirmed using NMR for the obtained white powder.

H-NMR (CDCl3): δ (ppm) = 7.84-7.95 (3H), 7.24-7.67 (34H)

Synthesis Example 49: Synthesis of Compound 2-148

<N, N-bis(phenyl-4-yl)-N-{6-(biphenyl-4-yl)-1,1': 4'1''-terphenyl-3-yl} amine (Compound 2 -148) Synthesis>

N, N-bis(phenyl-4-yl)-N-(6-bromo phenyl-3-yl) amine and phenyl boronic acid in the third step of Synthesis Example 24, N, N-bis(phenyl -4-yl)-N-(6-bromo-1,1': 4'1''-terphenyl-3-yl} Third in Synthesis Example 24 except that amine and 4-biphenyl boronic acid were used. N, N-bis(phenyl-4-yl)-N-{6-(phenyl-4-yl)-1,1': 4'1''-terphenyl-3 -Day} 9.4 g of amine white powder (yield 84%) was obtained.

The structure was confirmed using NMR for the obtained white powder.

H-NMR (CDCl3): δ (ppm) = 7.58-7.66 (12H), 7.23-7.54 (27H)

Synthesis Example 50: Synthesis of Compound 2-149

<N, N-bis(phenyl-4-yl)-N-{6-(biphenyl-3-yl)-1,1': 4'1''-terphenyl-3-yl} amine (Compound 2 -149) Synthesis>

N, N-bis(phenyl-4-yl)-N-(6-bromo phenyl-3-yl) amine and phenyl boronic acid in the third step of Synthesis Example 24, N, N-bis(phenyl Third process of Synthesis Example 24 except for using -4-yl)-N-(6-bromo-1,1': 4'1''-terphenyl-3-yl} amine and 3-phenyl boronic acid The reaction was performed under the same conditions as N, N-bis(phenyl-4-yl)-N-{6-(biphenyl-3-yl)-1,1': 4'1''-terphenyl-3 -Day} 9.6 g of amine white powder (yield 86%) was obtained.

The structure was confirmed using NMR for the obtained white powder.

H-NMR (CDCl3): δ (ppm) = 7.58-7.66 (10H), 7.26-7.52 (29H)

Synthesis Example 51: Synthesis of Compound 2-150

<N, N-bis(phenyl-4-yl)-N-{6-(phenyl-2-yl)-1,1': 4'1''-terphenyl-3-yl} amine (Compound 2- 150) Synthesis>

N,N-bis(phenyl-4-yl)-N-(6-bromo phenyl-3-yl) amine and phenyl boronic acid in the third step of Synthesis Example 24, instead of N, N-bis(phenyl Third process of Synthesis Example 24 except for using -4-yl)-N-(6-bromo-1,1': 4'1''-terphenyl-3-yl} amine and 2-phenyl boronic acid The reaction was carried out under the same conditions as N, N-bis(phenyl-4-yl)-N-{6-(phenyl-2-yl)-1,1': 4'1''- terphenyl-3- One} 9.6 g of amine white powder (yield 86%) was obtained.

The structure was confirmed using NMR for the obtained white powder.

H-NMR (CDCl3): δ (ppm) = 7.54-7.66 (10H), 7.08-7.49 (25H), 6.63-6.74 (4H)

Synthesis Example 52: Synthesis of Compound 2-151

<N, N-bis(9,9-dimethyl fluoren-2-yl)-N-(6-phenyl-1,1': 4'1''-terphenyl-4-yl) amine (compound 2- 151) Synthesis>

N, N-bis(phenyl-4-yl)-N-(6-bromo phenyl-3-yl) amine and phenyl boronic acid in the third step of Synthesis Example 24, N, N-bis(9 ,9-dimethyl fluoren-2-yl)-N-(6-bromo phenyl-3-yl) amine and 4-biphenyl boronic acid were used for reaction under the same conditions as in the third step of Synthesis Example 24 White powder of N, N-bis(9,9-dimethyl fluoren-2-yl)-N-(6-phenyl-1,1':4'1''-terphenyl-4-yl) amine 16.7 g (yield 92%) was obtained.

The structure was confirmed using NMR for the obtained white powder.

H-NMR (CDCl3): δ (ppm) = 7.62-7.70 (6H), 7.19-7.52 (25H), 1.50 (12H)

Synthesis Example 53: Synthesis of Compound 2-152

<N-(9,9-dimethyl fluoren-2-yl)-N-(6-phenyl biphenyl-3-yl)-N-(1,1 '4', 1''-terphenyl-4- 1) Synthesis of amine (Compound 2-152)>

Instead of N, N-bis(phenyl-4-yl)-N-(6-bromo phenyl-3-yl) amine in the third step of Synthesis Example 24, N-(6-bromo phenyl-3- 1) -N-(9,9-dimethyl fluoren-2-yl)-N-(1,1 '4', 1''-terphenyl-4-yl) The reaction was performed under the same conditions as in step 3 to perform N-(9,9-dimethyl fluoren-2-yl)-N-(6-phenyl biphenyl-3-yl)-N-(1,1 '4', 18.3 g (yield 74%) of a white powder of 1''-terphenyl-4-yl) amine was obtained.

The structure was confirmed using NMR for the obtained white powder.

H-NMR (CDCl3): δ (ppm) = 7.61-7.69 (10H), 7.12-7.52 (23H), 1.51 (6H)

Synthesis Example 54: Synthesis of Compound 2-153

<N-(9,9-dimethyl fluoren-2-yl)-N-{4-(naphthalen-2-yl)phenyl}-N-(6-phenyl biphenyl-3-yl) amine (Compound 2- 153) Synthesis>

Instead of N, N-bis(phenyl-4-yl)-N-(6-bromo phenyl-3-yl) amine in the third step of Synthesis Example 24, N-(6-bromo phenyl-3- 1)-N-(9,9-dimethyl fluoren-2-yl)-N-{4-(naphthalen-2-yl)phenyl} A reaction was carried out under the same conditions as in the third step of Synthesis Example 24 except that amine was used. Perform the white of N-(9,9-dimethyl fluoren-2-yl)-N-{4-(naphthalen-2-yl)phenyl}-N-(6-phenyl biphenyl-3-yl) amine 8.8 g of powder (63% yield) was obtained.

The structure was confirmed using NMR for the obtained white powder.

H-NMR (CDCl3): δ (ppm) = 8.08 (1H), 7.76-7.94 (4H), 7.60-7.71 (4H), 7.13-7.54 (22H), 1.52 (6H)

Synthesis Example 55: Synthesis of Compound 2-154

<N-(9,9-dimethyl fluoren-2-yl)-N-{4-(naphthalen-2-yl)phenyl}-N-(6-phenyl-1,1': 4'1''- Terphenyl-4-yl) Synthesis of amine (Compound 1-154)>

N-(6-bromo) instead of N, N-bis(phenyl-4-yl)-N-(6-bromo phenyl-3-yl) amine and phenyl boronic acid in the third step of Synthesis Example 24 Synthesis except using phenyl-3-yl)-N-(9,9-dimethyl fluoren-2-yl)-N-{4-(naphthalen-2-yl) phenyl} amine and 4-biphenyl boronic acid The reaction was performed under the same conditions as the third step of Example 24 to perform N-(9,9-dimethyl fluoren-2-yl)-N-{4-(naphthalen-2-yl)phenyl}-N-(6- 10.4 g (yield 67%) of a white powder of phenyl-1,1':4'1''-terphenyl-4-yl) amine was obtained.

The structure was confirmed using NMR for the obtained white powder.

H-NMR (CDCl3): δ (ppm) = 8.12 (1H), 7.78-7.92 (4H), 7.60-7.71 (6H), 7.21-7.54 (24H), 1.53 (6H)

Synthesis Example 56: Synthesis of Compound 2-155

<N-4-biphenyl-N-(9,9-dimethyl fluoren-2-yl)-N-(6-phenyl-4'-(naphthalen-1-yl)phenyl-4-yl) amine (compound Synthesis of 2-155)

N-4-biphenyl- in place of N, N-bis(phenyl-4-yl)-N-(6-bromo phenyl-3-yl) amine and phenyl boronic acid in the third step of Synthesis Example 24 Synthesis Example 24 except that N-(6-bromophenyl-3-yl)-N-(9,9-dimethyl fluoren-2-yl) amine and 4-(naphthalen-1-yl) phenyl boronic acid were used. The reaction was performed under the same conditions as the third step of N-4-biphenyl-N-(9,9-dimethyl fluoren-2-yl)-N-(6-phenyl-4'-(naphthalene-1- 1)phenyl-4-yl) 17.8 g of a white powder of amine (yield 89%) was obtained.

The structure was confirmed using NMR for the obtained white powder.

H-NMR (CDCl3): δ (ppm) = 7.85-7.96 (3H), 7.18-7.74 (32H), 1.53 (6H)

Synthesis Example 57: Synthesis of Compound 2-156

<N-(9,9-dimethyl fluoren-2-yl)-N-{4-(naphthalen-1-yl)phenyl}-N-(6-phenyl biphenyl-3-yl) amine (Compound 2- 156) Synthesis>

Instead of N, N-bis(phenyl-4-yl)-N-(6-bromo phenyl-3-yl) amine in the third step of Synthesis Example 24, N-(6-bromo phenyl-3- 1)-N-(9,9-dimethyl fluoren-2-yl)-N-{4-(naphthalen-1-yl) phenyl} A reaction was carried out under the same conditions as in the third step of Synthesis Example 24, except that amine was used. Perform the white of N-(9,9-dimethyl fluoren-2-yl)-N-{4-(naphthalen-1-yl)phenyl}-N-(6-phenyl biphenyl-3-yl) amine 17.8 g of powder (yield 89%) was obtained.

The structure was confirmed using NMR for the obtained white powder.

H-NMR (CDCl3): δ (ppm) = 8.10-8.13 (1H), 7.86-7.94 (2H), 7.72-7.75 (2H), 7.14-7.58 (26H), 1.54 (6H)

Synthesis Example 58: Synthesis of Compound 2-157

<N-(9,9-dimethyl fluoren-2-yl)-N-{4-(naphthalen-1-yl)phenyl}-N-(6-phenyl -1,1': 4'1''- Synthesis of terphenyl-4-yl) amine (Compound 2-157)>

N-(6-bromo) instead of N, N-bis(phenyl-4-yl)-N-(6-bromo phenyl-3-yl) amine and phenyl boronic acid in the third step of Synthesis Example 24 Synthesis except using phenyl-3-yl)-N-(9,9-dimethyl fluoren-2-yl)-N-{4-(naphthalen-1-yl) phenyl} amine and 4-biphenyl boronic acid The reaction was performed under the same conditions as the third step of Example 24 to perform N-(9,9-dimethyl fluoren-2-yl)-N-{4-(naphthalen-1-yl)phenyl}-N-(6- 19.9 g (yield 89%) of a white powder of phenyl-1,1':4'1''-terphenyl-4-yl) amine was obtained.

The structure was confirmed using NMR for the obtained white powder.

H-NMR (CDCl3): δ (ppm) = 8.07-8.13 (1H), 7.88-7.96 (2H), 7.16-7.72 (32H), 1.54 (6H)

Synthesis Example 59: Synthesis of Compound 2-158

<N-4-biphenyl-N-{4-(9,9-dimethyl fluoren-2-yl)phenyl}-N-{6-phenyl-1,1': 3'1''-terphenyl- Synthesis of 4-yl} amine (Compound 2-158)>

N-4-biphenyl- in place of N, N-bis(phenyl-4-yl)-N-(6-bromo phenyl-3-yl) amine and phenyl boronic acid in the third step of Synthesis Example 24 Preparation of Synthesis Example 24 except that N-(6-bromophenyl-3-yl)-N-{4-(9,9-dimethyl fluoren-2-yl) phenyl} amine and 3-phenyl boronic acid were used. The reaction was carried out under the same conditions as in step 3 to perform N-4-biphenyl-N-{4-(9,9-dimethyl fluoren-2-yl)phenyl}-N-{6-phenyl-1,1': 3'1''-terphenyl-4-yl} amine white powder 8.7g (yield 49%) was obtained.

The structure was confirmed using NMR for the obtained white powder.

H-NMR (CDCl3): δ (ppm) = 7.74-7.82 (2H), 7.58-7.76 (6H), 7.16-7.48 (29H), 1.57 (6H)

Synthesis Example 60: Synthesis of Compound 2-159

<N, N-bis{4-(naphthalen-2-yl)phenyl}-N-(6-phenyl-1,1': 4'1''-terphenyl-3-yl) amine (Compound 2- 159 Synthesis of N> N, N-bis(phenyl-4-yl)-N-(6-bromo phenyl-3-yl) amine in the third step of Synthesis Example 24, N, N-bis{4 -(Naphthalen-2-yl)phenyl}-N-(6-bromo-1,1': 4'1''- terphenyl-3-yl) except for using amine and the third step of Synthesis Example 24 N, N-bis{4-(naphthalen-2-yl)phenyl}-N-(6-phenyl-1,1': 4'1''-terphenyl-3-yl) by performing the reaction under the same conditions 5.1 g of an amine white powder (yield 65%) was obtained.

The structure was confirmed using NMR for the obtained white powder.

H-NMR (CDCl3): δ (ppm) = 8.10 (1H), 7.87-7.96 (6H), 7.71-7.84 (6H), 7.22-7.60 (26H)

Synthesis Example 61: Synthesis of Compound 3-1

<4,4''-bis {(biphenyl-4-yl)-phenyl amino}-2-phenyl-1,1'; Synthesis of 4', 1''-terphenyl (Compound 3-1)>

In a nitrogen-substituted reaction vessel (6-bromo-1,1'-biphenyl-3-yl)-(1,1'-biphenyl-4-yl) phenyl amine 18.0 g, 4- {N- (phenyl -4-day) -N-phenyl amino} 10.2 g of phenyl boronic acid (1,1'-biphenyl-4-yl) phenyl amino (1,1'-biphenyl-4'-yl) boronic acid pinacol ester 21.8g tetrakis triphenyl phosphine palladium 0.87g, potassium carbonate 6.3g, water 46ml, toluene 144ml, ethanol 36ml was added and heated and stirred under reflux for 18 hours. After cooling and adding 100 ml of water, an organic layer was collected by a separation operation. The organic layer was subjected to dehydration treatment with anhydrous magnesium sulfate, concentrated, and the residue was purified by column chromatography, 4,4''- bis {(biphenyl-4-yl)-phenylamino}-2-phenyl-1 ,One '; 12.9 g (yield 43%) of a white powder of 4', 1''-terphenyl (Compound 3-1) was obtained.

The structure was confirmed by using NMR on the obtained white powder.

¹ H-NMR (CDCl3): δ (ppm) = 7.65-7.61 (4H), 7.57-7.07 (40H).

Synthesis Example 62: Synthesis of Compound 3-9

<4,4''-bis {(biphenyl-4-yl)-phenyl amino} -3,3'- diphenyl -1,1'; 4', 1''- Synthesis of Terphenyl (Compound 3-9)>

4,4''-bis {(biphenyl-4-yl)-amino} -3,3'-diphenyl-1,1' in a nitrogen-substituted reaction vessel; 4', 1''- terphenyl 16.3 g, iodine benzene 18.6 g, copper powder 0.29 g, potassium carbonate 9.61 g, 3,5-di-tert-butyl salicylic acid 1.85 g, sodium hydrogen sulfite 0.47 g, dodecyl benzene 20 ml was added, heated, stirred at 190-200° C. for 17 hours, then cooled to add 1500 ml of toluene, 40 g of silica gel, and 20 g of active clay, followed by stirring. After removing insoluble matters by filtration, concentrate and repeat recrystallization using benzene to 4,4''- bis {(non-phenyl-4-yl)-phenyl amino} -3,3'-diphenyl-1,1'; 9.65 g (yield 49%) of a white powder of 4', 1''-terphenyl (compound 3-9) was obtained.

The structure was confirmed by using NMR on the obtained white powder.

¹ H-NMR (CDCl3): δ (ppm) = 7.62 (4H), 7.52 (4H), 7.45 (4H), 7.36-7.04 (32H), 6.99 (4H).

Synthesis Example 63: Synthesis of Compound 3-12

<4,4''-bis {(biphenyl-4-yl)-phenyl amino} -3-phenyl-1,1'; Synthesis of 3'1''-terphenyl (Compound 3-12)>

4-{(biphenyl-4-yl)-phenyl amino} -4'- {(biphenyl-4-yl)-amino}-3-phenyl -1,1' in the nitrogen-substituted reaction vessel; 3', 1'- terphenyl 17.0g, bromobenzene 4.12g, palladium acetate 0.13g, tri-tert-butyl phosphine 50% (w/v) toluene solution 0.33ml, tert-butoxy sodium 2.73g, 190 ml of toluene was added, heated, and stirred at 80° C. for 3 hours. After cooling and filtering, the insoluble matter was removed, concentrated, and purified by column chromatography (carrier: silica gel, eluent: toluene/n-hexane). The precipitated solid was collected by adding acetone to collect 4,4''-bis {(non-phenyl-4-yl)-phenyl amino}-3-phenyl-1,1'; 13.29 g (yield 71%) of a white powder of 3'1''-terphenyl (Compound 3-12) was obtained.

The structure was confirmed by using NMR on the obtained white powder.

¹ H-NMR (CDCl3): δ (ppm) = 7.62-7.58 (4H), 7.55-7.49 (4H), 7.48-7.38 (6H), 7.37-7.05 (30H).

Synthesis Example 64: Synthesis of Compound 3-23

<4-Bis(phenyl-4-yl)amino-4'- {(biphenyl-4-yl)-phenylamino)}-synthesis of 2,6-diphenyl-biphenyl (compound 3-23)>

In a nitrogen-substituted reaction vessel, 16.0 g of 4-bis(phenyl-4-yl)amino-2,6-diphenyl bromobenzene, 4-{N-(biphenyl-4-yl)-N-phenyl amino} 10.2 g of phenyl boronic acid, 0.60 g of tetrakis triphenylphosphine palladium, 4.62 g of potassium carbonate, 60 ml of water, 320 ml of toluene and 60 ml of ethanol were added, heated and stirred under reflux for 18 hours. After cooling and adding 200 ml of water, an organic layer was collected by a separation operation. The organic layer was dehydrated using anhydrous magnesium sulfate, adsorbed and purified using 40 g of silica gel, and then concentrated and dispersed to obtain a formulation. Recrystallization with Toluene / Ethanol to the Preparation Repeat recrystallization with ethyl acetate to 4-bis(phenyl-4-yl)amino-4'-{(non-phenyl-4-yl)-phenylamino)}-2,6 -Diphenyl-biphenyl (Compound 3-23) to give a white powder 12.7g (yield 57%).

The structure was confirmed by using NMR on the obtained white powder.

¹ H-NMR (CDCl3): δ (ppm) = 7.65-7.53 (8H), 7.48-6.97 (36H), 6.79-6.73 (4H).

Synthesis Example 65: Synthesis of Compound 3-24

<4- Bis (phenyl-4-yl) amino-4'- {(biphenyl-4-yl)-phenyl amino)}-Synthesis of 2-phenyl-1,1'-biphenyl (compound 3-24) >

In a nitrogen-substituted reaction vessel (6-bromo-1,1'-biphenyl-3-yl)-bis(phenyl-4-yl)amine 10.0g, 4-(N-(biphenyl-4-yl) -N-phenyl amino} phenyl boronic acid 7.9g, tetrakis triphenyl phosphine palladium 0.60g, potassium carbonate 5.0g, water 30ml, toluene 80ml, ethanol 40ml was added and heated and stirred under reflux for 16 hours. After cooling and adding 100 ml of water, an organic layer was collected by a separation operation. The organic layer was concentrated by dehydration using anhydrous magnesium sulfate, and the residue was purified by column chromatography, 4-bis(phenyl-4-yl)amino-4'-((biphenyl-4-yl)-phenylamino) }-5.3 g of white powder of 2-phenyl-1,1'-biphenyl (compound 3-24) (yield 37%) was obtained.

The structure was confirmed by using NMR on the obtained white powder.

¹ H-NMR (CDCl3): δ (ppm) = 7.65-7.56 (8H), 7.52-7.14 (28H), 7.08-6.99 (8H).

Synthesis Example 66: Synthesis of Compound 3-26

<4-{(naphthalene-1-yl) phenyl-4-yl} (biphenyl-4-yl) amino -4'- {(biphenyl-4-yl)-phenyl amino)}-2-phenyl-1 ,1'- Biphenyl (compound 3-26) synthesis>

To the nitrogen-substituted reaction vessel (6-bromo-1,1'-biphenyl-3-yl)-{(naphthalen-1-yl)phenyl-4-yl} (biphenyl-4-yl)amine 10.0 g , 4- {N- (biphenyl-4-yl) -N-phenyl amino} phenyl boronic acid 7.3 g, tetrakistriphenyl phosphine palladium 0.60 g, potassium carbonate 4.6 g, water 30 ml, toluene 80 ml, ethanol 40 ml It was heated and stirred under reflux for 16 hours. After cooling and adding 100 ml of water, an organic layer was collected by a separation operation. The organic layer was concentrated by dehydration using anhydrous magnesium sulfate, the residue was purified by column chromatography, and 4-{(naphthalen-1-yl) phenyl-4-yl} (biphenyl-4-yl) amino -4' -{(Biphenyl-4-yl)-phenyl amino)}-9.7 g (yield 69%) of a white powder of 2-phenyl-1,1'-biphenyl (compound 3-26) was obtained.

The structure was confirmed by using NMR on the obtained white powder.

¹ H-NMR (CDCl3): δ (ppm) = 8.08-8.07 (1H), 7.95-7.87 (2H), 7.66-6.99 (43H).

Synthesis Example 67: Synthesis of Compound 3-27

<4-{(naphthalene-2-yl) phenyl-4-yl} (biphenyl-4-yl) amino -4'- {(biphenyl-4-yl)-phenyl amino)}-2-phenyl-1 ,1'- Synthesis of biphenyl (Compound 3-27)>

7.5 g of (6-bromo-1,1'-biphenyl-3-yl)-{(naphthalen-2-yl)phenyl-4-yl} (biphenyl-4-yl)amine in a nitrogen-substituted reaction vessel , 4- {N- (biphenyl-4-yl) -N-phenyl amino} phenyl boronic acid 5.5g, tetrakistriphenyl phosphine palladium 0.40g, potassium carbonate 3.4g, water 23ml, toluene 60ml, ethanol 30ml It was further heated out and stirred for 16 hours under reflux. After cooling and adding 100 ml of water, an organic layer was collected by a separation operation. The organic layer was concentrated by dehydration using anhydrous magnesium sulfate, and the residue was purified by column chromatography, and 4-{(naphthalen-2-yl) phenyl-4-yl} (non-phenyl-4-yl) amino-4' -{(Biphenyl-4-yl)-phenyl amino)}-2-phenyl-1,1'- 6.1 g of white powder (compound 3-27) (yield 58%) was obtained

The structure was confirmed by using NMR on the obtained white powder.

¹ H-NMR (CDCl3): δ (ppm) = 8.07 (1H), 7.95-7.76 (4H), 7.68-6.98 (41H).

Synthesis Example 68: Synthesis of Compound 3-29

<4-bis {(naphthalene-1-yl) phenyl-4-yl} amino-4'- {(biphenyl-4-yl)-phenyl amino)}-2-phenyl-biphenyl (compound 3-29) The synthesis of>

In a nitrogen-substituted reaction vessel (6-bromo-1,1'-biphenyl-3-yl)-bis {(naphthalen-1-yl) phenyl-4-yl} amine 10.0 g, 4- {N- ( Biphenyl-4-yl) -N-phenyl amino} 6.7 g of phenyl boronic acid, tetrakis triphenyl phosphine palladium 0.50 g, potassium carbonate 4.2 g, water 30 ml, toluene 80 ml ethanol 40 ml was added and heated, reflux for 16 hours While stirring. After cooling and adding 100 ml of water, an organic layer was collected by a separation operation. The organic layer was concentrated by dehydration using anhydrous magnesium sulfate, the residue was purified by column chromatography, and 4-bis {(naphthalen-1-yl) phenyl-4-yl} amino-4'- {(non phenyl-4 -Day)-Phenyl amino)}-2-phenyl-biphenyl (Compound 3-29) to obtain 10 g (yield 73%) of a white powder.

The structure was confirmed by using NMR on the obtained white powder.

¹ H-NMR (CDCl3): δ (ppm) = 8.12-8.10 (2H), 7.97-7.88 (4H), 7.63-7.01 (42H).

Synthesis Example 69: Synthesis of Compound 3-30

<4-{(9,9-dimethyl fluoren-2-yl) phenyl-4-yl} (biphenyl-4-yl) amino -4'- {(biphenyl-4-yl)-phenyl amino)} -Synthesis of 3-phenyl-1,1'-biphenyl (Compound 3-30)>

In a nitrogen-substituted reaction vessel (6-bromo-1,1'-biphenyl-3-yl)-{(9,9-dimethyl fluoren-2-yl) phenyl-4-yl} (biphenyl-4 -1) amine 12.1 g, 4- {N- (biphenyl-4-yl) -N-phenyl amino} phenyl boronic acid 8.9 g, tetrakis triphenyl phosphine palladium 0.70 g, potassium carbonate 5.6 g, water 40 ml, 100 ml of toluene and 50 ml of ethanol were added, heated, and stirred under reflux for 16 hours. After cooling and adding 100 ml of water, an organic layer was collected by a separation operation. The organic layer was concentrated by dehydration using anhydrous magnesium sulfate, the residue was purified by column chromatography, and 4-{(9,9-dimethyl fluoren-2-yl) phenyl-4-yl} (phenyl-4-yl ) Amino-4'- {(biphenyl-4-yl)-phenylamino)}-3-phenyl-1,1'- obtained a white powder 8.3g (yield 49%) of biphenyl (compound 3-30) .

The structure was confirmed by using NMR on the obtained white powder.

¹ H-NMR (CDCl3): δ (ppm) = 7.71-7.15 (34H), 7.09-6.99 (8H), 1.51 (6H).

Examples 1 to 9: Preparation of organic light emitting device

The ITO glass was patterned to have a light emitting area of 2 mm×2 mm, and then washed. After mounting the ITO glass in the vacuum chamber, the base pressure 1 × 10 ^- and then to the ⁶ torr described DNTPD (700 Å), the following Table 1 on the ITO, which is represented by [Chemical Formula A] or [Chemical Formula B] After film formation in the order of compound (250 kPa), a compound (50 kPa) represented by [Chemical Formula C] or [Chemical Formula D] is formed as the electron blocking layer material. Then, as the host [BH1] and a dopant [BD1] a film-forming (250Å), and then, the electron transport layer [Formula E-2] a mixture of 3 wt% to 250 Å, the electron injection layer [Formula E-1] Was formed in the order of 10 10 and Al (1000 Å) to prepare an organic light emitting device. The characteristics of the organic light emitting device were measured at 0.4 mA.

<DNTPD>

<BH1> <BD1>

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

Comparative Examples 1 to 8

An organic light emitting device was manufactured in the same manner, except that the following <H 1> or <H 2> was used as the hole transport compound used in Examples 1 to 9, and the properties of the organic light emitting device were measured at 0.4 mA and shown in Table 1 below. Shown. The structures of <H 1> and <H 2> are as follows.

<H 1> <H 2>

Hole transport layer Electron blocking layer CIEx CIEy cd/A ELmax Comparative Example 1 H 1 - 0.1358 0.1110 8.66 456 Comparative Example 2 Compound 1-13 0.1358 0.1108 9.58 456 Comparative Example 3 Compound 2-136 0.1374 0.1072 9.76 456 Comparative Example 4 Compound 3-27 0.1376 0.1057 9.32 456 Comparative Example 5 H 2 - 0.1336 0.1130 8.57 457 Comparative Example 6 Compound 1-13 0.1362 0.1098 9.13 456 Comparative Example 7 Compound 2-136 0.1381 0.1102 9.26 456 Comparative Example 8 Compound 3-27 0.1377 0.1087 9.07 457 Example 1 Formula 13 Compound 1-13 0.1362 0.1111 11.16 456 Example 2 Compound 2-136 0.1361 0.1081 10.97 456 Example 3 Compound 3-27 0.1376 0.1061 10.66 456 Example 4 Formula 35 Compound 1-13 0.1362 0.1111 11.14 456 Example 5 Compound 2-136 0.1370 0.1083 10.93 456 Example 6 Compound 3-27 0.1375 0.1058 10.49 456 Example 7 Chemical Formula 87 Compound 1-13 0.1363 0.1098 11.28 456 Example 8 Compound 2-136 0.1372 0.1110 11.13 456 Example 9 Compound 3-27 0.1376 0.1062 10.76 456

As shown in Table 1, the organic light emitting device according to the present invention shows higher luminous efficiency than <H 1> and <H 2>, which are frequently used as hole transport layer materials according to the prior art, and also uses an electron blocking layer. It can be seen that the efficiency is higher when the electron blocking layer according to the present invention is used than when not.

Claims (17)

A first electrode;
A second electrode opposed to the first electrode;
An organic light emitting device including a hole transport layer, an electron blocking layer and a light emitting layer sequentially interposed between the first electrode and the second electrode,
The hole transport layer includes at least one amine compound represented by the following [Formula A] or [Formula B]; The electron blocking layer is an organic light emitting device comprising at least one amine compound represented by the following [Chemical Formula C] or [Chemical Formula D].
[Formula A]

[Formula B]

In [Chemical Formula A] and [Chemical Formula B], A1, A2, E and F are the same or different from each other, and are independently substituted or unsubstituted aromatic hydrocarbon rings having 6 to 50 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 five-membered ring with carbon atoms connected to the substituents R1 and R2;
The linking groups L1 to L6 are the same as or different from each other, and are independently selected from a single bond or a substituted or unsubstituted arylene group having 6 to 60 carbon atoms;
The M is any one selected from CR ₄ R ₅ , O, S;
The substituents R1 to R2, R4 to R5, and Ar1 to Ar4 are the same or different from each other, and independently of each other, hydrogen, deuterium, a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, substituted or unsubstituted 6 to 50 carbon atoms An aryl group, a substituted or unsubstituted cycloalkyl group having 3 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, Any one selected from halogen groups,
R1 and R2 may be connected to each other to form an alicyclic, aromatic monocyclic or polycyclic ring;
Wherein p1 and p2, r1 and r2, s1 and s2 are integers of 1 to 3, respectively, when each of them is 2 or more, each of the linkers L1 to L6 is the same or different from each other,
Ar1 and Ar2 may be connected to each other to form a ring, and Ar3 and Ar4 may be connected to each other to form a ring;
X is 1,
y is 0,
In Formula A, two carbon atoms adjacent to each other in the A2 ring combine with * in the structural formula Q1 to form a condensed ring,
In Formula B, two carbon atoms adjacent to each other in the A1 ring are combined with * in the structural formula Q2 to form a condensed ring, and two carbon atoms adjacent to each other in the A2 ring are combined with * in the structural formula Q1 to form a condensed ring. To form.

[Formula C]

In the above [Formula C],
The substituents R11 to R13 are the same or different, and each independently hydrogen, deuterium, substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, substituted or unsubstituted aryl group having 6 to 50 carbon atoms, substituted or unsubstituted carbon number 3 to 30 cycloalkyl group, 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, any one selected from halogen groups,
The substituents Ar5 to Ar8 are the same or different, and are independently substituted or unsubstituted aryl groups having 6 to 40 carbon atoms;
Wherein n is an integer of 0 to 4, and when n is 2 or more, each aromatic ring containing the substituent R13 is the same or different from each other,
m1 to m3 are integers from 0 to 4, and when they are 2 or more, each of R11, R12, or R13 is the same or different from each other,
The carbon atom of the aromatic ring to which the substituents R11 to R13 are not bonded is bonded to hydrogen or deuterium.

[Formula D]

In the above [Formula D],
The substituents R21 to R23 are the same or different, and independently of each other, 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 carbon number 3 to 30 cycloalkyl group, 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, any one selected from halogen groups,
The substituents Ar9 to Ar12 are the same or different, and each independently substituted or unsubstituted aryl group having 6 to 40 carbon atoms,
Here, the'substitution' in the'substituted or unsubstituted' in the above [Formula A] to [Formula D] is deuterium, cyano group, halogen group, nitro group, an alkyl group having 1 to 24 carbon atoms, 1 to 24 carbon atoms Substituted with one or more substituents selected from the group consisting of halogenated alkyl groups, 6 to 24 aryl groups, 7 to 24 arylalkyl groups, 1 to 24 alkylsilyl groups, 6 to 24 arylsilyl groups it means. According to claim 1,
A1, A2, E and F in Formula A and Formula B are the same or different, and an organic light-emitting device characterized in that they are independently substituted or unsubstituted aromatic hydrocarbon rings having 6 to 50 carbon atoms. According to claim 2,
The substituted or unsubstituted aromatic hydrocarbon ring having 6 to 50 carbon atoms is the same or different, and an organic light emitting device, characterized in that any one selected from [Structural Formula 10] to [Structural Formula 21] independently of each other.
[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 [Formula 10] to [Formula 21] is to form a 5-membered ring containing carbon atoms connected to R1 and R2, or to form a 5-membered ring containing M in Formulas Q1 and Q2. Means a binding site,
When the aromatic hydrocarbon rings of [Structural Formulas 10] to [Structural Formula 21] correspond to the A1 ring or A2 ring, and when combined with Structural Formula Q1 or Structural Formula Q2, two adjacent carbon atoms among them combine with * of Structural Formula Q1 Or in combination with * in structural formula Q2 to form a condensed ring;
In [Structural Formulas 10] to [Structural Formula 21], R is the same as R1 and R2 defined in claim 1, m is an integer of 1 to 8, and when m is 2 or more or R is 2 or more, each R May be the same or different from each other. delete According to claim 1,
The linking groups L1 to L6 in the formulas A and B are the same or different, and are each independently a single bond, or the following [Structural Formula 22], [Structural Formula 23], [Structural Formula 25], [Structural Formula 27], [Structural Formula 28] ], [Structural Formula 30]
p1 and p2, r1 and r4, s1 and s2 are organic light emitting devices, characterized in that 1 or 2, respectively.
[Structural Formula 22] [Structural Formula 23] [Structural Formula 25]

[Structural Formula 27] [Structural Formula 28] [Structural Formula 30]

According to claim 1,
The amine compound represented by [Chemical Formula C] is an organic light-emitting device, characterized in that represented by the following [Chemical Formula C1].
[Chemical Formula C1]

In the above [Chemical Formula C1],
The substituents Ar13 to Ar16 are the same or different, and each independently a substituted or unsubstituted aryl group having 6 to 40 carbon atoms,
The substituent R24 is the same as R13 defined in claim 1,
Wherein n1 is an integer of 2 to 4, in this case, each aromatic ring containing the substituent R24 is the same or different from each other,
m4 is an integer from 0 to 4, and when m4 is 2 or more, each R24 is the same or different from each other, and the carbon atom of the aromatic ring to which the substituent R24 in parentheses is not bonded is bonded to hydrogen or deuterium. According to claim 1,
The amine compound represented by [Chemical Formula C] is an organic light emitting device, characterized in that represented by the following [Chemical Formula C2].
[Chemical Formula C2]

In the above [Chemical Formula C2],
The substituents Ar17 to Ar20 are the same or different, and each independently substituted or unsubstituted aryl group having 6 to 40 carbon atoms,
The substituents Ar21 to Ar24 are the same or different, and each independently hydrogen, deuterium, a substituted or unsubstituted aryl group having 6 to 40 carbon atoms, a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted carbon number 3 to 30 cycloalkyl group,
The substituent R25 is the same as R13 defined in claim 1,
N2 is an integer of 0 to 2, and when n2 is 2, each of the aromatic rings including the substituent R25 is the same or different from each other,
m5 is an integer from 0 to 4, and when m5 is 2 or more, each R25 is the same or different from each other, and the carbon atom of the aromatic ring in which the substituent R25 in parentheses is not bonded is bonded to hydrogen or deuterium. The method of claim 6,
The substituent R24 in the formula C1 is hydrogen or deuterium,
The substituents Ar13 to Ar16 are the same or different, and the organic light-emitting device, characterized in that each independently substituted or unsubstituted aryl group having 6 to 20 carbon atoms. The method of claim 7,
The substituent R25 in the formula C2 is hydrogen or deuterium,
The substituents Ar17 to Ar20 are the same or different, and the organic light-emitting device, characterized in that each independently substituted or unsubstituted aryl group having 6 to 20 carbon atoms. According to claim 1,
The substituents Ar9 to Ar12 in Formula D are the same or different, and are organic light-emitting devices, which are independently substituted or unsubstituted aryl groups having 6 to 20 carbon atoms. According to claim 1,
The amine compounds represented by the formula A or formula B are the following <Formula 1> to <Formula 3>, <Formula 5>, <Formula 7> to <Formula 9>, <Formula 11> to <Formula 14>, <Formula 21> to <Formula 24>, <Formula 27>, <Formula 29> to <Formula 34>, <Formula 37> to <Formula 44>, <Formula 55> to <Formula 57>, <Formula 61>, <Formula 61> 63, <Formula 65>, <Formula 66>, <Formula 68>, <Formula 70> to <Formula 90>, <Formula 92>, <Formula 94>, <Formula 97> to <Formula 104>, <Formula 106>, <formula 107>, <formula 109> to <formula 111>, <formula 114>, <formula 115> to <formula 117>, <formula 122> to <formula 124>, <formula 127> to <formula 132>, <Formula 134> to <Formula 144>, <Formula 146>, <Formula 148> to <Formula 165> organic light emitting device, characterized in that any one selected from the group.
<Formula 1><Formula2><Formula3>

<Formula 5>

<Formula 7><Formula8><Formula9>

<Formula 11><Formula12>

<Formula 13><Formula14>

<Formula 21>

<Formula 22><Formula23><Formula24>

<Formula 27>

<Formula 29><Formula30>

<Formula 31><Formula32><Formula33>

<Formula 34>

<Formula 37><Formula38><Formula39>

<Formula 40><Formula41><Formula42>

<Formula 43><Formula44>

<Formula 55><Formula56><Formula57>

<Formula 61><Formula63>

<Formula 65><Formula66>

<Formula 68>

<Formula 70><Formula71><Formula72>

<Formula 73><Formula74><Formula75>

<Formula 76><Formula77><Formula78>

<Formula 79><Formula80><Formula81>

<Formula 82><Formula83><Formula84>

<Formula 85><Formula86><Formula87>

<Formula 88><Formula89><Formula90>

<Formula 92><Formula94>

<Formula 97><Formula98><Formula99>

<Formula 100><Formula101><Formula102>

<Formula 103><Formula104>

<Formula 106><Formula107>

<Formula 109><Formula110><Formula111>

<Formula 114>

<Formula 115><Formula116><Formula117>

<Formula 122><Formula123>

<Formula 124>

<Formula 127><Formula128><Formula129>

<Formula 130><Formula131><Formula132>

<Formula 134><Formula135>

<Formula 136><Formula137><Formula138>

<Formula 139><Formula140><Formula141>

<Formula 142><Formula143><Formula144>

<Formula 146>

<Formula 148><Formula149><Formula150>

<Formula 151><Formula152><Formula153>

<Formula 154><Formula155><Formula156>

<Formula 157><Formula158><Formula159>

<Formula 160><Formula161><Formula162>

<Formula 163><Formula164><Formula165>

The method of claim 6,
The amine compounds represented by the formula (C1) are <Compound 1-1> to <Compound 1-6>, <Compound 1-9> to <Compound 1-11>, <Compound 1-13> to <Compound 1-25 >, <Compound 1-27> to <Compound 1-33>, <Compound 1-35> to <Compound 1-38> organic light emitting device, characterized in that any one selected from the group.
<Compound 1-1><Compound1-2><Compound1-3>

<Compound 1-4><Compound1-5><Compound1-6>

<Compound 1-9>

<Compound 1-10><Compound1-11>

<Compound 1-13><Compound1-14><Compound1-15>

<Compound 1-16><Compound1-17><Compound1-18>

<Compound 1-19><Compound1-20><Compound1-21>

<Compound 1-22><Compound1-23><Compound1-24>

<Compound 1-25><Compound1-27>

<Compound 1-28><Compound1-29><Compound1-30>

<Compound 1-31><Compound1-32><Compound1-33>

<Compound 1-35><Compound1-36>

<Compound 1-37><Compound1-38>

The method of claim 7,
The amine compound represented by the formula C2 is an organic light emitting device, characterized in that any one selected from the group represented by the following compounds 3-1 to compound 3-43.
<Compound 3-1><Compound3-2><Compound3-3>

<Compound 3-4><Compound3-5><Compound3-6>

<Compound 3-7><Compound3-8><Compound3-9>

<Compound 3-10><Compound3-11><Compound3-12>

<Compound 3-13><Compound3-14><Compound3-15>

<Compound 3-16><Compound3-17><Compound3-18>

<Compound 3-19><Compound3-20><Compound3-21>

<Compound 3-22><Compound3-23><Compound3-24>

<Compound 3-25><Compound3-26><Compound3-27>

<Compound 3-28><Compound3-29><Compound3-30>

<Compound 3-31><Compound3-32><Compound3-33>

<Compound 3-34><Compound3-35><Compound3-36>

<Compound 3-37><Compound3-38><Compound3-39>

<Compound 3-40><Compound3-41><Compound3-42>

<Compound 3-43>

According to claim 1,
The amine compound represented by the formula (D) is <Compound 2-1> to <Compound 2-9>, <Compound 2-12>, <Compound 2-14> to <Compound 2-32>, <Compound 2-37 > To <Compound 2-45>, <Compound 2-50> to <Compound 2-57>, <Compound 2-62> to <Compound 2-69>, <Compound 2-74> to <Compound 2-81> , <Compound 2-86> to <Compound 2-100>, <Compound 2-105> to <Compound 2-159>, the organic light emitting device, characterized in that any one selected from the group.
<Compound 2-1><Compound2-2><Compound2-3>

<Compound 2-4><Compound2-5><Compound2-6>

<Compound 2-7><Compound2-8><Compound2-9>

<Compound 2-12>

<Compound 2-14><Compound2-15>

<Compound 2-16><Compound2-17><Compound2-18>

<Compound 2-19><Compound2-20><Compound2-21>

<Compound 2-22><Compound2-23><Compound2-24>

<Compound 2-25><Compound2-26><Compound2-27>

<Compound 2-28><Compound2-29><Compound2-30>

<Compound 2-31><Compound2-32>

<Compound 2-37><Compound2-38><Compound2-39>

<Compound 2-40><Compound2-41><Compound2-42>

<Compound 2-43><Compound2-44><Compound2-45>

<Compound 2-50><Compound2-51>

<Compound 2-52><Compound2-53><Compound2-54>

<Compound 2-55><Compound2-56><Compound2-57>

<Compound 2-62><Compound2-63>

<Compound 2-64><Compound2-65><Compound2-66>

<Compound 2-67><Compound2-68><Compound2-69>

<Compound 2-74><Compound2-75>

<Compound 2-76><Compound2-77><Compound2-78>

<Compound 2-79><Compound2-80><Compound2-81>

<Compound 2-86><Compound2-87>

<Compound 2-88><Compound2-89><Compound2-90>

<Compound 2-91><Compound2-92><Compound2-93>

<Compound 2-94><Compound2-95><Compound2-96>

<Compound 2-97><Compound2-98><Compound2-99>

<Compound 2-100>

<Compound 2-105>

<Compound 2-106><Compound2-107><Compound2-108>

<Compound 2-109><Compound2-110><Compound2-111>

<Compound 2-112><Compound2-113><Compound2-114>

<Compound 2-115><Compound2-116><Compound2-117>

<Compound 2-118><Compound2-119><Compound2-120>

<Compound 2-121><Compound2-122><Compound2-123>

<Compound 2-124><Compound2-125><Compound2-126>

<Compound 2-127><Compound2-128><Compound2-129>

<Compound 2-130><Compound2-131><Compound2-132>

<Compound 2-133><Compound2-134><Compound2-135>

<Compound 2-136><Compound2-137><Compound2-138>

<Compound 2-139><Compound2-140><Compound2-141>

<Compound 2-142><Compound2-143><Compound2-144>

<Compound 2-145><Compound2-146><Compound2-147>

<Compound 2-148><Compound2-149><Compound2-150>

<Compound 2-151><Compound2-152><Compound2-153>

<Compound 2-154><Compound2-155><Compound2-156>

<Compound 2-157><Compound2-158><Compound2-159>

According to claim 1,
The organic light emitting device is an organic light emitting device characterized in that it further comprises at least one of a hole injection layer, an electron transport layer, and an electron injection layer. The method of claim 15,
At least one layer selected from each of the layers is an organic light emitting device, characterized in that formed by a deposition process or a solution process. According to claim 1,
The organic light emitting device includes a flat panel display device; Flexible display devices; A monochromatic or white flat panel lighting device; And, Monochromatic or white flexible lighting device; Organic light-emitting device characterized in that it is used in any one device selected from.

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