WO2015174682A1 - Heterocyclic compound containing aromatic amine group, and organic light-emitting device comprising same - Google Patents

Abstract

The present invention relates to a heterocyclic compound containing an aromatic amine group and an organic light-emitting device comprising the same and, more specifically, to a heterocyclic compound and an organic light-emitting device comprising the same, the heterocyclic compound being excellent in brightness and light emission efficiency and being able to exhibit long-life and excellent device characteristics when being used as an organic light-emitting material.

Description

Heterocyclic compound comprising an aromatic amine group and an organic light emitting device comprising the same

The present invention relates to a heterocyclic compound including an aromatic amine group and an organic light emitting device including the same, and more particularly, when used as an organic light emitting material, it is excellent in brightness and luminous efficiency, and can show excellent device characteristics of long life. It relates to a heterocyclic compound and an organic light emitting device comprising the same.

Organic light emitting diodes (OLEDs) are displays using self-luminous phenomena, and are full-color due to their advantages such as large viewing angles, lighter and simpler, and faster response speeds than liquid crystal displays. Application to display or lighting is expected.

In general, an organic light emitting phenomenon refers to a phenomenon of converting electrical energy into light energy using an organic material. An organic light emitting device using the organic light emitting phenomenon generally has a structure including an anode, a cathode, and an organic material layer therebetween. In this case, the organic material layer is often formed of a multi-layered structure composed of different materials to increase the efficiency and stability of the organic light emitting device, for example, it may be made of a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, an electron injection layer. When the voltage is applied between the two electrodes in the structure of the organic light emitting device, holes are injected into the organic material layer at the anode and electrons are injected into the organic material layer, and excitons are formed when the injected holes and the electrons meet each other. When it falls back to the ground, it glows. Such organic light emitting devices are known to have characteristics such as self-luminous, high brightness, high efficiency, low driving voltage, wide viewing angle, high contrast, and high speed response.

The material used as the organic material layer in the organic light emitting device may be classified into a light emitting material and a charge transport material such as a hole injection material, a hole transport material, an electron transport material, an electron injection material and the like according to a function. The light emitting material may be classified into a polymer type and a low molecular type according to molecular weight, and may be classified into a fluorescent material derived from a singlet excited state of electrons and a phosphorescent material derived from a triplet excited state of electrons according to a light emitting mechanism. . In addition, the light emitting material may be classified into blue, green, and red light emitting materials and yellow and orange light emitting materials required to achieve a better natural color according to the light emitting color.

On the other hand, when only one material is used as the light emitting material, there is a problem that the maximum light emission wavelength is shifted to a long wavelength due to intermolecular interaction, and the color purity decreases or the efficiency of the device decreases due to the light emission attenuation effect, thereby increasing color purity and energy. Host-dopant systems can be used as luminescent materials to increase luminous efficiency through transition.

The principle is that when a small amount of dopant having an energy band gap smaller than that of the host forming the light emitting layer is mixed in the light emitting layer, excitons generated in the light emitting layer are transported to the dopant, thereby producing high efficiency light. At this time, since the wavelength of the host shifts to the wavelength of the dopant, light having a desired wavelength can be obtained according to the type of dopant to be used.

As a related art for a dopant compound in such a light emitting layer, Korean Patent Publication No. 10-2008-0015865 (2008.02.20) discloses an organic light emitting device using an indenofluorene derivative having an aryl amine bonded thereto. No. 10-2012-0047706 (20012.05.14) discloses a compound having a structure in which dibenzofuran or dibenzothiophenefluorene is present in one molecule or benzofuran or dibenzothiophene is present together with carbazole. The organic light emitting element used is disclosed.

However, despite the above efforts, the luminance and luminous efficiency are superior to the organic light emitting materials manufactured by the prior art including the prior art, and the necessity of developing a new organic light emitting material having long life characteristics is continuously. It is a required situation.

Therefore, the first technical problem to be achieved by the present invention can be used in the light emitting layer of an organic light emitting diode (OLED), excellent brightness and luminous efficiency, and a novel organic that can show excellent long-life device characteristics It is to provide a light emitting material.

Another object of the present invention is to provide an organic light emitting device including the organic light emitting material.

The present invention provides an amine compound represented by the following [Formula A] or [Formula B] in order to achieve the first technical problem.

[Formula A]

[Formula B]

In [Formula A] and [Formula B], A ₁ , A ₂ , E, and F are the same as or different from each other, and each independently substituted or unsubstituted aromatic hydrocarbon ring having 6 to 50 carbon atoms, or substituted or unsubstituted. Ring aromatic heterocyclic ring 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 A ₂ form a condensed ring by forming a 5-membered ring with carbon atoms connected to the substituents R1 and R2, respectively. ;

The linking groups L ₁ to L ₁₂ are the same as or different from each other, and each independently represent a single bond, a substituted or unsubstituted alkylene group having 1 to 60 carbon atoms, a substituted or unsubstituted alkenylene group having 2 to 60 carbon atoms, a substituted or Unsubstituted C2-C60 alkynylene group, substituted or unsubstituted C3-C60 cycloalkylene group, substituted or unsubstituted C2-C60 heterocycloalkylene group, substituted or unsubstituted C6-C60 An arylene group or a substituted or unsubstituted heteroarylene group having 2 to 60 carbon atoms;

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

The substituents R ₁ to R ₉ , Ar ₁ to Ar ₈ are the same as or different from each other, and are each independently hydrogen, deuterium, a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted carbon group having 6 to 50 carbon atoms. An aryl group, a substituted or 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 carbon number 5 to 30 30 cycloalkenyl groups, substituted or unsubstituted heteroaryl groups having 2 to 50 carbon atoms, substituted or unsubstituted heterocycloalkyl groups having 2 to 30 carbon atoms, substituted or unsubstituted alkoxy groups having 1 to 30 carbon atoms, substituted or unsubstituted A substituted aryloxy group having 6 to 30 carbon atoms, a substituted or unsubstituted alkylthioxy group having 1 to 30 carbon atoms, a substituted or unsubstituted arylthioxy group having 5 to 30 carbon atoms, substituted or unsubstituted An alkylamine group having 1 to 30 carbon atoms, a substituted or unsubstituted arylamine group having 5 to 30 carbon atoms, a substituted or unsubstituted alkylsilyl group having 1 to 30 carbon atoms, a substituted or unsubstituted arylsilyl group having 5 to 30 carbon atoms , A substituted or unsubstituted alkyl germanium group 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 R ₁ and R ₂ 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;

P1 to p4, r1 to r4, and s1 to s4 are each an integer of 1 to 3, and when each of them is 2 or more, each of the linking groups L ₁ to L ₁₂ are the same as or different from each other,

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

Ar ₁ and Ar ₂ , Ar ₃ and Ar ₄ , Ar ₅ and Ar ₆ , and Ar ₇ and Ar ₈ may be connected to each other to form a ring;

In Formula A, two carbon atoms adjacent to each other in the A ₂ ring combine with * of Structural Formula Q1 to form a condensed ring,

In Formula B, two carbon atoms adjacent to each other in the A ₁ ring combine with * of Structural Formula Q ₂ to form a condensed ring, and two carbon sources adjacent to each other in the A ₂ ring

The ruler is combined with * of Structural Formula Q1 to form a condensed ring.

In another aspect, the present invention, the first electrode; A second electrode opposed to the first electrode; And an organic layer interposed between the first electrode and the second electrode, wherein the organic layer comprises at least one organic light emitting compound represented by Formula A or Formula B of the present invention. .

According to the present invention, the amine compound represented by the above [Formula A] or [Formula B] is excellent in brightness and luminous efficiency compared to the conventional material, and can show excellent device characteristics of long life, an organic light emitting device having improved characteristics It can be used to.

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

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

The present invention provides an amine compound represented by the following [Formula A] or [Formula B] as an organic light emitting compound that can be used in the light emitting layer of the organic light emitting device.

[Formula A]

[Formula B]

In [Formula A] and [Formula B], A ₁ , A ₂ , E, and F are the same as or different from each other, and each independently substituted or unsubstituted aromatic hydrocarbon ring having 6 to 50 carbon atoms, or substituted or unsubstituted. Ring aromatic heterocyclic ring having 2 to 40 carbon atoms;

Two carbon atoms adjacent to each other in the aromatic ring of A ₁ and two carbon atoms adjacent to each other in the aromatic ring of A ₂ are each a condensed ring by forming a 5-membered ring with carbon atoms connected to the substituents R ₁ and R ₂ . To form;

The linking groups L ₁ to L ₁₂ are the same as or different from each other, and each independently represent 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 substitution or Unsubstituted C2-C60 alkynylene group, substituted or unsubstituted C3-C60 cycloalkylene group, substituted or unsubstituted C2-C60 heterocycloalkylene group, substituted or unsubstituted C6-C60 An arylene group or a substituted or unsubstituted heteroarylene group having 2 to 60 carbon atoms;

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

The substituents R ₁ to R ₉ , Ar ₁ to Ar ₈ are the same as or different from each other, and are each independently hydrogen, deuterium, a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted carbon group having 6 to 50 carbon atoms. Aryl group, substituted or unsubstituted alkenyl group having 2 to 30 carbon atoms, substituted or unsubstituted alkynyl group having 2 to 20 carbon atoms, substituted or unsubstituted cycloalkyl group having 3 to 30 carbon atoms, substituted or unsubstituted carbon number 5 A cycloalkenyl group having from 30 to 30, a substituted or unsubstituted heteroaryl group having 2 to 50 carbon atoms, a substituted or unsubstituted heterocycloalkyl group having 2 to 30 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 30 carbon atoms, substituted or Unsubstituted aryloxy group having 6 to 30 carbon atoms, substituted or unsubstituted alkylthioxy group having 1 to 30 carbon atoms, substituted or unsubstituted arylthioxy group having 5 to 30 carbon atoms, substituted or unsubstituted An alkylamine group having 1 to 30 carbon atoms, a substituted or unsubstituted arylamine group having 5 to 30 carbon atoms, a substituted or unsubstituted alkylsilyl group having 1 to 30 carbon atoms, a substituted or unsubstituted arylsilyl group having 5 to 30 carbon atoms , A substituted or unsubstituted alkyl germanium group having 1 to 30 carbon atoms, a substituted or unsubstituted aryl germanium group cyano group having 1 to 30 carbon atoms, a nitro group, a halogen group, any one selected from

The R ₁ and R ₂ may be connected to each other to form an alicyclic or aromatic monocyclic or polycyclic ring, and the carbon atoms of the formed alicyclic or aromatic monocyclic or polycyclic ring are N, O, P, Si, S May be substituted with any one or more heteroatoms selected from Ge, Se, and Te;

P1 to p4, r1 to r4, and s1 to s4 are each an integer of 1 to 3, and when each of them is 2 or more, each of the linking groups L ₁ to L ₁₂ are the same as or different from each other,

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

Ar ₁ and Ar ₂ , Ar ₃ and Ar ₄ , Ar ₅ and Ar ₆ , and Ar ₇ and Ar ₈ may be connected to each other to form a ring;

In Formula A, two carbon atoms adjacent to each other in the A ₂ ring combine with * of Structural Formula Q ₁ to form a condensed ring,

In the formula B, two carbon atoms adjacent to each other in the A ₁ ring are bonded to * of the structural formula Q ₂ to form a condensed ring, and two carbon atoms adjacent to each other in the A2 ring are bonded to * of the structural formula Q1 To form a condensed ring;

'Substituted' in the 'substituted or unsubstituted' is deuterium, cyano group, halogen group, hydroxy group, nitro group, alkyl group of 1 to 24 carbon atoms, halogenated alkyl group of 1 to 24 carbon atoms, alkenyl group of 1 to 24 carbon atoms , Alkynyl group having 1 to 24 carbon atoms, heteroalkyl group having 1 to 24 carbon atoms, aryl group having 6 to 24 carbon atoms, arylalkyl group having 6 to 24 carbon atoms, heteroaryl group having 2 to 24 carbon atoms or heteroarylalkyl group having 2 to 24 carbon atoms , Alkoxy group having 1 to 24 carbon atoms, alkylamino group having 1 to 24 carbon atoms, arylamino group having 1 to 24 carbon atoms, heteroaryl group having 1 to 24 carbon atoms, alkylsilyl group having 1 to 24 carbon atoms, arylsilyl having 1 to 24 carbon atoms It means that the group is substituted with one or more substituents selected from the group consisting of aryloxy group having 1 to 24 carbon atoms.

In the above formula (A) or compound is the formula (A) represented by the formula (B) in the present invention, groups are amine in the case where the structural formula Q ₁ is connected to A ₂ ring including the Ar ₁ and Ar ₂ be be bonded to A ₂ ring structure has a characteristic, and to be a structural formula Q ₂ in the formula (B) connected to the a ₁ ring, formula Q ₁ a is be an amine group is bonded, including the Ar ₁ and Ar ₂ wherein a ₂ ring when connected to a ₂ rings Has structural characteristics.

On the other hand, when considering the range of the alkyl group or the aryl group in the "substituted or unsubstituted C1-30 alkyl group", "substituted or unsubstituted C5-50 aryl group", and the like, The range of carbon number of the alkyl group having 1 to 30 carbon atoms and the aryl group having 5 to 50 carbon atoms means the total carbon number constituting the alkyl portion or the aryl portion when viewed as unsubstituted without considering the substituted portion. will be. For example, a 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, means an aromatic system composed of a hydrocarbon including one or more rings, and when the aryl group has a substituent, the aryl group may be fused to each other with neighboring substituents to further form a ring. Can be.

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 may be a Atom, hydroxy group, nitro group, cyano group, silyl group, amino group (-NH ₂ , -NH (R), -N (R ') (R''),R' and R "are independently of each other 1 to 10 carbon atoms Alkyl group, in this case an " 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, An alkenyl group of 24, an alkynyl group of 1 to 24 carbon atoms, a heteroalkyl group of 1 to 24 carbon atoms, It may be substituted with a heteroaryl group of a small number of 6 to 24 aryl group, C 6 -C 24 arylalkyl group, having 2 to 24 carbon atoms or heteroaryl group having 2 to 24.

The heteroaryl group, which is a substituent used in the compound of the present invention, contains 1, 2 or 3 heteroatoms selected from N, O, P, Si, S, Ge, Se, Te, and has 2 to 24 carbon atoms where the remaining ring atoms are carbon. Refers to a ring aromatic system, wherein the rings may be fused to form a ring. At least one hydrogen atom of the heteroaryl group may be substituted with the same substituent as in the case of the aryl group.

In the present invention, the aromatic heterocycle means that at least one aromatic carbon in the aromatic hydrocarbon ring is substituted with at least one hetero atom selected from N, O, P, Si, S, Ge, Se, Te.

Specific examples of the alkyl group which is a substituent used in the present invention include methyl, ethyl, propyl, isopropyl, isobutyl, sec-butyl, tert-butyl, pentyl, iso-amyl, hexyl and the like, and at least one of the alkyl groups The hydrogen atom can be substituted by the same substituent as the case of the said 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. At least one hydrogen atom of the alkoxy group may be substituted with the same substituent as in the case of 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, silyl, diphenylvinylsilyl and methylcyclo Butylsilyl, dimethylfurylsilyl, and the like, and at least one hydrogen atom in the silyl group may be substituted with the same substituent as in the case of the aryl group.

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

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

 [Structure 10] [Structure 11] [Structure 12]

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

 [Structure 16] [Structure 17] [Structure 18]

[Structure 19] [Structure 20] [Structure 21]

"-*" In [formula 10] to [formula 21] forms a 5-membered ring including carbon atoms linked to the substituents R ₁ and R ₂ , or 5 including M in the above formulas Q ₁ and Q ₂ Means a binding site for forming a torus,

When the aromatic hydrocarbon ring of [formula 10] to [formula 21] is bonded to the structural Q ₁ or the structural Q ₂ while the ring corresponds to the A ₁ ring or the A ₂ ring, the two carbon atoms adjacent to each other among the above-mentioned structural formulas Combine with * of Q ₁ or with * of structural Q ₂ to form a condensed ring;

In [formula 10] to [formula 21], R is the same as R ₁ and R ₂ defined above, m is an integer of 1 to 8, when m is 2 or more or R is 2 or more, each R is It may be the same or different from each other.

In an embodiment, A ₁ , A ₂ , E, and F in Formula A or Formula B of the present invention may be the same as or different from each other, and may be independently substituted or unsubstituted aromatic hetero rings having 2 to 30 carbon atoms. have.

As described above, when A ₁ , A ₂ , E, and F in Formula A or Formula B are the same or different, and each independently correspond to a substituted or unsubstituted aromatic hetero ring having 2 to 30 carbon atoms, Aromatic hetero rings may be the same or different and may be independently selected from [Formula 31] to [Formula 40].

[Structure 31] [Structure 32] [Structure 33] [Structure 34]

[Structure 35] [Structure 36] [Structure 37]

[Formula 38] [Formula 39] [Formula 40]

In [Formula 31] to [Formula 40],

T ₁ to T ₁₂ are the same as or different from each other, and each independently, C (R ₄₁ ), C (R ₄₂ ) (R ₄₃ ), N, N (R ₄₄ ), O, S, Se, Te, Si ( R ₄₅ ) (R ₄₆ ) and Ge (R ₄₇ ) (R ₄₈ ), which may be any one of T ₁ to T ₁₂ are not all carbon atoms at the same time, wherein R ₄₁ to R ₄₈ are defined above The same as R ₁ and R _2, and two adjacent ones of T ₁ to T ₁₂ in the aromatic ring form a 5-membered ring including carbon atoms connected to the substituents R ₁ and R ₂ as carbon atoms, or the structural formula Q Containing a single bond for forming a five-membered ring containing oxygen atoms at ₁ and Q ₂ ,

When the aromatic hetero ring of [Formula 31] to [Formula 40] corresponds to A ₁ ring or A ₂ ring and is bonded with Structural Formula Q ₁ or Structural Formula Q ₂ , _two of the T ₁ to T ₁₂ adjacent to each other are carbon As an atom, it combines with * of structural formula Q ₁ or with * of structural Q ₂ to form a condensed ring.

In addition, the [Formula 33] may include a compound represented by the following [Formula 33-1] by the resonance structure according to the movement of electrons.

[Formula 33-1]

In [Formula 33-1], T ₁ to T ₇ are the same as T ₁ to T ₁₂ defined in [Formula 31] to [Formula 40].

In one embodiment, the [formula 31] to [formula 40] may be selected from heterocycles represented by the following [formula 41].

[Formula 41]

In [Formula 41],

X is the same as R ₁ and R ₂ defined above, m is an integer of 1 to 11, when m is 2 or more, a plurality of X are the same or different from each other,

In [Formula 41], two carbon atoms adjacent to each other in the aromatic ring form a five-membered ring including carbon atoms linked to the substituents R ₁ and R ₂ , or include oxygen atoms in the above-described formulas Q ₁ and Q ₂ . To form a five-membered ring,

In the [formula 41] The aromatic heterocyclic ring is A ₁ has two carbon atom the formula Q ₁ adjacent to take the ring, if binding to the ring, or A _2, while for the ring structural formula Q ₁ or the formula Q ₂ of a * and Or by combining with * in formula Q ₂ to form a condensed ring.

In one embodiment, the linking groups L ₁ to L ₁₂ in Formula A or Formula B of the present invention are each a single bond, or a substituted or unsubstituted arylene group having 6 to 20 carbon atoms, or a substituted or unsubstituted carbon number 2 It may be any one selected from the hetero arylene group of 20.

In this case, the linking group L ₁ to L ₁₂ is a single bond, or any one selected from the following [Formula 22] to [Formula 30],

p1 to p4, r1 to r4, s1 to s4 are each 1 or 2,

x can be one.

[Structure 22] [Structure 23] [Structure 24] [Structure 25]

[Structure 26] [Structure 27] [Structure 28] [Structure 29]

[Formula 30]

In the linking group, the carbon site of the aromatic ring may be bonded to hydrogen or deuterium.

More specifically, in this case y may be 1 and z may be zero.

In one embodiment, the substituents R1 and R2 in the formula (A) or formula (B) of the present invention are the same or different and are each independently a substituted or unsubstituted aryl group having 6 to 24 carbon atoms, and are connected to each other to form a ring. Or they may not be linked to each other to form a ring.

In one embodiment, the substituents R ₁ to R ₉ , Ar ₁ to Ar ₈ of the present invention are the same as or different from each other, and each independently hydrogen, deuterium, a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, and substituted. Or an unsubstituted cycloalkyl group having 3 to 30 carbon atoms, a substituted or unsubstituted heteroaryl group having 2 to 20 carbon atoms, at least one selected from O, N, S and Si, a cyano group and a halogen group It can be any one.

In the amine compound of Formula A or Formula B of the present invention, 'substituted' substituents in A ₁ , A ₂ , E, F, Ar ₁ to Ar ₈ , L ₁ to L ₁₂ , and R ₁ to R ₉ Is a cyano group, a halogen group, an alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 18 carbon atoms, an arylalkyl group having 6 to 18 carbon atoms, a heteroaryl group having 3 to 18 carbon atoms, an alkylsilyl group having 1 to 12 carbon atoms, and 6 carbon atoms It may be any one selected from the group consisting of arylsilyl group of 18 to.

In addition, the amine compound of the present invention may be any one selected from the following [Formula 1] to [Formula 239].

<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>

<Formula 166> <Formula 167> <Formula 168>

<Formula 169> <Formula 170> <Formula 171>

<Formula 172> <Formula 173> <Formula 174>

<Formula 175> <Formula 176> <Formula 177>

<Formula 178> <Formula 179> <Formula 180>

<Formula 181> <Formula 182> <Formula 183>

<Formula 184> <Formula 185> <Formula 186>

<Formula 187> <Formula 188> <Formula 189>

<Formula 190> <Formula 191> <Formula 192>

<Formula 193> <Formula 194> <Formula 195>

<Formula 196> <Formula 197> <Formula 198>

<Formula 199> <Formula 200> <Formula 201>

<Formula 202> <Formula 203> <Formula 204>

<Formula 205> <Formula 206> <Formula 207>

<Formula 208> <Formula 209> <Formula 210>

<Formula 211> <Formula 212> <Formula 213>

<Formula 214> <Formula 215> <Formula 216>

<Formula 217> <Formula 218> <Formula 219>

<Formula 220> <Formula 221> <Formula 222>

<Formula 223> <Formula 224> <Formula 225>

<Formula 226> <Formula 227> <Formula 228>

<Formula 229> <Formula 230> <Formula 231>

<Formula 232> <Formula 233> <Formula 234>

<Formula 235> <Formula 236> <Formula 237>

<Formula 238> <Formula 239>

In addition, the present invention is a first electrode; A second electrode opposed to the first electrode; And an organic layer interposed between the first electrode and the second electrode, wherein the organic layer includes at least one organic light emitting compound of the present invention.

In the present invention, "(organic layer) contains at least one organic compound" means "(organic layer) one organic compound belonging to the scope of the present invention or two or more different compounds belonging to the organic compound category. May include. "

In addition, the organic layer including the organic light emitting compound of the present invention may include at least one of a hole injection layer, a hole transport layer, a functional layer having a hole injection function and a hole transport function at the same time, a light emitting layer, an electron transport layer, and an electron injection layer. have.

In this case, the organic layer interposed between the first electrode and the second electrode may include a light emitting layer, the light emitting layer is composed of a host and a dopant, the organic light emitting compound of the present invention may be used as a dopant.

Meanwhile, in the present invention, a host material may be used as the dopant in the light emitting layer. When the light emitting layer 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), TAZ, Balq, beryllium bis (benzoquinolin-10-noate) olate: Bebq2), ADN, compound 201, compound 202, BCP, oxadiazole derivatives such as PBD, BMD, BND may be used, but is not limited thereto.

TAZ BAlq

<Compound 201> <Compound 202> BCP

In the electron transport layer used in the present invention, the organometallic compound represented by the formula (C) may be used alone or in combination with the electron transport layer material.

[Formula C]

In [Formula C],

Y is a portion in which any one selected from C, N, O and S is directly bonded to the M to form a single bond, and any one selected from C, N, O and S forms a coordination bond to the M And a ligand chelated by the single bond and the coordination bond

M is an alkali metal, alkaline earth metal, aluminum (Al) or boron (B) atom, and OA is a monovalent ligand capable of single bond or coordination with 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 5 to 50 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 30 carbon atoms, a substituted or unsubstituted carbon group having 2 to 20 carbon atoms An 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 at least one selected from O, N, S and Si as a substituted or unsubstituted hetero atom It is any one selected from a heteroaryl group having 2 to 50 carbon atoms,

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, any one of m = 1 to 3, and n is any one of 0 to 2 to satisfy m + n = 3;

The '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, arylsilyl group, It is meant to be substituted with one or more substituents selected from the group consisting of an aryloxy group, an aryl group, a heteroaryl group, germanium, phosphorus and boron.

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

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

[Formula C4] [Formula C5] [Formula C6]

[Formula C7] [Formula C8] [Formula C9] [Formula C10]

[Formula C11] [Formula C12] [Formula C13]

[Formula C14] [Formula C15] [Formula C16]

[Formula C17] [Formula C18] [Formula C19] [Formula C20]

[Formula C21] [Formula C22] [Formula C23]

[Formula C24] [Formula C25] [Formula C26]

[Formula C27] [Formula C28] [Formula C29] [Formula C30]

[Formula C31] [Formula C32] [Formula C33]

[Formula C34] [Formula C35] [Formula C36]

[Formula C37] [Formula C38] [Formula C39]

In [Formula C1] to [Formula C39],

R is the same as or different from each other, and each independently hydrogen, deuterium, halogen, cyano group, a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a 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 Selected from the group, and may be connected to adjacent substituents with alkylene or alkenylene to form a spirogory or fused ring.

Hereinafter, the organic light emitting diode 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 organic light emitting layer 50, an electron transport layer 60 and a cathode 80, if necessary, the hole injection layer 30 and the electron The injection layer 70 may be further included. In addition, an intermediate layer of one or two layers may be further formed, and a hole blocking layer or an electron blocking layer may be further formed.

Referring to Figure 1 with respect to the organic light emitting device and a manufacturing method of the present invention. First, the anode 20 is formed by coating an anode electrode material on the substrate 10. As the substrate 10, a substrate used in a conventional organic EL device is used. An organic substrate or a transparent plastic substrate excellent in transparency, surface smoothness, ease of handling, and waterproofness is preferable. As the anode electrode material, indium tin oxide (ITO), indium zinc oxide (IZO), tin oxide (SnO ₂ ), zinc oxide (ZnO), and the like, which are transparent and have excellent conductivity, are used.

The hole injection layer 30 is formed by vacuum-heat deposition or spin coating of the hole injection layer material on the anode 20 electrode. Next, the hole transport layer 40 is formed by vacuum thermal evaporation or spin coating of the hole transport layer material on the hole injection layer 30.

The hole injection layer material may be used without particular limitation as long as it is commonly used in the art, for example, 2-TNATA [4,4 ', 4 "-tris (2-naphthylphenyl-phenylamino) -triphenylamine] , NPD [N, N'-di (1-naphthyl) -N, N'-diphenylbenzidine)], TPD [N, N'-diphenyl-N, N'-bis (3-methylphenyl) -1,1'- biphenyl-4,4'-diamine], DNTPD [N, N'-diphenyl-N, N'-bis- [4- (phenyl-m-tolyl-amino) -phenyl] -biphenyl-4,4'-diamine ] Etc. However, this invention is not necessarily limited to this.

In addition, the material of the hole transport layer is not particularly limited as long as it is commonly used in the art, 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) and the like can be used. However, the present invention is not necessarily limited thereto.

Subsequently, the organic light emitting layer 50 is stacked on the hole transport layer 40, and a hole blocking layer (not shown) is selectively formed on the organic light emitting layer 50 by a vacuum deposition method or a spin coating method. can do. The hole blocking layer prevents such a problem by using a material having a very low highest Occupied Molecular Orbital (HOMO) level because when the hole is introduced into the cathode through the organic light emitting layer is reduced the lifetime and efficiency of the device. . In this case, the hole blocking material to be used is not particularly limited, but should have an ionization potential higher than the light emitting compound while having an electron transport ability, and typically BAlq, BCP, TPBI, and the like may 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 cathode forming metal is vacuum-heated on the electron injection layer 70. The organic EL device is completed by vapor deposition to form a cathode 80 electrode. The metal for forming the cathode may be lithium (Li), magnesium (Mg), aluminum (Al), aluminum-lidium (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.

In addition, the light emitting layer may be formed of a host and a dopant.

Moreover, according to the specific example of this invention, it is preferable that the thickness of the said light emitting layer is 50-2,000 GPa.

In this case, the host used in the emission layer may be a compound represented by Formula 1A to Formula 1D.

[Formula 1A]

In Formula 1A,

Ar _7, Ar ₈ and Ar ₉ are the same as or different from each other, and each independently, a single bond, a substituted or unsubstituted C ₅ -C ₆₀ aromatic linking group, or a substituted or unsubstituted C ₂ -C ₆₀ heteroaromatic linking group;

R ₂₁ to R ₃₀ are the same as or different from each other, and each independently hydrogen, deuterium, a halogen atom, a hydroxyl group, a cyano group, a nitro group, an amino group, an amidino group, a hydrazine, a hydrazone, a carboxyl group or a salt thereof, a sulfonic acid group or Salts thereof, phosphoric acid or salts thereof, substituted or unsubstituted alkyl groups having 1 to 60 carbon atoms, substituted or unsubstituted alkenyl groups having 2 to 60 carbon atoms, substituted or unsubstituted alkynyl groups having 2 to 60 carbon atoms, substituted or unsubstituted Substituted alkoxy group having 1 to 60 carbon atoms, substituted or unsubstituted alkylthio group having 1 to 60 carbon atoms, substituted or unsubstituted cycloalkyl group having 3 to 60 carbon atoms, substituted or unsubstituted aryl having 6 to 60 carbon atoms A group, a substituted or unsubstituted aryloxy group having 5 to 60 carbon atoms, a substituted or unsubstituted arylthio group having 5 to 60 carbon atoms, a substituted or unsubstituted heteroaryl group having 2 to 60 carbon atoms, Substituted or unsubstituted (alkyl) amino group having 1 to 60 carbon atoms, di (substituted or unsubstituted alkyl group having 1 to 60 carbon atoms), or (substituted or unsubstituted aryl having 6 to 60 carbon atoms), di (substituted Or an unsubstituted aryl) amino group having 6 to 60 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 and boron. Each substituent may form a condensed ring with a group adjacent to each other;

E, f and g are the same as or different from each other, and each independently an integer of 0 or 1 to 4;

The two sites marked with * of the anthracene may be identical to or different from each other, and may independently combine with the P or Q structure to constitute an anthracene-based derivative selected from Formulas 1Aa-1 to 1Aa-3.

[Formula 1Aa-1] [Formula 1Aa-2] [Formula 1Aa-3]

Here, the 'substituted' in the 'substituted or unsubstituted' is deuterium, cyano group, halogen group, hydroxy group, nitro group, alkyl group of 1 to 24 carbon atoms, halogenated alkyl group of 1 to 24 carbon atoms, of 1 to 24 carbon atoms Alkenyl group, C1-C24 alkynyl group, C1-C24 heteroalkyl group, C6-C24 aryl group, C6-C24 arylalkyl group, C2-C24 heteroaryl group, or C2-C24 hetero Arylalkyl group, alkoxy group having 1 to 24 carbon atoms, alkylamino group having 1 to 24 carbon atoms, arylamino group having 1 to 24 carbon atoms, heteroarylaryl group having 1 to 24 carbon atoms, alkylsilyl group having 1 to 24 carbon atoms, and 1 to 24 carbon atoms It means substituted with one or more substituents selected from the group consisting of an arylsilyl group, aryloxy group having 1 to 24 carbon atoms.

[Formula 1B]

In Formula 1B,

Ar ₁₇ to Ar ₂₀ may be the same as or different from each other, and each independently the same substituent as defined in Ar ₇ to Ar ₈ in Formula 1A, and R ₆₀ to R ₆₃ may be defined in R ₂₁ to R ₃₀ of Formula 1A. And the same substituent as described above.

The w and ww are the same or different from each other, the x and xx are the same or different from each other, the w + ww and x + xx values are the same or different from each other and are each independently an integer of 0-3. In addition, y and yy are the same as or different from each other, z and zz are the same as or different from each other, and y + yy to z + zz are 2 or less, and are integers of 0 to 2, respectively.

[Formula 1C]

In Chemical Formula 1C,

Ar ₂₁ to Ar ₂₄ may be the same as or different from each other, and each independently the same substituent as defined in Ar ₇ to Ar ₈ of Formula 1A, and R ₆₄ to R ₆₇ may be selected from R ₂₁ to R ₃₀ of Formula 1A. It consists of the same substituent as defined.

In addition, ee to hh are the same as or different from each other and each independently an integer of 1 to 4, and ii to ll are the same or different from each other and each independently an integer of 0 to 4.

[Formula 1D]

In Chemical Formula 1D,

Ar ₂₅ to Ar ₂₇ are the same as or different from each other, and each independently include the same substituent as defined in Ar ₇ to Ar ₈ of Formula 1A, and R ₆₈ to R ₇₃ are the same as or different from each other, and each independently It consists of the same substituent as defined in R <_21> -R <_30> of 1A, and each substituent may form the saturated or unsaturated cyclic structure with adjacent ones. In addition, the mm to ss are the same as or different from each other and are each independently an integer of 0 to 4.

More specifically, the host may be represented by any one selected from the group represented by the following [Host 1] to [Host 56], but is not limited thereto.

[Host1] [Host2] [Host3] [Host4]

[Host5] [Host6] [Host7] [Host8]

[Host 9] [Host 10] [Host 11] [Host 12]

[Host13] [Host14] [Host15] [Host16]

[Host17] [Host18] [Host19] [Host20]

[Host21] [Host22] [Host23] [Host24]

[Host25] [Host26] [Host27] [Host28]

[Host29] [Host30] [Host31] [Host32]

[Host33] [Host34] [Host35] [Host36]

[Host37] [Host38] [Host39] [Host40]

[Host41] [Host42] [Host43] [Host44]

[Host45] [Host46] [Host47] [Host48]

[Host 49] [Host 50] [Host 51] [Host 52]

[Host53] [Host54] [Host55] [Host56]

In addition to the dopant and the host, the emission layer may further include various hosts and various dopant materials.

In the present invention, one or more layers selected from the hole injection layer, the hole transport layer, the electron blocking layer, the light emitting layer, the hole blocking layer, the electron transport layer and the electron injection layer may be formed by a single molecule deposition method or a solution process. Here, the deposition method refers to a method of forming a thin film by evaporating a material used as a material for forming each layer by heating or the like in a vacuum or low pressure state, and the solution process forms the respective layers. A method of forming a thin film by mixing a material used as a material for the solvent with a solvent and 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 is a flat panel display device; Flexible display devices; Monochrome or white flat lighting devices; And a solid or white flexible lighting device; can be used in any one device selected from.

Hereinafter, the present invention will be described in more detail with reference to preferred examples. 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)

Synthesis Example 1 Synthesis of Chemical Formula 1

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

[Intermediate 1-a] was synthesized according to Scheme 1 below.

<Scheme 1>

<Intermediate 1-a>

Methyl 5-bromo-2-iodobenzoate (25.0 g, 73 mmol), 4-dibenzofuranboronic acid (18.7 g, 88 mmol), tetrakis (triphenylphosphine) palladium (1.7 in a 500 mL round bottom flask reactor g, 0.15 mmol) and potassium carbonate (20.2 g, 146.7 mmol) were added, followed by 125 mL of toluene, 125 mL of tetrahydrofuran, and 50 mL of water. The temperature of the reactor was raised to 80 degrees and stirred for 10 hours. After 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. (75.0g, 60.1%)

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

Intermediate 1-b was synthesized according to Scheme 2:

<Scheme 2>

<Intermediate 1-a> <Intermediate 1-b>

<Intermediate 1-a> (17.0g, 45mmol), sodium hydroxide (2.14g, 54mmol) and ethanol 170ml were put into a 500mL round bottom flask reactor, and the mixture was stirred under reflux for 48 hours. After completion of the reaction by thin layer chromatography, the reaction 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. Recrystallized with dichloromethane and normal hexane to give <intermediate 1-b>. (14.5g, 88.6%)

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

Intermediate 1-c was synthesized according to Scheme 3:

<Scheme 3>

<Intermediate 1-b> <Intermediate 1-c>

<Intermediate 1-b> (14.5g, 39mmol) and 145ml of methanesulfonic acid were added to a 250ml round bottom flask reactor, and the temperature was raised to 80 degrees and stirred for 3 hours. After completion of the reaction by thin layer chromatography, the reaction 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. <Intermediate 1-c> was obtained. (11.50g, 83.4%)

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

Intermediate 1-d was synthesized according to Scheme 4 below:

<Scheme 4>

<Intermediate 1-c> <Intermediate 1-d>

<Intermediate 1-c> (11.5g, 33mmol) and 300ml of dichloromethane were added to a 1L round bottom flask reactor and stirred at room temperature. Bromine (3.4ml, 66mmol) was added dropwise by diluting to 50ml 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, and the resulting solid was filtered and washed with acetone.The solid was recrystallized from monochlorobenzene to obtain <Intermediate 1-d> (11.0 g, 78%).

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

Intermediate 1-e was synthesized according to Scheme 5 below:

Scheme 5

<Intermediate 1-d> <Intermediate 1-e>

2-bromobiphenyl (8.4g, 0.036mol) and tetrahydrofuran 110ml were added to a 250ml round bottom flask reactor and cooled to -78 degrees in a nitrogen atmosphere. Normal butyllithium (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> (11.0 g, 0.026 mol) was added little by little and stirred at room temperature. When the reaction solution color was changed, the reaction was terminated by TLC. 50 ml of H 2 O was added to terminate the reaction, and the mixture was extracted with ethyl acetate and water. The organic layer was separated, concentrated under reduced pressure, and recrystallized with acetonitrile to obtain <Intermediate 1-e>. (12.2g, 81.5%)

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

Intermediate 1-f was synthesized according to Scheme 6 below:

<Scheme 6>

<Intermediate 1-e> <intermediate 1-f>

<Intermediate 1-e> (12.0g, 0.021mol), 120ml of acetic acid and 2ml of sulfuric acid were added to a 250ml round bottom flask reactor, and the mixture was stirred under reflux for 5 hours. After the solid was formed, the reaction was confirmed by thin layer chromatography, and then cooled to room temperature. The resulting solid was filtered, washed with H 2 O and methanol, dissolved in monochlorobenzene, filtered through silica gel, concentrated and cooled to room temperature to obtain <Intermediate 1-f>. (10.7g, 90%>

Synthesis Example 1- (7): Synthesis of Chemical Formula 1

Formula 1 was synthesized according to Scheme 7:

Scheme 7

<Intermediate 1-f> <Formula 1>

<Intermediate 1-f> (5.0g, 0.009mol), Bis (4-tertylbutylphenyl) amine (6.0g, 0.021mol), Palladium (II) Acetate (0.08g, 0.4mmol) in 250ml round bottom flask reactor , Sodium tert-butoxide (3.4 g, 0.035 mol), tributyl butyl phosphine (0.07 g, 0.4 mmol), and 60 ml of toluene were added and stirred under reflux for 2 hours. After completion of the reaction, the mixture 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 then concentrated under reduced pressure. The material was separated and purified by column chromatography, and recrystallized with dichloromethane and acetone to obtain <Formula 1> (3.1 g, 36%).

MS (MALDI-TOF): m / z 964.5 [M ⁺ ]

Synthesis Example 2 Synthesis of Chemical Formula 33

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

According to Scheme 8, intermediate 2-a was synthesized:

Scheme 8

<Intermediate 2-a>

4-bromodibenzofuran (100.0 g, 0.405 mol), ethynyl trimethylsilane (47.7 g, 0.486 mol), [1,1'-bis (diphenylphosphino) ferrocene] dichloropalladium in a 2 L round bottom flask reactor 9.92 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 reaction mixture was cooled to room temperature, and 500 ml of heptane was added to terminate the reaction. Celite and silica gel pad was laid and filtered. The filtrate was concentrated under reduced pressure to obtain <Intermediate 2-a> (130 g, 84%).

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

According to Scheme 9, intermediate 2-b was synthesized:

Scheme 9

<Intermediate 2-a> <Intermediate 2-b>

<Intermediate 2-a> (130g, 0.492mol), potassium carbonate (101.9g, 0.738mol), methanol 650ml, tetrahydrofuran 650ml were added to a 2L round bottom flask reactor and stirred at room temperature for 2 hours. After completion of the reaction, 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, anhydrous treated with magnesium sulfate, filtered and concentrated under reduced pressure. <Intermediate 2-b> (82 g, 84%) in the form of an oil was obtained.

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

According to Scheme 10, intermediate 2-c was synthesized:

Scheme 10

<Intermediate 2-b> <Intermediate 2-c>

2-bromobiphenyl (66.0 g, 0.283 mol), <Intermediate 2-b> (65.3 g, 0.340 mol), [1,1'-bis (diphenylphosphino) ferrocene] dichro 2L round bottom flask reactor Ropalladium (6.94g, 0.008mol), copper iodide (1.62g, 0.008mol), triphenylphosphine (7.4g, 0.028mol), and 500ml of triethylamine were added and stirred under reflux for 5 hours in a nitrogen atmosphere. After completion of the reaction, the mixture was cooled to room temperature and 400 ml of heptane was added to terminate the reaction. Celite and silica gel pad was laid and filtered. The filtrate was concentrated under reduced pressure and the resulting solid was filtered to obtain <Intermediate 2-c> (80 g, 82%).

Synthesis Example 2- (4): Synthesis of Intermediate 2-d

According to Scheme 11, intermediate 2-d was synthesized:

Scheme 11

<Intermediate 2-c> <Intermediate 2-d>

<Intermediate 2-c> (80.0g, 0.232mol) was dissolved in 960ml of dichloromethane in a 2L round bottom flask reactor and cooled to -78 ° C 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 completion of the reaction, a saturated aqueous sodium thiosulfate solution was added thereto and stirred. Extracted with dichloromethane and water, the organic layer was separated and concentrated under reduced pressure. The crystals were caught with methanol to obtain <Intermediate 2-d> (67 g, 61.3%).

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

According to Scheme 12, intermediate 2-e was synthesized:

Scheme 12

<Intermediate 2-d> <Intermediate 2-e>

150 ml of <Intermediate 2-d> (54.8 g, 0.117 mol) and tetrahydrofuran were dissolved in a 500 ml round bottom flask reactor and cooled to -78 degrees in a nitrogen atmosphere. 1.6 mole normal butylium (62.4 ml, 0.1 mol) was added dropwise to the cooled solution, followed by stirring 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, the mixture was extracted with ethyl acetate and water. The organic layer was separated, anhydrous treated with magnesium sulfate, filtered and concentrated under reduced pressure. <Intermediate 2-e> (33.2 g, 76%) in the form of an oil was obtained.

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

According to Scheme 13, intermediate 2-f was synthesized:

Scheme 13

<Intermediate 2-e> <Intermediate 2-f>

<Intermediate 2-e> (33.3 g, 0.063 mol), 330 ml of acetic acid and 3 ml of sulfuric acid were added to a 1 L round bottom flask reactor, and the mixture was stirred under reflux for 3 hours. After completion of the reaction by thin layer chromatography, the reaction mixture was cooled to room temperature. The resulting solid is filtered and washed with H 2 O, methanol. <Intermediate 2-f> was obtained. (28.6 g, 88%>

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

According to Scheme 14, intermediate 2-g was synthesized:

Scheme 14

<Intermediate 2-f> <Intermediate 2-g>

<Intermediate 2-f> (20.0 g, 0.039 mol) and 200 ml of dichloromethane were dissolved in a 1 L round bottom flask reactor. Bromine (6 ml, 0.118 mol) was diluted and added dropwise in 40 ml of dichloromethane while stirring at room temperature. After stirring for 12 hours at room temperature, 100 ml of methanol was added to the reaction mixture, and the resulting solid was filtered and washed with methanol. The material was recrystallized from 1,2-dichlorobenzene and acetone to obtain <Intermediate 2-g> (16g, 60%).

Synthesis Example 2- (8): Synthesis of Chemical Formula 33

According to Scheme 15, Formula 33 was synthesized:

Scheme 15

<Intermediate 2-g> <Formula 33>

<Formula 33> (2.5 g, 31%) was obtained in the same manner as in Synthesis Example 1- (7), except that <intermediate 2-g> was used instead of <intermediate 1-f>.

MS (MALDI-TOF): m / z 1064.5 [M ⁺ ]

Synthesis Example 3 Synthesis of Chemical Formula 49

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

According to Scheme 16, intermediate 3-a was synthesized:

Scheme 16

<Intermediate 3-a>

1-hydroxy 2-naphthalic acid (50 g, 266 mmol), methanol 1000 ml, sulfuric acid 100 ml were added to a 2 L round bottom flask reactor, and the mixture was stirred under reflux for 100 hours. After confirming the reaction termination by TLC, the mixture was cooled to room temperature. The solution was concentrated under reduced pressure and extracted with dichloromethane and water. The organic layer was separated, anhydrous treated with magnesium sulfate, filtered, and concentrated under reduced pressure, followed by crystallization by adding an excess of heptane to obtain <Intermediate 3-a> (39 g, 72.6%).

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

Intermediate 3-b was synthesized according to Scheme 17 below:

Scheme 17

<Intermediate 3-a> <Intermediate 3-b>

<Intermediate 3-a> (39.0 g, 193 mmol) and 390 ml of acetic acid were added to a 1 L round bottom flask reactor, and the mixture was stirred at room temperature. Bromine (11.8 ml, 231 mmol) was diluted in 80 ml of acetic acid and added dropwise to the reaction solution. The reaction solution was stirred at room temperature for 5 hours. After the reaction was completed, the produced solid was filtered, and after the heptane slurry, <intermediate 3-b> (50 g, 90%) was obtained.

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

Intermediate 3-c was synthesized according to Scheme 18 below:

Scheme 18

<Intermediate 3-b> <Intermediate 3-c>

<Intermediate 3-b> (50g, 178mmol) and dichloromethane were added to a 2L round bottom flask reactor. Pyridine (28.1 g, 356 mmol) was added to the reaction solution in a nitrogen atmosphere and stirred at room temperature for 20 minutes. The reaction solution was cooled to 0 deg. And trifluoromethanesulphonic anhydride (65.24 g, 231 mmol) was added dropwise in a nitrogen atmosphere. After stirring for 3 hours, the reaction was terminated by TLC. 20 ml of water was added thereto, followed by stirring for 10 minutes. The reaction solution was concentrated under reduced pressure and separated by column to obtain <Intermediate 3-c> (45 g, 61%).

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

Intermediate 3-d was synthesized according to Scheme 19 below:

Scheme 19

<Intermediate 3-c> <Intermediate 3-d>

<Intermediate 3-c> (45.0g, 0.109mol), 4-dibenzoboronic acid (25.4g, 0.120mol), tetrakis (triphenylphosphine) palladium (2.5g, 0.22mmol) in 1L round bottom flask reactor Potassium carbonate (30.1 g, 0.218 mol) was added thereto, 300 mL of toluene, 130 mL of ethanol, and 90 mL of water were added thereto. The temperature of the reactor was raised to 80 degrees and stirred for 5 hours. After 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 3-d. (22.0g, 46.1%)

Synthesis Example 3- (5): Synthesis of Intermediate 3-e

Intermediate 3-e was synthesized according to Scheme 20 below:

Scheme 20

<Intermediate 3-d> <Intermediate 3-e>

<Intermediate 3-d> (22.0, 0.051mol), sodium hydroxide (2.65g, 0.066mol) in a 1L round bottom flask reactor was stirred under reflux for 48 hours. After the reaction was completed, 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. Recrystallized with dichloromethane and normal hexane to give <intermediate 3-e>. (17.6g, 82.7%)

Synthesis Example 3- (6): Synthesis of Intermediate 3-f

Intermediate 3-f was synthesized according to Scheme 21 below:

Scheme 21

<Intermediate 3-e> <Intermediate 3-f>

<Intermediate 3-e> (17.6g, 0.042mol) and 170ml of methanesulfonic acid were added to a 500ml round bottom flask reactor, and the temperature was raised to 80 degrees and stirred for 3 hours. After completion of the reaction by thin layer chromatography, the reaction 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 pad of silica gel. The filtrate was concentrated by heating and recrystallized with acetone to obtain <Intermediate 3-f>. (12g, 71%)

Synthesis Example 3- (7): Synthesis of Intermediate 3-g

Intermediate 3-g was synthesized according to Scheme 22 below:

Scheme 22

<Intermediate 3-f> <Intermediate 3-g>

In a 1 L round bottom flask reactor <intermediate 3-f> (12.0 g, 0.030 mol) and 360 ml of dichloromethane were added. Bromine (3.1 ml, 0.06 mol) was diluted and added dropwise in 40 ml of dichloromethane while stirring at room temperature. After stirring for 12 hours at room temperature, 100 ml of methanol was added to the reaction mixture, and the resulting solid was filtered and washed with methanol. The material was recrystallized from 1,2-dichlorobenzene and acetone to obtain <Intermediate 3-g> (10.3 g, 71.7%).

Synthesis Example 3- (8): Synthesis of Intermediate 3-h

Intermediate 3-h was synthesized according to Scheme 23 below:

Scheme 23

<Intermediate 3-g> <Intermediate 3-h>

<Intermediate 3-h> (10.0 g, 73.4%) was obtained in the same manner as in Synthesis Example 1- (5), except that <intermediate 3-g> was used instead of <intermediate 1-d>.

Synthesis Example 3- (9): Synthesis of Intermediate 3-i

Intermediate 3-i was synthesized according to Scheme 24 below:

Scheme 24

<Intermediate 3-h> <Intermediate 3-i>

<Intermediate 3-i> (6.3 g, 64.8%) was obtained in the same manner as in Synthesis Example 1- (6), except that <intermediate 3-h> was used instead of <intermediate 1-e>.

Synthesis Example 3- (10): Synthesis of Chemical Formula 49

Formula 49 was synthesized according to Scheme 25 below:

Scheme 25

<Intermediate 3-i> <Formula 49>

<Formula 49> (3.0 g, 36.1%) was obtained in the same manner as in Synthesis Example 1- (7), except that <Intermediate 3-i> was used instead of <Intermediate 1-f>.

MS (MALDI-TOF): m / z 1014.5 [M ⁺ ]

Synthesis Example 4 Synthesis of Chemical Formula 76

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

According to Scheme 26, intermediate 4-a was synthesized:

Scheme 26

<Intermediate 4-a>

1-bromodibenzofuran (20.0g, 0.081mmol), bis (pinacolato) diboron (26.7g, 0.105mol), [1,1'-bis (diphenylphosphino) ferrocene in 500ml round bottom flask reactor ] Dichloropalladium (1.3g, 0.002mol), potassium acetate (19.9g, 0.202mol) and 200ml of 1,4-dioxane were added and stirred under reflux for 10 hours.

After the reaction was completed, the celite pad was filtered. The filtrate was concentrated under reduced pressure, column separated, and recrystallized with dichloromethane and heptane to obtain <Intermediate 4-a> (17.0 g, 70%).

Synthesis Example 4- (2): Synthesis of Intermediate 4-b

According to Scheme 27, intermediate 4-b was synthesized:

Scheme 27

<Intermediate 4-a> <Intermediate 4-b>

<Intermediate 4-b> (13.1 g, 68.9%) was obtained using the same method as in Synthesis Example 1- (1), except that <intermediate 4-a> was used instead of 4-dibenzoboronic acid.

Synthesis Example 4- (3): Synthesis of Intermediate 4-c

According to Scheme 28, intermediate 4-c was synthesized:

Scheme 28

<Intermediate 4-b> <Intermediate 4-c>

<Intermediate 4-c> (11 g, 87%) was obtained in the same manner as in Synthesis Example 1- (2), except that <Intermediate 4-b> was used instead of <Intermediate 1-a>.

Synthesis Example 4- (4): Synthesis of Intermediate 4-d

According to Scheme 29, intermediate 4-d was synthesized:

Scheme 29

<Intermediate 4-c> <Intermediate 4-d>

<Intermediate 4-d> (9.0 g, 86%) was obtained in the same manner as in Synthesis Example 1- (3), except that <Intermediate 4-c> was used instead of <Intermediate 1-b>.

Synthesis Example 4- (5): Synthesis of Intermediate 4-e

According to Scheme 30, intermediate 4-e was synthesized:

Scheme 30

<Intermediate 4-d> <Intermediate 4-e>

<Intermediate 4-e> (6.7g, 60.7%) was obtained by the same method as in Synthesis Example 1- (4), except that <Intermediate 4-d> was used instead of <Intermediate 1-c>.

Synthesis Example 4- (6): Synthesis of Intermediate 4-f

According to Scheme 31, intermediate 4-f was synthesized:

Scheme 31

<Intermediate 4-e> <Intermediate 4-f>

<Intermediate 4-f> (5.2g, 55%) was obtained by the same method as in Synthesis Example 1- (5), except that <Intermediate 4-e> was used instead of <Intermediate 1-d>.

Synthesis Example 4- (7): Synthesis of Intermediate 4-g

Intermediate 4-g was synthesized according to Scheme 32 below:

Scheme 32

<Intermediate 4-f> <Intermediate 4-g>

<Intermediate 4-g> (4.3g, 85.3%) was obtained by the same method as in Synthesis Example 1- (6), except that <Intermediate 4-f> was used instead of <Intermediate 1-e>.

Synthesis Example 4- (8): Synthesis of Chemical Formula 76

Formula 76 was synthesized according to Scheme 33 below:

Scheme 33

<Intermediate 4-g> <Formula 76>

Except for using <Intermediate 4-g> instead of <Intermediate 1-f> in Synthesis Example 1- (7), and using the same method to obtain <Formula 76> (2.5g, 34%).

MS (MALDI-TOF): m / z 964.5 [M ⁺ ]

Synthesis Example 5 Synthesis of Chemical Formula 89

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

According to Scheme 34, intermediate 5-a was synthesized:

Scheme 34

<Intermediate 5-a>

2-Penoxyaniline (25.0, 0.135mol), hydrochloric acid and 30ml of water were added to a 1L round-bottomed reactor, and the mixture was cooled to 0 ° C and stirred for 1 hour. At the same temperature, 75 ml of an aqueous solution of sodium nitride (11.2 g, 0.162 mol) was added dropwise to the reaction solution, followed by stirring for 1 hour. When 75 ml of an aqueous solution of potassium iodide (44.8 g, 0.270 mol) was added dropwise, the reaction solution was added dropwise so that the temperature of the reaction solution did not exceed 5 degrees. After stirring for 5 hours at room temperature, the reaction was completed and washed with aqueous sodium sulphate solution and extracted with ethyl acetate and water. The organic layer was separated and concentrated under reduced pressure, and then purified by column chromatography to obtain <Intermediate 5-a> (22.6 g, 56.5%).

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

According to Scheme 35, intermediate 5-b was synthesized:

Scheme 35

<Intermediate 1-d> <Intermediate 5-a> <Intermediate 5-b>

<Intermediate 5-in the same manner as in Synthesis Example 1- (5), except that <intermediate 3-g> was used instead of <intermediate 1-d> and <intermediate 5-a> instead of 2-bromobiphenyl. b> (19.6 g, 70.4%).

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

According to Scheme 36, intermediate 5-c was synthesized:

Scheme 36

<Intermediate 5-b> <Intermediate 5-c>

<Intermediate 5-c> (14.2 g, 74.7%) was obtained in the same manner as in Synthesis Example 1- (6), except that <intermediate 5-b> was used instead of <intermediate 1-e>.

Synthesis Example 5- (4): Synthesis of Chemical Formula 89

According to Scheme 37, formula 89 was synthesized:

Scheme 37

<Intermediate 5-c> <Formula 89>

<Intermediate 5-c> is substituted for <Intermediate 5-c> in place of <Intermediate 1-f> in Synthesis Example 1- (7) instead of bis (4-tertarybutylphenyl) amine. Except that the amine was used, the same method was used to obtain <Formula 89> (2.4 g, 28%).

MS (MALDI-TOF): m / z 980.5 [M ⁺ ]

Synthesis Example 6 Synthesis of Formula 97

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

According to Scheme 38, intermediate 6-a was synthesized:

Scheme 38

<Intermediate 6-a>

4-dibenzoboronic acid (85.0 g, 0.401 mol), bismuth (III) nitrate pentahydrate (99.2 g, 0.200 mol) and 400 ml of toluene were added to a 2 L round bottom flask reactor, and the mixture was stirred at 70 ° C. for 3 hours. After completion of the reaction, the mixture was cooled to room temperature and the resulting solid was filtered. After washing with toluene <Intermediate 6-a> (61.5g, 72%) was obtained.

Synthesis Example 6- (2): Synthesis of Intermediate 6-b

Intermediate 6-b was synthesized according to Scheme 39 below:

Scheme 39

<Intermediate 6-a> <Intermediate 6-b>

Ethyl cyanoacetate (202.9 g, 1.794 mol) and 500 ml of dimethylformamide were added to a 2 L round bottom flask reactor. Potassium hydroxide (67.10 g, 1.196 mol) and potassium cyanide (38.95 g, 0.598 mol) were added thereto, and 200 ml of dimethylformamide was added thereto, followed by stirring at room temperature. <Intermediate 6-a> (127.5 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, 200ml of sodium hydroxide solution (25%) was added thereto, followed by stirring under reflux. After stirring for 3 hours, the mixture was cooled to room temperature, and extracted with etheracetate and water. The organic layer was separated, concentrated under reduced pressure, purified by column chromatography and purified to obtain <Intermediate 6-b> (20.0g, 16%).

Synthesis Example 6- (3): Synthesis of Intermediate 6-c

Intermediate 6-c was synthesized according to Scheme 40 below:

Scheme 40

<Intermediate 6-b> <Intermediate 6-c>

<Intermediate 6-b> (20.0g, 0.096mol), 600ml of ethanol and 170ml of potassium hydroxide solution (142.26g, 2.53mol) were added to a 2L round bottom flask reactor and stirred under reflux for 12 hours. After the reaction was completed, the mixture was cooled to room temperature. 400 ml of 6 normal hydrochloric acid was added to the reaction solution, and acidified. The resulting solid was stirred after 20 minutes and filtered. The solid was washed with ethanol to obtain <Intermediate 6-c> (17.0g, 88.5%).

Synthesis Example 6- (4): Synthesis of Intermediate 6-d

Intermediate 6-d was synthesized according to Scheme 41 below:

Scheme 41

<Intermediate 6-c> <Intermediate 6-d>

<Intermediate 6-c> (17.0 g, 0.075 mol) and 15 ml of sulfuric acid were added to a 2 L round bottom flask reactor, and the mixture was stirred under reflux for 72 hours. After the reaction was completed, the mixture was extracted with ethyl acetate and water after cooling to room temperature. The organic layer was separated and washed with an aqueous sodium hydrogen carbonate solution. The organic layer was concentrated with reduced pressure and methanol was added to the resulting solid to obtain <Intermediate 6-d> (14.0 77.6%).

Synthesis Example 6- (5): Synthesis of Intermediate 6-e

Intermediate 6-d was synthesized according to Scheme 42 below:

Scheme 42

<Intermediate 6-d> <Intermediate 6-e>

<Intermediate 6-e> (9.1 g, 48%) was obtained using the same method as in Synthesis Example 5- (1), except that <intermediate 6-d> was used instead of 2-phenoxyaniline.

Synthesis Example 6-6: Synthesis of Intermediate 6-f

Intermediate 6-f was synthesized according to Scheme 43 below:

Scheme 43

<Intermediate 6-e> <Intermediate 4-a> <Intermediate 6-f>

<Intermediate 6-f> (5.3 g, 52.3) using the same method as in Synthesis Example 4- (2), except that <Intermediate 6-e> was used instead of methyl 5-bromo-2-iodobenzoate. %) Was obtained.

Synthesis Example 6-7: Synthesis of Intermediate 6-g

Intermediate 6-g was synthesized according to Scheme 44 below:

Scheme 44

<Intermediate 6-f> <Intermediate 6-g>

<Intermediate 6-g> (4.5 g, 88.1%) was obtained in the same manner as in Synthesis Example 1- (2), except that <intermediate 6-f> was used instead of <intermediate 1-a>.

Synthesis Example 6- (8): Synthesis of Intermediate 6-h

Intermediate 6-h was synthesized according to Scheme 45 below:

Scheme 45

<Intermediate 6-g> <Intermediate 6-h>

<Intermediate 6-h> (3.8 g, 88.8%) was obtained in the same manner as in Synthesis Example 1- (3), except that <intermediate 6-g> was used instead of <intermediate 1-b>.

Synthesis Example 6-9: Synthesis of Intermediate 6-i

Intermediate 6-i was synthesized according to Scheme 46 below:

Scheme 46

<Intermediate 6-h> <Intermediate 6-i>

<Intermediate 6-i> (3g, 55%) was obtained by the same method as in Synthesis Example 1- (4), except that <Intermediate 6-h> was used instead of <Intermediate 1-c>.

Synthesis Example 6- (10): Synthesis of Intermediate 6-j

Intermediate 6-j was synthesized according to Scheme 47 below:

Scheme 47

<Intermediate 6-i> <Intermediate 6-j>

<Intermediate 6-j> (2.5 g, 64%) was obtained using the same method as in Synthesis Example 1- (5), except that <Intermediate 6-i> was used instead of <Intermediate 1-d>.

Synthesis Example 6- (10): Synthesis of Intermediate 6-k

Intermediate 6-k was synthesized according to Scheme 48 below:

Scheme 48

<Intermediate 6-j> <Intermediate 6-k>

<Intermediate 6-k> (2.2g, 90.4%) was obtained by the same method as in Synthesis Example 1- (6), except that <Intermediate 6-j> was used instead of <Intermediate 1-e>.

Synthesis Example 6-11: Synthesis of Intermediate 6-L

Intermediate 6-l was synthesized according to Scheme 49 below:

Scheme 49

<Intermediate 6-l>

1-bromo-4- (2-naphthyl) benzene (10.0g, 0.035mol), 4-tert-butylaniline (5.8g, 0.039mol), tris (dibenzylideneacetone) di in 250ml round bottom flask reactor Palladium (0) (0.65g, 0.0007mol), sodium tert-butoxide (6.79g, 0.0706mol), 2,2'-bis (diphenylphosphino) -1,1'-binaphthalene (0.44g, 0.0007 mol) toluene 100ml was added and stirred under reflux for 3 hours. After completion of the reaction, the mixture was extracted with cold ethyl acetate and water. The organic layer was separated, anhydrous treated with magnesium sulfate, and then concentrated under reduced pressure. Separation and purification by column chromatography gave <Intermediate 6-l> (10 g, 80%).

Synthesis Example 6- (12): Synthesis of Chemical Formula 97

Formula 97 was synthesized according to Scheme 50 below:

Scheme 50

<Intermediate 6-k> <Intermediate 6-l> <Formula 97>

The same method was used as in Synthesis Example 1- (7) except that <Intermediate 6-k> was used instead of <Intermediate 1-f> and <Intermediate 6-l> instead of bis (4-tertarybutylphenyl) amine. (97 g, 38%) was obtained.

MS (MALDI-TOF): m / z 1194.5 [M ⁺ ]

Synthesis Example 7 Synthesis of Chemical Formula 45

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

According to Scheme 51, intermediate 7-a was synthesized:

Scheme 51

<Intermediate 7-a>

1,2-dibromobenzene (20.0g, 0.085mol), 4-fluorobenzoboronic acid (14.2g, 0.102mol), tetrakis (triphenylphosphine) palladium (2.9g, 0.0025) in 500mL round bottom flask reactor mmol), potassium carbonate (23.4 g, 0.169 mol) was added thereto, 100 mL of toluene, 100 mL of tetrahydrofuran, and 40 mL of water were added thereto. The temperature of the reactor was raised to 80 degrees and stirred for 10 hours. After 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 7-a. (14.1g, 66.2%)

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

According to Scheme 52, intermediate 7-b was synthesized:

Scheme 52

<Intermediate 1-d> <Intermediate 7-a> <Intermediate 7-b>

<Intermediate 7-b> (12.2 g, 79%) was obtained in the same manner as in Synthesis Example 1- (5), except that <intermediate 7-a> was used instead of 2-bromobiphenyl.

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

According to Scheme 53, intermediate 7-c was synthesized:

Scheme 53

<Intermediate 7-b> <Intermediate 7-c>

<Intermediate 7-c> (8.2 g, 69.3%) was obtained in the same manner as in Synthesis Example 1- (6), except that <intermediate 7-b> was used instead of <intermediate 1-e>.

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

According to Scheme 54, intermediate 7-d was synthesized:

Scheme 54

<Intermediate 7-d>

<Intermediate 7-d> (14.0 g, 72) was obtained in the same manner as in Synthesis Example 6- (11), except that 4-bromobiphenyl was used instead of 1-bromo4- (2-naphthyl) benzene. %) Was obtained.

Synthesis Example 7- (5): Synthesis of Chemical Formula 45

According to Scheme 55, Formula 45 was synthesized:

Scheme 55

<Intermediate 7-c> <Intermediate 7-d> <Formula 45>

The same method was used as in Synthesis Example 1- (7) except that <Intermediate 7-c> was used instead of <intermediate 1-f> and <intermediate 7-d> instead of bis (4-tertarybutylphenyl) amine. (2.4 g, 28%) was obtained.

MS (MALDI-TOF): m / z 1022.4 [M ⁺ ]

Synthesis Example 8 Synthesis of Formula 105

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

According to Scheme 56, intermediate 8-a was synthesized:

Scheme 56

<Intermediate 3-d> <Intermediate 8-a>

Bromobenzene (25.46g, 0.163mol) and tetrahydrofuran 170ml were added to a 500ml round bottom flask reactor and cooled to -78 degrees in a nitrogen atmosphere. Normal butyllithium (1.6 mol) (95.6 ml, 0.153 mol) was added dropwise to the cooled reaction solution. After stirring for 1 hour at the same temperature <intermediate 3-d> (22.0g, 0.051mol) was added and stirred at room temperature for 3 hours. After the reaction was completed 50ml of water and stirred for 30 minutes. After extraction with ethyl acetate and water, the organic layer was separated and concentrated under reduced pressure. 200 ml of acetic acid and 1 ml of hydrochloric acid were added to the concentrated material, and the mixture was stirred at 80 ° C. After the reaction was completed, the reaction mixture was cooled to room temperature, and the produced solid was filtered. After washing with methanol to obtain <Intermediate 8-a> (20.0g, 73%).

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

According to Scheme 57, intermediate 8-b was synthesized:

Scheme 57

<Intermediate 8-a> <Intermediate 8-b>

In a 1 L round bottom flask reactor, <Intermediate 8-a> (20.0 g, 0.037 mol) and 600 ml of chloroform were added. Bromine (5.7 ml, 0.112 mol) was diluted in 40 ml of chloroform and added dropwise while stirring at room temperature. After stirring for 12 hours at room temperature, 100 ml of methanol was added to the reaction mixture, and the resulting solid was filtered and washed with methanol. The material was recrystallized from 1,2-dichlorobenzene and acetone to obtain <Intermediate 8-b> (14.0 g, 61.7%).

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

According to Scheme 58, intermediate 8-c was synthesized:

Scheme 58

<Intermediate 8-c>

Intermediate 8- was used in the same manner as in Synthesis Example 6- (11), except that 1-bromo-4- (trimethylsilyl) benzene was used instead of 1-bromo4- (2-naphthyl) benzene. c> (13.1 g, 72.1%).

Synthesis Example 8- (4): Synthesis of Chemical Formula 105

According to Scheme 59, Formula 105 was synthesized:

Scheme 59

<Intermediate 8-b> <Intermediate 8-c> <Formula 105>

The same method was used as in Synthesis Example 1- (7) except that <Intermediate 8-b> was used instead of <Intermediate 1-f> and <Intermediate 8-c> instead of bis (4-tertarybutylphenyl) amine. (105 g, 35%) was obtained.

MS (MALDI-TOF): m / z 1048.5 [M ⁺ ]

Synthesis Example 9 Synthesis of Chemical Formula 220

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

According to Scheme 60, intermediate 9-a was synthesized:

Scheme 60

<Intermediate 9-a>

<Intermediate 9-a> (18.0 g, 61.8%) using the same method as in synthesis example 1- (1), except that 4-dibenzothiophenboronic acid was used instead of 4-dibenzofuranboronic acid. Got.

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

According to Scheme 61, intermediate 9-b was synthesized:

Scheme 61

<Intermediate 9-a> <Intermediate 9-b>

<Intermediate 9-b> (15.0 g, 86.5%) was obtained in the same manner as in Synthesis Example 1- (2), except that <Intermediate 9-a> was used instead of <Intermediate 1-a>.

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

According to Scheme 62, intermediate 9-c was synthesized:

Scheme 62

<Intermediate 9-b> <Intermediate 9-c>

<Intermediate 9-c> (12.0 g, 83.9%) was obtained in the same manner as in Synthesis Example 1- (3), except that <Intermediate 9-b> was used instead of <Intermediate 1-b>.

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

Intermediate 9-d was synthesized according to Scheme 63 below:

Scheme 63

<Intermediate 9-c> <Intermediate 9-d>

<Intermediate 9-d> (11.0 g, 75.4%) was obtained in the same manner as in Synthesis Example 1- (4), except that <Intermediate 9-c> was used instead of <Intermediate 1-c>.

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

Intermediate 9-e was synthesized according to Scheme 64 below:

Scheme 64

<Intermediate 9-d> <Intermediate 9-e>

<Intermediate 9-e> (11.2 g, 75.6%) was obtained in the same manner as in Synthesis Example 1- (5), except that <Intermediate 9-d> was used instead of <Intermediate 1-d>.

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

Intermediate 9-f was synthesized according to Scheme 65 below:

Scheme 65

<Intermediate 9-e> <intermediate 9-f>

<Intermediate 9-f> (8.7 g, 80.1%) was obtained in the same manner as in Synthesis Example 1- (6), except that <intermediate 9-e> was used instead of <intermediate 1-e>.

Synthesis Example 9- (7): Synthesis of Chemical Formula 220

Formula 220 was synthesized according to Scheme 66 below:

Scheme 66

<Intermediate 9-f> <Intermediate 8-c> <Formula 220>

The same method was used as in Synthesis Example 1- (7) except that <Intermediate 9-f> was used instead of <Intermediate 1-f> and <Intermediate 8-c> instead of bis (4-tertarybutylphenyl) amine. To obtain <Formula 220> (3.2 g, 36.6%).

Synthesis Example 10 Synthesis of Chemical Formula 224

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

According to Scheme 67, intermediate 10-a was synthesized:

Scheme 67

<Intermediate 6-e> <Intermediate 10-a>

Except for using Intermediate 6-e instead of Methyl 5-bromo-2-iodobenzoate in Synthesis Example 4- (2) instead of <Intermediate 4-a> 4-dibenzothiophenic boronic acid, Using the same method, <Intermediate 10-a> (20.2 g, 84.3%) was obtained.

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

According to Scheme 68, intermediate 10-b was synthesized:

Scheme 68

<Intermediate 10-a> <Intermediate 10-b>

<Intermediate 10-b> (16.5 g, 84.6%) was obtained in the same manner as in Synthesis Example 1- (2), except that <intermediate 10-a> was used instead of <intermediate 1-a>.

Synthesis Example 10- (3): Synthesis of Intermediate 10-c

According to Scheme 69, intermediate 10-c was synthesized:

<Scheme 69>

<Intermediate 10-b> <Intermediate 10-c>

<Intermediate 10-c> (12.4 g, 78.7%) was obtained in the same manner as in Synthesis Example 1- (3), except that <intermediate 10-b> was used instead of <intermediate 1-b>.

Synthesis Example 10- (4): Synthesis of Intermediate 10-d

According to Scheme 70, intermediate 10-d was synthesized:

Scheme 70

<Intermediate 10-c> <Intermediate 10-d>

<Intermediate 10-d> (3g, 62.5%) was obtained by the same method as in Synthesis Example 1- (4), except that <Intermediate 10-c> was used instead of <Intermediate 1-c>.

Synthesis Example 10- (5): Synthesis of Intermediate 10-e

According to Scheme 71, intermediate 10-e was synthesized:

Scheme 71

<Intermediate 10-d> <Intermediate 10-e>

<Intermediate 10-e> (10.2 g, 72.0%) was obtained in the same manner as in Synthesis Example 1- (5), except that <intermediate 10-d> was used instead of <intermediate 1-d>.

Synthesis Example 10- (6): Synthesis of Intermediate 10-f

According to Scheme 72, intermediate 10-f was synthesized:

Scheme 72

<Intermediate 10-e> <intermediate 10-f>

<Intermediate 10-f> (8.7 g, 87.6%) was obtained in the same manner as in Synthesis Example 1- (6), except that <intermediate 10-e> was used instead of <intermediate 1-e>.

Synthesis Example 10- (7): Synthesis of Chemical Formula 224

According to Scheme 73, Formula 224 was synthesized:

Scheme 73

<Intermediate 10-f> <Intermediate 7-d> <Formula 224>

The same method was used as in Synthesis Example 1- (7) except that <Intermediate 10-f> was used instead of <intermediate 1-f> and <intermediate 7-d> instead of bis (4-tertarybutylphenyl) amine. (224 g, 33.8%) was obtained.

Synthesis Example 11 Synthesis of Chemical Formula 225

Synthesis Example 11- (1): Synthesis of Intermediate 11-a

According to Scheme 74, intermediate 11-a was synthesized:

Scheme 74

<Intermediate 11-a>

1-bromo-3-iodobenzene (25.0 g, 88 mmol) was added to a 500 ml round bottom flask, and 200 ml of tetrahydrofuran was added to dissolve it. The reaction solution was cooled to -78 degrees under nitrogen atmosphere. Normal butyllithium (60.75ml, 97mmol) was slowly added dropwise to the cooled solution for 30 minutes and stirred at the same temperature for 1 hour. Trimethylborate (11 g, 106 mmol) was added dropwise at the same temperature and stirred overnight at room temperature. 2N hydrochloric acid was added dropwise to the reaction solution, followed by acidification and stirring for 1 hour. The mixture was extracted with ethyl acetate, concentrated under reduced pressure from the organic layer, and cold crystallized into normal hexane. <Intermediate 11-a> was obtained. (12g, 67.6%)

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

According to Scheme 75, intermediate 11-b was synthesized:

Scheme 75

<Intermediate 11-a> <Intermediate 11-b>

Except that methyl 2-bromobenzoate was used instead of methyl 5-bromo-2-iodobenzoate in Synthesis Example 4- (2), instead of <intermediate 4-a>, <intermediate 11-a> was used. <Intermediate 11-b> (10.2 g, 68.5%) was obtained using the method.

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

According to Scheme 76, intermediate 11-c was synthesized:

Scheme 76

<Intermediate 11-b> <Intermediate 11-c>

<Intermediate 11-b> (10.2g, 35mmol) and tetrahydrofuran 100ml were put into a 250ml round bottom flask and cooled to 0 ° C in a nitrogen atmosphere. Methylmagnesium bromide (17.5 ml, 53 mmol) was added dropwise to the cooled reaction solution. After completion of the dropwise addition, the mixture was stirred for 2 hours at room temperature and stirred for 2 hours at reflux, followed by cooling to room temperature. 0.2 normal hydrochloric acid was slowly added dropwise to the reaction solution and acidified, followed by extraction with ethyl acetate and water. The organic layer was separated and concentrated under reduced pressure, followed by column separation to obtain <intermediate 11-c> (7.6g, 74.5%).

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

According to Scheme 77, intermediate 11-d was synthesized:

Scheme 77

<Intermediate 11-c> <Intermediate 11-d>

<Intermediate 11-c> (20.0 g, 69 mmol), 300 ml of acetic acid and 1 ml of hydrochloric acid were added to a 500 ml round bottom flask, and the mixture was stirred under reflux. After completion of the reaction by thin layer chromatography, the reaction mixture was cooled to room temperature. Methylene chloride and water were added and the organic layer was separated and concentrated under reduced pressure. Separation by column chromatography gave <Intermediate 11-d> (8.2 g, 43.7%).

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

According to Scheme 78, intermediate 11-e was synthesized:

Scheme 78

<Intermediate 11-d> <Intermediate 11-e>

Intermediate 11-d (8.2 g, 30 mmol), bis (pinacolato) diboron (9.9 g, 39 mmol), [1,1'-bis (diphenylphosphino) ferrocene] dik in 250 ml round bottom flask reactor Loropalladium (0.5 g, 0.001 mol), potassium acetate (7.4 g, 75 mmol) and 80 ml of 1,4-dioxane were added thereto, and the mixture was stirred under reflux for 10 hours. After the reaction was completed, the celite pad was filtered. The filtrate was concentrated under reduced pressure, separated by column and recrystallized with dichloromethane and heptane to obtain <intermediate 11-e> (7.0g, 72.8%).

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

According to Scheme 79, intermediate 11-f was synthesized:

Scheme 79

<Intermediate 11-e> <intermediate 11-f>

<Intermediate 11-f> (8.2 g, 68.6%) was obtained in the same manner as in Synthesis Example 1- (1), except that <Intermediate 11-e> was used instead of 4-dibenzofuranboronic acid. .

Synthesis Example 11- (7): Synthesis of Intermediate 11-g

According to Scheme 80, intermediate 11-g was synthesized:

Scheme 80

<Intermediate 11-f> <Intermediate 11-g>

<Intermediate 11-g> (6.5 g, 82.1%) was obtained in the same manner as in Synthesis Example 1- (2), except that <Intermediate 11-f> was used instead of <Intermediate 1-a>.

Synthesis Example 11- (8): Synthesis of Intermediate 11-h

According to Scheme 81, intermediate 11-h was synthesized:

Scheme 81

<Intermediate 11-g> <Intermediate 11-h>

<Intermediate 11-h> (5.0 g, 80.6%) was obtained in the same manner as in Synthesis Example 1- (3), except that <intermediate 11-g> was used instead of <intermediate 1-b>.

Synthesis Example 11- (9): Synthesis of Intermediate 11-i

According to Scheme 82, intermediate 11-i was synthesized:

<Scheme 82>

<Intermediate 11-h> <Intermediate 11-i>

<Intermediate 11-i> (3.5 g, 57.8%) was obtained in the same manner as in Synthesis Example 1- (4), except that <Intermediate 11-h> was used instead of <Intermediate 1-c>.

Synthesis Example 11- (10): Synthesis of Intermediate 11-j

According to Scheme 83, intermediate 11-j was synthesized:

Scheme 83

<Intermediate 11-i> <Intermediate 11-j>

<Intermediate 11-j> (3.0 g, 64%) was obtained in the same manner as in Synthesis Example 1- (5), except that <Intermediate 11-i> was used instead of <Intermediate 1-d>.

Synthesis Example 11- (11): Synthesis of Intermediate 11-k

According to Scheme 84, intermediate 11-k was synthesized:

Scheme 84

<Intermediate 11-j> <Intermediate 11-k>

<Intermediate 11-k> (2.2 g, 75.6%) was obtained in the same manner as in Synthesis Example 1- (6), except that <intermediate 11-j> was used instead of <intermediate 1-e>.

Synthesis Example 11- (12): Synthesis of Chemical Formula 225

According to Scheme 85, formula 225 was synthesized:

Scheme 85

<Intermediate 11-k> <Formula 225>

Chemical Formula 225 (1.8 g, 48.7%) was obtained in the same manner as in Synthesis Example 1- (7), except that <Intermediate 11-k> was used instead of <Intermediate 1-f>.

Synthesis Example 12 Synthesis of Chemical Formula 226

Synthesis Example 12- (1): Synthesis of Intermediate 12-a

According to Scheme 86, intermediate 12-a was synthesized:

Scheme 86

<Intermediate 12-a>

2-Iodonitrobenzene (15.0g, 0.060mol), 2-bromophenylboronic acid (13.3g, 0.066mol), palladium acetate (0.67g, 0.003mol), potassium carbonate (16.6) in a 1L round bottom flask reactor g, 0.120 mol) and triphenylphosphine (2.37 g, 0.009 mol) were added thereto, 525 mL of toluene, 60 mL of ethanol, and 60 mL of water were added thereto. The temperature of the reactor was raised to 100 degrees and stirred for 18 hours. After 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 12-a>. (14.0g, 83.6%)

Synthesis Example 12- (2): Synthesis of Intermediate 12-b

According to Scheme 87, intermediate 12-b was synthesized:

Scheme 87

<Intermediate 12-a> <Intermediate 12-b>

In a 250 ml round bottom flask, <Intermediate 12-a> (14.0 g, 0.050 mol), triphenylphosphine (33.01 g, 0.126 mol) and N, N-dimethylacetamide (100 ml) were added and stirred at 180 ° for 14 hours. It was. After the reaction was completed, the reaction mixture was cooled to room temperature, poured into 200 ml of water, and stirred. Extraction was performed with ethyl acetate, and the organic layer was separated and concentrated under reduced pressure. <Intermediate 12-b> (7.0 g, 56.5%) was obtained by column separation.

Synthesis Example 12- (3): Synthesis of Intermediate 12-c

According to Scheme 88, intermediate 12-c was synthesized:

Scheme 88

<Intermediate 12-b> <Intermediate 12-c>

<Intermediate 12-b> (7.0 g, 0.028 mol) and tetrahydrofuran 140 ml were added to a 250 ml round bottom flask, and sodium hydride (60%) (1.19 g, 0.029 mol) was stirred at room temperature for 30 minutes and then cooled to 0 ° C. . Iodomethane (3.5 ml, 0.057 mol) was added dropwise to the cooled reaction solution, and the temperature was raised to room temperature and stirred for 18 hours. When the reaction was completed, poured into 100ml of water, extracted with ethyl acetate and separated the organic layer. The organic layer was anhydrous treated with anhydrous magnesium sulfate, filtered and concentrated under reduced pressure, and then separated by column chromatography to obtain <Intermediate 12-c> (7.2 g, 92.7%).

Synthesis Example 12- (4): Synthesis of Intermediate 12-d

According to Scheme 89, intermediate 12-d was synthesized:

Scheme 89

<Intermediate 12-c> <Intermediate 12-d>

<Intermediate 12-d> (6.1 g, 71.7%) was obtained in the same manner as in Synthesis Example 4- (1), except that <Intermediate 12-c> was used instead of 1-bromodibenzofuran.

Synthesis Example 12- (5): Synthesis of Intermediate 12-e

According to Scheme 90, intermediate 12-e was synthesized:

Scheme 90

<Intermediate 12-d> <Intermediate 12-e>

<Intermediate 12-e> (5.2 g, 73.7%) was obtained in the same manner as in Synthesis Example 1- (1), except that <Intermediate 12-d> was used instead of 4-dibenzofuranboronic acid.

Synthesis Example 12- (6): Synthesis of Intermediate 12-f

According to Scheme 91, intermediate 12-f was synthesized:

Scheme 91

<Intermediate 12-e> <intermediate 12-f>

<Intermediate 12-f> (8.2 g, 85%) was obtained in the same manner as in Synthesis Example 1- (2), except that <intermediate 12-e> was used instead of <intermediate 1-a>.

Synthesis Example 12- (7): Synthesis of Intermediate 12-g

According to Scheme 92, intermediate 12-g was synthesized:

Scheme 92

<Intermediate 12-f> <intermediate 12-g>

<Intermediate 12-g> (6.7 g, 85.8%) was obtained using the same method as in Synthesis Example 1- (3), except that <Intermediate 12-f> was used instead of <Intermediate 1-b>.

Synthesis Example 12- (8): Synthesis of Intermediate 12-h

In accordance with Scheme 93, intermediate 12-h was synthesized:

Scheme 93

<Intermediate 12-g> <Intermediate 12-h>

<Intermediate 12-h> (4.3 g, 52.7%) was obtained in the same manner as in Synthesis Example 1- (4), except that <intermediate 12-g> was used instead of <intermediate 1-c>.

Synthesis Example 12- (9): Synthesis of Intermediate 12-i

According to Scheme 94, intermediate 12-i was synthesized:

Scheme 94

<Intermediate 12-h> <intermediate 12-i>

<Intermediate 12-i> (4.0 g, 68.9%) was obtained in the same manner as in Synthesis Example 1- (5), except that <intermediate 12-h> was used instead of <intermediate 1-d>.

Synthesis Example 12- (10): Synthesis of Intermediate 12-j

According to Scheme 95, intermediate 12-j was synthesized:

Scheme 95

<Intermediate 12-i> <intermediate 12-j>

<Intermediate 12-j> (3.2 g, 82.5%) was obtained in the same manner as in Synthesis Example 1- (6), except that <intermediate 12-i> was used instead of <intermediate 1-e>.

Synthesis Example 12- (11): Synthesis of Chemical Formula 226

According to Scheme 96, Formula 226 was synthesized:

<Scheme 96>

<Intermediate 12-j> <Intermediate 7-d> <Formula 226>

The same method was used as in Synthesis Example 1- (7) except that <Intermediate 12-j> was used instead of <Intermediate 1-f> and <Intermediate 7-d> instead of bis (4-tertarybutylphenyl) amine. (2.3 g, 40.7%) was obtained.

Examples 1 to 11: Preparation of organic light emitting device

The light emitting area of the ITO glass was patterned to have a size of 2 mm x 2 mm and then washed. After mounting the ITO glass in the vacuum chamber, the base pressure was 1 × 10 ^-7 torr, and then DNTPD (700 kPa) and α-NPD (300 kPa) were deposited on the ITO in the order of [BH1]. 3% of the compound according to the present invention as described in 1 was mixed and formed into a film (250 Pa), and then the electron injection layer was 300 Pa in a ratio of 1: 1 in the ratio of [Formula E-1] and [Formula E-2]. [Formula E-1] was formed into a film of 5 Å, Al (1000 Å) in order to manufacture an organic light emitting device. The emission characteristics of the organic light emitting device was measured at 0.4 mA.

[DNTPD] [α-NPD]

[BH1] [Formula E-1] [Formula E-2]

Comparative Examples 1 and 2

An organic light emitting diode was manufactured in the same manner as in the Example 1 to 11 except that [BD1] and [BD2] were used instead of the compound used, and the emission characteristics of the organic light emitting diode were measured at 0.4 mA. The structures of [BD1] and [BD2] are as follows.

[BD1] [BD2]

For the organic light emitting diodes manufactured according to Examples 1 to 11 and Comparative Examples 1 and 2, voltage, current, luminance, color coordinates, and lifetime were measured, and the results are shown in the following [Table 1]. T97 means the time taken for the luminance to decrease to 97% of the initial luminance.

Table 1 Voltage Current density (mA / cm ² ) Brightness (cd / m ² ) CIEx CIEy T97 Comparative Example 1 [BD1] 4.1 10 515 0.143 0.150 42 Comparative Example 2 [BD2] 4.0 10 550 0.141 0.154 40 Example 1 [Formula 1] 3.8 10 750 0.130 0.133 98 Example 2 [Formula 33] 3.8 10 880 0.136 0.133 110 Example 3 [Formula 24] 3.8 10 667 0.133 0.117 125 Example 4 [Formula 45] 3.8 10 650 0.133 0.115 113 Example 5 [Formula 49] 3.8 10 980 0.132 0.181 110 Example 6 3.8 10 679 0.141 0.116 121 Example 7 3.8 10 801 0.138 0.110 120 Example 8 3.8 10 780 0.134 0.120 100 Example 9 [Formula 97] 3.8 10 816 0.134 0.121 120 Example 10 [Formula 101] 3.8 10 710 0.133 0.120 105 Example 11 3.8 10 850 0.130 0.164 118

As shown in Table 1, the amine compound according to the present invention is much more excellent in luminance and luminous efficiency than the case of using the compounds of Comparative Example 1 and Comparative Example 2 according to the prior art, can show excellent device characteristics of long life, It shows the high applicability as an organic light emitting element.

According to the present invention, it is possible to manufacture an organic light emitting device having excellent device characteristics of high brightness, high light emission and long life, there is industrial applicability.

Claims (18)

An amine compound represented by the following [Formula A] or [Formula B]. [Formula A]

[Formula B]

In [Formula A] and [Formula B], A ₁ , A ₂ , E, and F are the same as or different from each other, and each independently substituted or unsubstituted aromatic hydrocarbon ring having 6 to 50 carbon atoms, or substituted or unsubstituted. Ring aromatic heterocyclic ring having 2 to 40 carbon atoms; Two carbon atoms adjacent to each other in the aromatic ring of A ₁ and two carbon atoms adjacent to each other in the aromatic ring of A ₂ are each a condensed ring by forming a 5-membered ring with carbon atoms connected to the substituents R ₁ and R ₂ . To form; The linking groups L ₁ to L ₁₂ are the same as or different from each other, and each independently represent a single bond, a substituted or unsubstituted alkylene group having 1 to 60 carbon atoms, a substituted or unsubstituted alkenylene group having 2 to 60 carbon atoms, a substituted or Unsubstituted C2-C60 alkynylene group, substituted or unsubstituted C3-C60 cycloalkylene group, substituted or unsubstituted C2-C60 heterocycloalkylene group, substituted or unsubstituted C6-C60 An arylene group or a substituted or unsubstituted heteroarylene group having 2 to 60 carbon atoms; M is any one selected from NR ₃ , CR ₄ R ₅ , SiR ₆ R ₇ , GeR ₈ R ₉ , O, S, Se; The substituents R ₁ to R ₉ , Ar ₁ to Ar ₈ are the same as or different from each other, and are each independently hydrogen, deuterium, a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted carbon group having 6 to 50 carbon atoms. Aryl group, substituted or unsubstituted C2-C30 alkenyl group, substituted or unsubstituted C2-C20 alkynyl group, substituted or unsubstituted C3-C30 cycloalkyl group, substituted or unsubstituted C5-C5 30 cycloalkenyl groups, substituted or unsubstituted heteroaryl groups having 2 to 50 carbon atoms, substituted or unsubstituted heterocycloalkyl groups having 2 to 30 carbon atoms, substituted or unsubstituted alkoxy groups having 1 to 30 carbon atoms, substituted or unsubstituted A substituted aryloxy group having 6 to 30 carbon atoms, a substituted or unsubstituted alkyl thioxy group having 1 to 30 carbon atoms, a substituted or unsubstituted arylthioxy group having 5 to 30 carbon atoms, substituted or unsubstituted An alkylamine group having 1 to 30 carbon atoms, a substituted or unsubstituted arylamine group having 5 to 30 carbon atoms, a substituted or unsubstituted alkylsilyl group having 1 to 30 carbon atoms, a substituted or unsubstituted arylsilyl group having 5 to 30 carbon atoms , A substituted or unsubstituted alkyl germanium group 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 R ₁ and R ₂ may be connected to each other to form an alicyclic or aromatic monocyclic or polycyclic ring, and the carbon atoms of the formed alicyclic or aromatic monocyclic or polycyclic ring are N, O, P, Si, S , Ge, Se, Te may be substituted with any one or more heteroatoms; P1 to p4, r1 to r4, and s1 to s4 are each an integer of 1 to 3, and when each of them is 2 or more, each of the linking groups L ₁ to L ₁₂ are the same as or different from each other, X is an integer of 1 or 2, y and z are the same or different, and each independently an integer of 0 to 3, Ar ₁ and Ar ₂ , Ar ₃ and Ar ₄ , Ar ₅ and Ar ₆ , and Ar ₇ and Ar ₈ may be connected to each other to form a ring; In Formula A, two carbon atoms adjacent to each other in the A ₂ ring combine with * of Structural Formula Q1 to form a condensed ring, Of the A ₁ ring within two carbon atom the adjacent form a condensed ring by combining with * in the structural formula Q _2, and The two carbon atoms by the A ₂ in the adjacent ring the formula Q ₁ in formula B * and Combine to form a condensed ring; 'Substituted' in the 'substituted or unsubstituted' is deuterium, cyano group, halogen group, hydroxy group, nitro group, alkyl group of 1 to 24 carbon atoms, halogenated alkyl group of 1 to 24 carbon atoms, alkenyl group of 1 to 24 carbon atoms , Alkynyl group having 1 to 24 carbon atoms, heteroalkyl group having 1 to 24 carbon atoms, aryl group having 6 to 24 carbon atoms, arylalkyl group having 6 to 24 carbon atoms, heteroaryl group having 2 to 24 carbon atoms or heteroarylalkyl group having 2 to 24 carbon atoms , Alkoxy group having 1 to 24 carbon atoms, alkylamino group having 1 to 24 carbon atoms, arylamino group having 1 to 24 carbon atoms, heteroaryl group having 1 to 24 carbon atoms, alkylsilyl group having 1 to 24 carbon atoms, arylsilyl having 1 to 24 carbon atoms It means that the group is substituted with one or more substituents selected from the group consisting of aryloxy group having 1 to 24 carbon atoms. The method of claim 1, A ₁ , A ₂ , E, and F in Formula A or Formula B are the same or different, and each independently represent a substituted or unsubstituted aromatic hydrocarbon ring having 6 to 50 carbon atoms. The method of claim 2, The aromatic hydrocarbon ring is the same or different, and independently of each other amine compound, characterized in that any one selected from [formula 10] to [formula 21]. [Structure 10] [Structure 11] [Structure 12]

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

[Structure 16] [Structure 17] [Structure 18]

[Structure 19] [Structure 20] [Structure 21]

"-*" In [formula 10] to [formula 21] forms a 5-membered ring including carbon atoms linked to the substituents R ₁ and R ₂ , or 5 including M in the above formulas Q ₁ and Q ₂ Means a binding site for forming a torus, When the aromatic hydrocarbon ring of [formula 10] to [formula 21] is bonded to the structural Q ₁ or the structural Q ₂ while the ring corresponds to the A ₁ ring or the A ₂ ring, the two carbon atoms adjacent to each other among the above-mentioned structural formulas Combine with * of Q ₁ or with * of structural Q ₂ to form a condensed ring; In [Formula 10] to [Formula 21] wherein R is the same as R ₁ and R ₂ defined in claim 1, m is an integer of 1 to 8, when m is 2 or more or R is 2 or more, respectively R may be the same or different from each other. The method of claim 1, The linking groups L ₁ to L ₁₂ may each be a single bond or any one selected from a substituted or unsubstituted arylene group having 6 to 20 carbon atoms, or a substituted or unsubstituted hetero arylene group having 2 to 20 carbon atoms. An amine compound. The method of claim 4, wherein The linking group L ₁ to L ₁₂ is a single bond, or any one selected from the following [formula 22] to [formula 30], p1 to p4, r1 to r4, s1 to s4 are each 1 or 2, x is 1, The amine compound characterized by the above-mentioned. [Structure 22] [Structure 23] [Structure 24] [Structure 25]

[Structure 26] [Structure 27] [Structure 28] [Structure 29]

[Formula 30]

In the linking group, the carbon site of the aromatic ring may be bonded to hydrogen or deuterium. The method of claim 5, y is 1, and z is 0. The method of claim 1, The substituents R ₁ and R ₂ in Formula A or Formula B are the same or different and each independently represent a substituted or unsubstituted aryl group having 6 to 24 carbon atoms, and are connected to each other to form a ring. Amine compounds. The method of claim 1, The substituents R ₁ and R ₂ in Formula A or Formula B are the same or different and each independently represent a substituted or unsubstituted aryl group having 6 to 24 carbon atoms, and are not connected to each other to form a ring. An amine compound characterized by the above-mentioned. The method of claim 1, The substituents R ₁ to R ₉ , Ar ₁ to Ar ₈ are the same as or different from each other, and independently from each other, hydrogen, deuterium, a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, a substituted or unsubstituted carbon atom 3 to 30 Is a cycloalkyl group, a substituted or unsubstituted heteroaryl group having 2 or 20 carbon atoms having any one or more selected from O, N, S and Si, cyano group, halogen group Amine compounds. The method of claim 1, A ₁ , A ₂ , E and F in Formula A or Formula B are the same as or different from each other, and are independently substituted or unsubstituted aromatic hetero rings having 2 to 30 carbon atoms. The method of claim 10, The aromatic hetero ring is the same or different, and independently of each other amine compound, characterized in that any one selected from [formula 31] to [formula 40].  [Structure 31] [Structure 32] [Structure 33] [Structure 34]

[Structure 35] [Structure 36] [Structure 37]

[Formula 38] [Formula 39] [Formula 40]

In [Formula 31] to [Formula 40], T ₁ to T ₁₂ are the same as or different from each other, and each independently, C (R ₄₁ ), C (R ₄₂ ) (R ₄₃ ), N, N (R ₄₄ ), O, S, Se, Te, Si ( R ₄₅ ) (R ₄₆ ) and Ge (R ₄₇ ) (R ₄₈ ), which may be any one of T ₁ to T ₁₂ are not all carbon atoms at the same time, wherein R ₄₁ to R ₄₈ are defined above The same as R ₁ and R _2, and two adjacent ones of T ₁ to T ₁₂ in the aromatic ring form a 5-membered ring including carbon atoms connected to the substituents R ₁ and R ₂ as carbon atoms, or the structural formula Q Containing a single bond for forming a five-membered ring containing oxygen atoms at ₁ and Q ₂ , When the aromatic hetero ring of [Formula 31] to [Formula 40] corresponds to A ₁ ring or A ₂ ring and is bonded with Structural Formula Q ₁ or Structural Formula Q ₂ , _two of the T ₁ to T ₁₂ adjacent to each other are carbon As an atom, it combines with * of structural formula Q ₁ or with * of structural Q ₂ to form a condensed ring. The method according to any one of claims 1 to 11, The substituents substituted in A ₁ , A ₂ , E, F, Ar ₁ to Ar ₈ , L ₁ to L ₁₂ , and R ₁ to R ₉ may be a cyano group, a halogen group, an alkyl group having 1 to 6 carbon atoms, or a carbon number. It is any one selected from the group consisting of an aryl group having 6 to 18, an arylalkyl group having 6 to 18 carbon atoms, a heteroaryl group having 3 to 18 carbon atoms, an alkylsilyl group having 1 to 12 carbon atoms, and an arylsilyl group having 6 to 18 carbon atoms. An amine compound. The method of claim 1, Any one amine compound selected from [Formula 1] to [Formula 239]. <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>

<Formula 166> <Formula 167> <Formula 168>

<Formula 169> <Formula 170> <Formula 171>

<Formula 172> <Formula 173> <Formula 174>

<Formula 175> <Formula 176> <Formula 177>

<Formula 178> <Formula 179> <Formula 180>

<Formula 181> <Formula 182> <Formula 183>

<Formula 184> <Formula 185> <Formula 186>

<Formula 187> <Formula 188> <Formula 189>

<Formula 190> <Formula 191> <Formula 192>

<Formula 193> <Formula 194> <Formula 195>

<Formula 196> <Formula 197> <Formula 198>

<Formula 199> <Formula 200> <Formula 201>

<Formula 202> <Formula 203> <Formula 204>

<Formula 205> <Formula 206> <Formula 207>

<Formula 208> <Formula 209> <Formula 210>

<Formula 211> <Formula 212> <Formula 213>

<Formula 214> <Formula 215> <Formula 216>

<Formula 217> <Formula 218> <Formula 219>

<Formula 220> <Formula 221> <Formula 222>

<Formula 223> <Formula 224> <Formula 225>

<Formula 226> <Formula 227> <Formula 228>

<Formula 229> <Formula 230> <Formula 231>

<Formula 232> <Formula 233> <Formula 234>

<Formula 235> <Formula 236> <Formula 237>

<Formula 238> <Formula 239>

A first electrode; A second electrode opposed to the first electrode; And An organic layer interposed between the first electrode and the second electrode; wherein the organic layer comprises at least one organic light emitting compound of any one of claims 1 to 11 and 13; device. The method of claim 14, And the organic layer includes at least one of a hole injection layer, a hole transport layer, a hole injection function, and a hole injection function, and at least one of a functional layer, an emission layer, an electron transport layer, and an electron injection layer. The method of claim 15, The organic layer interposed between the first electrode and the second electrode includes a light emitting layer, The light emitting layer comprises a host and a dopant, wherein the organic light emitting compound is used as a dopant. 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. The method of claim 14, The organic light emitting device is a flat panel display device; Flexible display devices; Monochrome or white flat lighting devices; And a monochromatic or white flexible lighting device. The organic light emitting device of claim 1, wherein the organic light emitting device is used.

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