KR102293894B1 - Condensed fluorene derivative comprising heterocyclic ring - Google Patents

Abstract

The present invention relates to a condensed fluorene derivative containing a heterocyclic ring, and more particularly, when used as an organic light emitting material, it is excellent in luminance and luminous efficiency, and a heterocyclic compound capable of showing excellent device characteristics of a long lifespan It relates to an intermediate for

Description

Condensed fluorene derivative comprising heterocyclic ring }

The present invention relates to a condensed fluorene derivative containing a heterocyclic ring, and more particularly, when used as an organic light emitting material, it is excellent in luminance and luminous efficiency, and a heterocyclic compound capable of showing excellent device characteristics of a long lifespan It relates to an intermediate for

An organic light emitting diode (OLED) is a display using a self-luminescence phenomenon, has a large viewing angle, can be lightweight and compact compared to a liquid crystal display, and has advantages such as a fast response speed. ) is expected to be applied to displays or lighting.

In general, the organic light emitting phenomenon refers to a phenomenon in which electric energy is converted into light energy using an organic material. An organic light emitting device using an organic light emitting phenomenon generally has a structure including an anode and a cathode and an organic material layer therebetween. Here, the organic layer is often formed of a multi-layered structure composed of different materials in order to increase the efficiency and stability of the organic light emitting device, for example, a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, an electron injection layer, and the like. In the structure of the organic light emitting device, when a voltage is applied between the two electrodes, holes are injected into the organic material layer from the anode and electrons from the cathode are injected into the organic material layer. When the injected holes and electrons meet, excitons are formed, and the excitons When it falls back to the ground state, it lights up. Such an organic light emitting device is known to have characteristics such as self-luminescence, high luminance, high efficiency, low driving voltage, wide viewing angle, high contrast, and high-speed response.

A material used as an organic layer in an organic light emitting device may be classified into a light emitting material and a charge transport material, for example, a hole injection material, a hole transport material, an electron transport material, an electron injection material, and the like, according to functions. The light emitting material can be classified into a high molecular type and a low molecular type according to molecular weight, and can be classified into a fluorescent material derived from a singlet excited state of an electron and a phosphorescent material derived from a triplet excited state of an electron according to a light emitting mechanism. . In addition, the light emitting material may be divided into blue, green, and red light emitting materials and yellow and orange light emitting materials necessary for realizing a better natural color according to the emission color.

On the other hand, when only one material is used as a light emitting material, the maximum emission wavelength is shifted to a longer wavelength due to intermolecular interaction, and there is a problem in that the color purity is lowered or the efficiency of the device is decreased due to the emission attenuation effect. Therefore, increase in color purity and energy A host-dopant system can be used as a luminescent material to increase the luminous efficiency through transition.

The principle is that when a small amount of a dopant having a smaller energy band gap than that of a host forming the emission layer is mixed in the emission layer, excitons generated in the emission layer are transported to the dopant to emit light with high efficiency. At this time, since the wavelength of the host moves to the wavelength band of the dopant, light having a desired wavelength may be obtained according to the type of the dopant used.

As a prior art related to a dopant compound in such a light emitting layer, Korean Patent Publication No. 10-2008-0015865 (February 20, 2008) discloses an organic light emitting device using an indenofluorene derivative to which an arylamine is bonded. In No. 10-2012-0047706 (20012.05.14), a compound having a structure in which dibenzofuran or dibenzothiophene is present together with fluorene or benzofuran or dibenzothiophene is present together with carbazole in one molecule An organic light emitting device is disclosed.

However, despite the above efforts, a new organic light emitting material having superior luminance and luminous efficiency and long lifespan compared to organic light emitting materials manufactured by the prior art including the prior art, and intermediates for manufacturing them The need for the development of compounds is a situation that is continuously required.

Patent Publication No. 10-2008-0015865 (2008.02.20)

Laid-Open Patent Publication No. 10-2012-0047706 (2012.05.14)

Accordingly, the first technical task of the present invention is to provide a novel intermediate compound for preparing a compound that can be used as a material for an organic light emitting diode (OLED).

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

[Formula A]

[Formula B]

In the [Formula A] and [Formula B], A ₁ , A ₂ , E and F are each the same or different from each other, and each independently a substituted or unsubstituted aromatic hydrocarbon ring having 6 to 50 carbon atoms, or a substituted or unsubstituted an 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} form a 5-membered ring with a carbon atom connected to _{the substituents R 1} and R _{2 , respectively.} to form;

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

The substituents R ₁ to R ₉ are the same or different from each other, and each independently hydrogen, deuterium, a substituted or unsubstituted C 1 to C 30 alkyl group, a substituted or unsubstituted C 6 to C 50 aryl group, substituted or unsubstituted 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 cycloalkenyl group having 5 to 30 carbon atoms, A substituted or unsubstituted C2 to C50 heteroaryl group, a substituted or unsubstituted C2 to C30 heterocycloalkyl group, a substituted or unsubstituted C1 to C30 alkoxy group, a substituted or unsubstituted C6 to C30 of an aryloxy group, a substituted or unsubstituted C1 to C30 alkylthioxy group, a substituted or unsubstituted C5 to C30 arylthioxy group, a substituted or unsubstituted C1 to C30 alkylamine group, a substituted or unsubstituted A substituted or unsubstituted C5 to C30 arylamine group, a substituted or unsubstituted C1 to C30 alkylsilyl group, a substituted or unsubstituted C5 to C30 arylsilyl group, or a substituted or unsubstituted C1 to C30 alkyl Any one selected from a germanium group, a substituted or unsubstituted C5 to C30 arylgermanium group, a cyano group, a nitro group, and a halogen group,

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, aromatic monocyclic or polycyclic ring are N, O, P, Si, S , Ge, Se, may be substituted with any one or more heteroatoms selected from Te;

Wherein s1, s3 and s4 are each independently the same or different integers from 0 to 3, and s2 is an integer from 1 to 3,

When s1 to s4 are an integer of 2 or more, each X ₁ to X ₄ are the same as or different from each other,

The X ₁ to X ₄ are each independently the same as or different from each other, and are hydrogen, deuterium, or a leaving group,

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

In Formula B, two carbon atoms adjacent to each other _{in the ring A 1 are bonded to * of the structural formula Q 2} to form a condensed ring, and two carbon atoms adjacent to each other in the ring _{A 2 are bonded to * in the structural formula Q1} to form a condensed ring.

According to the present invention, the compound represented by the [Formula A] or [Formula B] can be utilized as an intermediate of an organic light emitting material, and the light emitting material finally obtained when manufacturing the light emitting material using the intermediate is compared with the existing material. It is possible to provide an organic light emitting device having excellent luminance and luminous efficiency and exhibiting excellent device characteristics of a long lifespan.

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

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

The present invention provides an intermediate compound for preparing an organic light emitting material that can be used in an organic light emitting device. More specifically, the intermediate compound is represented by the following [Formula A] or [Formula B].

[Formula A]

[Formula B]

In the [Formula A] and [Formula B], A ₁ , A ₂ , E and F are each the same or different from each other, and each independently a substituted or unsubstituted aromatic hydrocarbon ring having 6 to 50 carbon atoms, or a substituted or unsubstituted an 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} form a 5-membered ring with a carbon atom connected to _{the substituents R 1} and R _{2 , respectively.} to form;

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

The substituents R ₁ to R ₉ are the same or different from each other, and each independently hydrogen, deuterium, a substituted or unsubstituted C 1 to C 30 alkyl group, a substituted or unsubstituted C 6 to C 50 aryl group, substituted or unsubstituted 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 cycloalkenyl group having 5 to 30 carbon atoms, A substituted or unsubstituted C2 to C50 heteroaryl group, a substituted or unsubstituted C2 to C30 heterocycloalkyl group, a substituted or unsubstituted C1 to C30 alkoxy group, a substituted or unsubstituted C6 to C30 of an aryloxy group, a substituted or unsubstituted C1 to C30 alkylthioxy group, a substituted or unsubstituted C5 to C30 arylthioxy group, a substituted or unsubstituted C1 to C30 alkylamine group, a substituted or unsubstituted A substituted or unsubstituted C5 to C30 arylamine group, a substituted or unsubstituted C1 to C30 alkylsilyl group, a substituted or unsubstituted C5 to C30 arylsilyl group, or a substituted or unsubstituted C1 to C30 alkyl Any one selected from a germanium group, a substituted or unsubstituted C5 to C30 arylgermanium group, a cyano group, a nitro group, and a halogen group,

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, aromatic monocyclic or polycyclic ring are N, O, P, Si, S , Ge, Se, may be substituted with any one or more heteroatoms selected from Te;

Wherein s1, s3 and s4 are each independently the same or different integers from 0 to 3, and s2 is an integer from 1 to 3,

When s1 to s4 are an integer of 2 or more, each X ₁ to X ₄ are the same as or different from each other,

The X ₁ to X ₄ are each independently the same as or different from each other, and are hydrogen, deuterium, or a leaving group,

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

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

'Substitution' in 'substituted or unsubstituted' means deuterium, a cyano group, a halogen group, a hydroxyl group, a nitro group, an alkyl group having 1 to 24 carbon atoms, a halogenated alkyl group having 1 to 24 carbon atoms, an alkenyl group having 1 to 24 carbon atoms. , C1-C24 alkynyl group, C1-C24 heteroalkyl group, C6-C24 aryl group, C6-C24 arylalkyl group, C2-C24 heteroaryl group or C2-C24 heteroarylalkyl group , C1-C24 alkoxy group, C1-C24 alkylamino group, C1-C24 arylamino group, C1-C24 hetero arylamino group, C1-C24 alkylsilyl group, C1-C24 arylsilyl group, means substituted with one or more substituents selected from the group consisting of an aryloxy group having 1 to 24 carbon atoms.

The compound represented by Formula A in the present invention is Structural formula Q1 is _{connected to the A 2 ring, and in this case, X 2} represented by hydrogen, deuterium or a leaving group is necessarily bound to the _{A 2 ring.}

In addition, in the compound represented by Formula B, the structural formula Q ₂ is _{connected to the A 1} ring, the structural formula Q1 is _{connected to the A 2 ring, and in this case, X 2} represented by hydrogen, deuterium or a leaving group must be bonded to the A _{2 ring} have structural characteristics.

On the other hand, considering the range of the alkyl group or aryl group in the "substituted or unsubstituted alkyl group having 1 to 30 carbon atoms" and "substituted or unsubstituted aryl group having 5 to 50 carbon atoms" in the present invention, 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 number of carbon atoms constituting the alkyl part or the aryl part when viewed as unsubstituted without considering the substituted part of the substituent. will be. For example, a phenyl group substituted with a butyl group at the para-position should be considered to correspond to an aryl group having 6 carbon atoms substituted with a butyl group having 4 carbon atoms.

The aryl group as a substituent used in the compound of the present invention means an aromatic system consisting of a hydrocarbon including one or more rings, and when the aryl group has a substituent, it is fused with neighboring substituents to form an additional ring. can

Specific examples of the aryl group include a phenyl group, o-biphenyl group, m-biphenyl group, p-biphenyl group, o-terphenyl group, m-terphenyl group, p-terphenyl group, naphthyl group, anthryl group, phenanthryl group, and aromatic groups such as phenylenyl, pyrenyl, indenyl, fluorenyl, tetrahydronaphthyl, perylenyl, chrysenyl, naphthacenyl, acenaphthylenyl, indacenyl, fluoranthenyl, and the like. At least one hydrogen atom of the aryl group is a deuterium atom, a halogen atom, a hydroxyl group, a nitro group, a cyano group, a silyl group, an amino group (-NH ₂ , -NH(R), -N(R')(R''), R ' and R' are each independently an alkyl group having 1 to 10 carbon atoms, in this case referred to as an "alkylamino group"), an amidino group, a hydrazine group, a hydrazone group, a carboxyl group, a sulfonic acid group, a phosphoric acid group, an alkyl group having 1 to 24 carbon atoms, A halogenated alkyl group having 1 to 24 carbon atoms, an alkenyl group having 1 to 24 carbon atoms, an alkynyl group having 1 to 24 carbon atoms, a heteroalkyl group having 1 to 24 carbon atoms, an aryl group having 6 to 24 carbon atoms, an arylalkyl group having 6 to 24 carbon atoms, an arylalkyl group having 6 to 24 carbon atoms. It may be substituted with a heteroaryl group having 2 to 24 carbon atoms or a heteroarylalkyl group having 2 to 24 carbon atoms.

The heteroaryl group as a substituent used in the compound of the present invention includes 1, 2 or 3 heteroatoms selected from N, O, P, Si, S, Ge, Se, and Te, and the remaining ring atoms are carbon atoms having 2 to 24 carbon atoms. of a ring aromatic system, wherein the rings may be fused to form a ring. And one or more hydrogen atoms in the heteroaryl group may be substituted with the same substituents as in the case of the aryl group.

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

Specific examples of the alkyl group as 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 may be substituted with the same substituent as in the case of the above aryl group.

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

Specific examples of the silyl group as a substituent used in the compound of the present invention include trimethylsilyl, triethylsilyl, triphenylsilyl, trimethoxysilyl, dimethoxyphenylsilyl, diphenylmethylsilyl, silyl, diphenylvinylsilyl, 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, A 1} , A ₂ , E and F in Formula A or Formula B of the present invention may be the same or different, and independently of each other, may be a substituted or unsubstituted aromatic hydrocarbon ring having 6 to 50 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 hydrocarbon ring having 6 to 50 carbon atoms, the The aromatic hydrocarbon ring may be the same or different, and may each independently be any one selected from [Structural Formula 10] to [Structural Formula 21].

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

[Structural formula 13] [Structural formula 14] [Structural formula 15]

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

[Formula 19] [Formula 20] [Formula 21]

In the [Structural Formula 10] to [Structural Formula 21], "-*" forms a 5-membered ring including a carbon atom connected _{to the substituents R 1} and R ₂ , or 5 including M in _{the structural formulas Q 1} and Q ₂ It means a binding site for forming a ring,

When the aromatic hydrocarbon ring of [Structural Formula 10] to [Structural Formula 21] is _{bonded to Structural Formula Q 1} or Structural Formula Q ₂ while the ring corresponds to the _{A 1} ring or the A ₂ ring, two carbon atoms adjacent to each other are selected from the above structural formula Combined with * of Q _{1 or combined with * of Structural Formula Q 2} to form a condensed ring;

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

In the present invention, the leaving groups X ₁ to X ₄ are each independently the same as or different from each other, and are hydrogen, deuterium, or a leaving group.

Here, the leaving group (leaving group) can be used without limitation in kind as long as it can be released to introduce a desired substituent instead of the leaving group in order to design a molecular structure to be used as a material for an organic light emitting device do.

Illustratively, the leaving group may be released when reacting with a secondary amine, and the introduced substituent may be separated to be converted into a tertiary amine, and as another example, a boric acid group having an aryl group or an alkyl group, etc. It may be a leaving group that can be released so that an aryl group such as anthracene is introduced by the Suzuki coupling reaction.

In one embodiment, as the leaving group, a halogen selected from Cl, Br, F, and I, an alkyl sulfonate having 1 to 30 carbon atoms, an aryl sulfonate having 6 to 40 carbon atoms, an aryl having 7 to 40 carbon atoms Any one selected from alkyl sulfonates and halogenated alkyl sulfonates having 1 to 30 carbon atoms may be used, and preferably, a halogen selected from Cl, Br, F, and I may be used.

When the leaving group is halogen, s2 is 1, s1, s3, and s4 may be the same or different from each other, and may be 0 or 1 independently of each other. That is, in Formulas A and B, _{the halogen bonded to the A 2} ring is one, and the halogen bonded to the A ₁ ring, the E ring, or the F ring may be absent or one.

_{In one embodiment, the substituents R 1} and R ₂ in Formula A or Formula B of the present invention 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 a ring may form, or may not be connected to each other to form a ring.

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

In addition, in the compound of Formula A or Formula B of the present invention _{, the 'substituted' substituent in A 1} , A ₂ , E, F, R ₁ to R ₉ is a cyano group, a halogen group, or 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, an arylsilyl group having 6 to 18 carbon atoms, halogenated having 1 to 6 carbon atoms It may be any one selected from the group consisting of an alkyl group.

In addition, the compound according to the present invention may be any one selected from the following [Compound 1] to [Compound 108] .

[Compound 1] [Compound 2] [Compound 3]

[Compound 4] [Compound 5] [Compound 6]

[Compound 7] [Compound 8] [Compound 9]

[Compound 10] [Compound 11] [Compound 12]

[Compound 13] [Compound 14] [Compound 15]

[Compound 16] [Compound 17] [Compound 18]

[Compound 19] [Compound 20] [Compound 21]

[화합물 22] [화합물 23] [화합물 24]

[Compound 22] [Compound 23] [Compound 24]

[Compound 25] [Compound 26] [Compound 27]

[Compound 28] [Compound 29] [Compound 30]

[Compound 31] [Compound 32] [Compound 33]

[Compound 34] [Compound 35] [Compound 36]

[Compound 37] [Compound 38] [Compound 39]

[Compound 40] [Compound 41] [Compound 42]

[Compound 43] [Compound 44] [Compound 45]

[Compound 46] [Compound 47] [Compound 48]

[Compound 49] [Compound 50] [Compound 51]

[Compound 52] [Compound 53] [Compound 54]

[Compound 55] [Compound 56] [Compound 57]

[Compound 58] [Compound 59] [Compound 60]

[Compound 61] [Compound 62] [Compound 63]

[Compound 64] [Compound 65] [Compound 66]

[Compound 67] [Compound 68] [Compound 69]

[Compound 70] [Compound 71] [Compound 72]

[Compound 73] [Compound 74] [Compound 75]

[Compound 76] [Compound 77] [Compound 78]

[Compound 79] [Compound 80] [Compound 81]

[Compound 82] [Compound 83] [Compound 84]

[Compound 85] [Compound 86] [Compound 87]

[Compound 88] [Compound 89] [Compound 90]

[Compound 91] [Compound 92] [Compound 93]

[Compound 94] [Compound 95] [Compound 96]

[Compound 97] [Compound 98] [Compound 99]

[Compound 100] [Compound 101] [Compound 102]

[Compound 103] [Compound 104] [Compound 105]

[Compound 106] [Compound 107] [Compound 108]

In addition, the compound represented by Formula A or Formula B according to the present invention may react with an amine to produce an amine derivative.

In an embodiment, the amine may be a primary amine or a secondary amine, and may be reacted with a secondary amine to form a tertiary amine for use as a material for an organic light emitting device.

This may be represented by Scheme A by the reaction of Formula A with a secondary amine or Scheme B by the reaction of Formula B with a secondary amine.

[Scheme A]

[Scheme B]

The compounds represented by Chemical Formulas A and B, which are starting materials in Schemes A and B, are as defined above, and R _{a and R b} in the secondary amine are the same or different from each other, and independently of each other are defined as previously defined. Same as R ₁ and R _{2 .} In this case, R _a and R _b in the secondary amine may each be an aryl group having 6 to 40 carbon atoms.

In this case, the secondary amine is preferably used more than the content of the leaving group included in Formula A or Formula B.

For example, in Formula A, when s1 is 2, s2 is 1, and s3 included in Q1 is 0, at least 2 equivalents of the secondary amine must be used in the reaction.

Also, in the present invention, a linking group may be provided between the secondary amine and the tertiary amine.

As the linking group, an alkylene group, an alkenylene group, an alkynylene group, a cycloalkylene group, a heterocycloalkylene group, an arylene group, or a heteroarylene group can be used, and preferably the same or different from each other, and independently of each other, substituted or An unsubstituted C 1 to C 60 alkylene group, a substituted or unsubstituted C 2 to C 60 alkenylene group, a substituted or unsubstituted C 2 to C 60 alkynylene group, a substituted or unsubstituted C 3 to C 60 cyclo An alkylene group, a substituted or unsubstituted heterocycloalkylene group having 2 to 60 carbon atoms, a substituted or unsubstituted arylene group having 6 to 60 carbon atoms, or a substituted or unsubstituted heteroarylene group having 2 to 60 carbon atoms, etc. is an A ₁ ring, A _{bond may be between the A 2} ring, the E ring or the F ring and each nitrogen atom to which they may be connected.

The reaction of the compounds represented by the formulas A and B with the substituents to be introduced such as the secondary amine and the aryl group can be easily prepared by, for example, Suzuki coupling.

_{Illustratively, when X 1} to X ₄ are halogen in Schemes A1 and B1, a substituent R such as an amine group or an aryl group may be introduced by the following reaction.

[Scheme A1]

[Scheme B1]

The compounds represented by Chemical Formulas A and B, which are starting materials in Schemes A1 and B1, are as defined above, and R in the boron compound is the same as _{R 1} and R _{2 as defined above.}

The organic light emitting compound synthesized by the Suzuki coupling may be used as a material for an organic light emitting device in the present invention. More specifically, the present invention provides a first electrode; a second electrode opposite 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 described above.

Illustratively, the compound into which an amine group is introduced as the prepared final compound may be used as a material for an organic light emitting device in the present invention.

In the present invention, "(organic layer) includes one or more organic compounds" means "one organic compound belonging to the scope of the present invention or two or more different compounds belonging to the scope of the organic compound. may be construed as".

In addition, the organic layer containing 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.

At this time, the organic layer interposed between the first electrode and the second electrode may include a light emitting layer, the light emitting layer consists of a host and a dopant, and the finally prepared compound of the present invention is the organic light emitting compound as a dopant. can be used

Meanwhile, in the present invention, a host material may be used in addition to a dopant for the emission layer. When the emission 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 100 parts by weight of the host, but is not limited thereto.

Meanwhile, as the material for the electron transport layer in the present invention, a known electron transport material may be used as it functions to stably transport electrons injected from an electron injection electrode (Cathode). Examples of known electron transport materials include quinoline derivatives, particularly tris(8-quinolinolate)aluminum (Alq3), TAZ, Balq, beryllium bis(benzoquinolin-10- Materials such as olate: Bebq2), ADN, compound 201, compound 202, BCP, and oxadiazole derivatives PBD, BMD, BND, etc. may be used, but are not limited thereto.

<Compound 201> <Compound 202> BCP

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

1 is a cross-sectional view showing the structure of an organic light emitting device of the present invention. The organic light emitting device according to the present invention includes an anode 20, a hole transport layer 40, an organic light emitting layer 50, an electron transport layer 60 and a cathode 80, and if necessary, a hole injection layer 30 and electrons. The injection layer 70 may be further included, and in addition to that, it is possible to further form an intermediate layer of one or two layers, and a hole blocking layer or an electron blocking layer may be further formed.

Referring to FIG. 1, an organic light emitting diode and a manufacturing method thereof of the present invention will be described as follows. First, the anode 20 is formed by coating an anode electrode material on the substrate 10 . Here, as the substrate 10, a substrate used in a conventional organic EL device is used, and an organic substrate or a transparent plastic substrate excellent in transparency, surface smoothness, handling and waterproofing properties is preferable. In addition, as a material for the anode electrode, indium tin oxide (ITO), indium zinc oxide (IZO), tin oxide (SnO ₂ ), zinc oxide (ZnO), etc., which are transparent and have excellent conductivity, are used.

A hole injection layer 30 is formed by vacuum thermal evaporation or spin coating of a 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, the present invention is not necessarily limited thereto.

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), etc. can be used. However, the present invention is not necessarily limited thereto.

Subsequently, an organic light emitting layer 50 is laminated on the hole transport layer 40 and a hole blocking layer (not shown) is selectively deposited on the organic light emitting layer 50 by a vacuum deposition method or a spin coating method to form a thin film. can do. The hole blocking layer serves to prevent this problem by using a material having a very low HOMO (Highest Occupied Molecular Orbital) level because the lifetime and efficiency of the device are reduced when holes are introduced into the cathode through the organic light emitting layer. . In this case, the hole blocking material used is not particularly limited, but has an electron transport ability and has an ionization potential higher than that of a light emitting compound, and typically BAlq, BCP, TPBI, etc. may be used.

After depositing the electron transport layer 60 on the hole blocking layer through a vacuum deposition method or a spin coating method, an electron injection layer 70 is formed, and a metal for forming a cathode is vacuum heated on the electron injection layer 70 . By vapor deposition to form the cathode 80 electrode, the organic EL device is completed. Here, as the metal for forming the cathode, lithium (Li), magnesium (Mg), aluminum (Al), aluminum-lithium (Al-Li), calcium (Ca), magnesium-indium (Mg-In), magnesium-silver ( Mg-Ag) may be used, and in order to obtain a top light emitting device, a transmissive cathode using ITO or IZO may be used.

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

In addition, according to a specific example of the present invention, the thickness of the light emitting layer is preferably 50 to 2,000 Å.

In this case, the host used in the light emitting layer may be 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]

[Host9] [Host10] [Host11] [Host12]

[Host 13] [Host 14] [Host 15] [Host 16]

[Host 17] [Host 18] [Host 19] [Host 20]

[Host 21] [Host 22] [Host 23] [Host 24]

[Host 25] [Host 26] [Host 27] [Host 28]

[Host 29] [Host 30] [Host 31] [Host 32]

[Host 33] [Host 34] [Host 35] [Host 36]

[Host 37] [Host 38] [Host 39] [Host 40]

[Host 41] [Host 42] [Host 43] [Host 44]

[Host 45] [Host 46] [Host 47] [Host 48]

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

[Host 53] [Host 54] [Host 55] [Host 56]

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

In addition, 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 through heating in a vacuum or low pressure state, and the solution process is to form each layer It refers to a method of mixing a material used as a material for a solvent with a solvent and forming a thin film through methods such as inkjet printing, roll-to-roll coating, screen printing, spray coating, dip coating, spin coating, and the like.

In addition, the organic light emitting device in the present invention is a flat panel display device; flexible display devices; devices for flat-panel lighting, either monochromatic or white; and a device for flexible lighting of a single color or a white color; may be used in any one device selected from

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

(Example)

Synthesis Example 1: Synthesis of Compound 1

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

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

<Scheme 1>

<Intermediate 1-a>

Methyl 5-bromo-2-iodobenzoate (25.0g, 73mmol), 4-dibenzofuranboronic acid (18.7g, 88mmol), tetrakis(triphenylphosphine)palladium (1.7 g, 0.15mmol), potassium carbonate (20.2 g, 146.7mmol) were added, and toluene 125 mL, tetrahydrofuran 125 mL, and water 50 mL were added. The temperature of the reactor was raised to 80 degrees and stirred for 10 hours. When the reaction was completed, the temperature of the reactor was lowered to room temperature, extraction was performed 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 (75.0 g, 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 170ml of ethanol were put in a 500mL round-bottom flask reactor, and the mixture was stirred under reflux for 48 hours. After confirming the completion of the reaction by thin layer chromatography, it was cooled to room temperature. To the cooled solution, 2-normal hydrochloric acid was added dropwise and acidified, and the resulting solid was filtered after stirring for 30 minutes. Recrystallization from dichloromethane and n-hexane gave <Intermediate 1-b> (14.5 g, 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>

In a 250ml round bottom flask reactor, <Intermediate 1-b> (14.5g, 39mmol) and 145ml of methanesulfonic acid were added, the temperature was raised to 80°C, and the mixture was stirred for 3 hours. After confirming the completion of the reaction by thin film chromatography, it was cooled to room temperature. The reaction solution was slowly added dropwise to 150 ml of ice water and stirred for 30 minutes. The resulting solid was filtered and washed with water and methanol to obtain <Intermediate 1-c> (11.50 g, 83.4%).

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

Intermediate 1-d was synthesized according to Scheme 4:

<Scheme 4>

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

<Intermediate 1-c> (11.5 g, 33 mmol) and 300 ml of dichloromethane were placed in a 1L round-bottom flask reactor and stirred at room temperature. Bromine (3.4ml, 66mmol) was diluted in 50ml of dichloromethane and added dropwise, followed by stirring at room temperature for 8 hours. After completion of the reaction, 100 ml of acetone was added to the reaction vessel and stirred. The resulting solid was filtered and washed with acetone. The solid was recrystallized from monochlorobenzene to obtain <Intermediate 1-d> (11.0 g, 78%).

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

Intermediate 1-e was synthesized according to Scheme 5:

<Scheme 5>

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

In a 250ml round-bottom flask reactor, 2-bromobiphenyl (8.4g, 0.036mol) and 110ml of tetrahydrofuran were added and cooled to -78°C 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 stirring the reaction solution for 2 hours, <Intermediate 1-d> (11.0 g, 0.026 mol) was added little by little and stirred at room temperature. When the color of the reaction solution changed, completion of the reaction was confirmed by TLC. 50 ml of H2O was added to complete the reaction, and the mixture was extracted with ethyl acetate and water. The organic layer was separated, concentrated under reduced pressure, and recrystallized from acetonitrile to obtain <Intermediate 1-e> (12.2 g, 81.5%).

Synthesis Example 1-(6): Synthesis of compound 1

Compound 1 was synthesized according to Scheme 6:

<Scheme 6>

<Intermediate 1-e> <Compound 1>

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

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

Formula 1 was synthesized according to Scheme 7:

<Scheme 7>

<Compound 1> <Formula 1>

In a 250ml round-bottom flask reactor, <Compound 1> (5.0g, 0.009mol), bis(4-tertbutylphenyl)amine (6.0g, 0.021mol), palladium(II)acetate (0.08g, 0.4mmol), sodium Tertiary butoxide (3.4 g, 0.035 mol), tritertiary 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, it was cooled to room temperature. The reaction solution was extracted with dichloromethane and water. The organic layer was separated, anhydrous treatment with magnesium sulfate, and then concentrated under reduced pressure. The material was separated and purified by column chromatography, and then recrystallized from dichloromethane and acetone to obtain <Formula 1> (3.1 g, 36%).

MS (MALDI-TOF): m/z 964.5 [M ⁺ ]

Synthesis Example 2: Synthesis of compound 3

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

Intermediate 2-a was synthesized according to Scheme 8 below:

<Scheme 8>

<Intermediate 2-a>

In a 2L round-bottom flask reactor, 4-bromodibenzofuran (100 g, 0.405 mol), (1R, 2R)-cyclohexane-1,2-diamine (46.21 g, 0.404 mol), acetamide (71.7 g, 1.21 mol) , copper (I) iodide (77.08 g, 0404 mol), potassium carbonate (200 g, 0.809 mol), and 1000 ml of toluene were added and stirred under reflux overnight. After the reaction was completed, it was filtered through a pad of celite and washed with ethyl acetate. The filtrate was extracted with water and ethyl acetate to separate the organic layer. The organic layer was filtered and concentrated under reduced pressure after anhydrous treatment with magnesium sulfate. The material was recrystallized from dichloromethane and petroleum ether to obtain <Intermediate 2-a> (50 g, 32%).

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

Intermediate 2-b was synthesized according to Scheme 9:

<Scheme 9>

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

In a 2L round-bottom flask reactor, <Intermediate 2-a> (50g, 0.222mol) and 600ml of acetic acid were dissolved and stirred at room temperature. Bromine (11.37ml, 0.222mol) was diluted in 200ml of acetic acid and added dropwise to the reaction solution, followed by stirring for 4 hours. After the reaction was completed, the resulting solid was filtered and washed with water. The solid was dissolved in 1000 ml of a tetrahydrofuran/water/ethanol ratio 1:1:1 solution, potassium hydroxide (250g, 1.11mol) was added thereto, and the mixture was stirred under reflux overnight. After completion of the reaction, the solvent was concentrated under reduced pressure and extracted with ethyl acetate and water. The organic layer was separated, anhydrous treatment with magnesium sulfate, filtered, and concentrated under reduced pressure. It was recrystallized from ethyl acetate and heptane to obtain <Intermediate 2-b> (40 g, 68.7%).

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

Intermediate 2-c was synthesized according to Scheme 10:

<Scheme 10>

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

<Intermediate 2-b> (40g, 0.153mol), bis(pinacolato)diboron (51.67g, 0.183mol), and 400ml of acetonitrile were placed in a 1L round-bottom flask reactor and stirred at room temperature. To the reaction solution, tertiary-butylnitrile (26.2g, 0229mol) was added little by little, the temperature was raised, and the mixture was stirred at 80°C for 2 hours. After completion of the reaction, it was cooled to room temperature. The reaction solution was concentrated under reduced pressure and separated by column chromatography to obtain <Intermediate 2-c> (20 g, 35%).

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

Intermediate 2-d was synthesized according to Scheme 11 below:

<Scheme 11>

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

Except for using <Intermediate 2-c> instead of methyl 2-bromo benzoate and 4-dibenzofuranboronic acid instead of methyl 5-bromo-2-iodobenzoate in Synthesis Example 1-(1), Using the same method, <Intermediate 2-d> (12.0 g, 67%) was obtained.

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

Intermediate 2-e was synthesized according to Scheme 12:

<Scheme 12>

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

<Intermediate 2-e> (10.0 g, 86%) was obtained in the same manner except that <Intermediate 2-d> was used instead of <Intermediate 1-a> in Synthesis Example 1-(2).

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

Intermediate 2-f was synthesized according to Scheme 13 below:

<Scheme 13>

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

<Intermediate 2-f> (8.4 g, 88%) was obtained in the same manner except that <Intermediate 2-e> was used instead of <Intermediate 1-b> in Synthesis Example 1-(3).

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

Intermediate 2-g was synthesized according to Scheme 14 below:

<Scheme 14>

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

<Intermediate 2-g> (8 g, 66%) was obtained in the same manner except that <Intermediate 2-f> was used instead of <Intermediate 1-d> in Synthesis Example 1-(5).

Synthesis Example 2-(8): Synthesis of compound 3

Compound 3 was synthesized according to Scheme 15:

<Scheme 15>

<Intermediate 2-g> <Compound 3>

<Compound 3> (5.8 g, 74%) was obtained in the same manner as in Synthesis Example 1-(6), except that <Intermediate 2-g> was used instead of <Intermediate 1-e>.

Synthesis Example 2-(9): Synthesis of Formula 2

Formula 2 was synthesized according to Scheme 16 below:

<Scheme 16>

<Compound 3> <Formula 2>

In Synthesis Example 1-(7), <Formula 2> (2.7) g, 39%) was obtained.

MS (MALDI-TOF): m/z 573.21 [M ⁺ ]

Synthesis Example 3: Synthesis of compound 10

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

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

<Scheme 17>

<Intermediate 3-a>

In a 500ml round-bottom flask, 1-bromo-3-iodobenzene (25.0g, 88mmol) was added, and 200ml of tetrahydrofuran was added and dissolved. The reaction solution was cooled to -78°C under a nitrogen atmosphere. Normal butyl lithium (60.75 ml, 97 mmol) was slowly added dropwise to the cooled solution over 30 minutes, followed by stirring at the same temperature for 1 hour. Trimethylborate (11 g, 106 mmol) was added dropwise at the same temperature and stirred at room temperature overnight. The reaction solution was acidified by dropwise addition of 2-N hydrochloric acid, followed by stirring for 1 hour. Extraction was performed with ethyl acetate, the organic layer was separated and concentrated under reduced pressure, and cold n-hexane was added thereto and crystallized to obtain <Intermediate 3-a> (12g, 67.6%).

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

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

<Scheme 18>

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

Except for using <Intermediate 3-a> instead of 4-dibenzofuranboronic acid with methyl 2-bromobenzoate instead of methyl 5-bromo-2-iodobenzoate in Synthesis Example 1-(1), <Intermediate 3-b> (10.2 g, 68.5%) was obtained by the same method.

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

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

<Scheme 19>

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

<Intermediate 3-b> (10.2g, 35mmol) and 100ml of tetrahydrofuran were added to a 250ml round bottom flask and cooled to 0°C in a nitrogen atmosphere. Methylmagnesium bromide (17.5ml, 53mmol) was added dropwise to the cooled reaction solution. After completion of the dropwise addition, the reaction was stirred at room temperature for 2 hours and reflux stirring for 2 hours, and then cooled to room temperature. 0.2 normal hydrochloric acid was slowly added dropwise to the reaction solution for acidification, 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 3-c> (7.6 g, 74.5%).

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

Intermediate 3-d was synthesized according to Scheme 20:

<Scheme 20>

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

<Intermediate 3-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 confirming the completion of the reaction by thin film chromatography, it was cooled to room temperature. Methylene chloride and water were added for extraction, and the organic layer was separated and concentrated under reduced pressure. After separation by column chromatography, <Intermediate 3-d> (8.2 g, 43.7%) was obtained.

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

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

<Scheme 21>

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

<Intermediate 3-d> (8.2g, 30mmol), bis(pinacolato)diboron (9.9g, 39mmol), [1,1'-bis(diphenylphosphino)ferrocene]dick in a 250ml 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 and stirred under reflux for 10 hours. After completion of the reaction, the celite pad was filtered. The filtrate was concentrated under reduced pressure, separated by column, and recrystallized from dichloromethane and heptane to obtain <Intermediate 3-e> (7.0 g, 72.8%).

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

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

<Scheme 22>

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

<Intermediate 3-f> (8.2 g, 68.6%) was obtained in the same manner except that <Intermediate 3-e> was used instead of 4-dibenzofuranboronic acid in Synthesis Example 1-(1) .

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

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

<Scheme 23>

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

<Intermediate 3-g> (6.5 g, 82.1%) was obtained in the same manner except that <Intermediate 3-f> was used instead of <Intermediate 1-a> in Synthesis Example 1-(2).

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

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

<Scheme 24>

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

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

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

Intermediate 3-i was synthesized according to Scheme 25 below:

<Scheme 25>

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

<Intermediate 3-i> (3.5 g, 57.8%) was obtained in the same manner except that <Intermediate 3-h> was used instead of <Intermediate 1-c> in Synthesis Example 1-(4).

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

Intermediate 3-j was synthesized according to Scheme 26 below:

<Scheme 26>

<Intermediate 3-i> <Intermediate 3-j>

<Intermediate 3-j> (3.0 g, 64%) was obtained in the same manner except that <Intermediate 3-i> was used instead of <Intermediate 1-d> in Synthesis Example 1-(5).

Synthesis Example 3-(11): Synthesis of compound 10

According to Scheme 27, compound 10 was synthesized:

<Scheme 27>

<Intermediate 3-j> <Compound 10>

<Compound 10> (2.2 g, 75.6%) was obtained in the same manner as in Synthesis Example 1-(6), except that <Intermediate 3-j> was used instead of <Intermediate 1-e>.

Synthesis Example 3-(12): Synthesis of Formula 3

According to Scheme 28 below, Formula 3 was synthesized:

<Scheme 28>

<Compound 10> <Formula 3>

<Formula 3> (1.8 g, 48.7%) was obtained by using the same method, except that <Compound 10> was used instead of <Compound 1> in Synthesis Example 1-(7).

Synthesis Example 4: Synthesis of compound 29

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

Intermediate 4-a was synthesized according to Scheme 29 below:

<Scheme 29>

<Intermediate 4-a>

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

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

Intermediate 4-b was synthesized according to Scheme 30 below:

<Scheme 30>

<Intermediate 1-d> <Intermediate 4-a> <Intermediate 4-b>

<Intermediate 4-b> (12.2 g, 79%) was obtained in the same manner as in Synthesis Example 1-(5), except that <Intermediate 4-a> was used instead of 2-bromobiphenyl.

Synthesis Example 4-(3): Synthesis of compound 29

According to Scheme 31, compound 29 was synthesized:

<Scheme 31>

<Intermediate 4-b> <Compound 29>

<Compound 29> (8.2 g, 69.3%) was obtained in the same manner as in Synthesis Example 1-(6), except that <Intermediate 4-b> was used instead of <Intermediate 1-e>.

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

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

<Scheme 32>

<Intermediate 4-c>

In a 250ml round bottom flask reactor, 4-bromobiphenyl (8.2g, 0.035mol), 4-tertbutylaniline (5.8g, 0.039mol), tris(dibenzylideneacetone)dipalladium(0) (0.65g, 0.0007) mol), sodium tert-butoxide (6.79 g, 0.0706 mol), 2,2'-bis (diphenylphosphino) -1,1'-binaphthalene (0.44 g, 0.0007 mol) 100 ml of toluene was added and refluxed for 3 hours. stirred. After completion of the reaction, the mixture was cooled to room temperature and extracted with ethyl acetate and water. The organic layer was treated with magnesium sulfate and then concentrated under reduced pressure. After separation by column chromatography, <Intermediate 4-c> (7.6 g, 72%) was obtained.

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

According to Scheme 33 below, Formula 4 was synthesized:

<Scheme 33>

<Compound 29> <Intermediate 4-c> <Formula 4>

<Formula 4> using the same method except that <Compound 29> was used instead of <Compound 1> in Synthesis Example 1-(7) and <Intermediate 4-c> was used instead of bis(4-tertbutylphenyl)amine > (2.4 g, 28%) was obtained.

MS (MALDI-TOF): m/z 1022.4 [M ⁺ ]

Synthesis Example 5: Synthesis of compound 49

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

Intermediate 5-a was synthesized according to Scheme 34 below:

<Scheme 34>

<Intermediate 5-a>

In a 1L round-bottom flask reactor, 2-phenoxyaniline (25.0, 0.135 mol), 30 ml of hydrochloric acid, and 150 ml of water were added, cooled to 0°C, and stirred for 1 hour. At the same temperature, 75 ml of sodium nitrite (11.2 g, 0.162 mol) aqueous solution was added dropwise, followed by stirring for 1 hour. 75 ml of an aqueous solution of potassium iodide (44.8 g, 0.270 mol) was added dropwise, taking care that the temperature of the reaction solution did not exceed 5 degrees. After stirring at room temperature for 5 hours, after completion of the reaction, the mixture was washed with an aqueous sodium thiosulfate solution and extracted with ethyl acetate and water. The organic layer was concentrated under reduced pressure and separated by column chromatography to obtain <Intermediate 5-a> (22.6 g, 56.5%).

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

Intermediate 5-b was synthesized according to Scheme 35 below:

<Scheme 35>

<Intermediate 5-a> <Intermediate 5-b>

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

Synthesis Example 5-(3): Synthesis of compound 49

Intermediate 5-c was synthesized according to Scheme 36 below:

<Scheme 36>

<Intermediate 5-b> <Compound 49>

<Compound 49> (14.2 g, 74.7%) was obtained in the same manner except that <Intermediate 5-b> was used instead of <Intermediate 1-e> in Synthesis Example 1-(6).

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

According to Scheme 37 below, Formula 5 was synthesized:

<Scheme 37>

<Compound 49> <Formula 5>

<Formula 5> (2.4 g, 28%) was obtained by using the same method except that <Compound 49> was used instead of <Compound 1> in Synthesis Example 1-(7).

MS (MALDI-TOF): m/z 980.5 [M ⁺ ]

Synthesis Example 6: Synthesis of compound 37

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

Intermediate 6-a was synthesized according to Scheme 38 below:

<Scheme 38>

<Intermediate 6-a>

In a 2L round-bottom flask reactor, 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, and the mixture was stirred in a nitrogen atmosphere 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> (61.5 g, 72%) was obtained.

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

Intermediate 6-b was synthesized according to Scheme 39:

<Scheme 39>

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

Ethylcyanoacetate (202.9g, 1.794mol) and 500ml of dimethylformamide were placed in a 2L round-bottom flask reactor. Potassium hydroxide (67.10g, 1.196mol) and potassium cyanide (38.95g, 0.598mol) were added, 200ml of dimethylformamide was added, and the mixture was stirred at room temperature. After adding <Intermediate 6-a> (127.5 g, 0.737 mol) little by little to the reaction solution, the reaction solution was stirred at 50°C for 72 hours. After completion of the reaction, 200 ml of sodium hydroxide aqueous solution (25%) was added and stirred under reflux. After stirring for 3 hours, it was cooled to room temperature, and extracted with ethyl acetate and water. The organic layer was separated, concentrated under reduced pressure, and separated by column chromatography to obtain <Intermediate 6-b> (20.0 g, 16%).

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

Intermediate 6-c was synthesized according to Scheme 40:

<Scheme 40>

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

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

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

Intermediate 6-d was synthesized according to Scheme 41:

<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 2L round-bottom flask reactor, and the mixture was stirred under reflux for 72 hours. After completion of the reaction, the mixture was cooled to room temperature and extracted with ethyl acetate and water. The organic layer was separated and washed with an aqueous sodium hydrogen carbonate solution. An excess of methanol was added to the organic layer during concentration under reduced pressure, and the resulting solid was filtered to obtain <Intermediate 6-d> (14.0 g, 77.6%).

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

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

<Scheme 42>

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

<Intermediate 6-e> (9.1 g, 48%) was obtained in the same manner 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 6-f>

Except for using <Intermediate 6-e> instead of methyl 5-bromo-2-iodobenzoate in Synthesis Example 1-(1) and 4-dibenzothiophenboronic acid instead of 4-dibenzofuranboronic acid , to obtain <Intermediate 6-f> (20.2 g, 84.3%) using the same method.

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> (16.5 g, 84.6%) was obtained by using the same method except that <Intermediate 6-f> was used instead of <Intermediate 1-a> in Synthesis Example 1-(2)

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> (12.4 g, 78.7%) 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, 62.5%) was obtained in the same manner except that <Intermediate 6-h> was used instead of <Intermediate 1-c> in Synthesis Example 1-(4)

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> (10.2 g, 72.0%) was obtained in the same manner except that <Intermediate 6-i> was used instead of <Intermediate 1-d> in Synthesis Example 1-(5).

Synthesis Example 6-(11): Synthesis of compound 37

According to Scheme 48, compound 37 was synthesized:

<Scheme 48>

<Intermediate 6-j> <Compound 37>

<Compound 37> (8.7 g, 87.6%) was obtained in the same manner as in Synthesis Example 1-(6), except that <Intermediate 6-j> was used instead of <Intermediate 1-e>.

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

According to Scheme 49 below, Formula 6 was synthesized:

<Scheme 49>

<Compound 37> <Intermediate 4-c> <Formula 6>

<Formula 6> using the same method, except that <Compound 37> was used instead of <Compound 1> in Synthesis Example 1-(7) and <Intermediate 4-c> was used instead of bis(4-tertbutylphenyl)amine > (2.8 g, 33.8%) was obtained.

MS (MALDI-TOF): m/z 1110.5 [M ⁺ ]

Synthesis Example 7: Synthesis of compound 58

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

According to Scheme 50, Intermediate 7-a was synthesized:

<Scheme 50>

<Intermediate 7-a>

In a 2L round-bottom flask reactor, 1-hydroxy 2-naphthalic acid (50g, 266mmol), methanol 1000ml, and sulfuric acid 100ml were added and stirred under reflux for 100 hours. After confirming the completion of the reaction by TLC, it was cooled to room temperature. The solution was concentrated under reduced pressure and extracted with dichloromethane and water. The organic layer was separated, anhydrous treatment with magnesium sulfate, filtered and concentrated under reduced pressure, and then heptane was added in excess and crystallized to obtain <Intermediate 7-a> (39 g, 72.6%).

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

Intermediate 7-b was synthesized according to Scheme 51 below:

<Scheme 51>

<Intermediate 7-a> <Intermediate 7-b>

<Intermediate 7-a> (39.0 g, 193 mmol) and 390 ml of acetic acid were placed in a 1L round-bottom flask reactor and 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 completion of the reaction, the resulting solid was filtered, and after a heptane slurry, <Intermediate 7-b> (50 g, 90%) was obtained.

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

Intermediate 7-c was synthesized according to Scheme 52 below:

<Scheme 52>

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

<Intermediate 7-b> (50g, 178mmol) and dichloromethane were added to a 2L round-bottom flask reactor and stirred. In a nitrogen atmosphere, pyridine (28.1 g, 356 mmol) was added to the reaction solution and stirred at room temperature for 20 minutes. After the reaction solution was cooled to 0°C, trifluoromethanesulfonic anhydride (65.24 g, 231 mmol) was added dropwise in a nitrogen atmosphere. After stirring for 3 hours, after confirming the completion of the reaction by TLC, 20 ml of water was added and stirred for 10 minutes. The reaction solution was concentrated under reduced pressure and separated by column chromatography to obtain <Intermediate 7-c> (45 g, 61%).

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

Intermediate 7-d was synthesized according to Scheme 53:

<Scheme 53>

<Intermediate 7-c> <Intermediate 7-d>

<Intermediate 7-c> (45.0g, 0.109mol), 4-dibenzofuranboronic acid (25.4g, 0.120mol), tetrakis(triphenylphosphine)palladium (2.5g, 0.22mmol) in a 1L round-bottom flask reactor ), potassium carbonate (30.1 g, 0.218 mol) was added, and 300 mL of toluene, 130 mL of ethanol, and 90 mL of water were added. The temperature of the reactor was raised to 80 degrees and stirred for 5 hours. When the reaction was completed, the temperature of the reactor was lowered to room temperature, extraction was performed with ethyl acetate, and the organic layer was separated. The organic layer was concentrated under reduced pressure and separated by column chromatography to obtain an intermediate 7-d (22.0 g, 46.1%).

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

Intermediate 7-e was synthesized according to Scheme 54 below:

<Scheme 54>

<Intermediate 7-d> <Intermediate 7-e>

<Intermediate 7-d> (22.0, 0.051 mol) and sodium hydroxide (2.65 g, 0.066 mol) were put in a 1L round-bottom flask reactor, and the mixture was stirred under reflux for 48 hours. After completion of the reaction, it was cooled to room temperature. To the cooled solution, 2-normal hydrochloric acid was added dropwise and acidified, and the resulting solid was filtered after stirring for 30 minutes. Recrystallization from dichloromethane and n-hexane gave <Intermediate 7-e> (17.6 g, 82.7%).

Synthesis Example 7-(6): Synthesis of intermediate 7-f

Intermediate 7-f was synthesized according to Scheme 55 below:

<Scheme 55>

<Intermediate 7-e> <Intermediate 7-f>

<Intermediate 7-e> (17.6 g, 0.042 mol) and 170 ml of methanesulfonic acid were placed in a 500 ml round-bottom flask reactor, the temperature was raised to 80°C, and the mixture was stirred for 3 hours. After confirming the completion of the reaction by thin film chromatography, it was cooled to room temperature. The reaction solution was slowly added dropwise to 150 ml of ice water and stirred for 30 minutes. The resulting solid was filtered and washed with water and methanol. The solid was dissolved in monochlorobenzene and filtered through a silica gel pad. The filtrate was concentrated by heating and recrystallized with acetone to obtain <Intermediate 7-f> (12 g, 71%).

Synthesis Example 7-(7): Synthesis of intermediate 7-g

Intermediate 7-g was synthesized according to Scheme 56 below:

<Scheme 56>

<Intermediate 7-f> <Intermediate 7-g>

<Intermediate 7-f> (12.0 g, 0.030 mol) and 360 ml of dichloromethane were placed in a 1L round-bottom flask reactor. Bromine (3.1 ml, 0.06 mol) was diluted in 40 ml of dichloromethane and added dropwise while stirring at room temperature. The mixture was stirred at room temperature for 12 hours, and after completion of the reaction, 100 ml of methanol was added, the resulting solid was filtered and washed with methanol. Recrystallization from 1,2-dichlorobenzene and acetone gave <Intermediate 7-g> (10.3 g, 71.7%).

Synthesis Example 7-(8): Synthesis of intermediate 7-h

Intermediate 7-h was synthesized according to Scheme 57 below:

<Scheme 57>

<Intermediate 7-g> <Intermediate 7-h>

<Intermediate 7-h> (10.0 g, 73.4%) was obtained in the same manner except that <Intermediate 7-g> was used instead of <Intermediate 1-d> in Synthesis Example 1-(5).

Synthesis Example 7-(9): Synthesis of compound 58

Compound 58 was synthesized according to Scheme 58:

<Scheme 58>

<Intermediate 7-h> <Compound 58>

<Compound 58> (6.3 g, 64.8%) was obtained in the same manner as in Synthesis Example 1-(6), except that <Intermediate 7-h> was used instead of <Intermediate 1-e>.

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

Formula 7 was synthesized according to Scheme 59 below:

<Scheme 59>

<Compound 58> <Formula 7>

<Formula 7> (3.0 g, 36.1%) was obtained by using the same method except that <Compound 58> was used instead of <Compound 1> in Synthesis Example 1-(7).

MS (MALDI-TOF): m/z 1014.5 [M ⁺ ]

Synthesis Example 8: Synthesis of Formula 59

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

Intermediate 8-a was synthesized according to Scheme 60:

<Scheme 60>

<Intermediate 8-a>

In a 500ml round bottom flask reactor, 1-bromodibenzofuran (20.0g, 0.081mmol), bis(pinacolato)diboron (26.7g, 0.105mol), [1,1'-bis(diphenylphosphino)ferrocene ] Dichloropalladium (1.3 g, 0.002 mol), potassium acetate (19.9 g, 0.202 mol), and 200 ml of 1,4-dioxane were added and stirred under reflux for 10 hours. After completion of the reaction, the celite pad was filtered. The filtrate was concentrated under reduced pressure, separated by column, and recrystallized from dichloromethane and heptane to obtain <Intermediate 8-a> (17.0 g, 70%).

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

Intermediate 8-b was synthesized according to Scheme 61 below:

<Scheme 61>

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

<Intermediate 8-b> (13.1 g, 68.9%) was obtained in the same manner as in Synthesis Example 1-(1), except that <Intermediate 8-a> was used instead of 4-dibenzofuranboronic acid.

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

According to Scheme 62, Intermediate 8-c was synthesized:

<Scheme 62>

<Intermediate 8-b> <Intermediate 8-c>

<Intermediate 8-c> (11 g, 87%) was obtained in the same manner except that <Intermediate 8-b> was used instead of <Intermediate 1-a> in Synthesis Example 1-(2).

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

Intermediate 8-d was synthesized according to Scheme 63 below:

<Scheme 63>

<Intermediate 8-c> <Intermediate 8-d>

<Intermediate 8-d> (9.0 g, 86%) was obtained in the same manner except that <Intermediate 8-c> was used instead of <Intermediate 1-b> in Synthesis Example 1-(3).

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

Intermediate 8-e was synthesized according to Scheme 64 below:

<Scheme 64>

<Intermediate 8-d> <Intermediate 8-e>

<Intermediate 8-e> (6.7 g, 60.7%) was obtained in the same manner except that <Intermediate 8-d> was used instead of <Intermediate 1-c> in Synthesis Example 1-(4).

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

According to Scheme 65, Intermediate 8-f was synthesized:

<Scheme 65>

<Intermediate 8-e> <Intermediate 8-f>

<Intermediate 8-f> (5.2 g, 55%) was obtained in the same manner except that <Intermediate 8-e> was used instead of <Intermediate 1-d> in Synthesis Example 1-(5).

Synthesis Example 8-(7): Synthesis of compound 59

Compound 59 was synthesized according to Scheme 66 below:

<Scheme 66>

<Intermediate 8-f> <Compound 59>

<Compound 59> (4.3 g, 85.3%) was obtained in the same manner as in Synthesis Example 1-(6), except that <Intermediate 8-f> was used instead of <Intermediate 1-e>.

Synthesis Example 8-(8): Synthesis of Formula 8

Formula 8 was synthesized according to Scheme 67:

<Scheme 67>

<Compound 59> <Formula 8>

<Formula 8> (2.5 g, 34%) was obtained in the same manner except that <Compound 59> was used instead of <Compound 1> in Synthesis Example 1-(7).

MS (MALDI-TOF): m/z 964.5 [M ⁺ ]

Synthesis Example 9: Synthesis of compound 61

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

According to Scheme 68, Intermediate 9-a was synthesized:

<Scheme 68>

<Intermediate 9-a>

2-Iodonitrobenzene (15.0 g, 0.060 mol), 2-bromophenylboronic acid (13.3 g, 0.066 mol), palladium acetate (0.67 g, 0.003 mol), 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, and 525 mL of toluene, 60 mL of ethanol, and 60 mL of water were added. The temperature of the reactor was raised to 100 degrees and stirred for 18 hours. When the reaction was completed, the temperature of the reactor was lowered to room temperature, extraction was performed with ethyl acetate, and the organic layer was separated. The organic layer was concentrated under reduced pressure and separated by column chromatography to obtain <Intermediate 9-a> (14.0 g, 83.6%).

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

Intermediate 9-b was synthesized according to Scheme 69 below:

<Scheme 69>

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

Put <Intermediate 9-a> (14.0g, 0.050mol), triphenylphosphine (33.01g, 0.126mol), N,N-dimethylacetamide (100ml) in a 250ml round bottom flask and stir at 180° for 14 hours did. When the reaction was completed, it was cooled to room temperature, poured into 200 ml of water, and stirred. The organic layer was separated and concentrated under reduced pressure by extraction with ethyl acetate. After separation by column chromatography, <Intermediate 9-b> (7.0 g, 56.5%) was obtained.

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

According to Scheme 70, Intermediate 9-c was synthesized:

<Scheme 70>

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

<Intermediate 9-b> (7.0 g, 0.028 mol) and 140 ml of tetrahydrofuran were put in a 250 ml round-bottom flask, and sodium hydride (60%) (1.19 g, 0.029 mol) was stirred at room temperature for 30 minutes, followed by cooling and stirring to 0°C. . After dropwise addition of iodomethane (3.5ml, 0.057mol) to the cooled reaction solution, the temperature was raised to room temperature and stirred for 18 hours. When the reaction was completed, it was poured into 100 ml of water, extracted with ethyl acetate, and the organic layer was separated. The organic layer was dried over anhydrous magnesium sulfate, filtered, concentrated under reduced pressure, and separated by column chromatography to obtain <Intermediate 9-c> (7.2 g, 92.7%).

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

Intermediate 9-d was synthesized according to Scheme 71 below:

<Scheme 71>

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

<Intermediate 9-d> (6.1 g, 71.7%) was obtained in the same manner as in Synthesis Example 8-(1), except that <Intermediate 9-c> was used instead of 1-bromodibenzofuran.

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

Intermediate 9-e was synthesized according to Scheme 72 below:

<Scheme 72>

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

<Intermediate 9-e> (5.2 g, 73.7%) was obtained in the same manner except that <Intermediate 9-d> was used instead of 4-dibenzofuranboronic acid in Synthesis Example 1-(1)

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

According to Scheme 73, the intermediate 9-f was synthesized:

<Scheme 73>

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

<Intermediate 9-f> (8.2 g, 85%) was obtained in the same manner except that <Intermediate 9-e> was used instead of <Intermediate 1-a> in Synthesis Example 1-(2).

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

Intermediate 9-g was synthesized according to Scheme 74 below:

<Scheme 74>

<Intermediate 9-f> <Intermediate 9-g>

<Intermediate 9-g> (6.7 g, 85.8%) was obtained in the same manner except that <Intermediate 9-f> was used instead of <Intermediate 1-b> in Synthesis Example 1-(3).

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

Intermediate 9-h was synthesized according to Scheme 75 below:

<Scheme 75>

<Intermediate 9-g> <Intermediate 9-h>

<Intermediate 9-h> (4.3 g, 52.7%) was obtained in the same manner except that <Intermediate 9-g> was used instead of <Intermediate 1-c> in Synthesis Example 1-(4).

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

According to Scheme 76, Intermediate 9-i was synthesized:

<Scheme 76>

<Intermediate 9-h> <Intermediate 9-i>

<Intermediate 9-i> (4.0 g, 68.9%) was obtained in the same manner except that <Intermediate 9-h> was used instead of <Intermediate 1-d> in Synthesis Example 1-(5).

Synthesis Example 9-(10): Synthesis of compound 61

According to Scheme 77, compound 61 was synthesized:

<Scheme 77>

<Intermediate 9-i> <Compound 61>

<Compound 61> (3.2 g, 82.5%) was obtained in the same manner except that <Intermediate 9-i> was used instead of <Intermediate 1-e> in Synthesis Example 1-(6).

Synthesis Example 9-(11): Synthesis of Chemical Formula 9

According to Scheme 78, formula 9 was synthesized:

<Scheme 78>

<Compound 61> <Intermediate 4-c> <Formula 9>

<Formula 9> using the same method, except that <Compound 61> was used instead of <Compound 1> in Synthesis Example 1-(7) and <Intermediate 4-c> was used instead of bis(4-tertbutylphenyl)amine > (2.3 g, 40.7%) was obtained.

MS (MALDI-TOF): m/z 1017.5 [M ⁺ ]

Synthesis Example 10: Synthesis of compound 64

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

Intermediate 10-a was synthesized according to Scheme 79 below:

<Scheme 79>

<Intermediate 10-a>

In a 2L round bottom flask reactor, 4-bromodibenzofuran (100.0 g, 0.405 mol), ethynyl trimethylsilane (47.7 g, 0.486 mol), [1,1'-bis (diphenylphosphino) ferrocene] dichloropalladium ( 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 in a nitrogen atmosphere for 5 hours. After completion of the reaction, it was cooled to room temperature, and 500 ml of heptane was added to complete the reaction. It was filtered over a pad of celite and silica gel. The filtrate was concentrated under reduced pressure to obtain <Intermediate 10-a> (130 g, 84%).

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

Intermediate 10-b was synthesized according to Scheme 80 below:

<Scheme 80>

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

<Intermediate 10-a> (130g, 0.492mol), potassium carbonate (101.9g, 0.738mol), 650ml methanol, 650ml tetrahydrofuran were placed in 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 treatment with magnesium sulfate, filtered, and concentrated under reduced pressure to obtain <Intermediate 10-b> (82 g, 84%) in the form of an oil.

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

Intermediate 10-c was synthesized according to Scheme 81 below:

<Scheme 81>

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

2-Bromobiphenyl (66.0 g, 0.283 mol), <Intermediate 10-b> (65.3 g, 0.340 mol), [1,1'-bis (diphenylphosphino) ferrocene] dichloro in a 2L round-bottom flask reactor Ropalladium (6.94 g, 0.008 mol), copper iodide (1.62 g, 0.008 mol), triphenylphosphine (7.4 g, 0.028 mol), and 500 ml of triethylamine were added and stirred under reflux in a nitrogen atmosphere for 5 hours. After completion of the reaction, it was cooled to room temperature, and 400 ml of heptane was added to complete the reaction. It was filtered over a pad of celite and silica gel. The filtrate was concentrated under reduced pressure and the resulting solid was filtered to obtain <Intermediate 10-c> (80 g, 82%).

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

Intermediate 10-d was synthesized according to Scheme 82 below:

<Scheme 82>

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

In a 2L round-bottom flask reactor, <Intermediate 10-c> (80.0 g, 0.232 mol) was dissolved in 960 ml of dichloromethane and cooled to -78°C in a nitrogen atmosphere. To the cooled solution, iodine monochloride (278.4 ml, 0.279 mol) was added dropwise and stirred at room temperature for 12 hours. After completion of the reaction, a saturated aqueous sodium thiosulfate solution was added and stirred. The organic layer was separated by extraction with dichloromethane and water and concentrated under reduced pressure. The crystals were captured with methanol to obtain <Intermediate 10-d> (67 g, 61.3%).

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

Intermediate 10-e was synthesized according to Scheme 83 below:

<Scheme 83>

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

<Intermediate 10-d> (54.8 g, 0.117 mol) and 150 ml of tetrahydrofuran were dissolved in a 500 ml round-bottom flask reactor, and then cooled to -78°C in a nitrogen atmosphere. To the cooled solution, 1.6 mol n-butylyrium (62.4 ml, 0.1 mol) was added dropwise and stirred at the same temperature for 1 hour. 9-Floorenone (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 treatment with magnesium sulfate, filtered, and concentrated under reduced pressure to obtain <Intermediate 10-e> (33.2 g, 76%) in the form of an oil.

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

Intermediate 10-f was synthesized according to Scheme 84 below:

<Scheme 84>

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

<Intermediate 10-e> (33.3 g, 0.063 mol), 330 ml of acetic acid, and 3 ml of sulfuric acid were added to a 1L round-bottom flask reactor, and the mixture was stirred under reflux for 3 hours. After confirming the completion of the reaction by thin film chromatography, it was cooled to room temperature. The resulting solid was filtered and washed with H 2 O and methanol to obtain <Intermediate 10-f> (28.6 g, 88%>).

Synthesis Example 10-(7): Synthesis of compound 64

According to Scheme 85, compound 64 was synthesized:

<Scheme 85>

<Intermediate 10-f> <Compound 64>

<Intermediate 10-f> (20.0g, 0.039mol) and 200ml of dichloromethane were put and dissolved in a 1L round-bottom flask reactor. Bromine (6ml, 0.118mol) was diluted in 40ml of dichloromethane and added dropwise while stirring at room temperature. The mixture was stirred at room temperature for 12 hours, and after completion of the reaction, 100 ml of methanol was added, the resulting solid was filtered and washed with methanol. <Compound 64> (16 g, 60%) was obtained by recrystallization from 1,2-dichlorobenzene and acetone.

Synthesis Example 10-(8): Synthesis of Chemical Formula 10

According to Scheme 86, formula 10 was synthesized:

<Scheme 86>

<Compound 64> <Formula 10>

<Formula 10> (2.5 g, 31%) was obtained in the same manner except that <Compound 64> was used instead of <Compound 1> in Synthesis Example 1-(7).

MS (MALDI-TOF): m/z 1064.5 [M ⁺ ]

Synthesis Example 11: Synthesis of Chemical 73

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

Intermediate 11-a was synthesized according to Scheme 87 below:

<Scheme 87>

<Intermediate 7-d> <Intermediate 11-a>

Bromobenzene (25.46g, 0.163mol) and 170ml of tetrahydrofuran were added to a 500ml round-bottom flask reactor and cooled to -78°C in a nitrogen atmosphere. 1.6M n-butyllithium (95.6ml, 0.153mol) was added dropwise to the cooled reaction solution. After stirring at the same temperature for 1 hour, <Intermediate 7-d> (22.0 g, 0.051 mol) was added, followed by stirring at room temperature for 3 hours. After completion of the reaction, 50 ml of water was added and stirred for 30 minutes. After extraction with ethyl acetate and water, the organic layer was separated and concentrated under reduced pressure. 200 ml of acetic acid and 1 ml of hydrochloric acid were added to the concentrated material, and the temperature was raised to 80 degrees and stirred. After completion of the reaction, the mixture was cooled to room temperature and the resulting solid was filtered. After washing with methanol, <Intermediate 11-a> (20.0 g, 73%) was obtained.

Synthesis Example 11-(2): Synthesis of compound 73

According to Scheme 88, compound 73 was synthesized:

<Scheme 88>

<Intermediate 11-a> <Compound 73>

<Intermediate 11-a> (20.0 g, 0.037 mol) and 600 ml of chloroform were placed in a 1L round-bottom flask reactor. Bromine (5.7 ml, 0.112 mol) was diluted in 40 ml of chloroform and added dropwise while stirring at room temperature. The mixture was stirred at room temperature for 12 hours, and after completion of the reaction, 100 ml of methanol was added, the resulting solid was filtered and washed with methanol. <Compound 73> (14.0 g, 61.7%) was obtained by recrystallization from 1,2-dichlorobenzene and acetone.

Synthesis Example 11-(3): Synthesis of intermediate 11-b

Intermediate 11-b was synthesized according to Scheme 89 below:

<Scheme 89>

<Intermediate 11-b>

<Intermediate 11-b> (13.1g, 72.1) using the same method except that 1-bromo-4-(trimethylsilyl)benzene was used instead of 4-bromobiphenyl in Synthesis Example 4-(4) %) was obtained.

Synthesis Example 11-(4): Synthesis of Formula 11

According to Scheme 90 below, Formula 11 was synthesized:

<Scheme 90>

<Compound 73> <Intermediate 11-b> <Formula 11>

<Formula 11> using the same method except that <Compound 73> was used instead of <Compound 1> in Synthesis Example 1-(7) and <Intermediate 11-b> was used instead of bis(4-tertbutylphenyl)amine > (3.0 g, 35%) was obtained.

MS (MALDI-TOF): m/z 1048.5 [M ⁺ ]

Synthesis Example 12: Synthesis of compound 105

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

According to Scheme 91, Intermediate 12-a was synthesized:

<Scheme 91>

<Intermediate 12-a>

In a 2L round-bottom flask reactor, 4-dibenzofuranboronic acid (85.0g, 0.401mol), bismuth(III)nitrate pentahydrate (99.2g, 0.200mol), and 400ml toluene were added and stirred at 70°C in a nitrogen atmosphere 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 12-a> (61.5 g, 72%) was obtained.

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

Intermediate 12-b was synthesized according to Scheme 92:

<Scheme 92>

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

Ethylcyanoacetate (202.9g, 1.794mol) and 500ml of dimethylformamide were placed in a 2L round-bottom flask reactor. Potassium hydroxide (67.10g, 1.196mol) and potassium cyanide (38.95g, 0.598mol) were added, 200ml of dimethylformamide was added, and the mixture was stirred at room temperature. <Intermediate 12-a> (127.5 g, 0.737 mol) was added little by little to the reaction solution, followed by stirring at 50°C for 72 hours. After completion of the reaction, 200 ml of sodium hydroxide aqueous solution (25%) was added and stirred under reflux. After stirring for 3 hours, it was cooled to room temperature, and extracted with ethyl acetate and water. The organic layer was separated, concentrated under reduced pressure, and separated by column chromatography to obtain <Intermediate 12-b> (20.0 g, 16%).

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

Intermediate 12-c was synthesized according to Scheme 93:

<Scheme 93>

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

<Intermediate 12-b> (20.0 g, 0.096 mol), 600 ml of ethanol, and 170 ml of an aqueous potassium hydroxide solution (142.26 g, 2.53 mol) were placed in a 2L round-bottom flask reactor and stirred under reflux for 12 hours. When the reaction was completed, it was cooled to room temperature. 400 ml of 6N hydrochloric acid was added to the reaction solution for acidification, and the resulting solid was stirred for 20 minutes and then filtered. After washing the solid with ethanol, <Intermediate 12-c> (17.0 g, 88.5%) was obtained.

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

Intermediate 12-d was synthesized according to Scheme 94:

<Scheme 94>

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

<Intermediate 12-c> (17.0 g, 0.075 mol) and 15 ml of sulfuric acid were put in a 2L round-bottom flask reactor, and the mixture was stirred under reflux for 72 hours. After completion of the reaction, the mixture was cooled to room temperature and extracted with ethyl acetate and water. The organic layer was separated and washed with an aqueous sodium hydrogen carbonate solution. An excess of methanol was added to the organic layer during concentration under reduced pressure, and the resulting solid was filtered to obtain <Intermediate 12-d> (14.0 g, 77.6%).

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

Intermediate 12-e was synthesized according to Scheme 95:

<Scheme 95>

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

<Intermediate 12-e> (9.1 g, 48%) was obtained in the same manner as in Synthesis Example 5-(1), except that <Intermediate 12-d> was used instead of 2-phenoxyaniline.

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

Intermediate 12-f was synthesized according to Scheme 96:

<Scheme 96>

<Intermediate 12-e> <Intermediate 8-a> <Intermediate 12-f>

<Intermediate 12-f> (5.3g, 52.3) using the same method except that <Intermediate 12-e> was used instead of methyl 5-bromo-2-iodobenzoate in Synthesis Example 8-(2) %) was obtained.

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

Intermediate 12-g was synthesized according to Scheme 97:

<Scheme 97>

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

<Intermediate 12-g> (4.5 g, 88.1%) was obtained in the same manner except that <Intermediate 12-f> was used instead of <Intermediate 1-a> in Synthesis Example 1-(2).

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

Intermediate 12-h was synthesized according to Scheme 98:

<Scheme 98>

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

<Intermediate 12-h> (3.8 g, 88.8%) was obtained in the same manner as in Synthesis Example 1-(3), except that <Intermediate 12-g> was used instead of <Intermediate 1-b>.

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

Intermediate 12-i was synthesized according to Scheme 99:

<Scheme 99>

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

<Intermediate 12-i> (3 g, 55%) was obtained by using the same method, except that <Intermediate 12-h> was used instead of <Intermediate 1-c> in Synthesis Example 1-(4)

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

Intermediate 12-j was synthesized according to Scheme 100:

<Scheme 100>

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

<Intermediate 12-j> (2.5 g, 64%) was obtained in the same manner except that <Intermediate 12-i> was used instead of <Intermediate 1-d> in Synthesis Example 1-(5)

Synthesis Example 12-(11): Synthesis of compound 105

Compound 105 was synthesized according to Scheme 101:

<Reaction Scheme 101>

<Intermediate 12-j> <Compound 105>

<Compound 105> (2.2 g, 90.4%) was obtained in the same manner except that <Intermediate 12-j> was used instead of <Intermediate 1-e> in Synthesis Example 1-(6).

Synthesis Example 12-(12): Synthesis of intermediate 12-k

Intermediate 12-k was synthesized according to Scheme 102 below:

<Scheme 102>

<Intermediate 12-k>

In a 250ml round-bottom flask reactor, 1-bromo-4-(2-naphthyl)benzene (10.0g, 0.035mol), 4-tertbutylaniline (5.8g, 0.039mol), tris(dibenzylideneacetone)di Palladium (0) (0.65 g, 0.0007 mol), sodium tert-butoxide (6.79 g, 0.0706 mol), 2,2'-bis(diphenylphosphino)-1,1'-binaphthalene (0.44 g, 0.0007) mol) 100 ml of toluene was added, and the mixture was stirred under reflux for 3 hours. After completion of the reaction, the mixture was cooled to room temperature and extracted with ethyl acetate and water. The organic layer was separated, anhydrous treatment with magnesium sulfate, and then concentrated under reduced pressure. It was separated and purified by column chromatography to obtain <Intermediate 12-k> (10 g, 80%).

Synthesis Example 12-(13): Synthesis of Formula 12

Formula 12 was synthesized according to Scheme 103:

<Scheme 103>

<Compound 105> <Intermediate 12-k> <Formula 12>

<Formula 12> using the same method, except that <Compound 105> was used instead of <Compound 1> in Synthesis Example 1-(7) and <Intermediate 12-k> was used instead of bis(4-tertbutylphenyl)amine > (1.6 g, 38%) was obtained.

MS (MALDI-TOF): m/z 1194.5 [M ⁺ ]

Synthesis Example 13: Synthesis of compound 14

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

According to Scheme 104, the intermediate 13-a was synthesized:

<Scheme 104>

<Intermediate 13-a>

<Intermediate 13-a> (18.0 g, 61.8%) using the same method except that 4-dibenzothiophenboronic acid was used instead of 4-dibenzofuranboronic acid in Synthesis Example 1-(1) got

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

Intermediate 9-b was synthesized according to Scheme 105:

<Scheme 105>

<Intermediate 13-a> <Intermediate 13-b>

<Intermediate 13-b> (15.0 g, 86.5%) was obtained in the same manner except that <Intermediate 13-a> was used instead of <Intermediate 1-a> in Synthesis Example 1-(2).

Synthesis Example 13-(3): Synthesis of Intermediate 13-c

According to Scheme 106, the intermediate 13-c was synthesized:

<Scheme 106>

<Intermediate 13-b> <Intermediate 13-c>

<Intermediate 13-c> (12.0 g, 83.9%) was obtained in the same manner as in Synthesis Example 1-(3), except that <Intermediate 13-b> was used instead of <Intermediate 1-b>.

Synthesis Example 13-(4): Synthesis of intermediate 13-d

Intermediate 13-d was synthesized according to Scheme 107:

<Scheme 107>

<Intermediate 13-c> <Intermediate 13-d>

<Intermediate 13-d> (11.0 g, 75.4%) was obtained in the same manner as in Synthesis Example 1-(4), except that <Intermediate 13-c> was used instead of <Intermediate 1-c>.

Synthesis Example 13-(5): Synthesis of Intermediate 13-e

Intermediate 13-e was synthesized according to Scheme 108:

<Scheme 108>

<Intermediate 13-d> <Intermediate 13-e>

<Intermediate 13-e> (11.2 g, 75.6%) was obtained in the same manner except that <Intermediate 13-d> was used instead of <Intermediate 1-d> in Synthesis Example 1-(5).

Synthesis Example 13-(6): Synthesis of compound 14

Compound 14 was synthesized according to Scheme 109:

<Scheme 109>

<Intermediate 13-e> <Compound 14>

<Compound 14> (8.7 g, 80.1%) was obtained in the same manner as in Synthesis Example 1-(6), except that <Intermediate 13-e> was used instead of <Intermediate 1-e>.

Synthesis Example 13-(7): Synthesis of Formula 13

Formula 13 was synthesized according to Scheme 110:

<Scheme 110>

<Compound 14> <Intermediate 11-b> <Formula 13>

<Formula 13> using the same method, except that <Compound 14> was used instead of <Compound 1> in Synthesis Example 1-(7) and <Intermediate 11-b> was used instead of bis(4-tertbutylphenyl)amine > (3.2 g, 36.6%) was obtained.

Examples 1 to 8: Preparation of organic light emitting device

After patterning so that the light emitting area of the ITO glass becomes 2mm*2mm in size, it was washed. After the ITO glass was mounted in a vacuum chamber, the base pressure was set to 1*10 ^{- 7} torr, and then a film was formed on the ITO in the order of DNTPD (700 Å), α-NPD (300 Å), [BH1] and the table below After mixing 3% of the compound according to the present invention described in 1 to form a film (250 Å), then [Formula E-1] and [Formula E-2] as an electron transport layer in a 1:1 ratio of 300 Å, electron injection layer [Formula E-1] was formed into a film in the order of 5 Å, Al (1000 Å) to prepare an organic light emitting diode. The emission characteristics of the organic light emitting device were measured at 0.4 mA.

[DNTPD] [α-NPD]

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

Comparative Examples 1 and 2

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

[BD1] [BD2]

For the organic light emitting devices 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 Table 1 below. T97 means the time it takes for the luminance to decrease to 97% compared to the initial luminance.

Voltage current density
(mA/cm ² ) luminance
(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 4] 3.8 10 650 0.133 0.115 113 Example 3
[Formula 5] 3.8 10 801 0.138 0.110 120 Example 4
[Formula 7] 3.8 10 980 0.132 0.181 110 Example 5
[Formula 8] 3.8 10 679 0.141 0.116 121 Example 6
[Formula 10] 3.8 10 880 0.136 0.133 110 Example 7
[Formula 11] 3.8 10 850 0.130 0.164 118 Example 8
[Formula 12] 3.8 10 816 0.134 0.121 120

As shown in Table 1, the amine compound according to the present invention has much superior luminance and luminous efficiency than the case of using the compounds of Comparative Examples 1 and 2 according to the prior art, and can show excellent device characteristics with a long lifespan, It has shown that it has high applicability as an organic light emitting device.

Claims (10)

A compound represented by the following [Formula A].
[Formula A]

In the [Formula A], A ₁ , A ₂ and E are the same or different from each other, and each independently a substituted or unsubstituted aromatic hydrocarbon ring having 6 to 50 carbon atoms, or a substituted or unsubstituted C 2 to 40 carbon atom an aromatic heterocyclic ring, wherein rings A1 and E are unsubstituted with a halogen group, and ring A2 is unsubstituted with a halogen group, except when X2 is a halogen group;
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} form a 5-membered ring with a carbon atom connected to _{the substituents R 1} and R _{2 , respectively.} to form;
wherein M is _{any one selected from NR 3} , SiR ₆ R ₇ , GeR ₈ R ₉ , O, and S;
The substituents R ₁ to R ₃ , R ₆ to R ₉ are the same or different from each other, and each independently represents hydrogen, deuterium, a substituted or unsubstituted C 1 to C 30 alkyl group, a substituted or unsubstituted C 6 to C 50 aryl group, a substituted or unsubstituted A cycloalkyl group having 3 to 30 carbon atoms, a substituted or unsubstituted heteroaryl group having 2 to 50 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, Any one selected from a cyano group, a nitro group, and a halogen group,
The R ₁ and R ₂ may be connected to each other to form an alicyclic, aromatic monocyclic or polycyclic ring;
S2 is 1, s1 and S3 are each 0,
Wherein X ₁ to X ₃ are each independently the same as or different from each other, and a halogen selected from Cl, Br, F and I, an alkyl sulfonate having 1 to 30 carbon atoms, an aryl sulfonate having 6 to 40 carbon atoms, 7 to 40 carbon atoms is any one leaving group selected from among arylalkyl sulfonates and halogenated alkyl sulfonates having 1 to 30 carbon atoms,
In Formula A, _{two carbon atoms adjacent to each other in the ring A 2} combine with * of the structural formula Q1 to form a condensed ring,
'Substitution' in the 'substituted or unsubstituted' is deuterium, a cyano group, a halogen group, a nitro group, an alkyl group having 1 to 24 carbon atoms, a halogenated alkyl group having 1 to 24 carbon atoms, an aryl group having 6 to 24 carbon atoms, a carbon number At least one substituent selected from the group consisting of an arylalkyl group having 6 to 24 carbon atoms, a heteroaryl group having 2 to 24 carbon atoms, a heteroarylalkyl group having 2 to 24 carbon atoms, an alkylsilyl group having 1 to 24 carbon atoms, and an arylsilyl group having 1 to 24 carbon atoms. means to be replaced with
However, 8-bromo-3,3-dimethyl-1,3-dihydroindeno [2,1-b] carbazole is excluded. According to claim 1,
_{A 1} , A ₂ and E in Formula A are the same or different from each other, and each independently represents a substituted or unsubstituted C 6 to C 50 aromatic hydrocarbon ring. 3. The method of claim 2,
The aromatic hydrocarbon ring is the same or different, and each independently [Structural Formula 10] to [Structural Formula 21], characterized in that any one selected from the compound.
[Structural formula 10] [Structural formula 11] [Structural formula 12]

[Structural formula 13] [Structural formula 14] [Structural formula 15]

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

[Formula 19] [Formula 20] [Formula 21]

In the [Structural Formula 10] to [Structural Formula 21], "-*" _{forms a 5-membered ring including carbon atoms connected to the substituents R 1} and R ₂ , or to form a 5-membered ring including M in the Structural Formula Q1 means a binding site for
When the aromatic hydrocarbon ring of [Structural Formula 10] to [Structural Formula 21] _{corresponds to the A 2} ring and is combined with Structural Formula Q1, two adjacent carbon atoms among them are combined with * of Structural Formula Q1 to form a condensed ring, ;
In the [Structural Formula 10] to [Structural Formula 21], R is the same as R ₁ and R ₂ as defined above, m is an integer of 1 to 8, and when m is 2 or more, each R may be the same or different from each other . According to claim 1,
The leaving groups X ₁ to X ₃ are the same or different from each other, and each independently represents a halogen selected from Cl, Br, F, and I. According to claim 1,
The substituents R ₁ and R ₂ in Formula A are the same or different, and each independently represent a substituted or unsubstituted C6-C24 aryl group, and are linked to each other to form a ring. According to claim 1,
The substituents R ₁ and R ₂ in Formula A are the same or different, and each independently represents a substituted or unsubstituted C6-C24 aryl group, characterized in that they are not connected to each other to form a ring compound. According to claim 1,
The substituents R ₁ to R ₃ , R _{6 To} R ₉ are the same as or different from each other, and each independently represents hydrogen, deuterium, a substituted or unsubstituted C 6 to C 20 aryl group, a substituted or unsubstituted C 3 to C 30 cycloalkyl group, a substituted or unsubstituted and a heteroaryl group having 2 to 20 carbon atoms having at least one selected from O, N, S and Si as a heteroatom, a cyano group, and a halogen group. 7. The method according to any one of claims 1 to 6,
The A ₁ , A ₂ , E, R _{1 To} R ₃ , The _{substituents to be 'substituted' in R 6} to R ₉ are cyano group, halogen group, alkyl group having 1 to 6 carbon atoms, aryl group having 6 to 18 carbon atoms, arylalkyl group having 6 to 18 carbon atoms, heteroaryl group having 3 to 18 carbon atoms. , A compound, characterized in that any one selected from the group consisting of an alkylsilyl group having 1 to 12 carbon atoms, an arylsilyl group having 6 to 18 carbon atoms, and a halogenated alkyl group having 1 to 6 carbon atoms. According to claim 1,
Among the compounds represented by the following [Compound 2], [Compound 3], [Compound 8], [Compound 12], [Compound 15], [Compound 17], [Compound 30], [Compound 56], and [Compound 60] any one compound selected.

[Compound 2] [Compound 3] [Compound 8]

[Compound 12] [Compound 15] [Compound 17]

[Compound 30] [Compound 56] [Compound 60] By reacting the compound according to claim 1 with a primary amine or a secondary amine, at least one of the leaving groups in the compound is substituted with an amine group from which one hydrogen has been removed in the primary amine or secondary amine to obtain an amine derivative A method for producing an amine derivative, characterized in that it is prepared.

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