TWI512080B - Polycyclic compound including nitrogen and organic light emitting device using the same - Google Patents

Description

Nitrogen-containing polycyclic compound and organic light-emitting device using same

The present invention relates to a novel nitrogen-containing polycyclic compound and an organic light-emitting device comprising the polycyclic compound.

An electroluminescent device is a self-luminous display device that has the advantages of wide viewing angle, excellent contrast, and fast reaction rate.

In the structure of an organic light-emitting device, an organic film is sandwiched between two electrodes. When a voltage is applied to the organic light-emitting device having the structure, electrons injected from the two electrodes are combined with a hole in an organic film to form an electron-hole pair, and the organic light-emitting device emits light, and then the light-emitting device emits light. The electron-hole pair disappeared. Wherein, the organic film may be composed of a single layer or, if necessary, a plurality of layers.

The material for the organic film may have a function of illuminating if necessary, for example, a compound which is used alone as a light-emitting layer, or a main light which is used as a main light-dopant light-emitting layer may be used. A compound of a body or a dopant. In addition to the aforementioned materials, it is also possible to use holes, transfer holes, barrier electrons, barrier holes, electron transport or electron injection. The compound is used as a material for an organic film.

In order to enhance the performance, life or efficiency of the organic light-emitting device, it is required to develop a material for an organic film.

The present invention provides a novel nitrogen-containing polycyclic compound and an organic light-emitting device comprising the polycyclic compound.

The present invention provides a compound represented by the following Chemical Formula 1:

In Chemical Formula 1, R ₁ is a C ₆ to C ₆₀ monocyclic or polycyclic substituted or unsubstituted aryl group; or a C ₂ to C ₆₀ monocyclic or polycyclic ring is substituted or not the substituted nitrogen-containing aromatic (heteroaryl); R ₂ a line of a C ₁ to C ₆₀ linear or branched chain of substituted or unsubstituted alkyl (alkyl) or a C ₆ to C ₆₀ monocyclic or of a polycyclic substituted or unsubstituted aryl group; and R ₃ to R ₇ are the same or different from each other, and are each independently selected from a straight or branched chain substituted or unsubstituted by hydrogen, C ₁ to C ₆₀ Alkyl, C ₂ to C ₆₀ linear or branched substituted or unsubstituted alkenyl, C ₂ to C ₆₀ linear or branched substituted or unsubstituted alkynyl , C ₃ to C ₆₀ of monocyclic or polycyclic substituted or non-substituted cycloalkyl (cycloalkyl), C ₆ to C ₆₀ of monocyclic or polycyclic substituted or non-substituted aromatic group and a substituted or A group of unsubstituted _C10 to _C60 spiro groups.

The present invention further provides an organic light-emitting device comprising: an anode, a cathode, and an organic material layer having more than one layer sandwiched between the anode and the cathode, wherein the organic material layer comprises the compound of Chemical Formula 1.

The compounds described in the present invention can be used as materials for the organic material layer of the organic light-emitting device. The compound can be used as a hole injecting material, a hole transporting material, a light emitting material, an electron transporting material, and an electron injecting material in an organic light emitting device. The compound is particularly suitable for use as a material for the hole transport layer and/or electron transport layer of the organic light-emitting device. Alternatively, the compound can be used as a luminescent material, for example, the compound can be used as a phosphorescent host material.

The invention will be described in detail below.

The compound described in the present invention can be represented by Chemical Formula 1. Specifically, the structural characteristics, the use of a core structure and the substituent groups (particularly R ₁ and R ₂ substituents of the group), the compound of formula 1 can be used as the organic material layer material of organic light emitting device. In particular, the compound having the aforementioned structure has characteristics suitable for transporting electrons of the organic light-emitting device.

In the present invention, an alkyl group includes a straight chain or a branched chain having 1 to 60 carbon atoms, and may be further substituted with another substituent. The alkyl group may have a carbon number of from 1 to 60, preferably from 1 to 40, more preferably from 1 to 20.

In the present invention, the alkenyl group includes a carbon atom of 2 to 60 Straight or branched, and may be further substituted with another substituent. The alkenyl group may have a carbon number of 2 to 60, preferably 2 to 40, more preferably 2 to 20.

In the present invention, an alkynyl group includes a straight chain or a branched chain having 2 to 60 carbon atoms, and may be further substituted with another substituent. The alkynyl group may have a carbon number of 2 to 60, preferably 2 to 40, more preferably 2 to 20.

In the present invention, the cycloalkyl group includes a monocyclic or polycyclic ring having 3 to 60 carbon atoms, and may be further substituted with another substituent. Wherein, the polycyclic ring means that the cycloalkyl group is directly bonded to another ring group or undergoes condensation; the other ring group may also be a cycloalkyl group, but may also be another ring group, for example, a heterocycloalkyl group, an aromatic group. Base, heteroaromatic group, etc. The cycloalkyl group may have a carbon number of from 3 to 60, preferably from 3 to 40, more preferably from 5 to 20.

In the present invention, the aryl group includes a monocyclic or polycyclic ring having 6 to 60 carbon atoms, and may be further substituted with another substituent. Wherein, the polycyclic ring means that the aromatic group is directly bonded to another ring group or undergoes condensation; the other ring group may also be an aromatic group, but may also be another ring group such as a cycloalkyl group, a heterocycloalkyl group, or a heterocyclic group. Aromatic groups, etc. The aromatic group may have a carbon number of 6 to 60, preferably 6 to 40, more preferably 6 to 20. Specific examples of the aryl group include phenyl, biphenyl, and triphenylene. (triphenyl), naphthyl, anthryl, chrysenyl, phenanthrenyl, perylenyl, fluoranthenyl, triphenyl ( Triphenylenyl), phenalenyl, pyrenyl, tetracenyl, pentacenyl, fluorenyl, indenyl, acenaphthylenyl or Its condensed ring, but not limit.

In the present invention, the nitrogen-containing heteroaryl group includes an N hetero atom and a monocyclic or polycyclic ring having 2 to 60 carbon atoms, and may be further substituted with another substituent. In the present invention, unless otherwise mentioned, the heteroaryl group contains S, O or N as a hetero atom, and a monocyclic or polycyclic ring having 2 to 60 carbon atoms, and may be further substituted by another substituent. . Wherein, the polycyclic ring means that the heteroaryl group is directly bonded to another ring group or undergoes condensation, wherein the other ring group may be a heteroaryl group, but may also be another ring group, for example, a cycloalkyl group, a hetero group. A cycloalkyl group, an aromatic group or the like. The heteroaromatic group may have a carbon number of 2 to 60, preferably 2 to 40, more preferably 3 to 20. Specific examples of the heteroaryl group include: pyridyl, pyrrolyl, pyrimidyl, pyridazinyl, furanyl, thienyl, imidazolyl ( Imidazolyl), pyrazolyl, oxazolyl, isoxazolyl, thiazolyl, isothiazolyl, triazolyl, furazanyl ), oxadiazolyl, thiadiazolyl, dithiazolyl, tetrazolyl, pyranyl, thiopyranyl, diazinyl ( Diazinyl), oxazinyl, thiazinyl, dioxinyl, triazinyl, tetrazinyl, quinolyl, isoquine Isoquinolyl, quinazolinyl, isoquinazolinyl, acridinyl, phenanthridinyl, imidazopyridinyl, diazonaphthyl ( Diazanaphthalenyl), triazaindene, indolyl, benzothiazolyl (benzothiazolyl), benzoxazolyl, benzoimidazolyl, benzothiophene group, benzofuran group, dibenzothiophene group, Dibenzofuran group, carbazolyl, benzocarbazolyl, phenazinyl or a condensed ring thereof, but not limited thereto.

In the present invention, the helical group is a group containing a helical structure and may have 15 to 60 carbon atoms. For example, the helical group may include a structure in which a 2,3-dihydro-1H-indene group or a cyclohexane group is helically bonded ( Spiro-bonded) to a fluorene group. In particular, the helical group includes groups of the following structural formula:

"Substituted or unsubstituted" means unsubstituted or substituted with one or more substituents selected from C ₁ to C ₆₀ straight or branched alkyl; C ₂ to C ₆₀ straight Chain or branched alkenyl; C ₂ to C ₆₀ straight or branched alkynyl; C ₃ to C ₆₀ monocyclic or polycyclic cycloalkyl; C ₂ to C ₆₀ monocyclic or polycyclic heterocyclic Alkyl; C ₆ to C ₆₀ monocyclic or polycyclic aromatic groups; C ₂ to C ₆₀ monocyclic or polycyclic heteroaryl; C ₂ to C ₆₀ monocyclic or polycyclic heterocycloalkyl; C ₁₀ a helical group to C ₆₀ ; and a C ₁ to C ₂₀ alkyl group, a C ₆ to C ₆₀ monocyclic or polycyclic substituted or unsubstituted aromatic group or a C ₂ to C ₆₀ monocyclic or polycyclic ring A group consisting of a substituted or unsubstituted heteroaryl group substituted or unsubstituted amine. These additional substituents may be further substituted.

According to an embodiment of the present invention, R ₁ in Chemical Formula 1 contains a nitrogen-containing heteroaromatic group. The "nitrogen-containing heteroaryl group" means a substituted or unsubstituted nitrogen-containing heteroaryl group of R ₁ or an aromatic group substituted with a substituted or unsubstituted nitrogen-containing heteroaryl group, wherein the aromatic group comprises a group in which two or more aromatic groups are bonded together.

According to an embodiment of the present invention, R ₁ in Chemical Formula ₁ contains a nitrogen-containing monocyclic heteroaryl group. The "nitrogen-containing aromatic group of monocyclic heteroaryl" means a R ₁ lines of a substituted or unsubstituted aromatic nitrogen-containing monocyclic heteroaromatic group or a substituted or unsubstituted with a warp of a nitrogen-containing monocyclic heteroaromatic group instead of base.

The nitrogen-containing heteroaromatic group may have 1 to 3 N, which may be a pyridine group, a pyrimidine group, a triazine group, or a quinoline group. Or isoquinoline group.

The nitrogen-containing monocyclic heteroaryl group may have 1 to 3 N groups.

The nitrogen-containing heteroaryl group is unsubstituted or substituted with an additional substituent. When the nitrogen-containing substituent of the aromatic-based group substituted by, C which may be an aromatic group of ₆ to ₆₀ C, or with C ₂ to C ₆₀ heteroaryl group C ₆ to C ₆₀ aryl unsubstituted or substituted by .

Under this embodiment of the invention one embodiment, in the Chemical Formula 1 R ₁ comprising a single ring heteroaromatic group of nitrogen, and of the nitrogen-containing monocyclic heteroaromatic group may be a pyridyl group, pyrimidinyl group, triazinyl group.

One embodiment of the invention under this embodiment, in the Department of Chemical Formula 1 R ₁ substituted or non-substituted pyridyl group, substituted or non-substituted pyrimidine group, a substituted or non-substituted triazine groups or with An aromatic group substituted with one or more substituted or unsubstituted pyridyl groups, pyrimidine groups, and triazine groups.

Under this embodiment, in the Chemical Formula 1 R _1, one embodiment of the invention-based group substituted by pyridyl or unsubstituted, the substituted or non-substituted pyrimidinyl group or a substituted or non-substituted triazinyl group; or A phenyl group substituted with one or more substituted or unsubstituted pyridyl groups, pyrimidine groups, and triazine groups.

In an embodiment of the present invention, Chemical Formula 1 can be represented by the following Chemical Formula 2:

In Chemical Formula 2, L is a C ₆ to C ₆₀ monocyclic or polycyclic substituted or unsubstituted arylene, Het is a C ₂ to C ₆₀ monocyclic or polycyclic substituted or unsubstituted The substituted nitrogen-containing heteroaromatic group, n is an integer of 0 to 2 and p is an integer of 1 or 2, and R ₂ to R ₇ are the same as defined in Chemical Formula 1.

According to an embodiment of the present invention, in Chemical Formula 2, n is 0 or 1 or 2, and L is a phenylene.

According to an embodiment of the present invention, in Chemical Formula 2, Het is a substituted or unsubstituted pyridyl group, pyrimidine group or triazine group.

According to an embodiment of the present invention, in Chemical Formula 2, Het is a substituted or unsubstituted pyridyl group, a pyrimidine group or a triazine group, and when Het is substituted, the substituent group is a C. ₆ to C ₆₀ monocyclic or polycyclic substituted or unsubstituted aromatic groups.

According to an embodiment of the present invention, in Chemical Formula 2, Het is a substituted or unsubstituted pyridyl group, a pyrimidine group or a triazine group, and when Het is substituted, the substituent group is a C. ₆ to C ₆₀ monocyclic or polycyclic substituted or unsubstituted aryl group which is unsubstituted or substituted with a C ₆ to C ₆₀ aryl group or a C ₂ to C ₆₀ heteroaryl group.

According to an embodiment of the present invention, in Chemical Formula 2, Het is a substituted or unsubstituted pyridyl group, a pyrimidine group or a triazine group, and when Het is substituted, the substituent group is a phenyl group. , biphenyl, terphenyl, naphthyl or phenanthryl, and may be further substituted by phenyl, biphenyl, triphenyl, naphthyl or phenanthryl, pyridyl, pyrimidine or tri Substituted by a azine group.

In an embodiment of the present invention, Chemical Formula 1 can be represented by the following Chemical Formula 3: [Chemical Formula 3]

In Chemical Formula 3, R ₈ is a C ₆ to C ₆₀ monocyclic or polycyclic substituted or unsubstituted aromatic group or a C ₂ to C ₆₀ monocyclic or polycyclic substituted or unsubstituted nitrogen-containing heteroaromatic The base, and m is an integer from 0 to 9, R ₂ to R ₇ are the same as defined in Chemical Formula 1, and L and n are the same as defined in Chemical Formula 2.

According to an embodiment of the present invention, in Chemical Formula 3, n is 0 or 1 or 2, and L is a stretching phenyl group.

According to an embodiment of the present invention, in Chemical Formula 3, m is 1 or 2, and R ₈ is an aromatic group or a nitrogen-containing heteroaryl group having 1 to 3 rings.

According to an embodiment of the present invention, in Chemical Formula 3, m is 1 or 2, and R ₈ is a phenyl group, a naphthyl group, a phenanthryl group, a terphenyl group, a pyridyl group, a bipyridine group, or a pyrimidinyl group. a group, a bipyrimidine group, a triazine group, a bitriazine group, a quinolyl group, an isoquinolyl group or a phenanthridyl group.

In an embodiment of the present invention, Chemical Formula 1 can be represented by the following Chemical Formula 4:

In Chemical Formula 4, X1 and X2 are a C ₆ to C ₆₀ monocyclic or polycyclic substituted or unsubstituted aromatic hydrocarbon ring, or a C ₂ to C ₆₀ monocyclic or polycyclic ring. The substituted or unsubstituted aromatic hetero ring, the R ₂ to R ₇ systems are the same as defined in the chemical formula 1, and the L and n systems are the same as defined in the chemical formula 2.

According to an embodiment of the present invention, in Chemical Formula 4, n is 0 or 1 or 2, and L is a stretching phenyl group.

According to an embodiment of the present invention, in Chemical Formula 4, Contains the following structure:

In these structural formulas, Y ₁ to Y ₆ are each CRR ' , NR, S or O, Z ₁ to Z ₃ are each S or O, and R and R' are the same or different from each other, and each is hydrogen, a C ₁ to C ₆₀ linear or branched substituted or unsubstituted alkyl group or a C ₆ to C ₆₀ monocyclic or polycyclic substituted or unsubstituted aromatic group.

According to an embodiment of the present invention, in Chemical Formula 1, R ₂ is a C ₁ to C ₂₀ linear or branched alkyl group substituted or unsubstituted, or a C ₆ to C ₂₀ monocyclic or polycyclic ring. Substituted or unsubstituted aryl group.

According to an embodiment of the present invention, in Chemical Formula 1, R ₂ is a methyl group, a phenyl group or a naphthyl group.

According to an embodiment of the present invention, in Chemical Formula 1, R ₃ to R ₇ are each independently hydrogen, a C ₁ to C ₆₀ linear or branched substituted or unsubstituted alkyl group, or a C ₆ to C ₆₀ single A cyclic or polycyclic substituted or unsubstituted aryl group.

According to an embodiment of the present invention, in Chemical Formula 1, R ₃ to R ₇ are hydrogen.

According to an embodiment of the present invention, the compound of Chemical Formula 1 may be selected from the following compounds:

The foregoing compounds can be prepared by the following preparations. Those skilled in the art will be able to add or remove a substituent according to the following preparations, if necessary. Further, the position or type of the substituent may be selected differently, and further, the starting material, the reaction material, the reaction conditions and the like may be modified according to the usual knowledge in the technical field.

Another embodiment of the present invention provides an organic light-emitting device comprising the aforementioned compound of the chemical formula 1. Specifically, the organic light-emitting device includes an anode, a cathode, and an organic material layer having more than one layer sandwiched between the anode and the cathode, wherein the organic material layer One or more layers contain the compound of the chemical formula 1.

1 to 3 illustrate a stacking sequence of electrodes and organic material layers of an organic light-emitting device in an embodiment of the present invention. However, the scope of the present invention is not limited to these drawings, and the structure of the organic light-emitting device known in the art can also be applied to the present invention.

1 illustrates an anode 200, an organic material layer 300, and a cathode 400 stacked sequentially on a substrate 100 in an organic light-emitting device. However, the organic light-emitting device is not limited to the structure, and as shown in FIG. 2, an organic light-emitting device in which a cathode, an organic material layer, and an anode are sequentially stacked on a substrate may be implemented.

Figure 3 illustrates the case of a multilayer organic material layer. The organic light-emitting device of FIG. 3 includes a hole injection layer 301, a hole transport layer 302, a light-emitting layer 303, an electron transport layer 304, and an electron injection layer 305. However, the scope of the present invention is not limited to the stacked structure, and if necessary, other layers may be omitted in addition to the light-emitting layer, and other functional layers may be added.

The organic light-emitting device of the present invention can be prepared by using materials and methods known in the art, except that one or more layers of the organic material layer contain the compound of the chemical formula 1.

In the organic light-emitting device, the compound of the chemical formula 1 may constitute one or more layers of the organic material alone, however, if necessary, the compound may be mixed with another substance to form an organic material layer.

In an organic light-emitting device, the compound of the chemical formula 1 can be used as a hole injecting material, a hole transporting material, a light emitting material, an electron transporting material, and an electron injecting material.

According to an embodiment of the present invention, the compound of the chemical formula 1 can be used as a material of a hole transport layer and/or an electron transport layer of an organic light-emitting device, and a specific embodiment thereof is the organic material containing the compound of the chemical formula 1. The layer can be an electron transport layer of the organic light-emitting device.

According to another embodiment of the present invention, the compound of the chemical formula 1 It can be used as a luminescent material for the organic light-emitting device. In a specific embodiment, the organic material layer containing the compound of the chemical formula 1 may be a light-emitting layer of the organic light-emitting device.

The compound of Chemical Formula 1 can be used as a phosphorescent host illuminant material. At this time, the compound of Chemical Formula 1 is used together with a luminescent dopant, which can be known in the art.

For example, to LL'MX, LL'L "M, LMXX ' , L 2 MX phosphorescent dopant material represented by the L ₃ M and can be used in the present invention, but the scope of the present invention is not limited to these examples.

In the present invention, L, L ' , L " , X and X ' are different bidentate ligands, and M forms a metal of octahedral complexes.

M may be iridium, platinum, osmium or the like.

L is an anionic bidentate ligand that coordinates to a hetero atom through a sp2 carbon atom to M, and X can function to capture electrons or holes. L is not limited to the following examples, including: 2-(1-naphthyl)benzoxazole, 2-phenylbenzoxazole, 2-phenyl 2-phenylbenzothiazole, 7,8-benzoquinoline, thienylpyridine, phenylpyridine, benzothienylpyridine, 3- 3-methoxy-2-phenylpyridine, tolylpyridine, and the like. X is not limited to the following examples, including: acetylacetonate (acetylacetonate, Acac), hexafluoroacetylacetonate, salicylidene, picolinate, 8-hydroxyquinolinate, and the like.

More specific examples are shown below, but X is not limited to this:

According to the present invention, in the organic light-emitting device, other materials than the compound of the chemical formula 1 will be exemplified as follows, but the examples are for illustrative purposes only, and do not limit the scope of the present invention, and are known in the art. Replacement of materials.

A material having a relatively large work function, such as a transparent conductive oxide, a metal or a conductive polymer, can be used as the anode material.

A material having a relatively small work function, such as a metal, a metal oxide or a conductive polymer, can be used as the cathode material.

Well-known hole injecting materials can also be used as the hole injecting material. For example, a phthalocyanine compound can be used, such as copper phthalocyanine disclosed in U.S. Patent No. 4,356,429 or disclosed in the literature. Material, 6, p. 677 (1994)) Starbust-type amine derivatives, such as TCTA; m-MTDATA; m-MTDAPB; soluble conductive polymers, polyaniline ( Polyaniline, Pani)/dodecylbenzenesulfonic acid (DBSA) or poly(3,4-ethylenedioxythiophene (PEDOT)/poly-4-styrenesulfonic acid (poly(3,4-ethylenedioxythiophene) Poly(4-styrenesulfonate, PSS), polyaniline (Pani)/camphor sulfonic acid (CSA) or polyaniline (Pani)/poly-4-styrene sulfonate (PSS).

Pyrazoline derivatives, arylamine-based derivatives, stilbene derivatives, triphenyldiamine derivatives, etc. can be used as the hole The material is transported, and a low molecular weight or high molecular weight material can also be used as the hole transport material.

Oxadiazole derivatives, anthraquinodimethane and its derivatives, benzoquinone and its derivatives, naphthoquinone and its derivatives, anthraquinone and its derivatives , tetracyanoanthraquinodimethane and its derivatives, fluorenone derivatives, diphenyldicyanoethylene and its derivatives, diphenyl hydrazine (diphenoquinone) derivatives, metal complexes of 8-hydroxyquinoline and derivatives thereof can be used as the electron transporting material, and high molecular weight and low molecular weight materials can also be used as the electron transporting material.

For example, lithium fluoride (LiF) is typically used as the electron injecting material in the art, but the invention is not limited thereto.

A red, green or blue luminescent material can be used as the luminescent material, and if necessary, two or more luminescent materials can be used in combination. Further, a fluorescent material and a phosphorescent material can also be used as the luminescent material. As the luminescent material, it is possible to use a material which combines the holes injected from the anode and the cathode with electrons and emit light, but it is also possible to use a material in which the main illuminant material and the dopant material participate in luminescence.

In the present invention, the organic light-emitting device may further include a hole blocking layer and/or an electron blocking layer, and the material thereof may be a material known in the art.

According to an embodiment of the present invention, the organic light-emitting device includes a light-emitting layer containing the compound of the chemical formula 1, and further includes a hole barrier layer sandwiched between the light-emitting layer and the cathode. The luminescent layer may further comprise a luminescent dopant.

100‧‧‧Substrate

200‧‧‧Anode

300‧‧‧ organic material layer

301‧‧‧ hole injection layer

302‧‧‧ hole transport layer

303‧‧‧Lighting layer

304‧‧‧Electronic transport layer

305‧‧‧Electronic injection layer

400‧‧‧ cathode

1 to 3 are schematic diagrams showing the stacking sequence of electrodes and organic material layers of an organic light-emitting device according to an embodiment of the invention.

4 and 5 are E _OX values obtained by CV measurement of Compound 16 of the present invention.

Figures 6 and 7 are E _OX values obtained from CV measurements of Compound 26 of the present invention.

8 and 9 are E _OX values obtained by CV measurement of Compound 49 of the present invention.

Figure 10 and Figure 11 are the E _OX values obtained from the CV measurement of Compound 50 of the present invention.

Figure 12 and Figure 13 are the E _OX values obtained from the CV measurement of Compound 89 of the present invention.

14 and 15 are E _OX values obtained by CV measurement of Compound 90 of the present invention.

Figure 16 is a graph showing the results of UV measurement of Compound 16 of the present invention.

Figure 17 is a graph showing the results of PL measurement of Compound 16 of the present invention at 263 nm.

Figure 18 is a graph showing the results of UV measurement of Compound 26 of the present invention.

Figure 19 is a graph showing the results of PL measurement of Compound 26 of the present invention at 327 nm.

Figure 20 is a graph showing the results of LTPL (-78 °C) measurement of Compound 49 of the present invention.

Figure 21 is a graph showing the results of UV measurement of Compound 49 of the present invention.

Figure 22 is a graph showing the results of PL measurement at 261 nm of Compound 49 of the present invention.

Figure 23 is a graph showing the results of LTPL (-78 °C) measurement of Compound 50 of the present invention.

Figure 24 is a graph showing the results of UV measurement of Compound 50 of the present invention.

Figure 25 is a graph showing the results of PL measurement of 416 nm of the compound of the present invention.

Figure 26 is a graph showing the results of LTPL (-78 °C) measurement of Compound 89 of the present invention.

Figure 27 is a graph showing the results of UV measurement of Compound 89 of the present invention.

Figure 28 is a graph showing the results of PL measurement of Compound 89 of the present invention at 259 nm.

Figure 29 is a graph showing the results of LTPL (-78 °C) measurement of Compound 90 of the present invention.

Figure 30 is a graph showing the results of UV measurement of Compound 90 of the present invention.

Figure 31 is a graph showing the results of PL measurement at 331 nm for Compound 90 of the present invention.

The following description will explain the present invention in detail by way of examples. However, the examples are merely illustrative of the invention and do not limit the scope of the invention.

Synthesis Experimental Example (1): Preparation of a compound having a substituent in Table 1 below

Preparation of Compound 1-1

After dissolving 20 g (93 mmol, 1 eq.) of methyl 2-bromobenzoate in 180 ml of THF, 7.44 g of NaH was added, and the mixture was stirred for 30 minutes. After the completion of the stirring, 11.17 g (93 mmol, 1 eq.) of acetophenone was slowly added, and the mixture was stirred at normal temperature for 2 hr and heated at 100 ° C for 16 hr. Upon completion of the reaction, the temperature was cooled to room temperature, and then the product was extracted with ethyl acetate, 1N HCl, aqueous NaHCO ₃ and water. After the extraction, the extract was separated and purified by column chromatography to obtain 25.6 g (yield: 90%) of Compound 1-1.

Preparation of Compound 1-2

After dissolving 25.6 g (84 mmol, 1 eq.) of compound 1-1 in 160 ml of DMF, 6 ml (92.4 mmol, 1.1 eq.) of H ₂ NNH _{2 was added} . H ₂ O, the mixture was stirred at room temperature for 6 hr. When the reaction was completed, the product was extracted with ethyl acetate and water. After extraction, the extract was separated and purified by column chromatography to give 20 g (79%) of Compound 1-2.

Preparation of Compound 1-3

After dissolving 20 g (66 mmol, 1 eq.) of compound 1-2 in 240 ml of DMF, 1.25 g (6.6 mmol, 0.1 eq.) of CuI and 14.8 g (80.4 mmol, 1.2 eq.) of 4-bromobenzaldehyde (4-bromobenzaldehyde) were added. The mixture was stirred for 30 minutes, and after completion of the stirring, 66 ml of NH _{3 was} added. H ₂ O, the mixture was stirred at 100 ° C for 24 hr. When the reaction was completed, the product was extracted with ethyl acetate and water. After extraction, the extract was separated and purified by column chromatography to obtain 15 g ( 56%) Compound 1-3.

Preparation of compound 1-4

After 15 g (37 mmol, 1 eq.) of compound 1-3 was dissolved in 60 ml of DMF, 1.25 g (6.6 mmol, 0.1 eq.) of CuI was added, and the mixture was stirred at 100 ° C for 24 hr, and when the reaction was completed, ethyl acetate was used. The product is extracted with water, and after extraction, the extract is separated and purified by column chromatography to obtain 10 g (80%) of compound 1-4.

Preparation of Compound S-1

After dissolving S-2 (1 eq.) in 300 ml of 1,4-dioxane, 2,2,3,3,7,7,8,8-octamethyl-1 was added. , 4,6,9-tetraoxa-514-boron helix [4.4] decane (2,2,3,3,7,7,8,8-octamethyl-1,4,6,9-tetraoxa-514 -boraspiro [4.4] nonane) (2 eq.), PdCl ₂ (dppf) (0.05 eq.) and KOAc (3 eq.), the mixture was stirred at 80 ° C for 24 hr, and when the reaction was completed, dichloromethane was used. The product is extracted with water, and after extraction, the extract is separated and purified by column chromatography to obtain S-1.

Preparation of Compound P1

After compound 1-4 was dissolved in a mixed solvent of toluene/ethanol/H ₂ O (mixing ratio 5:1:1), Pd(PPh ₃ ) ₄ (0.05 eq.), K _{2 was} added. CO ₃ (3 eq.) and compound S-1 (1.3 eq.), the mixture was heated for 4 hr. When the reaction was completed, the product was extracted with dichloromethane and water. After extraction, the extract was applied to the column chromatography. The analytical method is isolated and purified to obtain the compound P1.

Synthesis Experimental Example (2): Preparation of a Compound Having a Substituent in Table 2 below

Preparation of Compound 1-1

This compound was prepared by the same preparation method as the compound 1-1 in Synthesis Experimental Example (1).

Preparation of Compound 1-2

This compound was used in the synthesis of compound 1-2 in the experimental example (1). The same preparation method was used to prepare.

Preparation of Compound S-3

After dissolving S-4 (1 eq.) in THF, the temperature was cooled to -78 ° C, n-BuLi was added, and the mixture was stirred for 1 hr. After the completion of the stirring, DMF (5 eq.) was added, and the mixture was stirred for 24 hr. When the reaction is completed, the product is extracted with dichloromethane and water. After extraction, the extract is separated and purified by column chromatography to obtain S-3.

Preparation of Compound 2-3

After dissolving 20 g (66 mmol, 1 eq.) of compound 1-2 in 240 ml of DMF, 1.25 g (6.6 mmol, 0.1 eq.) of CuI and compound S-3 (1.2 eq.) were added, and the mixture was stirred for 30 minutes and stirred. After that, add 66 ml of NH ₃ . H ₂ O, then, the mixture is stirred at 100 ° C for 24 hr. When the reaction is completed, the product is extracted with ethyl acetate and water. After extraction, the extract is separated and purified by column chromatography. Compound 2-3.

Preparation of Compound P2

After dissolving the compound 2-3 (1 eq.) in 60 ml of DMF, CuI (0.1 eq.) was added, and the mixture was stirred at 100 ° C for 24 hr. When the reaction was completed, the product was extracted with ethyl acetate and water. The extract is separated and purified by column chromatography to obtain the compound P2.

Synthesis Experimental Example (3): Preparation of a Compound Having a Substituent in Table 3 below

Preparation of Compound 3-1

After dissolving 20 g (93 mmol, 1 eq.) of methyl-2-bromobenzoate in 180 ml of THF, 7.44 g of NaH was added, and the mixture was stirred for 30 minutes. After the completion of the stirring, 5.4 g (93 mmol, 1 eq.) was slowly added. Acetone, then, the mixture was stirred at room temperature for 2 hr, then heated to 100 ° C for 16 hr, and when the reaction was completed, the temperature was cooled to room temperature, and then, ethyl acetate, 1 N HCl, NaHCO were sequentially used. ₃ aqueous solution and water to extract the product. After the extraction, the extract was separated and purified by column chromatography to give 22 g (98%) of Compound 3-1.

Preparation of Compound 3-2

After dissolving 22 g (91 mmol, 1 eq.) of compound 3-1 in 180 ml of DMF, 12 ml (100.1 mmol, 1.1 eq.) of H ₂ NNH _{2 was added} . H ₂ O, the mixture is stirred at normal temperature for 6 hr. When the reaction is completed, the product is extracted with ethyl acetate and water. After extraction, the extract is separated and purified by column chromatography to obtain 19 g. (88%) Compound 3-2.

Preparation of Compound 3-3

After dissolving 19 g (80 mmol, 1 eq.) of compound 3-2 in 160 ml of DMF, 1.5 g (8 mmol, 0.1 eq.) of CuI and 17.7 g (96 mmol, 1.2 eq.) of 4-bromobenzaldehyde were added and the mixture was stirred 30 Minutes, after the completion of the addition, add 80 ml of NH ₃ . H ₂ O, the mixture is stirred at 100 ° C for 24 hr. When the reaction is completed, the product is extracted with ethyl acetate and water. After extraction, the extract is separated and purified by column chromatography to obtain 20 g. (73%) Compound 3-3.

Preparation of compound 3-4

After dissolving 20 g (59 mmol, 1 eq.) of compound 3-3 in 120 ml of DMF, 1.14 g (6 mmol, 0.1 eq.) of CuI was added, and the mixture was stirred at 100 ° C for 24 hr. When the reaction was completed, ethyl acetate was used. The product is extracted by water, and after extraction, the extract is separated and purified by column chromatography to obtain 17 g (85%) of compound 3-4.

Preparation of Compound S-5

After dissolving S-6 (1 eq.) in 300 ml of 1,4-dioxane 1,4-dioxane, add 2,2,3,3,7,7,8,8-octamethyl-1,4 , 6,9-tetraoxa-514-boron helix [4.4] decane (2,2,3,3,7,7,8,8-octamethyl-1,4,6,9-tetraoxa-514-boraspiro [4.4] nonane) (2 eq.), PdCl ₂ (dppf) (0.05 eq.) and KOAc (3 eq.), the mixture was stirred at 80 ° C for 24 hr, and when the reaction was completed, dichloromethane and water were used. The product is extracted, and after extraction, the extract is separated and purified by column chromatography to obtain S-5.

Preparation of Compound P3

After compound 3-4 was dissolved in a mixed solvent of toluene/ethanol/water (mixing ratio 5:1:1), Pd(PPh ₃ ) ₄ (0.05 eq.), K ₂ CO ₃ (3 eq.) and compound S were added. -5 (1.3 eq.), the mixture is heated for 4 hr. When the reaction is completed, the product is extracted with dichloromethane and water. After extraction, the extract is separated and purified by column chromatography. Compound P3.

Synthesis Experimental Example (4): Preparation of a Compound Having a Substituent in Table 4 below

Preparation of Compound S-7

The preparation method of the compound was the same as the preparation method of the compound S-3 in the synthesis experimental example (2) except that S-8 was used instead of S-4.

Preparation of compound 4-3

The preparation method of the compound was the same as the preparation method of the compound 2-3 in the synthesis experimental example (2) except that the compound 3-2 was used instead of 2-2.

Preparation of Compound P4

The preparation method of the compound was the same as the preparation method of the compound P2 in the synthesis experimental example (2) except that the compound 4-3 was used instead of 2-3.

Synthesis Experimental Example (5): Preparation of Compound 49

Preparation of Compound 49-1

In a single necked rbf, (9,9-dimethyl-9H-fluoren-2-yl)boronic acid (25.9 g, 108 mmol) , 1-bromo-2-nitrobenzene (20 g, 99 mmol), Pd(PPh ₃ ) ₄ (5.7 g, 4.95 mmol), K ₂ CO ₃ (27.3 g, 198 mmol) And a mixture of THF (250 ml) / H ₂ O (50 ml) was refluxed at 110 ° C for 24 hr. Then, the aqueous layer was removed, and the organic layer was dried over MgSO ₄ , and then collected. ₂ , Hexane: methylene chloride = 2:1) was isolated to give Compound 41-1 (21 g, 61%).

Preparation of Compound 49-2

a mixture of compound 49-1 (20 g, 63.4 mmol), PPh ₃ (49.8 g, 190 mmol) and 1,2-dichlorobenzene (300 ml) in a single neck rbf at 180 °C, under nitrogen atmosphere, reflux for 1 hr, the 1,2-dichlorobenzene was removed by distillation, and then the mixture was separated by column chromatography (SiO ₂ , hexane : dichloromethane = 3:1). The white solid compound 49-2 (6.6 g, 36%) and the compound 74-1 (7.5 g, 41%).

Preparation of Compound 49

Compound 49-2 (4.8 g, 16.9 mmol), compound 1-4 (6.4 g, 16 mmol), Cu (1 g, 16.9 mmol), 18-crown-6-ether in a single-neck rbf (18-crown-6-ether) (550 mg, 1.69 mmol), a mixture of K ₂ CO ₃ (7 g, 50.7 mmol) and o- DCB (130 ml) at 180 ° C under nitrogen, refluxed for 60 hr, and transferred by distillation. In addition to 1,2-dichlorobenzene, the mixture was separated by column chromatography (SiO ₂ , hexane:dichloromethane = 2:1) to afford compound 49 as white solid (3.8 g, 37% ).

Synthesis Experimental Example (6): Preparation of Compound 50

Preparation of Compound 50-1

In a single neck rbf, 2-bromo-9,9-diphenyl-9H-fluorene (40 g, 100.67 mmol), diboron _{(51.1g, 201.34mmol), PdCl 2} (dppf) (2.2g, 3.02mmol), KOAc (29.6g, 302.01mmol) and DMF (400ml) the mixture was refluxed, the mixture was extracted with MC, dried MgSO _4, and then The DMF was removed by a vacuum rotary evaporator, and the obtained concentrate was separated by column chromatography (SiO ₂ , hexane : methylene chloride = 1:1) to afford white solid compound 50-1 (41 g, 91 %).

Preparation of Compound 50-2

In a single neck rbf, compound 50-1 (41 g, 92.26 mmol), 1-bromo-2-nitrobenzene (18.6 g, 92.26 mmol), Pd (PPh ₃ ) ₄ (10.6 g, 9.2 mmol), a mixture of K ₂ CO ₃ (26.6 g, 192.5 mmol) and THF (500 ml) / water (100 ml), refluxed at 110 ° C for 24 hr, after the aqueous layer was removed, then the organic layer was dried over MgSO _4, the organic layer was concentrated by column chromatography (SiO _2, hexane: dichloromethane = 1: 1) were separated to give a yellow solid compound 50-2 (26.3g, 65%).

Preparation of Compound 50-3

In a single neck rbf, compound 50-2 (26.3 g, 59.8 mmol), PPh ₃ (47 g, 179.4 mmol) and 1,2-dichlorobenzene (300 ml) were refluxed for 18 hours at 180 ° C under nitrogen atmosphere. The 1,2-dichlorobenzene is removed by distillation, and the remaining mixture is separated by column chromatography (SiO ₂ , hexane: dichloromethane = 3:1) to give a white solid compound 50- 3 (9g, 37%).

Preparation of compound 50

In a single neck rbf, compound 50-3 (5.1 g, 12.5 mmol), compound 1-4 (5 g, 12.5 mmol), Pd(OAc) ₂ (280 mg, 1.25 mmol), K ₃ PO ₄ (5.3 g) , 25 mmol), a mixture of P(t-Bu) ₃ (6 ml, 3.75 mmol) and toluene/water (120 ml / 30 ml) at 110 ° C under a nitrogen atmosphere, reflux for 24 hours, the reaction was extracted with MC, MgSO ₄ Drying, then concentrating, the concentrate was purified with MC/MeOH, filtered with ACN at high temperature, then dissolved in MC, and the crystals were filtered, and the crystals were filtered. Compound 50 (6.7 g, 73%) was obtained.

Synthesis Experimental Example (7): Preparation of Compound 59

Preparation of Compound 59-1

In a single neck rbf, 2-bromo-9,9-dimethyl-9H-fluorene (15 g, 54.91 mmol), benzo[b] a mixture of benzo[b]-thiophen-2-yltributylstannane (34.8 g, 82.3 mmol), Pd(PPh ₃ ) ₄ and toluene (350 ml) at 110 ° C in a nitrogen atmosphere. refluxed for 12 hours, concentrated in vacuo, the mixture to silica gel (silica gel) was filtered using CH ₂ Cl ₂ / MeOH to precipitate a compound, the compound was filtered with EtOH at elevated temperature, to give an opaque white solid compound 59-1 (15.7 g, 87%).

Preparation of Compound 59-2

The mixture solution of compound 59-1 (15.7g, 48mmol), AcOH (260ml) solution, HNO ₃ (6ml, 143mmol) and AcOH (260ml), under a nitrogen atmosphere, was slowly added to a single neck rbf then The mixture was heated to 60 ° C, followed by stirring for 30 minutes. Then, the mixture was cooled to normal temperature. After filtration, it was washed with distilled water (500 ml), and the obtained material was dried in a vacuum oven at 50 ° C for 12 hr to obtain a yellow solid compound 59-2. (16.1 g, 90%).

Preparation of Compound 59-3

In a single neck rbf, a mixture of compound 59-2 (16.1 g, 43 mmol), PPh ₃ (33.8 g, 129 mmol) and 1,2-dichlorobenzene (250 ml) was refluxed at 200 ° C under a nitrogen atmosphere. After the hour, the 1,2-dichlorobenzene was removed by distillation, and the mixture was separated by column chromatography (SiO ₂ , hexane: dichloromethane = 2:1) to give a pale reddish brown solid compound 59 -3 (3.0 g, 20%).

Preparation of Compound 59

Compound 59-3 (2 g, 5.85 mmol), Compound 1-4 (2.59 g, 6.45 mmol), Cu (374 mg, 5.85 mmol), 18-crown in a single-neck rbf 6-Ether (191 mg, 0.58 mmol), a mixture of K ₂ CO ₃ (1.6 g, 11.78 mmol) and o- DCB (25 ml) was refluxed at 180 ° C under a nitrogen atmosphere for 60 hours, and was removed by distillation. Dichlorobenzene, and the remaining mixture was separated by column chromatography (SiO ₂ , hexanes: methylene chloride = 3:1) to afford solid compound 59 (2.8 g, 72%).

Synthesis Experimental Example (8): Preparation of Compound 64

Preparation of Compound 64-1

(9,9-Dimethyl-9H-indol-2-yl)boronic acid (25.95 g, 109 mmol), 3-bromothia-naphthene (10 ml, 72.5 mmol), Pd (PPh _{3) 4} (4.189 g, 3.625 mmol), a mixture of K ₂ CO ₃ (30.06 g, 217.5 mmol), toluene (200 ml), ethanol (40 ml) and water (40 ml), and the mixture was stirred at reflux temperature for 4 hr. Concentration with a solvent, followed by extraction with EtOAc to give a solid, which was washed with methanol and filtered to afford white solid compound 64-1 (30 g, 87%).

Preparation of Compound 64-2

Compound 64-1 (21.3g, 65.3mmol), AcOH (1,260ml) added and the mixture HNO ₃ (5.9ml, 130mmol) and AcOH (12ml) in the nitrogen atmosphere was slowly added to a single neck rbf in Then, the mixture was heated to 60 ° C, stirred for 30 minutes, and the mixture was cooled to normal temperature. After filtration, it was washed with distilled water (400 ml), and the obtained material was dried in a vacuum oven at 50 ° C for 12 hr to obtain a bright yellow solid compound 64-2 ( 21.0 g, 95%).

Preparation of Compound 64-3

A mixture of compound 64-2 (29.5 g, 79.4 mmol), PPh ₃ (54.8 g, 198.5 mmol) and 1,2-dichlorobenzene (450 ml) in a single neck rbf at 180 ° C under nitrogen atmosphere. After refluxing for 4 hours, the 1,2-dichlorobenzene was removed by distillation, and the remaining mixture was separated by column chromatography (SiO ₂ , hexane: dichloromethane = 4:1) to give a solid compound. 64-3 (15g, 55%).

Preparation of compound 64

Compound 64-3 (4 g, 11.7 mmol), Compound 1-4 (5.18 g, 12.9 mmol), Cu (748 mg, 11.7 mmol), 18-crown in a single-neck rbf a mixture of 6-ether (383 mg, 1.17 mmol), K ₂ CO ₃ (3.2 g, 23.56 mmol) and o- DCB (50 ml) was refluxed for 60 hours at 180 ° C under nitrogen, and was removed by distillation. 2-Dichlorobenzene, and the remaining mixture was separated by column chromatography (SiO ₂ , hexane: methylene chloride = 3:1) to afford solid compound 64 (5.2 g, 67%).

Synthesis Experimental Example (9): Preparation of Compound 70

Preparation of Compound 70-1

In a single neck rbf, dibenzo[b,d]thiophen-4-yl boronic acid (23 g, 107.9 mmol), 3-bromobenzene [b ] 3-bromobenzo[b]thiophene (27 g, 118.7 mmol), K ₂ CO ₃ (10 g, 10.8 mmol), water (90 ml) and 1,4-dioxane (360 ml) The mixture was refluxed for 12 hours at 110 ° C. After concentration, the mixture was extracted with CH ₂ Cl ₂ (3×300 ml) and distilled water (150 ml). in CH ₂ Cl ₂ / MeOH and precipitated, filtered to give a brown solid may compound 70-1 (26.5g, 77%).

Preparation of Compound 70-2

Compound 70-1 (26g, 82.1mmol), AcOH (400ml) solution, HNO ₃ (10ml, 246.4mmol) and AcOH (400ml) a solution of a mixture in a nitrogen atmosphere, was slowly added to a single neck rbf then , heated to 60 ° C, stirred for 30 minutes, the mixture was cooled to room temperature, filtered, washed with distilled water (800 ml), the obtained material was dissolved in CH ₂ Cl ₂ (200 ml), the water layer was removed, and then reduced The organic layer was concentrated under pressure, and the concentrate was adsorbed first, and separated by column chromatography (SiO ₂ , hexane: dichloromethane = 3:1) to obtain a yellow solid compound 70-2 (19.6). g, 66%).

Preparation of Compound 70-3

A mixture of compound 70-2 (17.9 g, 49.6 mmol), PPh ₃ (38.7 g, 148.4 mmol) and 1,2-dichlorobenzene (500 ml) in a single neck rbf at 180 ° C under a nitrogen atmosphere. After refluxing for 12 hours, the 1,2-dichlorobenzene was removed by distillation, then the mixture was precipitated with CH ₂ Cl ₂ /MeOH and filtered, then chromatographic chromatography (SiO ₂ , hexane : dichloromethane = 2: 1) Separation gave opaque white solid compound 70-3 (10 g, 61%).

Preparation of Compound 70

Compound 70-3 (10 g, 30.35 mmol), Compound 1-4 (13.34 g, 33.38 mmol), Cu (1.9 mg, 30.35 mmol), 18-crown in a single-neck rbf a mixture of -6-ether (987 mg, 3.03 mmol), K ₂ CO ₃ (8.3 g, 60.7 mmol) and o- DCB (100 ml) was refluxed at 180 ° C under a nitrogen atmosphere for 60 hours, and was removed by distillation. 2-dichlorobenzene, and then by column chromatography analysis (of SiO _2, hexane: dichloromethane = 2: 1) to be isolated, can be obtained opaque white solid compound 70 (13.6g, 69%).

Synthesis Experimental Example (10): Preparation of Compound 73

Preparation of Compound 73-1

Sulfuric acid (1.4 ml, 0.1 eq) was slowly added to 1,2-dicyclohexanone (30.0 g, 1.0 eq), phenylhydrazine hydrochloride in a single neck rbf under a nitrogen atmosphere. A mixture of phenylhydrazine hydrochloride (77.37 g, 2.0 eq) and ethanol (1,000 ml) was then stirred at 60 ° C for 4 hr. The solution was cooled to room temperature and filtered to give a yellow brown solid. (69g, 93%).

Preparation of Compound 73-2

Compound 73-1 (68.9 g, 1.0 eq), acetic acid (700 ml) and trifluoroacetic acid (46.5 ml, 2.4 eq) were placed in a single neck rbf and then stirred at 100 ° C for 15 hr. The solution was cooled to room temperature, washed with acetic acid and hexanes and filtered to give an ivory solid compound 73-2 (27.3 g, 42%).

Preparation of Compound 73-3

Compound 73-2 (2.1 g, 1.0 eq), iodobenzene (2.5 g, 1.5 eq), Cu (0.312 g, 0.6 eq), 18- in a single neck rbf with nitrogen filling. crown-6 _{(0.433g, 0.2eq), K 2} CO 3 (3.397g, 3.0eq) with a mixture of 1,2-dichlorobenzene (20ml) was stirred for 16hr at the reflux temperature a, the solution was cooled to room The mixture was extracted with MC/water, concentrated, and separated by column chromatography (SiO ₂ , hexane: ethyl acetate = 10:1) to give white solid compound 73-3 (1.76). g, 64%).

Preparation of Compound 73

Compound 73-3 (1.7 g, 5.11 mmol), Compound 1-4 (2 g, 5.11 mmol), Cu (324 mg, 5.11 mmol), 18-crown in a single-neck rbf 6-ether (166 mg, 0.51 mmol), a mixture of K ₂ CO ₃ (1.4 g, 0.22 mmol) and o- DCB (10 ml) was refluxed for 60 hours at 180 ° C under nitrogen filling, and 1 was removed by distillation. 2-dichlorobenzene, and then by column chromatography analysis (of SiO _2, hexane: dichloromethane = 2: 1) to be isolated, can be obtained solid compound 73 (1.1g, 33%).

Synthesis Experimental Example (11): Preparation of Compound 74

Compound 74-1 (1 g, 3.53 mmol), Compound 1-4 (1.2 g, 3.53 mmol), Pd(OAc) ₂ (80 mg, 0.353 mmol), in a single-neck rbf, A mixture of K ₃ PO ₄ (1.4 g, 7.06 mmol), P(t-Bu) ₃ (1.5 ml, 1 mmol) and o- DCB (10 ml) was refluxed at 100 ° C for 24 hours, and the mixture was extracted with MC and used. dried MgSO _4, and then by column chromatography analysis (of SiO _2, hexane: dichloromethane = 2: 1) to be isolated, can be obtained solid compound 74 (1.35g, 64%).

Synthesis Experimental Example (12): Preparation of Compound 79

Preparation of Compound 79-1

In a rbf, diphenyl[b,d]furan-2-yl boronic acid (20 g, 94.33 mmol), 1-bromo-2-nitrobenzene A solution of (1-bromo-2-nitrobenze) (19 g, 94.33 mmol), K ₂ CO ₃ (26 g, 188 mmol), water (45 ml) and 1,4-dioxane (300 ml) was refluxed at 110 ° C. After concentrating, the mixture was extracted with CH ₂ Cl ₂ (3×200 ml) and distilled water (120 ml), filtered over silica gel, concentrated, and then applied to the column chromatography (SiO ₂ , hexane: dichloride Methane = 8:1) was isolated to give the ivory solid compound 79-1 (18.2 g, 67%).

Preparation of Compound 79-2

In a single neck rbf, a mixture of compound 79-1 (19 g, 65.6 mmol), PPh ₃ (51.6 g, 197 mmol) and 1,2-dichlorobenzene (400 ml) was refluxed at 180 ° C under nitrogen. After 12 hours, the 1,2-dichlorobenzene was removed by distillation, then the mixture was precipitated with CH ₂ Cl ₂ /MeOH and filtered, then applied to column chromatography (SiO ₂ , hexane : dichloromethane = 2:1) Separation gave the compound 79-2 (6.7 g, 39%) as white solid.

Preparation of Compound 79

Compound 79-2 (6.7 g, 26 mmol), Compound 1-4 (10.4 g, 26 mmol), Cu (1.6 g, 26 mmol), 18-crown-6 in a single-neck rbf a mixture of ether (847 mg, 2.6 mmol), K ₂ CO ₃ (7.1 g, 52 mmol) and o- DCB (100 ml) at 180 ° C under nitrogen, reflux for 48 hours, and 1, 2 by distillation. dichlorobenzene, and the resulting mixture to the column of chromatography (SiO _2, hexane: dichloromethane = 3: 1) to be separated, obtained as white solid compound 79 (7.2g, 48%).

Synthesis Experimental Example (13): Preparation of Compound 89

The synthesis method of the compound was the same as that of the preparation of the compound 49 except that the compound 3-4 of the synthesis example (3) was replaced by the compound 1-4 of the synthesis example (1).

Synthesis Experimental Example (14): Preparation of Compound 90

The synthesis method of the compound was the same as that of the preparation of the compound 50 except that the compound 3-4 of the synthesis example (3) was replaced by the compound 1-4 of the synthesis example (1).

Synthesis Experimental Example (15): Preparation of Compound 99

The synthesis method of the compound was the same as that of the preparation of the compound 60 except that the compound 3-4 of the synthesis example (3) was replaced by the compound 1-4 of the synthesis example (1).

Synthesis Experimental Example (16): Preparation of Compound 104

The synthesis method of the compound was the same as that of the preparation of the compound 64 except that the compound 3-4 of the synthesis example (3) was replaced by the compound 1-4 of the synthesis example (1).

Synthesis Experimental Example (17): Preparation of Compound 110

The synthesis method of the compound was the same as that of the preparation of the compound 70 except that the compound 3-4 of the synthesis example (3) was replaced by the compound 1-4 of the synthesis example (1).

Synthesis Experimental Example (18): Preparation of Compound 113

The synthesis method of the compound was the same as that of the preparation of the compound 73 except that the compound 3-4 of the synthesis example (3) was replaced by the compound 1-4 of the synthesis example (1).

Synthesis Experimental Example (19): Preparation of Compound 119

The synthesis method of the compound was the same as that of the preparation of the compound 79 except that the compound 3-4 of the synthesis example (3) was replaced by the compound 1-4 of the synthesis example (1).

Synthesis Experimental Example (20): Preparation of Compound 129

Preparation of Compound S9

Preparation of Compound S9-1

After dissolving 20 g (93 mmol, 1 eq.) of methyl-2-bromobenzoate in 180 ml of THF, 7.44 g of NaH was added, and the resulting mixture was stirred for 30 minutes. After the completion of the stirring, 11.17 g (93 mmol) was slowly added. 1 eq.) acetophenone, the resulting mixture was stirred at room temperature for 2 hr, and heated at 100 ° C for 16 hr. When the reaction was completed, the temperature was cooled to room temperature, and then the obtained product was sequentially subjected to ethyl acetate, 1N HCl. The NaHCO ₃ aqueous solution was extracted with water. After the extraction, the extract was separated and purified by column chromatography to obtain 25.6 g (90%) of S9-1.

Preparation of Compound S9-2

After dissolving 25.6 g (84 mmol, 1 eq.) of compound S9-1 in 160 ml of DMF, 6 ml (92.4 mmol, 1.1 eq.) of H ₂ NNH _{2 was added} . H ₂ O, the resulting mixture was stirred at room temperature for 6 hr, and when the reaction was completed, the obtained product was extracted with ethyl acetate and water. After extraction, the extract was separated and purified by column chromatography to obtain 20 g (79%) of S9-2.

Preparation of Compound S9-3

After dissolving 20 g (66 mmol, 1 eq.) of the compound S9-2 in 240 ml of DMF, 1.25 g (6.6 mmol, 0.1 eq.) of CuI and 14.8 g (80.4 mmol, 1.2 eq.) of 4-bromobenzaldehyde were added, and the mixture was obtained. Stir for 30 minutes. After the completion of the stirring, add 66 ml of NH ₃ . H ₂ O, and the resulting mixture was stirred at 100 ° C for 24 hr. When the reaction was completed, the obtained product was extracted with ethyl acetate and water. After extraction, the extract was separated and purified by column chromatography to obtain 15 g (56%) of S9-3.

Preparation of Compound S9

After 15 g (37 mmol, 1 eq.) of the compound S9-3 was dissolved in 60 ml of DMF, 1.25 g (6.6 mmol, 0.1 eq.) of CuI was added, and the resulting mixture was stirred at 100 ° C for 24 hr, and when the reaction was completed, the obtained product was obtained. Acetic acid Ethyl ester is extracted with water. After the extraction, the extract was separated and purified by column chromatography to obtain 10 g (80%) of S9.

Preparation of Compound 129

The synthesis method of this compound was the same as that of the preparation of the compound 49 except that the compound S9 was used instead of the compound 1-4 of the synthesis example (1).

Synthesis Experimental Example (21): Preparation of Compound 139

The synthesis method of the compound was the same as that of the compound 59 except that the compound S9 was used instead of the compound 1-4 of the synthesis example (1).

Synthesis Experimental Example (22): Preparation of Compound 144

The compound was synthesized in the same manner as the compound 64 except that the compound S9 was used instead of the compound 1-4 of the synthesis example (1).

The results of the compounds prepared in the same manner in the synthesis experimental examples and the confirmed synthesis thereof are shown in Table 5.

Test example 1

The highest occupied molecular orbital (HOMO), the lowest unoccupied molecular orbital (LUMO), and the band gap of Compound 16, Compound 26, Compound 49, Compound 50, Compound 89, and Compound 90 are used by the following methods. The CV measuring device (measured by Princeton Applied Research Inc., model: Parstat 2273) was measured, and the results are shown in Tables 7 to 12 below.

1. Preparation of electrolyte solution, standard solution and test solution

(1) Electrolyte solution: 3.3 g of tetrabutylammonium tetrafluoroborate was placed in a 100 ml volumetric flask, and methylene chloride was added to prepare a 100 ml electrolyte solution.

(2) Standard solution: Approximately 1 mg of NPB was placed in a 10 ml volumetric flask, and the electrolyte solution was added to prepare a 10 ml solution, which was then used as a standard solution.

(3) Test solution: Take a compound as a sample, weigh approximately 1 mg of the compound, place it in a 10 ml volumetric flask, and add the electrolyte to dissolve. The solution was made into a 10 ml solution, which was then used as a test solution.

2. Analysis conditions

3. CV measurement method

A 6 ml standard solution was prepared using NPB and the electrolyte solution.

A working electrode, a reference electrode and an auxiliary electrode are arranged.

Nitrogen gas was introduced into the solution for about 30 seconds, and then measurement was started.

When the measurement is completed, the electrodes are cleaned using MC and acetone, and then the prepared test solution is measured by the aforementioned measurement method.

4. Calculated equation

Homo=-5.5-(E _ox (test compound)-E _ox (NPB)) eV

Band gap (HOMO-LUMO)=1240/UV absorption limit (absorption edge)

Figures 4 and 5 show the E _ox values for Compound 16 derived from CV measurements.

Figures 6 and 7 show the E _ox values for Compound 26 derived from CV measurements.

Figures 8 and 9 show the E _ox values for compound 49 derived from CV measurements.

Figures 10 and 11 show the E _ox values derived from CV measurements for Compound 50.

Figures 12 and 13 show the E _ox values for Compound 89 derived from CV measurements.

Figures 14 and 15 show the E _ox values for compound 90 derived from CV measurements.

In Figures 4 to 15, the y-axis represents current (unit: A) and x The axis represents the potential (unit: V).

Meanwhile, the T1 values of the compounds 49, 50, 89 and 90 are shown in Table 13 below. The T1 value is derived from the low temperature peak wavelength values (PL nmax values). In particular, the T1 value was calculated using a Hitachi-F7000 (HITACHI-F7000), 2-methyltetrahydrofuran dilution at -196 ° C (77 K) and the formula [T1 (eV) = 1240 /PL is the shortest peak wavelength (nm)].

Meanwhile, FIG. 16 shows a UV measurement chart of Compound 16.

Figure 17 shows a PL measurement of Compound 16 at 263 nm.

Figure 18 shows a UV measurement of Compound 26.

Figure 19 shows a PL measurement of Compound 26 at 327 nm.

Figure 20 shows a LTPL (-78 °C) measurement chart of Compound 49.

Figure 21 shows a UV measurement of Compound 49.

Figure 22 shows a PL measurement of Compound 49 at 261 nm.

Figure 23 shows a LTPL (-78 °C) measurement chart of Compound 50.

Figure 24 shows a UV measurement of Compound 50.

Figure 25 shows a PL measurement of Compound 50 at 264 nm.

Figure 26 shows a LTPL (-78 °C) measurement chart of Compound 89.

Figure 27 shows a UV measurement of Compound 89.

Figure 28 shows a PL measurement of Compound 89 at 259 nm.

Figure 29 shows a LTPL (-78 °C) measurement plot of Compound 90.

Figure 30 shows a UV measurement of Compound 90.

Figure 31 shows a PL measurement of Compound 90 at 331 nm.

The y-axis and the x-axis of Figures 16 to 31 are intensity and wavelength (unit: nm), respectively.

Comparative Example 1: Manufacture of an OLED device

First, the glass of the transparent electrode ITO film for OLED (manufactured by Samsung-Corning Co., Ltd.) was ultrasonically washed with trichloroethylene, acetone, ethanol and distilled water in sequence, and then Isopropyl alcohol is washed.

Next, an ITO substrate is fixed to a substrate holder of a vacuum evaporation apparatus, and the vacuum evaporation apparatus is evacuated until a vacuum of 10 ^-7 torr, and then a layer of the following 4 is vapor deposited. 4',4"-tris(N,N-(2-naphthyl)-phenylamino)triphenylamine, 4,4',4"-tris(N,N-(2-naphthyl)-phenylamino)triphenyl amine, 2-TNATA), a 600 Å hole injection layer is applied to the ITO substrate.

Next, in another cavity of the vacuum evaporation apparatus, an electric current is passed, and the following N,N'-bis(α-naphthyl)-N,N'-diphenyl-4,4'-diamine is evaporated. (N, N'-bis (α-naphthyl)-N, N'-diphenyl-4, 4'-diamine, NPB) compound, a hole transport layer having a thickness of 250 Å is formed on the hole injection layer.

After the hole injection layer and the hole transport layer are formed, one of the light-emitting layers is formed thereon. The following main illuminant material (α-AND) as a luminescent material is placed in one of the chambers of the vacuum evaporation apparatus, and the following dopant (BD1) is placed in the other chamber.

Then, the two cavities are simultaneously heated, and the dopant is deposited at a deposition rate ratio (main illuminant material: dopant = 95:5) of 5 wt%, and a thickness of 200 Å is deposited on the hole transport layer. Material layer.

Next, the following tris(8-hydroxyquinoline) aluminum (III), Alq3, was deposited as an electron transport layer to a thickness of 200 Å.

Then, lithium fluoride (LiF), which is an electron injecting layer, is deposited to a thickness of 10 Å. In addition, an OLED is fabricated to deposit an aluminum cathode having a thickness of 1200 Å.

At this time, all of the organic compounds used to produce the OLED device were subjected to vacuum-sublimed and purified at 10 ^-6 to 10 ^-8 Torr.

Example 1: Manufacture of OLED devices

The OLED was produced in the same manner as in the comparative example except that the prepared compound 1 to 38 was used instead of the tris(8-hydroxyquinoline)aluminum (III) used as the electron transport layer material in the comparative example.

Test Example 2: Evaluation of OLED characteristics

The OLED manufactured above was measured for driving voltage (Op.V) and power efficiency (cd/A) at 1000 cd/m ² , and the time when the efficiency was reduced to 50%, as shown in Table 14 below.

Comparative Example 2: Manufacture of an OLED device

The glass of the transparent electrode ITO film for OLED (manufactured by Samsung-Corning Co., Ltd.) was ultrasonically washed with trichloroethylene, acetone, ethanol and distilled water in sequence, and then washed with isopropyl alcohol.

Next, an ITO substrate was fixed to the substrate holder of a vacuum evaporation apparatus, and then the following 4,4',4"-tris(N,N-(2-naphthyl)-anilino)triphenylamine (2- TNATA), placed in one of the chambers of the vacuum evaporation apparatus.

Then, the cavity is evacuated until 10 ^-6 torr, and then a current is applied to evaporate 2TNATA, and a hole injection layer having a thickness of 600 Å is deposited on the ITO substrate. The following N,N'-bis(α-naphthyl)-N,N'-diphenyl-4,4'-diamine (NPB) is placed in another chamber of the vacuum evaporation apparatus, A current is applied to the cavity, and the compound is evaporated to form a hole transport layer having a thickness of 300 Å deposited on the hole injection layer.

After the hole injection layer and the hole transport layer are formed, a green phosphorescent material having the following structure is deposited thereon as a light-emitting layer. In a cavity of the vacuum evaporation apparatus, 4,4'-bis(carbazol-9-yl)biphenyl (CBP) is regarded as a The green light-emitting main illuminant material is evaporated to a thickness of 350 Å, and at the same time, tris(2-phenylpyridine)iridium(III), Ir(ppy) ₃ ) is vapor-deposited together. The number is about 10% of the number of the main illuminant materials.

Next, the following 2,9-dimethyl-4,7-diphenyl-1,10-morpholine (2,9-dimethyl-4,7-diphenyl-1) was deposited as a hole barrier material. , 10-phenanthroline, BCP), 50 Å thick, and the following tris(8-hydroxy-quinolinato)aluminum (Alq ₃ ) deposited as an electron transport layer, 200 Å thick.

Then, lithium fluoride (LiF) was deposited to a thickness of 10 Å to serve as an electron injecting layer, and in addition, an OLED-based aluminum cathode having a thickness of 1000 Å was deposited.

At this time, all of the organic compounds used to produce the OLED device were subjected to vacuum-sublimed and purified at 10 ^-6 to 10 ^-8 Torr.

[Example 2]

The apparatus produced using other materials used the same method as that used in Comparative Example 2 except that the material of the following Table 15 was used instead of CBP as the green light-emitting layer.

Test Example 3: Evaluation of OLED characteristics

The OLED manufactured above was measured for driving voltage (Op.V) and power efficiency (cd/A) at 1000 cd/m ² , and the time when the efficiency was reduced to 50%, as shown in Table 15 below.

The above-mentioned embodiments are merely examples for convenience of description, and the scope of the claims is intended to be limited to the above embodiments.

100‧‧‧Substrate

200‧‧‧Anode

300‧‧‧ organic material layer

400‧‧‧ cathode

Claims (18)

A compound represented by the following chemical formula 1: Wherein, in Chemical Formula 1, R ₁ is a C ₆ to C ₆₀ monocyclic or polycyclic substituted or unsubstituted aryl group or a C ₂ to C ₆₀ monocyclic or polycyclic ring substituted or unsubstituted a nitrogen-containing heteroaryl group; R ₂ is a linear or branched unsubstituted alkyl group of C ₁ to C ₆₀ or a C ₆ to C ₆₀ monocyclic or polycyclic substituted or unsubstituted aromatic group; And R ₃ to R ₇ are the same or different from each other, and are each independently selected from a linear or branched alkyl group which is substituted or unsubstituted by hydrogen, C ₁ to C ₆₀ , and a linear chain of C ₂ to C ₆₀ Or a branched or unsubstituted alkenyl group, a C ₂ to C ₆₀ linear or branched substituted or unsubstituted alkynyl group, a C ₃ to C ₆₀ monocyclic or polycyclic ring substituted or not a group consisting of a substituted cycloalkyl group, a C ₆ to C ₆₀ monocyclic or polycyclic substituted or unsubstituted aryl group, and a substituted or unsubstituted C ₁₀ to C ₆₀ spiro group . The compound of claim 1, wherein in Chemical Formula 1, R ₁ comprises an aza-containing heteroaryl group. The compound according to claim 1, wherein, in Chemical Formula 1, R ₁ is a substituted or unsubstituted nitrogen-containing heteroaryl group or a substituted or unsubstituted nitrogen-containing monocyclic heteroaryl group. Substituted aromatic group. The compound according to claim 1, wherein, in Chemical Formula 1, R ₁ comprises a nitrogen-containing monocyclic heteroaryl group, and the nitrogen-containing monocyclic heteroaryl group is a pyridyl group or a pyrimidine group. Or a triazine group. The compound of claim 1, wherein the chemical formula 1 is represented by the following chemical formula 2: Wherein, in Chemical Formula 2, L is a C ₆ to C ₆₀ monocyclic or polycyclic substituted or unsubstituted arylene; Het is a C ₂ to C ₆₀ monocyclic or polycyclic substituted or unsubstituted The nitrogen-containing heteroaromatic group; n is an integer of 0 to 2 and p is an integer of 1 or 2; and R ₂ to R ₇ are the same as defined in Chemical Formula 1. The compound according to claim 1, wherein the chemical formula 1 is represented by the following chemical formula 3: [Chemical Formula 3] Wherein, in Chemical Formula 3, R ₈ is a C ₆ to C ₆₀ monocyclic or polycyclic substituted or unsubstituted aromatic group or a C ₂ to C ₆₀ monocyclic or polycyclic substituted or unsubstituted one Azaheteroaryl; and m is an integer from 0 to 9; L is a C ₆ to C ₆₀ monocyclic or polycyclic substituted or unsubstituted arylene; n is an integer from 0 to 2; _{The 2} to R ₇ systems are the same as defined in Chemical Formula 1. The compound according to claim 1, wherein the chemical formula 1 is represented by the following chemical formula 4: Wherein, in Chemical Formula 4, X1 and X2 are a C ₆ to C ₆₀ monocyclic or polycyclic substituted or unsubstituted aromatic hydrocarbon ring or a C ₂ to C ₆₀ monocyclic or polycyclic ring substituted or not Substituted aromatic heterocyclic ring; L series - C ₆ to C ₆₀ monocyclic or polycyclic substituted or unsubstituted arylene; n is an integer from 0 to 2; and R ₂ to R ₇ are related to the chemical formula The definition in 1 is the same. The compound of claim 7, wherein the Is selected from the following structural formula: In the formulas, Y ₁ to Y ₆ are each CRR ' , NR, S or O; Z ₁ to Z ₃ are each S or O; and R and R' are the same or different from each other, and each is hydrogen, a C ₁ to C ₆₀ linear or branched substituted or unsubstituted alkyl group or a C ₆ to C ₆₀ monocyclic or polycyclic substituted or unsubstituted aromatic group. The compound according to claim 1, wherein, in Chemical Formula 1, R ₂ is a C ₁ to C ₂₀ linear or branched unsubstituted alkyl group or a C ₆ to C ₂₀ monocyclic or poly A substituted or unsubstituted aromatic group. The compound according to claim 1, wherein, in Chemical Formula 1, R ₃ to R ₇ are each independently a hydrogen, a C ₁ to C ₆₀ linear or branched substituted or unsubstituted alkyl group. Or a C ₆ to C ₆₀ monocyclic or polycyclic substituted or unsubstituted aryl group. The compound according to claim 1, wherein, in Chemical Formula 1, R ₃ to R ₇ are each independently hydrogen. The compound of claim 1, wherein the compound of the formula 1 is selected from the group consisting of the following compounds: An organic light-emitting device comprising: an anode; a cathode; a layer containing more than one layer of organic material sandwiched between the anode and the cathode; wherein one or more layers of the organic material layer are included in the first to The compound of the chemical formula 1 according to any one of the 12 items. The organic light-emitting device according to claim 13, wherein the organic material layer containing the compound of the chemical formula 1 is one or more layers selected from the group consisting of a hole injection layer, a hole transport layer, a light-emitting layer, an electron transport layer, and an electron. A group of injection layers. The organic light-emitting device according to claim 13, wherein the organic material layer containing the compound of the chemical formula 1 is an electron transport layer. The organic light-emitting device according to claim 13, wherein the organic material layer containing the compound of the chemical formula 1 is a light-emitting layer. The organic light-emitting device of claim 16, wherein the light-emitting layer further comprises a light-emitting dopant. The organic light-emitting device of claim 16, further comprising: a hole barrier layer interposed between the light-emitting layer and the cathode.