KR101897044B1 - Organic metal compounds and organic light emitting diodes comprising the same - Google Patents

Abstract

The present invention relates to a novel organometallic compound represented by the following formula (1) and an organic electroluminescent device including the same, wherein the organic electroluminescent device comprising the organometallic compound according to the present invention is characterized in that Thermal characteristics and luminous efficiency are excellent.
[Chemical Formula 1]

Description

TECHNICAL FIELD The present invention relates to an organic metal compound and an organic electroluminescent device including the organic metal compound,

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an organic metal compound and an organic electroluminescent device including the organic metal compound. More particularly, the present invention relates to an organic metal compound having excellent thermal characteristics and luminous efficiency, and an organic electroluminescent device including the same.

In recent years, the demand for a flat display device having a small space occupation has been increasing due to the enlargement of a display device. The liquid crystal display, which is a typical flat display device, has an advantage of being lighter than a conventional CRT (cathode ray tube) angle is limited and a back light is necessarily required. On the other hand, an organic light emitting diode (OLED), which is a new flat display device, is a display using a self-luminous phenomenon and has a wide viewing angle and can be made thinner and thinner than a liquid crystal display, And in recent years, application to a full-color display or illumination is expected.

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

A material used as an organic material layer in an organic electroluminescent device can be classified into a light emitting material and a charge transporting material such as a hole injecting material, a hole transporting material, an electron transporting material, and an electron injecting material depending on functions. The light emitting material may be classified into a polymer type and a low molecular type depending on the molecular weight and may be classified into a fluorescent material derived from singlet excited state of electrons and a phosphorescent material derived from the triplet excited state of electrons according to an emission mechanism . Further, the light emitting material can be classified into blue, green, and red light emitting materials and yellow and orange light emitting materials required to realize better natural color depending on the luminescent color.

On the other hand, when only one material is used as a light emitting material, there arises a problem that the maximum light emission wavelength shifts to a long wavelength due to intermolecular interaction, the color purity decreases, or the efficiency of the device decreases due to the light emission attenuating effect. A host-dopant system can be used as a light-emitting material in order to increase the light-emitting efficiency through the light-emitting layer.

When the dopant having a smaller energy band gap than the host forming the light emitting layer is mixed with a small amount of the light emitting layer, the excitons generated in the light emitting layer are transported to the dopant to emit light with high efficiency. At this time, since the wavelength of the host is shifted to the wavelength band of the dopant, light of a desired wavelength can be obtained depending on the type of dopant used.

In order for the organic electroluminescent device to sufficiently exhibit the above-described excellent characteristics, materials constituting the organic material layer in the device, such as a hole injecting material, a hole transporting material, a light emitting material, an electron transporting material, and an electron injecting material are supported by a stable and efficient material However, the development of a stable and efficient organic material layer material for an organic electroluminescence device has not been sufficiently developed yet. Therefore, there is a continuing need in the art for the development of new materials.

The principle of luminescence in a light emitting material is that excitons (excitons) are formed by the combination of electrons and holes injected from both electrodes. In this case, fluorescence in singlet excitons and phosphorescence in triplet excitons are involved. A phosphorescent material using a triplet exciton having a generation probability of 75% exhibits a luminous efficiency higher than that of a fluorescent material using a singlet exciton having a generation probability of 25%.

High efficiency phosphors that can be applied to organic electroluminescent devices are very limited. In molecular structures that can easily emit phosphorescence, Ir, Pt, Eu, and Tb are used as metal complexes containing a metal having a large atomic number, , Re, Rh, Os, and the like, and the luminescence characteristics are determined depending on the type of the ligand. However, since the luminance is low and the stability of the material is low, the application to practical devices is limited and researches on new luminescent materials have been actively conducted, and development of materials having excellent phosphorescent luminescent efficiency has been demanded.

The first technical problem to be solved by the present invention is to provide an organometallic compound having excellent thermal properties and high luminous efficiency.

A second object of the present invention is to provide an organic electroluminescent device including the organometallic compound.

In order to achieve the first technical object, the present invention provides an organometallic compound represented by the following Chemical Formula 1.

[Chemical Formula 1]

In the above formula (1)

R and Z are each independently selected from the group consisting of hydrogen, deuterium, cyano, halogen, hydroxy, nitro, alkyl of 1-40 carbon atoms, alkoxy of 1-40 carbon atoms, alkylamino of 1-40 carbon atoms, An aryloxy group having 3 to 40 carbon atoms, an arylamino group having 3 to 40 carbon atoms, an alkylsilyl group having 1 to 40 carbon atoms, an arylsilyl group having 6 to 40 carbon atoms, an aryl group having 6 to 40 carbon atoms, 40 heteroaryl groups, germanium groups, phosphorus, and boron,

A, B, C, D and E are each independently a substituted or unsubstituted aromatic ring, a substituted or unsubstituted heterocyclic ring,

Wherein X is carbon or nitrogen, at least two of which contain nitrogen coordinating to the platinum metal,

G is a chemical bond or an alkylene of 1 to 4 carbon atoms which may be substituted with (R-Z1) n,

Each of n and i is independently an integer of 0 to 40, and when n and i are 2 or more, plural R and Z are the same or different,

M is an integer of 0 or 1,

In the above formula (1), adjacent functional groups may combine with each other to form a saturated or unsaturated ring, or a saturated or unsaturated ring having a hetero atom.

According to an embodiment of the present invention, the formula 1 may be more specifically selected from the group consisting of the following formulas (2) to (17).

[Chemical Formula 2] < EMI ID =

[Chemical Formula 7] [Chemical Formula 8] [Chemical Formula 9]

[Chemical Formula 11] [Chemical Formula 12] [Chemical Formula 13]

[Chemical Formula 14] [Chemical Formula 15]

Wherein R, Z, A, B, C, D, E, X, G, n, m and i are as defined in the above formula (1).

In order to achieve the second technical object of the present invention,

Anode; Cathode; And a layer interposed between the anode and the cathode and including an organometallic compound represented by the formula (1).

The organic electroluminescent device including the organic metal compound represented by Formula 1 according to the present invention in the organic material layer is very useful for display and illumination because of its excellent thermal characteristics and excellent luminous efficiency.

1 is a schematic view of an organic electroluminescent device according to one embodiment of the present invention.
FIG. 2 is a diagram showing TGA and DSC of Formula 19 according to an embodiment of the present invention. FIG.
FIG. 3 is a graph showing TGA and DSC of Formula 20 according to an embodiment of the present invention. FIG.
4 is a graph showing TGA and DSC of Formula 23 according to an embodiment of the present invention.
5 is a graph showing TGA and DSC of [Formula 190] according to an embodiment of the present invention.
6 is a graph showing EL spectra of [Formula 19] and Comparative Example 1 (BTPIr) according to an embodiment of the present invention.

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

Specific examples of the alkyl group include a methyl group, ethyl group, propyl group, isobutyl group, sec-butyl group, tert-butyl group, pentyl group, iso-amyl group, hexyl group, heptyl group, octyl group, stearyl group, trichloro Methyl group, trifluoromethyl group and the like, and at least one hydrogen atom of the alkyl group may be substituted with a substituent selected from the group consisting of a deuterium atom, a halogen atom, a hydroxy group, a nitro group, a cyano group, a trifluoromethyl group, a silyl group ), A substituted or unsubstituted amino group (-NH ₂ , -NH (R), -N (R ') (R ") wherein R, R' and R" are each independently an alkyl group having 1 to 24 carbon atoms A sulfonyl group, a phosphoric acid group, an alkyl group having 1 to 24 carbon atoms, a halogenated alkyl group having 1 to 24 carbon atoms, a halogenated alkyl group having 2 to 24 carbon atoms (e.g., an alkyl group having 1 to 24 carbon atoms) An alkenyl group, an alkynyl group having 2 to 24 carbon atoms, a heteroalkyl group having 1 to 24 carbon atoms, It may be substituted with a heteroaryl group of a small number of 5 to 24 aryl group, C 6 -C 24 aryl group, a C 3 -C 24 heteroaryl group, or having a carbon number of 3 to 24.

Specific examples of the alkoxy group include a methoxy group, an ethoxy group, a propoxy group, an isobutyloxy group, a sec-butyloxy group, a pentyloxy group, an isoamyloxy group and a hexyloxy group. May be substituted with the same substituent as the case.

Specific examples of the aryl group include a phenyl group, a 2-methylphenyl group, a 3-methylphenyl group, a 4-methylphenyl group, a 4-ethylphenyl group, an o- Naphthyl group, 1-methylnaphthyl group, 2-methylnaphthyl group, anthryl group, phenanthryl group, 2-methylphenyl group, , A pyrenyl group, a fluorenyl group, a tetrahydronaphthyl group and the like, and they can be substituted with the same substituents as in the case of the alkyl group. For example, "arylamino group" when it is substituted with an amino group, "arylsilyl group" when it is substituted with a silyl group, and "aryloxy group" when it is substituted with an oxy group.

Specific examples of the heteroaryl group include pyridinyl, pyrimidinyl, triazinyl, indolinyl, quinolinyl, pyrrolidinyl, piperidinyl, morpholinyl, piperidinyl, A thiazolyl group, a benzothiazolyl group, a triazolyl group, an imidazolyl group, a benzoimidazole group and the like, and one of the heteroaryl groups The above hydrogen atom may be substituted with the same substituent as in the case of the alkyl group.

The arylamino group may be at least one selected from the group consisting of a diphenylamine group, a phenylnaphthylamine group, a phenylbiphenylamine group, a naphthylbiphenylamine group, a dinaphthylamine group, a diphenylamine group, a dianthracenylamine group, Methyl-biphenylamine group, a 9-methyl-anthracenylamine group, a ditolylamine group, a phenyltolylamine group, a triphenylaminophenylamine group, a phenylbiphenylamino group, Phenylamine group, naphthylphenylaminophenylbiphenylamine group, and the like, but are not limited thereto.

The scope of the present invention is not limited thereby, but the organometallic compound represented by the formula (1) may be more specifically selected from the group consisting of the following formulas (18) to (201).

[Chemical Formula 20] [Chemical Formula 20]

[Chemical Formula 22] [Chemical Formula 23] [Chemical Formula 25]

[Chemical Formula 28] [Chemical Formula 28]

[Chemical Formula 32] [Chemical Formula 32]

[Chemical Formula 35] [Chemical Formula 35]

[Chemical Formula 40] [Chemical Formula 40] [Chemical Formula 40]

[Chemical Formula 43] [Chemical Formula 44] [Chemical Formula 45]

[Chemical Formula 48] [Chemical Formula 48] [Chemical Formula 48]

[Chemical Formula 51] [Chemical Formula 52] [Chemical Formula 53]

[Chemical Formula 55] [Chemical Formula 55] [Chemical Formula 55]

[Chemical Formula 60] [Chemical Formula 61]

[Chemical Formula 62] [Chemical Formula 65] [Chemical Formula 65]

[Chemical Formula 67] [Chemical Formula 68] [Chemical Formula 69]

[Chemical Formula 71] [Chemical Formula 72] [Chemical Formula 73]

[Chemical Formula 75] [Chemical Formula 76] [Chemical Formula 77]

[Formula 79] [Formula 80] [Formula 81]

[Chemical Formula 82]

[Chemical Formula 88] [Chemical Formula 88] [Chemical Formula 89]

[Chemical Formula 91] [Chemical Formula 92] [Chemical Formula 93]

[Chemical Formula 95] [Chemical Formula 96] [Chemical Formula 97]

[Chemical Formula 100] [Chemical Formula 100]

[Formula 103] [Formula 103]

[Chemical Formula 10] [Chemical Formula 10] [Chemical Formula 10] [Chemical Formula 10]

[Formula 110] [Formula 111] [Formula 112] [Formula 113]

[Chemical Formula 115]

[Chemical Formula 120] [Chemical Formula 120] [Chemical Formula 120]

[Formula 124] [Formula 124] [Formula 125]

[Formula 126] < EMI ID = 129.1 >

[Formula 130] < EMI ID = 131.0 >

[Formula 135] [Formula 135] [Formula 137]

[Chemical Formula 140] [Chemical Formula 140] [Chemical Formula 140]

[Chemical Formula 144] [Chemical Formula 144] [Chemical Formula 145]

[Chemical Formula 146] [Chemical Formula 148] [Chemical Formula 149]

[Formula 15] [Formula 15] [Formula 15] [Formula 15]

[Chemical Formula 155] [Chemical Formula 156] [Chemical Formula 157]

[Formula 15] [Formula 15] [Formula 15] [Formula 15] [Formula 15]

[166] [165] [165]

[Formula 166] [Formula 169] [Formula 169]

[173] [173] [173]

[Formula 177] [Formula 177] [Formula 177]

[Formula 181] [Formula 181] [Formula 181] [Formula 181]

[Formula 182] [Formula 184] [Formula 184]

[Formula 188] [Formula 188] [Formula 189]

[Formula 19] [Formula 19] [Formula 193] [Formula 193]

[Formula 19] [Formula 19] [Formula 19] [Formula 19] [Formula 19]

[201] [201] [201]

Further, the present invention provides an organic electroluminescent device comprising an anode, a cathode, and an organometallic compound interposed between the anode and the cathode and represented by the formula (1).

Further, the present invention provides an organic electroluminescent device comprising an anode, a cathode, and an organometallic compound interposed between the anode and the cathode and represented by the formula (1).

In this case, the layer containing the organic metal compound is preferably a light emitting layer between the anode and the cathode, and a hole injecting layer, a hole transporting layer, an electron blocking layer, a hole blocking layer, an electron transporting layer, ≪ RTI ID = 0.0 > and / or < / RTI >

As a specific example, a hole transport layer (HTL) may be further stacked, and an electron transport layer (ETL) may be further stacked between the cathode and the organic emission layer. An electron donor molecule having a low ionization potential is used as the material of the hole transport layer. A diamine, triamine or tetraamine derivative having a basic skeleton of triphenylamine is used as the hole transport layer. It is widely used.

In the present invention, the material for 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'- , 1-biphenyl] -4,4'-diamine (TPD) or N, N'-di (naphthalene-1-yl) -N, N'-diphenylbenzidine (a-NPD).

A hole injection layer (HIL) may be additionally formed on the lower portion of the hole transport layer. The material for the hole injection layer is not particularly limited as long as it is commonly used in the art. For example, (4,4 ', 4 "-tri (N-carbazolyl) triphenylamine) or m-MTDATA (4,4', 4" -tris- (3-methylphenyl phenylamino) triphenylamine) and the like can be used.

In addition, the electron transport layer used in the organic electroluminescent device according to the present invention can transport electrons supplied from the cathode smoothly to the organic luminescent layer and inhibit the movement of holes which are not bonded in the organic luminescent layer, .

The material of the electron transport layer is not particularly limited as long as it is commonly used in the art. For example, oxadiazole derivative PBD, BMD, BND or Alq ₃ can be used.

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

The organic electroluminescent device according to the present invention can be used for a display device, a display device, an element for a single color or a white light, and the like.

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

The organic electroluminescent device of the present invention and its manufacturing method will be described with reference to FIG. First, an anode electrode material is coated on the substrate 10 to form an anode 20. Here, as the substrate 10, an organic substrate or a transparent plastic substrate which is excellent in transparency, surface smoothness, ease of handling, and waterproofness is used as a substrate used in a conventional organic EL device. As the material for the anode electrode, indium tin oxide (ITO), indium zinc oxide (IZO), tin oxide (SnO ₂ ), zinc oxide (ZnO) and the like which are transparent and excellent in conductivity are used.

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

A hole blocking layer (not shown) is selectively formed on the organic light emitting layer 50 by a vacuum deposition method or a spin coating method to form a thin film on the organic light emitting layer 50 can do. In the case where holes are injected into the cathode through the organic light-emitting layer, the lifetime and the efficiency of the device are reduced, and thus the hole blocking layer plays a role of preventing such a problem by using a material having a very low HOMO (Highest Occupied Molecular Orbital) level . In this case, the hole blocking material to be used is not particularly limited, but it is required to have an ionization potential higher than that of the light emitting compound while having electron transporting ability. Typically, BAlq, BCP, TPBI and the like can be used.

After the electron transport layer 60 is deposited on the hole blocking layer by a vacuum deposition method or a spin coating method, an electron injection layer 70 is formed, and a cathode forming metal is deposited on the electron injection layer 70 in a vacuum heat- And the cathode 80 is formed by vapor deposition to complete the organic EL device. Here, as the metal for forming the cathode, lithium, magnesium, aluminum, aluminum-lithium, calcium, magnesium-magnesium, Mg-Ag), and a transmissive cathode using ITO or IZO can be used to obtain a top light-emitting device.

According to another embodiment of the present invention, at least one layer selected from the hole injecting layer, the hole transporting layer, the electron blocking layer, the light emitting layer, the hole blocking layer, the electron transporting layer and the electron injecting layer is formed by a single molecular deposition method or a solution process And the organic electroluminescent device according to the present invention can be used for a display device, a display device, and a monochromatic or white illumination device.

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

<Examples>

Synthesis Example 1 Synthesis of Compound Represented by Formula 19

(1) Synthesis of Compound Represented by Formula (1-a)

A compound represented by the formula (1-a) was synthesized by the following reaction scheme (1).

[Reaction Scheme 1]

[Chemical Formula 1-a]

To a 500 ml round bottom flask was added 20.0 g (127 mmol) of 3-bromophenylboronic acid, 25.4 g (127 mmol) of 2-bromopyridine, 2.93 g (2.53 mmol) of tetrakistriphenylphosphine palladium, 40 ml of ethanol, 40 ml of ethanol and 200 ml of toluene were added and the mixture was refluxed for 12 hours. The temperature was lowered to room temperature and the reaction was terminated and filtered. The organic layer was extracted with diethyl ether and water, concentrated under reduced pressure, and then subjected to column purification (19.3 g, yield 65%) using ethyl acetate and n-hexane as eluent.

(2) Synthesis of Compound Represented by Formula (1-b)

[Chemical Formula 1-b] was synthesized by the following Reaction Scheme 2.

[Reaction Scheme 2]

[Chemical Formula 1-b]

To a 500 ml round bottom flask was added 20.0 g (116 mmol) of 3-bromoaniline, 85.6 g (233 mmol) of 2- (tributylstannyl) pyridine, 1.34 g (116 mmol) of tetrakistriphenylphosphine palladium, ml, and refluxed for 12 hours. After completion of the reaction, the temperature was cooled down to room temperature. The organic layer was extracted with ethyl acetate and water and concentrated under reduced pressure. Column purification was carried out using ethyl acetate and n-hexane as eluent. (12.7 g, 64% yield)

(3) Synthesis of Compound Represented by Formula (1-c)

The compound represented by the formula (1-c) was synthesized by the following reaction scheme [3].

[Reaction Scheme 3]

[Chemical Formula 1-c]

15.0 g (64.1 mmol) of the compound represented by the formula (1-a) obtained from the above-mentioned scheme 1 and 10.9 g of the compound represented by the formula 1-b obtained from the above scheme 2 _{64.1 mmol), Pd 2 (dba} ) 3 1.17 g (1.28 mmol), tri (tert-butyl) phosphine 0.260 g (1.28 mmol), sodium tert-butoxide, 12.3 g (128 mmol), ml of toluene 200 ml 20 Lt; / RTI &gt; After completion of the reaction, the temperature was lowered to room temperature and filtered. The organic layer was concentrated under reduced pressure, and then subjected to column purification using 14.9 g (yield: 72.0%) of ethyl acetate and n-hexane as eluent.

(4) Synthesis of a compound represented by the formula (1-d)

[Chemical Formula 1-d] was synthesized by the following Reaction Scheme 4.

[Reaction Scheme 4]

[Chemical formula 1-d]

10.0 g (43.1 mmol) of 1-iodo-3,5-dimethylbenzene was added to a 500 mL round bottom flask and dissolved in 200 mL of n-hexane. After cooling to -78 ° C, 27 ml of a normal butyl lithium solution (1.6 M in n-hexane) was slowly added dropwise under nitrogen. The temperature was raised to room temperature and stirred for 6 hours. The temperature was lowered to 0 &lt; 0 &gt; C and trimethylsilyltrifluoromethanesulfonic acid (0.5 M in THF) was slowly added dropwise. After completion of the reaction, the organic layer was extracted with n-hexane and water and concentrated under reduced pressure (5.80 g, yield 75%).

(5) Synthesis of Compound Represented by Formula (1-e)

[Chemical Formula 1-e] was synthesized by the following Reaction Scheme 5.

[Reaction Scheme 5]

[Formula 1-e]

10.0 g (56.1 mmol) of the compound represented by the formula (1-d) obtained in the above Reaction Scheme 4 and 3.13 g of the iron powder were dissolved in 75 ml of chloroform in a 500 ml round bottom flask. The reaction solution was cooled to 0 ° C, and 9.86 g (61.7 mmol) of bromine was slowly added dropwise to 25 ml of chloroform. After dropwise addition, the temperature was raised to room temperature and stirred for 2 hours. After completion of the reaction, the reaction solution was cooled, and an aqueous solution of sodium hydroxide was added slowly. The organic layer was extracted, concentrated under reduced pressure, and recrystallized from ethanol. (13.1 g, 91% yield)

(6) Synthesis of a compound represented by the formula (1-f)

The compound represented by the formula 1-f was synthesized according to the following Reaction Scheme 6.

[Reaction Scheme 6]

[Chemical Formula 1-f]

20.0 g (77.7 mmol) of the compound represented by the formula [1-e] obtained from the above-mentioned scheme 5 was dissolved in 200 ml of tert-butyl alcohol and water 1: 1 in a 500 ml round bottom flask. 25.8 g (163 mmol) of potassium permanganate was added to the reaction mixture, and the mixture was refluxed and stirred for 1 hour. After the temperature was lowered to room temperature, potassium permanganate (25.8 g, 163 mmol) was added and the mixture was refluxed for 18 hours. After completion of the reaction, the temperature was lowered to room temperature, filtered using Celite, and concentrated to 1/3 of the reaction product. The reaction was acidified by adding hydrochloric acid, precipitated and filtered. The resulting solid was dissolved in an aqueous solution of sodium hydrogencarbonate, and the aqueous layer was washed with diethyl ether. The aqueous layer was acidified with hydrochloric acid and the resulting precipitate was filtered (22.9 g, yield 93%).

(7) Synthesis of a compound represented by the formula (1-g)

A compound represented by the formula (1-g) was synthesized by the following reaction scheme (7).

[Reaction Scheme 7]

[Formula 1-g]

In a 1 L round bottom flask, 50.0 g (158 mmol) of the compound represented by the formula (1-f) obtained from the above scheme 6 was dissolved in 350 ml of methanol, 12 ml of sulfuric acid was added and the mixture was refluxed for 18 hours. After completion of the reaction, the temperature was lowered to room temperature and neutralized with aqueous sodium hydroxide solution. The mixture was extracted with diethyl ether. The organic layer was concentrated under reduced pressure and recrystallized using n-hexane. (50.6 g, yield 93%).

(8) Synthesis of Compound Represented by Formula (1-h)

[Chemical Formula 1-h] was synthesized by the following Reaction Scheme 8.

[Reaction Scheme 8]

[Chemical Formula 1-h]

20.0 g (61.8 mmol) of the compound represented by the formula (1-c) obtained from the scheme 3 and 23.5 g (68.0 mmol) of the compound represented by the formula 1-g obtained from the scheme 7 were added to a 500 ml round- 1.13 g (1.24 mmol) of Pd ₂ (dba) ₃ , 1.77 g (9.28 mmol) of copper iodide and 10.3 g (74.2 mmol) of potassium carbonate were dissolved in 200 ml of diphenyl ether and the mixture was heated to reflux for 48 hours. After completion of the reaction, the reaction mixture was cooled to room temperature and filtered. The organic layer was concentrated under reduced pressure, and then subjected to column purification (27.3 g, yield 75%) using ethyl acetate and n-hexane as eluent.

(9) Synthesis of a compound represented by the formula (1-i)

A compound represented by the formula (1-i) was synthesized by the following reaction scheme (9).

[Reaction Scheme 9]

[Chemical Formula 1-i]

16.5 g (105 mmol) of bromobenzene and 150 ml of tetrahydrofuran were added to a 500 ml round-bottomed flask under nitrogen, the temperature was lowered to -78 ° C., and 66 ml of a 1.6 M in n-hexane solution 105 mmol) was slowly added dropwise and stirred at -78 [deg.] C for 1 hour. 14 g (23.8 mmol) of the compound represented by the formula [1-h] obtained in the reaction scheme 8 was dissolved in 150 ml of tetrahydrofuran and added dropwise to the solution. When the dropping was over, the temperature was raised to room temperature and stirred for 3 hours. After completion of the reaction, an ammonium chloride aqueous solution was added and extracted with diethyl ether. The organic layer was concentrated, washed with n-hexane and dried. The dried crystals were dissolved in boiling acetic acid, hydrochloric acid was slowly added dropwise, and the mixture was refluxed for 3 hours. The solution was slowly dropped into ice water to obtain crystals. The resulting crystals were washed with ethanol, and then subjected to column purification using chloroform and n-hexane as developing solvents (11.8 g, yield 62%).

(10) Synthesis of Compound Represented by Formula 19

A compound represented by the formula (19) was synthesized by the following reaction scheme (10).

[Reaction Scheme 10]

[Chemical Formula 19]

11.8 g (20.1 mmol) of the compound represented by the formula (1-i), 3.15 g (20.1 mmol) of platinum chloride and 120 ml of cyanobenzene obtained from the reaction scheme 9 were placed in a 500 ml round bottom flask and refluxed for 24 hours . When the reaction was completed, the temperature was cooled down to room temperature. After the solvent was removed by distillation under reduced pressure, column purification was carried out using methylene chloride and n-hexane as developing solvents. (12.4 g, yield 62%).

MS: m / z Calcd 992.29; found 799. Anal. Calcd. for C ₅₇ H ₄₃ N ₃ PtSi: C, 68.93; H, 4.36; N, 4.23. Found: C, 69.15; H, 4.52 N, 4.11.

Synthesis Example 2 Synthesis of Compound Represented by Formula 20

(1) Synthesis of Compound Represented by Formula (2-a)

A compound represented by the general formula [2-a] was synthesized by the following reaction scheme [11].

[Reaction Scheme 11]

[Chemical Formula 2-a]

Was synthesized in the same manner as in [Scheme 5] of <Synthesis Example 1> to obtain 19.9 g (yield 67%) of the compound represented by the formula 2-a.

(2) Synthesis of a compound represented by the formula (2-b)

[Chemical Formula 2-b] was synthesized by the following Reaction Scheme 12.

[Reaction Scheme 12]

[Formula 2-b]

Was synthesized in the same manner as in [Scheme 6] of <Synthesis Example 1> to obtain 23.6 g (yield 95%) of the compound represented by the formula 2-b.

(3) Synthesis of Compound Represented by Formula 2-c

[Chemical Formula 2-c] was synthesized by the following Reaction Scheme (13).

[Reaction Scheme 13]

[Chemical Formula 2-c]

Was synthesized in the same manner as in [Scheme 7] of <Synthesis Example 1> to obtain 24.5 g (yield 95%) of the compound represented by the formula 2-c.

(4) Synthesis of a compound represented by the formula (2-d)

[Chemical Formula 2-d] was synthesized by the following Reaction Scheme 14.

[Reaction Scheme 14]

[Chemical Formula 2-d]

Was synthesized in the same manner as in [Reaction Scheme 8] of <Synthesis Example 1> to obtain 25.1 g (71%) of the compound represented by Formula 2-d.

(5) Synthesis of a compound represented by the formula (2-e)

[Chemical Formula 2-e] was synthesized by the following Reaction Scheme 15.

[Reaction Scheme 15]

[Chemical Formula 2-e]

Was synthesized in the same manner as in [Reaction Scheme 9] of <Synthesis Example 1> to obtain 21.7 g (yield 63%) of the compound represented by Formula 2-e.

(6) Synthesis of Compound Represented by Formula 20

A compound represented by the formula (20) was synthesized by the following reaction scheme [16].

[Reaction Scheme 16]

[Chemical Formula 5]

Was synthesized in the same manner as in [Synthesis Example 10] of <Synthesis Example 1> to obtain 17.3 g (yield 64%) of the compound represented by Formula 20.

MS: m / z calcd 976.31; found 976. Anal. Calcd. for C ₅₈ H ₄₃ N ₃ Pt: C, 71.30; H, 4.44; N, 4.30. Found: C, 71.88; H, 4.56 N, 4.25.

&Lt; Synthesis Example 3 > Preparation of a compound represented by the formula (23)

(1) Synthesis of Compound Represented by Formula 3-a

[Chemical Formula 3-a] was synthesized by the following Reaction Scheme 17.

[Reaction Scheme 17]

[Formula 3-a]

Was synthesized in the same manner as in [Scheme 1] of <Synthesis Example 1> to obtain 19.3 g (yield 70%) of the compound represented by the formula 3-a.

(2) Synthesis of Compound Represented by Formula 3-b

[Chemical Formula 3-b] was synthesized by the following Reaction Scheme 18.

[Reaction Scheme 18]

[Formula 3-b]

Was synthesized in the same manner as in [Scheme 1] of <Synthesis Example 1> to obtain 15.9 g (yield 60%) of the compound represented by the formula 3-b.

(3) Synthesis of Compound Represented by Formula 3-c

[Chemical Formula 3-c] was synthesized by the following Reaction Scheme (19).

[Reaction Scheme 19]

[Chemical Formula 3-c]

Was synthesized in the same manner as in [Scheme 5] of <Synthesis Example 1> to obtain 15.3 g (62% yield) of the compound represented by the formula 3-c.

(4) Synthesis of Compound Represented by Formula 3-d

[Chemical formula 3-d] was synthesized by the following reaction scheme [Reaction formula 20].

[Reaction Scheme 20]

[Chemical formula 3-d]

Was synthesized in the same manner as in [Scheme 6] of <Synthesis Example 1> to obtain 15.9 g (yield 91%) of a compound represented by the formula 3-d.

(5) Synthesis of Compound Represented by Formula 3-e

[Chemical Formula 3-e] was synthesized by the following Reaction Formula 21.

[Reaction Scheme 21]

[Formula 3-e]

Was synthesized in the same manner as in [Scheme 7] of <Synthesis Example 1> to obtain 16.2 g (yield: 96%) of the compound represented by Formula 3-e.

(6) Synthesis of Compound Represented by Formula 3-f

[Chemical Formula 3-f] was synthesized by the following Reaction Formula 22.

[Reaction Scheme 22]

[Chemical Formula 3-f]

Was synthesized in the same manner as in [Reaction Scheme 8] of <Synthesis Example 1> to obtain 36.9 g (yield 80%) of the compound represented by Formula 3-f.

(7) Synthesis of Compound Represented by Formula 3-g

[Chemical Formula 3-g] was synthesized by the following Reaction Formula 23.

[Reaction Scheme 23]

[Formula 3-g]

Was synthesized in the same manner as in [Reaction Scheme 9] of <Synthesis Example 1> to obtain 31.3 g (yield 66%) of a compound represented by the formula 3-g.

(8) Synthesis of a compound represented by the formula (23)

A compound represented by the formula (23) was synthesized by the following reaction scheme (24).

[Reaction Scheme 24]

(23)

Was synthesized in the same manner as in [Reaction formula 10] of <Synthesis Example 1> to obtain 23.7 g (yield: 63%) of the compound represented by formula (23).

MS: m / z Calcd 1151.33; found 1151. Anal. Calcd. for C ₆₉ H ₄₄ N ₆ Pt: C, 71.93; H, 3.85; N, 7.29. Found: C, 71.25; H, 3.69 N, 7.38.

Synthesis Example 4 Synthesis of Compound Represented by Formula 37

(1) Synthesis of Compound Represented by Formula 4-a

[Chemical Formula 4-a] was synthesized by the following Reaction Scheme 25.

[Reaction Scheme 25]

[Chemical Formula 4-a]

To a 1 L round bottom flask was added 1-bromoamantane (15.0 g, 69.7 mmol), silver bromide (1.31 g, 6.97 mmol), triphenylphosphite (2.49 g, 6.97 mmol) and 230 mL of n-hexane. A solution of 3,5-dimethylphenyl magnesium bromide (1 M in Et ₂ O) (209 ml, 209 mmol) was slowly added dropwise under nitrogen, and the mixture was stirred for 64 hours after completion of the dropwise addition. A saturated aqueous ammonium chloride solution was added and the organic layer was extracted with normal hexane. The organic layer was concentrated under reduced pressure and then subjected to column purification. (10.1 g, 60% yield)

(2) Synthesis of Compound Represented by Formula 4-b

[Chemical Formula 4-b] was synthesized by the following Reaction Formula 26.

[Reaction Scheme 26]

[Formula 4-b]

Was synthesized in the same manner as in [Scheme 5] of <Synthesis Example 1> to obtain 18.6 g (yield 70%) of the compound represented by the formula 4-b.

(3) Synthesis of Compound Represented by Formula 4-c

[Chemical Formula 4-c] was synthesized by the following Reaction Scheme 27.

[Reaction Scheme 27]

[Chemical formula 4-c]

Was synthesized in the same manner as in [Scheme 6] of <Synthesis Example 1> to obtain 19.6 g (yield 89%) of the compound represented by the formula 4-c.

(4) Synthesis of Compound Represented by Formula 4-d

[Chemical Formula 4-d] was synthesized by the following Reaction Scheme 28.

[Reaction Scheme 28]

[Chemical formula 4-d]

Was synthesized in the same manner as in [Scheme 7] of <Synthesis Example 1> to obtain 19.4 g (yield 92%) of the compound represented by the formula 4-d.

(5) Synthesis of Compound Represented by Formula 4-e

[Chemical Formula 4-e] was synthesized by the following Reaction Scheme 29.

[Reaction Scheme 29]

[Chemical Formula 4-e]

Was synthesized in the same manner as in [Reaction Scheme 8] of [Synthesis Example 1] to obtain 31.3 g (yield 78%) of the compound represented by the formula 4-e.

(6) Synthesis of Compound Represented by Formula 4-f

[Chemical Formula 4-f] was synthesized by the following Reaction Scheme 30.

[Reaction Scheme 30]

[Chemical Formula 4-f]

Was synthesized in the same manner as in [Reaction Scheme 9] of <Synthesis Example 1> to obtain 29.1 g (yield 70%) of the compound represented by the formula 4-f.

(7) Synthesis of Compound Represented by Formula 37

A compound represented by the formula (37) was synthesized by the following reaction scheme [31].

[Reaction Scheme 31]

(37)

Was synthesized in the same manner as in [Scheme 10] of <Synthesis Example 1> to obtain 23.8 g (67%) of a compound represented by the formula (37).

MS: m / z calcd 1054.36; found 1054. Anal. Calcd. for C ₆₄ H ₄₉ N ₃ Pt: C, 72.85; H, 4.68; N, 3.98. Found: C, 72.99; H, 4.73 N, 3.81.

&Lt; Synthesis Example 5 > Preparation of a compound represented by the formula (48)

(1) Synthesis of a compound represented by the formula (5-a)

A compound represented by the following formula (5-a) was synthesized by the following reaction scheme (32).

[Reaction Scheme 32]

[Formula 5-a]

Was synthesized in the same manner as in [Scheme 6] of <Synthesis Example 1> to obtain 24.6 g (yield 93%) of a compound represented by the formula 5-a.

(2) Synthesis of Compound Represented by Formula 5-b

[Chemical Formula 5-b] was synthesized by the following Reaction Formula 33.

[Reaction Scheme 33]

[Chemical Formula 5-b]

Was synthesized in the same manner as in [Scheme 7] of <Synthesis Example 1> to obtain 27.0 g (yield 98%) of the compound represented by the formula 5-b.

(3) Synthesis of Compound Represented by Formula 5-c

[Chemical Formula 5-c] was synthesized by the following Reaction Scheme [34].

[Reaction Scheme 34]

[Chemical Formula 5-c]

Was synthesized in the same manner as in [Reaction Scheme 8] of <Synthesis Example 1> to obtain 22.6 g (71%) of the compound represented by the formula 5-c.

(4) Synthesis of Compound Represented by Formula 5-d

[Chemical Formula 5-d] was synthesized by the following Reaction Scheme 35.

[Reaction Scheme 35]

[Chemical formula 5-d]

Was synthesized in the same manner as in [Reaction Scheme 9] of <Synthesis Example 1> to obtain 28.6 g (yield 64%) of the compound represented by the formula 5-d.

(5) Synthesis of Compound Represented by Formula 48

A compound represented by the formula (48) was synthesized by the following reaction scheme.

[Reaction Scheme 36]

(33)

Was synthesized in the same manner as in [Scheme 10] of the above Synthesis Example 1 to obtain 22.1 g (yield 65%) of the compound represented by the formula (48).

MS: m / z Calcd 1208.41; found 1208. Anal. Calcd. for C ₆₆ H ₆₇ N ₃ PtSi ₄ : C, 72.85; H, 4.68; N, 3.98. Found: C, 72.99; H, 4.73 N, 3.81.

Synthesis Example 6 Synthesis of Compound Represented by Formula 90

(1) Synthesis of Compound Represented by Formula (6-a)

A compound represented by the formula [6-a] was synthesized by the following reaction scheme [37].

[Reaction Scheme 37]

[Chemical Formula 6-a]

Was synthesized in the same manner as in [Scheme 3] of <Synthesis Example 1> to obtain 19.6 g (yield 70%) of the compound represented by the formula 6-a.

(2) Synthesis of Compound Represented by Formula 6-b

[Chemical Formula 6-b] was synthesized by the following Reaction Scheme [38].

[Reaction Scheme 38]

[Chemical Formula 6-b]

Was synthesized in the same manner as in [Synthesis Example 9] of <Synthesis Example 1> to obtain 17.6 g (yield 68%) of the compound represented by the formula 6-b.

(3) Synthesis of Compound Represented by Formula 90

A compound represented by the following formula (90) was synthesized by the following scheme (Scheme 39).

[Reaction Scheme 39]

(90)

Was synthesized in the same manner as in [Reaction formula 10] of <Synthesis Example 1> to obtain 13.7 g (yield 64%) of the compound represented by the formula (90).

MS: m / z Calcd 1074.30; found 1074. Anal. Calcd. for C ₆₄ H ₄₁ N ₅ Pt: C, 71.50; H, 3.84; N, 6.51. Found: C, 70.88; H, 3.69; N, 6.63.

Synthesis Example 7 Synthesis of Compound Represented by Formula 110

(1) Synthesis of Compound Represented by Formula 7-a

A compound represented by the general formula [7-a] was synthesized by the following reaction scheme [40].

[Reaction Scheme 40]

[Formula 7-a]

Was synthesized in the same manner as in [Scheme 1] of <Synthesis Example 1> to obtain 18.7 g (yield 75.4%) of the compound represented by the formula 7-a.

(2) Synthesis of Compound Represented by Formula 7-b

[Chemical Formula 7-b] was synthesized by the following Reaction Scheme 41.

[Reaction Scheme 41]

[Formula 7-b]

Was synthesized in the same manner as in [Scheme 2] of <Synthesis Example 1> to obtain 14.1 g (yield 66%) of a compound represented by the formula 7-b.

(3) Synthesis of Compound Represented by Formula 7-c

[Chemical Formula 7-c] was synthesized by the following Reaction Scheme 42.

[Reaction Scheme 42]

[Chemical Formula 7-c]

Was synthesized in the same manner as in [Scheme 3] of <Synthesis Example 1> to obtain 15.7 g (yield 74%) of a compound represented by the formula 7-c.

(4) Synthesis of Compound Represented by Formula 7-d

[Chemical Formula 7-d] was synthesized by the following Reaction Formula 43.

[Reaction Scheme 43]

[Chemical Formula 7-d]

Was synthesized in the same manner as in [Scheme 8] of the above Synthesis Example 1 to obtain 25.9 g (yield 76%) of the compound represented by the formula 7-d.

(5) Synthesis of Compound Represented by Formula 7-e

A compound represented by the formula [7-e] was synthesized by the following reaction scheme [44].

[Reaction Scheme 44]

[Formula 7-e]

Was synthesized in the same manner as in [Scheme 9] of <Synthesis Example 1> to obtain 22.8 g (yield 65%) of a compound represented by the formula 7-e.

(6) Synthesis of Compound Represented by Formula 7-f

A compound represented by the formula [7-f] was synthesized by the following scheme (45).

[Reaction Scheme 45]

[Chemical Formula 7-f]

(30.0 g, 36.9 mmol), trimethylsilyl chloride (12.0 g, 111 mmol) and triethylamine (31 ml, 222 mmol) obtained in Reaction Scheme 44 were added to a 1 L round- ) And 300 ml of methylene chloride were added, followed by stirring for 12 hours. A saturated aqueous ammonium chloride solution was added and the organic layer was extracted with methylene chloride. The organic layer was concentrated under reduced pressure and then subjected to column purification. (25.4 g, yield 72%).

(7) Synthesis of Compound Represented by Formula 110

A compound represented by the formula (110) was synthesized according to the following scheme (46).

[Reaction Scheme 46]

&Lt; EMI ID =

Synthesis was conducted in the same manner as in Reaction Formula 10 of Synthesis Example 1 to obtain 18.6 g (yield: 61%) of the compound represented by the formula (95).

MS: m / z Calcd 1148.42; found 1148. Anal. Calcd. for C ₆₆ H ₆₃ N ₃ PtSi ₂ : C, 68.96; H, 5.52; N, 3.66. Found: C, 68.55; H, 5.41 N, 3.73.

Synthesis Example 8 Preparation of a compound represented by the formula (132)

(1) Synthesis of Compound Represented by Formula (8-a)

A compound represented by the following formula (8-a) was synthesized by the following reaction scheme (47).

[Reaction Scheme 47]

[Formula 8-a]

To a 500 ml round bottom flask was added pyrazole 10.0 g (147 mmol), MnCl ₂ .4H ₂ O 2.91 g (14.7 mmol), K ₃ PO ₄ .H ₂ O 67.7 g (294 mmol) 62.3 g (220 mmol) of iodobenzene, 3.35 g (29.4 mmol) of trans-1,2-diaminocyclohexane and 70 ml of water were added and refluxed for 24 hours. After the completion of the reaction, the temperature was cooled down to room temperature, methylene chloride was added thereto, and the mixture was filtered using celite. The filtrate was concentrated under reduced pressure, and then subjected to column purification using ethyl acetate and n-hexane as eluent. (25.6 g, yield 78%).

(2) Synthesis of Compound Represented by Formula (8-b)

[Chemical Formula 8-b] was synthesized by the following Reaction Scheme 48.

[Reaction Scheme 48]

[Formula 8-b]

Was synthesized in the same manner as in [Reaction Formula 47] in <Synthesis Example 8> to obtain 20.9 g (yield 75%) of a compound represented by the formula 8-b.

(3) Synthesis of Compound Represented by Formula (8-c)

A compound represented by the following formula (8-c) was synthesized by the following reaction scheme (49).

[Reaction Scheme 49]

[Formula 8-c]

20.0 g (106 mmol) of the compound represented by the formula 8-b], palladium / carbon catalyst (10%), 26.5 g (529 mmol) of hydrazine monohydrate, ethanol 200 ml and the mixture was refluxed for 1 hour. After completion of the reaction, the reaction product was hot-filtered using silica gel / celite, and then the solvent was concentrated under reduced pressure. (15.5 g, 92% yield)

(4) Synthesis of Compound Represented by Formula 8-d

[Chemical Formula 8-d] was synthesized by the following Reaction Scheme 50.

[Reaction Scheme 50]

[Chemical formula 8-d]

Was synthesized in the same manner as in [Scheme 3] of <Synthesis Example 1> to obtain 14.0 g (yield 69%) of the compound represented by the formula 8-d.

(5) Synthesis of Compound Represented by Formula 8-e

[Chemical Formula 8-e] was synthesized by the following Reaction Scheme [51].

[Reaction Scheme 51]

[Formula 8-e]

Was synthesized in the same manner as in [Reaction Scheme 8] of <Synthesis Example 1> to obtain 28.5 g (yield 78%) of the compound represented by the formula 8-e.

(6) Synthesis of Compound Represented by Formula 8-f

A compound represented by the following formula (8-f) was synthesized by the following reaction scheme [52].

[Reaction Scheme 52]

[Chemical Formula 8-f]

Was synthesized in the same manner as in [Synthesis Example 9] of Synthesis Example 1 to obtain 27.5 g (yield 65%) of the compound represented by the general formula [8-f].

(7) Synthesis of Compound Represented by Formula (132)

A compound represented by the formula (132) was synthesized by the following scheme (53).

[Reaction Scheme 53]

(132)

Was synthesized in the same manner as in [Scheme 10] of the above Synthesis Example 1 to obtain 20.8 g (yield: 61%) of the compound represented by the formula (132).

MS: m / z Calcd 1010.36; found 1010. Anal. Calcd. for C ₅₈ H ₄₉ N ₅ Pt: C, 68.90; H, 4.88; N, 6.93. Found: C, 68.77; H, 4.71 N, 7.01.

Synthesis Example 9: Preparation of a compound represented by the formula (162)

(1) Synthesis of Compound Represented by Formula 9-a

A compound represented by the following formula (9-a) was synthesized by the following reaction scheme.

[Reaction Scheme 54]

[Chemical Formula 9-a]

30.0 g (200 mmol) of 3-tert-butylphenol and 150 ml of pyridine were placed in a 500 ml round bottom flask. After cooling down to 0 ° C, 101 ml (599 mmol) of trifluoromethanesulfonic anhydride was slowly added dropwise. The temperature was raised to room temperature and stirred for 12 hours. After completion of the reaction, water was added, and the organic layer was extracted with diethyl ether. The organic layer was concentrated under reduced pressure and then subjected to column purification using ethyl acetate and n-hexane. (54.1 g, 96%).

(3) Synthesis of Compound Represented by Formula 9-b

A compound represented by the following formula (9-b) was synthesized by the following reaction scheme (55).

[Reaction Scheme 55]

[Formula 9-b]

30.0 g (106 mmol) of the compound represented by the formula 9-a, 1.46 g (1.59 mmol) of Pd ₂ (dba) _{3 and} 1.52 g (3.19 mmol) of X-Phos obtained in the reaction scheme [ ), 21.8 g (85.0 mmol) of DIBAL-Me ₃ and 500 ml of THF, and the mixture was refluxed for 4 hours. After completion of the reaction, the temperature was lowered and cooled to 0 ° C. A 2 M aqueous hydrochloric acid solution was slowly added dropwise to neutralize and the organic layer was extracted with diethyl ether. The organic layer was concentrated under reduced pressure and then distilled under reduced pressure. (14.3 g, 91% yield)

(4) Synthesis of Compound Represented by Formula 9-c

[Chemical Formula 9-c] was synthesized by the following Reaction Formula 56.

[Reaction Scheme 56]

[Chemical Formula 9-c]

Was synthesized in the same manner as in [Scheme 5] of <Synthesis Example 1> to obtain 20.8 g (yield 68%) of the compound represented by the formula 9-c.

(5) Synthesis of Compound Represented by Formula 9-d

[Chemical Formula 9-d] was synthesized by the following Reaction Scheme [57].

[Reaction Scheme 57]

[Chemical Formula 9-d]

Was synthesized in the same manner as in [Scheme 6] of <Synthesis Example 1> to obtain 22.9 g (yield 97%) of a compound represented by the formula 9-d.

(6) Synthesis of Compound Represented by Formula 9-e

[Chemical Formula 9-e] was synthesized by the following Reaction Scheme 58.

[Reaction Scheme 58]

[Formula 9-e]

Was synthesized in the same manner as in [Scheme 7] of <Synthesis Example 1> to obtain 23.4 g (yield 97%) of the compound represented by the formula 9-e.

(7) Synthesis of Compound Represented by Formula 9-f

[Chemical Formula 9-f] was synthesized by the following Reaction Formula 59.

[Reaction Scheme 59]

[Chemical Formula 9-f]

Was synthesized in the same manner as in [Reaction Scheme 8] of <Synthesis Example 1> to obtain 23.8 g (yield 75%) of the compound represented by the formula 9-f.

(8) Synthesis of a compound represented by the formula (9-g)

[Chemical Formula 9-g] was synthesized by the following Reaction Scheme 60.

[Reaction Scheme 60]

[Formula 9-g]

Was synthesized in the same manner as in [Reaction Scheme 9] of <Synthesis Example 1> to obtain 21.9 g (yield 73%) of a compound represented by the formula 9-g.

(9) Synthesis of a compound represented by the formula (162)

A compound represented by the formula (162) was synthesized by the following scheme (61).

[Reaction Scheme 61]

(162)

Was synthesized in the same manner as in [Scheme 10] of the above Synthesis Example 1 to obtain 19.4 g (yield 68%) of a compound represented by the formula (162).

Synthesis Example 10: Preparation of a compound represented by the formula (198)

(1) Synthesis of Compound Represented by Formula 10-a

A compound represented by the formula (10-a) was synthesized by the following scheme (Scheme 62).

[Reaction Scheme 62]

[Chemical Formula 10-a]

Was synthesized in the same manner as in [Scheme 10] of the above Synthesis Example 1 to obtain 12.4 g (yield 75%) of the compound represented by the formula 10-a.

(2) Synthesis of Compound Represented by Formula 10-b

The compound represented by the formula (10-b) was synthesized by the following scheme (Scheme 63).

[Reaction Scheme 63]

[Chemical Formula 10-b]

Was synthesized in the same manner as in [Scheme 1] of <Synthesis Example 1> to obtain 17.5 g (66%) of the compound represented by the formula 10-b.

(3) Synthesis of Compound Represented by Formula 10-c

The compound represented by the formula (10-c) was synthesized by the following reaction scheme (64).

[Reaction Scheme 64]

[Chemical Formula 10-c]

Was synthesized in the same manner as in [Scheme 1] of <Synthesis Example 1> to obtain 16.3 g (yield 69%) of a compound represented by the formula 10-c.

(4) Synthesis of Compound Represented by Formula 10-d

A compound represented by the formula [10-d] was synthesized by the following reaction scheme [65].

[Reaction Scheme 65]

[Chemical Formula 10-d]

Was synthesized in the same manner as in [Synthesis Example 49] of Synthesis Example 8 to obtain 13.1 g (yield 90%) of the compound represented by Formula 10-d.

(5) Synthesis of Compound Represented by Formula 10-e

The compound represented by the formula (10-e) was synthesized by the following scheme (Scheme 66).

[Reaction Scheme 66]

[Formula 10-e]

Was synthesized in the same manner as in [Scheme 3] of <Synthesis Example 1> to obtain 17.0 g (yield 74%) of a compound represented by the formula 10-e.

(6) Synthesis of a compound represented by the general formula [10-f]

The compound represented by the general formula [10-f] was synthesized by the following reaction scheme [67].

[Reaction Scheme 67]

[Chemical Formula 10-f]

Was synthesized in the same manner as in [Reaction Scheme 8] of <Synthesis Example 1> to obtain 19.7 g (yield 77%) of the compound represented by Formula 10-f.

(7) Synthesis of a compound represented by the formula (10-g)

A compound represented by the formula (10-g) was synthesized by the following scheme (68).

[Reaction Scheme 68]

[Chemical Formula 10-g]

Was synthesized in the same manner as in [Reaction Scheme 9] of <Synthesis Example 1> to obtain 17.1 g (yield 70%) of the compound represented by Formula 10-g.

(8) Synthesis of Compound Represented by Formula (198)

A compound represented by the formula (198) was synthesized by the following scheme (69).

[Reaction Scheme 69]

[198]

Was synthesized in the same manner as in [Reaction formula 10] of <Synthesis Example 1> to obtain 13.1 g (yield: 61%) of the compound represented by formula (198).

MS: m / z Calcd 938.27; found 938. Anal. Calcd. for C ₅₃ H ₃₇ N ₅ Pt: C, 67.79; H, 3.97; N, 7.46. Found: C, 67.99; H, 4.11; N, 7.56.

Synthesis Example 11 Synthesis of a compound represented by the formula (200)

(1) Synthesis of Compound Represented by Formula (11-a)

A compound represented by the formula (11-a) was synthesized by the following scheme (70).

[Reaction Scheme 70]

[Formula 11-a]

Was synthesized in the same manner as in [Scheme 1] of <Synthesis Example 1> to obtain 18.6 g (yield 68%) of the compound represented by Formula 11-a.

(2) Synthesis of Compound Represented by Formula (11-b)

The compound represented by the formula (11-b) was synthesized by the following reaction scheme (71).

[Reaction Scheme 71]

[Formula 11-b]

Was synthesized in the same manner as in [Scheme 2] of <Synthesis Example 1> to obtain 16.6 g (yield 65%) of a compound represented by the formula (11-b).

(3) Synthesis of Compound Represented by Formula 11-c

The compound represented by the formula (11-c) was synthesized by the following reaction scheme (72).

[Reaction Scheme 72]

[Chemical Formula 11-c]

Was synthesized in the same manner as in [Scheme 3] of <Synthesis Example 1> to obtain 15.7 g (yield 70%) of a compound represented by the formula (11-c).

(4) Synthesis of Compound Represented by Formula (11-d)

A compound represented by the formula (11-d) was synthesized by the following scheme (73).

[Reaction Scheme 73]

[Chemical Formula 11-d]

Was synthesized in the same manner as in [Reaction Scheme 8] of <Synthesis Example 1> to obtain 25.4 g (yield 80%) of the compound represented by Formula 11-d.

(5) Synthesis of Compound Represented by Formula 11-e

A compound represented by the formula (11-e) was synthesized by the following scheme (Scheme 74).

[Reaction Scheme 74]

[Formula 11-e]

Was synthesized in the same manner as in [Synthesis Example 9] of Synthesis Example 1 to obtain 21.7 g (yield 65%) of the compound represented by Formula 11-e.

(6) Synthesis of Compound Represented by Formula (200)

A compound represented by the formula (200) was synthesized by the following scheme (Scheme 75).

[Reaction Scheme 75]

(200)

Was synthesized in the same manner as in [Synthesis Example 10] of <Synthesis Example 1> to obtain 16.7 g (yield: 63%) of the compound represented by Formula 200.

MS: m / z Calcd 1076.34; found 1076. Anal. Calcd. for C ₆₆ H ₄₇ N ₃ Pt: C, 73.59; H, 4.40; N, 3.90. Found: C, 73.11; H, 4.32; N, 4.02.

&Lt; Examples 1 to 11 > Preparation of Organic Electroluminescent Device

The ITO glass was patterned to have a light emitting area of 2 mm x 2 mm and then cleaned. The substrate was mounted in a vacuum chamber was such that the base pressure is ^{1 × 10 -6 torr DNTPD (700} Å) an organic material over the ITO, NPD (300 Å), CBP + the compound produced according to the present invention (7% (300 Å), Alq ₃ (350 Å), LiF (5 Å) and Al (1,000 Å) were deposited in this order and measured at 0.4 mA.

[DNTPD]

[NPD]

[CBP]

[Alq ₃ ]

&Lt; Comparative Example 1 &

The organic electroluminescent device for the comparative example was prepared in the same manner except that BTPIr of the following structural formula was used in place of the compound prepared by the invention in the device structures of Examples 1 to 11 above.

[BTPIr]

division Host Dopant Doping concentration (%) ETL V Cd / A CIEx CIEy T ₈₀ (hr) Comparative Example 1 CBP BTPIr 7 Alq ₃ 4.2 6.1 0.66 0.32 76 Example 1 CBP Formula 4 7 Alq ₃ 3.7 14.6 0.67 0.33 255 Example 2 CBP Formula 5 7 Alq ₃ 3.6 13.5 0.67 0.33 217 Example 3 CBP 8 7 Alq ₃ 4.1 9.2 0.67 0.33 156 Example 4 CBP Formula 22 7 Alq ₃ 3.8 11.5 0.66 0.34 202 Example 5 CBP Formula 33 7 Alq ₃ 4.2 13.1 0.65 0.35 141 Example 6 CBP Formula 147 7 Alq ₃ 3.9 8.9 0.66 0.33 174 Example 7 CBP Formula 185 7 Alq ₃ 4.1 10.7 0.68 0.34 165

In order to measure the bandgaps of [Formula 19], [Formula 20], [Formula 23], [Formula 37], [Formula 48], [Formula 162], and Formula 200 according to the present invention, an absorption spectrophotometer / Vis absorption spectrometer and cyclic voltammetry.

division UVl _max PLl _max HOMO (eV) LUMO (eV) Band gap (eV) Formula 4 331, 393, 530 625 5.26 3.11 2.15 Formula 5 330, 395, 530 624 5.25 3.04 2.21 8 331, 399, 528 628 5.25 3.05 2.20 Formula 22 342, 408, 544 621 5.26 3.05 2.14 Formula 33 336, 404, 546 625 5.16 3.03 2.13 Formula 147 342, 401, 514 618 5.08 2.94 2.14 Formula 185 341, 406, 521 630 5.28 3.19 2.09

From the results of Examples 1 to 11, Comparative Example 1, and Table 1, it can be seen that the compound represented by Formula 1 according to the present invention is superior to BTPIr, Thermal characteristics, and luminous efficiency, it can be used for display devices, display devices, lighting, and the like.

10: substrate 20: anode
30: Hole injection layer 40: Hole transport layer
50: organic light emitting layer 60: electron transporting layer
70: electron injection layer 80: cathode

Claims (8)

An organometallic compound represented by any one of the following formulas (1-1) to (1-4)
[Formula 1-1] [Formula 1-2]

[Chemical Formula 1-3] [Chemical Formula 1-4]

In the above formulas 1-1 to 1-4,
X is CR &lt; ₁₄ &gt; or N,
R ₂ to R ₅ each independently represent a substituted or unsubstituted aryl group having 6 to 20 carbon atoms or a substituted or unsubstituted heteroaryl group having 3 to 20 carbon atoms (R ₂ and R ₃ , R ₄ and R ₅ Are not connected to each other to form a ring),
R ₁ and R ₆ to R ₁₄ are each independently selected from the group consisting of hydrogen, deuterium, cyano, halogen, nitro, substituted or unsubstituted alkyl having 1 to 20 carbon atoms, substituted or unsubstituted alkoxy having 1 to 7 carbon atoms, Or a substituted or unsubstituted C1-C7 alkylamino group, a substituted or unsubstituted C6-C20 arylamino group, a substituted or unsubstituted C3-C20 heteroarylamino group, a substituted or unsubstituted C1- A silyl group, a substituted or unsubstituted arylsilyl group having 6 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, a substituted or unsubstituted aryloxy group having 6 to 20 carbon atoms, and a substituted or unsubstituted carbon number 3 to 20 heteroaryl groups,
In the above R ₁ to R ₁₄ , the substituted or unsubstituted R ₁ to R ₁₄ may be further substituted with at least one Z, wherein Z is hydrogen, deuterium, cyano, halogen, nitro, An alkyl group having 1 to 7 carbon atoms, an alkoxy group having 1 to 7 carbon atoms, an alkylamino group having 1 to 7 carbon atoms, an arylamino group having 6 to 20 carbon atoms, a heteroarylamino group having 3 to 20 carbon atoms, an alkylsilyl group having 1 to 7 carbon atoms, An arylsilyl group having 6 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aryloxy group having 6 to 20 carbon atoms, and a heteroaryl group having 3 to 20 carbon atoms,
In the above formulas 1-1 to 1-4, adjacent functional groups may be bonded to each other to form a saturated or unsaturated hydrocarbon ring or a saturated or unsaturated hydrocarbon ring having a heteroatom. delete The method according to claim 1,
The organometallic compound according to any one of claims 1 to 4, wherein the organometallic compound is any one selected from the group consisting of:
[Chemical Formula 20] [Chemical Formula 20]

[Chemical Formula 22]

[Chemical Formula 28] [Chemical Formula 28]

[Chemical Formula 35]

[Chemical Formula 40] [Chemical Formula 40]

[Chemical Formula 43] [Chemical Formula 44] [Chemical Formula 45]

[Chemical Formula 48] [Chemical Formula 48] [Chemical Formula 48]

[Chemical Formula 50] [Chemical Formula 51]

[Chemical Formula 55] [Chemical Formula 55] [Chemical Formula 55]

[Chemical Formula 62] [Chemical Formula 65] [Chemical Formula 65]

[Chemical Formula 84]

[Chemical Formula 88] [Chemical Formula 88] [Chemical Formula 89]

[Chemical Formula 91] [Chemical Formula 92] [Chemical Formula 93]

[Chemical Formula 95] [Chemical Formula 96] [Chemical Formula 97]

[Chemical Formula 100] [Chemical Formula 100]

[Formula 103] [Formula 103]

[Chemical Formula 10] [Chemical Formula 10] [Chemical Formula 10] [Chemical Formula 10]

[Formula 110] [Formula 111] [Formula 112] [Formula 113]

&Lt; EMI ID = 116.1 &gt;

[Chemical Formula 120] [Chemical Formula 120] [Chemical Formula 120]

[Formula 124] [Formula 124] [Formula 125]

[Formula 126] &lt; EMI ID = 129.1 &gt;

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

[Formula 135] [Formula 135] [Formula 137]

[Chemical Formula 140] [Chemical Formula 140] [Chemical Formula 140]

[Chemical Formula 144] [Chemical Formula 144] [Chemical Formula 145]

[Chemical Formula 146] [Chemical Formula 148] [Chemical Formula 149]

[Formula 15] [Formula 15] [Formula 15] [Formula 15]

[173] [173] [173]

[Formula 181] [Formula 181] [Formula 181] [Formula 181]

[Chemical Formula 184] [Chemical Formula 184]

[Formula 188] [Formula 188] [Formula 188]

[Formula 19] [Formula 19] [Formula 193] [Formula 193]

[197] [197]

[201] [201] [201]

Anode;
Cathode; And
An organic electroluminescent element interposed between the anode and the cathode and comprising the compound according to claim 1. 5. The method of claim 4,
Wherein the compound is contained in the light emitting layer between the anode and the cathode. 6. The method of claim 5,
Wherein at least one layer selected from the group consisting of a hole injecting layer, a hole transporting layer, an electron blocking layer, a hole blocking layer, an electron transporting layer and an electron injecting layer is further interposed between the anode and the cathode. The method according to claim 6,
Wherein at least one layer selected from the group consisting of 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 is formed by a single molecular deposition method or a solution process. 5. The method of claim 4,
Wherein the organic electroluminescent device is used in a display device, a display device, or a device for monochromatic or white illumination.

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