KR101771529B1 - Heterocyclic compounds and organic light-emitting diode including the same - Google Patents

Abstract

The present invention relates to a novel cyclic ring compound and an organic electroluminescent device comprising the same as a light emitting material. Specifically, the cyclic ring compound represented by the following formula (1) and the organic electroluminescent device including the same, And the like.
0 [Formula 1]

Description

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

The present invention relates to a novel cyclic ring compound and an organic electroluminescent device comprising the same as a light emitting material. More particularly, the present invention relates to a stable cyclic compound having excellent light emission characteristics such as a driving voltage and a current efficiency, Device.

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, organic light emitting diodes (OLEDs), which are new flat display devices, are displays using self-luminescence phenomenon, which have a large viewing angle and can be made thinner and smaller than liquid crystal displays, And recently, application to a full-color display or illumination is expected.

In general, organic light emission phenomenon refers to a phenomenon in which an organic material is used to convert electric energy into light energy.

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 necessary for realizing 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.

Disclosure of Invention Technical Problem [8] The present invention provides a novel heterocyclic compound having low driving voltage and excellent light emitting efficiency.

A second object of the present invention is to provide an organic electroluminescent device including the above-mentioned heterocyclic compound.

In order to accomplish the first technical object, the present invention provides a compound represented by the following formula (1).

[Chemical Formula 1]

In this formula,

Wherein at least one of A ₁ and A ₂ is bonded to any two carbons of the above formula (1) to form a condensed ring,

R ₁ To R ₈ each independently represent a hydrogen atom, a deuterium atom, a halogen atom, a substituted or unsubstituted arylamino group having 6 to 40 carbon atoms, a substituted or unsubstituted aryloxy group having 3 to 40 carbon atoms, a substituted or unsubstituted 6 to 40 An aryl group, a substituted or unsubstituted heteroaryl group having 3 to 40 carbon atoms, a germanium group, phosphorus, boron,

X is O, S, CR < ₉ > R < _{10 &} And SiR < ₁₁ > R < ₁₂ >

R ₉ And R ₁₂ is wherein R ₁ To R < _{8 &} gt ;.

In order to solve the second technical problem, the present invention provides a semiconductor device comprising: an anode; Cathode; And a layer interposed between the anode and the cathode, the layer including the alicyclic ring compound represented by the formula (1).

According to the present invention, the cyclic ring compound represented by Formula 1 has stable and excellent luminescent characteristics as compared with the existing materials, so that the organic electroluminescent device including the cyclic compound can be operated at low voltage and improve the luminous efficiency.

1 is a schematic view of an organic electroluminescent device according to one embodiment of the present invention.
Description of the Related Art
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

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

The present invention is characterized by being represented by the above-mentioned formula (1) as a ring-form ring compound.

In the dicyclic ring compound of the above formula (1) according to the present invention, the substituent will be described in more detail as follows.

delete

delete

Specific examples of the alkyl group as the substituent used in the present invention include a methyl group, an ethyl group, a propyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, a pentyl group, an isoamyl group, a hexyl group, a heptyl group, A halogen atom, a hydroxyl group, a nitro group, a cyano group, a trifluoromethyl group, a silyl group (in this case, a " alkylsilyl group "hereinafter), a substituted or unsubstituted amino group _{(-NH 2, -NH (R)} , - N (R ') (R''), where R, R' and R" are each independently a carbon number A hydrazine group, a hydrazone group, a carboxyl group, a sulfonic acid group, a phosphoric acid group, an alkyl group having 1 to 24 carbon atoms, a halogenated alkyl group having 1 to 24 carbon atoms (for example, an alkyl group having 1 to 24 carbon atoms , An alkenyl group having 2 to 24 carbon atoms, an alkynyl group having 2 to 24 carbon atoms, By more than 24 heteroaryl group, a heteroarylalkyl group having a carbon number of 5 to 24 aryl group, C 6 -C 24 aryl group, a C 3 -C 24 heteroaryl group, or having from 3 to 24 of which may be substituted.

Specific examples of the alkoxy group used as the substituent in the compound of the present invention include methoxy, ethoxy, propoxy, isobutyloxy, sec-butyloxy, pentyloxy, isoamyloxy, And can be substituted with substituents similar to those in the case of the alkyl group.

Specific examples of the halogen group which is a substituent used in the compound of the present invention include fluorine (F), chlorine (Cl), bromine (Br) and the like.

Specific examples of the aryl group as the substituent group used in the compound of the present invention include a phenyl group, a 2-methylphenyl group, a 3-methylphenyl group, a 4-methylphenyl group, a 4-ethylphenyl group, Examples of the aryl group include phenyl group, 4-methylbiphenyl group, 4-ethylbiphenyl group, o-terphenyl group, m-terphenyl group, p-terphenyl group, 1-naphthyl group, , Anthryl group, phenanthryl group, pyrenyl group, fluorenyl group, tetrahydronaphthyl group and the like, which may be substituted with the same substituents as those in the case of the alkyl group.

Specific examples of the heteroaryl group used as the substituent in the compound of the present invention include pyridinyl, pyrimidinyl, triazinyl, indolinyl, quinolinyl, pyrrolidinyl, piperidinyl, An oxazolyl group, an oxadiazolyl group, a benzoxazolyl group, a thiazolyl group, a thiadiazolyl group, a benzothiazolyl group, a triazolyl group, an imidazolyl group, a benzoimidazole group, And at least one of the hydrogen atoms of the heteroaryl group may be substituted with the same substituent as the alkyl group.

In the present invention, the term "substituted or unsubstituted" means a group selected from the group consisting of a cyano group, a halogen group, a hydroxyl group, a nitro group, an alkyl group, an alkoxy group, an alkylamino group, an arylamino group, a heteroarylamino group, an alkylsilyl group, Substituted or unsubstituted with at least one substituent selected from the group consisting of an oxygen atom, an aryl group, a heteroaryl group, germanium, phosphorus, boron, hydrogen and deuterium.

At least one of A ₁ and A ₂ is bonded to any two carbons of the above-mentioned formula (1) having the above-described structure to form a condensed ring.

The present invention is not limited to the specific examples of the ring-opening cyclic compound according to the above-mentioned formula (1) having the above-mentioned structure. Specifically, any one of the compounds represented by the following formulas (2) to Lt; / RTI >

[Chemical Formula 2] < EMI ID =

[Chemical Formula 5] < EMI ID =

[Chemical Formula 8]

[Chemical Formula 12] [Chemical Formula 13]

[Chemical Formula 14]

[Chemical Formula 18] [Chemical Formula 19]

[Chemical Formula 20]

[Chemical Formula 23] [Chemical Formula 25]

[Chemical Formula 26]

[Chemical Formula 30] [Chemical Formula 30]

[Chemical Formula 32]

[Chemical Formula 35]

[Chemical Formula 38] [Chemical Formula 39]

[Chemical Formula 41]

[Chemical Formula 45]

[Chemical Formula 48] [Chemical Formula 48]

[Chemical Formula 50] [Chemical Formula 51]

[Chemical Formula 55] [Chemical Formula 55]

[Chemical Formula 57] [Chemical Formula 58]

[Chemical Formula 60] [Chemical Formula 61]

[Chemical Formula 62]

[Chemical Formula 65]

[Chemical Formula 70] [Chemical Formula 70]

[Chemical Formula 71] [Chemical Formula 72]

[Chemical Formula 75] [Chemical Formula 75]

[Formula 77] [Formula 79]

[Formula 80] [Formula 81]

[Chemical Formula 84]

[Chemical Formula 86]

[Chemical Formula 90] [Chemical Formula 90]

[Chemical Formula 93] [Chemical Formula 94]

[Formula 97] [Formula 97]

[Chemical Formula 99] [Chemical Formula 100]

[Formula 101] < EMI ID =

(106) < RTI ID = 0.0 > (106)

(109) < RTI ID = 0.0 >

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

≪ EMI ID = 113.1 >

≪ EMI ID = 116.1 >

[Chemical Formula 120]

[124] [124] [124]

[Formula 125]

[Formula 130] [Formula 130]

[Formula 131] [Formula 131]

[Chemical Formula 135] [Chemical Formula 135]

[Chemical Formula 138]

[Formula 140]

[Chemical Formula 144] [Chemical Formula 144]

[Chemical Formula 146] [Chemical Formula 147] [Chemical Formula 148]

[Chemical Formula 150] [Chemical Formula 150]

[Formula 154] [Formula 154]

[Chemical Formula 155]

[Formula 15] [Formula 15]

[Formula 161]

[166] [166] [166]

[169] [169] [169]

The method for producing the ring-opened ring compound according to the present invention is specifically shown in the following Examples.

The present invention also relates to a fuel cell comprising an anode; Cathode; And a layer interposed between the anode and the cathode, the layer including the alicyclic ring compound represented by the formula (1).

At this time, it is preferable that the layer including the ring-shaped ring compound is 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 >

In addition, according to another embodiment of the present invention, the thickness of the light emitting layer is preferably 50 to 2,000 ANGSTROM, and the light emitting layer may further include a material having the following structural formula

[Ir (ppy) ₃ ]

[Ir (chpy) ₃ ]

[Ir (mchpy) ₃ ]

As a specific example, a hole transport layer (HTL) may be additionally stacked, and an electron transport layer (ETL) may be further stacked between the cathode and the organic emission layer. The electron transport layer is deposited to facilitate the injection of holes from the anode. As the material of the hole transport layer, an electron donor molecule having a small ionization potential is used, and diamine, triamine or tetraamine derivative having a basic skeleton of triphenylamine 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) triphenyl-amine), m-MTDATA (4,4' -methylphenylphenylamino) triphenylamine) 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, however, to those skilled in the art that these embodiments are for further illustrating the present invention and that the scope of the present invention is not limited thereby.

<Examples>

Synthesis Example 1 Synthesis of Compound Represented by Formula 3

(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]

(0.081 mmol) of 2-bromocarbazole and 28.3 g (0.106 mmol) of 2-chloro-4,6-diphenyl-1,3,5-triazine were dissolved in 300 ml of DMSO. Then, 33.7 g ) 2 g (0.02 mmol) of copper (I) chloride was added and refluxed for 24 hours. After cooling the reaction solution to room temperature, the solvent was distilled off in a vacuum state. The mixture was extracted with toluene and water, and water was removed from the organic layer with anhydrous magnesium sulfate, and then the solvent was removed under reduced pressure. The reaction mixture was subjected to column separation with ethyl acetate and normal hexane, followed by vacuum drying to obtain 20 g of a compound represented by the formula (I-a). (Yield: 51%)

(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-a] [Chemical Formula 1-b]

(0.042 mmol) of N- (2-chloro-4,6-diphenyl-1,3,5-triazine) -2-bromocarbazole and 3.9 g (0.042 mmol) of aniline were dissolved in 200 ml of toluene, 0.8 g (0.001 mmol) of Pd [dba] ₃ , 0.5 g (0.001 mmol) of BINAP and 8.1 g (0.084 mmol) of sodium tertiary-butoxide were added and refluxed for 24 hours. After the reaction solution was cooled to room temperature, it was extracted with toluene and water. Water was removed from the organic layer with anhydrous magnesium sulfate, and the solvent was removed under reduced pressure. The reaction mixture was subjected to column separation using ethyl acetate and normal hexane, followed by vacuum drying to obtain 13.7 g of a compound represented by the formula (1-b). (Yield 67%)

(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-b] [Chemical Formula 1-c]

(2-chloro-4,6-diphenyl-1,3,5-triazine) -2-bromocarbazole used in Synthesis Example 1 (2) Synthesis was conducted in the same manner as in (2) of Synthesis Example 1, except that the compound represented by Formula (I-c) was used instead of the compound represented by Formula (I-b) . (Yield 64%)

(4) Synthesis of Compound Represented by Formula 3

A compound represented by the formula 3 was synthesized by the following reaction scheme 4.

[Reaction Scheme 4]

   [Chemical Formula 1-c] [Chemical Formula 3]

11.5 g (0.018 mmol) of the compound represented by the formula (1-c) synthesized in the above Reaction Scheme 3 was dissolved in 120 ml of tetrahydrofuran, cooled to -78 ^° C, tertiary-butyllithium (1.7 M pentane Solution) was added dropwise for 30 minutes and the mixture was further stirred for 1 hour.

4.1 g (0.018 mmol) of benzanthrone were dissolved in 40 ml of tetrahydrofuran, added to the reaction solution using a syringe, and then stirred for an additional 1 hour. After 1 hour, a saturated aqueous ammonium chloride solution was added and stirred for 30 minutes. The reaction mixture was extracted with water and ethyl acetate, dried over anhydrous magnesium sulfate, and vacuum dried to obtain the product. The unrefined compound was dissolved in 100 ml of acetic acid, a small amount of concentrated sulfuric acid was added, and the mixture was stirred at 60 ^° C for one day. After cooling, the precipitate was filtered, washed with water, washed with 5% aqueous sodium hydrogencarbonate solution and then subjected to column separation using a normal-hexane ethyl acetate solution. Ethanol was added to the obtained material for solidification, followed by filtration and vacuum drying to obtain 7.2 g of a compound represented by the formula (3). (Yield: 52%)

MS (MALDI-TOF): m / z 777 [M] ^&lt; ⁺ & gt ^;

Synthesis Example 2 Synthesis of Compound Represented by Formula 4

(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 [5].

[Reaction Scheme 5]

                                                     [Chemical Formula 2-a]

Except that 2-chloro-4,6-diphenyl-1,3,5-triazine was used in place of 2-chloro-4,6-diphenyl-1,3,5-triazine used in (1) Was synthesized by the same synthetic method as (1) in Synthesis Example 1, except that 5-pyrimidine was used to obtain 20 g of a compound represented by the formula (2-a). (Yield: 52%)

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

A compound represented by the formula (2-b) was synthesized by the following scheme (6).

[Reaction Scheme 6]

   [Chemical Formula 2-a] [Chemical Formula 2-b]

Except that the compound represented by the formula (2-a) was used instead of the compound represented by the formula (1-a) used in the above (2) Were synthesized by the same synthetic method to obtain 12.1 g of a compound represented by the formula (2-b). (Yield: 59%)

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

A compound represented by the formula (2-c) was synthesized by the following scheme [Reaction formula 7].

[Reaction Scheme 7]

    [Chemical Formula 2-b] [Chemical Formula 2-c]

Was synthesized in the same manner as in (3) of Synthesis Example 1 except that [Formula 2-b] was used in place of [Formula 1-b] used in (3) 2-c] was obtained. (Yield 64%)

(4) Synthesis of Compound Represented by Formula 4

[Chemical Formula 4] was synthesized by the following Reaction Scheme 8.

[Reaction Scheme 8]

    [Chemical formula 2-c] [Chemical formula 4]

(4) and (4) of Synthesis Example 1 were repeated except that the compound represented by Formula 2-c was used instead of the compound represented by Formula 1-c used in Synthesis Example 1 (4) Were synthesized by the same synthetic method to obtain 7.2 g of a compound represented by the formula (4). (Yield: 52%)

MS (MALDI-TOF): m / z 776 [M] ^&lt; ^{+ &}

Synthesis Example 3 Synthesis of Compound Represented by Formula 162

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

A compound represented by the general formula [3-a] was synthesized by the following scheme [Reaction formula 9].

[Reaction Scheme 9]

                                                   [Formula 3-a]

(3) of Synthesis Example 1 except that 9,9-dimethyl-2-iodofluorene was used in place of the compound represented by the formula (1-a) used in (2) To obtain 8 g of a compound represented by the formula (3-a). (Yield 60%)

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

[Chemical Formula 3-b] was synthesized by the following Reaction Scheme 10.

[Reaction Scheme 10]

   [Formula 3-a] [Formula 3-b]

8 g (0.028 mmol) of the compound represented by the formula (3-a) obtained in (1) of the above Synthesis Example 3 and 5.3 g (0.042 mmol) of bromomethyl methyl ether were dissolved in 80 ml of tetrahydrofuran , And 4.2 g (0.042 mmol) of triethylamine were added. After stirring for 5 hours in a nitrogen stream, distilled water was added and the organic layer was extracted. The extracted organic layer was subjected to column separation using n-hexane and tetrahydrofuran, followed by vacuum drying to obtain 6.7 g of a compound represented by the formula (3-b). (Yield: 72%)

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

[Chemical Formula 3-c] was synthesized by the following Reaction Scheme 11.

[Reaction Scheme 11]

  [Formula 3-b] [Formula 3-c]

6.7 g (0.02 mmol) of the compound represented by the formula (3-b) synthesized in the above (2) of the above Synthesis Example 3 was dissolved in 70 ml of purified tetrahydrofuran and then cooled to -78 ^° C to obtain n- 16.5 ml (0.026 mmol) of BuLi (1.6 M hexane solution) was slowly added dropwise. After stirring at the same temperature for 30 minutes, benzanthrone was added. After stirring at the same temperature for 40 minutes, the temperature was raised to room temperature and further stirred for 3 hours. The reaction was terminated with aqueous ammonium chloride solution and extracted with ethyl ether. Water was removed from the organic layer with anhydrous magnesium sulfate, and then the organic solvent was removed. The obtained solid was dispersed in ethanol, stirred for one day, filtered, and vacuum dried to disperse the intermediate in acetic acid, followed by adding a small amount of concentrated sulfuric acid and refluxing for 4 hours. The obtained solid was filtered, washed with ethanol, and then vacuum-dried to obtain 9.3 g of a compound represented by the formula (3-c). (Yield 66%)

(4) Synthesis of Compound Represented by Formula 162

A compound represented by the formula (162) was synthesized by the following reaction scheme [12].

[Reaction Scheme 12]

                      [Chemical Formula 3-c] [Chemical Formula 162]

The compound represented by the above formula (3-c) was obtained in the same manner as in the above Synthesis Example 2, except that 2-chloro-4,6-diphenyl-1,3,5- (2-chloro-4,6-diphenyl-1,3,5-triazine was used in place of pyrimidine, 6.3 g of the compound was obtained. (Yield: 46%)

MS (MALDI-TOF): m / z 728 [M] ^&lt; ^{+ &}

Synthesis Example 4 Synthesis of Compound Represented by Formula 131

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

A compound represented by the formula (4-a) was synthesized by the following reaction scheme [13].

[Reaction Scheme 13]

                                                    [Chemical Formula 4-a]

Instead of N- (2-chloro-4,6-diphenyl-1,3,5-triazine) -2-bromocarbazole used in (2) Was synthesized by the same synthetic method as (2) in Synthesis Example 1, except that thiophene was used to obtain 12.3 g of a compound represented by the formula 4-a. (Yield: 59%)

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

[Chemical Formula 4-b] was synthesized by the following Reaction Scheme 14.

[Reaction Scheme 14]

   [Formula 4-a] [Formula 4-b]

Was synthesized in the same manner as in the synthesis example 1, except that the compound represented by the formula (4-a) was used instead of the compound represented by the formula (1-b) used in the formula (3) -b] was obtained. (Yield: 61%)

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

[Chemical Formula 4-c] was synthesized by the following Reaction Scheme 15.

[Reaction Scheme 15]

 [Chemical Formula 4-b] [Chemical Formula 4-c]

(4-b) and 3-bromobenzanthrone instead of benzanthrone instead of the compound represented by formula (1-c) used in (4) Was synthesized by the same synthetic method as (4) in Synthesis Example 1 to obtain 7.2 g of the compound represented by the formula (4-c). (Yield: 42%)

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

[Chemical formula 4-d] was synthesized by the following scheme [Scheme 16].

[Reaction Scheme 16]

    [Chemical formula 4-c] [Chemical formula 4-d]

7.2 g (0.011 mmol) of the compound represented by the formula (4-c) synthesized in the above (3) (Reaction formula 15) of the above Synthesis Example 4 were dissolved in 70 ml of toluene, 3.1 g (0.012 mmol) of bispinacolatodiaboron, 0.18 g (0.0001 mmol) of PdCl ₂ (dppf) and 2.2 g (0.022 mmol) of potassium acetate were added in this order, and the mixture was refluxed for 24 hours. After completion of the reaction, the reaction mixture was extracted with toluene and water, the water was removed with anhydrous magnesium sulfate, and the solvent was removed under reduced pressure. The reaction mixture was subjected to column separation using ethyl acetate and n-hexane, followed by vacuum drying to obtain 4 g of a compound represented by the formula (4-d). (Yield: 52%)

(5) Synthesis of a compound represented by the formula (131)

A compound represented by the formula (131) was synthesized by the following reaction scheme [17].

[Reaction Scheme 17]

     [Chemical Formula 4-d] [Chemical Formula 131]

3.9 g (0.006 mmol) of the compound represented by the formula 4-d] obtained from the above-mentioned synthesis 4 (4) [Reaction formula 16] and 2 g of 2-chloro-4,6-diphenyl-1,3,5- (0.004 mmol) of Pd [PPh ₃ ] ₄ were added in this order, followed by the addition of 1 g (0.007 mmol) of potassium carbonate in an amount of 0.09 g (0.0001 mmol), followed by dissolving in 50 ml of toluene and refluxing for 24 hours. After completion of the reaction, the reaction mixture was extracted with toluene and water, the water was removed with anhydrous magnesium sulfate, and the solvent was removed under reduced pressure. The reaction mixture was subjected to column separation using dichloromethane and normal-hexane, followed by vacuum drying to obtain 1 g of a compound represented by the formula (131). (Yield: 34%)

MS (MALDI-TOF): m / z 794 [M] ^&lt; ⁺ & gt ^;

Synthesis Example 5 Synthesis of Compound Represented by Formula 103

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

[Formula 5-a] was synthesized by the following Reaction Scheme 18.

[Reaction Scheme 18]

                                             [Formula 5-a]

(3) of Synthesis Example 4 except that 2-bromodibenzothiophene was used in place of the compound represented by the formula (4-d) used in (3) To obtain 27 g of a compound represented by the formula (5-a). (Yield: 76%)

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

A compound represented by the formula (5-b) was synthesized by the following scheme (Scheme 19).

[Reaction Scheme 19]

 [Formula 5-a] [Formula 5-b]

Except that [Formula 5-a] was used in place of [Formula 4-d] used in Synthesis Example 4 (4) [Reaction Formula 16] and 2-chloro-4,6-diphenyl-1,3,5-tri Synthesis was conducted in the same manner as in (4) of Synthesis Example 4, except that bromonobenzene was used in place of azene to obtain 13 g of a compound represented by the formula (5-b). (Yield: 74%)

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

[Chemical Formula 5-c] was synthesized by the following Reaction Formula (20).

[Reaction Scheme 20]

     [Chemical Formula 5-b] [Chemical Formula 5-c]

13 g (0.043 mmol) of the compound represented by the formula (5-b) synthesized in (2) of the above Synthesis Example 5 and 27.9 g (0.106 mmol) of triphenylphosphine were placed, And refluxed for 48 hours. After completion of the reaction, the reaction mixture was distilled under vacuum to remove the solvent and extracted with toluene and water. The water was removed with anhydrous magnesium sulfate and the solvent was removed under reduced pressure. The reaction mixture was subjected to column separation using ethyl acetate and n-hexane, followed by vacuum drying to obtain 5.2 g of a compound represented by the formula (5-c). (Yield: 45%)

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

[Chemical Formula 5-d] was synthesized by the following Reaction Scheme (21).

[Reaction Scheme 21]

    [Chemical Formula 5-c] [Chemical Formula 5-d]

(3) and (3) of Synthesis Example 1 were repeated except that the compound represented by the formula 5-c was used instead of the compound represented by the formula 1-b used in the above (3) Synthesis was conducted by the same synthetic method to obtain 3.5 g of a compound represented by the formula (5-d). (Yield: 43%)

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

[Chemical Formula 5-e] was synthesized by the following Reaction Formula 22.

[Reaction Scheme 22]

  [Chemical Formula 5-d] [Chemical Formula 5-e]

Except that the compound represented by the formula 5-d was used instead of the compound represented by the formula 4-b used in the synthesis example 4 (2) [Reaction formula 14] Was synthesized by the same synthetic method to obtain 2.6 g of a compound represented by the formula (5-d). (Yield 50%)

(6) Synthesis of Compound Represented by Formula 5-f

[Formula 5-f] was synthesized by the following Reaction Scheme 23.

[Reaction Scheme 23]

    [Chemical Formula 5-e] [Chemical Formula 5-f]

Except that the compound represented by the formula 5-e was used instead of the compound represented by the formula 4-c used in the synthesis example 4 (3) [Reaction formula 15] Synthesis was conducted to obtain 1.7 g of a compound represented by the formula (5-f). (Yield: 61%)

(7) Synthesis of Compound Represented by Formula 103

A compound represented by the formula (103) was synthesized according to the following scheme (Scheme 24).

[Reaction Scheme 24]

    [Chemical Formula 5-f]

Except that the compound represented by the formula 5-f was used instead of the compound represented by the formula 4-d used in the synthesis example 4 (4) [Reaction formula 16] Synthesis was conducted in the same manner to obtain 0.5 g of a compound represented by the formula (103). (Yield: 37%)

MS (MALDI-TOF): m / z 792 [M] ^&lt; ^{+ &}

Examples 1 to 5 Production of an organic electroluminescent device including the compound synthesized by Synthesis Examples 1 to 5

The ITO glass was patterned to have a light emitting area of 2 mm x 2 mm and then cleaned. DNTPD (700Å) of ITO on the organic material so that after a then attached to a vacuum chamber base pressure was 1 × 10 ^-6 torr substrate, NPD (300Å), the compound + Ir (ppy) ₃ prepared according to the present invention ( Alq ₃ (350 Å), LiF (5 Å), and Al (1,000 Å).

[DNTPD]

[NPD]

[Ir (ppy) ₃ ]

[Alq ₃ ]

&Lt; Comparative Example 1 &

The organic electroluminescent device for the comparative example was fabricated in the same manner except that CBP was used instead of the compound prepared by the present invention as a host material in the device structure of the above example

[CBP]

division Host Dopant Doping concentration% ETL V ㏅ / A COLOR Comparative Example 1 CBP Ir (ppy) ₃ 10 Alq ₃ 7.2 36.2 green Example 1 (3) Ir (ppy) ₃ 10 Alq ₃ 6.3 41.1 green Example 2 Formula 4 Ir (ppy) ₃ 10 Alq ₃ 6.3 42.3 green Example 3 (103) Ir (ppy) ₃ 10 Alq ₃ 5.9 40.5 green Example 4 Formula 131 Ir (ppy) ₃ 10 Alq ₃ 6.0 41.3 green Example 5 Formula 162 Ir (ppy) ₃ 10 Alq ₃ 5.4 43.1 green

From the results of Examples 1 to 5, Comparative Examples 1 and Table 1, it can be seen that the organic electroluminescent device comprising the dicyclic ring compound according to the present invention as a host material has a structure in which the host material is CBP The driving voltage is low and the current efficiency is excellent. Therefore, it can be seen that the organic EL device can be effectively used for display devices, display devices, and illumination.

Claims (9)

A dicyclic ring compound represented by the following formula 1:
[Chemical Formula 1]

In this formula,
At least one of the formulas (A ₁₎ and (A ₂₎ is bonded to any two carbons of the formula (1) to form a condensed ring,
R ₁ to R ₈ each independently represents a hydrogen atom, a deuterium atom, a halogen atom, a substituted or unsubstituted arylamino group having 6 to 40 carbon atoms, a substituted or unsubstituted aryloxy group having 3 to 40 carbon atoms, 40 aryl group and a substituted or unsubstituted, and selection from the group consisting of a heteroaryl group having 3 to 40,
X is selected from the group consisting of O, S, CR ₉ R ₁₀ and SiR ₁₁ R ₁₂ , and R ₉ to R ₁₂ are the same as defined for R ₁ to R ₈ . The method according to claim 1,
Wherein R ₁ to R ₁₂ is of the R ₁ to R ₁₂ is a hydrogen atom, a heavy hydrogen atom, or except for the case of a halogen atom, and each independently represents an alkyl group having 1 to 40 carbon atoms, having 1 to 40 carbon atoms in the alkyl group, having 6 to 40 carbon atoms An arylamino group, a heteroarylamino group having 3 to 40 carbon atoms, an aryl group having 6 to 40 carbon atoms, and a heteroaryl group having 3 to 40 carbon atoms. The method according to claim 1,
Is a compound selected from the group consisting of the following formulas (2) to (169):
[Chemical Formula 2] &lt; EMI ID =

[Chemical Formula 5] &lt; EMI ID =

[Chemical Formula 8]

[Chemical Formula 12] [Chemical Formula 13]

[Chemical Formula 14]

[Chemical Formula 18] [Chemical Formula 19]

[Chemical Formula 20]

[Chemical Formula 23] [Chemical Formula 25]

[Chemical Formula 26]

[Chemical Formula 30] [Chemical Formula 30]

[Chemical Formula 32]

[Chemical Formula 35]

[Chemical Formula 38] [Chemical Formula 39]

[Chemical Formula 41]

[Chemical Formula 45]

[Chemical Formula 48] [Chemical Formula 48]

[Chemical Formula 50] [Chemical Formula 51]

[Chemical Formula 55] [Chemical Formula 55]

[Chemical Formula 57] [Chemical Formula 58]

[Chemical Formula 60] [Chemical Formula 61]

[Chemical Formula 62]

[Chemical Formula 65]

[Chemical Formula 70] [Chemical Formula 70]

[Chemical Formula 71] [Chemical Formula 72]

[Chemical Formula 75] [Chemical Formula 75]

[Formula 77] [Formula 79]

[Formula 80] [Formula 81]

[Chemical Formula 84]

[Chemical Formula 86]

[Chemical Formula 90] [Chemical Formula 90]

[Chemical Formula 93] [Chemical Formula 94]

[Formula 97] [Formula 97]

[Chemical Formula 99] [Chemical Formula 100]

[Formula 101] &lt; EMI ID =

(106) &lt; RTI ID = 0.0 &gt; (106)

(109) &lt; RTI ID = 0.0 &gt;

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

&Lt; EMI ID = 113.1 &gt;

&Lt; EMI ID = 116.1 &gt;

[Chemical Formula 120]

[124] [124] [124]

[Formula 125]

[Formula 130] [Formula 130]

[Formula 131] [Formula 131]

[Chemical Formula 135] [Chemical Formula 135]

[Chemical Formula 138]

[Formula 140]

[Chemical Formula 144] [Chemical Formula 144]

[Chemical Formula 146] [Chemical Formula 147] [Chemical Formula 148]

[Chemical Formula 150] [Chemical Formula 150]

[Formula 154] [Formula 154]

[Chemical Formula 155]

[Formula 15] [Formula 15]

[Formula 161]

[166] [166] [166]

[169] [169] [169]

Anode;
Cathode;
And a layer containing a modified ring compound according to any one of claims 1 to 3 interposed between the anode and the cathode. 5. The method of claim 4,
Wherein the aliphatic cyclic compound is contained in the light emitting layer between the anode and the cathode. 6. The method of claim 5,
And 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. 6. The method of claim 5,
Wherein the thickness of the light emitting layer is 50 to 2,000 ANGSTROM. 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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