KR101791022B1 - spiro compounds and organic light-emitting diode including the same - Google Patents

Abstract

The present invention relates to a novel spiro compound and an organic electroluminescent device comprising the same as a luminescent material. Specifically, the spiro compound represented by the following formula (1) and the organic electroluminescent device There is an excellent effect in light emission characteristics.

Description

Spiro compounds and organic electroluminescent devices including the spiro compounds and organic light-

The present invention relates to a novel spiro compound and an organic electroluminescent device including the same as a luminescent material. More particularly, the present invention relates to a spiro compound having excellent luminescence characteristics such as a driving voltage and a current efficiency and a stable spiro compound and an organic electroluminescent 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, 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.

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 the Invention The present invention provides a novel spiro compound having low driving voltage and excellent luminescence efficiency.

A second object of the present invention is to provide an organic electroluminescent device including the spiro 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 the above formula (1)

R ₁ To R ₅ each independently represent a hydrogen atom, a heavy hydrogen 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, and boron,

A is an element selected from C and Si,

Cy ₁ And Cy ₂ is a 5- to 8-membered ring compound selected from a substituted or unsubstituted aryl group having 6 to 40 carbon atoms, a substituted or unsubstituted heterocyclic group having 3 to 40 carbon atoms,

L is a divalent linking group and is a methylene group.

delete

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

According to the present invention, the spiro compound represented by the formula (1) has excellent luminescence characteristics as compared with the existing materials, so that the organic electroluminescence device including the spiro compound can be driven at a 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.
2 is a representative diagram showing the structure of a spiro compound represented by the formula (1) according to 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 a novel spiro compound represented by the above-mentioned formula (1), in which various spiro compounds are introduced by using a spiro-based compound having a heteroatom as a basic skeleton.

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

In the above formula (1), each of the substituents is independently a hydrogen atom, a deuterium atom, a cyano group, a halogen atom, a hydroxy group, a nitro group, an alkyl group having 1 to 40 carbon atoms, an alkoxy group having 1 to 40 carbon atoms, An amino group, an arylamino group having 6 to 40 carbon atoms, a heteroarylamino 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, An aryloxy group, a heteroaryl group having 3 to 40 carbon atoms, a germanium group, phosphorus, and boron, and may be further substituted by such a substituent.

The substituents may be bonded to each other to form a condensed ring of a saturated or unsaturated aliphatic, aromatic, heteroaliphatic or heteroaromatic ring and may be attached together or fused together by a pendant method.

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.

The alkylene group of L in the compound of the present invention is an alkylene group having 1 to 10 carbon atoms as a divalent linking group derived from the above alkyl groups and at least one hydrogen in the alkylene group may be substituted with the same substituent as the alkyl group Do.

The L heteroaryl group as a divalent linking group in the compound of the present invention is a heteroaryl group having 3 to 40 carbon atoms as a divalent linking group derived from the above heteroaryl groups and at least one hydrogen of the heteroaryl group is the same as the substituent Lt; / RTI >

In the compound of the present invention, the L-aryl group which is a divalent linking group is a divalent linking group derived from the above aryl groups and is an aryl group having 6 to 40 carbon atoms, and at least one of the aryl groups may be substituted with the same substituent as the alkyl group .

The L alkenyl group which is a divalent linking group in the compound of the present invention may be a linear, branched or cycloalkenyl group having 3 to 10 carbon atoms, and may be 1-methyl-n-hexenyl, 1,2-dimethyl- N-hexenyl, 1-n-heptenyl, 2-n-heptenyl, 3-n-heptenyl, 4-n-heptenyl, 2-c-hexenyl, 1-ethyl-c-hexenyl, 1-c-heptenyl, 2-c-heptenyl, Decyl, 3-c-heptenyl, 4-c-heptenyl, 1-c-octenyl, 2-c-octenyl, 3-c-octenyl, Lt; RTI ID = 0.0 > substituent < / RTI >

The alkynyl group may be any of straight, branched or cyclic C2 to C40 carbon atoms, and examples thereof include an ethynyl group, a 1-propynyl group, a 2-propynyl group and a 2-butynyl group. At least one hydrogen in the alkynyl group can be substituted with the same substituent.

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

Although the present invention is not limited by the specific examples of the spiro compounds 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 .

[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 83]

[Chemical Formula 85]

[Chemical Formula 87]

[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 >

The production method of the spiro 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 including a spiro compound represented by the formula (1), interposed between the anode and the cathode.

In this case, the layer containing the spiro 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 and an electron injecting layer And at least one layer selected from the group consisting of

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 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) or m-MTDATA (4,4', 4 '' - triphenylamine), which is a copper phthalocyanine (CuPc) or starburst type amine, tris- (3-methylphenylphenylamino) triphenylamine).

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 7

(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]

50.0 g (0.295 mol) of diphenylamine and 38.10 ml (0.443 mol) of bromomethyl methyl ether were dissolved in 1000 ml of tetrahydrofuran, and then 44.85 g (0.443 mol) of triethylamine was slowly added dropwise to a 2000 ml round bottom flask, , The organic layer was separated using water and tetrahydrofuran, and concentrated under reduced pressure. The residue was separated by column chromatography using hexane and tetrahydrofuran as a developing solvent to obtain a solid, which was then purified by column chromatography 53.3 g of a compound was obtained. (Yield: 84.6%)

(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]

10.0 g (0.047 mol) of the compound represented by the formula (1-a) obtained in the above Reaction Scheme 1 was dissolved in 100 ml of tetrahydrofuran and stirred for 30 minutes under a nitrogen atmosphere. The temperature of the reaction was maintained at -78 ° C , And then 7.28 ml (0.047 mol) of normal butyl lithium in 1.6 M hexane solution is added dropwise for 1 hour. After stirring at the same temperature for 1 hour, 12.8 g (0.047 mol) of 2-bromoanthrone is dissolved in 50 ml of tetrahydrofuran and slowly added dropwise. After stirring at the same temperature for 1 hour, the temperature was raised to room temperature and stirred for 5 hours. The organic layer was separated using ammonium chloride aqueous solution and ethyl ether, and the resulting solid was washed with ethanol and dried. The dried material is dispersed in 100 ml of acetic acid, 2 ml of concentrated sulfuric acid is slowly added dropwise, and the mixture is refluxed for 5 hours. The resulting solid was filtered off under reduced pressure, washed with water and ethanol, recrystallized using ethanol, and the obtained solid was dried to obtain 14.04 g of a compound represented by the formula (1-b). (Yield: 86.5%)

(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]

17.39 g (0.041 mol) of the compound represented by the formula (1-b), 16.8 g (0.081 mol) of 2-bromonaphthalene and 11.2 g (0.081 mol) of potassium carbonate obtained in the above reaction scheme 2 were added to a 250 ml round bottom flask, 0.1 g (0.001 mol) of copper iodide, 0.1 g (0.001 mol) of copper and 150 ml of xylene were placed and refluxed for 2 days. After completion of the reaction, the reaction mixture was cooled to room temperature, and the organic layer was separated using water and ethyl acetate. The organic layer was separated and concentrated under reduced pressure, and then the residue was purified by column chromatography using hexane and ethyl acetate as eluent to obtain a solid. Was obtained. (Yield: 62.4%)

(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-c] [Chemical Formula 1-d]

12.06 g (0.022 mol) of the compound represented by the formula (1-c) obtained from the above-mentioned Reaction Scheme 1, Reaction Scheme 2 and Reaction Scheme 3 and 6.1 g of bis (pinacolato) diboron were added to a 250 ml round bottom flask 0.4 g (0.001 mol) of PdCl ₂ (dppf), 4.3 g (0.044 mol) of potassium acetate and 120 ml of toluene are put into a flask and refluxed for 12 hours. When the reaction is completed, the temperature is lowered to room temperature and extracted with toluene and water. The organic layer was concentrated under reduced pressure, followed by separation by column chromatography using hexane and methylene chloride as eluting solvents, and the solid was dried to obtain 7.28 g of a compound represented by the formula (1-d). (Yield: 54.4%)

(5) Synthesis of Compound Represented by Formula 7

[Chemical Formula 7] was synthesized by the following Reaction Scheme 5.

[Reaction Scheme 5]

   [Chemical Formula 1-d] [Chemical Formula 7]

7.28 g (0.012 mol) of the compound represented by the formula (1-d) obtained from the above-mentioned Reaction Scheme 1, Reaction Scheme 3 and Reaction Scheme 4 were added to a 250 ml round bottom flask, 70 ml of tetrahydrofuran, 40 ml of toluene and 15 ml of water were added to 2.6 g (0.011 mol) of (pyridyl) -pyridine, 0.3 g (0.001 mmol) of tetrakistriphenylphosphine palladium and 3.4 g Reflux over time. After completion of the reaction, the temperature is lowered to room temperature and extraction is carried out using toluene and water. The organic layer was concentrated under reduced pressure, and then separated by column chromatography using hexane and ethyl acetate as eluent. The solid was dried to obtain 4.89 g of a compound represented by the formula (7). (Yield: 65.1%)

MS (MALDI-TOF): m / z = 625.3 [M] ^&lt; ^{+ &}

EA (Elemental analysis): theoretical value - C 88.29%; H 4.99%; N, 6.72%

                                Actual value - C. 88.67%; H 5.10%; N, 6.23%

Synthesis Example 2 Synthesis of Compound Represented by Formula 31

[Chemical Formula 31] was synthesized by the following Reaction Formula 6

[Reaction Scheme 6]

   [Chemical Formula 1-d] [Chemical Formula 31]

Except that 2-bromo-7- (pyridyl) -pyridine was used instead of 2-bromo-6- (pyridyl) -pyridine in the above (5) 1 was obtained in the same manner as in the synthesis of the compound [31].

MS (MALDI-TOF): m / z = 625.3 [M] ^&lt; ^{+ &}

EA (Elemental analysis): theoretical value - C 88.29%; H 4.99%; N, 6.72%

Actual value - C. 88.40%; H 5.19%; N, 6.41%

Synthesis Example 3 Synthesis of Compound Represented by Formula 35

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

A compound represented by the formula (3-a) was synthesized by the following reaction scheme [7].

[Reaction Scheme 7]

                                                        [Formula 3-a]

20.0 g (0.061 mol) of 2-bromophorenone and 19.57 ml (0.122 mol) of 3M phenylmagnesium bromide solution are placed in a 500 ml round bottom flask. Stir for 3 hours, neutralize by pouring water, cool cold and then extract using diethyl ether. The organic matter is treated with magnesium sulfate to remove moisture, filtered under reduced pressure, and concentrated to dryness. The dried solid was dissolved in benzene, and sulfuric acid was added thereto, followed by refluxing for 3 hours. Cool the reaction mixture and neutralize with sodium bicarbonate. The mixture was extracted with chloroform, and water was removed with magnesium sulfate. The filtrate was concentrated under reduced pressure, and the residue was purified by column chromatography using hexane and chloroform. The solid was dried to obtain 24.62 g of the compound represented by the formula 3-a . (Yield: 76.0%)

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

A compound represented by the formula (3-b) was synthesized by the following Reaction Scheme 8.

[Reaction Scheme 8]

   [Formula 3-b] [Formula 3-a] [Formula 3-b]

Was synthesized in the same manner as in (3) of Synthesis Example 1, except that the compound represented by the formula (3-a) was used instead of the compound obtained in the above (3) 3-b] was obtained.

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

[Chemical Formula 3-c] was synthesized by the following Reaction Scheme 9.

[Reaction Scheme 9]

      [Formula 3-b] [Formula 3-c]

A compound represented by the following formula (3-c) was synthesized in the same manner as in (4) and (4)

(4) Synthesis of Compound Represented by Formula 35

A compound represented by the formula (35) was synthesized by the following reaction scheme (10).

[Reaction Scheme 10]

    [Chemical Formula 3-c] [Chemical Formula 35]

A compound represented by the formula (35) was synthesized by the same synthetic method as (1) and (scheme 6) in the above Synthesis Example 2.

MS (MALDI-TOF): m / z = 815.3 [M] ^&lt; ^{+ &}

EA (Elemental analysis): theoretical value - C 89.79%; H 5.06%; N, 5.15%

Actual value - C. 89.15%; H. 5.12%; N, 5.73%

Synthesis Example 4 Synthesis of Compound Represented by Formula 95

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

A compound represented by the formula (4-a) was synthesized by the following Reaction Scheme (11).

[Reaction Scheme 11]

                                                       [Chemical Formula 4-a]

A compound represented by the formula (4-a) was synthesized in the same manner as in the synthesis of (1) [scheme 1].

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

[Chemical Formula 4-b] was synthesized by the following Reaction Scheme 12.

[Reaction Scheme 12]

  [Formula 4-a] [Formula 4-b]

10.0 g (0.047 mol) of the compound represented by the formula [4-a] obtained from the above-mentioned scheme [11] was dissolved in 100 ml of tetrahydrofuran in a 500 ml round-bottomed flask and stirred for 30 minutes under a nitrogen atmosphere. , And then 7.28 ml (0.047 mol) of normal butyl lithium in 1.6 M hexane solution is added dropwise for 1 hour. After stirring at the same temperature for 1 hour, 9.1 g (0.047 mol) of Anthrone is dissolved in 50 ml of tetrahydrofuran and slowly added dropwise. After stirring at the same temperature for 1 hour, the temperature was raised to room temperature and stirred for 5 hours. The organic layer was separated using ammonium chloride aqueous solution and ethyl ether, and the resulting solid was washed with ethanol and dried. The dried material is dispersed in 100 ml of acetic acid, 2 ml of concentrated sulfuric acid is slowly added dropwise, and the mixture is refluxed for 5 hours. The resulting solid was filtered off under reduced pressure, washed with water and ethanol, recrystallized using ethanol, and the obtained solid was dried to obtain 14.04 g of a compound represented by the formula 4-b. (Yield: 86.5%)

(3) Synthesis of Compound Represented by Formula (95)

A compound represented by the formula (95) was synthesized by the following reaction scheme [13].

[Reaction Scheme 13]

 [Chemical Formula 4-b]

7.0 g (0.02 mol) of the compound represented by the formula [4-b] obtained from the above-mentioned reaction formula 12, 10.8 g (0.041 mol) of chlorodiphenyltriazine, 5.6 g (0.041 mol) 0.4 g (0.002 mol) of copper iodide, 1.6 g (0.003 mol) of copper, and 140 ml of xylene are placed and refluxed for 2 days. After the completion of the reaction, the temperature was lowered to room temperature, and the organic layer was separated using water and ethyl acetate. The organic layer was concentrated under reduced pressure, and then subjected to column chromatography using hexane and ethyl acetate as eluent to obtain 4.1 g of a compound represented by the following formula . (Yield: 35.4%)

MS (MALDI-TOF): m / z = 576.2 [M] ^&lt; ^{+ &}

EA (Elemental analysis): theoretical value - C 85.39%; H 4.89%; N, 9.72%

Actual value - C. 85.70%; H 4.91%; N. 9.39%

Synthesis Example 5 Synthesis of Compound Represented by Formula 104

A compound represented by the formula (104) was synthesized by the following reaction scheme (14).

[Reaction Scheme 14]

 [Chemical Formula 4-b]

Was synthesized by the same synthetic method except that chlorodimethyldiphenyltriazine was used instead of chlorodiphenyltriazine in (3) [Reaction Scheme 13] in Synthesis Example 4 to obtain a compound represented by Formula (104).

MS (MALDI-TOF): m / z = 604.3 [M] ^&lt; ^{+ &}

EA (Elemental analysis): theoretical value - C. 85.40%; H 5.33%; N. 9.26%

Actual value - C. 85.02%; H. 5.24%; N, 9.77%

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 Cd / A color Comparative Example 1 CBP Ir (ppy) ₃ 10 Alq ₃ 7.2 36.24 green Example 1 Formula 7 Ir (ppy) ₃ 10 Alq ₃ 5.82 40.84 green Example 2 31 Ir (ppy) ₃ 10 Alq ₃ 6.21 42.33 green Example 3 (35) Ir (ppy) ₃ 10 Alq ₃ 6.03 41.05 green Example 4 95 Ir (ppy) ₃ 10 Alq ₃ 5.77 42.30 green Example 5 (104) Ir (ppy) ₃ 10 Alq ₃ 5.96 40.95 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 spiro compound according to the present invention as a host material has an organic electroluminescent device in which the host material is CBP A driving voltage is low, and a current efficiency is excellent, it can be used effectively for a display device, a display device, and an illumination.

Claims (9)

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

In the above formula (1)
R ₁ to R ₂ are each independently 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 aryl group having 3 to 40 carbon atoms, a substituted or unsubstituted heteroaryl group having 3 to 40 carbon atoms,
R ₃ to R ₄ are each independently selected from a hydrogen atom, a substituted or unsubstituted aryl group having 6 to 40 carbon atoms, and a substituted or unsubstituted heteroaryl group having 3 to 40 carbon atoms,
R ₅ is selected from a substituted or unsubstituted aryl group having 6 to 40 carbon atoms and a substituted or unsubstituted heteroaryl group having 3 to 40 carbon atoms,
At least one of R ₁ to R ₅ is a substituted or unsubstituted heteroaryl group having 3 to 40 carbon atoms,
A is an element selected from C and Si,
Cy ₁ and Cy ₂ are a 5- to 8-membered ring compound selected from a substituted or unsubstituted aryl group having 6 to 40 carbon atoms and a substituted or unsubstituted heterocyclic group having 3 to 40 carbon atoms,
L is a divalent linking group and is a methylene group.
The method according to claim 1,
R ₁ to R ₅ (except when R ₁ to R ₅ are each a hydrogen atom, a deuterium atom or a halogen atom), Cy ₁ and Cy ₂ each independently represent a hydrogen atom, a deuterium atom, A spiro compound which is selected from the group consisting of an alkyl group having 1 to 40 carbon atoms, an aryl group having 6 to 40 carbon atoms, an aryloxy group having 3 to 40 carbon atoms, and a heteroaryl group having 3 to 40 carbon atoms.
The method according to claim 1,
A spiro compound represented by any one of the following formulas (2) to (118):
[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 83]

[Chemical Formula 85]

[Chemical Formula 87]

[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;

Anode;
Cathode; And
An organic electroluminescent device comprising a layer containing a spiro 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 spiro 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, a hole blocking layer, an electron transporting layer, an electron injecting layer and an electron blocking 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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