KR101506761B1 - Organic compound and organic electroluminescent devices using the same - Google Patents

Abstract

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel organic light emitting compound and an organic electroluminescent device including the same. More particularly, the present invention relates to a novel organic light emitting compound used for hole injection, hole transport, .

Description

TECHNICAL FIELD [0001] The present invention relates to an organic compound and an organic electroluminescent device using the organic compound.

The present invention relates to a novel organic compound that can be used as a material for an organic electroluminescence device and an organic electroluminescence device including the same.

A study on organic electroluminescent (EL) devices (hereinafter simply referred to as "organic EL devices") led to blue electroluminescence using anthracene single crystals in 1965, starting from the observation of organic thin film luminosity of Bernanose in the 1950s, (Tang) and a functional layer of a light emitting layer. In order to produce high efficiency and high number of organic EL devices, the organic EL device has been developed to introduce each characteristic organic material layer in the device, leading to the development of specialized materials used therefor.

In the organic electroluminescent device, when a voltage is applied between two electrodes, holes are injected into the anode, and electrons are injected into the organic layer from the cathode. When the injected holes and electrons meet, an exciton is formed. When the exciton falls to the ground state, light is emitted. The material used as the organic material layer may be classified into a light emitting material, a hole injecting material, a hole transporting material, an electron transporting material, and an electron injecting material depending on functions.

The luminescent material can be classified into blue, green and red luminescent materials according to luminescent colors and yellow and orange luminescent materials necessary for realizing better natural colors. Further, in order to increase the color purity and to increase the luminous efficiency through energy transfer, a host / dopant system can be used as a luminescent material. The dopant material can be divided into a fluorescent dopant using an organic material and a phosphorescent dopant using a metal complex compound containing heavy atoms such as Ir and Pt. At this time, since the phosphorescent material can theoretically improve the luminous efficiency up to 4 times as compared with the fluorescent material, researches on phosphorescent host materials as well as phosphorescent dopants have been conducted.

Up to now, hole injecting layer, hole transporting layer. NPB, BCP, and Alq ₃ are widely known as the hole blocking layer and the electron transporting layer, and anthracene derivatives as a luminescent material have been reported as fluorescent dopant / host material. In particular, the phosphor has a great advantage in improving the efficiency aspects of the light-emitting material materials _{Firpic, Ir (ppy) 3,} (acac) Ir (btp) 2 Ir metal complex compound is blue (blue), which includes the same as the green ( green and red dopant materials, and CBP is a phosphorescent host material.

However, existing materials have advantages in terms of light emitting properties, but they are not satisfactory in terms of lifetime in OLED devices because of low glass transition temperature and poor thermal stability. Therefore, development of materials with higher performance is required.

Republic of Korea public patent 2010-0105099

It is an object of the present invention to provide a novel organic compound having an excellent thermal stability due to a high glass transition temperature.

It is another object of the present invention to provide an organic electroluminescent device including the novel organic compound and having improved driving voltage, luminous efficiency, and the like.

The present invention provides a compound represented by the following formula (1): < EMI ID =

In Formula 1,

A and B are each a substituted or unsubstituted six-membered cycle;

Ar ₁ and Ar ₂ are each independently a substituted or unsubstituted C ₁ to C ₄₀ alkyl group, a substituted or unsubstituted C ₃ to C ₄₀ cycloalkyl group, a substituted or unsubstituted heterocyclic group having 3 to 40 nuclear atoms An alkyl group, a substituted or unsubstituted C ₆ to C ₆₀ aryl group, a substituted or unsubstituted heteroaryl group having 5 to 60 nuclear atoms, a substituted or unsubstituted C ₁ to C ₄₀ alkyloxy group, hwandoen C ₆ ~ C ₆₀ aryloxy group, a substituted or unsubstituted C ₁ ~ C ₄₀ alkyl silyl group, a substituted or unsubstituted C ₆ ~ C ₆₀ aryl silyl group, or a C ₆ unsubstituted or substituted in the the aryl amine group of ₆₀ ~ C,

At this time, one or more substituents respectively introduced into the alkyl group, cycloalkyl group, heterocycloalkyl group, aryl group, heteroaryl group, alkyloxy group, aryloxy group, alkylsilyl group, arylsilyl group and arylamine group are each independently selected from deuterium , A cyano group, a C ₁ to C ₄₀ alkyl group, a C ₃ to C ₄₀ cycloalkyl group, a heterocycloalkyl group having 3 to 40 nuclear atoms, a C ₆ to C ₆₀ aryl group, a heteroaryl group having 5 to 60 nuclear atoms Group, a C ₁ to C ₄₀ alkyloxy group, a C ₆ to C ₆₀ aryloxy group, and a C ₆ to C ₆₀ arylamine group, wherein the plurality of substituents may be the same or different;

R ₁ to R ₈ each independently represent hydrogen, deuterium, halogen, a substituted or unsubstituted C ₁ to C ₄₀ alkyl group, a substituted or unsubstituted C ₃ to C ₄₀ cycloalkyl group, a substituted or unsubstituted nucleus atom number A substituted or unsubstituted C ₆ to C ₆₀ aryl group, a substituted or unsubstituted heteroaryl group having 5 to 60 nuclear atoms, a substituted or unsubstituted C ₁ to C ₄₀ alkyl aryloxy group, arylsilyl a substituted or unsubstituted C ₆ ~ C ₆₀ of the aryloxy group, a substituted or unsubstituted C ₁ ~ C ₄₀ alkyl silyl group, a substituted or unsubstituted C ₆ ~ C ₆₀ of the group, or a substituted Or an unsubstituted C ₆ to C ₆₀ arylamine group,

At this time, one or more substituents respectively introduced into the alkyl group, cycloalkyl group, heterocycloalkyl group, aryl group, heteroaryl group, alkyloxy group, aryloxy group, alkylsilyl group, arylsilyl group and arylamine group are each independently selected from deuterium , A cyano group, a C ₁ to C ₄₀ alkyl group, a C ₃ to C ₄₀ cycloalkyl group, a heterocycloalkyl group having 3 to 40 nuclear atoms, a C ₆ to C ₆₀ aryl group, a heteroaryl group having 5 to 60 nuclear atoms Group, a C ₁ to C ₄₀ alkyloxy group, a C ₆ to C ₆₀ aryloxy group, and a C ₆ to C ₆₀ arylamine group, and the plurality of substituents may be the same or different.

The present invention also provides an organic electroluminescent device comprising (i) an anode, (ii) a cathode, and (iii) one or more organic layers sandwiched between the anode and the cathode, wherein at least one One of them is an organic electroluminescent device comprising the above compound.

Here, the organic compound layer containing the compound is preferably at least one selected from the group consisting of a hole injection layer, a hole transport layer and a light emitting layer, and more preferably a phosphorescent host or a fluorescent dopant of the light emitting layer.

The compound represented by the general formula (1) of the present invention is excellent in heat resistance, hole injection and transportation performance, and light emitting performance. Therefore, it is preferable that the compound represented by the general formula (1) has at least one of phosphorescent / fluorescent host and dopant of the hole injection layer, Can be applied.

Accordingly, when the novel compound of the present invention is used, an organic electroluminescent device having excellent light emitting performance, low driving voltage, high current efficiency, and long life can be manufactured, and a full color display panel can do.

Hereinafter, the present invention will be described.

The present invention provides a compound represented by the above formula (1) having a higher molecular weight than a conventional organic EL device material (for example, 4,4-dicarbazolybiphenyl (hereinafter referred to as "CBP" . When the above compound is used in an organic EL device, driving voltage and efficiency aspects of the device can be improved.

The compound represented by Formula 1 has fused indole skeletons at both terminals of naphthalene and has a wide band gap (sky blue to red) by controlling the energy level by various substituents. Thus, the phosphorescent characteristics of the device can be improved, and the hole injecting ability and / or transporting ability, luminous efficiency, driving voltage, lifetime characteristics and the like can be improved. Therefore, it can be applied not only as a light emitting layer but also as a hole transporting layer, a hole injecting layer, a host, etc. by the introduction of various substituents. In particular, since the compound has a wide band gap due to the indole based basic skeleton, it can exhibit excellent characteristics as a light emitting host material compared to conventional CBP.

In addition, the molecular weight of the compound is significantly increased due to various aromatic ring substituents introduced into the indole-based basic skeleton, whereby the glass transition temperature is improved, and thus it can have higher thermal stability than the conventional CBP . Thus, devices comprising the compounds of the present invention can significantly improve durability and lifetime characteristics.

In addition, when the compound is used as a positive hole injection / transport layer, a blue, green and / or red phosphorescent host material or a fluorescent dopant material of an organic EL device, it can exert an excellent effect in terms of efficiency and lifetime compared to CBP. Accordingly, the compound represented by the formula (1) according to the present invention can greatly contribute to the improvement of the performance and lifetime of the organic EL device, and particularly the lifetime improvement of the device has a great effect in maximizing the performance in the full color organic light emitting panel.

In the compound represented by Formula 1, A and B are each a substituted or unsubstituted 6-membered cycle, which are pendant or fused to each other to form a substituted or unsubstituted ring, To form a naphthalene derivative.

The naphthalene derivative may be substituted with at least _{one selected} from the group consisting of deuterium, halogen, substituted or unsubstituted C ₁ to C ₄₀ alkyl group, substituted or unsubstituted C ₃ to C ₄₀ cycloalkyl group, substituted or unsubstituted heterocycloalkyl group having 3 to 40 nuclear atoms , A substituted or unsubstituted C ₆ to C ₆₀ aryl group, a substituted or unsubstituted heteroaryl group having 5 to 60 ring atoms, a substituted or unsubstituted C ₁ to C ₄₀ alkyloxy group, a C ₆ ~ C ₆₀ of the aryloxy group, a substituted or unsubstituted C ₁ ~ C ₄₀ alkyl silyl group, a substituted or unsubstituted C ₆ ~ C ₆₀ aryl silyl group, and a substituted or unsubstituted C ₆ ~ C An aryl group, an aryloxy group, an aryloxy group, an aryloxy group, an aryloxy group, an aryloxy group, an aryloxy group, an aryloxy group, an aryloxy group, and an arylamine group having a carbon number of 1 to ₆₀ , The one or more substituents introduced into the arylamine group, respectively, A halogen atom, a cyano group, a C ₁ to C ₄₀ alkyl group, a C ₃ to C ₄₀ cycloalkyl group, a heterocycloalkyl group having 3 to 40 nuclear atoms, a C ₆ to C ₆₀ aryl group, A heteroaryl group having ₁ to ₆₀ carbon atoms, a C ₁ to C ₄₀ alkyloxy group, a C ₆ to C ₆₀ aryloxy group, and a C ₆ to C ₆₀ arylamine group, with the plurality of substituents being the same or different Can be different.

In the compound represented by Formula 1, Ar ₁ and Ar ₂ are each independently a substituted or unsubstituted C ₆ to C ₆₀ aryl group, a substituted or unsubstituted heteroaryl group having 5 to 60 ring atoms, A substituted or unsubstituted C ₆ to C ₆₀ arylamine group. The aryl group, heteroaryl group and arylamine group are each independently selected from the group consisting of deuterium, a halogen, a cyano group, a C ₁ to C ₄₀ alkyl group, a C ₃ to C ₄₀ cycloalkyl group, a heterocycloalkyl group having 3 to 40 nuclear atoms , A C ₆ to C ₆₀ aryl group, a heteroaryl group having 5 to 60 nuclear atoms, a C ₁ to C ₄₀ alkyloxy group, a C ₆ to C ₆₀ aryloxy group, and a C ₆ to C ₆₀ arylamine group And a plurality of substituents may be the same or different.

More preferably, Ar ₁ and Ar ₂ each independently represent a substituted or unsubstituted phenyl group, a substituted or unsubstituted naphthyl group, a substituted or unsubstituted pyridyl group, a substituted or unsubstituted pyrimidinyl group a pyrimidinyl group, a substituted or unsubstituted triazinyl group, a substituted or unsubstituted quinolyl group, or a substituted or unsubstituted indolyl group, and the phenyl group, A halogen atom, a cyano group, a C ₁ to C ₄₀ alkyl group, a C ₃ to C ₄₀ alkyl group, a substituted or unsubstituted C ₁ to C ₄₀ alkyl group, a substituted or unsubstituted aryl group, ₄₀ cycloalkyl group, the nuclear atoms 3 to 40 heterocycloalkyl group, C ₆ ~ C ₆₀ aryl group, the number of nuclear atoms of 5 to 60 of the heteroaryl group, C ₁ ~ alkyloxy group of C _40, C ₆ ~ C ₆₀ aryloxy, and C ₆ ~ selected from the group consisting of C ₆₀ arylamine A plurality of substituents may be the same or different.

More preferably, Ar < _{1 >} and Ar < ₂ > each independently may be selected from the group consisting of Substituent S1 to Substituent S138.

Examples of the compound represented by the formula (1) according to the present invention include compounds represented by the following formulas (2) to (8), but are not limited thereto.

In the above Chemical Formulas 2 to 8,

Ar ₁ and Ar _2, R ₁ to R ₈ are each as defined in formula (1)

R ₉ to R ₁₂ each independently represent hydrogen, deuterium, halogen, a substituted or unsubstituted C ₁ to C ₄₀ alkyl group, a substituted or unsubstituted C ₃ to C ₄₀ cycloalkyl group, a substituted or unsubstituted nucleus atom number A substituted or unsubstituted C ₆ to C ₆₀ aryl group, a substituted or unsubstituted heteroaryl group having 5 to 60 nuclear atoms, a substituted or unsubstituted C ₁ to C ₄₀ alkyl aryloxy group, arylsilyl a substituted or unsubstituted C ₆ ~ C ₆₀ of the aryloxy group, a substituted or unsubstituted C ₁ ~ C ₄₀ alkyl silyl group, a substituted or unsubstituted C ₆ ~ C ₆₀ of the group, or a substituted Or an unsubstituted C ₆ to C ₆₀ arylamine group,

At this time, one or more substituents respectively introduced into the alkyl group, cycloalkyl group, heterocycloalkyl group, aryl group, heteroaryl group, alkyloxy group, aryloxy group, alkylsilyl group, arylsilyl group and arylamine group are each independently selected from deuterium , A cyano group, a C ₁ to C ₄₀ alkyl group, a C ₃ to C ₄₀ cycloalkyl group, a heterocycloalkyl group having 3 to 40 nuclear atoms, a C ₆ to C ₆₀ aryl group, a heteroaryl group having 5 to 60 nuclear atoms Group, a C ₁ to C ₄₀ alkyloxy group, a C ₆ to C ₆₀ aryloxy group, and a C ₆ to C ₆₀ arylamine group, and the plurality of substituents may be the same or different.

The following formulas are typical examples of the compound of formula (I) of the present invention, but the compound of formula (I) of the present invention is not limited to those exemplified below.

"Unsubstituted alkyl" used in the present invention is a linear or branched saturated hydrocarbon having 1 to 40 carbon atoms, and examples thereof include methyl, ethyl, propyl, isobutyl, sec-butyl, pentyl, iso-amyl, .

"Unsubstituted cycloalkyl" includes monocyclic or polycyclic non-aromatic hydrocarbon groups of 3 to 40 carbon atoms. Examples of such cycloalkyls include, but are not limited to, cyclopropyl, cyclopentyl, cyclohexyl, norbornyl, adamantine, and the like.

"Unsubstituted heterocycloalkyl" means a non-aromatic moiety of 3 to 40 nucleus atoms in which at least one of the carbons, preferably one to three carbons, is replaced with a heteroatom such as N, O or S . Non-limiting examples thereof include morpholine, piperazine, and the like.

"Unsubstituted aryl" means an aromatic moiety having from 6 to 60 carbon atoms, either a single ring or a combination of two or more rings. Two or more rings may be attached to each other in a pendant or fused form to each other. Examples of aryl include, but are not limited to, phenyl, naphthyl, phenanthryl, anthryl, and the like.

"Unsubstituted heteroaryl" means a monoheterocyclic or polyheterocyclic aromatic moiety of 5 to 60 nucleus atoms in which at least one carbon, preferably one to three carbons, of the ring is replaced by N, O, S Or < RTI ID = 0.0 > Se. ≪ / RTI > It is interpreted that two or more rings may be attached to each other in a pendant or fused form to each other and further include a condensed form with an aryl group. Examples of heteroaryl include 6-membered monocyclic rings such as pyridyl, pyrazinyl, pyrimidinyl, pyridazinyl, and triazinyl; Such as phenoxathienyl, indolizinyl, indolyl, purinyl, quinolyl, benzothiazole, carbazolyl, and the like. Includes rings and is also meant to include 2-furanyl, N-imidazolyl, 2-isoxazolyl, 2-pyridinyl, 2-pyrimidinyl and the like.

"Unsubstituted alkyloxy" means alkyl having from 1 to 40 carbon atoms attached to oxygen and is understood to include linear, branched or cyclic structures. Examples of alkyloxy groups include, but are not limited to, methoxy, ethoxy, n-propoxy, 1-propoxy, t-butoxy, n-butoxy, pentoxy and the like.

"Unsubstituted aryloxy" includes phenyloxy, naphthyloxy, diphenyloxy and the like having 5 to 60 carbon atoms, and "unsubstituted arylamine" means an amine substituted with aryl having 6 to 60 carbon atoms.

"Fused ring" means a fused aliphatic ring, a fused aromatic ring, a fused heteroaliphatic ring, a fused heteroaromatic ring, or a combination thereof.

The compounds of formula 1 of the present invention can be synthesized according to the general synthetic methods ( Chem. Rev. , 60 : 313 (1960); J. Chem. SOC . 4482 (1955); Chem. Rev. 95: 2457 (1995 ). Detailed synthesis of the compound of the present invention will be described in detail in Synthesis Examples to be described later.

Meanwhile, the present invention provides an organic electroluminescent device comprising a compound represented by the above-mentioned formula (1), preferably a compound represented by the following formulas (2) to (8).

Specifically, the present invention provides a fuel cell comprising: an anode; A cathode; And at least one organic material layer interposed between the anode and the cathode, wherein at least one of the one or more organic material layers is a compound represented by the formula (1), preferably a compound represented by the following formula And a compound represented by the formula (1). At this time, the compounds of the formulas (1) to (8) may be included singly or in plurality.

The organic compound layer containing the compound represented by the formula (1) of the present invention, preferably the compound represented by the formulas (2) to (8) may be any one or more of a hole injecting layer, a hole transporting layer and a light emitting layer. And may be included in the organic EL device as the material of the hole injection layer and the hole transport layer. In this case, the organic EL device can maximize the hole injection / transport capability. Further, it can be used as a light emitting layer material of an organic EL device, preferably a blue, green and / or phosphorescent host, and a fluorescent dopant, thereby providing improved efficiency and lifetime.

In addition, the compound represented by Formula 1 according to the present invention, preferably Formula 2 to Formula 8, has a high glass transition temperature. Therefore, when the compound is used as the organic material layer of the organic light emitting device, the crystallization in the organic light emitting device is minimized, so the driving voltage of the device can be lowered and the light emitting efficiency, thermal stability and lifetime characteristics can be improved .

Non-limiting examples of the structure of the organic EL device according to the present invention may include a substrate, an anode, a hole injecting layer, a hole transporting layer, a light emitting layer, an electron transporting layer, and a cathode sequentially laminated. At least one of the hole injecting layer, the hole transporting layer, and the light emitting layer may include the compound represented by the above formula (1). Further, the compound of the present invention can be used as a phosphorescent host or a fluorescent dopant of the light emitting layer. An electron injection layer may be disposed on the electron transport layer.

In addition, the organic EL device according to the present invention may have an insulating layer or an adhesive layer inserted into the interface between the electrode and the organic layer as well as the structure in which the anode, one or more organic layers and the cathode are sequentially stacked, as described above.

In the organic EL device according to the present invention, the organic material layer containing the compound represented by Formula 1 may be formed by a vacuum deposition method or a solution coating method. Examples of the solution coating method include, but are not limited to, spin coating, dip coating, doctor blading, inkjet printing, or thermal transfer.

The organic EL device according to the present invention may be formed by using materials and methods known in the art, except that at least one layer of the organic material layer is formed so as to contain the compound represented by the formula (1) of the present invention .

For example, a silicon wafer, quartz or glass plate, a metal plate, a plastic film or a sheet can be used as the substrate.

Examples of the positive electrode material include metals such as vanadium, chromium, copper, zinc, and gold, or alloys thereof; Metal oxides such as zinc oxide, indium oxide, indium tin oxide (ITO), and indium zinc oxide (IZO); ZnO: Al or SnO _2: a combination of a metal and an oxide such as Sb; Conductive polymers such as polythiophene, poly (3-methylthiophene), poly [3,4- (ethylene-1,2-dioxy) thiophene] (PEDT), polypyrrole and polyaniline; Or carbon black, but are not limited thereto.

Examples of the negative electrode material include metals such as magnesium, calcium, sodium, potassium, titanium, indium, yttrium, lithium, gadolinium, aluminum, silver, tin or lead or alloys thereof; Layer structure materials such as LiF / Al or LiO ₂ / Al, but are not limited thereto.

The electron injecting layer and the electron transporting layer are not particularly limited, and ordinary materials known in the art can be used.

Hereinafter, the present invention will be described in detail with reference to the following examples. However, the following examples are for illustrative purposes only and are not intended to limit the scope of the present invention.

[Preparation Example 1] Synthesis of 1,8-dihydrocarbazolo [4,3-c] carbazole

<Preparation Step 1-1> Synthesis of 1,5-bis (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) naphthalene

1,5-dibromonaphthalene (30 g, 0.105 mol), 4,4,4 ', 4', 5,5,5 ', 5'-octamethyl-2,2'- dioxaborolane (80 g, 0.315 mol), palladium bisdiphenylphosphinoferrocene dichloro (Pd (dppf) Cl ₂ ) (8.57 g, 10 mol%), potassium acetate (KOAc) (61.78 g, 0.63 mol% N, N-dimethylformamide (DMF) (1000 ml) were mixed and stirred at 130 ° C for 12 hours.

After the reaction was completed, the reaction mixture was extracted with ethyl acetate, and the residue was purified by column chromatography (Hexane: EA = 5: 1 (v / v)) to remove moisture with MgSO ₄ . , 5-tetramethyl-1,3,2-dioxaborolan-2-yl) naphthalene (22.1 g, yield 55%).

^{1 H-NMR: δ 1.42 (} s, 24H), 7.51 (t, 2H), 8.06 (d, 2H), 8.88 (d, 2H)

<Preparation step 1-2> 1,5- bis (2- nitrophenyl ) Synthesis of naphthalene

1-bromo-2-nitrobenzene (23.31 g, 115.37 mmol) and 1,5-bis (4,4,5,5-tetramethyl-1,3,2 -dioxaborolan-2-yl) naphthalene (20 g, 54.94 mmol), NaOH (13.19 g, 329.63 mmol) and Toluene / H ₂ O (200 ml / 100 ml) were mixed and then palladium- insert the phosphine _{(Pd (PPh 3) 4)} (6.34 g, 10 mol%), the mixture was stirred at 120 ℃ for 12 hours.

After completion of the reaction, the reaction temperature was cooled to room temperature to obtain a solid product, and then the solid product was filtered. Subsequently, the filtered solid product was recrystallized from dichloromethane and acetone to obtain 1.5-bis (2-nitrophenyl) naphthalene (12.41 g, yield 61%) as a yellow solid.

^{1 H-NMR: δ 7.52 (} t, 2H), 7.62 (t, 2H), 7.89 (t, 2H), 8.05 (d, 2H), 8.12 (d, 2H), 8.32 (d, 2H), 8.53 ( d, 2H)

&Lt; Preparation step 1-3 > dihydrocarbazolo [4,3-c] carbazole

Bis (2-nitrophenyl) naphthalene (10 g, 27 mmol) obtained in <preparation step 1-2> was dissolved in triphenylphosphine (35.41 g, 135 mmol) and o- dichlorobenzene After mixing, they were stirred for 12 hours.

After completion of the reaction, o-dichlorobenzene was removed, and the organic layer was extracted with dichloromethane. Then, water was removed from the obtained organic layer using MgSO ₄ and purified by column chromatography (Hexane: EA = 3: 1 (v / v)) to obtain 1,8-dihydrocarbazolo [4,3- g, yield: 43%).

^{1 H-NMR: δ 7.53 (} d, 2H), 7.64 (t, 2H), 8.08 (t, 2H), 8.14 (d, 2H), 8.33 (d, 2H), 8.54 (d, 2H), 8.75 ( s, 2H)

[Preparation Example 2] Synthesis of 4,11-diphenyl-1,8-dihydrocarbazolo [4,3-c] carbazole

<Preparation Step 2-1> Synthesis of 1,5-bis (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) naphthalene

(22.1 g, yield 55%) of 1,5-bis (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) naphthalene was obtained in the same manner as in the preparation step 1-1 of Preparation Example 1, ).

<Preparation step 2-2> 1,5- bis (5- bromo -2- nitrophenyl ) Synthesis of naphthalene

Except that 2,4-dibromo-1-nitrobenzene (15.52 g, 55.25 mmol) was used in place of 1-bromo-2-nitrobenzene used in Preparation Step 1-2 of Preparation Example 1, 1,5-bis (5-bromo-2-nitrophenyl) naphthalene (6.53 g, yield 47%) was obtained in the same manner as in preparation step 1-2.

^{1 H NMR: δ 7.56 (t} , 2H), 7.84 (d, 2H), 8.01 (d, 2H), 8.36 (d, 2H), 8.57 (d, 2H), 8.61 (s, 2H)

<Preparation step 2-3> 4, 11- dibromo -1,8- dihydrocarbazolo [4,3-c] carbazole

Preparation of Preparation Example 1 The procedure of Preparation Example 1 was repeated except that 1,5-bis (5-bromo-2-nitrophenyl) naphthalene (prepared in Preparation Example 2-2) Dibromo-1,8-dihydrocarbazolo [4,3-c] carbazole (prepared according to Preparation Example 1) was used in place of 3.43 g, yield 39%).

^{1 H NMR: δ 7.57 (d} , 2H), 8.02 (d, 2H), 8.35 (d, 2H), 8.56 (d, 2H), 8.61 (s, 2H), 8.77 (s, 2H)

<Preparation Step 2-4> Synthesis of 4,11-diphenyl-1,8-dihydrocarbazolo [4,3-c] carbazole

Phenylboronic acid (1.65 g, 13.57 mmol) was used instead of 1-bromo-2-nitrobenzene (23.31 g, 115.37 mmol) used in Preparation Example 1-2 of Preparation Example 2, Prepared in Preparation Example 2, instead of 4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) naphthalene (20 g, 54.94 mmol) Preparation step 1-2 of Preparation Example 2 was repeated except that 1,8-dihydrocarbazolo [4,3-c] carbazole (3 g, 6.46 mmol) was used and THF was used instead of toluene Followed by stirring.

After completion of the reaction, the reaction mixture was extracted with dichloromethane, and the residue was purified by column chromatography (Hexane: MC = 1: 1 (v / v)) to remove moisture with MgSO ₄ . dihydrocarbazolo [4,3-c] carbazole (2.31 g, yield 78%).

^{1 H-NMR: δ 7.59 (} d, 2H), 7.64 (m, 6H), 7.71 (m, 4H), 8.05 (d, 2H), 8.12 (d, 2H), 8.33 (d, 2H), 8.54 ( s, 2 H), 8.78 (s, 2 H)

Preparation Example 3 Synthesis of 13,14-dihydrocarbazolo [1,2-a] carbazole and 1,4-dihydrocarbazolo [2,3-b] carbazole

<Preparation Step 3-1> Preparation of 2,7-bis (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) naphtha alene Synthesis of

Preparation step 1-Preparation of Preparation Example 1 The procedure of Preparation Example 1 was repeated, except that 2,7-dibromonaphthalene (30 g, 104.91 mmol) was used instead of 1,5-dibromonaphthalene used in <preparation step 1-1> 1>, 2,7-bis (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) naphtha alene (22.33 g, yield 56%) was obtained.

^{1 H-NMR: δ 1.43 (} s, 24H), 7.57 (d, 2H), 8.53 (d, 2H), 8.86 (s, 2H)

&Lt; Preparation step 3-2 > bis (2- nitrophenyl ) Synthesis of naphthalene

(Preparation Step 3-A) instead of 1,5-bis (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) naphthalene used in <Preparation Step 1-2> (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) naphthalene (20 g, 52.63 mmol) obtained in Example 1 and using THF instead of toluene 2,7-bis (2-nitrophenyl) naphthalene (11.5 g, yield 59%) was obtained in the same manner as in <Preparation step 1-2> of Preparation Example 1,

^{1 H-NMR: δ 7.53 (} d, 2H), 7.63 (t, 2H), 7.86 (t, 2H), 8.04 (d, 2H), 8.11 (d, 2H), 8.34 (s, 2H), 8.54 ( d, 2H)

Preparation Step 3-3 Preparation of 13,14-dihydrocarbazolo [1,2-a] carbazole and 1,4-dihydrocarbazolo [2,3-b] carbazole Synthesis of

(2-nitrophenyl) naphthalene (obtained in Preparation 3-2) instead of 1,5-bis (2-nitrophenyl) naphthalene used in Preparation Example 1-3 of Preparation Example 1 Dihydrocarbazolo [1,2-a] carbazole (2.56 g, yield: 31%) was obtained in the same manner as in <Preparation step 1-3> of Preparation Example 1, And 1,4-dihydrocarbazolo [2,3-b] carbazole (2.4 g, yield 29%).

13,14-dihydrocarbazolo [1,2-a] 1 the carbazole H-NMR: δ 7.55 ( d, 2H), 7.65 (t, 2H), 8.09 (t, 2H), 8.15 (d, 2H), 8.32 ( d, 2H), 8.53 (d, 2H), 8.76 (s, 2H)

1,4-dihydrocarbazolo [2,3-b] 1 H-NMR of the carbazole: δ 7.54 (s, 2H ), 7.64 (t, 2H), 8.10 (t, 2H), 8.16 (s, 2H), 8.33 ( d, 2H), 8.53 (d, 2H), 8.78 (s, 2H)

Preparation Example 4 Synthesis of 5,12-dihydrocarbazolo [2,1-a] carbazole and 5,12-dihydrocarbazolo [3,2-b] carbazole

<Preparation Step 4-1> Synthesis of 2,6-bis (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) naphthalene

Preparation step 1-Preparation of Preparation Example 1 was repeated except that 2,6-dibromonaphthalene (30 g, 104.89 mmol) was used instead of 1,5-dibromonaphthalene used in <Preparation step 1-1> 1>, 2,6-bis (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) naphthalene (21.13 g, yield 53%) was obtained.

^{1 H-NMR: δ 1.44 (} s, 24H), 7.56 (d, 2H), 8.61 (d, 2H), 8.85 (s, 2H)

<Preparation step 4-2> The 2,6- bis (2- nitrophenyl ) Synthesis of naphthalene

Bis (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) naphthalene used in Preparation Example 1-2 of Preparation Example 1 was used instead of 2,6-bis Preparation Example 1 was repeated except that 4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) naphthalene (20 g, 52.63 mmol) was used and THF was used instead of toluene. 2,2-bis (2-nitrophenyl) naphthalene (12.28 g, yield 63%) was obtained in the same manner as in Preparation step 1-2.

^{1 H-NMR: δ 7.54 (} d, 2H), 7.63 (t, 2H), 7.85 (t, 2H), 8.03 (d, 2H), 8.13 (d, 2H), 8.32 (s, 2H), 8.53 ( d, 2H)

Preparation Step 4-3 Preparation of 5,12-dihydrocarbazolo [2,1-a] carbazole and 5,12-dihydrocarbazolo [3,2-b] carbazole Synthesis of

(2-nitrophenyl) naphthalene (10 g) obtained in Preparation <Step 4-2> was used instead of 1,5-bis (2-nitrophenyl) naphthalene used in Preparation < , 26.98 mmol) was used in place of 5,12-dihydrocarbazolo [2,1-a] carbazole (2.48 g, yield 30%) and 5,12-dihydrocarbazolo [3,2-b] carbazole (2.65 g, yield 32%).

5,12-dihydrocarbazolo [2,1-a] 1 H-NMR of the carbazole: δ 7.54 (d, 2H ), 7.66 (t, 2H), 8.08 (t, 2H), 8.14 (d, 2H), 8.33 ( d, 2H), 8.52 (d, 2H), 8.77 (s, 2H)

5,12-dihydrocarbazolo [3,2-b] carbazole in ^{1 H-NMR: δ 7.55 (} s, 2H), 7.65 (t, 2H), 8.10 (t, 2H), 8.13 (s, 2H), 8.34 ( d, 2H), 8.54 (d, 2H), 8.78 (s, 2H)

[ Synthetic example  1] Compound Inv Synthesis of -1

<Synthesis Step 1-1> Synthesis of 1-phenyl-1,8-dihydrocarbazolo [4,3-c] carbazole

Dihydrocarbazolo [4,3-c] carbazole (5 g, 16.32 mmol), iodobenzene (4.99 g, 24.48 mmol) and Cu powder (0.1 g, 1.63 mmol) in a nitrogen stream, , K ₂ CO ₃ (2.26 g, 16.32 mmol), Na ₂ SO ₄ (2.32 g, 16.32 mmol) and nitrobenzene (100 ml) were mixed and stirred at 190 ° C for 12 hours. After the reaction was terminated, the nitrobenzene was removed, the organic layer was separated with methylene chloride, and then the water was removed using MgSO ₄ . The solvent of the organic layer was removed and the residue was purified by column chromatography (Hexane: MC = 1: 1 (v / v)) to obtain 1.43 g of 1-phenyl-1,8- dihydrocarbazolo [4,3- %).

<Synthesis step 1-2> Synthesis of compound Inv-1

1-phenyl-1,8-dihydrocarbazolo [4,3-c] pyridine synthesized in Synthesis Step 1-1 was used instead of 1,8-dihydrocarbazolo [4,3- 2-bromo-4,6-diphenyl-1,3,5-triazine (4.9 g, 15.69 mmol) was used instead of iodobenzene (4.99 g, 24.48 mmol) The compound Inv-1 (4.04 g, 63%) was obtained in the same manner as in the above <synthesis step 1-1>.

GC-Mass (theory: 613.23 g / mol, measured: 613 g / mol)

Elemental Analysis: C, 84.15; H, 4.43; N, 11.41

[ Synthetic example  2] Compound Inv Synthesis of -2

<Synthesis Step 2-1> Synthesis of 1-phenyl-1,8-dihydrocarbazolo [4,3-c] carbazole

1-phenyl-1,8-dihydrocarbazolo [4,3-c] carbazole (4.43 g, yield 71%) was obtained in the same manner as in <Synthesis step 1-1> of Synthesis Example 2.

<Synthesis Step 2-2> Synthesis of Compound Inv-2

3- (3-bromophenyl) pyridine (2.76 g, 11.78 mmol) was used instead of the 2-bromo-4,6-diphenyl-1,3,5-triazine used in Synthesis Step 1-2 in Synthesis Example 1 , The compound Inv-2 (3.03 g, yield 72%) was obtained in the same manner as in <Synthesis step 1-2> of the above Synthesis Example 1.

GC-Mass (calculated: 535.20 g / mol, measured: 535 g / mol)

Elemental Analysis: C, 87.45; H, 4.70; N, 7.84

[ Synthetic example  3] Compound Inv Synthesis of -3

<Synthesis Step 3-1> Synthesis of 1-phenyl-1,8-dihydrocarbazolo [4,3-c] carbazole

1-phenyl-1,8-dihydrocarbazolo [4,3-c] carbazole (4.43 g, yield 71%) was obtained in the same manner as in <Synthesis step 1-1> of Synthesis Example 2.

<Synthesis step 3-2> Synthesis of compound Inv-3

2-bromo-4,6-diphenylpyridine (3.65 g, 11.77 mmol) was used instead of the 2-bromo-4,6-diphenyl-1,3,5-triazine used in Synthesis Step 1-2 in Synthesis Example 1 , The compound Inv-3 (3.36 g, yield 70%) was obtained in the same manner as in <Synthesis step 1-2> of the above Synthesis Example 1.

GC-Mass (calculated: 611.24 g / mol, measured: 611 g / mol)

Elemental Analysis: C, 87.45; H, 4.70; N, 7.84

[ Synthetic example  4] Compound Inv Synthesis of -4

<Synthesis Step 4-1> Synthesis of 1-phenyl-1,8-dihydrocarbazolo [4,3-c] carbazole

1-phenyl-1,8-dihydrocarbazolo [4,3-c] carbazole (4.43 g, yield 71%) was obtained in the same manner as in <Synthesis step 1-1> of Synthesis Example 2.

<Synthesis step 4-2> Synthesis of compound Inv-4

Except that 4-bromoisoquinoline (2.45 g, 11.77 mmol) was used instead of 2-bromo-4,6-diphenyl-1,3,5-triazine used in Synthesis Step 1-2 in Synthesis Example 1, Was carried out in the same manner as in <Synthesis step 1-2> of the above Synthesis Example 1 to obtain a compound Inv-4 (2.72 g, yield 68%).

GC-Mass (calculated: 509.19 g / mol, measured: 509 g / mol)

Elemental Analysis: C, 87.45; H, 4.70; N, 7.84

[ Synthetic example  5] Compound Inv Synthesis of -5

The compound 1,8-dihydrocarbazolo [4,3-c] carbazole (5 g, 16.32 mmol), 2-bromo-6-phenylpyridine (9.55 g, 40.80 mmol) and Cu powder 0.1 g, 1.63 mmol), K ₂ CO ₃ (2.26 g, 16.32 mmol), Na ₂ SO ₄ (2.32 g, 16.32 mmol) and nitrobenzene (100 ml) were mixed and stirred at 190 ° C for 12 hours. After the reaction was terminated, the nitrobenzene was removed, the organic layer was separated with methylene chloride, and then the water was removed using MgSO ₄ . Then, the solvent of the organic layer was removed, and the residue was purified by column chromatography (Hexane: EA = 3: 1 (v / v)) to obtain Compound Inv-5 (6.5 g, yield 65%).

GC-Mass (calculated: 612.23 g / mol, measured: 612 g / mol)

Elemental Analysis: C, 87.45; H, 4.70; N, 7.84

[ Synthetic example  6] compound Inv Synthesis of -6

Diphenyl-1,8-dihydrocarbazolo [4,3-c] pyridine synthesized in Preparation Example 2 instead of 1,8-dihydrocarbazolo [4,3- c] carbazole (3 g, 5.62 mmol) instead of 2-bromo-4,6-diphenyl-1,3,5-triazine used in Synthesis Example 1-2, Synthesis Step 1-1 and Synthesis Step 1-2 of Synthesis Example 1 were repeated except that 2,3'-bipyridine (1.98 g, 8.42 mmol) was used to synthesize Compound Inv-6 (2.05 g, yield 53%).

GC-Mass (calculated: 688.26 g / mol, measured: 688 g / mol)

Elemental Analysis: C, 87.45; H, 4.70; N, 7.84

[ Synthetic example  7] Compound Inv Synthesis of -7

Diphenyl-1,8-dihydrocarbazolo [4,3-c] pyridine synthesized in Preparation Example 2 instead of 1,8-dihydrocarbazolo [4,3- 3-bromobiphenyl (3.81 g, 16.36 mmol) was used in place of iodobenzene and 2-bromo-4,6-diphenyl- <Synthesis step 1-1> and <Synthesis step 1> of Synthesis Example 1 were repeated except that 5-bromo-2,2'-bipyridine (1.73 g, 7.35 mmol) -2>, a compound Inv-7 (1.95 g, yield 52%) was obtained.

GC-Mass (calculated: 764.29 g / mol, measured: 764 g / mol)

Elemental Analysis: C, 87.45; H, 4.70; N, 7.84

[ Synthetic example  8] compound Inv Synthesis of -8

Diphenyl-1,8-dihydrocarbazolo [4,3-c] pyridine synthesized in Preparation Example 2 instead of 1,8-dihydrocarbazolo [4,3- bromo-4,6-diphenyl-3,6-dicarboxylate used in the synthesis step 1-2 was obtained by using 4-bromobiphenyl (3.81 g, 16.36 mmol) instead of iodobenzene, <Synthesis step 1-1> and <Synthesis step 1-2> of the above Synthesis Example 1 were repeated except that 2-bromo-4,6-diphenylpyrimidine (2.3 g, 7.38 mmol) was used instead of 1,3,5- 2> to obtain Compound Inv-8 (2.4 g, yield 58%).

GC-Mass (calculated: 840.33 g / mol, measured: 840 g / mol)

Elemental Analysis: C, 88.54; H, 4.79; N, 6.66

[ Synthetic example  9] compound Inv Synthesis of -9

Diphenyl-1,8-dihydrocarbazolo [4,3-c] carbazole (3 g, 6.55) synthesized in Preparation Example 2 instead of 1,8-dihydrocarbazolo [4,3- mmol) and 2-bromo-4,6-diphenylpyrimidine (3.06 g, 9.82 mmol) was used instead of 2-bromo-6-phenylpyridine. 9 (3.37 g, yield 56%).

GC-Mass (calculated: 918.35 g / mol, measured: 918 g / mol)

Elemental Analysis: C, 86.25; H, 4.61; N, 9.14

[ Synthetic example  10] compound Inv Synthesis of -10

Diphenyl-1,8-dihydrocarbazolo [4,3-c] carbazole (3 g, 6.54) synthesized in Preparation Example 2 instead of 1,8-dihydrocarbazolo [4,3- mmol) and 4-bromo-N, N-diphenylaniline (3.18 g, 9.81 mmol) was used in place of 2-bromo-6-phenylpyridine. 10 (3.34 g, yield 54%).

GC-Mass (944.39 g / mol, measured: 944 g / mol)

Elemental Analysis: C, 88.95; H, 5.12; N, 5.93

[ Synthetic example  11] compound Inv Synthesis of -11

Dihydrocarbazolo [1,2-a] carbazole (prepared in Preparation Example 3 instead of 1,8-dihydrocarbazolo [4,3-c] carbazole used in Synthesis Example 1-1 in Synthesis Example 1 , 16.32 mmol) and 4-bromo-2-phenylpyrimidine (2.77 g, 11.77 mmol) instead of 2-bromo-4,6-diphenyl-1,3,5- (2.15 g, yield 51%) was obtained in the same manner as in < Synthesis Step 1-1 > and < Synthesis Step 1-2 >

GC-Mass (calculated: 536.20 g / mol, measured: 536 g / mol)

Elemental Analysis: C, 85.05; H, 4.51; N, 10.44

[ Synthetic example  12] compound Inv Synthesis of -12

5 g of 13,14-dihydrocarbazolo [1,2-a] carbazole synthesized in Preparation Example 3 instead of 1,8-dihydrocarbazolo [4,3-c] carbazole used in Synthesis Step 1-1 of Synthesis Example 1, 16.32 mmol), 4-bromobiphenyl (5.71 g, 24.48 mmol) was used in the place of iodobenzene, and 2-bromo-4,6-diphenyl-1,3,5-triazine Synthesis step 1-1> and <Synthesis step 1-2> of Synthesis Example 1 were repeated except that 3- (4-bromophenyl) pyridine (2.3 g, 9.81 mmol) Inv-12 (1.72 g, yield 43%).

GC-Mass (calculated: 611.24 g / mol, measured: 611 g / mol)

Elemental Analysis: C, 88.35; H, 4.78; N, 6.87

[ Synthetic example  13] Compound Inv Synthesis of -13

5 g of 13,14-dihydrocarbazolo [1,2-a] carbazole synthesized in Preparation Example 3 instead of 1,8-dihydrocarbazolo [4,3-c] carbazole used in Synthesis Step 1-1 of Synthesis Example 1, 16.32 mmol), 4-bromobiphenyl (5.71 g, 24.48 mmol) was used in the place of iodobenzene, and 2-bromo-4,6-diphenyl-1,3,5-triazine Synthesis step 1-1> and <Synthesis step 1-2> of Synthesis Example 1 were repeated except that 2-bromo-4,6-diphenylpyridine (3.04 g, 9.81 mmol) Compound Inv-13 (1.85 g, yield 41%) was obtained.

GC-Mass (687.27 g / mol, measured: 687 g / mol)

Elemental Analysis: C, 89.06; H, 4.84; N, 6.11

[ Synthetic example  14] Compound Inv Synthesis of -14

5 g of 13,14-dihydrocarbazolo [1,2-a] carbazole synthesized in Preparation Example 3 instead of 1,8-dihydrocarbazolo [4,3-c] carbazole used in Synthesis Step 1-1 of Synthesis Example 1, 16.32 mmol) was used in place of iodobenzene and l- (4-bromophenyl) naphthalene (6.93 g, 24.48 mmol) was used in place of iodobenzene. <Synthesis step 1-1> of Synthesis Example 1 was repeated except that 2-bromo-4,6-diphenyl-1,3,5-triazine (2.76 g, 8.85 mmol) And <Synthesis step 1-2>, compound Inv-14 (1.7 g, yield 39%) was obtained.

GC-Mass (739.27 g / mol, measured: 739 g / mol)

Elemental Analysis: C, 86.04; H, 4.50; N, 9.47

[ Synthetic example  15] Compound Inv Synthesis of -15

Dihydrocarbazolo [1,2-a] carbazole (3 g, 9.79 mmol) synthesized in Preparation Example 3 was used instead of 1,8-dihydrocarbazolo [4,3- Inv-15 (3.31 g, yield 55%) was obtained in the same manner as in Synthesis Example 5, except that 5-bromo-2-phenylpyrimidine (3.45 g, 14.69 mmol) was used in place of 2-bromo- ).

GC-Mass (theory: 614.22 g / mol, measured: 614 g / mol)

Elemental Analysis: C, 82.06; H, 4.26; N, 13.67

[ Synthetic example  16] compound Inv Synthesis of -16

Dihydrocarbazolo [2,3-b] carbazole (prepared in Preparation Example 3 instead of 1,8-dihydrocarbazolo [4,3-c] carbazole used in Synthesis Example 1-1 in Synthesis Example 1 , 16.32 mmol) was used in place of 2-bromo-4,6-diphenyl-1,3,5-triazine in Example 1 and 3-iodo-9-phenyl-9H- , Inv-16 (3.42 g, yield 70%) was obtained in the same manner as in <Synthesis step 1-1> and <Synthesis step 1-2> of the above Synthesis Example 1, .

GC-Mass (calculated: 623.24 g / mol, measured: 623 g / mol)

Elemental Analysis: C, 88.58; H, 4.69; N, 6.74

[ Synthetic example  17] Compound Inv Synthesis of -17

Dihydrocarbazolo [2,3-b] carbazole (prepared in Preparation Example 3 instead of 1,8-dihydrocarbazolo [4,3-c] carbazole used in Synthesis Example 1-1 in Synthesis Example 1 , 16.32 mmol), 2-bromo-5-phenylpyrimidine (2.77 g, 11.77 mmol) was used instead of 2-bromo-4,6-diphenyl-1,3,5- (2.36 g, yield 56%) was obtained in the same manner as in < Synthesis step 1-1 > and < Synthesis step 1-2 >

GC-Mass (calculated: 536.20 g / mol, measured: 536 g / mol)

Elemental Analysis: C, 85.05; H, 4.51; N, 10.44

[ Synthetic example  18] compound Inv Synthesis of -18

Dihydrocarbazolo [2,3-b] carbazole (prepared in Preparation Example 3 instead of 1,8-dihydrocarbazolo [4,3-c] carbazole used in Synthesis Example 1-1 in Synthesis Example 1 Bromo-4,6-diphenyl-1, 2-bromo-6-phenylpyridine (5.73 g, 24.48 mmol) was used instead of iodobenzene. Synthesis step 1-1] and <Synthesis step 1-2> of Synthesis Example 1, except that 2-bromoquinoline (2.04 g, 9.79 mmol) was used in place of 3,5-triazine, Inv-18 (2.22 g, yield 58%).

GC-Mass (calculated: 586.22 g / mol, measured: 586 g / mol)

Elemental Analysis: C, 85.98; H, 4.47; N, 9.55

[ Synthetic example  19] Compound Inv -19 Synthesis

Dihydrocarbazolo [2,3-b] carbazole (prepared in Preparation Example 3 instead of 1,8-dihydrocarbazolo [4,3-c] carbazole used in Synthesis Example 1-1 in Synthesis Example 1 , 16.32 mmol), 2-bromo-6-phenylpyridine (5.73 g, 24.48 mmol) was used in place of iodobenzene, <Synthesis step 1-1> and <Synthesis step 1-2> of Synthesis Example 1 were repeated except that 4-bromo-N, N-diphenylaniline (3.17 g, 9.79 mmol) To obtain Compound Inv-19 (2.94 g, yield 64%).

GC-Mass (theory: 702.28 g / mol, measured: 702 g / mol)

Elemental Analysis: C, 87.15; H, 4.88; N, 7.97

[ Synthetic example  20] compound Inv Synthesis of -20

Dihydrocarbazolo [2,3-b] carbazole (prepared in Preparation Example 3 instead of 1,8-dihydrocarbazolo [4,3-c] carbazole used in Synthesis Example 1-1 in Synthesis Example 1 , 16.32 mmol) and that 5'-bromo- (1,1 ', 3', 1 ") terphenyl (7.57 g, 24.48 mmol) was used instead of iodobenzene. (Inv-20) (2.19 g, yield 51%) was obtained in the same manner as in Synthesis Step 1-1> and <Synthesis Step 1-2>.

GC-Mass (calculated: 765.29 g / mol, measured: 765 g / mol)

Elemental Analysis: C, 86.25; H, 4.61; N, 9.14

[ Synthetic example  21] Compound Inv Synthesis of -21

Dihydrocarbazolo [2,1-a] carbazole synthesized in Preparation Example 4 instead of 1,8-dihydrocarbazolo [4,3-c] carbazole used in Synthesis Example 1-1 of Synthesis Example 1 , 16.32 mmol) and 3- (4-bromophenyl) pyridine (2.75 g, 11.77 mmol) instead of 2-bromo-4,6-diphenyl-1,3,5- (2.18 g, yield 52%) was obtained in the same manner as in <Synthesis Step 1-1> and <Synthesis Step 1-2> of Synthesis Example 1,

GC-Mass (calculated: 535.20 g / mol, measured: 535 g / mol)

Elemental Analysis: C, 87.45; H, 4.70; N, 7.84

[ Synthetic example  22] compound Inv Synthesis of -22

Dihydrocarbazolo [2,1-a] carbazole synthesized in Preparation Example 4 instead of 1,8-dihydrocarbazolo [4,3-c] carbazole used in Synthesis Example 1-1 of Synthesis Example 1 , 16.32 mmol) was used instead of 4-bromo-N, N-diphenylaniline (3.81 g, 11.77 (Inv-22) (2.9 g, yield 59%) was obtained in the same manner as in <Synthesis Step 1-1> and <Synthesis Step 1-2> of Synthesis Example 1,

GC-Mass (calculated: 625.25 g / mol, measured: 625 g / mol)

Elemental Analysis: C, 88.29; H, 4.99; N, 6.72

[ Synthetic example  23] Compound Inv Synthesis of -23

Dihydrocarbazolo [2,1-a] carbazole synthesized in Preparation Example 4 instead of 1,8-dihydrocarbazolo [4,3-c] carbazole used in Synthesis Example 1-1 of Synthesis Example 1 , 16.32 mmol) was used in place of 2-bromo-4,6-diphenyl-1,3,5-triazine, and 4- (4-bromophenyl) -3,5- Synthesis step 1-1] and <Synthesis step 1-2> of Synthesis Example 1, except that 4H-1,2,4-triazole (4.43 g, 11.77 mmol) Inv-23 (2.55 g, yield 48%).

GC-Mass (calculated: 677.26 g / mol, measured: 677 g / mol)

Elemental Analysis: C, 85.06; H, 4.61; N, 10.33

[ Synthetic example  24] Compound Inv Synthesis of -24

Dihydrocarbazolo [2,1-a] carbazole synthesized in Preparation Example 4 instead of 1,8-dihydrocarbazolo [4,3-c] carbazole used in Synthesis Example 1-1 of Synthesis Example 1 , 16.32 mmol), 2-bromonaphthalene (5.07 g, 24.48 mmol) was used in place of iodobenzene and 2-bromo-4,6-diphenyl-1,3,5- Synthesis step 1-1] and <Synthesis step 1-2> of Synthesis Example 1, except that 2-bromo-6-phenylpyridine (2.44 g, 10.40 mmol) Inv-24 (1.75 g, yield 43%).

GC-Mass (calculated: 585.22 g / mol, measured: 585 g / mol)

Elemental Analysis: C, 88.18; H, 4.65; N, 7.17

[ Synthetic example  25] Compound Inv Synthesis of -25

Dihydrocarbazolo [2,1-a] carbazole (3 g, 9.79 mmol) synthesized in Preparation Example 4 was used in place of 1,8-dihydrocarbazolo [4,3- Inv-25 (3.13 g, yield 57%) was obtained in the same manner as in Synthesis Example 5, except that 2-bromoquinoline (3.06 g, 14.69 mmol) was used instead of 2-bromo-6-phenylpyridine.

GC-Mass (calculated: 560.20 g / mol, measured: 560 g / mol)

Elemental Analysis: C, 85.69; H, 4.31; N, 9.99

[ Synthetic example  26] compound Inv Synthesis of -26

Dihydrocarbazolo [3,2-b] carbazole synthesized in Preparation Example 4 instead of 1,8-dihydrocarbazolo [4,3-c] carbazole used in Synthesis Example 1-1 of Synthesis Example 1 , 16.32 mmol) was used in place of 2-bromo-4,6-diphenyl-1,3,5-triazine in place of 1- (4-bromophenyl) Syn-1-1] and <Synthesis 1-2> of Synthesis Example 1, except that benzo [d] imidazole (4.11 g, 11.77 mmol) 3.42 g, yield 67%).

GC-Mass (calculated: 650.25 g / mol, measured: 650 g / mol)

Elemental Analysis: C, 86.74; H, 4.65; N, 8.61

[ Synthetic example  27] Compound Inv -27

Dihydrocarbazolo [3,2-b] carbazole synthesized in Preparation Example 4 instead of 1,8-dihydrocarbazolo [4,3-c] carbazole used in Synthesis Example 1-1 of Synthesis Example 1 , 16.32 mmol), 5'-bromo- (1,1 ', 3', 1 ") terphenyl (7.57 g, 24.48 mmol) was used in place of iodobenzene, Except that 2-bromo-4,6-diphenylpyridine (2.61 g, 8.42 mmol) was used in place of 2-bromo-4,6-diphenyl-1,3,5- 1-1 &gt; and &lt; Synthesis step 1-2 &gt;, compound Inv-27 (2.14 g, yield 50%) was obtained.

GC-Mass (calculated: 763.30 g / mol, measured: 763 g / mol)

Elemental Analysis: C, 89.62; H, 4.88; N, 5.50

[ Synthetic example  28] Compound Inv -28 Synthesis

Dihydrocarbazolo [3,2-b] carbazole (3 g, 9.79 mmol) synthesized in Preparation Example 4 was used instead of 1,8-dihydrocarbazolo [4,3- Except that 3,3 '- (5-bromo-1,3-phenylene) dipyridine (4.57 g, 14.69 mmol) was used in place of 2-bromo-6-phenylpyridine. Inv-28 (3.83 g, yield 51%).

GC-Mass (calculated: 766.28 g / mol, measured: 766 g / mol)

Elemental Analysis: C, 84.57; H, 4.47; N, 10.96

[ Synthetic example  29] Compound Inv Synthesis of -29

Dihydrocarbazolo [3,2-b] carbazole (3 g, 9.79 mmol) synthesized in Preparation Example 4 was used instead of 1,8-dihydrocarbazolo [4,3- (3 g, yield 50%) was obtained in the same manner as in Synthesis Example 5, except that 2- (4-bromophenyl) pyridine (3.44 g, 14.69 mmol) was used in place of 2-bromo-6- %).

GC-Mass (calculated: 612.23 g / mol, measured: 612 g / mol)

Elemental Analysis: C, 86.25; H, 4.61; N, 9.14

[ Synthetic example  30] Compound Inv Synthesis of -30

Dihydrocarbazolo [3,2-b] carbazole (3 g, 9.79 mmol) synthesized in Preparation Example 4 was used instead of 1,8-dihydrocarbazolo [4,3- Inv-30 (3.13 g, yield 57%) was obtained in the same manner as in Synthesis Example 5, except that 3-bromoquinoline (3.06 g, 14.69 mmol) was used instead of 2-bromo-6-phenylpyridine.

GC-Mass (calculated: 560.20 g / mol, measured: 560 g / mol)

Elemental Analysis: C, 85.69; H, 4.31; N, 9.99

[Example 1] Production of organic EL device

The compound Inv-1 synthesized in Synthesis Example 1 was subjected to high-purity sublimation purification by a conventionally known method, and then a green organic EL device was produced in the following manner.

Glass substrate coated with ITO (Indium tin oxide) thin film with thickness of 1500 Å was washed with distilled water ultrasonic wave. After the distilled water was washed, the substrate was ultrasonically washed with a solvent such as isopropyl alcohol, acetone, or methanol, dried and transferred to a UV OZONE cleaner (Power Sonic 405), the substrate was cleaned using UV for 5 minutes, .

M-MTDATA (60 nm) / TCTA (80 nm) / Inv compound + 10% Ir (ppy) ₃ on the ITO transparent electrode (anode) prepared above as a host using the compound Inv- (300 nm) / BCP (10 nm) / Alq ₃ (30 nm) / LiF (1 nm) / Al (200 nm).

The structures of m-MTDATA, TCTA, Ir (ppy) ₃ and BCP are as follows.

[Examples 2 to 30] Preparation of organic EL device

Inv-2 to Inv-30 synthesized in Synthesis Examples 2 to 30, respectively, were used instead of the compound Inv-1 used as a luminescent host material in the formation of the light emitting layer in Example 1, Thereby preparing an organic EL device.

[Comparative Example 1] Fabrication of organic EL device

An organic EL device was fabricated in the same manner as in Example 1, except that CBP was used instead of the compound Inv-1 used as a luminescent host material in forming the light emitting layer in Example 1. The structure of CBP is as follows.

[Evaluation example]

The driving voltage, current efficiency and emission peak at a current density of 10 mA / cm 2 were measured for the organic EL devices manufactured in Examples 1 to 30 and Comparative Example 1, respectively, and the results are shown in Table 1 below.

Sample Host Driving voltage
(V) EL peak
(nm) Current efficiency
(cd / A) Example 1 Inv-1 6.78 516 41.4 Example 2 Inv-2 6.77 516 41.6 Example 3 Inv-3 6.64 515 40.2 Example 4 Inv-4 6.69 515 41.1 Example 5 Inv-5 6.70 517 41.3 Example 6 Inv-6 6.75 516 42.1 Example 7 Inv-7 6.77 517 41.5 Example 8 Inv-8 6.79 516 41.2 Example 9 Inv-9 6.86 517 39.4 Example 10 Inv-10 6.85 518 38.8 Example 11 Inv-11 6.65 516 42.0 Example 12 Inv-12 6.68 516 41.3 Example 13 Inv-13 6.69 517 42.2 Example 14 Inv-14 6.74 516 40.9 Example 15 Inv-15 6.84 517 40.0 Example 16 Inv-16 6.83 518 40.3 Example 17 Inv-17 6.78 517 42.4 Example 18 Inv-18 6.86 517 40.6 Example 19 Inv-19 6.89 518 40.3 Example 20 Inv-20 6.85 518 39.8 Example 21 Inv-21 6.73 516 40.2 Example 22 Inv-22 6.64 517 40.5 Example 23 Inv-23 6.86 517 39.2 Example 24 Inv-24 6.69 516 39.8 Example 25 Inv-25 6.84 517 38.9 Example 26 Inv-26 6.79 515 40.1 Example 27 Inv-27 6.66 516 39.5 Example 28 Inv-28 6.87 518 38.9 Example 29 Inv-29 6.75 517 38.8 Example 30 Inv-30 6.79 517 40.0 Comparative Example 1 CBP 6.93 516 38.2

As a result of the experiment, the green organic EL devices of Examples 1 to 30 using the compounds (Inv-1 to Inv-30) represented by the formula (1) according to the present invention as the host material of the light emitting layer, It was confirmed that the organic EL device exhibited better current efficiency and better driving voltage than the green organic EL device.

While the present invention has been particularly shown and described with reference to exemplary embodiments thereof, it is to be understood that the invention is not limited to the disclosed embodiments, but, on the contrary, It is natural.

Claims (8)

1. An organic electroluminescent device comprising: (i) an anode, (ii) a cathode, and (iii) one or more organic layers sandwiched between the anode and the cathode,
Wherein the one or more organic layers include a light emitting layer,
Wherein the light emitting layer comprises a compound represented by the following formula (5): &lt; EMI ID =
[Chemical Formula 5]

(In the above formula (5)
Ar ₁ and Ar ₂ each independently represent a substituted or unsubstituted C ₆ to C ₁₄ aryl group and a substituted or unsubstituted heteroaryl group having 5 to 14 nuclear atoms containing 1 to 3 N Lt; / RTI &gt;
The aryl group and the heteroaryl group may each independently have at least one substituent selected from the group consisting of a C ₆ to C ₁₄ aryl group and a heteroaryl group having 5 to 14 nuclear atoms containing one N atom And a plurality of substituents may be the same or different;
And R ₁ to R ₁₂ are each independently hydrogen. delete delete 1. An organic electroluminescent device comprising: (i) an anode, (ii) a cathode, and (iii) one or more organic layers sandwiched between the anode and the cathode,
Wherein the one or more organic layers include a light emitting layer,
Wherein the light emitting layer comprises a compound selected from the group consisting of the following compounds Inv-11 to Inv-15:

delete delete The organic electroluminescent device according to claim 1 or 4, wherein the compound is used as a phosphorescent host of the light emitting layer. The organic electroluminescent device according to claim 1 or 4, wherein the compound is used as a fluorescent dopant of the light emitting layer.