KR101577104B1 - Organic compounds and organic electro luminescence device comprising the same - Google Patents

Abstract

The present invention relates to a novel compound and an organic electroluminescent device including the same, and the compound according to the present invention is used for an organic compound layer, preferably a light emitting layer, of an organic electroluminescent device, And the like can be improved.

Description

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

Electroluminescent (EL) devices, which led to blue electroluminescence using anthracene single crystals in 1965, were followed up with the observation of the organic thin film emission of Bernanose in the 1950s. In 1987, Layer and a functional layer of a light-emitting layer. Thereafter, in order to form a high efficiency and high number of organic electroluminescent devices, each organic material layer has been developed into a form in which each organic material layer has been introduced into 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 organic layer in the anode, and electrons are injected into the organic layer in the cathode. When the injected holes and electrons meet, an exciton is formed. When the exciton falls to the ground state, light is emitted. At this time, the material used as the organic material layer can be classified into a light emitting material, a hole injecting material, a hole transporting material, an electron transporting material, an electron injecting material and the like depending on its function.

The luminescent material can be classified into blue, green and red luminescent materials according to luminescent colors and yellow and orange luminescent materials to realize 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 development of the phosphorescent material can theoretically improve the luminous efficiency up to 4 times as compared with the fluorescence, the phosphorescent dopant as well as phosphorescent host materials are being studied extensively.

Up to now, hole injecting layer, hole transporting layer. NPB, BCP and Alq ₃ are widely known as electron transporting layer materials and anthracene derivatives as light emitting layer materials. Particularly, metal complex compounds containing Ir such as Firpic, Ir (ppy) ₃ , (acac) Ir (btp) ₂ and the like having advantages in terms of efficiency improvement of the light emitting layer material are blue, green, (red) phosphorescent dopant material, and CBP is used as a phosphorescent host material.

However, conventional organic layer materials have advantages in terms of light emission characteristics, but their thermal stability is not very good due to their low glass transition temperature, and thus they are not satisfactory in terms of lifetime of an organic electroluminescent device. Therefore, development of an organic layer material having excellent performance is required.

Japanese Patent Application Laid-Open No. 2001-160489

The present invention has been made to solve the above problems and it is an object of the present invention to provide a novel compound capable of improving the efficiency, lifetime and stability of the organic electroluminescent device and an organic electroluminescent device using the compound.

In order to accomplish the above object, the present invention provides a compound represented by the following formula 1:

[Chemical Formula 1]

In Formula 1,

One of R ₁ and R _{2 ,} R ₂ and R ₃ , R ₃ and R ₄ is bonded to the following formula 2 to form a condensed ring,

(2)

In the formula (2), the dotted line represents a moiety which forms a condensed ring by combining with the formula (1)

X ₁ to X ₄ are each independently N or C (R ₁₁ )

Wherein R ₁ to R ₁₁ each independently represent hydrogen, deuterium, halogen, cyano group, C ₁ ~ alkynyl group of C ₄₀ alkyl group, C ₂ ~ C ₄₀ alkenyl group, C ₂ ~ C ₄₀ of, C ₆ ~ C ₄₀ the aryl group, the number of nuclear atoms of 5 to 40 heteroaryl group, C ₆ ~ C ₄₀ aryloxy group, alkyloxy group of C ₁ ~ C ₄₀ of, C ₆ ~ arylamine group of C _40, C ₃ ~ C ₄₀ A cycloalkyl group having 3 to 40 nuclear atoms, a C ₁ to C ₄₀ alkylsilyl group, a C ₁ to C ₄₀ alkylboron group, a C ₆ to C ₄₀ arylboron group, a C ₆ to C ₄₀ aralkyl group, An arylphosphine group of C ₆ to C ₄₀ , an arylphosphine oxide group of C ₆ to C ₄₀ , and an arylsilyl group of C ₆ to C ₄₀ , which may be bonded to adjacent groups to form a condensed ring,

Wherein Ar ₁ represents hydrogen, a C ₁ to C ₄₀ alkyl group, a C ₂ to C ₄₀ alkenyl group, a C ₂ to C ₄₀ alkynyl group, a C ₆ to C ₄₀ aryl group, a heteroaryl group having 5 to 40 nuclear atoms A C ₆ to C ₄₀ aryloxy group, a C ₁ to C ₄₀ alkyloxy group, a C ₆ to C ₄₀ arylamine group, a C ₃ to C ₄₀ cycloalkyl group, a heterocyclic group having 3 to 40 nuclear atoms alkyl group, C ₁ ~ C ₄₀ alkylsilyl group, C ₁ ~ C ₄₀ group of an alkyl boron, C ₆ ~ C ₄₀ aryl boron group, C ₆ ~ C ₄₀ aryl phosphine group, C ₆ ~ C ₄₀ aryl phosphine A pentacene group, a pentacene group, a pin oxide group, and an arylsilyl group of C ₆ to C ₄₀ ,

R ₁ to R ₁₁ And Ar _{1 represents} an alkyl group, alkenyl group, alkynyl group, aryl group, heteroaryl group, aryloxy group, alkyloxy group, arylamine group, cycloalkyl group, heterocycloalkyl group, alkylsilyl group, The arylphosphine group, the arylphosphine oxide group and the arylsilyl group are each independently selected from the group consisting of deuterium, halogen, cyano group, C ₁ to C ₄₀ alkyl group, C ₂ to C ₄₀ alkenyl group, C ₂ to C ₄₀ alkynyl group, C ₆ ~ C ₄₀ heteroaryl group, the aryl group, the number of nuclear atoms of 5 to ₄₀ C ₆ ~ C 40 aryloxy group, C ₁ ~ C ₄₀ alkyloxy group of, C ₆ ~ C ₄₀ aryl amine group, C _A C ₃ to C ₄₀ cycloalkyl group, a heterocycloalkyl group having 3 to 40 nuclear atoms, a C ₁ to C ₄₀ alkylsilyl group, a C ₁ to C ₄₀ alkylboron group, a C ₆ to C ₄₀ arylboron group, a C ₆ ~ C ₄₀ aryl phosphine group of, optionally substituted with one or more selected from the group C ₆ ~ C ₄₀ aryl phosphine oxide group, and a C ₆ ~ C ₄₀ aryl silyl group consisting of and, wherein, Number of substituents is the same as or different from each other.

The alkyl used in the present invention means a monovalent functional group obtained by removing a hydrogen atom from 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, hexyl, and the like.

The alkenyl used in the present invention means a monovalent functional group obtained by removing a hydrogen atom from a linear or branched unsaturated hydrocarbon having 2 to 40 carbon atoms and having at least one carbon-carbon double bond. Non-limiting examples thereof include vinyl, allyl, isopropenyl, 2-butenyl, and the like.

The alkynyl used in the present invention means a monovalent functional group obtained by removing a hydrogen atom from a linear or branched unsaturated hydrocarbon having 2 to 40 carbon atoms and having at least one carbon-carbon triple bond. Non-limiting examples thereof include ethynyl, 2-propynyl, and the like.

The cycloalkyl used in the present invention means a monovalent functional group obtained by removing a hydrogen atom from a monocyclic or polycyclic non-aromatic hydrocarbon having 3 to 40 carbon atoms (saturated cyclic hydrocarbon). Non-limiting examples thereof include cyclopropyl, cyclopentyl, cyclohexyl, norbornyl, adamantine, and the like.

The heterocycloalkyl used in the present invention means a monovalent functional group obtained by removing a hydrogen atom from a non-aromatic hydrocarbon (saturated cyclic hydrocarbon) having 3 to 40 nuclear atoms, and includes at least one carbon of the ring, preferably 1 To three carbons are substituted with a heteroatom such as N, O or S; Non-limiting examples thereof include morpholine, piperazine, and the like.

The aryl used in the present invention means a monovalent functional group obtained by removing a hydrogen atom from an aromatic hydrocarbon having 6 to 60 carbon atoms in which a single ring or two or more rings are combined. At this time, the two or more rings may be attached to each other in a simple attached or condensed form. Non-limiting examples thereof include phenyl, biphenyl, triphenyl, terphenyl, naphthyl, fluorenyl, phenanthryl, anthracenyl, indenyl and the like.

The heteroaryl used in the present invention is a monovalent functional group obtained by removing a hydrogen atom from a monoheterocyclic or polyheterocyclic aromatic hydrocarbon having 5 to 60 nuclear atoms and is a monovalent group having at least one carbon atom, Carbon atoms are replaced by heteroatoms such as nitrogen (N), oxygen (O), sulfur (S), or selenium (Se). At this time, the heteroaryl may be attached in a form in which two or more rings are attached or condensed to each other, and may further include a condensed form with an aryl group. Non-limiting examples of such heteroaryls 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. ring; And 2-furanyl, N-imidazolyl, 2-isoxazolyl, 2-pyridinyl, 2-pyrimidinyl and the like.

The alkyloxy used in the present invention means a monovalent functional group represented by RO-, wherein R is an alkyl having 1 to 40 carbon atoms and includes a linear, branched or cyclic structure . Non-limiting examples of such alkyloxy include methoxy, ethoxy, n-propoxy, 1-propoxy, t-butoxy, n-butoxy, pentoxy and the like.

The aryloxy used in the present invention means a monovalent functional group represented by R'O-, and R 'is aryl having 6 to 60 carbon atoms. Non-limiting examples of such aryloxy include phenyloxy, naphthyloxy, diphenyloxy, and the like.

The alkylsilyl used in the present invention means silyl substituted with alkyl having 1 to 40 carbon atoms, arylsilyl means silyl substituted with aryl having 6 to 60 carbon atoms, arylamine is substituted with aryl having 6 to 60 carbon atoms ≪ / RTI >

The condensed rings used in the present invention means condensed aliphatic rings, condensed aromatic rings, condensed heteroaliphatic rings, condensed heteroaromatic rings, or a combination thereof.

Also, the present invention is an organic electroluminescent device comprising a cathode, a cathode, and at least one organic layer sandwiched between the anode and the cathode, wherein at least one of the one or more organic layers includes the compound An organic electroluminescent device is provided.

The compound represented by the general formula (1) of the present invention is excellent in thermal stability and phosphorescence properties and can be applied to a light emitting layer of an organic electroluminescent device. Accordingly, when the compound represented by Formula 1 of the present invention is used as a phosphorescent host material in the light emitting layer, it is possible to provide an organic electroluminescent device having excellent light emitting performance, low driving voltage, high efficiency, and long life , And further, a full color display panel in which the performance and the lifetime are greatly improved can be provided.

Hereinafter, the present invention will be described in detail.

The novel compounds according to the present invention are characterized in that indole moieties are fused at the terminal of a 9,10-dihydrophenanthrene moiety to form a basic skeleton, and various substituents are bonded to the basic skeleton And is represented by the above formula (1).

The compound represented by the formula (1) of the present invention has a broad band gap (sky blue ~ red) due to an indole moiety bonded at the terminal of a 9,10-dihydrophenanthrene moiety. ) As well as bipolar characteristics of the whole molecule due to various aromatic ring substituents, so that it can be used not only as a light emitting layer but also as a hole transporting layer, a hole injecting layer and the like since it can increase the bonding force between holes and electrons.

Particularly, the aromatic ring substituent (R ₁ to R ₁₁ ) introduced into the compound significantly increases the molecular weight of the compound, thereby improving the glass transition temperature. Therefore, it is more preferable than the conventional CBP (4,4-dicarbazolylbiphenyl) And exhibits high thermal stability. Further, the compound represented by the general formula (1) of the present invention is also effective for inhibiting crystallization of the organic material layer.

That is, when the compound of Formula 1 according to the present invention is used as a positive hole injection / transport layer material of an organic electroluminescent device or a blue, green and / or red phosphorescent host material, The efficiency and lifetime of the electroluminescent device can be greatly improved. Further, the lifetime of the organic electroluminescent device can be maximized by maximizing the performance of the full-color organic electroluminescent panel.

The compound represented by formula (1) of the present invention is preferably selected from the group consisting of compounds represented by the following formulas (3) to (8).

(3)

[Chemical Formula 4]

[Chemical Formula 5]

[Chemical Formula 6]

(7)

[Chemical Formula 8]

In Formulas 3 to 8, R ₁ to R _{10 ,} X ₁ to X _4, and Ar ₁ are as defined in Formula 1.

In the compounds represented by the general formula (1) of the present invention, X ₁ to X ₄ are each independently N or C (R ₁₁ ). In consideration of lifetime and efficiency of the organic electroluminescent device, X ₁ to X ₄ are all C (R < ₁₁ >). Wherein a plurality of R < ₁₁ > are the same or different from each other.

In the compound represented by the general formula (1) of the present invention, R ₁ to R ₁₁ are each independently selected from the group consisting of hydrogen, deuterium, a C ₆ to C ₄₀ aryl group, a heteroaryl group having 5 to 40 nuclear atoms and a C ₆ to C ₄₀ aryl An amino group, and more preferably a hydrogen or a C ₆ to C ₄₀ aryl group.

In the compound represented by the formula (1) of the present invention, Ar ₁ is selected from the group consisting of C ₆ to C ₄₀ aryl groups, heteroaryl groups having 5 to 40 nuclear atoms, and C ₆ to C ₄₀ arylamine groups .

Specifically, in the compound represented by the general formula (1) of the present invention, Ar ₁ is preferably selected from the group consisting of the structures represented by the following S1 to S206.

In particular, Ar ₁ is the same as S1, S6, S14, S15, S19, S71, S72, S78, S79, S80, S81, S84, S90, S91, S92, S95, S102 , S103, S104, S105, S106, S107, S110, S122, S126, S119, S127, S130, S139, S145, S146, S147, S148, S149, S150, S166, S167, S168, S169, S170, S171, S175 , S176, S177, S178, S179, S180, S181, S188, S197, S198, S199, S200, S201, S202, S203, S204, S205 and S206.

Specific examples of the compound represented by the formula (1) of the present invention include the following compounds 1 to 280, but the present invention is not limited thereto.

The compound represented by formula (1) of the present invention can be synthesized in various ways with reference to the synthesis process of the following examples.

Meanwhile, the present invention provides an organic electroluminescent device comprising the compound represented by Formula 1, preferably the compound represented by Formula 3 to 8.

Specifically, the present invention is an organic electroluminescent device comprising an anode, a cathode, and one or more organic layers sandwiched between the anode and the cathode, wherein at least one of the one or more organic layers includes The compound represented by the above formula (1), preferably the compound represented by the above formulas (3) to (8). At this time, the compound represented by the formula (1) may be used singly or in combination of two or more.

The one or more organic layers including the compound represented by Formula 1 may be any one or more of a hole injecting layer, a hole transporting layer, a light emitting layer, an electron transporting layer, and an electron injecting layer, and may be a light emitting layer.

Specifically, the organic electroluminescent device of the present invention may include a host material in the light emitting layer, and the host material may include the compound represented by the above formula (1). As described above, when the compound represented by Formula 1 is contained as a light emitting layer material of an organic electroluminescent device, preferably, a blue, green, or red phosphorescent host, the bonding force between holes and electrons in the light emitting layer is increased. (Luminescence efficiency and power efficiency), lifetime, luminance, driving voltage, and the like can be improved.

The structure of the organic electroluminescent device of the present invention is not particularly limited and may be a structure in which a substrate, an anode, a hole injecting layer, a hole transporting layer, a light emitting layer, an electron transporting layer, and a cathode are sequentially stacked. In addition, an electron injection layer may be further stacked on the electron transport layer. In addition, the structure of the organic electroluminescent device of the present invention may be a structure in which not only an anode, one or more organic compound layers and a cathode are sequentially laminated but also an insulating layer or an adhesive layer is inserted into the interface between the electrode and the organic compound layer.

The organic electroluminescent device of the present invention is manufactured using materials and methods known in the art, except that at least one or more of the organic material layers (for example, the light emitting layer) is formed so as to include the compound represented by Formula 1 .

The organic material layer 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 substrate usable in the present invention is not particularly limited, and a silicon wafer, quartz, a glass plate, a metal plate, a plastic film and a sheet can be used.

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 or polyaniline; And carbon black, but are not limited thereto.

The negative electrode material may be a metal such as magnesium, calcium, sodium, potassium, titanium, indium, yttrium, lithium, gadolinium, aluminum, silver, tin or lead or an alloy thereof; And multi-layer structure materials such as LiF / Al or LiO ₂ / Al, but are not limited thereto.

Hereinafter, the present invention will be described in detail with reference to examples. However, the following examples are illustrative of the present invention, and the present invention is not limited by the following examples.

[ Preparation Example  1] 2,13- dihydro -1H- naphtho [2,1-a] carbazole and 6,12- dihydro -5H-naphtho [1,2-b] carbazole

≪ Step 1 > 2- (2- nitrophenyl ) -9,10- dihydrophenanthrene Synthesis of

2-bromo-9,10-dihydrophenanthrene, 3.22 g (19.34 mmol) of 2-nitrophenylboronic acid, 2.12 g (52.74 mmol) of NaOH and 200 ml / 100 ml of THF / H ₂ O was added and stirred. At 40 ℃ into the Pd (PPh _{3) 4} of 1.02 g (5 mol%) was stirred at 80 ℃ for 12 hours. After completion of the reaction, the reaction mixture was extracted with methylene chloride, and the mixture was filtered with MgSO ₄ . After removing the solvent of the filtered organic layer, 2- (2-nitrophenyl) -9,10-dihydrophenanthrene (4.19 g, 13.90 mmol, yield 79%) was obtained by column chromatography.

¹ H-NMR:? 2.84 (m, 4H), 7.33 (m, 4H), 7.69

≪ Step 2 > 2,13- dihydro -1H- naphtho [2,1-a] carbazole and 6,12- dihydro -5H-naphtho [1,2-b] carbazole

3.26 g (10.83 mmol) of 2- (2-nitrophenyl) -9,10-dihydrophenanthrene, 7.10 g (27.08 mmol) of triphenylphosphine and 60 ml of 1,2-dichlorobenzene were placed under a nitrogen stream and stirred for 12 hours. After completion of the reaction, 1,2-dichlorobenzene was removed and extracted with dichloromethane. The extracted organic layer was washed with MgSO ₄ and purified by column chromatography to obtain 2,13-dihydro-1H-naphtho [2,1-a] carbazole (0.96 g, 3.57 mmol, yield 33% -dihydro-5H-naphtho [1,2-b] carbazole (1.08 g, 4.00 mmol, yield 37%).

2,13-dihydro-1H-naphtho [ 2,1-a] 1 H-NMR of the carbazole: δ 2.83 (m, 4H ), 7.30 (m, 4H), 7.54 (m, 2H), 7.76 (m, 2H ), 8.01 (d, IH), 8.12 (d, IH), 10.01 (s, IH)

¹ 6,12-dihydro-5H-naphtho [ 1,2-b] carbazole H-NMR: δ 2.84 (m, 4H), 7.28 (m, 4H), 7.56 (m, 3H), 7.77 (d, 1H ), 8.12 (m, 2H), 10.21 (s, 1 H)

[ Preparation Example  2] 6,8- dihydro -5H- naphtho [2,1-b] carbazole and 6,13- dihydro -5H-naphtho [1,2-a] carbazole

≪ Step 1 > 3- (2- nitrophenyl ) -9,10- dihydrophenanthrene Synthesis of

Step 1 of Preparation Example 1 was repeated except that 3-bromo-9,10-dihydrophenanthrene (4.56 g, 17.60 mmol) was used instead of 2-bromo-9,10-dihydrophenanthrene to obtain 3- 2-nitrophenyl) -9,10-dihydrophenanthrene.

¹ H-NMR:? 2.85 (m, 4H), 7.28 (m, 5H), 7.69

≪ Step 2 > 6,8- dihydro -5H- naphtho [2,1-b] carbazole and 6,13- dihydro -5H-naphtho [1,2-a] carbazole

Step 2 of Preparation Example 1 was repeated except that 3- (2-nitrophenyl) -9,10-dihydrophenanthrene (3.26 g, 10.83 mmol) was used instead of 2- (2-nitrophenyl) The same procedure was followed to obtain 6,8-dihydro-5H-naphtho [2,1-b] carbazole and 6,13-dihydro-5H-naphtho [1,2-a] carbazole.

6,8-dihydro-5H-naphtho [ 2,1-b] carbazole 1 H-NMR of: δ 2.83 (m, 4H) , 7.28 (m, 5H), 7.49 (m, 1H), 7.66 (m, 3H ), 8.11 (d, 1 H), 10.07 (s, 1 H)

¹ H-NMR:? 2.83 (m, 4H), 7.32 (m, 5H), 7.52 (m, 2H), 7.77 ), 8.11 (d, 1 H), 10.22 (s, 1 H)

[ Preparation Example  3] 4- phenyl -2,13- dihydro -1H- naphtho [2,1-a] carbazole and 3- phenyl -6,12-dihydro-5H-naphtho [1,2-b] carbazole

<Step 1> 2- bromo -7- (2- nitrophenyl ) -9,10- dihydrophenanthrene Synthesis of

The procedure of Step 1 of Preparation Example 1 was repeated except that 2,7-dibromo-9,10-dihydrophenanthrene (5.95 g, 17.60 mmol) was used instead of 2-bromo-9,10- -bromo-7- (2-nitrophenyl) -9,10-dihydrophenanthrene.

^{1 H-NMR: δ 2.84 (} m, 4H), 7.48 (m, 5H), 7.86 (m, 3H), 8.01 (m, 2H)

<Step 2> Synthesis of 2- (2- nitrophenyl ) -7- phenyl -9,10- dihydrophenanthrene Synthesis of

2-bromo-7- (2-nitrophenyl) -9,10-dihydrophenanthrene (6.69 g, 17.60 mmol) was reacted with phenylboronic acid (2.36 g, 19.34 mmol) instead of 2-nitrophenylboronic acid in place of 2-bromo- 2- (2-nitrophenyl) -7-phenyl-9,10-dihydrophenanthrene was obtained by following the procedure of <Step 1> of Preparation Example 1,

^{1 H-NMR: δ 2.83 (} m, 4H), 7.28 (m, 2H), 7.51 (m, 6H), 7.83 (m, 5H), 8.02 (m, 2H)

&Lt; Step 3 > 4- phenyl -2,13- dihydro -1H- naphtho [2,1-a] carbazole and 3- phenyl -6,12-dihydro-5H-naphtho [1,2-b] carbazole

Except that 2- (2-nitrophenyl) -7-phenyl-9,10-dihydrophenanthrene (4.09 g, 10.83 mmol) was used in place of 2- (2-nitrophenyl) -9,10-dihydrophenanthrene. 2-a] carbazole and 3-phenyl-6,12-dihydro-5H-naphtho [1,2-b ] carbazole.

¹ H-NMR:? 2.83 (m, 4H), 7.28 (m, 1H), 7.50 (m, 8H), 7.78 (m, 3H), 8.05 (d, IH), 8.11 (d, IH), 10.01

¹ H-NMR:? 2.83 (m, 4H), 7.29 (m, 1H), 7.53 (m, 7H), 7.81 (m, 2 H), 8.11 (m, 2 H), 10.11 (s, 1 H)

[ Preparation Example  4] 2- phenyl -6,8- dihydro -5H- naphtho [2,1-b] carbazole and 2- phenyl -6,13-dihydro-5H-naphtho [1,2-a] carbazole

&Lt; Step 1 > 3- bromo -6- (2- nitrophenyl ) -9,10- dihydrophenanthrene Synthesis of

Step 1 of Preparation Example 3 was repeated except that 3,6-dibromo-9,10-dihydrophenanthrene (5.95 g, 17.60 mmol) was used instead of 2,7-dibromo-9,10-dihydrophenanthrene To obtain 3-bromo-6- (2-nitrophenyl) -9,10-dihydrophenanthrene.

^{1 H-NMR: δ 2.84 (} m, 4H), 7.48 (m, 4H), 7.76 (m, 4H), 8.01 (m, 2H)

<Step 2> Synthesis of 3- (2- nitrophenyl ) -6- phenyl -9,10- dihydrophenanthrene Synthesis of

Except that 3-bromo-6- (2-nitrophenyl) -9,10-dihydrophenanthrene (6.69 g, 17.60 mmol) was used instead of 2-bromo-7- (2- nitrophenyl) -9,10- dihydrophenanthrene (2-nitrophenyl) -6-phenyl-9,10-dihydrophenanthrene was obtained in the same manner as in <Step 2> of Example 3.

¹ H-NMR:? 2.83 (m, 4H), 7.32 (m, 4H), 7.51

<Step 3> 2- phenyl -6,8- dihydro -5H- naphtho [2,1-b] carbazole and 2- phenyl -6,13-dihydro-5H-naphtho [1,2-a] carbazole

Except that 3- (2-nitrophenyl) -6-phenyl-9,10-dihydrophenanthrene (4.09 g, 10.83 mmol) was used in place of 2- (2-nitrophenyl) -7- 5-naphtho [2,1-b] carbazole and 2-phenyl-6,13-dihydro-5H-naphtho [1 , 2-a] carbazole.

¹ H-NMR:? 2.83 (m, 4H), 7.38 (m, 4H), 7.50 (m, 6H), 7.71 (m, 2H) (m, 3 H), 8.05 (d, 1 H), 10.01 (s, 1 H)

¹ H-NMR:? 2.83 (m, 4H), 7.32 (m, 4H), 7.51 (m, 5H), 7.78 (m, 4 H), 8.04 (d, 1 H), 10.12 (s, 1 H)

[ Synthetic example  1] Synthesis of Compound 10

Dihydro-1H-naphtho [2,1-a] carbazole (3.0 g, 11.13 mmol), 2-chloro-4,6-diphenyl- 5-triazine (3.58 g, 13.36 mmol), NaH (0.44 g, 11.13 mmol) and DMF (80 ml) were mixed and stirred at room temperature for 3 hours. After completion of the reaction, water was added thereto, and the solid compound was filtered and purified by column chromatography to obtain the desired compound 10 (3.7 g, yield 66%).

GC-Mass (calculated: 500.59 g / mol, measured: 500 g / mol)

[ Synthetic example  2] Synthesis of Compound 13

2,13-dihydro-1H-naphtho [2,1-a] carbazole (3.0 g, 11.13 mmol), 2- (3-bromophenyl) 1,3,5-triazine (5.18 g, 13.36 mmol), Cu powder (0.35 g, 5.56 mmol), K 2 CO 3 (1.53 g, 11.13 mmol), Na 2 SO 4 (3.16 g, 22.26 mmol) and nitrobenzene (80 ml) were mixed and stirred at 190 占 폚 for 12 hours.

After the reaction was completed, the nitrobenzene was removed, the organic layer was separated with methylene chloride, and water was removed using MgSO ₄ . After removing the solvent of the organic layer, the residue was purified by column chromatography to obtain the desired compound 13 (4.0 g, yield 62%).

GC-Mass (calculated: 576.69 g / mol, measured: 576 g / mol)

[ Synthetic example  3] Synthesis of Compound 7

Synthesis Example 2 was repeated except that 6-bromo-2,3'-bipyridine (3.14 g, 13.36 mmol) was used instead of 2- (3-bromophenyl) -4,6-diphenyl- The same procedure was carried out to obtain Compound 7 (2.8 g, yield 59%) as a target compound.

GC-Mass (calculated: 423.51 g / mol, measured: 423 g / mol)

[ Synthetic example  4] Synthesis of Compound 20

2-chloro-4-phenylquinazoline (3.21 g, 13.36 mmol) was added to a solution of 2,13-dihydro-1H-naphtho [2,1-a] carbazole (3.0 g, 11.13 mmol) a mixture of _{Pd (OAc) 2 (0.12 g} , 0.55 mmol), NaO (t-bu) (2.14 g, 22.26 mmol), P (t-bu) 3 (0.22 g, 1.11 mmol) and Toluene (100 ml) Then, the mixture was stirred at 110 DEG 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 = 3: 1 (v / v)) to remove moisture with MgSO ₄ . %).

GC-Mass (calculated: 473.57 g / mol, measured: 473 g / mol)

[ Synthetic example  5] Synthesis of Compound 19

(Biphenyl-4-yl) -N- (4-bromophenyl) -9,9-dimethyl-9H-fluorene- 2-amine (6.9 g, 13.36 mmol) was used in place of the compound obtained in Preparation Example 1, to obtain the desired compound 19 (4.7 g, yield 60%).

GC-Mass (calculated: 704.9 g / mol, measured: 704 g / mol)

[ Synthetic example  6] Synthesis of Compound 45

Dihydro-5H-naphtho [1,2-b] carbazole (3.0 g, 11.13 mmol) synthesized in Preparation Example 1 was used instead of 2,2-dihydro-1H-naphtho [2,1- The procedure of Synthesis Example 1 was repeated to give the desired compound 45 (3.5 g, yield 62%).

GC-Mass (calculated: 500.59 g / mol, measured: 500 g / mol)

[ Synthetic example  7] Synthesis of Compound 48

Dihydro-5H-naphtho [1,2-b] carbazole (3.0 g, 11.13 mmol) synthesized in Preparation Example 1 was used instead of 2,1-dihydro-1H-naphtho [2,1- The procedure of Synthesis Example 2 was repeated to give the desired compound 48 (3.8 g, yield 59%).

GC-Mass (calculated: 576.69 g / mol, measured: 576 g / mol)

[ Synthetic example  8] Synthesis of Compound 47

Synthesis was carried out except that 2- (3-bromophenyl) -4,6-diphenylpyrimidine (5.17 g, 13.36 mmol) was used instead of 2- (3-bromophenyl) -4,6-diphenyl- The procedure of Example 7 was repeated to obtain the desired compound 47 (3.6 g, yield 56%).

GC-Mass (calculated: 575.7 g / mol, measured: 575 g / mol)

[ Synthetic example  9] Synthesis of Compound 80

Dihydro-5H-naphtho [2,1-b] carbazole (3.0 g, 11.13 mmol) synthesized in Preparation Example 2 was used instead of 2,1-dihydro-1H-naphtho [2,1- The procedure of Synthesis Example 1 was repeated to give the desired compound 80 (3.1 g, yield 55%).

GC-Mass (calculated: 500.59 g / mol, measured: 500 g / mol)

[ Synthetic example  10] Synthesis of Compound 83

Dihydro-5H-naphtho [2,1-b] carbazole (3.0 g, 11.13 mmol) synthesized in Preparation Example 2 was used instead of 2,1-dihydro-1H-naphtho [2,1- The procedure of Synthesis Example 2 was repeated to give the desired compound 83 (3.7 g, yield 57%).

GC-Mass (calculated: 576.69 g / mol, measured: 576 g / mol)

[ Synthetic example  11] Synthesis of Compound 85

2- (5-bromobiphenyl-3-yl) -4,6-diphenyl-1,3,5-triazine (6.2 g, , 13.36 mmol), the target compound, Compound 85 (4.2 g, yield: 58%) was obtained.

GC-Mass (calculated: 652.78 g / mol, measured: 652 g / mol)

[ Synthetic example  12] Synthesis of Compound 115

Dihydro-5H-naphtho [1,2-a] carbazole (3.0 g, 11.13 mmol) synthesized in Preparation Example 2 was used instead of 2,13-dihydro-1H-naphtho [2,1- (3.2 g, yield 57%) was obtained by carrying out the same procedure as in Synthesis Example 1, except that the compound

GC-Mass (calculated: 500.59 g / mol, measured: 500 g / mol)

[ Synthetic example  13] Synthesis of Compound 118

Dihydro-5H-naphtho [1,2-a] carbazole (3.0 g, 11.13 mmol) synthesized in Preparation Example 2 was used instead of 2,13-dihydro-1H-naphtho [2,1- The procedure of Synthesis Example 2 was repeated to obtain the desired compound 118 (3.9 g, yield 60%).

GC-Mass (calculated: 576.69 g / mol, measured: 576 g / mol)

[ Synthetic example  14] Synthesis of Compound 127

Dihydro-5H-naphtho [1,2-a] carbazole (3.0 g, 11.13 mmol) synthesized in Preparation Example 2 was used instead of 2,13-dihydro-1H-naphtho [2,1- But using 2- (4'-chlorobiphenyl-3-yl) -4,6-diphenyl-1,3,5-triazine (5.6 g, 13.36 mmol) instead of 2-chloro-4-phenylquinazoline The procedure of Example 4 was repeated to obtain the desired compound 127 (4.2 g, yield 58%).

GC-Mass (calculated: 652.78 g / mol, measured: 652 g / mol)

[ Synthetic example  15] Synthesis of Compound 125

Except that 2- (3-chlorophenyl) -4-phenylquinazoline (4.2 g, 13.36 mmol) was used instead of 2- (4'-chlorobiphenyl-3-yl) -4,6- diphenyl- , The target compound (125) (3.3 g, yield: 54%) was obtained.

GC-Mass (calculated: 549.66 g / mol, measured: 549 g / mol)

[ Synthetic example  16] Synthesis of Compound 124

Dihydro-5H-naphtho [1,2-a] carbazole (3.0 g, 11.13 mmol) synthesized in Preparation Example 2 was used instead of 2,13-dihydro-1H-naphtho [2,1- The procedure of Synthesis Example 5 was repeated to give the desired compound 124 (4.5 g, yield 57%).

GC-Mass (calculated: 704.9 g / mol, measured: 704 g / mol)

[ Synthetic example  17] Synthesis of Compound 185

Dihydro-5H-naphtho [1,2-b] carbazole (3.0 g, 11.13 mmol) synthesized in Preparation Example 3 instead of 2,13-dihydro-1H- mmol), the procedure of Synthetic Example 1 was repeated to give the desired compound 185 (4.0 g, yield 62%).

GC-Mass (calculated: 576.69 g / mol, measured: 576 g / mol)

[ Synthetic example  18] Synthesis of Compound 188

Dihydro-5H-naphtho [1,2-b] carbazole (3.0 g, 8.68 mmol) synthesized in Preparation Example 3 was used instead of 2,13-dihydro-1H- mmol), the target compound, 188 (4.4 g, yield 60%) was obtained by carrying out the same procedure as in Synthesis Example 2.

GC-Mass (calculated: 652.78 g / mol, measured: 652 g / mol)

[ Synthetic example  19] Synthesis of Compound 191

6,6 '- (5-bromo-1,3-phenylene) bis (2-phenylpyridine) (6.19 g, 13.36 mmol) was used instead of 2- (3-bromophenyl) -4,6- ), The procedure of Synthetic Example 18 was repeated to give the desired compound 191 (4.5 g, yield 55%).

GC-Mass (calculated: 727.89 g / mol, measured: 727 g / mol)

[ Synthetic example  20] Synthesis of Compound 150

Phenyl-2,13-dihydro-1H-naphtho [2,1-a] carbazole (3.0 g, 8.68 mmol) synthesized in Preparation Example 3 was used instead of 2,13-dihydro-1H-naphtho [ mmol), the procedure of Synthesis Example 1 was repeated to obtain the aimed compound 150 (3.7 g, yield 58%).

GC-Mass (calculated: 576.69 g / mol, measured: 576 g / mol)

[ Synthetic example  21] Synthesis of Compound 153

Phenyl-2,13-dihydro-1H-naphtho [2,1-a] carbazole (3.0 g, 8.68 mmol) synthesized in Preparation Example 3 was used instead of 2,13-dihydro-1H-naphtho [ mmol), the target compound, Compound 153 (4.5 g, yield 61%) was obtained by carrying out the same procedure as in Synthesis Example 2.

GC-Mass (calculated: 652.78 g / mol, measured: 652 g / mol)

[ Synthetic example  22] Synthesis of Compound 158

2,4-di (tert-phenyl-3-yl) -6-bromo-1,3,5-triazine (8.2) was used instead of 2- (3-bromophenyl) g, 13.36 mmol), the target compound 158 (5.3 g, yield 54%) was obtained.

GC-Mass (calculated: 881.07 g / mol, measured: 881 g / mol)

[ Synthetic example  23] Synthesis of Compound 157

Phenyl-2,13-dihydro-1H-naphtho [2,1-a] carbazole (3.0 g, 8.68 mmol) synthesized in Preparation Example 3 was used instead of 2,13-dihydro-1H-naphtho [ mmol) and 4- (biphenyl-4-yl) -2-chloroquinazoline (4.23 g, 13.36 mmol) was used in place of 2-chloro-4-phenylquinazoline. Compound 157 (4.3 g, yield 59%).

GC-Mass (calculated: 652.76 g / mol, measured: 652 g / mol)

[ Synthetic example  24] Synthesis of Compound 159

Phenyl-2,13-dihydro-1H-naphtho [2,1-a] carbazole (3.0 g, 8.68 mmol) synthesized in Preparation Example 3 was used instead of 2,13-dihydro-1H-naphtho [ mmol), the procedure of Synthetic Example 5 was repeated to give the desired compound 159 (4.9 g, yield 56%).

GC-Mass (calculated: 780.99 g / mol, measured: 780 g / mol)

[ Synthetic example  25] Synthesis of Compound 255

Phenyl-6,13-dihydro-5H-naphtho [1,2-a] carbazole (3.0 g, 8.68 mmol) synthesized in Preparation Example 4 instead of 2,13-dihydro-1H- mmol), the procedure of Synthesis Example 1 was repeated to obtain the desired compound 255 (3.8 g, yield 59%).

GC-Mass (calculated: 576.69 g / mol, measured: 576 g / mol)

[ Synthetic example  26] Synthesis of Compound 258

Phenyl-6,13-dihydro-5H-naphtho [1,2-a] carbazole (3.0 g, 8.68 mmol) synthesized in Preparation Example 4 instead of 2,13-dihydro-1H- mmol), the target compound 258 (4.2 g, yield 57%) was obtained by carrying out the same procedure as in Synthesis Example 2.

GC-Mass (calculated: 652.78 g / mol, measured: 652 g / mol)

[ Synthetic example  27] Synthesis of Compound 257

2-phenyl-6,13-dihydro-5H-naphtho [1,2-a] carbazole synthesized in Preparation Example 4 instead of 2,1-dihydro-1H-naphtho [2,1- , 8.68 mmol), the target compound 257 (4.0 g, yield 55%) was obtained.

GC-Mass (calculated: 651.8 g / mol, measured: 651 g / mol)

[ Synthetic example  28] Synthesis of Compound 220

Dihydro-5H-naphtho [2,1-b] carbazole (3.0 g, 8.68 mmol) synthesized in Preparation Example 4 instead of 2,13-dihydro-1H-naphtho [ mmol), the procedure of Synthesis Example 1 was repeated to obtain the desired compound 220 (3.6 g, yield 56%).

GC-Mass (calculated: 576.69 g / mol, measured: 576 g / mol)

[ Synthetic example  29] Synthesis of compound 223

Dihydro-5H-naphtho [2,1-b] carbazole (3.0 g, 8.68 mmol) synthesized in Preparation Example 4 instead of 2,13-dihydro-1H-naphtho [ mmol), the target compound was obtained in the same manner as in Synthesis Example 2, to obtain 223 (4.3 g, yield 59%) as a target compound.

GC-Mass (calculated: 652.78 g / mol, measured: 652 g / mol)

[ Synthetic example  30] Synthesis of Compound 225

Dihydro-5H-naphtho [2,1-b] carbazole (3.0 g, 8.68 mmol) synthesized in Preparation Example 4 instead of 2,13-dihydro-1H-naphtho [ mmol) was used in place of the compound obtained in the above Synthesis Example 11 to obtain the desired compound 225 (4.5 g, yield 55%).

GC-Mass (calculated: 728.88 g / mol, measured: 728 g / mol)

[ Example  1 to 30] Organic Field  Fabrication of light emitting device

Compounds synthesized in Synthesis Examples 1 to 30 were subjected to high purity sublimation purification by a conventionally known method, and then a green organic electroluminescent device was fabricated according to the following procedure.

First, a glass substrate coated with ITO (Indium Tin Oxide) with a thickness of 1500 Å was ultrasonically washed with distilled water. 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, Hoshin Tech), the substrate was cleaned using UV for 5 minutes, The substrate was transferred.

M-MTDATA (60 nm) / TCTA (80 nm) / compound of Synthesis Examples 1 to 30 + 10% Ir (ppy) ₃ (300 nm) / BCP (10 nm) / Alq ₃ ) / LiF (1 nm) / Al (200 nm) were stacked in this order to fabricate an organic electroluminescent device.

[ Comparative Example  1] Organic Field  Fabrication of light emitting device

A green organic electroluminescent device was fabricated in the same manner as in Example 1, except that CBP was used instead of the compound of Synthesis Example 1 as a luminescent host material in forming the light emitting layer.

The structures of m-MTDATA, TCTA, Ir (ppy) ₃ , BCP and CBP used in Examples 1 to 30 and Comparative Example 1 are as follows.

[ Evaluation example ]

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

Sample Host The driving voltage (V) Emission peak (nm) Current efficiency (cd / A) Example 1 Compound 10 6.65 520 41.8 Example 2 Compound 13 6.60 521 40.7 Example 3 Compound 7 6.60 519 43.2 Example 4 Compound 20 6.65 519 43.5 Example 5 Compound 19 6.55 519 41.7 Example 6 Compound 45 6.50 518 41.1 Example 7 Compound 48 6.55 517 42.6 Example 8 Compound 47 6.60 519 39.6 Example 9 Compound 80 6.45 520 39.8 Example 10 Compound 83 6.65 518 39.3 Example 11 Compound 85 6.60 521 40.2 Example 12 Compound 115 6.50 520 41.0 Example 13 Compound 118 6.55 519 41.3 Example 14 Compound 127 6.50 520 39.7 Example 15 Compound 125 6.60 520 40.2 Example 16 Compound 124 6.60 519 41.3 Example 17 Compound 185 6.55 517 39.7 Example 18 Compound 188 6.55 518 40.5 Example 19 Compound 191 6.55 518 41.3 Example 20 Compound 150 6.50 519 41.5 Example 21 Compound 153 6.50 520 41.2 Example 22 Compound 158 6.45 521 40.5 Example 23 Compound 157 6.65 520 39.3 Example 24 Compound 159 6.60 519 39.6 Example 25 Compound 255 6.50 517 38.8 Example 26 Compound 258 6.50 519 39.6 Example 27 Compound 257 6.55 518 42.5 Example 28 Compound 220 6.50 520 41.0 Example 29 Compound 223 6.60 520 40.5 Example 30 Compound 225 6.65 519 41.4 Comparative Example 1 CBP 6.93 516 38.2

As shown in Table 1, when the compound according to the present invention was used as a light emitting layer of a green organic electroluminescent device (Examples 1 to 30), compared with the conventional green organic electroluminescent device using CBP (Comparative Example 1) And the driving voltage are excellent.

Claims (7)

A compound represented by the following formula (7):
(7)

In Formula 7,
X ₁ to X ₄ are all C (R ₁₁ ), wherein a plurality of R _{11 s} may be the same as or different from each other,
Wherein R ₁ , R ₂ , R ₅ to R ₁₁ are each independently hydrogen,
Wherein Ar ₁ is selected from the group consisting of an arylamine C ₆ ~ C ₄₀ aryl group, the number of nuclear atoms of 5 to 40 heteroaryl group, and a C ₆ ~ C ₄₀ of,
The aryl, heteroaryl and arylamine groups of Ar ₁ are each independently selected from the group consisting of deuterium, cyano, C ₁ to C ₄₀ alkyl, C ₂ to C ₄₀ alkenyl, C ₂ to C ₄₀ alkynyl, C ₆ to C ₄₀ , ~ C ₄₀ aryl group, nuclear atoms aryl of from 5 to 40 heteroaryl group, a C ₆ ~ C ₄₀ aryloxy group, C ₁ ~ C ₄₀ alkyloxy group of, C ₃ ~ C ₄₀ cycloalkyl group and nuclear atoms And a heterocycloalkyl group having 3 to 40 carbon atoms. delete delete delete The method according to claim 1,
Wherein Ar ₁ is a compound being selected from the group consisting of structure represented by S1 to S140, S142, S143, S145 to S150, S152 to S154, S158 to S161, S166 to S169 and S171 to S206.

1. An organic electroluminescent device comprising an anode, a cathode, and at least one organic layer sandwiched between the anode and the cathode,
Wherein at least one of the one or more organic layers includes a compound according to any one of claims 1 to 5. The method according to claim 6,
Wherein the organic compound layer containing the compound is a light emitting layer.