KR20170003502A - Novel organic electroluminescent compounds and organic electroluminescent device using the same - Google Patents

Abstract

The present invention relates to a novel organic light emitting compound, and to an organic electroluminescent device adopting the same. More particularly, the organic light emitting compound is represented by chemical formula 1. An organic electroluminescent device comprising the organic light emitting compound in an electron transfer layer has low driving voltage and remarkably low electric power consumption.

Description

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

The present invention relates to a novel organic light emitting compound and an organic electroluminescent device employing the same. More particularly, the organic electroluminescent compound according to the present invention can be included in an electron transport layer of an organic light emitting device.

Among the display elements, an electroluminescence device (EL device) is a self-luminous display device having a wide viewing angle, excellent contrast and fast response speed. In 1987, Eastman Kodak Co., An organic EL device using an aromatic diamine and an aluminum complex having a low molecular weight as a material for forming a light emitting layer has been developed for the first time [Appl. Phys. Lett. 51, 913, 1987].

An organic EL device is a device that injects electric charge into an organic film formed between an electron injection electrode (cathode) and a hole injection electrode (anode) to form an electron and a hole. It is possible to form a device on a flexible transparent substrate such as a plastic substrate. Further, the device can be driven at a lower voltage (10 V or less) than a plasma display panel or an inorganic EL display, It has the advantage of being excellent in color.

In an organic EL device, an organic material can be largely divided into a light emitting material and a charge transporting material. The luminescent material is directly related to the luminescent color and the luminescent efficiency. Some required characteristics are that the luminescent quantum yield in the solid state must be high, the electron and hole mobility must be high, the luminescent material should not be easily decomposed in the vacuum deposition, A uniform thin film should be formed and stabilized.

Typical examples of conventional electron transfer materials include aluminum complexes such as tris (8-hydroxyquinoline) aluminum (III) (Alq) used before Kodak's multilayer thin film OLED in 1987 and bis (Bebq) such as 10-hydroxybenzo- [ h ] quinolinato beryllium (Bebq) [T. Sato et al. J. Mater. Chem . 10 (2000) 1151). However, in the case of these materials, since the OLED has been commercialized since 2002, the limit has begun to emerge. Since then, a number of high-performance electron-transporting materials have been studied and commercialized.

On the other hand, as non-metal complex series, the electron transfer materials of good characteristics that have been published so far include spiro- PBD [N. Johansson et al. Adv . Mater. 10 (1998) 1136], PyPySPyPy [M. Uchida et al. Chem . Mater. 13 (2001) 2680; and Kodak's TPBI [Y.-T. Tao et al. Appl. Phys. Lett . 77 (2000) 1575). However, there is still room for improvement in terms of electroluminescence characteristics and life span.

Particularly noteworthy in the conventional electron transferring material is that the driving voltage is merely slightly improved or the driving life of the device is remarkably lowered compared to the contents to be announced. Side effects. In order to achieve the target such as power consumption and brightness increase which are obstacles to the enlargement of OLED panel up to now, it is a reality that the above-mentioned side effects are a big obstacle.

Accordingly, an object of the present invention is to provide an organic light emitting compound having an excellent skeleton which is superior in luminous efficiency, power consumption, and device life to an existing electron transporting material in order to solve the above problems, And an organic electroluminescent device employing the same.

The present invention relates to an organic light emitting compound represented by the following general formula (1) and an organic electroluminescent device employing the same. The organic electroluminescent compound according to the present invention is contained in an electron transport layer of an organic electroluminescent device, There is an advantage that the luminous efficiency and the power consumption can be remarkably reduced.

The present invention provides an organic luminescent compound represented by the following general formula (1).

[Chemical Formula 1]

[In the above formula (1)

L is a chemical bond, a substituted or unsubstituted (C6-C30) arylene, a substituted or unsubstituted (C3-C30) heteroarylene, a substituted or unsubstituted 5 to 7 membered heterocycloalkylene, a substituted Or a 5- to 7-membered heterocycloalkylene in which at least one unsubstituted aromatic ring is fused, Substituted or unsubstituted (C3-C30) cycloalkylene, (C3-C30) cycloalkylene in which one or more substituted or unsubstituted aromatic rings are fused, substituted or unsubstituted adamantylene, substituted or unsubstituted (C2-C30) alkynylene, substituted or unsubstituted (C6-C30) aryl (C1-C30) alkylene, substituted or unsubstituted (C2-C30) alkenylene, substituted or unsubstituted Substituted or unsubstituted (C1-C30) alkylene, substituted or unsubstituted (C1-C30) alkylene, substituted or unsubstituted (C6-C30) arylenethio, -O- or -S-;

,

또는 하이드록시이거나 인접한 치환체와 융합고리를 포함하거나 포함하지 않는 (C3-C30)알킬렌 또는 (C3-C30)알케닐렌으로 연결되어 지환족 고리 및 단일환 또는 다환의 방향족 고리를 형성할 수 있으며;R ₁ to R ₄ , Ar ₁ and Ar ₂ are each independently selected from the group consisting of hydrogen, deuterium, halogen, substituted or unsubstituted (C 1 -C 30) alkyl, substituted or unsubstituted (C 6 -C 30) (C3-C30) cycloalkyl, substituted or unsubstituted (C6-C30) aryl, substituted or unsubstituted (C3-C30) heteroaryl, substituted or unsubstituted 5 to 7 membered heterocyclo Alkyl, a 5-to 7-membered heterocycloalkyl fused with one or more of a substituted or unsubstituted aromatic ring, Substituted or unsubstituted (C3-C30) cycloalkyl, (C3-C30) cycloalkyl substituted by one or more fused aromatic rings, substituted or unsubstituted adamantyl, substituted or unsubstituted (C7- C30) alkyl, bicycloalkyl, _{cyano, NR 11 R 12, BR 13} R 14, PR 15 R 16, P (= O) R 17 R 18 [R 11 to R ₁₈ independently represent a substituted or unsubstituted (C1 each other (C1-C30) alkyl, substituted or unsubstituted (C6-C30) aryl or substituted or unsubstituted (C3-C30) heteroaryl, substituted or unsubstituted tri (C6-C30) arylsilyl, substituted or unsubstituted tri (C6-C30) arylsilyl, substituted or unsubstituted (C6-C30) Substituted or unsubstituted (C1-C30) alkylthio, substituted or unsubstituted (C6-C30) aryloxy, substituted or unsubstituted , Substituted or unsubstituted (C1-C30) alkoxycarbonyl, substituted or unsubstituted Substituted or unsubstituted (C 1 -C 30) alkylcarbonyl, substituted or unsubstituted (C 6 -C 30) arylcarbonyl, substituted or unsubstituted (C 2 -C 30) alkenyl, substituted or unsubstituted Substituted or unsubstituted (C1-C30) alkylcarbonyloxy, substituted or unsubstituted (C6-C30) aryloxycarbonyl, substituted or unsubstituted (C1-C30) alkoxycarbonyloxy, substituted or unsubstituted (C6-C30) arylcarbonyloxy, substituted or unsubstituted (C6-C30) aryloxycarbonyloxy, carboxyl, nitro,

,

Or (C3-C30) alkylene or (C3-C30) alkenylene with or without a fused ring to form a monocyclic or polycyclic aromatic ring;

W is _{- (CR 41 R 42) m} -, - (R 41) C = C (R 42) -, -N (R 43) -, -S-, -O-, -Si (R 44) (R _{45) -, -P (R 46} ) -, -P (= O) (R 47) -, -C (= O) - or -B (R ₄₈₎ -, and

Each X is independently O, S, NR ₅ ;

R ₅ , R ₃₁ to R ₃₃ And R ₄₁ to R ₄₈ are as defined above for R ₁ to R ₄ , Ar ₁ and Ar ₂ ;

Wherein said heterocycloalkyl and heteroaryl comprise at least one heteroatom selected from B, N, O, S, P (= O), Si and P;

and m is an integer of 1 or 2.]

Substituents comprising " alkyl ", " alkoxy " and other " alkyl " moieties described in the present invention include both straight chain and branched forms.

&Quot; Aryl " in the present invention means an organic radical derived from an aromatic hydrocarbon by one hydrogen elimination and is a single or fused ring containing 4 to 7, preferably 5 or 6 ring atoms, And includes a form in which a plurality of aryls are connected by a single bond. Specific examples include phenyl, naphthyl, biphenyl, anthryl, indenyl, fluorenyl, phenanthryl, triphenylenyl, pyrenyl, perylenyl, crycenyl, naphthacenyl, fluoranthenyl, But is not limited thereto. The naphthyl includes 1-naphthyl and 2-naphthyl, anthryl includes 1-anthryl, 2-anthryl and 9-anthryl, and fluorenyl includes 1-fluorenyl, 2- Fluorenyl, 3-fluorenyl, 4-fluorenyl, and 9-fluorenyl.

"Heteroaryl" in the present invention includes 1 to 4 heteroatoms selected from B, N, O, S, P (= O), Si and P as aromatic ring skeletal atoms and the remaining aromatic ring skeletal atoms are carbon Means a 5 to 6 membered monocyclic heteroaryl and a polycyclic heteroaryl condensed with at least one benzene ring and may be partially saturated. The heteroaryl in the present invention also includes a form in which one or more heteroaryl is connected to a single bond. The heteroaryl groups include divalent aryl groups in which the heteroatoms in the ring are oxidized or trisubstituted to form, for example, an N-oxide or a quaternary salt. Specific examples include furyl, thiophenyl, pyrrolyl, imidazolyl, pyrazolyl, thiazolyl, thiadiazolyl, isothiazolyl, isoxazolyl, oxazolyl, oxadiazolyl, triazinyl, tetrazinyl, triazolyl, tetra Monocyclic heteroaryl such as pyrrolyl, pyrrolyl, pyrrolyl, pyrrolyl, pyrrolyl, pyrrolyl, pyrrolyl, pyrazinyl, pyrrolyl, pyrrolyl, pyrazinyl, pyrimidinyl, pyridazinyl, Benzyloxazolyl, isoindolyl, indolyl, indazolyl, benzothiadiazolyl, quinolyl, isoquinolyl, cinnolinyl, quinazolinyl, quinoxalinyl, carbazolyl, phenanthridinyl (Such as pyridyl N-oxide, quinolyl N-oxide), quaternary salts thereof, and the like, and the like, but are not limited thereto .

(C1-C30) alkylsilyl, di (C1-C30) alkyl (C6-C30) arylsilyl, (C6- (C1-C30) alkyloxycarbonyl, (C1-C30) alkyloxycarbonyl, (C1-C30) alkylthio, C1-C30) alkylcarbonyloxy "and the like may be limited to a carbon number of 1 to 20, and may be limited to a carbon number of 1 to 10. (C6-C30) aryl, di (C1-C30) alkyl (C6-C30) arylsilyl, tri (C6-C30) aryloxycarbonyloxy, (C6-C30) arylthio, (C6-C30) arylcarbonyl, Quot; and the like can be limited to 6 to 20 carbon atoms, and may be limited to 6 to 12 carbon atoms. The heteroaryl of " (C3-C30) heteroaryl " may be limited to from 4 to 20 carbon atoms and may be limited to from 4 to 12 carbon atoms. The heteroaryl of the "(C3-C30) cycloalkyl" may be limited to 3 to 20 carbon atoms and may be limited to 3 to 7 carbon atoms. The alkenyl or alkynyl of " (C2-C30) alkenyl or alkynyl " may be limited to from 2 to 20 carbon atoms and may be limited to from 2 to 10 carbon atoms.

The term " substituted or unsubstituted " in the present invention is independently selected from the group consisting of deuterium, halogen, (C1-C30) alkyl substituted or unsubstituted with halogen, (C6- A 5- to 7-membered heterocycloalkyl containing at least one selected from the substituted or unsubstituted (C3-C30) heteroaryl, B, N, O, S, P (= O), Si and P, (C3-C30) cycloalkyl, (C6-C30) cycloalkyl, (C1-C30) alkylsilyl, di (C1-C30) (C2-C30) alkenyl, (C2-C30) alkynyl, (C2-C30) alkynyl, cyano, _{carbazolyl, NR 21 R 22, BR 23} R 24, PR 25 R 26, P (= O) R 27 R 28 [R 21 to R ₂₈ are independently selected from (C1-C30) each alkyl, (C6- (C1-C30) alkyl, (C1-C30) alkyl (C6-C30) aryl (C6-C30) arylthio, (C1-C30) alkoxycarbonyl, (C1-C30) alkylthio, (C6-C30) arylcarbonyl, (C1-C30) alkoxycarbonyloxy, (C1-C30) alkylcarbonyloxy, (C6-C30) aryloxycarbonyloxy, carboxy, nitro, or hydroxy, or adjacent substituents are connected to form a ring.

Wherein L is a chemical bond or a group selected from the group consisting of phenylene, naphthylene, anthracenylene, biphenylene, fluorenylene, triphenylenylene, fluoranthenylene, clreshenylene, terphenylene, phenanthrylene, pyrenylene, Examples of the aryl group include an aryl group such as phenyl, naphthyl, naphthyl, naphthyl, naphthyl, naphthyl, naphthyl, cycloalkylene such as cyclopentylene, cyclohexylene, cycloheptylene and cyclooctylene, -O- or -S-, but is not limited thereto, and examples thereof include, but are not limited to, Can be further substituted as shown in Formula 1 above.

R ₁ to R ₅ , R ₃₁ to R ₃₃ And R ₄₁ to R ₄₈ independently represent hydrogen, deuterium, halogen such as alkyl, such as methyl, ethyl, propyl, butyl, pentyl, hexyl, ethylhexyl, heptyl or octyl, Aryl such as phenanthryl, terphenyl, pyrenyl, perylenyl, spirobifluorenyl, fluoranthenyl, chrysenyl and triphenylenyl, cyano, trimethylsilyl, triethylsilyl, dimethylethylsilyl, tributylsilyl Dialkylsilylsilyl such as dimethylphenylsilyl, or triarylsilyl such as triphenylsilyl and trinaphthylsilyl, but is not limited thereto, and may be further substituted as in Formula 1 have.

또는

로부터 선택되어지나, 이에 한정되는 것은 아니며, 상기 화학식 1에서와 같이 더 치환될 수 있다.Ar ₁ and Ar ₂ are each independently selected from the group consisting of hydrogen, deuterium, halogen such as alkyl such as methyl, ethyl, propyl, butyl, pentyl, hexyl, ethylhexyl, heptyl, octyl, phenyl, naphthyl, fluorenyl, Cycloalkyl such as phenanthryl, terphenyl, pyrenyl, perylenyl, spirobifluorenyl, fluoranthenyl, chrysenyl, triphenylenyl and the like, 1,2-dihydroacenaphthyl and the like, Heteroaryl such as aryl, dibenzothiophenyl, dibenzofuryl, carbazolyl, pyridyl, furyl, thienyl, quinolyl, triazinyl, pyrimidinyl, pyridazinyl, quinoxalinyl, phenanthrolinyl, Heterocycloalkyl fused with at least one aromatic ring such as pyrrolidino, benzopiperidino, dibenzomorpholino, dibenzoazepino, phenyl, naphthyl, fluorenyl, biphenyl, phenanthryl, terphenyl, Pyrenyl, perylenyl, spirobifluorenyl, fluoranthenyl, Aryl such as benzyl, benzyl, benzyl, benzyl, benzyl, benzyl, benzyl, benzyl, benzyl, benzyl, benzyl, benzyl, benzyl, Aryloxy such as biphenyloxy, arylthio such as biphenylthio, aralkyl such as biphenylmethyl, triphenylmethyl, and the like,

or

However, the present invention is not limited thereto, and it can be further substituted as shown in Formula 1.

또는

는 구체적으로 하기 구조로 예시될 수 있다. In addition,

or

Can be specifically exemplified by the following structures.

Wherein R ₄₁ to R ₄₈ are each independently a substituted or unsubstituted (C 1 -C 30) alkyl, a substituted or unsubstituted (C 6 -C 30) aryl or a substituted or unsubstituted (C 3 -C 30) heteroaryl, (C3-C30) alkylene or (C3-C30) alkenylene with or without a fused ring to form an alicyclic ring and a monocyclic or polycyclic aromatic ring.

The organic luminescent compound according to the present invention may be more specifically exemplified as the following compounds, but the following compounds are not intended to limit the present invention.

The organic luminescent compound according to the present invention can be prepared as shown in the following Reaction Scheme 1.

[Reaction Scheme 1]

[L, Ar ₁ and Ar ₂ , X and R ₁ to R ₄ in the above Reaction Scheme 1 are the same as defined in the above formula 1]

The present invention provides an organic electroluminescent device, wherein the organic electroluminescent device according to the present invention comprises a first electrode; A second electrode; And at least one organic material layer interposed between the first electrode and the second electrode, wherein the organic material layer comprises at least one organic light emitting compound of Formula 1. The organic luminescent compound is used as a material for the electron transport layer.

The organic material layer may include one or more layers including the organic light emitting compound of Formula 1 and a layer comprising a fluorescent host, a fluorescent dopant, a phosphorescent host, and a phosphorescent dopant. The organic electroluminescent layer The fluorescent host, fluorescent dopant, phosphorescent host or phosphorescent dopant applied to the device is not particularly limited.

The organic electroluminescent device of the present invention may include at least one compound selected from the group consisting of an arylamine compound and a styrylarylamine compound, Or styrylarylamine-based compounds are exemplified in Application Nos. 10-2008-0123276, 10-2008-0107606 or 10-2008-0118428, but are not limited thereto.

In addition, in the organic electroluminescent device of the present invention, in addition to the organic luminescent compound of Formula 1, an organic electroluminescent compound of group 1, group 2, group 4, periodic transition metal, group of lanthanide metal and group of d- , And the organic material layer may include a charge generation layer in addition to the light emitting layer.

In addition, a white organic electroluminescent device can be formed by simultaneously containing at least one organic compound layer that emits blue, green, or red light in addition to the organic light emitting compound of Formula (1) in the organic compound layer, and the blue, green, But are not limited to, those described in Application Serial Nos. 10-2008-0123276, 10-2008-0107606 or 10-2008-0118428.

In the organic electroluminescent device of the present invention, one layer selected from a chalcogenide layer, a metal halide layer and a metal oxide layer (hereinafter referred to as "surface layer ") is formed on the inner surface of at least one of the pair of electrodes, Or more. Concretely, it is preferable to dispose a halogenated metal layer or a metal oxide layer on the surface of the anode on the side of the light emitting medium layer and on the surface of the cathode on the side of the light emitting medium layer, with a chalcogenide (including oxide) layer of a metal of silicon and aluminum Do. Thus, stabilization of the drive can be obtained.

Examples of the chalcogenide include SiO _x (1? _X ? 2), AlO _x (1? _X ? 1.5), SiON and SiAlON. Examples of the halogenated metal include LiF, MgF ₂ , CaF ₂ , Rare-earth metals and the like. Preferable examples of the metal oxides include Cs ₂ O, Li ₂ O, MgO, SrO, BaO, CaO and the like.

In addition, in the organic electroluminescent device of the present invention, a mixed region of the electron transfer compound and the reducing dopant or a mixed region of the hole transport compound and the oxidative dopant is disposed on at least one surface of the pair of electrodes thus fabricated desirable. In this way, since the electron transfer compound is reduced to the anion, it becomes easy to inject and transfer electrons from the mixed region to the light emitting medium. Further, since the hole transport compound is oxidized and becomes a cation, it becomes easy to inject and transport holes from the mixed region into the light emitting medium. Preferred oxidizing dopants include various Lewis acids and acceptor compounds. Preferred reducing dopants include alkali metals, alkali metal compounds, alkaline earth metals, rare earth metals, and mixtures thereof.

Also, a white light emitting device having two or more light emitting layers can be manufactured using a reducing dopant layer as a charge generating layer.

The organic luminescent compound according to the present invention is included in the electron transport layer of the organic light emitting device to lower the driving voltage of the device, thereby remarkably reducing the luminous efficiency and power consumption.

Hereinafter, the organic luminescent compound according to the present invention, the method for producing the same, and the luminescent characteristics of the device will be described in order to facilitate a detailed understanding of the present invention, but the present invention is not limited thereto. And are not intended to limit the scope of the invention.

[Preparation Example 1] Preparation of Compound 46

compound C Manufacturing

20.0 g (183.2 mmol) of Compound A, 47.8 g (183.2 mmol) of Compound B and 150 mL of DMSO are mixed and heated at 180 占 폚. After 12 hours, cool to room temperature and add distilled water. The resulting solid was filtered under reduced pressure and recrystallized with EA / MeOH to obtain 26.0 g (74.24 mmol, 40.5%) of Compound C.

compound D Manufacturing

Dissolve 26.0 g (74.2 mmol) of Compound C in 300 mL of THF and slowly add 35.6 mL (89.1 mmol, 2.5 M in Hexane) of n- BuLi at -78 ° C. After stirring for 1 hour, add 12.4 mL (111.4 mmol) of trimethylborate. After stirring for 10 hours, add distilled water and extract with EA. After distillation under reduced pressure, the residue was recrystallized from MC / Hex to obtain 14.0 g (44.4 mmol, 60.0%) of Compound D.

compound F Manufacturing

Dissolve 20.0 g (108.5 mmol) of compound E in 1000 mL of THF and slowly add 83.1 mL (249.4 mmol, 3 M in diethyl ether) of phenylmagnesium bromide at room temperature. After stirring for 4 hours, distilled water was added, the resulting solid was filtered under reduced pressure, and the solid was recrystallized from EA to obtain 18.0 g (67.2 mmol, 62.3%) of Compound F.

compound 46 Manufacturing

Compound F 10.0 g (137.4 mmol), compound D 12.9 g (41.1 mmol), Pd (PPh 3) 4 1.7 g (1.5 mmol), K 2 CO 3 15.5 g of (112.1 mmol), distilled water 55 mL, toluene 200 mL Mixed and refluxed and stirred. After 8 hours, cool to room temperature and add distilled water. Extracted with MC, dried with magnesium sulfate, and distilled under reduced pressure. The residue was subjected to column separation to obtain 11.0 g (22.0 mmol, 59.2%) of Compound 46 .

[Preparation Example 2] Preparation of Compound 63

compound A Manufacturing

1,3-dibromobenzene 25.0 g (106.0 mmol ), 2-naphthalene boronic acid 18.2 g (106.0 mmol), Pd (PPh 3) 4 4.8 g (4.2 mmol), Na 2 CO 3 33.7 g (317.9 mmol), distilled water 150 mL, and 300 mL of toluene are mixed and stirred under reflux. After 12 hours, cool to room temperature and add distilled water. Extract with EA and dry with magnesium sulfate. The mixture was distilled under reduced pressure and then subjected to column separation to obtain Compound A (15.0 g, 53.0 mmol, 50.5%).

compound  B Manufacturing

Dissolve compound A (15.0 g, 53.0 mmol) in 200 mL of THF and slowly add 21 mL (53.0 mmol, 2.5 M in Hexane) of n- BuLi at -78 ° C. After 1 hour, add 4.8 g (26.5 mmol) of 1,3,5-trichloro-2,4,6-triazine in 100 mL of THF at -78 ° C. After stirring for 5 hours, distilled water was added and extracted with EA. Dried over magnesium sulfate, distilled under reduced pressure, and subjected to column separation to obtain 8.0 g (15.4 mmol, 59.2%) of Compound B.

compound E Manufacturing

Compound ( C ) (25.0 g, 199.7 mmol), Compound ( D ) (36.9 g, 199.7 mmol) and DMSO (200 mL) were mixed and heated at 180 ° C. After 12 hours, cool to room temperature and add distilled water. The resulting solid was filtered under reduced pressure and recrystallized from EA / MeOH to obtain 14.0 g (48.2 mmol, 24.2%) of compound E.

compound F Manufacturing

Dissolve 14.0 g (48.2 mmol) of compound E in 200 mL of THF and slowly add n- BuLi 19.2 mL (48.2 mmol, 2.5 M in Hexane) at -78 ° C. After stirring for 1 hour, add 6.9 mL (62.7 mmol) of trimethylborate. After stirring for 10 hours, add distilled water and extract with EA. After distillation under reduced pressure, column separation was conducted to obtain 8.0 g (31.4 mmol, 65.3%) of Compound F.

compound  63 Manufacturing

Compound B 4.0 g (7.7 mmol), Compound F 2.4 g (9.2 mmol), Pd (PPh 3) 4 0.4 g (0.3 mmol), Na 2 CO 3 2.4 g (23.1 mmol) of distilled water 10 mL, toluene mixed with 50 mL Followed by reflux stirring. After 8 hours, cool to room temperature and add distilled water. Extracted with MC, dried with magnesium sulfate, and distilled under reduced pressure. The mixture was subjected to column separation to obtain 3.4 g (4.9 mmol, 63.6%) of Compound 63 .

[Preparation Example 3] Preparation of Compound 67

compound C Manufacturing

Is heated in the compound A 30.0 g (162.8 mmol), Compound B 30.1 g (162.8 mmol), 180 ℃ a mixture of 200 mL DMSO. After 12 hours, cool to room temperature and add distilled water. The resulting solid was filtered under reduced pressure and subjected to column separation to obtain 11.0 g (31.5 mmol, 19.5%) of Compound C.

compound D Manufacturing

Dissolve 11.0 g (31.5 mmol) of compound C in 100 mL of THF and slowly add 12.5 mL (31.5 mmol, 2.5 M in Hexane) of n- BuLi at -78 ° C. After stirring for 1 hour, add 5.2 mL (47.2 mmol) of trimethylborate. After stirring for 10 hours, add distilled water and extract with EA. After distillation under reduced pressure, column separation was conducted to obtain 5.0 g of compound D (15.9 mmol, 51.3%).

compound F Manufacturing

Dissolve 22.6 mL (238.6 mmol) of 4-chloropyridine in 100 mL of MC and slowly add 95 mL (238.6 mmol, 2.5 M in Hexane) of n -BuLi at -15 ° C. After 1 hour, add 20.0 g (108.5 mmol) of 1,3,5-trichloro-2,4,6-triazine in 100 mL of MC at -15 ° C. After stirring for 5 hours, distilled water was added and extracted with EA. Dried over magnesium sulfate, distilled under reduced pressure, and subjected to column separation to obtain 11.0 g (40.8 mmol, 37.6%) of Compound ( F ).

compound 67 Manufacturing

Compound D 5.0 g (15.9 mmol), Compound F 4.3 g (15.9 mmol), Pd (PPh 3) 4 0.7 g (0.6 mmol), Na 2 CO 3 5.1 g (47.7 mmol) of distilled water 20 mL, toluene mixture to 100 mL Followed by reflux stirring. After 8 hours, cool to room temperature and add distilled water. Extracted with MC, dried over magnesium sulfate, distilled under reduced pressure, and then subjected to column separation to obtain 3.8 g (7.5 mmol, 50.3%) of compound 67 .

Organic luminescent compounds 1 to 72 were prepared using the methods of Preparation Examples 1 to 3, and ¹ H NMR and MS / FAB of the organic luminescent compounds prepared in Table 1 were shown.

[Table 1]

[Example 1] Fabrication of an OLED device using an organic light emitting compound according to the present invention

An OLED device having a structure using the light emitting material of the present invention was fabricated.

First, a transparent electrode ITO thin film (15 Ω / □) obtained from a glass for OLED (manufactured by Samsung Corning) was subjected to ultrasonic cleaning using trichlorethylene, acetone, ethanol and distilled water sequentially and then stored in isopropanol Respectively.

Next, an ITO substrate was placed in a substrate folder of a vacuum deposition apparatus, and 4,4 ', 4 "-tris (N, N- (2-naphthyl) -phenylamino) triphenylamine -TNATA) was added to the chamber and the chamber was evacuated until the degree of vacuum reached 10 -6 torr. Then, 2-TNATA was evaporated by applying current to the cell to deposit a 60 nm thick hole injection layer on the ITO substrate.

The NPB -diphenyl-4,4'-diamine into the (NPB), by applying a current to the cell - Then, to another cell of the vacuum vapor-deposit device structure, N, N 'N, N -bis (α-naphthyl)' And evaporated to deposit a hole transport layer having a thickness of 20 nm on the hole injection layer.

A hole injecting layer and a hole transporting layer were formed, and then a light emitting layer was deposited thereon as follows. The host material Dinaphthylanthracene (DNA) was added as a light emitting material to one cell in the vacuum vapor deposition equipment, and the other cell was loaded with the compound D having the following structure. Then, the two cells were heated together, and the deposition rate ratio of the compound D was 2 to 5 By weight of a hole transporting layer to deposit a light emitting layer with a thickness of 30 nm on the hole transporting layer.

Subsequently, compound 3 according to the present invention was deposited to a thickness of 20 nm as an electron transfer layer, and lithium quinolate (Liq) having the following structure was deposited as an electron injecting layer to a thickness of 1 to 2 nm and then using another vacuum deposition equipment An Al cathode was deposited to a thickness of 150 nm to fabricate an OLED.

Each compound was purified by vacuum sublimation at 10-6 torr and used as an OLED light emitting material.

[Comparative Example 1] Luminescence characteristics of OLED device using conventional light emitting material

Alq (tris (8-hydroxyquinoline) -aluminum (III)) having the following structure was vapor-deposited as an electron transfer layer to a thickness of 20 nm after forming the hole injecting layer, hole transporting layer and light emitting layer in Example 1, Lithium quinolate (Liq) as a layer was deposited to a thickness of 1 to 2 nm, and then an Al cathode was deposited to a thickness of 150 nm using another vacuum deposition apparatus to fabricate an OLED.

The luminescence efficiencies of the organic luminescent compound according to the present invention and the OLED device containing the conventional luminescent compound prepared in Example 1 and Comparative Example 1 were measured at 1,000 cd / m ² , respectively, and are shown in Table 2 below.

[Table 2]

It was confirmed that the compounds developed in the present invention show superior properties in terms of performance compared to conventional materials.

Claims (8)

An electron-transporting material comprising an organic light-emitting compound represented by the following formula (1).
[Chemical Formula 1]

In Formula 1,
L is substituted or unsubstituted (C6-C30) arylene, or substituted or unsubstituted (C3-C30) heteroarylene;
Ar ₁ and Ar ₂ are each independently selected from the group consisting of deuterium, halogen, substituted or unsubstituted (C 1 -C 30) alkyl, substituted or unsubstituted (C 6 -C 30) aryl, substituted or unsubstituted (C 3 -C 30) (C6-C30) aryl, substituted or unsubstituted 5- to 7-membered heterocycloalkyl, substituted or unsubstituted aromatic ring, and 5- to 7-membered hetero Cycloalkyl, Substituted or unsubstituted (C3-C30) cycloalkyl, (C3-C30) cycloalkyl substituted by one or more fused aromatic rings, substituted or unsubstituted adamantyl, substituted or unsubstituted (C7- C30) alkyl, bicycloalkyl, _{cyano, NR 11 R 12, BR 13} R 14, PR 15 R 16, P (= O) R 17 R 18 [R 11 to R ₁₈ independently represent a substituted or unsubstituted (C1 each other (C1-C30) alkyl, substituted or unsubstituted (C6-C30) aryl or substituted or unsubstituted (C3-C30) heteroaryl, substituted or unsubstituted tri (C6-C30) arylsilyl, substituted or unsubstituted tri (C6-C30) arylsilyl, substituted or unsubstituted (C6-C30) Substituted or unsubstituted (C1-C30) alkylthio, substituted or unsubstituted (C6-C30) aryloxy, substituted or unsubstituted , Substituted or unsubstituted (C1-C30) alkoxycarbonyl, substituted Substituted or unsubstituted (C2-C30) alkylcarbonyl, substituted or unsubstituted (C6-C30) arylcarbonyl, substituted or unsubstituted Substituted or unsubstituted (C 1 -C 30) alkylcarbonyloxy, substituted or unsubstituted (C 6 -C 30) aryloxycarbonyl, substituted or unsubstituted (C 1 -C 30) alkoxycarbonyloxy, substituted or unsubstituted (C6-C30) arylcarbonyloxy, substituted or unsubstituted (C6-C30) aryloxycarbonyloxy, carboxyl, nitro,

,

Or (C3-C30) alkylene or (C3-C30) alkenylene with or without a fused ring to form a monocyclic or polycyclic aromatic ring; Provided that when Ar ₁ or Ar ₂ is a substituted group, the substituent of the substituted group is not heteroaryl;
R ₁ to R ₄ independently of one another are hydrogen, deuterium, halogen, substituted or unsubstituted (C 1 -C 30) alkyl, substituted or unsubstituted (C 6 -C 30) aryl, substituted or unsubstituted (C 3 -C 30) Substituted or unsubstituted (C6-C30) aryl, substituted or unsubstituted (C3-C30) heteroaryl, substituted or unsubstituted 5- to 7-membered heterocycloalkyl, substituted or unsubstituted A 5- to 7-membered heterocycloalkyl wherein one or more aromatic rings are fused, Substituted or unsubstituted (C3-C30) cycloalkyl, (C3-C30) cycloalkyl substituted by one or more fused aromatic rings, substituted or unsubstituted adamantyl, substituted or unsubstituted (C7- C30) alkyl, bicycloalkyl, _{cyano, NR 11 R 12, BR 13} R 14, PR 15 R 16, P (= O) R 17 R 18 [R 11 to R ₁₈ independently represent a substituted or unsubstituted (C1 each other (C1-C30) alkyl, substituted or unsubstituted (C6-C30) aryl or substituted or unsubstituted (C3-C30) heteroaryl, substituted or unsubstituted tri (C6-C30) arylsilyl, substituted or unsubstituted tri (C6-C30) arylsilyl, substituted or unsubstituted (C6-C30) Substituted or unsubstituted (C1-C30) alkylthio, substituted or unsubstituted (C6-C30) aryloxy, substituted or unsubstituted , Substituted or unsubstituted (C1-C30) alkoxycarbonyl, substituted Substituted or unsubstituted (C2-C30) alkylcarbonyl, substituted or unsubstituted (C6-C30) arylcarbonyl, substituted or unsubstituted Substituted or unsubstituted (C 1 -C 30) alkylcarbonyloxy, substituted or unsubstituted (C 6 -C 30) aryloxycarbonyl, substituted or unsubstituted (C 1 -C 30) alkoxycarbonyloxy, substituted or unsubstituted (C6-C30) arylcarbonyloxy, substituted or unsubstituted (C6-C30) aryloxycarbonyloxy, carboxyl, nitro,

,

Or (C3-C30) alkylene or (C3-C30) alkenylene with or without a fused ring to form a monocyclic or polycyclic aromatic ring;
W is _{- (CR 41 R 42) m} -, - (R 41) C = C (R 42) -, -N (R 43) -, -S-, -O-, -Si (R 44) (R _{45) -, -P (R 46} ) -, -P (= O) (R 47) -, -C (= O) - or -B (R ₄₈₎ -, and
X is NR < _{5 &} gt ;;
R ₅ , R ₃₁ to R ₃₃ And R ₄₁ to R ₄₈ are as defined above for R ₁ to R ₄ ;
Wherein said heterocycloalkyl and heteroaryl comprise at least one heteroatom selected from B, N, O, S, P (= O), Si and P;
m is an integer of 1 or 2,
Provided that when X is NR ₅ and R ₅ is substituted or unsubstituted phenyl and L is substituted or unsubstituted (C6-C30) arylene, Ar ₁ and Ar ₂ are each a carbazole group, an arylamine group, a fluorene group And a spiro-fluorene group. The method according to claim 1,
The L, Ar ₁ and Ar ₂ , R ₁ to R ₅ , R ₃₁ to R ₃₃ And The substituents of R ₄₁ to R ₄₈ are independently selected from the group consisting of hydrogen, deuterium, halogen, substituted or unsubstituted (C 1 -C 30) alkyl, (C 6 -C 30) aryl, (C3-C30) heteroaryl, 5- to 7-membered heterocycloalkyl, 5- to 7-membered heterocycloalkyl in which one or more aromatic rings are fused, (C3-C30) cycloalkyl, (C6-C30) arylsilyl, tri (C6-C30) arylsilyl, adamantyl, (C7-C30) alkylsilyl, di (C1- alkyl bicycloalkyl, (C2-C30) alkenyl, (C2-C30) alkynyl, cyano, _{carbazolyl, NR 21 R 22, BR 23} R 24, PR 25 R 26, P (= O) R 27 R 28 [R ₂₁ to R ₂₈ are independently selected from (C1-C30) alkyl, (C6-C30) aryl or (C3-C30) heteroaryl. each other], (C6-C30) aralkyl (C1-C30) alkyl, (C1 (C1-C30) alkylthio, (C6-C30) aryloxy, (C6-C30) arylthio, (C1-C30) alkoxycarbamoyl, (C1-C30) alkylcarbonyl, (C6-C30) arylcarbonyl, (C6-C30) aryloxycarbonyl, (C1- C30) alkoxycarbonyloxy, C6-C30) arylcarbonyloxy, (C6-C30) aryloxycarbonyloxy, carboxyl, nitro or hydroxy, or adjacent substituents are connected to form a ring With the proviso that in the case of Ar ₁ and Ar ₂ , the (C3-C30) heteroaryl in which the (C6-C30) aryl is substituted or unsubstituted in the above group is excluded,
When X is NR ₅ and R ₅ is substituted or unsubstituted phenyl and L is substituted or unsubstituted (C6-C30) arylene, Ar ₁ and Ar ₂ may be a carbazole group, an arylamine group, a fluorene group, - < / RTI > fluorene group. An organic electroluminescent device comprising an electron transporting material according to any one of claims 1 to 3. The method of claim 3,
The organic light emitting device includes a first electrode; A second electrode; And at least one organic compound layer interposed between the first electrode and the second electrode, wherein the organic compound layer comprises at least one layer containing an electron transporting material including the organic light emitting compound of Formula 1, a fluorescent host, Or a layer comprising a phosphorescent host and a phosphorescent dopant. 5. The method of claim 4,
Wherein the organic material layer comprises at least one compound selected from the group consisting of an arylamine-based compound and a styrylarylamine-based compound. 5. The method of claim 4,
Wherein the organic layer further comprises at least one metal or complex compound selected from the group consisting of Group 1, Group 2, Group 4, Periodic transition metal, Lanthanide series metal and d-transition metal organic metal. Light emitting element. 5. The method of claim 4,
Wherein the organic material layer comprises a light emitting layer and a charge generating layer. 5. The method of claim 4,
Wherein at least one of the organic light emitting layers emitting blue, red, and green light is simultaneously included in the organic material layer to emit white light.