TW201204810A - Novel organic electroluminescent compounds and organic electroluminescent device using the same - Google Patents

Abstract

Provided are novel organic electroluminescent compounds and an organic electroluminescent device using the same. More particularly, the organic electroluminescent compound is represented by Chemical Formula 1: wherein X, Y, Ar1, Ar2, Ar4 and Ar5 are the same as defined in the detailed description. When used as a host material of an organic electroluminescent material of an OLED device, the organic electroluminescent compound exhibits good luminous efficiency and excellent life property of the material. Therefore, it may be used to manufacture OLEDs having very good operation life.

Description

201204810 VI. Description of the Invention: [Technical Field] The present invention relates to a novel organic electroluminescent compound and an organic electric field light-emitting device using the same. More specifically, it relates to a novel organic electroluminescent compound for use as an organic electroluminescent material and an organic electric field illuminating device using the same. [Prior Art] The most important factor determining the luminous efficiency of an organic light-emitting diode (OLED) is an organic electroluminescent material. Although fluorescent materials have been widely used as organic electroluminescent materials so far, in view of the electric field illuminating mechanism, the development of phosphorescent materials is one of the best methods for improving the luminous efficiency by up to 4 times (theoretical). To date, silver (III) complexes have been known as photo-curing materials, which include (acac) Ir(btp)2, Ir(ppy)3, and Firpic, which emit red, green, and blue light, respectively. In particular, many researches on phosphorescent materials have been conducted recently in Japan, Europe, and the United States.

CBP is currently the most widely known host material for phosphorescent materials. High efficiency OLEDs using hole blocking layers including BCP, BAlq, etc. have been reported. High-performance OLEDs using BAlq derivatives as the main body have been reported by Pioneer (Japan) and others. 4 95226

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While these materials provide good electric field luminescence properties, they have the following disadvantages: during high temperature deposition of vacuum, such materials may degrade due to low glass transition temperatures and poor thermal stability. Since the power efficiency of 〇LE1) is expressed in terms of (p//voltage) χ current efficiency, the power efficiency is inversely proportional to the voltage. Therefore, reducing the power consumption of the OLED requires high power efficiency. In fact, LEDs using phosphorescent materials provide better current power (candle/amperes (cd/A)) compared to OLEDs using fluorescent materials. However, with existing materials (eg, BAlq, CBP, etc.) When used as the main material of the light-filling material (4), the power efficiency (lumens/watt (lm/W)) of the OLED using the phosphorescent material due to the high driving voltage is not significantly superior to the power efficiency of the LED using the fluorescent material. Furthermore, the OLED device does not have a satisfactory operational life. Therefore, it is necessary to develop a more stable and high-performance host material. [Disclosure] [Technical Problem] Through intensive efforts to overcome the problems of the above conventional techniques, the inventors of the present application have invented a hard-field luminescent compound which realizes an organic electric field luminescent discharge having excellent efficiency and a significantly improved lifetime (IV). One of the purposes of Yu Chuanyue is to provide an organic electroluminescent compound which is comparable to the "dopant" (4) having a framework for providing better luminous efficiency and negligence with appropriate color coordinates, while solving the aforementioned problems. Another object of the invention is 95226 5 201204810 provides an organic electric field illuminating device having high luminous efficiency and improved lifetime properties. Technical Solution The present invention provides a novel organic electroluminescent compound represented by Chemical Formula 1 and an organic electric field illuminating device using the same. Organic electric field luminescent compounds have good 'good luminescence efficiency and excellent lifetime properties compared to existing host materials, so they can be used to manufacture OLED devices with very good operational lifetime.

Where (S is defined as in Chemical Formula 2, X is not _0_ or -S-; Y is not -S_, _C(Ri)(R2)-, _Si(R3) (R4)-, - n(r5)- or a divalent group selected from the group consisting of the following structures; 6 95226 201204810

Αγί to Ars and 匕 to l independently represent hydrogen, hydrazine, (Cl~C3〇) alkane, halogen (C1-C30) alkyl, dentate, cyano, (C3-C30) cycloalkyl, 5 to 7 Heterocycloalkyl, (C2-C30)alkenyl, (C2-C30)alkynyl, (C6-C3〇)aryl, (C1-C30)alkoxy, (C6_C3〇)aryloxy, (C3_C3 〇)heteroaryl, (C6-C30) aryl (C1-C30) alkyl, (C6_C3〇) arylthio, di(C1-C30)alkylamino, mono or di(C6_C3〇)arylamine Base, three π. 〖—^〇) alkyl (tri(Cl-C30)alkylsilyl), di(C1-C30)alkyl (C6__ C30) aryl fluorenyl, tris(C6_C3 fluorene) aryl fluorenyl, nitro Or each of hydroxy, H An to An and oxime to R55 via an alkyl group with or without a condensed c3 〇) or (C3-C30) an extended alkenyl group bonded to an adjacent substituent to form an alicyclic group , a monocyclic or polycyclic aromatic ring, or a monocyclic or polycyclic heteroaryl ring; VIII to An and 匕 to 匕 each of the alkyl, cycloalkyl, heterocycloalkyl, fluorenyl block And the heteroaryl group may further be selected from one or more selected from the group consisting of ruthenium, (otC1_C3()) alkyl, (C1~C30) alkyl, ", cyanide tomb, (C3-C30) cycloalkyl, 5 to 7 贞miscellaneous Ring filament, (C2_C3〇) dilute group, (C2_C3〇) block group, (C6-C30) aryl group, (c-C3〇) alkoxy group, (C6 C3〇) aryloxy group, (6) C3G) heteroaryl group, (G3_^3〇) heteroaryl group having a G3Q) silk substituent, (C3_C3〇)heteroaryl group having a (C6-C30) aryl substituent, CC6-C30) square group (c-C3Q) alkyl group, (10)-(10)) arylthio, mono or di(C1_C3G) aryl, mono or di(GM3G) sylamine, tris(C1-C30) sulphate, =(C1~C3()) alkyl (C6 -C30) Substituted by a group consisting of a group consisting of 2 (C6-C30) aragonite or a base group; 7 95226 201204810 L! to L3 are independently represented by a chemical bond or selected from (C6-C30) a divalent group of a group consisting of a aryl group, a (C3-C30) heteroaryl group, a bis((n-C30)alkyl fluorenyl group or a bis(C6-C30) aryl fluorenyl group; and the heterocycloalkyl group, The heteroaryl and heteroaryl rings may contain one or more heteroatoms selected from the group consisting of B, N, 0 and S. In the present invention, "alkyl", "alkoxy" and other substituents containing an "alkyl" moiety The base system includes both a straight chain and a branched chain. In the present invention, "aryl group" means that a hydrogen atom is removed from an aromatic hydrocarbon. An organic group, and may comprise from 4 to 7 members, especially 5 or 6 members, of a monocyclic or fused ring comprising a plurality of aryl groups having one or more single bonds therebetween. Specific examples of the aryl group include: benzene , naphthyl, biphenyl, anthracenyl, fluorenyl, fluorenyl, fluorenyl, triphenylenyl, fluorenyl, fluorenyl, fluorenyl, naphthacenyl, propylene F luoranthenyl, etc., but is not limited thereto. The naphthyl group includes a naphthyl group and a 2-naphthyl group. The thiol group includes a 1-fluorenyl group, a 2-fluorenyl group, and a 9-fluorenyl group. And the fluorenyl group includes a 1-fluorenyl group, a 2-fluorenyl group, a 3-fluorenyl group, a 4-fluorenyl group, and a 9-g group. In the present invention, the "heteroaryl group" means an aryl group containing one to four hetero atoms selected from the group consisting of ruthenium, osmium, 0, and S, and other remaining aromatic ring skeleton atoms as carbon atoms. The heteroaryl group may be a 5- or 6-membered monocyclic heteroaryl group or a polycyclic heteroaryl group condensed with one or more benzene rings, and may be partially saturated. The heteroaryl group also includes a heteroaryl group having one or more single bonds therebetween. The heteroaryl group includes a divalent aryl group in which a hetero atom on the ring can be oxidized or quaternized to form a salt such as an N-oxide and a quaternary salt. Specific examples thereof include: a monocyclic heteroaryl group such as a fluorenyl group, a stenyl group, a sigma sylylene group, a sigma base group, a ratio of 8 95226

S 201204810 Azyl, thiazolyl, thiadiazolyl, isothiazolyl, isoxazolyl, oxazolyloxadiazolyl, tri-farming, tetra- D-, triazolyl, tetrazolyl, furazolyl , pyridyl, pyridinyl, pyrimidinyl, fluorenyl, etc.; polycyclic heteroaryl, such as benzofuranyl, benzothienyl, isobenzofuranyl, benzimidazolyl, benzindene , stupid and isodecyl, benzoindole, benzoxyl, isodecyl, fluorenyl, oxazolyl, benzothiadiazolyl, quinolinyl, isoquinolinyl, Porphyrin group, quinazolinyl group, quinoxalinyl group, oxazolyl group, phenanthridine and benzodioxolyl, etc.; N-oxides thereof (such as pyridyl N-oxide and quinoline) The group N-oxide), its quaternary salt, and the like, but are not limited thereto. In the present invention, "(CBuC30)alkyl, tri(Cl_C3〇)alkylindenyl, mono(C1-C30)alkyl (C6-C30) anthracene, (C6-C30) aromatic (C1-C30) The alkyl moiety of the alkyl group, (C1-C30) alkoxy group, (C1-C30) sulphur group, and the like may have from 1 to 20 carbon atoms, more specifically from 1 to 10 carbon atoms. . "(〇6<30) aryl, bis(Cl-C30)alkyl (C6rc3〇) aryl, di(C6-C30) cleavage, (C6-C30) aryl (C1-C30) The base moiety of (C6-C30) aryloxy, (C6-C30) arylthio" or the like may have from 6 to 20 carbon atoms, more specifically from 6 to 12 carbon atoms. The heteroaryl portion of "(C3-C30)heteroaryl" may have 4 to 2 carbon atoms', more specifically 4 to 12 carbon atoms. "(C3-C30) ring-shaped, cycloalkyl moiety may have from 3 to 20 carbon atoms, more specifically from 3 to 7 carbon atoms. "(C2-C30)alkenyl or alkynyl" The alkenyl or alkynyl moiety can have from 2 to 20 carbon atoms' more specifically from 2 to 1 carbon atoms. 95226 9 201204810 Chemical formula Limited to this. 1

Is selected from the following structures, but not

Wherein, the definitions of Y and Αιί to Ar3 are the same as defined in Chemical Formula 1. Further, the chemical formula 1 *~^"-L2-Ls-• is selected from the following structures, but is not limited thereto: 10 95226

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The organic electroluminescent compound of the present invention can be specifically listed by the following compounds, but the present invention is not limited to the following compounds.

S 11 95226 201204810

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The present invention provides an organic electric field illuminating device, which has a spoon electrode, a second electrode, and one or more layers of organic layers interposed between the first and first electrodes, and has a power and a bait layer. The r 4 organic layer comprises an organic electroluminescent compound of one of the tables. 〇 化 予 于 于 于 有机 有机 有机 有机 有机 有机 有机 有机 有机 有机 有机 有机 有机 有机 有机 有机 有机 有机 有机

S 201204810 ^Electromechanical % luminescent compound When the body is an electric field illuminating body, the organic layer is an electric field luminescent layer incorporating a species or multiple luminescent dopants. The dopant to be applied to the organic electroluminescence device of the present invention is not particularly limited. In the organic electronic device of the present invention, the organic layer may further comprise, in addition to the organic electroluminescent compound represented by the chemical, a compound or a compound selected from the group consisting of an arylamine compound and a stupidyl arylamine compound. Groups of compounds. The arylamine compound or the stupid vinyl arylamine 5 is exemplified in Korean Patent Application No. 10-2008_0123276, No. 1, 〇〇8-7606, or No. 10-2008-01818428, but is not limited thereto. . In the organic electric field illuminating device of the present invention, the organic layer may further comprise one or more organic compounds selected from the group 1 in addition to the organic electroluminescent compound represented by Formula 1. A metal or complex compound of the group of transition metals, lanthanide metals, and d_transition elements of metals, Group 2, 4th, and 5th cycles. The organic layer may include an electric field luminescent layer and a charge generating layer. In addition, the organic layer may comprise, in addition to the organic electroluminescent compound represented by the chemical formula i, a layer or a plurality of organic electroluminescent layers emitting blue, green or red light to realize an organic electric field emitting device emitting white light. . A compound that emits blue light, green light, or red light is disclosed in Korean Patent Application No. 10-2008-0123276, No. 10-2008- 〇1〇76〇6, or No. 10-2008-0118428, but is not limited thereto. In the organic electric field light-emitting device of the present invention, a layer (hereinafter referred to as "surface layer") may be selected from a layer of a chalcogenide layer, a metal sequestration layer and a metal oxide layer. Electrode pair one bite two 95226

S 14 201204810 on the inner surface of the electrode. More specifically, a metal chalcogenide (including oxide) layer of ruthenium or aluminum may be disposed on the anode surface of the electric field luminescent medium layer and a metal halide layer or a metal oxide layer may be disposed on the electric field luminescent medium. On the cathode surface of the layer. Thereby, operational stability can be obtained. The chalcogen compound may be, for example, Si?x (l = x = 2), Al? x (l = X = 1.5), SiON, SiAlON or the like. The metal halide may be a fluoride such as LiF, MgF2, CaF2, a rare earth metal or the like. The metal oxide may be, for example, Cs2〇, Li2〇, %0, SrO, BaO, CaO, or the like. In the organic electric field light-emitting device of the present invention, it is also preferred to provide a mixed region of the electron transporting compound and the reducing dopant or a mixed region of the hole transporting compound and the oxidizing dopant in the electrode pair thus manufactured. At least on one surface. In this case, since the electron transporting compound is reduced to an anion, electrons are easily injected and transported from the mixed region to the electric field illuminating medium. Furthermore, since the hole transporting compound is oxidized to a cation, the hole is easily injected and transported from the mixed region to the electric field illuminating 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. Further, an electric field light-emitting device which emits white light having two or more layers of an electroluminescent layer can be produced by using a reducing dopant layer as a charge generating layer. Advantageous Effects Since the organic electroluminescent compound of the present invention is used as a host material of an organic electro-luminous material of an OLED device, it has good luminous efficiency and excellent life characteristics, so that it can be manufactured with excellent operation.

95226 S 201204810 The 0LED for life. Mode for Invention The present invention further describes the organic electroluminescent compound of the present invention, a process for preparing the compound, and a light-emitting property of a device using the compound. However, the following specific examples are for illustrative purposes only and are not intended to limit the scope of the invention in any way. [Preparation Example 1] Preparation of Compound 1

Preparation of Compound A First, 2,7-dibromo-9,9-diindenylhydrazine (150 g (g), 426 mmol (mmol)) was immersed in RBF (3 liter (L)) and replaced with nitrogen. Further, THF (2.1 L) was added. After the solution was cooled to -78 ° C, n-BuLi (170 mL, 16 95 226 s 201204810 2. 5 molar concentration (Μ) in hexane, 426 mmol) was added and stirred for an additional hour. Trimethylborate (53 mL, 469 mmol) was then added and stirred for 12 hours. When the reaction was completed with 2 M HCl, the mixture was taken out using acetic acid:Ss(EA)/water. The water was removed with MgS 4 and decompressed under reduced pressure. After the distillation was carried out, the compound A (70 g, 52%) was obtained by column separation (condition: MC: hexane = 1 : 1 。). Preparation of Compound B Compound A (70,220 mmol), 2-iodonitrobenzene (5 〇g, 200 mmol), Pd(PPh3)4 (7 g, 6 mmol), Na2C〇3 (64 g, 600 Mm) is added to RBF. Toluene (1 L), EtOH (0.5 L) and water (0.3 L) were then added to the mixture. The reaction mixture was disturbed at 9 0 C for 7.5 hours. After taking EA/water %, the remaining water was removed by MgSCh and steamed under reduced pressure. Crude compound B (90 g) was obtained by using a chloranil (MC) as a developing solvent. The next reaction was carried out without additional purification. Preparation of Compound C Compound B (90 g) was dissolved in P(0Et) 3 (750 mL), 1,2-difluoromethane (750 mL), and stirred at 150 C for 9 hours. After removing the solvent by steaming the crane water, compound c (26 g, 36%, yield in two steps) was obtained by separating the obtained liquid column (condition: MC:hexane = 1:10). Preparation of Compound D Cyanuric chloride cyanide (50 g, 91 mmol) was added to a round bottom flask (RBF), dissolved in THF (1·3 L), and then cooled to 0 Ϊ. Next, magnesium bromobromide (225 mL, a solution of diethyl ether in hexane, 675 mmol) was slowly added dropwise to the solution. The reaction solution was stirred for 3 hours and extracted with EA/EhO. Remove water with MgS〇4

17 95226 S 201204810 After distilling under reduced pressure, the crude compound D (37 g, 63%) was obtained by filtration using hexanes using MC as a solvent. Compound D showed sufficient purity for the next reaction. Preparation of Compound E DMF (40 mL) was added to the RBF and stirred under Nb and NaH (1.9 g, 60% dispersion in mineral oil, 50 〇1). A solution of Compound C (12 g, 33 mmol) dissolved in DMF (80 mL) was then slowly added dropwise to the suspension. After the mixture was stirred for 1 hour, a solution of Compound D (10.6 g, 40 mmol) dissolved in DMF (100 mL) was slowly added dropwise to the mixture. The reaction mixture was stirred for 12 hours. When the reaction was completed in H2?, the mixture was extracted using EA/H?? and distilled under reduced pressure. Compound E (12 g, 61%) was obtained by column separation (condition: MC:hexane = 1: 10). Preparation of Compound 1 Compound E (6 g, 1 mmol), Compound F (3.2 g, 15.2 mmol), Pd(PPh3)4 (〇. 58 g, 0.5 mmol), and K2C〇 3 (4.7 g, 34 mmol) was added to the RBF. Toluene (50 this), EtOH (25 mL) and H2 (17 RaL) were then added to the mixture. Stir the reaction mixture for 2 hours at rc. EA/HA extraction "to be removed by ||gS〇4 and after evaporation under reduced pressure" by column separation (condition MC: hexane: 1 〇) Compound 1 (4 g, 57%) was obtained. [Preparation 2] Preparation of Compound 6 18 95226

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Preparation of Compound A 2,7-Dibromo-9,9-diindenylhydrazine (150 g, 426 mmol) was first added to RBF (3 L) and replaced with nitrogen. THF (2.1 L) was added to the solution and the solution was cooled to -78 °C. After adding n-BuLi (170 mL, 2. 5 M in hexane, 426 mmol) to the solution, the mixture was stirred for an hour. Trimethyl borate (53 mL, 469 mmol) was added and stirred for 12 hours. When the reaction was completed with 2M HCl, the mixture was extracted using EA/Hz. After removing the water by MgS (h) and performing distillation under reduced pressure, the compound A (70 g, 52%) was obtained by column separation (condition: hexane = 1:10). Preparation of Compound B Compound A (70 g, 220 mmol), 2-iodonitrobenzene (5〇g, 2〇〇19 95226 3 201204810 mmol), Pd(PPh3)4 (7 g, 6 mmol), Na2〇〇3 (64 g) 5小时和搅拌。 The reaction mixture was stirred at 90 ° C for 7. 5 hours and was added to the mixture was stirred at 90 ° C and the mixture was stirred for 5 hours. The mixture was extracted with EA/IhO. After removing water with MgS 4 and distilling under reduced pressure, the crude compound b (90 g) was obtained by filtration using MC as a developing solvent. The next reaction. Preparation of Compound C Compound B (90 g) was dissolved in p(〇Et)3 (750 mL), 1,2-dibenzene (750 mL), and the mixture was stirred at 150 ° C for 9 hours. The solvent was removed by steaming, and the column was separated (yield: MC:hexane = 1 : 1 〇) to obtain a compound c (26 g, 36%, yield in two steps). The preparation will be 2, 4, 6- Pyrimidine (16.8 g, 91 mmol), phenylboronic acid (24. 4 g' 200 mmol), Pd (PPh3) 4 (5.3 g, 4.6 mmol), and Na2C〇3 (29 g, 273 mmol) Add to RBF. Toluene (35 〇 mL), Et 〇 H (1 〇〇 mL) and H 2 〇 (150 mL) were then added to the mixture. The reaction mixture was stirred for 3 hrs and extracted with EA/H2. After removing the water with MgS〇4 and distilling under reduced pressure, the compound G (14 g, 58%) was obtained by column separation (condition: MC:hexane = 1: 1 。). Ν2 and NaH (1.97 g, 60% dispersed in mineral oil, 49.3 mmol) BF (4 〇 mL) was added to the RBF and stirred under the conditions of RBF. The compound dissolved in DMF (80 mL) was then added. A solution of c (11.9 g, 32. 8 匪〇 1) was slowly added dropwise to the human suspension. The mixture was stirred for about i hours.

The solution of Compound G (1 〇 5 g, 39·4 〇1) in S 20 201204810 'combined in DMFC 100 mL) was slowly added dropwise to the mixture, and the reaction mixture was secreted for 12 hours. When the reaction is completed with h2〇, the mixture is extracted using ^鸠 and reduced. Compound H (10 g, 51%) was obtained by column separation (conditions MC: hexane = 1 : 10). Preparation of compound 6 enriched s H (5 g, 8.4 mm 〇i), compound f (2.7, 13 mmol), (h) 4 (〇.5 g, 0.4 mm 〇i), and k2c 〇3 (4 g, 29 mmol) was added. Then, stupid (40 mL), EtOH (230 mL), and H2 (14 mL) were added. The reaction mixture was stirred at 90 ° C for 12 hours and extracted with EA / H2. After removing water by MgS 4 and distilling under reduced pressure, the compound 1 (4 g, 68 %) was obtained by column separation (condition: MC:hexane = 1:10). [Preparation Example 3] 彳人1. Preparation of Compound 7 95226 201204810

Jk:

Preparation of Compound A 2,7-Dibromo-9,9-dimethyl (150 g, 426 mmol) was first added to RBF (3 L) and replaced with nitrogen. Further THF (2.1 L) was added to the solution, and the solution was cooled to -78 °C. n-BuLi (170 mL, 2.5 Μ in ED, 426 mmol) was added and the mixture was stirred for 1 hour. Trimethyl benzoate (53 mL, 469 mmol) was then added and the mixture was stirred for 12 hours. When the reaction was completed with 2 M HCl, the mixture was extracted using EA/H2. The water was removed by MgS 4 and distilled under reduced pressure, and the mixture was separated by column (M: hexane = 1: 10) to give Compound A (7 g, 52%). Preparation of Compound B 95226

S 22 201204810 Compound A (70 g, 220 mmol), 2-indole succinylbenzene (50 g, 200 mmol), Pd(PPh3)4 (7 g, 6 mmol), Na2C〇3 (64 g, 600 mmol) Join RBF. The reaction mixture was stirred at 90 ° C for 7. 5 hours and extracted with EA / h 2 。. MgS 〇 甲苯 L L L 。 甲苯 甲苯 甲苯 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 4 After removing the water and performing distillation under reduced pressure, the crude compound B (9 μg) was obtained by filtration using MC as a developing solvent. The next reaction was carried out without additional purification. Preparation of Compound C Compound B (90 g) was dissolved in p(〇Et) 3 (750 mL), 1,2-dichlorobenzene (750 mL). The mixture was stirred at i50 ° C for 9 hours and the solvent was removed with distilled water. The produced red liquid was subjected to column separation (conditions: MC:hexane = 1:10) to give compound c (26 g, 36%, yield in two steps). Preparation of Compound D

Dimerized gasified mice (50 g, 91 mmol) were added to RBF and dissolved in THF (1.3 L) and cooled to 〇 °C. Next, magnesium bromobromide (225 mL, 3M in diethyl ether, 675 mmol) was slowly added dropwise to the solution. The reaction solution was stirred for 3 hours and extracted with EA/0. After removal of water by MgS 4 and distillation under dust reduction, crude compound D (37 g, 63%) was obtained by using a silica as a developing solvent. Compound D showed sufficient purity for the next reaction. Preparation of Compound E DMF (40 mL) was added to RBF under N2 and NaH (1.9 g, 60% dispersion in mineral oil, 5 〇mL) was added to RBF. Then 23

S 95226 201204810 A solution of Compound C (12 g, 33 mmol) dissolved in DMF (80 mL) was slowly added dropwise to the suspension. After the mixture was stirred for 1 hour, a solution of Compound 0 (10.6 Å, 4 〇 111111 〇 1) dissolved in 0 ^ ^ (1 〇〇 11 ^) was slowly added dropwise to the mixture. The reaction mixture was stirred for 12 hours. When the reaction was completed in H2, the mixture was extracted using EA/H2 and then evaporated under reduced pressure. Compound E (12 g, 61%) was obtained by column separation (condition: MC: hexane = 1 : 10). Preparation of Compound 7 Compound E (6 g, 10 mmol), Compound 1 (3.2 g, 15.2 mmol), Pd (PPh3) 4 (0. 58 g, 0.5 mmol), and Na2C〇3 (2.1) g, 20 mmol) was added to the RBF. Then, toluene (60 mL), EtOH (30 mL), and H2 (10 mL) were added. The reaction mixture was stirred at 90 ° C for 12 hours and extracted with EA / H2. After removing water by MgS 4 and distilling under reduced pressure, the compound 7 (3.4 g, 49%) was obtained by column separation (condition: MC:hexane = 1:10). [Preparation Example 4] Preparation of Compound 8 24 95226

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Preparation of Compound A 2,7-Dibromo-9,9-diindenylhydrazine (150 g, 426 mmol) was first immersed in RBF (3 L) and replaced with nitrogen, followed by THF (2.1 L). The solution was cooled to -78 ° C, n-BuLi (170 mL, 2.5 M in hexanes, 426 mmol) was added and the mixture was stirred for one hour. Trimethyl borate (53 mL, 469 mmol) was added and stirred for 12 hours. When the reaction was completed with 2M HCl, the mixture was extracted using ethyl acetate (EA) /H2. After removing the water with MgS〇4 and performing distillation under reduced pressure, the compound a (70 g, 52« was obtained by subjecting the obtained solid to column separation (condition: MC:hexane = 1:10). Preparation of Compound B Compound A (70 g, 220 mmol), 2- degradated nitrobenzene (50 g, 200 25 95226 201204810 mmol), Pd(PPh3) 4 (7 g, 6 mmol), and Na2C〇3 (64 g, The 7.5 hr and the EA/H2 were stirred at 90 ° C. The reaction mixture was stirred at 90 ° C for 7. 5 hours with EA / H2. Extraction of hydrazine. Removal of water by MgS 4 and distillation under reduced pressure, followed by filtration of cerium oxide using MC as a developing solvent to obtain crude compound b (90 g). The next reaction was carried out without additional purification. Preparation of Compound C Compound B (9 μg) was dissolved in p(〇Et) 3 (750 mL), 1,2-dibenzene (750 mL), and the mixture was stirred for 9 hours at i5 (Tc) Distilled water was used to remove the solvent. By subjecting the produced red liquid to column separation (conditions MC: hexane = 1: 10), compound c (26 g, 36%, yield in two steps) was obtained. Preparation of Compound G 2, 4, 6-tris-pyrimidine (16.8 g, 91 mmol), phenylboronic acid (24. 4 g, 200 mmol), Pd(PPh3) 4 (5.3 g, 4.6 mmol), W&Na2C〇 3 (29

g, 273 mmol) was added to the RBF. Then, hydrazine (350 mL), EtOHClOO mL) and H2 hydrazine (150 mL) were added to the mixture. The reaction mixture was stirred at ribs for 3 hours and extracted with EA/HA. The compound G (14 g, 58%) was obtained by removing the water with MgS〇4 and purging under reduced pressure, by column separation (conditions: hexane: 1:1). Preparation of the compound hydrazine In the presence of RBF, Ν2 and NaH (1.79 g, 60% dispersed in mineral oil, 49.3 mmol) were added to the RBF, and DMF (4 〇) was added and stirred. A solution of compound c (11. 9 g, 32.8 mmol) 26 95226 s 201204810 dissolved in DMF (80 mL) was then slowly added dropwise to the suspension. The mixture was stirred for about 1 hour. A solution of Compound G (10.5 g, 39.4 mmol) dissolved in DMF (100 mL) was slowly added dropwise to the mixture, and the mixture was stirred for 12 hours. When the reaction was completed with H2, the mixture was extracted using EA/H2 and distilled under reduced pressure. Compound H (10 g, 51%) was obtained by column separation (conditions MC: hexanes 1:1). Preparation of Compound 8 Compound H (5 g, 8.4 mmol), Compound 1 (2.7 g, 13 mmol), Pd (PPh3) 4 (0.5 g, 0.4 mmol), and Na2C〇3 (1.88) g, 17 mmol) was added to the RBF. Then, toluene (60 mL), EtOH (30 m), and H2 (10 mL) were added. The reaction mixture was stirred at 90 ° C for 12 hours and extracted with EA / H 2 O. After removing the water by the MgSCh and distilling under reduced pressure, the compound 8 (3.6 g, 62%) was obtained by column separation (condition: MC:hexane = 1:10). An organic electric field luminescent compound was prepared according to the procedures of Preparation Examples 1 to 4. The series of Table 1 is the 1H NMR and MS/FAB data of the prepared electroluminescent compound.

S 27 95226 201204810 Table 1 Implementation No. 1 Ή NMR (CDCI3, 200 MHz) MS/FAB Measured value 1 δ = 1.72 (6H, s), 7.29C1H, m), 7.41(2H, m), 7.5 -7.52(7H, m), 7.54C1H, s), 7.58~7.63(2H, ra), 7.69(1H, m), 7.83(lH, m), 7_98(1H, m), 8·12~8· 2(3Η, m), 8.28(4H, m), 8.41-8.45(2H.m), 8.85(1H, s) 696.86 696.23 2 5 = 1.72(6H, s), 7.29(1H, m), 7.4 K2H, m), 7.5-7.52(7H, m), 7.54(1H, s), 7.63(1H, m), 7.69(1H, m), 7.83(lH, m), 7.98(1H, m), 8.05 -8.15(5H, m), 8.28(4H, m), 8.45(1H, m), 8_85(1H, s) 696.86 696.23 3 6 = 1.72(6H, s), 7.29C1H, m), 7.41(2H, In), 7.5-7.52(7H, m), 7.54(1H, s), 7.63(1H, m), 7.69(1H, m), 7.83~7.86(2H, m), 7.98~8(3H, m) , 8.12~8.15(2H, m), 8.28(4H, m), 8.45(1H, m), 8.850H, s) 696.86 696.23 4 δ = 1.72(6H, s), 7.29C1H, m). 7.41(2H , m), 7.48~7.52(9H, m), 7.54(1H, s), 7.57-7.63(3H, m), 7.69-7.7(2H, m). 7.83(1H, id), 7.98(1H, m ), 8.12-8.2(3H, m), 8.28(4H, m), 8.41-8.45(2H, m), 8.85(1H, s) 772.96 772.27 5 5 = 0.66C6H, s), 1.72C6H, s), 7.29(1H, m), 7.4K2H. m), 7.5-7.52(7H, in), 7. 54(1H, s), 7.59-7.63(2H, m). 7.72(1H, m), 7.89(1H, m), 7.98(1H, m), 8.06-8.12(3H, m), 8.19(1H, m), 8.28(4H, m), 8.45(1H, m), 8.85(1H, s) 755.01 754.26 6 5 = 1.72(6H, s), 7.29(1H, ra), 7.4K2H, m), 7.5~ 7.52(7H, ra), 7.54QH, s), 7.58-7.63(2H, m), 7.69(1H, m), 7.79'7.83(5H, m), 7.98(1H, m), 8.12-8.2(3H , in), 8.41~8.45(2H, m), 8.63(1H, s), 8.85(1H, s) 695.87 695.24 7 δ = 1.72(6H, s), 7.29-7.4K6H, m), 7.5-7.5K5H , m), 7.54(1H, s), 7.63-7.69(3H, m), 7.81~7.89(4H, m), 8.12-8.15(2H, m), 8.28(4H, m), 8.85(1H, s 680.79 680.26 8 S = 1.72(6H, s), 7.29'7.41(6H, in), 7.5-7.5K5H, m), 7.54(1H, s), 7.63-7.69(3H, m), 7.79-7.89( 8H, m), B.12-8.15(2H, m), 8.63(1H, s), 8.85(1H, s) B79.81 679.26 t 9 Γ ί δ = 1.72C6H, s), 7.05(2H, m ), 7.29-7.38(4H, m), 7.47-7.54C7H, m), 7.63'7.66(2H, m), 7.69(2H, s), 7.69(0H, n), 7.81-7.89(4H, m) , 8.12-8.15(2H, ra), 8.3(4H, m), 3.390H, s) 378.82 378.27 28 95226 201204810 10 δ = 1.72(6H, s), 7.25C1H, m), 7.32-7.4K6H, m) , 7.5K4H, m), 7.66-7.7K3H, m), 7.79-8C10H, m), 8.15 (1H, m), 8.55C1H, m), 8.63(1H, s) 679.81 679.26 11 δ = 1.72(6H, s), 7.25(1H, m), 7.32-7.4K6H, m), 7.5K5H, m) , 7.66-7.69(2H, m), 7.79-7.94(10H, m), 8.15(1H, m), 8·55(1Η, m), 8.630H, s) 679.81 679.26 12 δ = 1.72C6H, s) , 7.25(1H, m), 7.32-7.4K6H, m), 7.51-7.52(6H, m), 7.66-7.69(2H, m), 7.79~7.94(9H, m), 8.15(1H, m), 8.55(1H, ra), 8.63(1H, s) 679.81 679.26 13 δ = 1.72(6H, s), 7.25C1H, m), 7.32-7.44(7H, m), 7.5K4H, m), 7.66-7.69 ( 2H, m), 7.79-8(10H, m), 8.15(1H, m), 8.55(1H, m), 8.63(1H, s) 679.81 679.26 14 δ = 1.72(6H, s), 7.29C1H, m ), 7.37(4H, m), 7.45-7.52(10H, ra), 7.54(1H, s), 7.55-7.63(6H, m), 7.72(1H, m), 7.89(1H, m), 7.98( 1H, m), 8.06-8.12(3H, m), 8.19(1H, m), 8.45(1H, m), 8.85(1H, s) 724.00 723.24 15 δ = 0.66(6H, s), 7.29-7.35 ( 2H, m), 7.4K2H, m), 7.5-7.52(7H, m), 7.58-7.63(2H, m), 7.72(1H, s), 7.82(1H, m), 7.89C1H, s), 7.95 -7.98(2H, m), 8.12(1H, m), 8.2(1H, m), 8.28C4H, ra), 8.41-8.45(2H, m) 721.93 712.21 16 6 = 7.29(1H, m), 7.41( 2H, m), 7.5-7.52(7H, m), 7.58'7.63(2H, m ), 7.78(1H, s), 7.86(1H, s), 7.98(1H, m). 8.05-8.12(4H, n), 8.2(1H, m), 8.28(4H, m), 8.41-8.45( 2H, n) 686.84 686.16 17 δ = 0.66(6H, s), 7.29-7.4K7H, m), 7.5-7.5K5H, m), 7.63-7.66(2H,m), 7.720H, s), 7.81-7.85 (3H, m), 7.89C2H, 3), 7.89(0H, in), 7.95(1H, ra), 8.12(1H, m), 8.28(4H, m) 696.87 696.23 18 δ = 7.29-7.41(6H, m). 7.5-7.5K5H, m), 7.63-7.66(2H, in), 7.78(1H, s), 7.81-7.85(2H, m), 7.86(1H, s), 7.89(1H, m), 8.05-8.12(4H, m), 8.28(4H, m) 670.78 570.18 19 5 = 1.72(6H, s), 7.06C1H, m), 7.29(1H, m), 7.45-7.530H, m), 7.54( IH, s), 7.58-7.69(6H, m). 7.88(1H, m), 7.98(1H, .m), 8.12(1H, m), 8.2(1H, m), 8.28(1H, m), 8.36-8.46(4H, di), 8.85(1H, s) 694.88 694.24 29 95226 s 201204810 [Example 1] Production of OLED device using organic electroluminescent compound of the present invention OLED was produced using the organic electroluminescent material of the present invention Device. First, a transparent electrode ΙΤ0 film (150/□) obtained by using 0LED (manufactured by Samsung Corning) glass was washed with triethylene glycol, acetone, ethanol, and distilled water in the same manner, and stored in isopropyl alcohol for use. Then, the π 〇 substrate is assembled on the substrate of the vacuum vapor deposition apparatus, and 4, 4, 4,, _ bis (N, N-(2-naphthyl)-phenylamino) triphenylamine ( 2_TNATA) is placed in one of the chambers (ceU)f of the vacuum vapor deposition apparatus, and then the chamber is ventilated to a vacuum of 1〇-6 torr. Subsequently, a current is applied to the cell to evaporate 2_TNATA, and a hole injection layer having a thickness of 6 () nanometer (f) is formed on the ITG substrate. Next, 'N,N,-bis(α,naphthyl)_N,N,_diphenyl_4,4,diamine (_) is placed in another chamber of the vacuum vapor deposition apparatus, A current is applied to the chamber to evaporate, and an electric brittle layer having a thickness of 2 〇 (10) is formed on the hole injection layer. After the hole injection layer and the hole are formed, as follows, an electric field light-emitting layer is formed thereon. Compound ι was placed in a vacuum vapor phase to form a body and Ir(ppy) 3 [tris(2-benzoquinone) bite was used; as small as medium. Evaporate the two materials at different speeds*: Two: an electric field luminescent layer doped on the hole transport layer at a concentration of 4 to 1 〇 by weight, especially for a thickness of 30 nm. =, deposited on the electric field luminescent layer to a thickness of 2 quinolinol) aluminum (III) (A1) phase deposition thickness of i nra to 2 (10) electron transfer layer. Next, after the gas (lithium. 8-hydroxyquinoline clock (h), hlumquinQlate, Uq) having the following structure is used as an electron injection layer, a vacuum deposition apparatus of another 95226 30 201204810 is used to form a thickness of 150 nm. The aluminum cathode is used to fabricate an OLED. Each of the compounds used in the OLED was purified by vacuum sublimation at i〇-6 torr. Thus, when 6.3 volts (V) has been verified, a current of 4.3 mA/cm 2 (mA/cm 2 ) circulates and emits 1310 candelas per square meter (cd/m 2 ) of green light. [Example 2] An OLED device was produced in the same manner as in Example [1] except that Compound 6 was added as a material for the electroluminescent layer. Therefore, it has been verified that at 6·6 V, a current of 4.3 mA/cm2 flows and emits green light of 1220 cd/m2. [Example 3] A ruthenium LED device was produced in the same manner as in Example [1] except that Compound 10 was added as a host material of the electro-optic luminescent layer. Therefore, when it was verified at 6.4 V, a current of 4.1 mA/cm2 was flown and green light of 1150 cd/m2 was emitted. [Comparative Example 1] Manufacture of a 装置LED device using a conventional organic electroluminescent compound, an OLED device manufactured by the same method as in Example [1], except for forming a hole injection layer and a hole transfer layer (use and implementation) Example [After using bis(2-methyl I via base) (pair _ stupid) Ming (ιπ) (Mlq) instead of the hair-like organic electroluminescent compound as a further chamber for riding a direct-space deposition device The electric field illuminating host material. The GLED device was manufactured in the same manner as in Example i except that 4'4'~double (4) sitting _9-based was used. 95226 31 201204810 conjugated (CBP) was substituted for the compound of the present invention as an electric field illuminating The host material on the layer, and bis(2-mercapto-hydroxy-8-quinolyl)(p-phenylphenol) aluminum (III) (BAlq) was used as the hole blocking layer. Therefore, it has been verified that at 7.5 V, a current of 3.9 mA/cm2 flows and emits green light of 1000 cd/m2. The organic electroluminescent compound of the present invention has properties superior to those of conventional materials. Further, the apparatus using the organic electroluminescent compound of the present invention as a host material has superior electric field luminescent properties and lowers the driving voltage by 0.9 to 1.2 V, thereby improving power efficiency and improving power consumption. [Simple description of the diagram] None. [Main component symbol description] None.

32 95226 S

Claims (1)

201204810 VII, Shen Qing patent range: h An organic electric field luminescent compound represented by chemical formula 化学 ^, Wherein, (3⁄4 has the same definition as in Chemical Formula 2, X represents -0- or -S-r γ, _c(Ri)(R2)-, Si(R3)(R4)-, -N(5)- or A divalent group consisting of the following structures; * * An to An and Ri to Rs independently represent hydrogen, hydrazine, (^_C3〇) alkyl, S (C1_C30) alkyl, dentate, cyano, ( C3-C30) cycloalkyl, 5 to 7 membered heterocycloalkyl, (C2-C30), (C2_C3) alkynyl, (C6-C30) aryl, (C-C30) alkoxy, ( C6_C3〇) aryloxy, 1 S 95226 201204810 (C3-C30)heteroaryl, (C6-C30)aryl (C1-C30)alkyl, (C6-C30) arylthio, mono or di (a- C30) alkylamino group, mono or di(C6-C30) arylamino group, tri(C1-C30)alkyl fluorenyl group, di(ci-C30)alkyl group (C6-C30) aryl shiji, three (C6) -C30) arylsulfonyl, nitro or hydroxy, or each of αΓι to Ars and 1 to & each via a (C3_C3〇)alkylene or (C3-C30)alkylene linkage with or without condensed Adjacent substituents to form an alicyclic ring, a monocyclic or polycyclic aromatic ring, or a monocyclic or polycyclic heteroaryl ring; Αιί to An and 仏 to Rs each of the alkyl groups, The alkyl, heterocycloalkyl, alkenyl, alkynyl, aryl and heteroaryl groups may further be selected from one or more selected from the group consisting of hydrazine, (Cn-C30) alkyl, -(C1-C30) alkyl, self-priming , cyano, (C3-C30)cycloalkyl, 5- to 7-membered heterocycloalkyl, (C2-C30)alkenyl, (C2-C30)alkynyl, (C6-C30)aryl, (n-C30 Alkoxy, (C6-C30) aryloxy, (C3-C30)heteroaryl, (C3-C30)heteroaryl having (C1-C30)alkyl substituent, having (C6_C3〇)aryl Substituent (C3-C30)heteroaryl, (C6-C30)aryl(C1-C30)alkyl, (C6-C30) arylthio, mono or di(C1-C30)alkylamino, mono- or Di(C6_C3〇)arylamino, tri(Cn-C30)alkylindenyl, di(C1_C30)alkyl(C6 C3〇)arylindenyl, tris(C6-C30)arylfluorenyl, nitro or hydroxy The substituents of the group are substituted; 'Li to b is a chemical bond or is selected from (C6_C3〇) extended aryl, (C3-C30) heteroaryl, bis(n_C3〇), Shihji or Μ (Μ) The divalent group of the group consisting of aryl fluorenyl groups; and the heterocyclic, heteroaryl and heteroaryl rings may contain one or more hetero atoms from B, N, 0 and S. 95226 2 2012 An organic electroluminescent compound according to claim 1, wherein Not limited to this, it is selected from the following structures, but The definitions of Y and An to An are the same as those defined in the third paragraph of the patent application. The organic electroluminescent compound according to claim 1, wherein Li-k-h of the chemical formula 1 is selected from the following structures: 3 95226 S 201204810 An organic electric field light-emitting device comprising the organic electroluminescent compound according to any one of claims 3 to 3. 5. The organic electroluminescent device of claim 4, comprising: a first electrode; a second electrode; and one or more organic layers interposed between the first electrode and the second electrode; The organic layer includes an organic or electroluminescent compound and one or more phosphorescent dopants. The organic electroluminescent device of claim 5, wherein the organic layer further comprises one or more amine compounds selected from the group consisting of arylamine compounds and stupid vinyl arylamine compounds. An organic electric field light-emitting device according to claim 5, wherein the organic layer further comprises: or a plurality of transition metals selected from the group consisting of the i-th organometallic, the second, fourth, and fifth cycles a metal or complex compound of the group consisting of a metal and a d-transition element. An organic electric field illuminating device as described in claim 5, wherein the organic layer comprises an electro-optic layer and a charge generating layer. An organic electric field light-emitting device according to claim 5, which is an organic electric field light-emitting device that emits white light, wherein the organic layer further comprises one or more organic light-emitting materials that emit blue light, red light or green light. Floor. 95226 S 201204810 IV. Designated representative map: (1) The representative representative of the case is: There is no schema in this case. (2) A brief description of the symbol of the representative figure: None. 5. If there is a chemical formula in this case, please disclose the chemical formula that best shows the characteristics of the invention: S 3 95226