TW200844210A - Organic electroluminescent compounds and display device using the same - Google Patents

Abstract

The present invention relates to organic electroluminescent compounds represented by Chemical Formula 1: [Chemical Formula 1] wherein, group represents or A and B independently represent a chemical bond, R1 and R2 independently represent an aromatic ring or a fused multi-cyclic aromatic ring having two or more aromatic rings; R3 through R6 independently represent a linear or branched C1-C20 alkyl group with or without halogen substituent(s), a C5-C8 cycloalkyl group, or an aromatic group with or without halogen substituent(s); R11 through R14 independently represent hydrogen, C1-C8 alkyl group, C5-C8 cycloalkyl group, or an aromatic group with or without halogen substituent(s); and Ar1 through Ar4 independently represent an aromatic ring or a multi-cyclic aromatic ring wherein two or more aromatic rings have been fused; and display devices using the same as an electroluminescent material.

Description

[Technical Field] The present invention relates to a novel organic electroluminescent compound represented by Chemical Formula 1 and a display device using the same as an electroluminescent material. [Chemical Formula 1]

[Prior Art] The most important subject for the development of organic electroluminescent devices with high efficiency and long life is the development of high-efficiency luminescent materials. In view of the current development of electroluminescent materials, it has been shown that the electroluminescent properties of red or blue electroluminescent materials are lower compared to green electroluminescent materials. In order to achieve a full-color display, three luminescent materials (red, green, and blue) are used, and the lowest illuminating material among the three ultimately determines the performance of the entire panel. Therefore, in order to enhance the overall organic electroluminescent device

1 Tuyue b, the development of blue or red electroluminescent materials with high efficiency and long life _ important ^ ΤξΜ 〇 has developed diphenylanthracene, yang # u bebutadiene, blue The distyrylbenzene derivatives, and such compounds are used as photoluminescent materials. However, these compounds are known to have low film stability, and the stupid compounds have a tendency to be easily crystallized. A blue electroluminescent material having an improved film stability in the form of an olefin has been developed by Idemitsu (H. Takailin u 5 . Higashi C. Hosokawa, EP 388, 768 (1990)), which has a branched chain # u ' The hard base can inhibit crystallization. It is known from Kyushu University (Pro. SPIE, 1910, 6 200844210) that the improved film stability of stilbene benzene derivatives is due to electron acceptors and electron donors.

In addition, DPVBi (chemical formula A) from Ademitsu Kosan, aromatic vinyl derivatives such as DPVDPAN (chemical formula B), dinaphthyl anthracene (chemical formula C) from Kodak, and tetra(t-butyl) anthracene system (tetra(t-) Butyl)perylene (Chemical Formula D), as disclosed in EP 1063869 A1 (Idemitsu Kosan Co., Ltd.), Korean Patent Publication No. 2000-0048006 (Eastman Kodak Co., USA), and Japanese Patent Publication No. 1996-333569 , have been widely used as blue electroluminescent materials. [Chemical Formula A]

[Chemical Formula C] 7 200844210

〇 Since the glass transition temperature of the DPVBi of the chemical formula A is equal to or lower than 10 (TC, there is a problem of thermal stability, so the onion is introduced into the DPVDPAN (chemical formula B) in the biphenyl group of the above DPVBi to increase the glass transition temperature. It improves its thermal stability to 105 ° C. However, its color purity and luminous efficiency as a blue electroluminescent material are not satisfactory. Meanwhile, in the case of blue electroluminescent materials, when electro When the wavelength of the light is shifted from the current state to a longer wavelength, it is advantageous for electroluminescence efficiency. However, it does not meet the requirements of pure blue, so it is difficult to apply to the full color of the pure blue electroluminescent material. On the electroluminescent display. Therefore, in order to develop blue electroluminescent devices or full-color electroluminescent devices, the development of novel blue electroluminescent materials is an urgent issue, due to the conventional blue electroluminescent compound phase. It has lower luminous efficiency than other colors. Compared with traditional materials, the present invention significantly improves the performance of the host material, which is used as a solvent or energy in the electroluminescent material. The purpose of the present invention is to provide an excellent electroluminescence efficiency and a good use of citrus stalks. The chrome has a stack of electroluminescence VIII. The purpose is to provide a new type of organic electroluminescence. The present invention relates to a novel organic electroluminescent compound which is chemically modified.

Ar, R3wR4

/)-b-r2-n

Λγ3 I 1 ΑΓ2 N-RrA Ar4

^ and the heart is independently an aromatic ring, or a fused polycyclic aromatic ring R3 to R6 with two or more aromatic rings. A linear or branched Cl to a broad base with or without a _ To C8 loop wire, or «non-« substituent aryl group '· ^ R" to R丨4 series independently 笥, rprh 甘巧辽. To (:8-alkyl, c5- to, aryl group having no halogen substituent; fly, or

Ar 丨 to Aq is a fused aromatic scented ring which is independently aromatic, θ ^ ^ ^ ^ or /, one or singular aromatic ring; and a display device using the scorpion from the sputum as a pen luminescent material . In the chemical formula according to the present invention, each field has no unit, and when it is connected to ^ 200844210 or R2, it is called a "chemical bond". The organic electroluminescent compound according to the present invention is a pure compound having a high electroluminescence. The other and further objects, features, and advantages of the present invention will be more fully described below. [Embodiment] The compound of Chemical Formula 1 according to the present invention comprises a compound of the formula 2: [Chemical Formula 2]

[Chemical Formula 5]

10 200844210 [Chemical Formula 6]

Among the compounds represented by Chemical Formulas 2 to 6, 1 and R 2 are independently a aryl group or a fused polycyclic aromatic siloxane having a di- or singular aromatic ring, and the heart-to-heart system is independently or not having a halogen substituent. a linear or branched c 2G group, a C5 to Cs cycloalkyl group, or

An aromatic group with or without a halogen substituent; R main unit is independently hydrogen, Cl to C8, and C5 to (^8 ring: |: complete, or presenting not #3 eight times without i-substituent Aromatic group;

Ar丨 to A. It is a fused polycyclic aromatic ring which is independently an aromatic ring or a square scented core. In Chemical Formulas 2 to 6, specific examples of & and r2 include benzene, coix, onion, naphthacene, flu〇rene, and biphenyl; & Base, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, n-hexyl, n-heptyl, n-octyl, 2-ethylhexyl, ruthenium , difluoromethyl, pentafluoroethyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, phenyl, toluyl, fluorenylnaphthyl, 2-naphthyl, 2-fluoro Phenyl, or 4-fluorophenyl; R" to Rl4 are hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, n-hexyl , n-heptyl, n-octyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, phenyl, tolylhydryl, fluorenyl-naphthyl, 2-naphthyl, 2-fluorophenyl, or 4- Fluorophenyl; Ari to Ar4 phenyl, anthracenyl, diphenyl, pyridyl, biphenyl, naphthyl, anthryl, phenanthryl, naphthacenyl, Acenaphthenyl, sulfhydryl, sulfhydryl, or sulfhydryl 200844210 (perylenyl). The organic electroluminescent compound represented by one of Chemical Formulas 2 to 6 can be specifically exemplified as a compound having the following constitution:

12 200844210

13 200844210

14 200844210

15 200844210

16 200844210

17 200844210

18 200844210

Wherein R3 to R6 are a methyl group or an ethyl group, and R15 to R18 are a fluorenyl group, an ethyl group, or a phenyl group. Each compound represented by Chemical Formula 2, 3, or $ can be pierced through the reaction scheme shown in Reaction Scheme 1, the compound of Chemical Formula 4 can be produced via the reaction route of Reaction Scheme 2, and the compound of Chemical Formula 6 can be passed via Manufactured by the reaction route of Reaction Scheme 3. [Reaction Scheme 1]

19 200844210

Example

Hereinafter, the electroluminescent compound of the present invention, a method for producing the same, and an illuminating property of a device using the compound will be further described with reference to representative compounds of the present invention. This is for illustrative purposes only and is not intended to limit the invention in any way. [Synthesis Example 1] Synthesis of IF1-1 20 200844210

301(1F1-1) 2,5-a's stinky one (2.0 g, 7. 6 〇 millimoles (mm〇i)) (compound 111)

/ Valley in 50 liters of tetrahydrofuran (Tetrahydrofuran, THF), at a temperature of -80 ° C, add tert-butyl lithium (1.5 equivalents) to the 2,5-dibromodimethyl stupid THF solution (5 mL) was stirred at _4 (rC2 temperature under nitrogen atmosphere for 12 hours. After completion of stirring, 2_isopropoxy-4,4,5,5-tetramethyl- 1,3,2-dioxaborolane (4.3 g, 23.1 mmol) while maintaining the temperature of the reaction mixture at -80 ° C to form the borate compound of compound m ( 2.31 g, 6.42 mmol, the boronic ester compound (2.3 g) was dissolved in 50 ml of THF. 1-bromo-4-iodobenzene (3.80 g, 13.4 mmol) ), Pd(PPh3)4 (1.5 g, 1.29 mmol) and 2 水溶液 aqueous calcium carbonate solution (2 mL) were added to the THF solution, and the resulting mixture was heated under reflux for 1 hr. The precipitate gave Compound 112 (2.14 g, 5.14 mmol). Compound 112 (2. 14 g) was dissolved in 20 ml of pyridine and 2 EtOAc (15 mL) A carboxylic acid is formed at the end of 12. The solid obtained by extracting the organic layer is added to sulfuric acid, and the mixture is heated at a temperature of 80 ° C for 12 hours. After the sulfuric acid solution is cooled to room temperature, the solution is poured into crushed ice. The solid thus formed was extracted to obtain Compound 113 ( 1.70 g, 3.86 mmol). 21 200844210 Compound 113 (1.7 g) was added to Methylene glycol (30 ml) and added Hydrazine hydrate (0.58 g, 11,6 mmol) and potassium hydroxide (〇, 5 g), and the resulting mixture was heated under reflux for 48 hours. After heating at reflux The reaction mixture was cooled to room temperature and was taken up in ethyl acetate to give the ind (jen〇fjuorene) compound. After drying, the compound was dissolved in 3 mL of THF and at _78t: Under the temperature and nitrogen atmosphere, the barrier was added (2.20 g, 15.5 mmol), and then a solution of 1·8 Μn-butyl clock (n_|3Utyllithiinn) dissolved in THF (15 ml) was slowly added. After stirring the mixture for 1 hour, the temperature was raised to room temperature, and the mixture was stirred again. The reaction was quenched by the slow addition of 50 ml of water. After completion of the reaction, the organic layer of the reaction mixture was extracted and dried to give compound 114 ( 1.17 g, 2.50 mmol). Compound 114 (1.17 g) was dissolved in 30 mL of THF and butyl butyl lithium (1·5 eq.) was added. Preparation of boric acid of compound 114 using 2-isopropoxy-4,4,5,5-tetramethyl-1,3,2-dioxaborolan (1. 4 g ' 7.53 mmol) Ester compound (1.33 g, 2.37 mmol). The obtained borate compound (133 g) was dissolved in 3 ml of THF > gluten solution, and compound 201 (1·56 g, 4.81 mmol), Pd(PPh3)4 (〇, 56) was added. Gram, 0,48 mmol, and 2 Μ aqueous calcium carbonate solution (1 ml). After heating the reaction mixture under reflux for 12 hours, the precipitate thus formed was extracted with ethyl acetate, which was recrystallized and dried to give the title compound 301 (IF1-1) ( 1.50 g, 1· 88 millimoles), with a total yield of 24.7%. 4 Nuclear Magnetic Resonance (NMR) (200 megahertz (MHz), CDC13): δ=1·65 (s,12Η), 6.45-6.55 (m,12Η),6·6-6·65 (m,4Η) , 7.0-7·05 22 200844210 (m, 8H), 7.2-7.25 (d4, H), 7.65 (d, 2H), 7, 73 (d, 2H), 7.80 (s, 2H), 8.0-8.1 ( d, 2H) MS/FAB: 796 (measured value), 797.06 (calculated value). [Synthesis Example 2] Synthesis of IF1-2

According to the same procedure as described in Synthesis Example 1, the title compound of Compound 302 (IF1-2) ( 1.16 g, 1.30 mmol) was obtained with a total yield of 19.0%, except that Compound 114 (1.0 g, 2.14 mmol) was used. ), and Compound 201 was replaced with Compound 202 (1.61 g, 4.30 mmol).

]H NMR (200 MHz, CDC13): δ=1·65 (s,12H), 6.45-6.5 (m, 8Η), 6.6-6.65 (m,4Η),6·75-6·8 (m,4H) ), 7·0-7.05 (m, 8H), 7·45-7·55 (m, 6H), 7·65 (d, 2H), 7·75-7·85 (m, 6H), 8.0- 8.05 ( d, 2H) MS/FAB : 896 (measured value), 897.19 (calculated value). [Synthesis Example 3] Synthesis of IF1-3 23 200844210

1) Βυϋ

3〇3(IFl-3)

According to the same procedure as described in Synthesis Example 1, gram, U8 亳 Mo Er), & name compound 303 旲 旲 ear), the total yield η · 2%, except, using compound 114 (1 · 0 g ' 2.14 pen Mohr), and compound 201 was replaced by compound 2〇3 (丨克, * % mmol). NMR (200 MHz, CDC13): δ = 1·65 (s, 12H), 6.45-6.55 (m, 12Η), 6·6-6·65 (m, 4H), 7·0-7·05 (m , 8H), 7.2-7.25 (d, 4H), 7.55-7.57 (d, 8H), 7.65 (d, 2H), 7.75 (s, 2H), 7·8 (s, 2H), 8.0-8.05 (d , 2H) MS/FAB: 948 (measured value), 949.26 (calculated value). [Synthesis Example 4] Synthesis of IF1-4 24 200844210

According to the phase synchronization (IFM) described in Synthesis Example 1 (0.95 g, 0.92 millimolar to obtain the title compound of Compound 304), the total yield was 13,4%, except that Compound 114 (1·〇克, 2.14) was used. Monomolar), and compound 201 was replaced with compound 204 (1.90 g, 4.32 mmol). 1HNMR (200 MHz^CDC13): 6-1.63-1.65 (d ^ 24H) ^6.45-6.50 (d,8H) , 6.55-6.65 (m,6H) , 6.75 (s,2H) ,7.0-7,05 ( m, 8H), 7.58-7.65 (m, 6H), 7·73-7·85 (ηι, 6Η), 8.0-8.05 (d, 2H)

MS/FAB : 1028 (measured value), 1029.39 (calculated value) [Synthesis Example 5] Synthesis of IF2-1 25 200844210

305 (1 F2-1) 2,5-Dibromoxylene (2.0 g, 7.60 mmol) was dissolved in 50 mL of THF. Phenylboronic acid (1.95 g, 16.0 mmol), pd(PPh3)4 (1.95 g, 1.68 mmol), and 2 Μ calcium carbonate aqueous solution (25 ml) at -80 °C The solution was added to the 2,5-dibromoxylene in THF (50 mL). From the precipitate thus formed, Compound 115 (186 g, 7.2 mmol) was obtained. Compound 115 (1·86 g) was dissolved in 20 ml of pyridine, and a 2 Μ aqueous potassium permanganate solution (15 liter) was added to form a carboxylic acid at the end of the compound. The (4) obtained by extracting the organic layer was added to sulfuric acid, and the mixture was heated at a sail temperature for 12 hours. After the sulfuric acid solution was cooled to room temperature, the solution was chopped into ice. The solid thus formed is extracted, and the compound 丨16 5 8 is added to the compound (64 g) to be added to diethylene glycol (9 ml), and the ear is added to the mouth of the horse "amine (0.85 g ' 17.0 * mol) And potassium hydroxide (8 g), the mixture was heated under reflux for 48 hours. After heating was completed under reflux, 26 200844210, the reaction mixture was cooled to room temperature and extracted with ethyl acetate to obtain hydrazine. The compound was dissolved. After drying, the compound was dissolved in 3 () ml of THF, and methyl iodide (1·65 g, 116 mmol) was added at a temperature of -78 ° C under a nitrogen atmosphere, followed by slow dissolution. 1·8 Μn-butyllithium solution (12 ml) in THF. The mixture was stirred for 1 hour, then warmed to room temperature, the mixture was stirred again for 24 hours, and the reaction was quenched by slowly adding 5 liters of water. After completion of the reaction, the organic layer of the reaction mixture was extracted and completely dried to give Compound 1 ( 1.25 g, 4.03 mmol). Compound 117 (1·25 g, 4.03 mmol) and trimaldehyde. (1.8 g) added to 35% hydrogen bromide (HBr) dissolved in acetic acid (15 ml), and the mixture was heated at a temperature of 6 (rc) for 24 hours. The reaction mixture was cooled to room temperature, extracted and dried to give compound 118 ( 1.34 g, 2.70 mmol) and The compound was poured into a reaction flask. Tdethylphosphite (2.0 g, 12.0 mmol) was added at a temperature of 〇 ° C, and the mixture was heated at 150 ° C for 4 hours. The residual triethyl phosphite was removed by vacuum distillation, and the residue was extracted with ethyl acetate to give compound 119 (i 4 g, 2·30 mmol). Compound 119 (1.4 g) and compound 205 (1.3 g, 4.76 mmol) dissolved in THF (30 ml), added dropwise in THF; [.6 pot3⁄4 butyl alcohol (potassium tert-butoxide) solution (5 ml) in the mixture In the liquid, the temperature was slowly raised to room temperature to complete the reaction, and then excess water was poured to form a solid, which was then filtered, and recrystallized with THF-nonanol to obtain the title compound 3〇5 (IF2-1) ) (1·23 g, 1.45 mmol), total yield 19.1%. Towel NMR (200 MHz) CDC13) · δ=1.65 ( s,12Η),6 45-6 5 27 200844210 (m ' 12H) ' 6·6-6·65 ( m,4H), 6.95-7.05 ( m,12H),7·15 -7.2 (d,4H),7.57-7,6(d,2H),7.7-7,75(d,4H),7.9-8.0 (d, 2H) MS/FAB : 848 (actual value), (calculation value). [Synthesis Example 6] Synthesis of IF2-2

According to the same procedure as described in the synthesis of Example 5, the title compound (IF2-2) (0.95 g, 0.91 mmol) was obtained with a total yield of 16.8%, except that Compound 119 (1.0 g ' 1.64 m) was used. Mohr), and compound 205 was replaced with compound 2〇6 (丨28 g, 3.43 mmol). H NMR ( 200 MHz, CDC13) : δ = 1.65 ( s, 12H), 6.45-6.50 (d ' 4Η) ' 6.75-6.8 (m, 8Η), 7.0 (d, 4Η), 7.15-7.3 (m, 12H ), 7.4-7,6(m,14H) '7,7-7.75 (d,4H), 7.9-8.0(d,2H) MS/FAB : 1048 (constant value), iQ49 38 (calculated value). [Synthesis Example 7] Synthesis of IF2-3 28 200844210

^ m 旬 ^ shows the name of the compound 307

According to the phase synchronization IF2-3) (0.92 g, 1.08 mmol) described in Synthesis Example 5, she has a μ yield of 20 〇/〇, except that compound 119 (1, gram ' 1.64 house mole is used. And substituting compound 205 with compound 2〇7 (丨, 1 g, Μ millimolar). , HNMR (200 MHz^ CDC13): 5=1.65 (s^ 12H) ^ 6.45-6.5 (d^ 8H), 6.6-6.65 (m, 2H), 6·75-6·8 (ιώ, 4Η), 6.95 -7,25 (m, 16H) , 7,4-7.6 ( m,8H) , 7.7-7.75 ( d,4H ) , 7.9-8.0 ( d,2H ) MS/FAB :948 (actual value), 949.26 ( Calculated).

[Synthesis Example 8] Synthesis of IF2-4

29 200844210 λ According to the same procedure as described in Synthesis Example 5, the title compound 3〇8 (IF2-4) (0·71 g, 0·68 mmol) was obtained, the total yield was 12.6%, however, Compound 119 (1.00 g, 1.64 mmol) was used and compound 205 was replaced with compound 2 〇8 (1 gram, 3 43 mM). H NMR (200MHz, CDC13)· δ: 1.65 (s, 12Η), 6.45-6.5 (d, 4Η) ' 6.6-6.65 (m ' 2Η) ' 6.75-6.8 (m,8Η), 6.95-7,1 ( m, 10H) ' 7.2-7.25 (m ' 2H) ' 7.35-7.6 (m, 14H), 7.7-7.75 (d, 6H), 7.9-8.0 (d, 2H) MS/FAB : 1048 (measured value), 1049.38 (calculated value). [Synthesis Example 9] Synthesis of DF1-1

2-Bromo-9,9-dimethylhydrazine (2 such as _〇_9,9- to 11^1^1)

120) (2.0 g, 7.33 mmol) dissolved in 50 ml of THF and added at a temperature of -80 ° C to the third butyl lithium (1.5 eq.) to the 2-bromo-9,9-diindole Base THF solution (50 ml) and at -4 Torr. (; The temperature and nitrogen atmosphere were stirred for 30 hours 200844210 for 12 hours. Yuancheng stir; after mixing, add 2-isopropoxy-4,4,5,5-tetramethyl-1,3,2- Dioxaxy pentane (4.3 g ' 23.1 mmol) while maintaining the temperature of the reaction mixture at -8 (TC) to form the borate compound of compound 120 (2.16 g, 6.75 mmol), The boric acid cool compound (2.16 g) was dissolved in 50 ml of THF. 2-bromo-9,9-dimethylhydrazine (1.92 g, 7.03 mmol), Pd(PPh3)4 (0.97 g, 0.84) To the THF solution was added a millimolar, and a 2 Μ aqueous solution of calcium carbonate (15 ml), and the product was heated under reflux for 10 hours. From the precipitate formed therefrom, compound 121 (2·26 g, 5) was obtained. , 85 mmol.) Add compound 121 (2.66 g) and trioxane (2.26 g) to a solution of 35% HBr in acetic acid (20 ml) at 6 Torr. The reaction mixture was cooled to room temperature, extracted and dried to give compound i 22 (2.64 g, 4.62 mmol). Compound 122 (2·64 g) was poured into a reaction flask. Triethyl phosphite <3 42 g, 2 〇 6 mmoles was added at a temperature of C, and the mixture was heated at a temperature of 150 C for 4 hours. After the completion of the reaction, the residual phosphorous acid was removed by vacuum distillation k. The ethyl ester was extracted with ethyl acetate to give compound 123 (2.13 g, &lt;&quot;&quot;&quot;&quot;&quot;&quot;&quot;&quot;&quot;&quot; 6.81 mmol/combined in THF (40 liters), and added dropwise a solution of potassium hydroxide in THF (1 mL) in the mixed solution at the same temperature. Slowly warm to room temperature. In order to complete the reaction, the excess water was poured to produce a solid, which was then filtered, and after recrystallization from the methanol, the title compound was obtained as the compound 3〇9 (DF1_1) (I gram, 1.67 mmol). Rate 22 8%. 31 200844210 1HNMR( 200 MHz^ CDC13) : δ-1.65 ( s M2H) 56.45-6.5 (m^ 12H), 6,6-6.65 (m, 4H), 6.95-7.05 (m, 12H) ,7 15-7 2 (d, 4H) ' 7·5-7·65 (m ' 4H) ' 7.7-7.8 (m,4H), 7.85-7.9 (d,4H) MS/FAB ·· 924 (measured Value), 925.24 (calculated value) [Synthesis Example 10] Synthesis DF1-2

According to the same procedure as described in Synthesis Example 9, the title compound was obtained as the title compound 31 〇(DF1-2) (0·88 g '0.86 mmol), the total yield was 24.9%, except that Compound 123 (1 g, 1 was used) 46 mM) and compound 205 was replaced with compound 207 (1, 3 g, 3.19 mmol). H NMR (200 MHz ' CDC13) : δ = 1.65 ( s, 12 Η ), 6.45-6.5 (m, 8H), 6.6-6·65 (m, 2H), 6.75-6.8 (m, 4H), 6.95 -7·25 (m, 16H), 7.35-7.6 (m, l〇H), 7.7-7.8 (d, 4H), 7.8-7.9 (d, 4H) MS/FAB: 1024 (measured value), 1〇 25·36 (calculated value). [Synthesis Example 11] Synthesis of DF1-3 32 200844210

According to the phase described in Synthesis Example 9.

In the opposite step, the title (DFl-3) (0.56 g, 〇·55 祜 祜 化 、, ear), ', 、 yield 15.9 〇 / 〇, only, using compound 123 (1 g ' 1.46 house moles), and compound 205 was replaced with compound 2〇9 (i grammole). H NMR ( 200 MHz ' CDC13 ) : δ = 1 · 65 ( s, 12H ), 6.45-6.5 (m, 8H) , 6,6-6.65 (m, 4H) , 6.75-6.8 (m, 4H) , 6.95 -7.05 (m, 12H), 7.35-7,6 (m,10H), 7.7-7.8 (t,6H), 7.8-7.9 (d,4H) MS/FAB : 1024 (actual value), 1025.36 (calculated value ). [Synthesis Example 12] Synthesis of IF3-1 33 200844210

Add phenylboronic acid (1·1 gram, 9·〇2 mmol), Pd(PPh3)4 to a solution of compound 114 (2.0 g, 4,27 mmol) dissolved in THF (50 ml). (1 gram of ι·〇, 0·90 耄mol), and 2 Μ aqueous calcium carbonate solution (15 ml), and the obtained mixture was heated under reflux for 10 hours. From the precipitate thus formed, the compound i 24 (1·80 g, 3.90 mmol) was obtained. Compound 124 (1.80 g) and trimeric furfural (1.7 g) were added to a solution of 35% HBr in acetic acid (20 mL) at 60. (: The mixture was heated at a temperature of 24 hours. The reaction mixture was cooled to room temperature, extracted and dried to obtain a desert methyl derivative. The derivative was poured into a reaction flask at a temperature of 〇. Triethyl phosphite (2.57 g, 15.5 mmol) was added and the mixture was heated at a temperature of 150 ° C for 4 days. After completion of the reaction, the residual triethyl oxalate was removed by vacuum steaming. The residue was extracted with ethyl acetate to give compound 125 (1················· In 50 ml of the mixture, and dissolved in THF at a temperature of 〇ΐ·6Μ 34 200844210 potassium butoxide solution (8 ml) in the mixed solution. Slowly warm to room temperature to complete the reaction. An excess of water was added to give a solid which was then filtered. After recrystallized from ethanol, compound 312 (IF3_l) ( 165 g, m.m.) (yield: 165 g, m. : δ^Ι .65 ( s ^ 12H ) ^ 6.45-6.5 ( m ^ 8H), 6·6-6·65 (m, 2H), 6.75-6.8 (m, 4H) , 6.95-7.3 (m, 16H), 7·4-7·6 (ηι, 14Η), 7.65 (d, 2H), 7 75 (s, 2h), 7·8 (s, 2H), 7.95-8.05 (d, 2H) MS/FAB, 1100 (measured value), 1101·46 (calculated value) [Synthesis Example 13] Synthesis of IF3-2

According to the same procedure as described in Synthesis Example 12, the title compound 313 (IF3-2) (0·86 g, 0·78 mmol) was obtained with a total yield of 3 〇·4%, except that Compound 125 was used. (1 g '1·31 house Moule), and compound 207 was replaced with compound 209 (〇.9 g, 2.79 mmol). iHNMR (200 MHz, C: DC13) K.65 (s, 12 Η), 6.45-6.5 (m, 8H), 6.6-6.65 (m, 4H), 6.75-6.8 (m, 4H), 6·95-7 ·05 (m, 12H), 7.4-7.55 (m, 14H), 7.65 (d, 2H), 7, 7-7.75 (d, 4H), 35 200844210 7·8 (s ' 2H) ' 7.95-8.05 ( d, 2H) MS/FAB: 1100 (measured value), η〇1·46 (calculated value). [Synthesis Example 14] Synthesis of 〇F2-l

Adding tert-butyllithium (15 equivalents) to a temperature of -80 ° C to a 2,7-----9,9-dibromo-9,9- A solution of dimethylfluorene (Compound 126) (2.0 g, 5.68 mmol) (50 mL) was stirred at -40 ° C under a nitrogen atmosphere for 12 hours. After the completion of the stirring, 2-isopropoxy-4,4,5,5-tetradecyl-1,3,2-dioxaboropentane (0.95 g, 5.11 mmol) was added. While maintaining the temperature of the reaction mixture at _8 〇t:, to form a borate compound of Compound 126 (丨.86 g, 4.66 mmol), the boronate compound (1,86 g) was dissolved in 50. ML in THF. 2,7-dibromo-9,9-diindenyl hydrazine (1·56 g, 4.43 mmol), pd(PPh3)4 (〇·67 g, 0.58 m 36 200844210 mol), and 2 Μ An aqueous solution of calcium carbonate (1 ml) was added to the THF solution, and the resulting mixture was heated under reflux for 1 hr. From the precipitate thus formed, Compound 127 ( 2.12 g, 3.90 mmol) was obtained. Compound 127 (2·12 g, 4.27 mmol) was dissolved in 50 ml of THF, and boronic acid (!·00 g, 8.20 mmol), Pd(PPh3)4 (118 g, 1200 mg) was added. Mohr), and 2M aqueous calcium carbonate solution (2 mL) were added to the solution, and the resulting mixture was heated under reflux for 1 hr. From the precipitate formed thereby, the compound 128 ( 1.87 g, 3.48 mmol) was obtained. Compound 128 (1.87 g) and trioxane (18 g) were added to a 35% HBr solution (15 ml) in acetic acid, and the mixture was heated at a temperature of (10) 24 for 24 hours. The reaction mixture was cooled to room temperature, then extracted and dried to obtain a bromomethyl derivative, which was then poured into a reaction flask. Triethyl arsenate (2·30 g, 13.9 mmol) was added dropwise at a temperature of 15 Torr. (The mixture was heated at a temperature of 4 hours. After the completion of the reaction, the residual triethyl phosphite was removed by vacuum distillation and the residue was extracted with ethyl acetate to give Compound 129 (1 32 g, 157 / mmol) Compound 129 (1·32 g) and compound 205 (0·90 g, 3.30 mmol) were dissolved in THF (30 ml), and added to the tHf 1.6 Μ at the temperature of 〇 A solution of potassium dibutoxide (6 ml) in the mixed solution was slowly warmed to room temperature to complete the reaction. Then, excess water was poured to give a solid, followed by filtration of the solid. After recrystallization from ethanol, 'the title compound 314 was obtained. ( DF2-1 ) (1·28 g, 1.19 mmol), total yield 21.0% H NMR (200 MHz, CDC13) K65 (s, 12H), 6, 45-6.5 (m, 37 200844210 12H) , 6.6-6.65 (m, 4H), 6.95-7.05 (m, 12H), 7·15-7·2 (ιη, 4H) '7.45-7.5 (d'8H) '7.55-7.6 (m, 4H), 7.75-7.8(d,4H), 7.85-7.9 (d,4H) [Synthesis Example 15] Synthesis of DF2-2

(DF2-2) (0·86 g '0·73耄莫耳), the total yield was 17%, except that compound 129 (1.0 g, 1.19 mmol) was used, and compound 2〇9 (〇% g, 2 gram) replaced Compound 205.

iHNMR (2〇〇MHz, CDCl3): (4)·65(s, i2h), 6 45 6 5 (m, 8H), 6.6-6.8 (m, 8H), 6.95_7, 〇5(m, i2H), 7 35_76(m, 18H), 7.7-7.8 (t, 6H), 7.85-7.9 (d, 4H) 1^8/? 8: 8:1176 (measured value), 117756 (calculated value). [Examples] Preparation of an organic electro-optical photodiode (OLED) device by using the compound of the present invention has a qled device for fabricating a (tetra) electroluminescent material. First, sequentially, trichloroethylene, propylene oxide ( Indium Tin Oxide (ITO), Ethanol and Distilled Water for Transparent Electrode Indium Tin Film (15 ohms/unit area (in port)) 38 200844210 Ultrasonic rinsing, the film is from the glass used in OLED, and stored in isopropyl alcohol before use. in. Then, the ITO substrate is mounted in a substrate holder of the vacuum deposition chamber, and the 4,4',4"-tris(N,N-(2-naphthyl)-phenylamino group) shown in the following structural formula is stupid. The amine (4,4',4',tris-(N,N-(2-naphthy)-phenylamino)triphenylamine, 2-TNATA) is placed in one of the cells of the vacuum vapor deposition apparatus, and then The device is vented such that the degree of vacuum in the chamber reaches 1 〇 6 torr. Current is applied to the unit to evaporate 2-TNATA, thereby depositing a 60 nm (hole) hole injection layer (hole injection). Layer) on the ITO substrate.

Then, Ν,Ν'-(α-naphthyl)-N,Ν'-diphenyl-4,4'-diamine (N, N'-bis(a-naphthyl)-N, N'-diphenyl -4,4'-diamine, ΝΡΒ) is filled in another unit of the vacuum deposition chamber, and an electric current is applied to the unit to evaporate NPB, thereby vapor-depositing a hole transport layer having a thickness of 20 nm. ) on the hole injection layer.

39 200844210 After forming the hole injection layer and the hole transfer layer, an electroluminescent layer is vapor deposited thereon in the following manner. Dnaphthylamhracene (DNA) of the following structural formula is filled in a single crucible of the vacuum vapor deposition apparatus, and the electroluminescent material (for example, compound IF2 1 ) of the compound of the present invention is filled in another In the cell, and at a vapor deposition rate of 丨〇〇: ^, a 30 nm thick electroluminescent layer is vapor deposited on the hole transfer layer.

DNA

Then, 'vapor-deposited tris(8-hydroxyquinoline)aluminum(III) (tris(8-hydroxyquin〇line)alumimnn( HI) ' Alq) as a thick 20 nm pen The layer 5 is vapor-deposited and Htium quinolate (Liq) shown in the following structural formula is vapor-deposited as an electron injecting layer having a thickness of 1 nm to 2 nm. Thereafter, a 150 nm thick aluminum (A1) cathode was vapor-deposited by using another vapor deposition chamber to prepare a 0 LED. 40 200844210

Liq

In the case of i〇, the materials used by the vacuum sublimation OLEDi^ and the electroluminescence used as (10)D 1=this [than the "Example 1] manufacture of LEDs using conventional electroluminescent materials / ', according to the same steps as described in Example 1, the construction of the sound, the main entry layer and the - hole transfer s sub-Jia ~ Keen filled in the deposition chamber - the unit as a blue electro-material "simultaneously" the following structural formula The (4) shown is filled with another-single (four) dichromatic electroluminescent material. Qiu De, with lnn, &gt; ^ Λ ^ ', ', after a vapor deposition rate of 100:1, in the layer ^ vapor deposition - 30 nm thick electroluminescent layer. (10) Private

Then, according to the same procedure as described in Example 1, a vapor deposition-electron transfer layer and an electron injection layer, and by using another vacuum deposition chamber, vapor deposition-thick aluminum (A1) cathode having a thickness of 15 Å. To prepare a 〇 led. [Example 2] The electroluminescent property of the prepared OLED device, ^can light/square meter (5)-) and 2,_clouding/square meter, respectively, including the organic electricity of the present invention The luminescent rate of the OLED of the luminescent compound and the qled containing the conventional electroluminescent compound prepared from U 彳 1 is not shown in Table 1. For blue electroluminescent materials, 41 200844210 is very important in low-brightness and illuminating performance on the panel. Therefore, illuminating data of about 2,000 candelas per square meter is specially established as a standard to reflect illuminating performance. 0 [Table 1] No. EL Material I EL Material 2 EL Peak (nm) Luminous efficiency (cd/A) _ Color coordinate luminous efficiency / Υ @500 cd/m2 @2,000 cd/m2 X Υ 1 DNA IFl-l 451 3.67 2.89~~ _〇J55 0.137 26.8 2 DNA IF1-2 435 2.90 2.04— 0.151 0.092 ----—31.5 3 DNA IF1-3 435 3.0l 2.32 ^0.151 0.094 A 4 DNA IF1-4 438 2.95 2.20^ 0.151 0.093 ------- 31 7 5 DNA IF2-1 465 H.27 12.81 0.154 0.195 J 夏· / ------- 65.7 —6 DNA IF2-2 465 ll.7l \23~7~ ^0.166 0.202 ------- 61.2 7 DNA IF2-3 465 ΙΟ.33 12.8Τ~ 0.169 0.208 ' —--- 61 Q 8 DNA IF2-4 461 8.02 ΙΟ.90 0.158 0.192 56.8 9 DNA DFl-l 456 7.70 8.35 0.149 0.146 57 2~~ 10 DNA DF1-2 456 7.07 8.41 0.158 0.155 54 % 11 DNA DF1-3 455 6.73 7·81 0.147 0.128 61.〇~ 12 DNA IF3-1 453 6.61 6.76 0.155 0.132 51 2~ 13 DNA IF3-2 452 5.60 5.80 0.150 0.126 44 S 14 1 Strict DNA DF2-1 450 5.II 5.09 0.168 0.104 H · J ~4〇1~ 15 r L From hexa DNA ^ DF2-2 448 4.50 ^ 4.62 0.157 0.103 1 7 · i 44 R Comparing with the parent example I DNA 茈456, 484 4.45 3.62 0.160 0,200 22.3 As shown in Table 1, based on the "luminous efficiency / γ" similar to quantum efficiency, compare use

An organic electroluminescent compound is used as an OLED device for electroluminescent materials, and a 〇LED device using a well-known DNA (3 £) as a comparative example of a conventional electroluminescent material. As a result, it was revealed that the QLEDft of the organic electroluminescent compound of the present invention exhibited a higher "luminous efficiency / γ" value than the display device of the comparative example. In view of the fact that the organic electroluminescent compound of the present invention exhibits a high "luminous efficiency" value, the basic backbone of the organic electroluminescent compound of the present invention is a material having a quantum efficiency. Further, the organic electroluminescent compound of the present invention can achieve a higher efficiency and color purity of the phase 42 200844210 than the conventional electroluminescent compound. In particular, the "electroluminescence efficiency / Y" value of the IF2, DFl, and IF3 series is three times or more higher than that of the conventional electroluminescent compound. In general, it has been confirmed that a structure mainly comprising a bisstyrene-based double bond can significantly increase the efficiency. In the case where the chemical bond is formed by a double bond rather than the molecular structure in which only aromatics are attached, it is generally considered that the increase in performance is due to the improvement of the overlap between the individual aromatic rings in the molecular structure. As can be seen from Table 1, the "electroluminescence efficiency / Y" value of the compound of the present invention exhibits at least a 2-fold improvement in potency compared to the conventional materials, and this is derived from the present invention and the difluroene. The backbone significantly improves the effects of valuable performance. As described above, the organic electroluminescent compound of the present invention can be used as a high-efficiency blue electroluminescent material, and thus has a great advantage in brightness, power consumption, and lifetime as compared with the conventional full-color OLED. Fig. 1 is an electroluminescence spectrum using the IF2-1 of the present invention as an electroluminescent material and Comparative Example 1. Figures 2 through 4 show current density versus voltage performance, brightness versus voltage performance, and luminous efficiency versus current density performance for a 0 LED comprising the IF2-1 element of the present invention as an electroluminescent material. The organic electroluminescent compound of the present invention has high electroluminescence efficiency and extremely long life, and thus can be used for preparing an OLED having an extremely long operational life. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is an electroluminescence spectrum of an OLED using IF2-1 of the present invention as an electroluminescent material and an OLED of Comparative Example 1, and Fig. 2 is an IF2-1 using the present invention as an electric Current of the OLED of the luminescent material 43 200844210 t Curve of density versus voltage; Figure 3 is a plot of brightness variation versus operating voltage of OLED using IF2-1 of the invention as electroluminescent material; and Figure 4 A graph showing the change in electroluminescence efficiency versus current density of an OLED using the IF2-1 of the present invention as an electroluminescent material. [Main component symbol description] (none)

44

Claims (1)

200844210, Shenyi patent scope: "Machine-induced luminescent compounds, which are based on Chemical Formula 1 L1 匕学1] And R2 is independently an aromatic ring, or a fused group having two or more aromatic rings, and the R6 is independently a straight or branched Ci thiol or C5 to cs ring having or without a halogen substituent. An alkyl group, or an aromatic group with or without a halogen substituent; Rl1 to R14 are independently hydrogen, Cl to c8 alkyl, anthracene to cycloalkyl, or an aromatic group having or without an IS substituent; and Ari to &ι> is independently an aromatic ring or has two or more aromatic A fused polycyclic aromatic ring of the ring. 2. The organic electroluminescent compound according to claim 1, which is represented by one of the following Chemical Formulas 2 to 6: [Chemical Formula 2] 45 200844210 [Chemical Formula 3] [Chemical Formula 4] [Chemical Formula 5] [Chemical Formula 6] Wherein, Ri and 112 are independently aryl groups or fused polycyclic aromatic rings having two or more aromatic rings; R3 to R6 are independently straight or branched C! with or without halogen substituents; C2 alkyl, C5 to C8 cycloalkyl, or an aromatic group with or without a halogen substituent; 46 200844210 Pain R&quot; to R14 independently hydrogen, Ci to c8 alkyl, 〇5 to C8 Wei, or Or an aromatic group having no halogen substituent; and Ar, to Ar4 is independently an aromatic ring ' or a fused polycyclic aromatic ring having two or more aromatic rings. 3. The organic electroluminescent compound according to claim 2, wherein the chemical formulas 2 to 6 and R2 are selected from the group consisting of benzene, naphthalene, onion, naphthacene, fluorene, and Benzene; R3 to thiol, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, n-hexyl, n-heptyl, n-octyl , 2_ethylhexyl, n-decyl, trifluoromethyl, pentafluoroethyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, stupyl, indoleyl, n-naphthalene Base, 2-naphthyl, 2-fluorophenyl, or 4-fluorophenyl; Rn to R14 hydrogen, decyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, third Butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, phenyl, indolyl, indole naphthyl, 2-naphthyl , 2-fluorophenyl, or 4-fluorophenyl; and Ar! to Αι > phenyl, tolyl, xylyl, pyridinyl, biphenyl, naphthyl, anthryl, phenanthryl (phenanthryl), condensed tetraphenyl (naphthacenyl), sulfhydryl (acenaph) And an organic electroluminescent compound according to claim 3, which is selected from the group consisting of the compounds represented by the following chemical formula: 47 200844210 48 200844210 49 200844210 50 200844210 51 200844210 52 200844210 53 200844210 Wherein R3 to R6 are an anthracenyl group or an ethyl group, and R15 to R18 are an anthracenyl group, an ethyl group, or a phenyl group. An organic electroluminescent diode comprising an anode, a cathode, and an organic electroluminescent compound according to any one of claims 1 to 4 interposed between the anode and the cathode. 54