WO2007086701A1

WO2007086701A1 - Electroluminescent compounds comprising fluorene group and organic electroluminescent device using the same

Info

Publication number: WO2007086701A1
Application number: PCT/KR2007/000456
Authority: WO
Inventors: Il Won Choi; Chi Sik Kim; Hyo Nim Shin; Mi Ae Lee; Hwan Seung Shin; Mi Young Kwak; Hyuck Joo Kwon; Young Jun Cho; Nam Kyun Kim; Jung Su Baek; Bong Ok Kim; Sung Min Kim
Original assignee: Gracel Display Inc.
Priority date: 2006-01-27
Filing date: 2007-01-26
Publication date: 2007-08-02
Also published as: JP2009524701A; TWI340760B; KR100812178B1; JP5259426B2; CN101405365A; TW200732453A; EP1981951A4; KR20070078698A; EP1981951A1; CN101405365B

Abstract

The present invention relates to organic electroluminescent compounds represented by Chemical Formula 1 and an electroluminescent device comprising the compound in an electroluminescent layer. The electroluminescent compound according to the invention has good luminous efficiency and excellent lifetime of the material, so that an OLED device having very good operation lifetime can be prepared.

Description

ELECTROLUMINESCENT COMPOUNDS COMPMSING

Technical Field

[1] The present invention relates to an electroluminescent compound comprised of blue electroluminescent materials, which show excellent luminous property with high effi- άencyand excellent lifetime, and electroluminescent devices oomprising the same in the electroluminescent layer. Background Art

[2] Among display devices, electroluminescence (EL) devices, being self-luminous type display devices, have advantages of wide visual angle, excellent contrast as well as rapid re -oonse rate. Eastman Kodak firstly developed an organic EL device employing low molecular aromatic diamine and aluminum complex as a substance for forming an electroluminescent layer, in 1987 [Appl. Phys. Lett. 51, 913, 1987].

[3] The most important factor to determine luminous efficiency, lifetime or the lite in an organic EL device is electroluminescent material. Several properties required for such electroluminescent materials include that the material should have high fluorescent proton yield in solid state and high mobility of electrons and holes, is not easily decomposed during vapor-deposition in vacuo, and forms uniform and stable thin film.

[4] Organic electroluminescent materials can be generally classified into high- molecular materials and low-molecular materials. The low-molecular materials include metal complexes and purely organic electroluminescent materials which do not contain metal, from the aspect of molecular structure. Such electroluminescent materials include chelate complexes such as tris(8-quinolinolato)aluminum complexes, coumarin derivatives, tetraphenylbutadiene derivatives, bis(styrylarylene) derivatives, oxadia-ole derivatives. From those materials, it is reported that light emission of visible region from blue to red can be obtained, so that the realization of colored display device ϊs expected.

[5] In the meanwhile, for blue materials, a number of materials have been developed and commercialized since the development of DPYBi (Chemical Formula a) by Idemitsu-Kosan. In addition to the blue material system from Idemitsu-Kosan, dinaph- thylanthracene (Chemical Formula b), tetra(t-butyl)perylene (Chemical Formula c) system or the like have been known. Ebwever, extensive research and development should be performed with respect to these materials. The distrylcompound system of Idemitsu-Kosan, which is known to have highest efficiency up to now, has 6 ImAV of power efficiency and beneficial device lifetime of more than 30,000 hr. However, when it is applied to a full-color display, owing to the reduction of color purity over driving time, the lifetime is merely several thousand hours. In case of blue light, it becomes advantageous from the aspect of the luminous efficiency, if the light emitting wavelength is shifted a little toward longer wavelength. However, it is not easy to apply the material to a display of high quality because of unsatisfaDtory pure blue color. In addition, the research and development of such materials are urgent because of the problems in color purity, efficiency and thermal stability.

[6] [Chemical Formula a]

[7]

[8] [Chemical Formula b]

[9]

[10] [Chemical Formula c]

[H]

[12]

Disclosure of Invention Technical Problem [13] The object of the invention is to overcome and make up for the problems of those blue materials as described above, and provide electroluminescent compounds having improved luminous efficiency and lifetime of the device. Another object of the invention is to provide organic EL devices employing said electroluminescent compounds as electroluminescent material, which have high efficiency and long lifetime. Technical Solution

[14] The present inventors have made efforts in order to solve the problems of prior art as described above, and invented novelelectroluminescent compounds to realize an organic EL device having excellent luminous efficiency and noticeably improved life time.

[15] Thus, the present invention provides novel electroluminescent materials and electroluminescent devices containing said electroluminescent materialsin the electroluminescent layer. Specifically, the electroluminescent materials according to the present invention are characterized in that they are represented by following Chemical Formula 1:

[16] [Chemical Formula 1] [17]

[18] In Chemical Formula 1, Ar is a chemical bond or selected from indenofluorene, fluorene and spiro-fluorene as represented by following chemical formulas, Ar is selected from indenofluorene, fluorine andspiro-fluorene as represented by following chemical formulas:

[19]

[20] A and B independently represent a .chemical bond, or are selected from phenylene group, naphthylene group, biphenylene group, anthraoenyl group, perylenylene group or pyrenylene group,but the compounds wherein both A and Ar are chemical bonds are excluded.

[21] R through R are independently selected from C ~C alkyl, cycloalkyl, C ~C

1 20 1 20 alkyl having one or more halogen substituent(s), and phenyl or naphthyl having C -C alkyl substituent(s), more preferably R through R are independently selected from C ~C alkyl, C -C cycloalkyl, phenyl and naphthyl, and said halogen is selected from F,

1 ή

Cl and Br. Specifically, R through R are exemplified as methyl, ethyl, propyl, butyl, amyl, cyclopentyl, cyclohexyl, phenyl and naphthyl.

[22] Ar through Ar are independently! selected from C ~C aromatic or multicyclic aromatic ring, and the aromatic ring may contain hetero atom(s). [23] Preferably, Ar through Ar independently represent phenyl, tolyl, xylyl, pyridyl,

3 6 biphenyl, naphthyl, anthryl, phenanthryl, pyrenyl, naphthacenyl, acenaphthyl, perylenyl, chrysenyl, fluoranthenyl with or without alkyl (R IU ) substituent(s), wherein

,π .

R is selected from C ~C alkyl group, and n is an integer from 1 to 5.

[24]

[25] The electroluminescentoompounds represented by Chemical Formula 1 according to the present invention are specifically exemplified by following compounds: [26]

[29] DSF-I

[30]

[31] DPF-I [32]

[35] DIF-2 [36]

[37] DSF-2 [38]

[39] DPF-2 [40]

[41] DMF-2 [42]

[45] DSF-3 [46]

[47] DPF-3 [48]

[49] DMF-3

[50]

[51] DTIPIF-I [52]

[55] DSF-4 [56]

[57] DPF-4 [58]

[59] DMF-4 [60]

[72]

[77] DMF-21 [78] Among the electroluminescent compounds represented by Chemical Formula (1) according to the present invention, the compounds wherein Ar is same as Ar , Ar is

1 2 3 same as Ar , Ar is same as Ar , and A is same as B, that is symmetrical on the basis of

5 4 6 the double bond, can be prepared by coupling 2 moles of aldehyde compound via MacMurry reaction, as illustrated by Reaction Scheme 1:

[79] [Reaction Scheme 1] [80]

Ar_3χ O Ar_3v .Ar₃

N-A-Ar₁-CH !N-A-Ar₁-C=C-Ar₁-A-N;

Ar/ Ar₄' / 'Ar₄

2

[81] Among the compounds of Chemical Formula (1), asymmetrical compounds can be prepared by reducing and halogenating the aldehyde compound of Chemical Formula (3) to obtain the compound of Chemical Formula (4), which is then coupled with the compound of Chemical Formula (2) via Wittig reaction or Wadsworth- Hbrner-Emmons reaction (a modification of Wittig reaction).

[82] [Reaction Scheme 2] [83]

[84] [In the Reaction Scheme (2), Ar through Ar , and A and B are defined as above,

1 6 and X represents halogen, Cl or Br.]

[85] The compound represented by Chemical Formula 2, an important intermediate to prepare the compound according to the invention can be prepared by substituting the dibromoaryl compound with butyl lithium and reacting the product with DMF to prepare dibromoaldehyde compound, which is then subjected to substitution by a secondary amine in the presence of a catalyst, as illustrated by Reaction Scheme 3:

[86] [Reaction Scheme 3]

[87]

[88] The preparation of the compounds aooording to the present invention or intermediates thereof is not restricted to the reactions expressed by the Reaction Schemes described above, but a person having ordinary skill in the art may prepare the compounds by adopting known reactions in organic chemistry.

[89] In addition, the present invention provides an electroluminescent device comprising the electroluminescent represented by Chemical Formula (1) in the electroluminescent layer. More specifically, the invention provides an electroluminescent device employing the electroluminescent compound of Chemical Formula (1) according to the invention as a dopant together with a conventional host material in the electroluminescent layer. Brief Description of the Drawings

[90] Fig. 1 is a schematic view showing cross-sectional structure of the OLED devices of Example 1 and Comparative Example 1;

[91] Fig. 2 shows EL spectrums of Example 1 and Comparative Example 1;

[92] Fig. 3 is a curve showing luminance property versus driving voltage of the OLED aooording to Example 1;

[93] Fig. 4 is a curve showing current density property versus driving voltage of the

OLED of Example 1; and [94] Fig. 5 is a curve showing luminous efficiency property versus luminance of the

OLED device of Example 1. Mode for the Invention

[95] The present invention is further described with respect to the novel electroluminescent compounds according to the invention, a process for preparing the same and the electroluminescent properties of the device employing the same by referring to representative compounds according to the present invention, which are provided for illustration only but are not intended to be restrictive in any way.

[96] [Synthetic Example 1] Preparation of DEF-I (Compound 1201

[97]

[98] Preparation of Compound (112)

[99] Compound (111), 1,4-dibromo-p-xylene (200 g, 0.76 mol) and phenyl boronic add

(204 g, 1.67 mol), Pd(OAc) (0.34 g, 1.52 mmol), potassium carbonate (524 g, 3.79 mol) and n-Bu NBr (490 g, 1.51 mol) were suspended in 1.9 L of distilled water, and

4 the suspension was stirred at 70°Cfor 24 hours. After the reaction was completed, 2 L of distilled water was added to the reaction mixture, and the solid produced was filtered under reduced pressure, to obtain Compound (112) (196 g, 0.76 mol) as gray solid.

[100] Preparation of Compound (113)

[101] Gbmpound (112) (196 g, 0.76 mol) was dissolved in pyridine (1.23 L, 15.17 mol) and H O (2 L), and KMnO (420 g, 2.66 mol) was slowly added to the reaction

2 4 solution by ten portions, and the resultant mixture was heated under reflux for 48 hours. [102] Distilled water (5 L, at 50⁰C was added thereto, and the solid by-product was filtered off under reduced pressure. Addition of 35% HCl (3L) gave Gbmpound (113) (174 g, 0.55 mol) as white solid. [103] Preparation of Cbmpound (114)

[104] Gbmpound (113) thus prepared (174 g, 0.55 mol) was added to concentrated sulfuric add (1.8 L), and the mixture was stirred at 25⁰Cf or 4 hours.

[105] After completionof the reaction, ice water (6 L) was added, and the resultant mixture was stirred for 1 hour, and filtered under reduced pressure to obtain solid. To the solid, added was a solution of potassium carbonate (200 g) dissolved in distilled water (5 L). The resultant mixture was stirred for 1 hour and filtered under reduced pressure to obtain Cbmpound (114) (120 g, 0.43 mol) as purple solid.

[106] Preparation of Cbmpound Cl 15)

[107] Cbmpound (114) thus prepared (120,g, 0.43 mol) was dissolved in diethylene glycol (1.4 L), and potassium hydroxide (240 g, 4.25 mol) and hydraane hydrate (207 mL, 4.25 mol) were added thereto. The resultant mixture was stirred at 220°Cfor 48 hours.

[108] After cooling to ambient temperature, 20% hydrochloric acid solution (4 L) was added, and the mixture was stirred for 1 hour. Solid was obtained from the mixture by filtration under reduced pressure. To the solid, acetone and tetrahydrofurane (2 L, each) were added, and the mixture was stirred for 20 hours. Filtration under reduced pressure and drying gave Cbmpound (115), also referred to as indenofluorene (85 g, 0.34 mol, yield: 79%), as gray solid.

[109] Preparation of Cbmpound (116)

[110] To the solution of Cbmpound (115) (5.2 g, 20.5 mmol) dissolved in tetrahydrofuran (50 mL), n-BuLi (1.6 M in n-hexane) (29.4 mL, 47.0 mmol) was slowly added dropwise at -78⁰C After 1 hour of reaction, iodomethane (7.55 mL, 53.2 mmol) was added therto, and the temperature was ,slowly raised to ambient temperature. Stirring was continued at the same temperature for, 1 hour. Again, the temperature of the reaction mixture was dropped to -78°C n-BuLi (1.6 M in n-hexane) (37.1 mL, 59.3 mmol) was slowly added dropwise to the mixture. Afterl hour of reaction, iodomethane (7.55 mL, 53.2 mmol) was added therto, and the temperature was slowly raised to ambient temperature. Stirring was continued at the same temperature for 15 hour.Then, aqueous ammonium chloride solution (20 mL) and distilled water (15 mL) were added to quench the reaction. After removal of organic layer under reduced pressure, and recrystallization from n-hexane (100 mL), Cbmpound (116) (1.7 g, 5.48 mmol) was obtained.

[Ill] Preparation of Cbmpound Cl 17)

[112] Cbmpound (116) (1.7 g, 4.64 mmol) and FeCB (11.3 mg, 0.07 mmol) were dissolved in 30 tnL of chloroform, and the temperature of the mixture was adjusted to 0°Cby using an ice-bath. Bromine (0.72 ml, 13.9 mmol) dissolved in 5 mL of chloroform was slowly added dropwise thereto, and the mixture was stirred for 24 hours. After the reaction was completed, the reaction was quenched by saturated aqueous sodium thiosulfate solution (5OmL). The reaction mixture was separated, and the organic layer was removed under reduced pressure, and recrystallized from n- hexane (100 mL) to give Compound (117) (1.6 g, 3.42 mmol).

[113] Preparation of Compound (118)

[114] Compound (117) thus obtained (1.6 g, 3.42 mmol) was dissolved in tetrahydrofuran (40 mL), and n-BuLi(1.6 M in n-hexane)(4.8 mL, 3.0 mmol) was slowly added dropwise thereto at -78°C After stirring the reaction mixture for 30 minutes, N,N-dimethylformamide(0.3 mL, 4.14 mmol) was added thereto. Stirring was continued while slowly raising the temperature for 2 hours, and the reaction was quenched by adding aqueous NH Cl solution (20 mL) and distilled water (20 mL). The

4 organic layerwas separated, removed under reduced pressure, and recrystallized from 100 mL of methanol :n-hexane (1/1, vV) to obtain Compound (118) (1.1 g, 2.64 mmol).

[115] Preparation of Compound (119)

[116] The aldehyde compound (118) thus obtained (1.1 g, 2.6 mmol), diphenylamine (0.67 g, 4.0 mmol), cesium carbonate (1.29 g, 3.96 mmol) and palladium acetate (Pd(OAc) ) (18 mg, 0.08 mmol) were suspended in 100 mL of toluene. To the suspension, tri(t-butyl) phosphine (P(t-Bu) )(32 mg, 0.16 mmol) was added, and the mixture was stirred at 120°Cor 4 hours. Saturated aqueous ammonium chloride solution (30 mL) was added thereto, and the mixture was extracted with ethyl acetate (50 mL), filtered, and recrystallized from methanobn-hexane (1/1, vv) (50 mL) to obtain Compound (119) (1.2 g, 2.4 mmol).

[117] Preparation of Compound (120)

[118] Zinc dust (6.0 g, 92.4 mmol), TiCl (31 mL, 30.8 mmol) and tetrahydrofuran (26

4 mL) were stirred at -10°Cunder argon atmosphere. After 4 hours, Compound (119) (1.2 g, 2.4 mmol) was added thereto, and the mixture was stirred for 24 hours. After adding 30 mL of distilled water, the mixture was stirred for 1 hour, and filtered under reduced pressure. Then, acetone (30 mL) and dichloromethane (30 mL) were added, and the mixture was stirred and filtered under reduced pressure. To the solid produced, added was N,N-dimethylformamide (50 mL), and the resultant mixture was heated under reflux with stirring for 2 hours, filtered under reduced pressure, and dried to obtain Gbmpound (120, DIF-I) (0.93 g, 0.95 mmol, yield on the basis of Gbmpound (118): 72%) as yellow solid.

[119] ¹H NMR(CDCl , 200 MHz) : δl.67(s, 24H), 6.46(m, 8H), 6.61-6.62(m, 6H), 6.78(m, 2H), 6.99-7.01(m, 10H), 7.57(m, 2H), 7.70-7.74(m, 8H), 7.95(m, 2H)

[120] MSTFAB : 978(found) 979.30(calculated) [121] [Synthetic Example 2] Preparation of DSF- 1 (Compound 125) [122]

[123] Preparation of Compounds (121) and (122) [124] To 2-bromobiphenyl (6.27 g, 26.9 mmol) and magnesium powder (0.68 g, 28.2 mmol), diethyl ether (5 mL) was added, and the mixture was heated under reflux with stirring for 3 hours. To 2,7-dibromofluorenone (10 g, 29.6 mmol), diethyl ether solvent (5 mL) was added, and, after stirring, the mixture was slowly added to the reaction mixture. After stirring at 25°Cfor 24 hours, saturated aqueous ammonium chloride solution (50 mL) was placed in an ice-bath. After stirring for 1 hour, it was filtered, washed with 100 mL of distilled water, and filtered under reduced pressure to obtain crude Gbmpound (121), which was added to glacial acetic acid (40 mL) and heated under reflux for 2 hours. To the reaction solution, 30% hydrochloric acid solution (40 mL) was slowly added to form solid, which was then filtered under reduced pressure, washed with 100 mL of distilled water, recrylstallized from 50 mL of methanol, and dried under reduced pressure to obtain Gbmpound (122) (9.8 g, 20.7 mmol).

[125] Preparation of Gbmpound (123) [126] Gbmpound (123) was obtained according to the same synthetic procedure as for Gbmpound (118). Reaction was carried out by using Gbmpound (122) prepared as above (9.8 g, 20.7 mmol), tetrahydrofuran (40 mL), n-BuLi (1.6 M in n-hexane) (33.6 mL, 21 mmol) and N,N-dimethylformamide (2.1 mL, 29.0 mmol). Recrystallization from 30 mL of methanol and 30 mL of , n-hexane gave Gbmpound 123 (5.23 g, 12.36 mmol).

[127] Preparation of Gbmpound (124") [128] Gbmpound (124) was obtained according to the same synthetic procedure as for Compound (119). Reaction was carried out by using the aldehyde compound (123) prepared as above (5.23 g, 12.4 mmol), diphenylamine (3.14 g, 18.5 mmol), cesium carbonate (6.04 g, 18.5 mmol), Pd(OAc) (83 mg, 0.37 mmol), toluene (200 mL),

2

P(t-Bu) (150 mg, 0.74 mmol). Recrystallization from 100 mL of methanol:n-hexane (1/1, φ) gave Compound 124 (3.8 g, 7.4 mmol).

[129] Preparation of Compound (125) [130] Compound (125) was obtained according to the same synthetic procedure as for Compound (120). By using anc dust (4.85 g, 74.2 mmol), TiCl (IM solution in

4 dichloromethane) (30 mL, 29.7 mmol), tetrahydrofuran (26 mL) and Compound (124) (3.8 g, 7.4 mmol), Compound (125, DSF-I) (2.4 g, 2.4 mmol, yield on the basis of Compound (123): 39%) was obtained as white powder.

[131] ¹H NMR(CDCl , 200 MHz) : δ6.46(m, 8H), 6.58-6.62(m, 6H), 7.35(d, 2H), 6.99-7.01(m, 10H), 7.16-7.19(m, 8H), 7.35(m, 4H), 7.54-7.59(m, 4H), 7,71-7.72(m, 6H), 7.84(d, 2H)

[132] MSTFAB : 990(found) 991.22(calculated) [133] [Synthetic Example 3] Preparation of DPF-I (Compound 130) [134]

[135] Preparation of Compounds (126) and (127) [136] Diethyl ether (50 mL) was added to magnesium (4.9 g, 0.20 mol), and a solution of bromobenzene (31.4 g, 0.20 mmol) dissolved in 150 mL of diethyl ether was slowly added dropwise thereto. After heating the reaction mixture under reflux for 3 hours, a solution of 2,7-dibromofluorene (33.8 g, 0.10 mol) dissolved in 40 mL of diethyl ether was slowly added dropwise to the reaction mixture, which was then heated under reflux for 12 hours.

[137] After the reaction was completed, the precipitate generated was filtered under reduced pressure to obtain Compound (126) (41.5 g, 0.10 mmol). Compound (126) was dissolved in 145 mL of benzene, and trifluoromethanesulfonic add (45 mL) was slowly added dropwise thereto, while raising the temperature slowly. After stirring the mixture at 100°Cor 30 minutes, the reaction solution was added to ice-water to generate solid. The solid generated was filtered under reduced pressure, washed with 50 mL of methanol and 100 mL of diethyl ether, and dried under reduced pressure to obtain Compound (127) (27.1 g, 57.0 mmol) as pale yellow solid.

[138] Preparation of Gbmpo und (128)

[139] Compound (128) was obtained according to the same synthetic procedure as for Compound (118). By using Compound (127) (27.1 g, 56.9 mmol), tetrahydrofuran (120 mL), n-BuLi (1.6 M in n-hexane) (35.6 mL, 56.9 mmol) and N,N-dimethylformamide (6.2 mL, 79.7 mmol), Compound (128) (12.1 g, 28.4 mmol) was obtained.

[140] Preparation of Compound (129)

[141] Compound (129) was obtained according to the the same synthetic procedure as for Compound (119). By using the aldehyde compound (128) (12.1 g, 28.4 mmol), diphenylamine (7.3 g, 42.6 mmol), cesium carbonate (13.9 g, 42.6 mmol), Pd(OAc) (192 mg, 0.85 mmol), toluene (600 mL) and P(t-Bu) (347 mg, 1.7 mmol), Compound (129) (8.8 g, 17.1 mmol) was obtained.

[142] Preparation of Compound (130)

[143] Compound (130) was obtained according to the same synthetic procedure as for Compound (120). By using anc dust (11.2 g, 171 mmol), TiC14 (1 M solution in dichloromethane) (69 mL, 68.4 mmol), tetrahydrofuran (60 mL) and Compound (124)(8.8 g, 17.1 mmol), Compound (130, DSF-I) (5.6 g, 5.1 mmol, yield on the basis of Compound (128): 35%) was obtained as white solid.

[144] ¹H NMR(CDCl , 200 MHz) : δ6.46(m, 8H), 6.58-6.62(m, 6H), 6.75(d, 2H), 6.99-7.17(m, 30H), 7.54-7.59(m, 4H), 7.7 l(d, 2H), 7.84(m, 2H)

[145] M^FAB : 994(found) 995.26(calculated)

[146] [Synthetic Example 4] Preparation of DMF-I (Compound 134)

[147]

^Br-C^£>^{βr Br}^3^£)-^Br — ^■ — - ^a-Q→Q-^?H

[148] Preparation of Compound (131)

[149] Under nitrogen atmosphere, 2,7-dibromofluorene (50.0 g, 154.3 mmol) and potassium hydroxide (69.2 g, 1.23 mol) were dissolved in 700 mL of DMSO. The solution was chilled to 0⁰C and distilled water (113 mL) was slowly added dropwise thereto, and the resultant mixture was stirred for 1 hour. Then, iodomethane (CH J) (38.5 mL, 0.617 mol) was slowly added, and the resultant mixture was slowly warmed to ambient temperature, and stirred at the temperature for 15 hours. The reaction was quenched by adding 200 mL of distilled water to the reaction solution, and the reaction mixture was extracted with 300 mL of dichloromethane. The organic layer obtained was concentrated under reduced pressure, and purified by silica gel column chromatography (eluent: n-hexane:dichloromethane = 20:1) to obtain Compound (131) (53.O g, 0.15 mol).

[150] Preparation of Compound (132)

[151] Compound (132) was obtained aooording to the same synthetic procedure as for

Compound (118). By using Compound (131) (53.0 g, 0.15 mol), tetrahydrofuran (350 mL), n-BuLi (1.6 M in n-hexane) (63.2 mL, 158 mmol) and N,N-dimethylformamide (16.3 mL, 211 mmol), Compound (132) (20.9 g, 69.4 mmol) was obtained.

[152] Preparation of Compound (133)

[153] Compound (133) was obtained according to the same synthetic procedure as for Compound (119). By using the aldehyde compound (132) (20.9 g, 69.4 mmol), diphenylamine (12.5 g, 104.1 mmol), cesium carbonate (24.1 g, 104.1 mmol), Pd(OAc) (332 mg, 2.1 mmol), toluene (800 mL) and P(t-Bu) (0.60 g, 4.2 mmol), Compound (133) (15.2 g, 39.0 mmol) ₍w,as obtained.

[154] Preparation of Compound (134)

[155] Compound (134) was obtained aooording to the same synthetic procedure as for

Compound (120). By using anc dust (19.4 g, 390 mmol), TiCl (1 M solution in

4 dichloromethane) (120 mL, 156 mmol), tetrahydrofuran (104 mL) and Compound 133

(15.2 g, 39.0 mmol), Compound (134, DMF-I) (9.7 g, 12.9 mmol, yield on the basis of

Compound (132): 37%) was obtained as white solid. [156] ¹H NMR(CDCl , 200 MHz) : δl.67(s, 12H), 6.46(m, 8H), 6.58-6.62(m, 6H),

6.75(d, 2H), 6.99-7.01(m, 10H), 7.54-7.59(m, 4H), 7.71(d, 2H), 7.84(m, 2H) [157] MSFAB : 745(found) 746.98 (calculated) [158] [Synthetic Example 5] Preparation of DIF-2 (Compound 136)

[159]

[160] Preparation of Cbmpound (1351

[161] Gbmpound (135) was obtained axording to the same synthetic procedure as for

Compound (119). By using the aldehyde compound (118) (3.0 g, 7.2 mmol), N- phenylnaphthalene-2-amine (3.5 g, 10.8 mmol), cesium carbonate (1.3 g, 10.8 mmol), Pd(OAc) (48 mg, 0.22 mmol), toluene (100 mL) and P(t-Bu) (87 mg, 0.43 mmol), Gbmpound (135) (2.8 g, 5.0 mmol) was obtained.

[162] Preparation of Cbmpound (136)

[163] Cbmpound (136) was obtained according to the same synthetic procedure as for

Cbmpound (120). By using znc dust (4.0 g, 60.4 mmol), TiCl (1 M in

4 dichloromethane) (21 mL, 20.1 mmol), tetrahydrofuran (50 mL) and Gbmpound 135 (2.8 g, 5.0 mmol), Cbmpound (136, DIF-2) (2.3 g, 2.1 mmol, yield: 58%) was obtained as yellow solid. [164] ¹H NMR(CDCl , 200 MHz) : δ 1.67(s, 24H), 6.46(m, 4H), 6.61-6.62(m, 4H),

3

6.76-6.78(m, 6H), 6.99-7.09(m, 8H), 7.23(m, 2H), 7.44-7.55(m, 8H), 7.70-7.74(m,

8H), 7.95(m, 2H)

[165] MST⁷AB : 1078(found) 1079.41(calculated)

[166] [Synthetic Example 6] Preparation of DSF-2 f Cbmpound 138)

[167]

[168] Preparation of Gbmpound (1371

[169] Gbmpound (137) was obtained according to the same synthetic procedure as for

Gbmpound (119). By using the aldehyde compound (123) (6.8 g, 16.0 mmol), N- phenylnaphthalene-2-amine (5.3 g, 24.0 mmol), cesium carbonate (7.8 g, 24.1 mmol), Pd(OAc) (107 mg, 0.48 mmol), toluene (150 mL) and P(t-Bu) (194 mg, 0.96 mmol), z 3

Gbmpound (137) (7.5 g, 13.3 mmol) was obtained. [170] Preparation of Gbmpound α381

[171] Gbmpound (138) was obtained according to the same synthetic procedure as for

Gbmpound (120). By using anc dust (8.7 g, 133 mmol), TiCl (1 M solution in

4 dichloromethane) (53 mL, 53.2 mmol), tetrahydrofuran (65 mL) and Gbmpound 137 (7.5 g, 13.3 mmol), Gbmpound (138, DSF-2) (8.1 g, 7.5 mmol, yield: 93%) was obtained as pale gray solid. [172] ¹H NMR(CDCl 200 MHz) : δ6Λp(m, 4H), 6.58-6.62(m, 4H), 6.75-6.79(m, 6H), 6.99-7.23(m, 18H), 7.7 l(m, 4H), 7.44-7.59(m, 10H), 7.71-7.72(m, 6H), 7.84(m, 2H) [173] MSFAB : 1090(found) 1091.34(calculated) [174] [Synthetic Example 7] Preparation of DPF-2 (Compound 140)

[175]

[176] Preparation of Compound (139)

[177] Compound (139) was obtained according to the same synthetic procedure as for

Compound (119). By using the aldehyde compound (128) (6.8 g, 16.0 mmol), N- phenylnaphthalene-2-amine (5.3 g, 24.0 mmol), cesium carbonate (7.8 g, 24.1 mmol), Pd(OAc) (107 mg, 0.48 mmol), toluene (150 mL) and P(t-Bu) (194 mg, 0.96 mmol), Compound (139) (7.5 g, 13.3 mmol) was obtained.

[178] Preparation of Compound (140)

[179] Compound (140) was obtained according to the same synthetic procedure as for Compound (120). By using anc dust (8.7 g, 133 mmol), TiCl (1 M solution in

4 dichloromethane) (53 mL, 53.2 mmol), tetrahydrofuran (65 mL) and Compound 139

(7.48 g, 13.3 mmol), Compound (140, DPF-2) (8.1 g, 7.5 mmol, yield: 93%) was obtained as pale gray solid. [180] ¹H NMR(CDCl 200 MHz) : δ 6.46(m, 4H), 6.58-6.62(m, 4H), 6.75-6.79(m, 6H),

6.99-7.23(m, 30H), 7.44-7.59(m, 10H), 7.06(m, 2H), 7.84(m, 2H) [181] MSTAB : 1096(found) 1095.37(calculated)

[182] [Synthetic Example 8] Preparation of DMF-2 (Compound 142)

[183]

[184] Preparation of Compound (141)

[185] Compound (141) was obtained according to the same synthetic procedure as for Compound (119). By using the aldehyde compound (132) (5.3 g, 17.5 mmol), N- phenylnaphthalene-2-amine (4.1 g, 26.3 mmol), cesium carbonate (6.1 g, 26.3 mmol), Pd(OAc) (84 mg, 0.52 mmol), toluene (117 mL) and P(t-Bu) (152 mg, 1.1 mmol), Compound (141) (5.8 g, 13.2 mmol) was obtained.

[186] Preparation of Compound (142) [187] Cbmpound (142) was obtained according to the same synthetic procedure as for Gbmpound (120). By using znc dust (6.7 g, 68.0 mmol), TiCl (1 M solution in

4 dichloromethane) (41 mL, 27.2 mmol), tetrahydrofuran (50 mL) and Gbmpound 139

(5.8 g, 6.8 mmol), Cbmpound (142, DMF-2) (6.3 g, 7.4 mmol, yield: 84%) was obtained as pale gray solid. [188] ¹H NMR(CDCl , 200 MHz) : δ 1.67(s, 12H), 6.46-6.62(m, 8H), 6.76-6.79(m, 6H),

6.99-7.09(m, 8H), 7.23(m, 2H), 7.44-7.59(m, 10H), 7.7 l(m, 2H), 7.84(m, 2H) [189] MSTFAB : 846(found) 847.10(calculated) [190] [Synthetic Example 9] Preparation of DIF-3 CCbmpound 144)

[191]

[192] Preparation of Cbmpound (143)

[193] Cbmpound (143) was obtained according to the same synthetic procedure as for Cbmpound (119). By using the aldehyde oompound (118) (5.0 g, 12.0 mmol), di(naphthalene-3-yl)amine (4.8 g, 18.0 mmol), cesium carbonate (5.9 g, 18.0 mmol), Pd(OAc) (81 mg, 0.36 mmol), toluene (90 mL) and P(t-Bu) (145 mg, 0.72 mmol), Cbmpound (143) (5.7 g, 9.5 mmol) was obtained.

[194] Preparation of Cbmpound (144)

[195] Cbmpound (144) was obtained according to the same synthetic procedure as for

Cbmpound (120). By using anc dust (7.4 g, 0.11 mol), TiCl (1 M in dichloromethane)

4

(38 mL, 38 mmol), tetrahydrofuran (75 mL) and Cbmpound (143) (5.7 g, 9.5 mmol), Cbmpound (144, DIF-3) (4.0 g, 3.4 mmol, yield: 57%) was obtained as yellow solid.

[196] ¹H NMR(CDCl , 200 MHz) : δl.67(s, 24H), 6.61-6.79(m, 12H), 6.99(d, 2H),

7.09-7.23(m, 8H), 7.44-7.57(m, 14H), 7.70-7.74(m, 8H), 7.95(m, 2H)

[197] MST⁷AB : 1178(found) 1179.53(calculated)

[198] [Synthetic Example 10] Preparation of DSF-3 f Cbmpound 146)

[199]

[200] Preparation of Cbmpound (145) [201] Compound (145) was obtained aaoording to the same synthetic procedure as for

Compound (119). By using the spiro-type aldehyde compound (123) (5.9 g, 13.9 mmol), di(naphthalene-3-yl)amine (4.8 g, 18.0 mmol), cesium carbonate (6.8 g, 20.9 mmol), Pd(OAc)₂ (93 mg, 0.42 mmo%. toluene (90 mL) and P(t-Bu) (169 mg, 0.84 mmol), Compound (145) (6.6 g, 10.7 mmol) was obtained.

[202] Preparation of Compound ( 146)

[203] Compound (146) was obtained according to the same synthetic procedure as for

Compound (120). By using anc dust (7.Og, 0.11 mol), TiCl (1 M solution in

4 dichloromethane) (43 mL, 43 mmol), tetrahydrofuran (65 mL) and Compound 145 (6.6 g, 10.7 mmol), Compound (146, DSF-3) (7.0 g, 5.9 mmol, yield: 84%) was obtained as gray solid. [204] ¹H NMR(CDCl , 200 MHz) : δ 6.58(m, 2H), 6.75-6.79(m, 10H), 6.99(s, 2H),

3

7.09-7.23(m, 16H), 7.35-7.55(m, 20H), 7.71-7.72(m, 6H), 7.84(m, 2H) [205] MSFAB : 1190(found) 1191.46(calculated)

[206] rSvnthetic Example 11] Preparation of DPF-3 (Compound 148)

[207]

[208] Preparation of Compound (147)

[209] Compound (147) was obtained according to the same synthetic procedure as for

Compound (119). By using the spiro-type aldehyde compound (128) (4.3 g, 10.1 mmol), di(naphthalene-3-yl)amine (3.5 g, 15.2 mmol), cesium carbonate (5.0 g, 15.2 mmol), Pd(OAc) (68 mg, 0.30 mmol), toluene (66 mL) and P(t-Bu) (123 mg, 0.61

2 3 mmol), Compound (147) (4.8 g, 7.8 mmol) was obtained. [210] Preparation of Compound (148)

[211] Compound (148) was obtained according to the same synthetic procedure as for

Compound (120). By using anc dust (5.1 g, 78.0 mmol), TiCl (1 M solution in

4 dichloromethane) (31 mL, 31.2 mmol), tetrahydrofuran (47 mL) and Compound (147)

(4.8 g, 7.8 mmol), Compound (148, DPF-3) (5.1 g, 4.2 mmol, yield: 83%) was obtained as gray solid. [212] ¹H NMR(CDCl , 200 MHz) : δ6.58(m, 2H), 6.75-6.79(m, 10H), 6.99-7.23(m, 30H),

7.44-7.55(m, 16H), 7.71-7.84(m, 4H) [213] MSTFAB : 1194(found) 1195.49(calculated) [214] [Synthetic Example 12] Preparation of DMF-3 (Compound 1501 [215]

[216] Preparation of Compound 049) [217] Compound (149) was obtained according to the same synthetic procedure as for Compound (119). By using the spiro-type aldehyde compound (132) (5.6 g, 18.5mmol), di(naphthalene-3-yl)amine (4.6 g, 27.8 mmol), cesium carbonate (6.5 g, 27.8 mmol), Pd(OAc) (89 mg, 0.56 mmol), toluene (86 iriL) and P(t-Bu) (160 mg,

1.11 mmol), Compound (149) (6.3 g, 12.8 mmol) was obtained.

[218] Preparation of Compound (150) [219] Compound (150) was obtained according to the same synthetic procedure as for Compound (120). By using anc dust (6.7 g, 0.128 mol), TiCl (1 M solution in

4 dichloromethane) (41 mL, 51.2 mmol), tetrahydrofuran (62 mL) and Compound (149) (6.3 g, 12.8 mmol), Compound (150, DMF-3) (7.5 g, 7.9 mmol, yield: 85%) was obtained as gray solid.

[220] ¹H NMR(CDCl , 200 MHz) : δ 1.67(s, 12H), 6.58(m, 2H), 6.75-6.79(m, 10H), 6.99(s, 2H), 7.09-7.23(m, 8H), 7.44-7.55(m, 16H), 7.7 l(m, 2H), 7.84(m, 2H)

[221] MSTFAB : 946(found) 947.21(calculated) [222] [Synthetic Example 13] Preparation of DTPIF-I (Compound 155) [223]

[224] Preparation of Compound (151) [225] Diethyl ether (59 mL) was added to magnesium (5.8 g, 0.283 mol), and bro- mobenzene (37.2 g, 0.283 mol) diluted in 178 mL of diethyl ether was slowly added dropwise thereto. After heating the reaction mixture under reflux for 3 hours, a solution of Compound (114) (20.0 g, 70.8 mmol) dissolved in 47 mL of diethyl ether was slowly added dropwise to the reaction mixture, which was then heated under reflux for 12 hours. After the reaction was completed, the precipitate generated was filtered under reduced pressure to obtain intermediate product (24,6 g, 44.0 mmol). The intermediate product was dissolved in 172 mL of benzene, and the solution was slowly added dropwise to trifluoromethanesulfonic add (53 mL), while raising the temperature slowly. After stirring the mixture at 100°Cor 30 minutes, the reaction solution was added to ice-water (200 mL) to generate solid. The solid generated was filtered under reduced pressure, washed with 59 mL of methanol and 119 mL of diethyl ether, and dried under reduced pressure to obtain Compound (151) (32.1 g, 57.4 mmol) as pale yellow solid.

[226] Preparation of Compound (152)

[227] Compound (151) (32.1 g, 57.4 mmol) and ferric chloride (56 mg) were dissolved in chloroform (338 mL). A solution of bromine (33.9 g, 121 mmol) dissolved in 56 mL of chloroform was charged to a dropping funnel, and slowly added dropwise thereto at O⁰C After the addition was completed^ the reaction mixture was stirred for 1 hour. The reaction was quenched by adding saturated aqueous sodium thiosulfate solution. The reaction mixture was extracted with 500 mL of dichloromethane, and the organic layer was dried, filtered and recrystallized from dichloromethanerhexane (1/1, vv) (200 mL), to obtain Compound (152) (33.0 g, 46.0 mmol).

[228] Preparation of Compound (153)

[229] Compound (153) was obtained according to the same synthetic procedure as for Compound (118). By using Compound (152) (33.0 g, 46.0 mmol), tetrahydrofuran (146 mL), n-BuLi (1.6 M in n-hexane) (43 mL, 55.2 mmol) and N,N-dimethylformamide (6.2 mL, 64.4 mmol), Compound (153) (23.0 g, 34.5 mmol) was obtained.

[230] Preparation of Compound (154)

[231] Compound (154) was obtained according to the same synthetic procedure as for Compound (119). By using the aldehyde compound (153) (23.0 g, 34.5 mmol), diphenylamine (13.8 g, 51.8 mmol), cesium carbonate (26.4 g, 51.8mmol), Pd(OAc) i h 2

(365 mg, 1.0 mmol), toluene (1.2 L) and P(t-Bu) (660 mg, 2.1 mmol), Compound

(154) (23.4 g, 31.0 mmol) was obtained. [232] Preparation of Compound (155)

[233] Compound (155) was obtained according to the same synthetic procedure as for

Compound (120). By using anc dust (30.0 g, 0.31 mol), TiCl (1 M solution in

4 dichloromethane) (183 mL, 0.124 mol), tetrahydrofuran (160 mL) and Compound (154) (23.4 g, 31.0mmol), Gbmpound (155, DTPIF-I) (14.9 g, 10.0 mmol, yield on the basis of Gbmpound (153): 57%) was obtained as white powder.

[234] ¹H NMR(CDCl , 200 MHz) : δ 6.46(m, 8H), 6.61-6.62(m, 6H), 6.78(m, 2H),

7.01-7.14(m, 50H), 7.57(m, 2H), 7.67-7.70(m, 8H), 7.95(m, 2H)

[235] MOTAB : 1474(found) 1475.85(calculated)

[236] [Synthetic Example 14] Preparation of DTF-4 ( Gbmpound 157)

[237]

[238] Preparation of Gbmpound (156)

[239] Gbmpound (156) was obtained acording to the same synthetic procedure as for

Gbmpound (119). By using the aldehyde compound (118) (10.0 g, 24.0 mmol), N- phenylbiphenylamine (8.8 g, 36.0 mmol), cesium carbonate (11.7 g, 36.0 mmol), Pd(OAc) (161 mg, 0.72 mmol), toluene (90 mL) and P(t-Bu) (291 mg, 1.44 mmol), Gbmpound (156) (12.6 g, 21.6 mmol) was obtained.

[240] Preparation of Gbmpound (157)

[241] Gbmpound (157) was obtained according to the same synthetic procedure as for

Gbmpound (120). By using zinc dust (17.0 g, 0.26 mol), TiCl (1 M in

4 dichloromethane) (86 mL, 86 mmol), tetrahydrofuran (150 mL) and Gbmpound (156)

(12.6 g, 21.6 mmol), Gbmpound (157, DIF-4) (5.6 g, 5.0 mmol, yield: 41%) was obtained as yellow solid. i

[242] ¹H NMR(CDCl , 200 MHz) : δ 1.67(s, 24H), 6.46-6.62(m, 12H), 6.78(m, 2H),

6.99-7.01(m, 6H), 7.22-7.32(m, 10H), 7.48-7.57(m, 6H), 7.70-7.73(m, 8H), 7.95(m,

2H)

[243] MSTFAB : 1130(found) 1131.49(calculated) [244] [Synthetic Example 15] Preparation of DSF-4 (Gbmpound 159)

[245]

[246] Preparation of Gbmpound (158)

[247] Gbmpound (158) was obtained according to the same synthetic procedure as for

Gbmpound (119). By using the spiro-type aldehyde compound (123) (4.54 g, 10.7 mmol), N-phenylbiphenylamine (4.4 g, 18.0 mmol), cesium carbonate (5.25 g, 16.1 mmol), Pd(OAc) (71.6mg, 0.32 mmol), toluene (75 mL) and P(t-Bu) (130 mg, 0.65 mmol), Compound (158) (4.16 g, 7.1 mmol) was obtained. [248] Preparation of Compound (159)

[249] Compound (159) was obtained according to the same synthetic procedure as for

Compound (120). By using anc dust (4.7 g, 70.8 mmol), TiCl (1 M solution in

4 dichloromethane) (29 mL, 28.3 mmol), tetrahydrofuran (40 mL) and Compound (158) (4.16 g, 7.1 mmol), Compound (159, DSF-4) (6.02 g, 5.2 mmol, yield: 97%) was obtained as gray solid. [250] ¹H NMR(CDCl , 200 MHz) : δ6.46-6.58(m, 12H), 6.75(d, 2H), 6.99-7.01(m, 6H),

3

7.16-7.32(m, 22H), 7.48-7.59(m, 8H), 7.71-7.84(m, 8H) [251] MOTAB : 1142(found) 1143.42(calculated)

[252] [Synthetic Example 16] Preparation of DPF-4 (Compound 1611

[253]

[254] Preparation of Compound (160)

[255] Compound (160) was obtained according to the same synthetic procedure as for

Compound (119). By using the spiro-type aldehyde compound (128) (4.0 g, 9.40 mmol), N-phenylbiphenylamine (3.9 g, 14.1 mmol), cesium carbonate (4.6 g, 14.1 mmol), Pd(OAc) (63 mg, 0.28 mmol), toluene (66 mL) and P(t-Bu) (115 mg, 0.56

2 3 mmol), Compound (160) (3.7 g, 6.2 mmol) was obtained. [256] Preparation of Compound ( 161 ^")

[257] Compound (161) was obtained according to the same synthetic procedure as for

Compound (120). By using anc dust (4.2 g, 62.0 mmol), TiCl (1 M solution in

' , 4 dichloromethane) (26 mL, 24.8 mmol), tetrahydrofuran (36 mL) and Compound (160)

(3.7 g, 6.2 mmol), Compound (161, DPF-4) (5.3 g, 4.6 mmol, yield: 98%) was ob tained as gray solid. [258] ¹H NMR(CDCl , 200 MHz) : δ 6.46-6.62(m, 12H), 6.75(d, 2H), 6.99-7.32(m, 36H),

7.48-7.59(m, 8H), 7.71(m, 2H), 7.84(m, 2H) [259] MSFAB : 1176(found) 1147.75(calculated)

[260] [Synthetic Example 17] Preparation of DMF-4 (Compound 163^

[261]

[262] Preparation of Compound (162) [263] (impound (162) was obtained according to thesame synthetic procedure as for Compound (119). By using the aldehyde compound (132) (6.0 g, 19.9 mmol), N- phenylbiphenylamine (5.8 g, 29.9 mmol), cesium carbonate (6.9 g, 29.9 mmol), Pd(OAc) (65 mg, 0.60 mmol), toluene (99 mL) and P(t-Bu) (172 mg, 1.2 mmol),

2 T

Compound (162) (5.5 g, 11.8 mmol) was obtained after recrystallization from 60 mL of methanol.

[264] Preparation of Compound (163) [265] Compound (163) was obtained according to the same synthetic procedure as for Compound (120). By using znc dust (6.2 g, 118.0 mmol), TiCl (1 M solution in

4 dichloromethane) (38 mL, 47.2 mmol), tetrahydrofuran (53 mL) and Compound (162) (5.5 g, 11.8 mmol), Compound (163, DMF-4) (8.0 g, 8.8 mmol, yield: 88%) was obtained as gray solid.

[266] ¹H NMR(CDCl , 200 MHz) : δl.67(s, 12H), 6.46-6.62(m, 12H), 6.75(m, 2H), 6.99-7.01(m, 6H), 7.22-7.32(m, 10H), 7.48-7.59(m, 8H), 7.71-7.84(m, 4H)

[267] MSFAB : 888(found) 899.17(calculated) [268] [Synthetic Example 18] Preparation of DIF-Il (Compound 169) [269]

[270]

[271] Preparation of Cbmpound (164)

[272] In tetrahydrofuran (20 mL), dissolved are Compound (119) (1.2 g, 2.4 mmol),

NaBH (0,1 g, 3.6 mmol). The solution was oooled to 0⁰C, and 10 mL of methanol was

4 slowly added dropwise thereto. After stirring the mixture for 30 minutes, distilled water (50 mL) was added thereto to quench the reaction. The reaction mixture was extracted with ethyl acetate (30 mL), dried under reduced pressure, and purified by column chromatography (dichloromethane/hexane = 1/1) to obtain Cbmpound (164) (0.9 g, 1.8 mmol).

[273] Preparation of Cbmpound (165)

[274] Cbmpound (164) (0.9 g, 1.8 mmol) was charged to a reaction vessel, and triethyl phosphite (20 mL) was added to bedissolved therein under nitrogen atmosphere. To another eaction vessel, charged was triethyl phosphite (10 mL), and iodine (0.6 g, 1.8 mmol) was added in small portions with the lid open, while stirring at 0°C for 30 minutes. The mixture containing iodine and triethyl phosphite was charged to a reaction vessel containing Cbmpound (109). The temperature was raised to 150⁰C, and the mixture was stirred for 4 hours. When the reaction was completed, triethyl phosphite was removed by distillation under reduced pressure. The residue was washed with 500 mL of water, extracted with 500 mL of ethyl acetate, and driedunder reduced pressure. After purification via column chromatography (eluent: ethyl acetate/ hexane = 1/1) to obtain Cbmpound (165) (1.1 g, 1.7 mmol).

[275] Preparation of Cbmpound (166)

[276] Triphenylamine (5.0 g, 20.4 mmol), N-bromosucάnimide (3.6 g, 20.4 mmol) were dissolvedin 40 mL of dichloromethane under nitrogen atmosphere, and the solution was stirred at 25°C for 5 hours. Then,the reaction was quenched by adding 100 mL of distilled water. The mixture was extracted with dichloromethane (30 mL), dried under reduced pressure, and recrystallized from hexane (100 mL) to obtain the target compound (166) (5.2 g, 16.0 mmol).

[277] Preparation of Cbmpound (167)

[278] Cbmpound (166) (5.2 g, 16.0 mmol) thus obtained was dissolved in purified tetrahydrofuran (100 mL) under nitrogen stream, and the solution was cooled to -78°C. To the solution, n-butyl lithium (1.6M in hexane) (15.0 mL, 24.0 mmol) was slowly added dropwise, and the resultant mixture was stirred for 1 hour. Then, 2-isopropoxy-4,4,5,5-tetramethyl-l,3,2-dioxaborolane(6.5 mL, 32.0 mmol) was added thereto. The temperature was slowly raised to 25⁰C, and the mixture wasstirred at the same temperature for 1 day. The reaction was quenched by adding 200 mL of distilled water, and the mixture was extracted with 100 niL of ethyl acetate, dried under reduced pressure and recrystallized from tetrahydrofuran (20 mL) and methanol (200 mL), to obtain the target compound (167) (3.2 g, 8.6 mmol).

[279] Preparation of Gbmpound (168)

[280] After previously adjusting the temperature at 120⁰C, Gbmpound (118) (5.0 g, 11.9 mmol), Gbmpound (167) (5.3 g, 14.4 mmol), tetrakis palladium triphenylphosphine (Pd(PPh ) ) (1.4 g, 1.2 mmol) and aliquat 336 (0.6 mL, 1.2 mmol) were dissolved in

3 4 ,

100 mL of toluene. To the solution, aqueous 2M potassium carbonate solution (60 mL) was added and the mixture was heated under reflux with stirring for 4 hours. Then, the temperature was lowered to 25°C, and distilled water (150 mL) was added thereto to quench the reaction. The mixture was extracted with 100 mL of ethyl acetate, dried under reduced pressure, and recrystallized from methanol (100 mL) and tetrahydrofuran (20 mL), to obtain the target compound (168) (5.8 g, 9.9 mmol).

[281] Preparation of Gbmpound π.69^">

[282] Gbmpound (165) (6.2 g, 9.9 mmol) and Gbmpound (168) (5.8 g, 9.9 mmol) were charged to a reaction vessel, and dried under reduced pressure. After providing nitrogen atmosphere, tetrahydrofuran (200 mL) was added and dissolved therein, and the mixture was cooled to 0⁰C. To another vessel, potassium tert-butoxide (t-BuOK) (1.7 g, 14.8 mmol) dissolved in tetrahydrofuran (20 mL) was slowly added dropwise. After stirring at 0°Cfor 2 hours, distilled water (300 mL) was added thereto, and the resultant mixture was stirred. The solid generated was filtered under reduced pressure to obtain solidproduct, which was washed with methanol (200 mL x 3). The product was washed with ethyl acetate (50 mL) and recrystallized from tetrahydrofuran (50 mL) and methanol (300 mL) to obtain the target compound (169) (5.7 g, 5.4 mmol, yield: 55%).

[283] H NMR(CDCl 200 MHz) : δ 1.68(s, 24H), 6.46-6.62(m, 15H), 6.75(m, IH),

6.99-7.01(m, 10H), 7.24(m, 2H), 7.54-7.69(m, 6H), 7.71-7.77(m, 4H), 8.06-8.12(m, 12Hj,

[284] MSFAB : 1054(found) 1055.4(calculated)

[285] [Synthetic Example 19] Preparation of DIF- 12 (Gbmpound 170)

[286]

[287] The same procedure for preparing Gbmpound (120) in Synthetic Example 1 was repeated but using Gbmpound (168) (3.0 g, 5.1 mmol) instead of Gbmpound (119), to obtain Gbmpound (170) (2.8 g, 2.5 mmol, yield: 48%) as yellow solid.

[288] H NMR(CDCl , 200 MHz) : δ 1.67(s, 24H), 6.45-6.52(m, 12H), 6.64(m, 4H), 6.99-7.02(m, 10H), 7.23(m, 4H), 7.57-7.63(m, 4H), 7.73-7.74(m, 6H), 7.80(m, 2H), 7.95-8.01(m, 4H)

[289] MSFAB : 1130(found) miscalculated) [290] [Synthetic Example 20] Synthesis of DPF-I l (Gbmpound 174) [291]

[292]

[293] Preparation of Gbmpound (172) [294] The same procedure as Synthetic Example 18 was carried out but using Gbmpound (129) (8.8 g, 17.1 mmol) prepared from Synthetic Example 3, to obtain the target compound (172) (7.6 g, 11.9 mmol). ^'

[295] Preparation of Gbmpound ('174') [296] The same procedure as Synthetic Example 18 was carried out from Gbmpound (128) (12.1 g, 28.4 mmol) prepared from Synthetic Example 3, to provide Gbmpound (173), which was then reacted with Gbmpound (172) to obtain the target compound (174) (4.2 g, 3.9 mmol).

[297] H NMR(CDCl₁, 200 MHz) : δ6.46-6.52(m, 12H), 6.75(m, IH), 6.99-7.17(m, 32H), 7.54-7.60(m, 4H), 7.71(m, 2H), 7.77(m, IH), 7.84-7.92(m, 3H)

[298] MSTAB : 1070(found) 1071.3(calculated) [299] [Synthetic Example 21] Preparation of DPF-12 (Gbmpound 175) [300]

[301] The same procedure for preparing Compound (120) in Synthetic Example 1 was repeated but using Compound (173) (3,0 g, 5.1 mmol) instead of Compound (119), to obtain Compound (175) (2.5 g, 2.2 mmol, yield: 43%) as yellow solid.

[302] H NMR(CDCl₁, 200 MHz) : δ 6.46-6.52(m, 12H), 6.62(m, 4H), 6.99-7.23(m, 34H), 7.54-7.60(m, 4H), 7.71-7.77(m, 4H), 7.84-7.90(m, 4H)

[303] MOTAB : 1130(found) 1131.4(calculated) [304] [Synthetic Example 22] Preparation of DSF-Il (Compound 179) [305]

[306]

[307] Preparation of Compound (111) [308] The same procedure as Synthetic Example 18 wascarried out but using Compound (124) (4.3 g, 8.4 mmol) prepared from Synthetic Example 2, to obtain the target compound (177) (3.6 g, 5.7 mmol).

[309] Preparation of Compound (179) [310] The same procedure as Synthetic Example 18 was carried out from Compound (123) (5.0 g, 11.8 mmol) prepared from Synthetic Example 2, to provide Compound (178), which was then reacted with Compound (177) to obtain the target compound (179) (3.8 g, 3.6 mmol).

[311] H NMR(CDCl₃, 200 MHz) : δ 6.46-6.62(m, 15H), 6.75(m, IH), 6.93-7.01 (m, 10H),7.16-7.23(m,^" 10H), 7.35(m, 4H), 7.54-7.60(m, 4H), 7.71-7.90(m, 10H)

[312] MSΕAB : 1066(found) 1067.3(calculated) [313] [Synthetic Example 23] Preparation of DSF-12 (Compound 180) [314]

[315] The same procedure for preparing Compound (120) in Synthetic Example 1 was re- peatedbut using Compound (178) (3,0 g, 5.1 mmol) instead of Compound (119), to obtain Compound (180) (3.5 g, 3.3 mmol, yield: 60%) as yellow solid.

[316] H NMR(CDCl , 200 MHz) : δ6.46-6.52(m, 12H), 6.62(m, 4H), 6.99-7.02(m, 10H), 7.16-7.23(m, 12H), 7.35(m, 4H), 7.54-7.60(m, 4H), 7.71-7.72(m, 8H), 7.84-7.91(m, 4H)

[317] MSΦAB : 1142(found) 1143.4(calculated) [318] [Synthetic Example 24] Preparation of DMF-11 (Compound 184) [319]

[320]

[321] Preparation of Compound (182) [322] The same procedure as Synthetic Example 18 was carried out but using Compound (133) (5.0 g, 12.8 mmol) prepared from Synthetic Example 4, to obtain the target compound (182) (4.4 g, 8.6 mmol).

[323] Preparation of Compound (184) [324] The same procedure as Synthetic Example 18 was carried out from Compound (132) (5.0 g, 16.6 mmol) prepared from Synthetic Example 4, to provide Compound (183), which was then reacted with Compound (182) to obtain the target oompound (184) (3.8 g, 3.6 mmol).

[325] H NMR(CDCl , 200 MHz) : δl.67(s, 12H), 6.46-6.62(m, 15H), 6.75(d, IH), 6.99-7.01(m, 10H), 7.23(m, 2H), 7.54-7.59(m, 4H), 7.71(m, 2H), 7.77-7.90(m, 4H) [326] MSTPAB : 822(found) 823.1 (calculated) [327] [Synthetic Example 25] Preparation of DMF- 12 (Gbmpound 185) [328]

[329] The same procedure for preparing Gbmpound (120) in Synthetic Example 1 was repeated but using Gbmpound (183) (3.0 g, 6.4 mmol) instead of Gbmpound (119), to obtain Gbmpound (185) (3.4 g, 3.8 mmol, yield: 60%) as yellow solid.

[330] H NMR(CDCl , 200 MHz) : δ 1.67(s, 12H), 6.46-6.52(m, 12H), 6.62(m, 4H), 6.99-7.01(in, 10H), 7.23(m, 4H), 7.54-7.60(m, 4H), 7.71-7.90(m, 8H)

[331] MSFAB : 898(found) 899.1 (calculated) [332] [Synthetic Example 26] Preparation of DMF-21 (Gbmpound 187) [333]

[334] Triphenylamine (10.0 g, 40.7 mmol) was dissolved in 100 mL of N,N-dimethylformamide, and the solution was cooled to O⁰C. To another vessel, N,N-dimethylformamide (32 mL, 407.6 mmol) was charged, and cooled to 0, and POC13 was slowly added thereto.The mixture was stirred for 30 minutes, and slowly added dropwise to the vessel containing triphenylamine solution at O⁰C. The resultant mixture was further stirred at 45°C for 18 hours, and saturated sodium hydroxide solution was slowly poured thereto. Then, an exeessamount of water was added thereto, and the mixture stirred. The solid generated was filtered, and washed with water (twice) and methanol (twice) to obtain the target compound (186) (10.0 g, 36.6 mmol).

[335] Preparation of Gbmpound (187^ [336] Gbmpound (186) (2.1 g, 7.8 mmol) was reacted with Gbmpound (182) aaoording to the same procedure as Synthetic Example 18, to obtain the target compound (187) (3.0 g, 4.7 mmol, yield: 62%).

[337] HNMR(CDCl , 200 MHz) : δl.67(s, 6H), 6.46(m, 10H), 6.58-6.62(m, 5H), 6.75(m, IH), 6.79-7.01(m, 10H), 7.17(m, 2H), 7.54-7.59(m, 2H), 7.71(m, IH), 7.84(m, IH) [338] MSFAB : 629(found) 630.8(calculated) [339] [Example 1] Manufacture of OLED device [340] An OLED device was made by using the electroluminescent material according to the present invention as a dopant, as illustrated by Fig. 1.

[341] First, a transparent electrode ITO thin film (2) (15 Ω/D obtained from a glass for OLED (1) was subjected to ultrasonic washing withtrichloroethylene, acetone, ethanol and distilled water, subsequently, and stored in isopronanol before use.

[342] Then, an ITO substrate was equipped in a substrate folder of vacuum vapor-deposit device, and 4,4 ,4"-tris(N,N-(2-naphthyl)-phenylamino)triphenylamine (2-TNATA) represented by following structural formula was placed in a cell of the vacuum vapor- deposit device, which was then ventilated up to 10 ^" torr of vacuum in the chamber. Electric current was applied to the cell to evaporate 2-TNATA to vapor-deposit a hole injection layer (3) having 60 nm of thickness on the ITO substrate.

[343]

2-TNATA

[344] Then, to another cell of the vacuum vapor-deposit device, charged was N,N'-bis(α-naphthyl)-N,N'-diphenyl-4,4'-diamine (NPB) represented by following chemical formula, and electric current was applied to the cell to evaporate NPB to vapor-deposit a hole transport layer (4) having20 nm of thickness on the hole injection layer.

[345]

NPB

[346] After forming the hole transport layer, an electroluminescent layer (5) was vapor- deposited thereon as follows. In one cell of the vacuum vapor-deposit device, charged was dinaphthylanthrasene (DNA) represented by following chemical formula, and in another cell charged was a compound according to the present invention (e.g. Compound DPF-I) as an electroluminescent material. An electroluminescent layer was vapor-deposited on the hole transport layer by using the vapor-deposit rate of 100:1.

[347]

DNA

DPF-1

[348] Then, tris(8-hydroxyquinoline)aluminum (III) (AIq) represented by following structural formula was vapor-deposited as an electron transport layer (6) in a thickness of 20 nm, and lithium quinolate (Liq) represented by following structural formula was vapor-deposited as an electron injection layer (7) in a thickness from 1 to 2 nm. Thereafter, an Al cathode (8)was vapor-deposited in a thickness of 150 nm by using another vapor-deposit device,to manufacture an OLED.

[349]

AIq Liq

[350] Each substance employed in the OLED device was used after being purified by sublimation in vacuo at 10 ^" torr. [351] [Comparative Example 1] Manufacture of OLED device by using conventional electroluminescent material [352] A hole injection layer (3) and a hole transport layer (4) were formed as in Example 1. In one cell of the vacuum vapor-deposit device, charged was dinaphthylanthracene (DNA) as a blue electroluminescent material, and in another cell charged was perylene having the structure shown below. An electroluminescent layer (5) was vapor- deposited on the hole transport layer by using the vapor-deposit rate of 100:1.

[353]

perylene

[354] According to the same procedure as in Example 1, anelectron transport layer (6) and an electron injection layer (7) were vapor-deposited, and Al cathode (8) was deposited in a thickness of 150 nm by using another vapor-deposition device, to manufacture an OLED.

[355] [Example 2] Electroluminescent properties of the OLED manufactured

[356] Luminous efficiencies of OLEDs comprising the organic electroluminescent compound according to the invention prepared from Example 1 and the conventional electroluminescent compound prepared from Gbmparative Example 1 were measured

2 2 at 500 cd/m and 2,000 od/m , individually, of which the results are shown in Table 1. Since the luminescent properties in the range of lowluminance and those applied on a panel are very important in case of blue electroluminescent material, in particular, the data of luminance ofabout 2,000 od/m was established as the standard in order to reflect those properties. [357] Table 1

[358] As can be seen from Table 1, the OLED device employing the organic electroluminescent compounds according to the inventionas the electroluminescent material was compared to the OLED device of Comparative Example whbh employs widely known DNAφerylene as a conventional electroluminescent material, on the basis of "luminous effϊάencyΛT' value which shows similar tendency to proton efficiency. As the result, the OLED device employing the organic electroluminescent compound according to the present invention showed higher "luminous effiάencyΛT' value than that of Comparative Example.

[359] In view of the fact that the organic electroluminescent compound according to the invention showed higher "luminous efficiencyΛf "value, it is found that the organic electroluminescent compounds of the present invention is a material havinghigh proton efficiency. In addition, it is found that the organic electroluminescent compounds of the present invention can realize higher efficiency while having the similarcolor purity as compared to conventional electroluminescent compounds. In particular, in case of the series of DPF- 1,2 and 3, the "luminous efficiency/^" value was enhanced by about 2.5 to 3-folds as compared to conventional electroluminescent compound.

[360] Thus, the organic electroluminescent compounds axording to the present invention can be used as a blue electroluminescent material of high efficiency, being very advantageous in view of luminance of OLED in full-colored display, power consumption and lifetime of the device as compared to conventional devices.

[361] Fig. 2 shows EL spectrum of DPF-I as an electroluminescent material axording to the invention and that of Comparative Example 1. Figs. 3 to 5 show the current density-voltage property, luminance-voltage property and luminous efficiency-current density property of the OLED comprising DPF-I, respectively. As can be seen from Figs. 3-5, the current density-voltage property, luminance-voltage property and luminous efficiency-current density property of the OLED according to the invention were excellent. Industrial Applicability

[362] The novel organic electroluminescent compounds according to the present invention may be employed in electroluminescent layer of an electroluminescent device, and have good luminouseffidency and excellent life properties, thereby providing OLEDs having very long lifetime of operation.

Claims

Claims [1] An electroluminescent compound represented by following Chemical Formula 1:

[Chemical Formula 1]

wherein, Ar is a chemical bond or selected from indenofluorene, fluorene and spiro-fluorene as represented by following chemical formulas, Ar is selected

2 from indenofluorene, fluorine and spiro-fluorene as represented by following chemical formulas:

A and B independently represent a chemical bond, or are selected from phenylene group, naphthylene group, biphenylene group, anthracenyl group, perylenylene group and pyrenylene group; R through R are independently selected from C ~C alkyl, cycloalkyl, C ~C

1 20 1 20 alkyl having one or more halogen substituent(s), and phenyl or naphthyl having

C -C alkyl substituent(s);

Ar through Ar are independently selected from C ~C aromatic or multicyclic

3 6 5 20 aromatic ring, and the aromatic ring may oontain hetero atom(s); but the compounds wherein both A and Ar are chemical bonds are excluded.

[2] An electroluminescent compound according to claim 1, wherein Ar and Ar are independently selected from following structures:

wherein, R is selected from C ~C alkyl group with or without halogen substituent(s); and n is an integer from 1 to 5.

[3] An electroluminescent compound aacording to claim 2, wherein R through R are independently selected from C ~C alkyl, a C ~C cycloalkyl, phenyl and naphthyl.

[4] An electroluminescent compound according to claim 3, wherein Ar is same as

[5] An electroluminescent device comprising an electroluminescent compound according to any one of claims 1 to 5. [6] An electroluminescent device aα»rding to claim 6, in which the electroluminescent compound is used as a dopant material in an electroluminescent layer.