KR101171232B1 - Spiro Compound and Organic Light Emitting Device Including the Same - Google Patents

Abstract

The present invention relates to a spiro compound and an organic light emitting device comprising the same, according to the present invention, by improving the unstable thermal stability which is a problem of the conventional compound for organic light emitting devices, not only excellent quantum efficiency but also thermal stability And it provides a spiro compound having excellent film stability and an organic light emitting device comprising the same.

Description

Spiro Compound and Organic Light Emitting Device Including the Same

The present invention relates to a spiro compound, and more particularly, to a spiro compound having excellent thermal stability, film stability and quantum efficiency, and an organic electroluminescent device comprising the same.

The organic light emitting device has a simpler structure, has various advantages in manufacturing process, and has high luminance and viewing angle compared to other flat panel display devices such as a liquid crystal display (LCD), a plasma display panel (PDP), and a field emission display (FED). Due to its excellent characteristics, fast response speed and low driving voltage, development is being actively conducted to be used as a light source for a flat panel display such as a wall-mounted TV or a back light of a display, an illumination, a billboard.

In general, an organic light emitting diode recombines holes injected from an anode and electrons injected from a cathode when a DC voltage is applied to form an exciton, an electron-hole pair, and the excitons return to a stable ground state to emit corresponding energy. It is converted to light by transmitting it to the material.

In order to increase the efficiency and stability of organic light emitting devices, a low-voltage driving organic light emitting device is reported by forming a stacked organic thin film between two opposite electrodes by CW Tang of Eastman Kodak Corporation (CW Tang, SA Vanslyke, Applied Physics). Letters, Vol. 51, p. 913, 1987), studies on organic materials for multilayer thin film structured organic light emitting diodes have been actively conducted. The lifetime of the stacked organic light emitting diode is deeply related to the thermal stability of the thin film and the material. For example, when the thermal stability of the material is inferior, crystallization of the material occurs at a high temperature or a driving temperature, which causes a shortening of the life of the device.

Although spirobifluorene has been reported as a conventional spiro-based compound structure that can be used in an organic light emitting device, the spirobifluorene compound has a problem of low thermal stability.

Therefore, the first technical problem to be achieved by the present invention is to solve the problems of the prior art, the hole transport material of the organic EL device, the dopant material of the light emitting layer, the host material of the light emitting layer, the electron transport material, the host of the fluorescent material, fluorescence When applied to devices and phosphorescent devices, such as to provide a spiro compound having excellent quantum efficiency and excellent thermal stability and film stability.

The second technical problem to be achieved by the present invention is to provide an organic electroluminescent device comprising the spiro compound having high efficiency of the device, long drive life and high thermal stability.

The present invention provides a spiro compound represented by the following formula (1).

In Chemical Formula 1,

R ¹ to R ⁶ are the same as or different from each other, and all may not be a hydrogen atom,

,

,

, 또는

이고, R¹ 내지 R⁶ 중 나머지는 각각 독립적으로 수소원자, C_1-9의 알킬기, C_{6 -30}의 아릴기 또는 C_{5 -30}의 헤테로 아릴기이며,R ¹ to R ⁶ At least one of each independently

,

,

, or

R ¹ to R ⁶ The remaining are each independently a hydrogen atom, a heteroaryl group of the C _1-9 alkyl group, C _{6 -30} aryl group, or C _{5 -30} of,

And R ¹ to R ⁶ At least one of each may independently combine with a carbon atom of a neighboring benzene ring to form a fused aromatic ring or a fused hetero aromatic ring,

The alkyl groups of the R ⁷ to R ⁹ is a hydrogen atom or a C _1-9, each independently,

Wherein Ar ¹ to Ar ⁴ is a heteroaryl group are each independently a hydrogen atom, C _{6 -30} aryl group or a C _{5 -30.}

인 것을 특징으로 한다.According to the present invention, the R ¹ to R ⁶ At least one of

It is characterized by that.

인 것을 특징으로 한다.In addition, according to the present invention, the R ¹ to R ⁶ At least one of

It is characterized by that.

인 것을 특징으로 한다.In addition, according to an embodiment of the present invention, the R ¹ to R ⁶ At least one of

It is characterized by that.

인 것을 특징으로 한다.In addition, according to an embodiment of the present invention, the R ¹ to R ⁶ At least one of

It is characterized by that.

In one embodiment of the present invention, the R ¹ to R ⁶ Are each independently of the other an aryl group, a hydrogen atom or a C _{6 -30,} wherein Ar ¹ to Ar ⁴ each independently can be an aryl date of a hydrogen atom or a C _{6 -30,} more preferably the R ¹ to R ⁶ The remainder is a hydrogen atom, Ar ¹ to Ar ⁴ may be a hydrogen atom.

One aspect of the invention the first electrode; A second electrode; Light emitting layer; And a hole transport layer, wherein the light emitting layer includes a host and a dopant, and the hole transport layer provides an organic light emitting device comprising the spiro compound of the present invention.

According to one embodiment of the invention, the host is characterized in that it comprises a spiro compound of the invention.

According to an embodiment of the present invention, the organic light emitting device further comprises an electron transport layer.

Here, the electron transport layer is characterized in that it comprises a spiro compound of the present invention.

One aspect of the invention the first electrode; A second electrode; Light emitting layer; In an organic light emitting device comprising an electron transport layer and a hole transport layer, the light emitting layer comprises a host and a dopant, the host provides an organic light emitting device, characterized in that it comprises a spiro compound of the present invention.

Here, the electron transport layer is characterized in that it comprises a spiro compound of the present invention.

According to one embodiment of the present invention, the organic light emitting device may further include one or more layers of a hole injection layer and an electron injection layer.

One aspect of the invention the first electrode; A second electrode; Light emitting layer; An organic electroluminescent device comprising an electron transport layer and a hole transport layer, wherein the light emitting layer comprises a host and a dopant, the electron transport layer provides an organic light emitting device comprising the spiro compound of claim 1.

The spiro compound of the present invention can be applied to the hole transport material of the organic EL device, the dopant material of the light emitting layer, the host material of the light emitting layer, the electron transport material, the host of the fluorescent material, the fluorescent device and the phosphorescent device, etc. The organic light emitting device including the compound not only has excellent quantum efficiency, but also has excellent thermal stability and film stability, so that the driving life of the device is long and the device stability is high.

1 is a view schematically showing the structure of an organic light emitting device according to the present invention.
2 is a view showing the efficiency and luminance of the Examples and Comparative Examples according to the present invention.

Hereinafter, a preferred embodiment of a spiro compound and an organic light emitting device including the same according to the present invention will be described in detail with reference to the formula or the accompanying drawings.

 The present invention provides a spiro compound represented by the following formula (1).

[Formula 1]

In Chemical Formula 1,

R ¹ to R ⁶ are the same as or different from each other, and all may not be a hydrogen atom,

,

,

, 또는

이고, 상기 R¹ 내지 R⁶ 중 나머지는 각각 독립적으로 수소원자, C_{1 -9}의 알킬기, C_{6 -30}의 아릴기 또는 C_{5 -30}의 헤테로 아릴기이며,R ¹ to R ⁶ At least one of each independently

,

,

, or

And R ¹ to R ⁶ The remaining are each independently a hydrogen atom, a heteroaryl group of the alkyl group of C _{1 -9,} C _{6 -30} aryl group or a C _{5 -30,}

And R ¹ to R ⁶ At least one of each may independently combine with a carbon atom of a neighboring benzene ring to form a fused aromatic ring or a fused hetero aromatic ring,

The alkyl groups of the R ⁷ to R ⁹ is a hydrogen atom or a C _1-9, each independently,

Wherein Ar ¹ to Ar ⁴ is a heteroaryl group, each independently represent a hydrogen atom, C _{6 -30} aryl group or a C _{5 -30.}

인 것을 특징으로 한다.According to the present invention, the R ¹ to R ⁶ At least one of

It is characterized by that.

인 것을 특징으로 한다.In addition, according to the present invention, the R ¹ to R ⁶ At least one of

It is characterized by that.

인 것을 특징으로 한다.In addition, according to the present invention, the R ¹ to R ⁶ At least one of

It is characterized by that.

인 것을 특징으로 한다.In addition, according to the present invention, the R ¹ to R ⁶ At least one of

It is characterized by that.

In the present invention, the R ¹ to R ⁶ Are each independently of the other an aryl group, a hydrogen atom or a C _{6 -30,} wherein Ar ¹ to Ar ⁴ each independently can be an aryl date of a hydrogen atom or a C _{6 -30,} more preferably the R ¹ to R ⁶ The remainder is a hydrogen atom, Ar ¹ to Ar ⁴ may be a hydrogen atom.

R ¹ to R ⁶ And Ar ¹ to Ar ⁴ of the C _{6 -30} aryl group, as specific examples, a phenyl group, 1-naphthyl, 2-naphthyl group, 1-anthryl group, 2-anthryl group, 9-anthryl group, 1- Phenanthryl group, 2-phenanthryl group, 3-phenanthryl group, 4-phenanthryl group, 9-phenanthryl group, 1-naphthacenyl group, 2-naphthacenyl group, 9-naphthacenyl group, 1-pyrenyl group , 2-pyrenyl group, 4-pyrenyl group, 2-biphenylyl group, 3-biphenylyl group, 4-biphenylyl group, p-terphenyl-4-yl group, p-terphenyl-3-yl group, p-terter Phenyl-2-yl group, m-terphenyl-4-yl group, m-terphenyl-3-yl group, m-terphenyl-2-yl group, o-tolyl group, m-tolyl group, p-tolyl group, p- tert-butylphenyl group, p- (2-phenylpropyl) phenyl group, 3-methyl-2-naphthyl group, 4-methyl-1-naphthyl group, 4-methyl-1-anthryl group, 4-methylbiphenylyl group or 4-tert-butyl-p-terphenyl-4-yl group etc. are mentioned.

Also R ¹ to R ⁶ And Ar ¹ to Ar ⁴ of the C _{6 -30} Specific examples of the heteroaryl group of 1-pyrrolyl group, 2-pyrrolyl group, 3-pyrrolyl group, pyrazinyl the group, pyrimidinyl group, a pyrido chewy, 2-pyridine group, 3 -Pyridinyl group, 4-pyridinyl group, 1-indolyl group, 2-indolyl group, 3-indolyl group, 4-indolyl group, 5-indolyl group, 6-indolyl group, 7-indolyl group, 1-isoindoleyl group , 2-isoindolyl group, 3-isoindolyl group, 4-isoindolyl group, 5-isoindolyl group, 6-isoindolyl group, 7-isoindolyl group, 2-furyl group, 3- Furyl group, 2-benzofuranyl group, 3-benzofuranyl group, 4-benzofuranyl group, 5-benzofuranyl group, 6-benzofuranyl group, 7-benzofuranyl group, 1-isobenzofuranyl group, 3-isobenzo Furanyl group, 4-isobenzofuranyl group, 5-isobenzofuranyl group, 6-isobenzofuranyl group, 7-isobenzofuranyl group, 1-dibenzofuranyl group, 2-dibenzofuranyl group, 3-dibenzofuran Diary, 6-dibenzofuranyl group, 7-dibenzo Lanyl group, 8-dibenzofuranyl group, 9-dibenzofuranyl group, 2-benzothiophene, 3-benzothiophene, 4-benzothiophene, 5-benzothiophene, 6-benzothiophene, 7-benzo Ciophene, 1-dibenzothiophene, 2-dibenzothiophene, 3-dibenzothiophene, 4-dibenzothiophene, 6-dibenzothiophene, 7-dibenzothiophene, 8-dibenzosai Offen, 9-dibenzothiophene, 2-benzophosphole, 3-benzophosphole, 4-benzophosphole, 5-benzophosphole, 6-benzophosphole, 7-benzophosphole, 1-dibenzoforce Pole, 2-Dibenzophosphole, 3-Dibenzophosphole, 4-Ibenzophosphole, 6-Ibenzophosphole, 7-Dibenzophosphole, 8-Dibenzophosphole, 9-Ibenzophosphole, 2- Benzophosphole oxide, 3-benzophosphole oxide, 4-benzophosphole oxide, 5-benzophosphole oxide, 6-benzophosphole oxide, 7-benzophosphole oxide, 1-dibenzophosphole oxide, 2- Dibenzophosphoxide, 3-diben Crude phosphol oxide, 4-dibenzophosphole oxide, 6-dibenzophosphole oxide, 7-dibenzophosphole oxide, 8-dibenzophosphole oxide, 9-dibenzophospholeoxide, quinolyl group, 3- Quinolyl, 4-quinolyl, 5-quinolyl, 6-quinolyl, 7-quinolyl, 8-quinolyl, 1-isoquinolyl, 3-isoquinolyl, 4- Isoquinolyl group, 5-isoquinolyl group, 6-isoquinolyl group, 7-isoquinolyl group, 8-isoquinolyl group, 2-quinoxalinyl group, 5-quinoxalinyl group, 6-quinoxalinyl group , 1-phenanthridinyl group, 2-phenanthridinyl group, 3-phenanthridinyl group, 4-phenanthridinyl group, 6-phenanthridinyl group, 7-phenanthridinyl group, 8-phenanthridinyl group, 9-phenanthridinyl group, 10-phenanthridinyl group, 1-acridinyl group, 2-acridinyl group, 3-acridinyl group, 4-acridinyl group, 9-acridinyl group, 1 , 7-phenanthroline-2-yl, 1,7-phenanthroline-3-yl, 1,7-phenanthroline-4-yl, 1,7-phenan Roline-5-Diary, 1,7-phenanthroline-6-diary, 1,7-phenanthroline-8-diary, 1,7-phenanthroline-9-diary, 1,7-phenanthroline- 10-diary, 1,8-phenanthroline-2-yl, 1,8-phenanthroline-3-yl, 1,8-phenanthroline-4-yl, 1,8-phenanthroline-5- Diary, 1,8-phenanthroline-6-diary, 1,8-phenanthroline-7-diary, 1,8-phenanthroline-9-diary, 1,8-phenanthroline-10-diary, 1,9-phenanthroline-2-yl, 1,9-phenanthroline-3-yl, 1,9-phenanthroline-4-yl, 1,9-phenanthroline-5-yl, 1, 9-phenanthroline-6-diary, 1,9-phenanthroline-7-diary, 1,9-phenanthroline-8-diary, 1,9-phenanthroline-10-diary, 1,10- Phenanthroline-2-yl, 1,10-phenanthroline-3-yl, 1,10-phenanthroline-4-yl, 1,10-phenanthroline-5-diary, 2,9-phenanthrole Lin-1-yl, 2,9-phenanthroline-3-yl, 2,9-phenanthroline-4-yl, 2,9-phenanthroline-5-diary, 2,9-phenanthroline- 6-diary, 2,9-phenanthroline-7-diary, 2,9-phenanthroline-8-diary, 2,9-phenanthroline-10-diary, 2,8-phenant Lin-1-yl, 2,8-phenanthroline-3-yl, 2,8-phenanthroline-4-yl, 2,8-phenanthroline-5-diary, 2,8-phenanthroline- 6-diary, 2,8-phenanthroline-7-diary, 2,8-phenanthroline-9-diary, 2,8-phenanthrolineyl group, 2,7-phenanthroline-1-yl group, 2 , 7-phenanthroline-3-yl, 2,7-phenanthroline-4-yl, 2,7-phenanthroline-5-diary, 2,7-phenanthroline-6-diary, 2,7 -Phenanthroline-8-diary, 2,7-phenanthroline-9-diary, 2,7-phenanthroline-10-diary, 1-phenazineyl group, 2-phenazinediary group, 1-phenothiazin Diary, 2-phenothiazin diary, 3-phenothiazin diary, 4-phenothiazin diary, 10-phenothiazin diary, 1-phenoxazine diary, 2-phenoxazine diary, 3-phenoxazine diary, 4- Phenoxazineyl group, 10-phenoxazineyl group, 2-oxazolyl group, 4-oxazolyl group, 5-oxazolyl group, 2-oxadiazolyl group, 5-oxadiazolyl group, 3-furazanyl group, 2- Thienyl group, 3-thienyl group, 2-methylpyrrole-1-yl group, 2-methylpyrrole-3-yl group, 2-methylpyrrole-4-yl group, 2 -Methylpyrrole-5-yl group, 3-methylpyrrole-1-yl group, 3-methylpyrrole-2-yl group, 3-methylpyrrole-4-yl group, 3-methylpyrrole-5-yl group, 2-tert-butylpyrrole -4-yl group, 3- (2-phenylpropyl) pyrrole-1-yl group, 2-methyl-1-indolyl group, 4-methyl-1-indolyl group, 2-methyl-3-indolyl group, 4-methyl- 3-indolyl group, 2-tert-butyl-1-indolyl group, 4-tert-butyl-1-indolyl group, 2-tert-butyl-3-indolyl group or 4-tert-butyl-3-indolyl group Can be mentioned.

In addition, the R ¹ to R ⁹ a C ₁ alkyl group and specific examples include methyl, ethyl of _-9, n- propyl, n- pentyl, n- butyl, n- hexyl, n- heptyl, n- octyl, iso A propyl group, sec-butyl group, isobutyl group, tert- butyl group, etc. are mentioned.

In order to improve the problem of the spiro compound containing the existing spirobifluorene (spirobifluorene) in the present invention has a double spiro structure as a new material having the advantages of the spiro structure and improved thermal stability and film stability A double spirobifluorene-based structure has been developed. Thermal stability was improved through organic compounds having a double spirobifluorene structure compared to a single spirobifluorene structure. The double spirobifluorene structure having a double spiro structure has a more rigid structure and a structure that is difficult to crystallize, thereby preventing crystallization during film formation, thereby improving thermal stability. .

Hereinafter, although the structural formula of 1-240 of the spiro compound of this invention is illustrated in Table 1, this invention is not limited to these compounds.

compound Chemical structural formula compound Chemical structural formula One

2

3

4

5

6

7

8

9

10

11

12

13

14

15

16

17

18

19

20

21

22

23

24

25

26

27

28

29

30

31

32

33

34

35

36

37

38

39

40

41

42

43

44

45

46

47

48

49

50

51

52

53

54

55

56

57

58

59

60

61

62

63

64

65

66

67

68

69

70

71

72

73

74

75

76

77

78

79

80

81

82

83

84

85

86

87

88

89

90

91

92

93

94

95

96

97

98

99

100

101

102

103

104

105

106

107

108

109

110

111

112

113

114

115

116

117

118

119

120

121

122

123

124

125

126

127

128

129

130

131

132

133

134

135

136

137

138

139

140

141

142

143

144

145

146 147

148

149

150

151

152

153

154

155

156

157

158

159

160

161

162

163

164

165

166

167

168

169

170

171

172

173

174

175

176

177

178

179

180

181

182

183

184

185

186

187

188

189

190

191

192

193

194

195

196

197

198

199

200

201

202

203

204

205

206

207 208

209

210

211

212

213

214

215

216

217

218

219

220

221

222

223

224

225

226

227

228

229

230

231

232

233

234

235

236

237

238

239

240

An organic EL device according to the present invention will be described with reference to the accompanying drawings. 1 is a view schematically showing the structure of an organic EL device of the present invention. The organic light emitting device including the spiro compound represented by Chemical Formula 1 may be realized in various structures.

According to an aspect of the present invention, the organic light emitting device includes: a first electrode 110; Second electrode 150; Light emitting layer 130; And a hole transport layer 120, wherein the light emitting layer is an organic light emitting device including a host and a dopant, and the hole transport layer 120 is characterized in that it comprises a spiro compound of the present invention.

According to an embodiment of the present invention, the host may include the spiro compound of the present invention.

In addition, according to an embodiment of the present invention, the organic light emitting device may further include an electron transport layer (140).

Here, the electron transport layer 140 may include a spiro compound of the present invention.

In addition, an aspect of the present invention, the organic light emitting device includes a first electrode (110); Second electrode 150; Light emitting layer 130; An electron transport layer 140 and a hole transport layer 120, the light emitting layer is an organic electroluminescent device comprising a host and a dopant, the host is characterized in that it comprises a spiro compound of the present invention.

The electron transport layer is characterized in that it comprises a spiro compound of the present invention.

The organic light emitting device according to an embodiment of the present invention may further include at least one layer selected from a hole injection layer and an electron injection layer to improve luminous efficiency.

In addition, one aspect of the invention the first electrode; A second electrode; Light emitting layer; An organic light emitting device comprising an electron transport layer and a hole transport layer, wherein the light emitting layer includes a host and a dopant, wherein the electron transport layer includes the spiro compound of claim 1. have.

The organic light emitting device is preferably supported by a transparent substrate. The material of the transparent substrate is not particularly limited as long as it has good mechanical strength, thermal stability and transparency. For example, glass, a transparent plastic film, etc. can be used.

As the anode material of the organic EL device of the present invention, a metal, an alloy, an electrically conductive compound having a work function of 4 eV or more, or a mixture thereof can be used. Specifically, transparent conductive materials such as Au or CuI, ITO (indium tin oxide), SnO ₂ and ZnO which are metals are mentioned. The thickness of the positive electrode film is preferably 10 to 200 nm.

As a negative electrode material of the organic EL device of the present invention, a metal, an alloy, an electrically conductive compound or a mixture thereof having a work function of less than 4 eV can be used. Specifically, Na, Na-K alloy, calcium, magnesium, lithium, lithium alloy, indium, aluminum, magnesium alloy, aluminum alloy is mentioned. In addition, aluminum / AlO ₂ , aluminum / lithium, magnesium / silver or magnesium / indium may be used. The thickness of the negative electrode film is preferably 10 to 200 nm. In order to increase the luminous efficiency of the organic EL device, at least one electrode preferably has a light transmittance of 10% or more. The sheet resistance of the electrode is preferably several hundred Ω / mm or less. The thickness of the electrode is 10 nm to 1 m, more preferably 10 to 400 nm. Such an electrode may be manufactured by forming the above electrode material into a thin film through vapor deposition or sputtering such as chemical vapor deposition (CVD), physical vapor deposition (PVD), or the like.

The hole transport layer or the hole injection layer of the present invention is a material commonly used as a hole transport material among photoconductive materials as a hole transport material and a hole injection material, and a known material used for the formation of a hole transport layer or a hole injection layer of an organic EL device. It may include. For example, N, N-dicarbazolyl-3,5-benzene (mCP), poly (3,4-ethylenedioxythiophene): polystyrenesulfonate (PEDOT: PSS), N, N'-di (1-naphthyl) -N, N '-diphenylbenzidine (NPD), N, N'-diphenyl-N, N'-di (3-methylphenyl) -4,4'-diaminobiphenyl (TPD), N, N'-diphenyl-N, N'-Dinaphthyl-4,4'-diaminobiphenyl, N, N, N'N'-tetra-p-tolyl-4,4'-diaminobiphenyl, N, N, N'N ' Porphyrin compound derivatives such as tetraphenyl-4,4'-diaminobiphenyl, copper (II) 1,10,15,20-tetraphenyl-21H, 23H-porphyrin, aromatic tertiary in the main chain or side chain Polymer with amine, 1,1-bis (4-di-p-tolylaminophenyl) cyclohexane, N, N, N-tri (p-tolyl) amine, 4, 4 ', 4'-tris [N- Triarylamine derivatives such as (3-methylphenyl) -N-phenylamino] triphenylamine, carbazole derivatives such as N-phenylcarbazole and polyvinylcarbazole, phthalocyanine derivatives such as metal-free phthalocyanine, copper phthalocyanine, starburst Amine May be a conductor, enamine stilbene derivatives, derivatives of aromatic tertiary amines and styrylamine compounds, polysilane and the like.

The electron transport layer of the present invention is a known electron transport material, for example diphenylphosphine oxide-4- (triphenylsilyl) phenyl (TSPO1), Alq ₃ , 2,5-diaryl silol derivative (PyPySPyPy), perfluorinated compound (PF -6P), Octasubstituted cyclooctatetraene compounds (COTs).

In the organic light emitting device of the present invention, the electron injection layer, the electron transport layer, the hole transport layer and the hole injection layer may be formed of a single layer containing one or more kinds of the above-mentioned compounds, or may be stacked on different kinds of compounds. It may consist of a plurality of layers to contain.

The light emitting layer of the organic electroluminescent device of the present invention may include a known light emitting material, for example, a phosphorescent fluorescent material, a fluorescent brightener, a laser dye, an organic scintillator and a reagent for fluorescence analysis. Specifically, a carbazole compound, a phosphine oxide compound, a carbazole phosphine oxide compound, bis ((3,5-difluoro-4-cyanophenyl) pyridine) iridium picolinate (FCNIrpic), tris (8-hydroxyquinoline) aluminum ( Alq ₃ ), polyaromatic compounds such as anthracene, phenanthrene, pyrene, chrysene, perylene, coronene, rubrene and quinacridone, oligophenylene compounds such as quiterphenyl, 1,4-bis (2-methyl Styryl) benzene, 1,4-bis (4-methylstyryl) benzene, 1,4-bis (4-methyl-5-phenyl-2-oxazolyl) benzene, 1,4-bis (5-phenyl- 2-oxazolyl) benzene, 2,5-bis (5-t-butyl-2-benzoxazolyl) thiophene, 1,4-diphenyl-1,3-butadiene, 1,6-diphenyl-1, Scintillators for liquid scintillation such as 3,5-hexatriene, 1,1,4,4-tetraphenyl-1,3-butadiene, metal complexes of auxin derivatives, coumarin pigments, dicyano methylene pyran pigments and dicyano methylene Thiopyran pigment, polymethine pigment, oxobenzanthracene Pigments, xanthene pigments, carbostyryl pigments, perylene pigments, oxazine compounds, stilbene derivatives, spiro compounds, oxadiazole compounds and the like.

Each layer constituting the organic EL device of the present invention can be formed into a thin film through a known method such as vacuum deposition, spin coating or casting, or can be produced using a material used in each layer. There is no particular limitation on the film thickness of each layer, and it can be appropriately selected depending on the properties of the material, but can usually be determined in the range of 2 nm to 5000 nm.

Since the compound of Chemical Formula 1 according to the present invention may be formed by a vacuum deposition method, the thin film forming process is simple and has an advantage of being easily obtained as a homogeneous thin film having little pin holes.

Hereinafter, a spiro compound and a method of manufacturing an organic light emitting device including the same according to the present invention will be described in more detail with reference to Examples. However, this is for illustrative purposes and the scope of the present invention is not limited thereby.

[Example]

According to the present invention, a spy compound of the present invention was first prepared, and an organic light emitting device was manufactured using the compound. The following Preparation Examples and Examples are intended to specifically illustrate the present invention, whereby the present invention should not be limited.

Manufacturing example  1.Intermediate 2,2'- Dibromo biphenyl  Synthesis of compounds

10 g of 1,2-dibromobenzene was dissolved in 100 ml of tetrahydrofuran and the temperature was made to -78 ° C. Thereafter, 8.8 ml of butyllithium was slowly added dropwise. Slowly raised to room temperature. The reaction was terminated by distilled water and extracted with dichloromethane to dry the solvent. The reaction was purified by recrystallization from nucleic acid to afford the intermediate 2,2'-dibromobiphenyl compound.

Manufacturing example  2. Synthesis of Intermediate (1)

2 g of 2,2'-dibromobiphenyl was dissolved in 15 ml of tetrahydrofuran and the temperature was made to -78 ° C. Thereafter, 5.6 ml of butyllithium was slowly added dropwise. The mixture was stirred for 2 hours as it was and 3.6 g 2-bromo-9H-fluorenone dissolved in 35 ml tetrahydrofuran was slowly added dropwise. Slowly raised to room temperature. 50 ml of 2% aqueous sodium hydrogen carbonate solution was added to the solution and stirred. Extract with dichloromethane and dry the solvent. 50 ml of acetic acid is added to this solid and the temperature is dissolved. 5 ml of sulfuric acid was added and refluxed at 120 ° C. After the reaction, the solvent was dried after extraction using dichloromethane and distilled water. This solid was filtered and the compound intermediate (1) was obtained.

Preparation Example 3 Synthesis of Compound 1

     1.4 g of compound intermediate (1), 0.93 g of diphenylamine, and 0.029 g of palladium acetate (2) were added and dissolved in 30 ml of toluene. When the reagents were dissolved, 0.52 g of 1 mol solution sodium-tert-butoxide and 2.20 g of tert-phosphine were added dropwise. Reflux while maintaining the temperature at 120 ° C. After the reaction, the mixture is extracted with dichloromethane and distilled water to dry the solvent. The solid was filtered to obtain Compound 1 as a pale yellow powder. Compound 1 showed a high glass transition temperature of 142 ℃.

The analysis data obtained by nuclear magnetic resonance and mass spectrometry are as follows.

NMR-1H (200 MHz, CDCl3): δ 7.75 (d, 2H), 7.50 (d, 2H), 7.35-7.16 (m, 22H), 6.81 (t, 4H), 6.63 (m, 8H), 6.55 (s, 2H), 6.39 (d, 2H)

MS (FAB) m / z 814 [(M + 1) ⁺ ].

Preparation Example 4 Synthesis of Compound 2

30 g of tetrahydrofuran was added to 1.4 g of the compound intermediate (1) to make the temperature at -78 ° C. Thereafter, 2.19 ml of butyllithium was slowly added dropwise. After stirring for 2 hours while maintaining the temperature, 1.2 g of chlorodiphenylphosphine was slowly added dropwise and raised to room temperature. After completion of the reaction, 10 ml of methanol was added thereto and stirred, and after extraction, the solvent was dried. Dichloromethane was added to this solid, and a small amount of hydrogen peroxide was added, stirring, and the compound 2 which has the above-mentioned typical compound structure of white phosphine oxide was obtained. Compound 2 showed a high glass transition temperature of 156 ℃.

The analysis data obtained by nuclear magnetic resonance and mass spectrometry are as follows.

NMR-1H (200 Hz, CDCl3): 7.77-7.75 (m, 12H), 7.45 (m, 12H), 7.27 (d, 4H), 7.16-7.14 (m, 6H), 6.98-6.95 (m, 6H)

MS (FAB) m / z 878 [(M + l) ⁺ ].

Preparation Example 5 Synthesis of Compound 6

1.4 g of compound intermediate (1), 0.46 g of diphenylamine, and 0.015 g of palladium acetate (2) were added and dissolved in 30 ml of toluene. When the reagents were dissolved, 0.26 g of 1 mol solution sodium-tert-butoxide and 1.10 g of tert-phosphine were added dropwise. Reflux while maintaining the temperature at 120 ° C. After the reaction, the mixture is extracted with dichloromethane and distilled water to dry the solvent. This solid is dissolved in 30 ml of tetrahydrofuran and the temperature is lowered to -78 ° C. 1.5 ml of butyllithium was slowly added dropwise and stirred while maintaining the temperature for 2 hours. 0.5 g of chlorodiphenylphosphine was slowly added dropwise and the temperature was raised to room temperature. After completion of the reaction, 10 ml of methanol was added to the mixture, followed by stirring. After extraction, the solvent was dried. Dichloromethane was added to this solid, and a small amount of hydrogen peroxide was added while stirring to obtain compound 6 which is a white phosphine oxide.

Compound 6 synthesized showed a high glass transition temperature of 150 ℃.

The analysis data obtained by nuclear magnetic resonance and mass spectrometry are as follows.

NMR-1H (200 Hz, CDCl3): 7.77-7.75 (m, 7H), 7.50-7.35 (m, 10H), 7.20-7.14 (m, 12H), 6.98-6.95 (m, 3H), 6.81 (m, 2H ), 6.63-6.55 (m, 5H), 6.39 (d, 1H)

MS (FAB) m / z 845 [(M + l) ⁺ ].

Preparation Example 6 Synthesis of Intermediate 4-Bromo-9,9'-Spirobi [Fluorene]

After 3 g of 2,2'-dibromobiphenyl was dissolved in 15 ml of tetrahydrofuran, the temperature was set to -78 ° C. 4.61 ml of butyllithium was slowly added dropwise and stirred for 2 hours. 2 g of 9H-fluorenone was dissolved in 25 ml of tetrahydrofuran, and slowly added dropwise thereto, and the temperature was raised to room temperature. After the reaction, 40 ml of a 2% aqueous sodium hydrogen carbonate solution was added and stirred. After extraction with dichloromethane the solvent was dried. Extract with dichloromethane and dry the solvent. 50 ml of acetic acid is added to this solid and the temperature is dissolved. 5 ml of hydrochloric acid was added and refluxed at 120 ° C. After the reaction, the solvent was dried after extraction using dichloromethane and distilled water. The solid was filtered to obtain the intermediate 4-bromo-9,9'-spirobi [fluorene].

Preparation Example 7 Synthesis of Intermediate (2)

After dissolving 5.7 g of 4-bromo-9,9'-spirobi [fluorene] in 76 ml of tetrahydrofuran, the temperature was set to -78 ° C. 7.4 ml of butyllithium was slowly added dropwise and stirred for 2 hours. After dissolving 6.3 g of 2,7-dibromo-fluorenone in 123 ml of tetrahydrofuran, the mixture was slowly added dropwise and the temperature was raised to room temperature. After the reaction, 200 ml of a 2% aqueous sodium hydrogen carbonate solution was added and stirred. After extraction with dichloromethane the solvent was dried. Extract with dichloromethane and dry the solvent. 100 ml of acetic acid is added to this solid and the temperature is dissolved. 10 ml of hydrochloric acid was added and refluxed at 120 ° C. After the reaction, the solvent was dried after extraction using dichloromethane and distilled water. This solid was filtered and the compound intermediate (2) could be obtained.

Manufacturing example  8. Synthesis of Compound 3

1 g of compound intermediate (2), 0.66 g of diphenylamine, and 0.021 g of palladium acetate (2) are added and dissolved in 30 ml of toluene. When the reagents were dissolved, 0.37 g of 1 mol solution sodium-tert-butoxide and 0.3 g of tert-phosphine were added dropwise. Reflux while maintaining the temperature at 120 ° C. After the reaction, the mixture is extracted with dichloromethane and distilled water to dry the solvent. The solid was filtered to obtain Compound 4 as a pale yellow powder.

Compound 3 synthesized showed a high glass transition temperature of 140 ℃.

The analysis data obtained by nuclear magnetic resonance and mass spectrometry are as follows.

NMR-1H (200 Hz, CDCl3): 7.75 (d, 2H), 7.50 (d, 2H), 7.36-7.35 (m, 4H), 7.20-7.16 (m, 16H), 6.81 (m, 4H), 6.63 ( m, 8H), 6.55 (s, 2H), 6.39 (d, 2H)

MS (FAB) m / z 814 [(M + l) ⁺ ].

Manufacturing example  9. Synthesis of Compound 4

30 g of tetrahydrofuran was added to 1.5 g of the compound intermediate (2) to make the temperature at -78 ° C. Thereafter, 2.35 ml of butyllithium was slowly added dropwise. After stirring for 2 hours while maintaining the temperature, 1.3 g of chlorodiphenylphosphine was slowly added dropwise and raised to room temperature. After completion of the reaction, 10 ml of methanol was added thereto and stirred, and after extraction, the solvent was dried. Dichloromethane was added to this solid, and a small amount of hydrogen peroxide was added, and the compound 4 which has the above-mentioned typical compound structure of white phosphine oxide was obtained.

Compound 4 showed a high glass transition temperature of 151 ℃.

The analysis data obtained by nuclear magnetic resonance and mass spectrometry are as follows.

NMR-1H (200 Hz, CDCl3): 7.77-7.75 (m, 12H), 7.45 (d, 12H), 7.36-7.35 (m, 4H), 7.19-7.14 (m, 10H), 6.98 (d, 2H)

MS (FAB) m / z 878 [(M + l) ⁺ ].

Manufacturing example  10. Synthesis of Compound 5

1.4 g of compound intermediate (2), 0.46 g of diphenylamine, and 0.015 g of palladium acetate (2) were added and dissolved in 30 ml of toluene. When the reagents were dissolved, 0.26 g of 1 mol solution sodium-tert-butoxide and 1.10 g of tert-phosphine were added dropwise. Reflux while maintaining the temperature at 120 ° C. After the reaction, the mixture is extracted with dichloromethane and distilled water to dry the solvent. This solid is dissolved in 30 ml of tetrahydrofuran and the temperature is lowered to -78 ° C. 1.5 ml of butyllithium was slowly added dropwise and stirred while maintaining the temperature for 2 hours. 0.5 g of chlorodiphenylphosphine was slowly added dropwise and the temperature was raised to room temperature. After completion of the reaction, 10 ml of methanol was added to the mixture, followed by stirring. After extraction, the solvent was dried. Dichloromethane was added to this solid, and a small amount of hydrogen peroxide was added while stirring to obtain compound 5 which is a white phosphine oxide.

Compound 5 showed a high glass transition temperature of 147 ℃.

The analysis data obtained by nuclear magnetic resonance and mass spectrometry are as follows.

NMR-1H (200 Hz, CDCl3): 7.77-7.75 (m, 7H), 7.50-7.45 (m, 7H), 7.36-7.35 (m, 4H), 7.20-7.14 (m, 13H), 6.98 (d, 2H) ), 6.81 (t, 2H), 6.63 (m, 4H), 6.34 (s, 1H), 6.18 (d, 1H)

MS (FAB) m / z 845 [(M + l) ⁺ ].

Manufacturing example  11.Intermediate 2,2'- Dibromo -4,4'- Dimethylbiphenyl  synthesis

10 g of 1,2-dibromo-4-methylbenzene was dissolved in 100 ml of tetrahydrofuran. The temperature was lowered to −78 ° C. and 9 ml of butyllithium was slowly added dropwise and stirred.

The temperature was slowly raised to room temperature. Extraction was performed with dichloromethane and pure water. The solvent was dried and then recrystallized with nucleic acid to obtain an intermediate 2,2'-dibromo-4,4'-dimethylbiphenyl compound in a crystalline state.

Manufacturing example  12. Synthesis of Intermediate (3)

2 g of 2,2'-dibromo-4,4'-dimethylbiphenyl was dissolved in 15 ml of tetrahydrofuran and the temperature was made to -78 ° C. Thereafter, 5.6 ml of butyllithium was slowly added dropwise. The mixture was stirred for 2 hours as it was and 3.6 g 2-bromo-9H-fluorenone dissolved in 35 ml tetrahydrofuran was slowly added dropwise. Slowly raised to room temperature. 50 ml of 2% aqueous sodium hydrogen carbonate solution was added to the solution and stirred. Extract with dichloromethane and dry the solvent. 50 ml of acetic acid is added to this solid and the temperature is dissolved. 5 ml of sulfuric acid was added and refluxed at 120 ° C. After the reaction, the solvent was dried after extraction using dichloromethane and distilled water. The solid was filtered to obtain the compound intermediate (3).

Manufacturing example  11.Synthesis of Compound 100

2 g of compound intermediate (3), 1.9 g of diphenylamine, and 0.064 g of palladium acetate (2) were added and dissolved in 30 ml of toluene. When the reagents were dissolved, 1.3 g of 1 mol solution sodium-tert-butoxide and 4.8 g of tert-phosphine were added dropwise. Reflux while maintaining the temperature at 120 ° C. After the reaction, the mixture is extracted with dichloromethane and distilled water to dry the solvent. The solid was filtrated to obtain Compound 100 as a pale yellow powder.

No glass transition temperature was observed.

The analysis data obtained by nuclear magnetic resonance and mass spectrometry are as follows.

NMR-1H (200 MHz, CDCl3): δ 7.75 (d, 2H), 7.50 (d, 2H), 7.35 (d, 2H), 7.20-7.16 (m, 12H), 7.07 (s, 4H), 6.81 (t, 4H), 6.63 (m, 8H), 6.55 (s, 2H), 6.39 (d, 2H), 2.34 (s, 6H)

MS (FAB) m / z 840 [(M + 1) ⁺ ].

Manufacturing example  12. Intermediate 4- Bromo -2,7- Dimethyl -9,9'- Of spiroby [fluorene]  synthesis

After 3 g of 2,2'-dibromo-4,4'-dimethylbiphenyl was dissolved in 15 ml of tetrahydrofuran, the temperature was set to -78 ° C. 4.61 ml of butyllithium was slowly added dropwise and stirred for 2 hours. 2 g of 9H-fluorenone was dissolved in 25 ml of tetrahydrofuran, and slowly added dropwise thereto, and the temperature was raised to room temperature. After the reaction, 40 ml of a 2% aqueous sodium hydrogen carbonate solution was added and stirred. After extraction with dichloromethane the solvent was dried. Extract with dichloromethane and dry the solvent. 50 ml of acetic acid is added to this solid and the temperature is dissolved. 5 ml of hydrochloric acid was added and refluxed at 120 ° C. After the reaction, the solvent was dried after extraction using dichloromethane and distilled water. The solid was filtered to obtain the intermediate 4-bromo-2,7-dimethyl-9,9'-spirobi [fluorene].

Production Example 13 . Synthesis of Intermediate (4)

After dissolving 5.7 g of 4-bromo-2,7-dimethyl-9,9'-spirobi [fluorene] in 76 ml of tetrahydrofuran, the temperature was set to -78 ° C. 7.4 ml of butyllithium was slowly added dropwise and stirred for 2 hours. After dissolving 6.3 g of 2,7-dibromo-fluorenone in 123 ml of tetrahydrofuran, the mixture was slowly added dropwise and the temperature was raised to room temperature. After the reaction, 200 ml of a 2% aqueous sodium hydrogen carbonate solution was added and stirred. After extraction with dichloromethane the solvent was dried. Extract with dichloromethane and dry the solvent. 100 ml of acetic acid is added to this solid and the temperature is dissolved. 10 ml of hydrochloric acid was added and refluxed at 120 ° C. After the reaction, the solvent was dried after extraction using dichloromethane and distilled water. This solid was filtered and the compound intermediate (4) was obtained.

Preparation Example 14 Synthesis of Compound 117

2 g of compound intermediate (4), 1.9 g of diphenylamine, and 0.064 g of palladium acetate (2) were added and dissolved in 30 ml of toluene. When the reagents were dissolved, 1.3 g of 1 mol solution sodium-tert-butoxide and 4.8 g of tert-phosphine were added dropwise. Reflux while maintaining the temperature at 120 ° C. After the reaction, the mixture is extracted with dichloromethane and distilled water to dry the solvent. This solid was filtrated to give Compound 117 as a pale yellow powder.

No glass transition temperature was observed.

The analysis data obtained by nuclear magnetic resonance and mass spectrometry are as follows.

NMR-1H (200 MHz, CDCl3): δ7.75 (d, 2H), 7.50 (d, 2H), 7.35 (d, 2H), 7.20-7.16 (m, 14H), 6.98 (s, 2H), 6.81 (t, 4H), 6.63 (m, 8H), 6.55 (s, 2H), 6.39 (d, 2H), 2.34 (s, 6H)

MS (FAB) m / z 840 [(M + 1) ⁺ ].

Preparation Example 15 Synthesis of Intermediate 2,7-Diphenyl-9H-Fluorenone

2 g of 2,7-dibromo-9H-fluorene-9-one, 1.5 g of phenylboronic acid, and 0.68 g of tetrakis (phenylphosphine) palladium (0) were dissolved in 30 ml of tetrahydrofuran. 30 ml of a 2 mol potassium carbonate aqueous solution was put in a reactor and refluxed while maintaining the temperature at 120 ° C. After the reaction was extracted with dichloromethane and the solvent was dried. This solid was filtered to obtain an intermediate 2,7-diphenyl-9H-fluorenone compound.

Preparation Example 16 Synthesis of Intermediate 4-Bromo-2 ', 7'-diphenyl-9,9'-spirobi [fluorene]

After 3 g of 2,2'-dibromobiphenyl was dissolved in 15 ml of tetrahydrofuran, the temperature was set to -78 ° C. 4.61 ml of butyllithium was slowly added dropwise and stirred for 2 hours. 2 g of 2,7-diphenyl-9H-fluorenone was dissolved in 25 ml of tetrahydrofuran, and slowly added dropwise thereto, and the temperature was raised to room temperature. After the reaction, 40 ml of a 2% aqueous sodium hydrogen carbonate solution was added and stirred. After extraction with dichloromethane the solvent was dried. Extract with dichloromethane and dry the solvent. 50 ml of acetic acid is added to this solid and the temperature is dissolved. 5 ml of hydrochloric acid was added and refluxed at 120 ° C. After the reaction, the solvent was dried after extraction using dichloromethane and distilled water. The solid was filtered to obtain the intermediate 4-bromo-2 ', 7'-diphenyl-9,9'-spirobi [fluorene].

Preparation Example 17 Synthesis of Intermediate (5)

5.7 g of 4-bromo-2 ', 7'-diphenyl-9,9'-spirobi [fluorene] was dissolved in 76 ml of tetrahydrofuran and the temperature was set to -78 deg. 4.9 ml of butyllithium were slowly added dropwise and stirred for 2 hours. After dissolving 4.2 g of 2,7-dibromo-fluorenone in 123 ml of tetrahydrofuran, the mixture was slowly added dropwise and the temperature was raised to room temperature. After the reaction, 200 ml of a 2% aqueous sodium hydrogen carbonate solution was added and stirred. After extraction with dichloromethane the solvent was dried. Extract with dichloromethane and dry the solvent. 100 ml of acetic acid is added to this solid and the temperature is dissolved. 10 ml of hydrochloric acid was added and refluxed at 120 ° C. After the reaction, the solvent was dried after extraction using dichloromethane and distilled water. The solid was filtered to obtain the intermediate (5).

Preparation Example 18 Synthesis of Compound 66

  2 g of compound intermediate (5), 2.1 g of diphenylamine, and 0.075 g of palladium acetate (2) were added and dissolved in 30 ml of toluene. When the reagents were dissolved, 1.9 g of 1 mol solution sodium-tert-butoxide and 6.5 g of tert-phosphine were added dropwise. Reflux while maintaining the temperature at 120 ° C. After the reaction, the mixture is extracted with dichloromethane and distilled water to dry the solvent. This solid was filtered to give Compound 66 as a pale yellow powder.

No glass transition temperature was observed.

The analysis data obtained by nuclear magnetic resonance and mass spectrometry are as follows.

NMR-1H (200 MHz, CDCl3): δ 7.81 (d, 2H), 7.57-7.36 (m, 18H), 7.20-7.16 (m, 12H), 6.81 (t, 4H), 6.63 (m, 8H) , 6.55 (s, 2H), 6.39 (d, 2H)

MS (FAB) m / z 964 [(M + 1) ⁺ ].

Preparation Example 19 Synthesis of Intermediate 2,7-Dimethyl-Fluorenone

2 g of 2,7'-dibromo-9H-fluorenone, 1.2 g of bromomethane, and 0.03 g of aluminum trichloride were dissolved in 30 ml of acetonitrile. The temperature was maintained at 100 ° C. and refluxed. Filtration and purification with dichloromethane gave the intermediate 2,7-dimethyl-fluorenone compound.

Preparation Example 20 Synthesis of Intermediate 4-Bromo-2 ', 7'-dimethyl-9,9'-spirobi [fluorene]

After 3 g of 2,2'-dibromobiphenyl was dissolved in 15 ml of tetrahydrofuran, the temperature was set to -78 ° C. 4.61 ml of butyllithium was slowly added dropwise and stirred for 2 hours. 2 g of 2,7-dimethyl-9H-fluorenone was dissolved in 25 ml of tetrahydrofuran, and slowly added dropwise thereto, and the temperature was raised to room temperature. After the reaction, 40 ml of a 2% aqueous sodium hydrogen carbonate solution was added and stirred. After extraction with dichloromethane the solvent was dried. Extract with dichloromethane and dry the solvent. 50 ml of acetic acid is added to this solid and the temperature is dissolved. 5 ml of hydrochloric acid was added and refluxed at 120 ° C. After the reaction, the solvent was dried after extraction using dichloromethane and distilled water. The solid was filtered to obtain intermediate 4-bromo-2 ', 7'-dimethyl-9,9'-spirobi [fluorene].

Preparation Example 21 Synthesis of Intermediate (6)

5.7 g of 4-bromo-2 ', 7'-dimethyl-9,9'-spirobi [fluorene] was dissolved in 76 ml of tetrahydrofuran and the temperature was set to -78 deg. 7.4 ml of butyllithium was slowly added dropwise and stirred for 2 hours. After dissolving 6.3 g of 2,7-dibromo-fluorenone in 123 ml of tetrahydrofuran, the mixture was slowly added dropwise and the temperature was raised to room temperature. After the reaction, 200 ml of a 2% aqueous sodium hydrogen carbonate solution was added and stirred. After extraction with dichloromethane the solvent was dried. Extract with dichloromethane and dry the solvent. 100 ml of acetic acid is added to this solid and the temperature is dissolved. 10 ml of hydrochloric acid was added and refluxed at 120 ° C. After the reaction, the solvent was dried after extraction using dichloromethane and distilled water. This solid was filtered and obtained to obtain the intermediate (6).

Preparation Example 22 Synthesis of Compound 49

2 g of compound intermediate (6), 1.9 g of diphenylamine and 0.064 g of palladium acetate (2) were added, and dissolved in 30 ml of toluene. When the reagents were dissolved, 1.3 g of 1 mol solution sodium-tert-butoxide and 4.8 g of tert-phosphine were added dropwise. Reflux while maintaining the temperature at 120 ° C. After the reaction, the mixture is extracted with dichloromethane and distilled water to dry the solvent. The solid was filtered and purified to obtain Compound 49 as a pale yellow powder.

No glass transition temperature was observed.

The analysis data obtained by nuclear magnetic resonance and mass spectrometry are as follows.

NMR-1H (200 MHz, CDCl3): δ7.63 (d, 2H), 7.50 (d, 2H), 7.36 (d, 2H), 7.20-7.15 (m, 14H), 6.99 (d, 2H), 6.81 (t, 4H), 6.63 (m, 8H), 6.55 (s, 2H), 6.39 (d, 2H), 2.34 (s, 6H)

MS (FAB) m / z 840 [(M + 1) ⁺ ].

Preparation Example 23 Synthesis of Intermediate 3,4-Dibromophenyl

2 g of 1,2,4-tribromobenzene, 0.92 g of phenylboronic acid, and 0.36 g of tetrakis (phenylphosphine) palladium (0) were dissolved in 30 ml of tetrahydrofuran. 30 ml of a 2 mol potassium carbonate aqueous solution was put in a reactor and refluxed while maintaining the temperature at 120 ° C. After the reaction was extracted with dichloromethane and the solvent was dried. This solid was filtered to give the intermediate 3,4-dibromophenyl compound.

Preparation Example 24 Synthesis of Intermediate 2 '', 3'-Dibromo-Para-Quarterphenyl

10 g of 3,4-dibromophenyl was dissolved in 100 ml of tetrahydrofuran. The temperature was lowered to -78 ° C and 6.6 ml of butyllithium was slowly added dropwise and stirred.

The temperature was slowly raised to room temperature. Extraction was performed with dichloromethane and pure water. The solvent was dried and then recrystallized with nucleic acid to obtain an intermediate 2 '', 3'-dibromo-para-quaterphenyl compound in a crystalline state.

Manufacturing example  25. Synthesis of Intermediate (7)

2 g of 2 '', 3'-dibromo-para-quaterphenyl was dissolved in 15 ml of tetrahydrofuran and the temperature was made to -78 ° C. Thereafter, 4.3 ml of butyllithium was slowly added dropwise. After stirring for 2 hours, 2.8 g 2-bromo-9H-fluorenone dissolved in 35 ml tetrahydrofuran was slowly added dropwise. Slowly raised to room temperature. 50 ml of 2% aqueous sodium hydrogen carbonate solution was added to the solution and stirred. Extract with dichloromethane and dry the solvent. 50 ml of acetic acid is added to this solid and the temperature is dissolved. 5 ml of sulfuric acid was added and refluxed at 120 ° C. After the reaction, the solvent was dried after extraction using dichloromethane and distilled water. The solid was filtered to obtain the compound intermediate (7).

Manufacturing example  26. Synthesis of Compound 83

2 g of compound intermediate 7, 2.1 g of diphenylamine, and 0.075 g of palladium acetate (2) were added and dissolved in 30 ml of toluene. When the reagents were dissolved, 1.9 g of 1 mol solution sodium-tert-butoxide and 6.5 g of tert-phosphine were added dropwise. Reflux while maintaining the temperature at 120 ° C. After the reaction, the mixture is extracted with dichloromethane and distilled water to dry the solvent. This solid was filtered to give Compound 66 as a pale yellow powder.

No glass transition temperature was observed.

The analysis data obtained by nuclear magnetic resonance and mass spectrometry are as follows.

NMR-1H (200 MHz, CDCl3): δ7.75 (d, 2H), 7.52-7.35 (m, 18H), 7.20-7.16 (m, 12H), 6.81 (t, 4H), 6.63 (m, 8H) , 6.55 (s, 2H), 6.39 (d, 2H)

MS (FAB) m / z 964 [(M + 1) ⁺ ].

Manufacturing example  27. Intermediate 4- Bromo -2,7- Diphenyl -9,9'- Of spiroby [fluorene]  synthesis

After dissolving 3 g of 2 '', 3'-dibromo-para-quaterphenyl in 15 ml of tetrahydrofuran, the temperature was set to -78 ° C. 3.1 ml of butyllithium were slowly added dropwise and stirred for 2 hours. 1.39 g of 9H-fluorenone was dissolved in 25 ml of tetrahydrofuran, and slowly added dropwise thereto, and the temperature was raised to room temperature. After the reaction, 40 ml of a 2% aqueous sodium hydrogen carbonate solution was added and stirred. After extraction with dichloromethane the solvent was dried. Extract with dichloromethane and dry the solvent. 50 ml of acetic acid is added to this solid and the temperature is dissolved. 5 ml of hydrochloric acid was added and refluxed at 120 ° C. After the reaction, the solvent was dried after extraction using dichloromethane and distilled water. The solid was filtered to obtain the intermediate 4-bromo-2,7-diphenyl-9,9'-spirobi [fluorene].

Manufacturing example  28. Synthesis of Intermediate (8)

After dissolving 5.7 g of 4-bromo-2,7-diphenyl-9,9'-spirobi [fluorene] in 76 ml of tetrahydrofuran, the temperature was set to -78 ° C. 4.99 ml of butyllithium was slowly added dropwise and stirred for 2 hours. After dissolving 4.22 g of 2,7-dibromo-fluorenone in 123 ml of tetrahydrofuran, the mixture was slowly added dropwise and the temperature was raised to room temperature. After the reaction, 200 ml of a 2% aqueous sodium hydrogen carbonate solution was added and stirred. After extraction with dichloromethane the solvent was dried. Extract with dichloromethane and dry the solvent. 100 ml of acetic acid is added to this solid and the temperature is dissolved. 10 ml of hydrochloric acid was added and refluxed at 120 ° C. After the reaction, the solvent was dried after extraction using dichloromethane and distilled water. The solid was filtered to obtain the intermediate compound (8).

Manufacturing example  29. Synthesis of Compound 127

2 g of compound intermediate (8), 2.1 g of diphenylamine, and 0.075 g of palladium acetate (2) were added and dissolved in 30 ml of toluene. When the reagents were dissolved, 1.9 g of 1 mol solution sodium-tert-butoxide and 6.5 g of tert-phosphine were added dropwise. Reflux while maintaining the temperature at 120 ° C. After the reaction, the mixture is extracted with dichloromethane and distilled water to dry the solvent. This solid was filtered to give Compound 127 as a pale yellow powder. No glass transition temperature was observed.

The analysis data obtained by nuclear magnetic resonance and mass spectrometry are as follows.

MR-1H (200 MHz, CDCl3): δ7.75 (d, 2H), 7.58-7.35 (m, 18H), 7.20-7.16 (m, 12H), 6.81 (t, 4H), 6.63 (d, 8H) , 6.55 (s, 2H), 6.39 (d, 2H)

MS (FAB) m / z 964 [(M + 1) ⁺ ].

Manufacturing example  30. Synthesis of Compound 137

2 g of compound intermediate (1), 0.84 g of pyridin-3-ylboronic acid, and 0.36 g of tetrakis (phenylphosphine) palladium (0) are dissolved in 30 ml of tetrahydrofuran. 30 ml of 2M aqueous potassium carbonate solution was added dropwise and refluxed while maintaining the temperature at 120 ° C. The reaction solution was extracted with dichloromethane, the solvent was dried and the solid was filtered to give compound 137.

No glass transition temperature was observed.

The analysis data obtained by nuclear magnetic resonance and mass spectrometry are as follows.

MR-1H (200 MHz, CDCl3): δ 9.24 (s, 2H), 8.70 (d, 2H), 8.42 (d, 2H), 7.81-7.75 (m, 4H), 7.57 (t, 4H), 7.44 ( d, 2H), 7.35-7.16 (m, 12H)

MS (FAB) m / z 632 [(M + 1) ⁺ ].

Manufacturing example  31. Synthesis of Compound 149

Add 1 g of compound intermediate (1), 0.65 g of diphenylamine, and 0.02 g of palladium acetate (2), and dissolve in 30 ml of toluene. When the reagents were dissolved, 0.3 g of 1 mol solution sodium-tert-butoxide and 0.31 g of tert-phosphine were added dropwise. Reflux while maintaining the temperature at 120 ° C. After the reaction, the mixture is extracted with dichloromethane and distilled water to dry the solvent. This solid was filtered to give Compound 149 as a pale yellow powder.

No glass transition temperature was observed.

The analysis data obtained by nuclear magnetic resonance and mass spectrometry are as follows.

MR-1H (200 MHz, CDCl3): δ 8.55 (d, 2H), 8.12 (d, 2H), 7.94 (d, 2H), 7.75 (d, 2H), 7.63 (d, 2H), 7.50 (t, 2H), 7.33-7.14 (m, 16H), 6.98-6.95 (m, 6H)

MS (FAB) m / z 808 [(M + 1) ⁺ ].

Example  One

Compound 1 synthesized in the present invention was applied as a hole transport layer material of the green phosphor to prepare a green phosphor.

The structure of the device is ITO / DNTPD (N, N'-diphenyl-N, N'-bis- [4- (phenyl-m-tolyl-amino) -phenyl] -biphenyl-4,4'-diamine, 60nm) / Compound 1 (30 nm) / TMM004 (Merck Co.): Ir (ppy) ₃ (30 nm, 10%) / Alq ₃ (20 nm) / LiF / Al.

Fabrication of the device was performed in the following manner. The ITO substrate was washed with pure water and isopropyl alcohol for 30 minutes in ultrasonic waves, and the surface of the ITO substrate was treated with short wavelength ultraviolet rays, and the organic material was vacuum deposited under a pressure of ¹ × 10 ⁻⁶ torr. DNTPD, Compound 1, and Alq ₃ were deposited at a rate of 0.1 nm / s to form films corresponding to each thickness. PH1 was vacuum deposited with an Ir (ppy) ₃ dopant, where the deposition rate was 0.1 nm / s, Ir (ppy) ₃ was 0.01 nm / s. LiF was formed at a thickness of 1 nm at a rate of 0.01 nm / s, and Al was formed at a thickness of 100 nm at a deposition rate of 0.5 nm / sec. After the device was formed, the device was sealed using a CaO absorbent and a glass cover glass.

Example 2

Compound 6 synthesized in the present invention was applied as a material of the hole transport layer of the green phosphor to prepare a green phosphor.

The structure of the device is ITO / DNTPD (N, N'-diphenyl-N.N'-bis- [4- (phenyl-m-tolyl-amino) -phenyl] -biphenyl-4,4'-diamine, 60nm) / Compound 6 (30 nm) / PH1: Ir (ppy) ₃ (30 nm, 10%) / Alq ₃ (20 nm) / LiF / Al.

Fabrication of the device was performed in the following manner. The ITO substrate was washed with pure water and isopropyl alcohol for 30 minutes in ultrasonic waves, and the surface of the ITO substrate was treated with short wavelength ultraviolet rays, and the organic material was vacuum deposited under a pressure of ¹ × 10 ⁻⁶ torr. DNTPD, Compound 6, and Alq ₃ were deposited at a rate of 0.1 nm / s to form films corresponding to each thickness, and PH1 was vacuum-deposited with Ir (ppy) ₃ dopant. At this time, the deposition rate was 0.1 nm / s. , Ir (ppy) ₃ was 0.01 nm / s. LiF was formed at a thickness of 1 nm at a rate of 0.01 nm / s, and Al was formed at a thickness of 100 nm at a deposition rate of 0.5 nm / sec. After the device was formed, the device was sealed using a CaO absorbent and a glass cover glass.

The quantum efficiencies of Examples 1 to 4 and Comparative Examples 1 and 2 are described in G. Gu and SR Forrest, IEEE Journal of Selected Topics in Quantum Electronics, Vol. 4, No. 1, January / February 1998, p. 83 -99).

Referring to FIG. 2, the green phosphor manufactured in the present invention showed a maximum quantum efficiency of 17.8%.

Example  3

Compound 2 synthesized in the present invention was applied as an electron transport layer material of the green phosphor to prepare a green phosphor.

The structure of the device is ITO / DNTPD (60nm) / N, N'-di (1-naphthyl) -N, N'-diphenylbenzidine (NPB, 30 nm) / (4,4'-N, N'-dicarbazole) biphenyl (CBP): Ir (ppy) ₃ (30 nm, 10%) / Compound 2 (20 nm) / LiF / Al.

Fabrication of the device was performed in the following manner. The ITO substrate was washed with pure water and isopropyl alcohol for 30 minutes in ultrasonic waves, and the surface of the ITO substrate was treated with short wavelength ultraviolet rays, and the organic material was vacuum deposited under a pressure of ¹ × 10 ⁻⁶ torr. DNTPD, Compound 2, and NPB were deposited at a rate of 0.1 nm / s to form films corresponding to each thickness. CBP was vacuum deposited with Ir (ppy) ₃ dopant, and the deposition rate was 0.1 nm / s for CBP. Ir (ppy) ₃ was 0.01 nm / s. LiF was formed at a thickness of 1 nm at a rate of 0.01 nm / s, and Al was formed at a thickness of 100 nm at a deposition rate of 0.5 nm / sec. After the device was formed, the device was sealed using a CaO absorbent and a glass cover glass.

The fabricated device had a quantum efficiency of 10.5%.

Example 4

Compound 2 synthesized in the present invention was applied as a host material of the green phosphor to prepare a green phosphor.

The structure of the device was ITO / DNTPD (60 nm) / NPB (30 nm) / Compound 2: Ir (ppy) ₃ (30 nm, 10%) / Alq ₃ (20 nm) / LiF / Al.

Fabrication of the device was performed in the following manner. The ITO substrate was washed with pure water and isopropyl alcohol for 30 minutes in ultrasonic waves, and the surface of the ITO substrate was treated with short wavelength ultraviolet rays, and the organic material was vacuum deposited under a pressure of ¹ × 10 ⁻⁶ torr. DNTPD, NPB, and Alq ₃ were deposited at a rate of 0.1 nm / s to form films corresponding to each thickness. Compound 2 was vacuum deposited with Ir (ppy) ₃ dopant, and the deposition rate was 0.1 nm / s. s and Ir (ppy) ₃ were 0.01 nm / s. LiF was formed at a thickness of 1 nm at a rate of 0.01 nm / s, and Al was formed at a thickness of 100 nm at a deposition rate of 0.5 nm / sec. After the device was formed, the device was sealed using a CaO absorbent and a glass cover glass.

The fabricated device had a quantum efficiency of 10.5%.

Comparative Example 1

As a comparative example, devices were fabricated using NPB, which is generally applied as a hole transport layer material. The device structure was ITO / DNTPD (60 nm) / NPB (30 nm) / PH1: Ir (ppy) ₃ (30 nm, 10%) / Alq ₃ (20 nm) / LiF / Al.

The device was fabricated in the same manner as in Example 1, except that Compound 1 was not used as the hole transport material and NPB was used instead.

Referring to FIG. 2, the green phosphorescent device of the present structure exhibited low quantum efficiency of 6.7%.

Quantum efficiency comparison data is shown in Table 2.

Quantum Efficiency (%) Color coordinates Example 1 16.5 (0.31, 0.62) Example 2 11.5 (0.32, 0.62) Example 3 10.9 (0.28, 0.63) Example 4 9.1 (0.28, 0.60) Comparative Example 1 6.3 (0.31, 0.59)

Claims (15)

A spiro compound represented by the following formula (1).
[Formula 1]

In Chemical Formula 1,
R ¹ to R ⁶ are the same as or different from each other, and all may not be a hydrogen atom,
R ¹ to R ⁶ At least one of each independently

,

,

, or

And R ¹ to R ⁶ The remaining are each independently a hydrogen atom, a heteroaryl group of the alkyl group of C _{1 -9,} C _{6 -30} aryl group or a C _{5 -30,}
And R ¹ to R ⁶ At least one of each independently may combine with a carbon atom of a neighboring benzene ring to form a conjugated aromatic ring or a conjugated heteroaromatic ring,
The alkyl groups of the R ⁷ to R ⁹ is a hydrogen atom or a C _1-9, each independently,
Wherein Ar ¹ to Ar ⁴ is a heteroaryl group are each independently a hydrogen atom, C _{6 -30} aryl group or a C _{5 -30.} According to claim 1, wherein R ¹ to R ⁶ At least one of

Spyro compound, characterized in that. According to claim 1, wherein R ¹ to R ⁶ At least one of

Spyro compound, characterized in that. According to claim 1, wherein R ¹ to R ⁶ At least one of

Spyro compound, characterized in that. According to claim 1, wherein R ¹ to R ⁶ At least one of

Spyro compound, characterized in that. According to claim 1, wherein R ¹ to R ⁶ Are each independently of the other an aryl group, a hydrogen atom or a C _{6 -30,} wherein Ar ¹ to Ar ⁴ is selected from the compounds as a spy, it characterized in that each independently represents a hydrogen atom or an aryl group of C _{6 -30.} According to claim 6, wherein R ¹ to R ⁶ The rest of the hydrogen atoms, Ar ¹ to Ar ⁴ is a spiro compound, characterized in that a hydrogen atom. A first electrode; A second electrode; Light emitting layer; And a hole transport layer, wherein the light emitting layer includes a host and a dopant.
The hole transport layer is an organic light emitting device, characterized in that it comprises a spiro compound of claim 1. The organic light emitting device of claim 8, wherein the host comprises a spiro compound of claim 1. The organic light emitting device of claim 8, wherein the organic light emitting device further comprises an electron transport layer. The organic light emitting device of claim 10, wherein the electron transport layer comprises a spiro compound of claim 1. A first electrode; A second electrode; Light emitting layer; In the organic light emitting device comprising an electron transport layer and a hole transport layer, the light emitting layer comprises a host and a dopant,
The host is an organic light emitting device, characterized in that it comprises a spiro compound of claim 1. The organic light emitting device of claim 12, wherein the electron transport layer comprises a spiro compound of claim 1. The organic light emitting device of claim 12, wherein the organic light emitting device further comprises at least one of a hole injection layer and an electron injection layer. A first electrode; A second electrode; Light emitting layer; In the organic light emitting device comprising an electron transport layer and a hole transport layer, the light emitting layer comprises a host and a dopant,
The electron transport layer is an organic electroluminescent device, characterized in that it comprises a spiro compound of claim 1.

Images