JP5205858B2 - Novel benzo [c] fluorene derivatives and uses thereof - Google Patents
Novel benzo [c] fluorene derivatives and uses thereof Download PDFInfo
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- JP5205858B2 JP5205858B2 JP2007208332A JP2007208332A JP5205858B2 JP 5205858 B2 JP5205858 B2 JP 5205858B2 JP 2007208332 A JP2007208332 A JP 2007208332A JP 2007208332 A JP2007208332 A JP 2007208332A JP 5205858 B2 JP5205858 B2 JP 5205858B2
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- benzo
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- FRIJWEQBTIZQMD-UHFFFAOYSA-N Benzo[c]fluorene Chemical class C1=CC2=CC=CC=C2C2=C1CC1=CC=CC=C12 FRIJWEQBTIZQMD-UHFFFAOYSA-N 0.000 title claims description 19
- -1 biphenylyl group Chemical group 0.000 claims description 218
- 125000004432 carbon atom Chemical group C* 0.000 claims description 28
- 238000005401 electroluminescence Methods 0.000 claims description 22
- 125000003118 aryl group Chemical group 0.000 claims description 16
- 125000005843 halogen group Chemical group 0.000 claims description 10
- 229910052757 nitrogen Inorganic materials 0.000 claims description 10
- 125000003545 alkoxy group Chemical group 0.000 claims description 9
- 238000002347 injection Methods 0.000 claims description 9
- 239000007924 injection Substances 0.000 claims description 9
- 125000001424 substituent group Chemical group 0.000 claims description 8
- 125000006165 cyclic alkyl group Chemical group 0.000 claims description 7
- 125000004122 cyclic group Chemical group 0.000 claims description 7
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 7
- 125000004104 aryloxy group Chemical group 0.000 claims description 6
- 125000001072 heteroaryl group Chemical group 0.000 claims description 6
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 6
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 6
- 230000005525 hole transport Effects 0.000 claims description 5
- 125000000623 heterocyclic group Chemical group 0.000 claims description 3
- 125000001624 naphthyl group Chemical group 0.000 claims description 3
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 3
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 claims description 3
- 125000003983 fluorenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3CC12)* 0.000 claims description 2
- 125000004653 anthracenylene group Chemical group 0.000 claims 1
- 125000005428 anthryl group Chemical group [H]C1=C([H])C([H])=C2C([H])=C3C(*)=C([H])C([H])=C([H])C3=C([H])C2=C1[H] 0.000 claims 1
- 125000005567 fluorenylene group Chemical group 0.000 claims 1
- 125000004957 naphthylene group Chemical group 0.000 claims 1
- 125000004076 pyridyl group Chemical group 0.000 claims 1
- 125000005551 pyridylene group Chemical group 0.000 claims 1
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 49
- 238000000921 elemental analysis Methods 0.000 description 37
- 230000015572 biosynthetic process Effects 0.000 description 36
- 238000003786 synthesis reaction Methods 0.000 description 36
- 238000006243 chemical reaction Methods 0.000 description 34
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 27
- 239000000126 substance Substances 0.000 description 27
- 239000010410 layer Substances 0.000 description 25
- 238000004949 mass spectrometry Methods 0.000 description 25
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 22
- 239000000243 solution Substances 0.000 description 22
- 239000000463 material Substances 0.000 description 21
- 238000005259 measurement Methods 0.000 description 20
- 238000005160 1H NMR spectroscopy Methods 0.000 description 16
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 16
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 15
- 150000001875 compounds Chemical class 0.000 description 15
- XYFCBTPGUUZFHI-UHFFFAOYSA-N phosphine group Chemical group P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 14
- 238000000434 field desorption mass spectrometry Methods 0.000 description 13
- 238000000034 method Methods 0.000 description 13
- 229910052763 palladium Inorganic materials 0.000 description 13
- MFRIHAYPQRLWNB-UHFFFAOYSA-N sodium tert-butoxide Chemical compound [Na+].CC(C)(C)[O-] MFRIHAYPQRLWNB-UHFFFAOYSA-N 0.000 description 12
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 11
- 239000012299 nitrogen atmosphere Substances 0.000 description 11
- 239000003054 catalyst Substances 0.000 description 10
- 239000012153 distilled water Substances 0.000 description 10
- 229940078552 o-xylene Drugs 0.000 description 10
- BWHDROKFUHTORW-UHFFFAOYSA-N tritert-butylphosphane Chemical compound CC(C)(C)P(C(C)(C)C)C(C)(C)C BWHDROKFUHTORW-UHFFFAOYSA-N 0.000 description 10
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 9
- 125000002947 alkylene group Chemical group 0.000 description 9
- 238000010898 silica gel chromatography Methods 0.000 description 9
- 239000002904 solvent Substances 0.000 description 9
- 239000002585 base Substances 0.000 description 8
- 150000002941 palladium compounds Chemical class 0.000 description 7
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 7
- 238000005406 washing Methods 0.000 description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- 230000009477 glass transition Effects 0.000 description 6
- YJVFFLUZDVXJQI-UHFFFAOYSA-L palladium(ii) acetate Chemical compound [Pd+2].CC([O-])=O.CC([O-])=O YJVFFLUZDVXJQI-UHFFFAOYSA-L 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- 239000007983 Tris buffer Substances 0.000 description 5
- 239000000460 chlorine Substances 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 229920006395 saturated elastomer Polymers 0.000 description 5
- 239000011780 sodium chloride Substances 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- PCLIMKBDDGJMGD-UHFFFAOYSA-N N-bromosuccinimide Chemical compound BrN1C(=O)CCC1=O PCLIMKBDDGJMGD-UHFFFAOYSA-N 0.000 description 4
- WGQKYBSKWIADBV-UHFFFAOYSA-N benzylamine Chemical compound NCC1=CC=CC=C1 WGQKYBSKWIADBV-UHFFFAOYSA-N 0.000 description 4
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 4
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- ODHXBMXNKOYIBV-UHFFFAOYSA-N triphenylamine Chemical compound C1=CC=CC=C1N(C=1C=CC=CC=1)C1=CC=CC=C1 ODHXBMXNKOYIBV-UHFFFAOYSA-N 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- 125000000732 arylene group Chemical group 0.000 description 3
- 239000006227 byproduct Substances 0.000 description 3
- XCJYREBRNVKWGJ-UHFFFAOYSA-N copper(II) phthalocyanine Chemical compound [Cu+2].C12=CC=CC=C2C(N=C2[N-]C(C3=CC=CC=C32)=N2)=NC1=NC([C]1C=CC=CC1=1)=NC=1N=C1[C]3C=CC=CC3=C2[N-]1 XCJYREBRNVKWGJ-UHFFFAOYSA-N 0.000 description 3
- 125000005549 heteroarylene group Chemical group 0.000 description 3
- 239000012044 organic layer Substances 0.000 description 3
- 238000000746 purification Methods 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- NHDODQWIKUYWMW-UHFFFAOYSA-N 1-bromo-4-chlorobenzene Chemical compound ClC1=CC=C(Br)C=C1 NHDODQWIKUYWMW-UHFFFAOYSA-N 0.000 description 2
- 125000001637 1-naphthyl group Chemical group [H]C1=C([H])C([H])=C2C(*)=C([H])C([H])=C([H])C2=C1[H] 0.000 description 2
- 125000001622 2-naphthyl group Chemical group [H]C1=C([H])C([H])=C2C([H])=C(*)C([H])=C([H])C2=C1[H] 0.000 description 2
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 2
- 125000004860 4-ethylphenyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)C([H])([H])C([H])([H])[H] 0.000 description 2
- 125000000590 4-methylphenyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)C([H])([H])[H] 0.000 description 2
- DIVZFUBWFAOMCW-UHFFFAOYSA-N 4-n-(3-methylphenyl)-1-n,1-n-bis[4-(n-(3-methylphenyl)anilino)phenyl]-4-n-phenylbenzene-1,4-diamine Chemical compound CC1=CC=CC(N(C=2C=CC=CC=2)C=2C=CC(=CC=2)N(C=2C=CC(=CC=2)N(C=2C=CC=CC=2)C=2C=C(C)C=CC=2)C=2C=CC(=CC=2)N(C=2C=CC=CC=2)C=2C=C(C)C=CC=2)=C1 DIVZFUBWFAOMCW-UHFFFAOYSA-N 0.000 description 2
- CRHRWHRNQKPUPO-UHFFFAOYSA-N 4-n-naphthalen-1-yl-1-n,1-n-bis[4-(n-naphthalen-1-ylanilino)phenyl]-4-n-phenylbenzene-1,4-diamine Chemical compound C1=CC=CC=C1N(C=1C2=CC=CC=C2C=CC=1)C1=CC=C(N(C=2C=CC(=CC=2)N(C=2C=CC=CC=2)C=2C3=CC=CC=C3C=CC=2)C=2C=CC(=CC=2)N(C=2C=CC=CC=2)C=2C3=CC=CC=C3C=CC=2)C=C1 CRHRWHRNQKPUPO-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 241000284156 Clerodendrum quadriloculare Species 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- 238000005481 NMR spectroscopy Methods 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 235000019270 ammonium chloride Nutrition 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 239000002635 aromatic organic solvent Substances 0.000 description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Chemical compound BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 2
- 239000012295 chemical reaction liquid Substances 0.000 description 2
- DMBHHRLKUKUOEG-UHFFFAOYSA-N diphenylamine Chemical compound C=1C=CC=CC=1NC1=CC=CC=C1 DMBHHRLKUKUOEG-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 150000002220 fluorenes Chemical class 0.000 description 2
- 235000019253 formic acid Nutrition 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 125000000040 m-tolyl group Chemical group [H]C1=C([H])C(*)=C([H])C(=C1[H])C([H])([H])[H] 0.000 description 2
- 238000000691 measurement method Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- NIHNNTQXNPWCJQ-UHFFFAOYSA-N o-biphenylenemethane Natural products C1=CC=C2CC3=CC=CC=C3C2=C1 NIHNNTQXNPWCJQ-UHFFFAOYSA-N 0.000 description 2
- 125000003261 o-tolyl group Chemical group [H]C1=C([H])C(*)=C(C([H])=C1[H])C([H])([H])[H] 0.000 description 2
- MUJIDPITZJWBSW-UHFFFAOYSA-N palladium(2+) Chemical compound [Pd+2] MUJIDPITZJWBSW-UHFFFAOYSA-N 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000001953 recrystallisation Methods 0.000 description 2
- 238000001771 vacuum deposition Methods 0.000 description 2
- 239000008096 xylene Substances 0.000 description 2
- SLLDDDJWIRFAGU-UHFFFAOYSA-N 1,2-dichlorocycloocta-1,5-diene Chemical compound ClC1=C(Cl)CCC=CCC1 SLLDDDJWIRFAGU-UHFFFAOYSA-N 0.000 description 1
- YJTKZCDBKVTVBY-UHFFFAOYSA-N 1,3-Diphenylbenzene Chemical group C1=CC=CC=C1C1=CC=CC(C=2C=CC=CC=2)=C1 YJTKZCDBKVTVBY-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- RHDYQUZYHZWTCI-UHFFFAOYSA-N 1-methoxy-4-phenylbenzene Chemical compound C1=CC(OC)=CC=C1C1=CC=CC=C1 RHDYQUZYHZWTCI-UHFFFAOYSA-N 0.000 description 1
- 125000004201 2,4-dichlorophenyl group Chemical group [H]C1=C([H])C(*)=C(Cl)C([H])=C1Cl 0.000 description 1
- 125000004215 2,4-difluorophenyl group Chemical group [H]C1=C([H])C(*)=C(F)C([H])=C1F 0.000 description 1
- 125000004174 2-benzimidazolyl group Chemical group [H]N1C(*)=NC2=C([H])C([H])=C([H])C([H])=C12 0.000 description 1
- 125000006276 2-bromophenyl group Chemical group [H]C1=C([H])C(Br)=C(*)C([H])=C1[H] 0.000 description 1
- 125000004182 2-chlorophenyl group Chemical group [H]C1=C([H])C(Cl)=C(*)C([H])=C1[H] 0.000 description 1
- 125000004198 2-fluorophenyl group Chemical group [H]C1=C([H])C(F)=C(*)C([H])=C1[H] 0.000 description 1
- 125000002941 2-furyl group Chemical group O1C([*])=C([H])C([H])=C1[H] 0.000 description 1
- 125000004204 2-methoxyphenyl group Chemical group [H]C1=C([H])C(*)=C(OC([H])([H])[H])C([H])=C1[H] 0.000 description 1
- TXBIZRLVIDXDGB-UHFFFAOYSA-N 2-methylpropylphosphane Chemical compound CC(C)CP TXBIZRLVIDXDGB-UHFFFAOYSA-N 0.000 description 1
- 125000004105 2-pyridyl group Chemical group N1=C([*])C([H])=C([H])C([H])=C1[H] 0.000 description 1
- 125000000175 2-thienyl group Chemical group S1C([*])=C([H])C([H])=C1[H] 0.000 description 1
- 125000005809 3,4,5-trimethoxyphenyl group Chemical group [H]C1=C(OC([H])([H])[H])C(OC([H])([H])[H])=C(OC([H])([H])[H])C([H])=C1* 0.000 description 1
- 125000004189 3,4-dichlorophenyl group Chemical group [H]C1=C([H])C(Cl)=C(Cl)C([H])=C1* 0.000 description 1
- 125000003762 3,4-dimethoxyphenyl group Chemical group [H]C1=C([H])C(OC([H])([H])[H])=C(OC([H])([H])[H])C([H])=C1* 0.000 description 1
- 125000004211 3,5-difluorophenyl group Chemical group [H]C1=C(F)C([H])=C(*)C([H])=C1F 0.000 description 1
- 125000004179 3-chlorophenyl group Chemical group [H]C1=C([H])C(*)=C([H])C(Cl)=C1[H] 0.000 description 1
- 125000004180 3-fluorophenyl group Chemical group [H]C1=C([H])C(*)=C([H])C(F)=C1[H] 0.000 description 1
- 125000003682 3-furyl group Chemical group O1C([H])=C([*])C([H])=C1[H] 0.000 description 1
- 125000004207 3-methoxyphenyl group Chemical group [H]C1=C([H])C(*)=C([H])C(OC([H])([H])[H])=C1[H] 0.000 description 1
- 125000003349 3-pyridyl group Chemical group N1=C([H])C([*])=C([H])C([H])=C1[H] 0.000 description 1
- 125000001541 3-thienyl group Chemical group S1C([H])=C([*])C([H])=C1[H] 0.000 description 1
- 125000004800 4-bromophenyl group Chemical group [H]C1=C([H])C(*)=C([H])C([H])=C1Br 0.000 description 1
- 125000001255 4-fluorophenyl group Chemical group [H]C1=C([H])C(*)=C([H])C([H])=C1F 0.000 description 1
- 125000004861 4-isopropyl phenyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)C([H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 125000004172 4-methoxyphenyl group Chemical group [H]C1=C([H])C(OC([H])([H])[H])=C([H])C([H])=C1* 0.000 description 1
- 125000000339 4-pyridyl group Chemical group N1=C([H])C([H])=C([*])C([H])=C1[H] 0.000 description 1
- SJVOYVUTRSZMKW-UHFFFAOYSA-N 7,7-dimethylbenzo[c]fluorene Chemical compound C1=CC2=CC=CC=C2C2=C1C(C)(C)C1=CC=CC=C12 SJVOYVUTRSZMKW-UHFFFAOYSA-N 0.000 description 1
- POBOXVWTBBJWMG-UHFFFAOYSA-N 7,7-diphenylbenzo[c]fluorene Chemical compound C1=CC=CC=C1C1(C=2C=CC=CC=2)C(C=CC=2C3=CC=CC=2)=C3C2=CC=CC=C21 POBOXVWTBBJWMG-UHFFFAOYSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical group [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- HKMTVMBEALTRRR-UHFFFAOYSA-N Benzo[a]fluorene Chemical group C1=CC=CC2=C3CC4=CC=CC=C4C3=CC=C21 HKMTVMBEALTRRR-UHFFFAOYSA-N 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- JFEQSRPBWVSMQH-YECBDVDUSA-N CC1C=CC=CC1N(c(cc1)ccc1N[C@H](CC1)C1N(C1=C(C=CC=C2)C2=CCC1)c1ccccc1)c1c(cccc2)c2ccc1 Chemical compound CC1C=CC=CC1N(c(cc1)ccc1N[C@H](CC1)C1N(C1=C(C=CC=C2)C2=CCC1)c1ccccc1)c1c(cccc2)c2ccc1 JFEQSRPBWVSMQH-YECBDVDUSA-N 0.000 description 1
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- XQVWYOYUZDUNRW-UHFFFAOYSA-N N-Phenyl-1-naphthylamine Chemical compound C=1C=CC2=CC=CC=C2C=1NC1=CC=CC=C1 XQVWYOYUZDUNRW-UHFFFAOYSA-N 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 229910021605 Palladium(II) bromide Inorganic materials 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- RBYGDVHOECIAFC-UHFFFAOYSA-L acetonitrile;palladium(2+);dichloride Chemical compound [Cl-].[Cl-].[Pd+2].CC#N.CC#N RBYGDVHOECIAFC-UHFFFAOYSA-L 0.000 description 1
- 229910001854 alkali hydroxide Inorganic materials 0.000 description 1
- 229910000102 alkali metal hydride Inorganic materials 0.000 description 1
- 150000008046 alkali metal hydrides Chemical class 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 125000000748 anthracen-2-yl group Chemical group [H]C1=C([H])C([H])=C2C([H])=C3C([H])=C([*])C([H])=C([H])C3=C([H])C2=C1[H] 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- WXNOJTUTEXAZLD-UHFFFAOYSA-L benzonitrile;dichloropalladium Chemical compound Cl[Pd]Cl.N#CC1=CC=CC=C1.N#CC1=CC=CC=C1 WXNOJTUTEXAZLD-UHFFFAOYSA-L 0.000 description 1
- 238000009529 body temperature measurement Methods 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- LNAMMBFJMYMQTO-FNEBRGMMSA-N chloroform;(1e,4e)-1,5-diphenylpenta-1,4-dien-3-one;palladium Chemical compound [Pd].[Pd].ClC(Cl)Cl.C=1C=CC=CC=1\C=C\C(=O)\C=C\C1=CC=CC=C1.C=1C=CC=CC=1\C=C\C(=O)\C=C\C1=CC=CC=C1.C=1C=CC=CC=1\C=C\C(=O)\C=C\C1=CC=CC=C1 LNAMMBFJMYMQTO-FNEBRGMMSA-N 0.000 description 1
- 125000002676 chrysenyl group Chemical group C1(=CC=CC=2C3=CC=C4C=CC=CC4=C3C=CC12)* 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 125000001559 cyclopropyl group Chemical group [H]C1([H])C([H])([H])C1([H])* 0.000 description 1
- SWXVUIWOUIDPGS-UHFFFAOYSA-N diacetone alcohol Natural products CC(=O)CC(C)(C)O SWXVUIWOUIDPGS-UHFFFAOYSA-N 0.000 description 1
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 1
- BIHHBTVQFPVSTE-UHFFFAOYSA-N ethyl 2-bromobenzoate Chemical compound CCOC(=O)C1=CC=CC=C1Br BIHHBTVQFPVSTE-UHFFFAOYSA-N 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- RBTKNAXYKSUFRK-UHFFFAOYSA-N heliogen blue Chemical compound [Cu].[N-]1C2=C(C=CC=C3)C3=C1N=C([N-]1)C3=CC=CC=C3C1=NC([N-]1)=C(C=CC=C3)C3=C1N=C([N-]1)C3=CC=CC=C3C1=N2 RBTKNAXYKSUFRK-UHFFFAOYSA-N 0.000 description 1
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000003707 hexyloxy group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])O* 0.000 description 1
- 239000012433 hydrogen halide Substances 0.000 description 1
- 229910000039 hydrogen halide Inorganic materials 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000012442 inert solvent Substances 0.000 description 1
- 150000007529 inorganic bases Chemical class 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 238000004255 ion exchange chromatography Methods 0.000 description 1
- 125000003253 isopropoxy group Chemical group [H]C([H])([H])C([H])(O*)C([H])([H])[H] 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- LZWQNOHZMQIFBX-UHFFFAOYSA-N lithium;2-methylpropan-2-olate Chemical compound [Li+].CC(C)(C)[O-] LZWQNOHZMQIFBX-UHFFFAOYSA-N 0.000 description 1
- NIXOIRLDFIPNLJ-UHFFFAOYSA-M magnesium;benzene;bromide Chemical compound [Mg+2].[Br-].C1=CC=[C-]C=C1 NIXOIRLDFIPNLJ-UHFFFAOYSA-M 0.000 description 1
- NXPHGHWWQRMDIA-UHFFFAOYSA-M magnesium;carbanide;bromide Chemical compound [CH3-].[Mg+2].[Br-] NXPHGHWWQRMDIA-UHFFFAOYSA-M 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- IBHBKWKFFTZAHE-UHFFFAOYSA-N n-[4-[4-(n-naphthalen-1-ylanilino)phenyl]phenyl]-n-phenylnaphthalen-1-amine Chemical compound C1=CC=CC=C1N(C=1C2=CC=CC=C2C=CC=1)C1=CC=C(C=2C=CC(=CC=2)N(C=2C=CC=CC=2)C=2C3=CC=CC=C3C=CC=2)C=C1 IBHBKWKFFTZAHE-UHFFFAOYSA-N 0.000 description 1
- 125000006606 n-butoxy group Chemical group 0.000 description 1
- HUMMCEUVDBVXTQ-UHFFFAOYSA-N naphthalen-1-ylboronic acid Chemical compound C1=CC=C2C(B(O)O)=CC=CC2=C1 HUMMCEUVDBVXTQ-UHFFFAOYSA-N 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 150000007530 organic bases Chemical class 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 125000003854 p-chlorophenyl group Chemical group [H]C1=C([H])C(*)=C([H])C([H])=C1Cl 0.000 description 1
- PBDBXAQKXCXZCJ-UHFFFAOYSA-L palladium(2+);2,2,2-trifluoroacetate Chemical compound [Pd+2].[O-]C(=O)C(F)(F)F.[O-]C(=O)C(F)(F)F PBDBXAQKXCXZCJ-UHFFFAOYSA-L 0.000 description 1
- LXNAVEXFUKBNMK-UHFFFAOYSA-N palladium(II) acetate Substances [Pd].CC(O)=O.CC(O)=O LXNAVEXFUKBNMK-UHFFFAOYSA-N 0.000 description 1
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 1
- JKDRQYIYVJVOPF-FDGPNNRMSA-L palladium(ii) acetylacetonate Chemical compound [Pd+2].C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O JKDRQYIYVJVOPF-FDGPNNRMSA-L 0.000 description 1
- INIOZDBICVTGEO-UHFFFAOYSA-L palladium(ii) bromide Chemical compound Br[Pd]Br INIOZDBICVTGEO-UHFFFAOYSA-L 0.000 description 1
- 125000004115 pentoxy group Chemical group [*]OC([H])([H])C([H])([H])C([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- 125000002080 perylenyl group Chemical group C1(=CC=C2C=CC=C3C4=CC=CC5=CC=CC(C1=C23)=C45)* 0.000 description 1
- 125000005561 phenanthryl group Chemical group 0.000 description 1
- 125000001644 phenoxazinyl group Chemical group C1(=CC=CC=2OC3=CC=CC=C3NC12)* 0.000 description 1
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 description 1
- RPGWZZNNEUHDAQ-UHFFFAOYSA-N phenylphosphine Chemical compound PC1=CC=CC=C1 RPGWZZNNEUHDAQ-UHFFFAOYSA-N 0.000 description 1
- 150000003003 phosphines Chemical class 0.000 description 1
- 108091008695 photoreceptors Proteins 0.000 description 1
- 125000001388 picenyl group Chemical group C1(=CC=CC2=CC=C3C4=CC=C5C=CC=CC5=C4C=CC3=C21)* 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- RPDAUEIUDPHABB-UHFFFAOYSA-N potassium ethoxide Chemical compound [K+].CC[O-] RPDAUEIUDPHABB-UHFFFAOYSA-N 0.000 description 1
- BDAWXSQJJCIFIK-UHFFFAOYSA-N potassium methoxide Chemical compound [K+].[O-]C BDAWXSQJJCIFIK-UHFFFAOYSA-N 0.000 description 1
- LPNYRYFBWFDTMA-UHFFFAOYSA-N potassium tert-butoxide Chemical compound [K+].CC(C)(C)[O-] LPNYRYFBWFDTMA-UHFFFAOYSA-N 0.000 description 1
- 125000002572 propoxy group Chemical group [*]OC([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 125000001725 pyrenyl group Chemical group 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 125000005920 sec-butoxy group Chemical group 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- QDRKDTQENPPHOJ-UHFFFAOYSA-N sodium ethoxide Chemical compound [Na+].CC[O-] QDRKDTQENPPHOJ-UHFFFAOYSA-N 0.000 description 1
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical class O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 1
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000004434 sulfur atom Chemical group 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 125000004213 tert-butoxy group Chemical group [H]C([H])([H])C(O*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- ZGNPLWZYVAFUNZ-UHFFFAOYSA-N tert-butylphosphane Chemical compound CC(C)(C)P ZGNPLWZYVAFUNZ-UHFFFAOYSA-N 0.000 description 1
- 150000004685 tetrahydrates Chemical class 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- DZQQRNFLQBSVBN-UHFFFAOYSA-N tri(butan-2-yl)phosphane Chemical compound CCC(C)P(C(C)CC)C(C)CC DZQQRNFLQBSVBN-UHFFFAOYSA-N 0.000 description 1
- TUQOTMZNTHZOKS-UHFFFAOYSA-N tributylphosphine Chemical compound CCCCP(CCCC)CCCC TUQOTMZNTHZOKS-UHFFFAOYSA-N 0.000 description 1
- 125000003866 trichloromethyl group Chemical group ClC(Cl)(Cl)* 0.000 description 1
- WLPUWLXVBWGYMZ-UHFFFAOYSA-N tricyclohexylphosphine Chemical compound C1CCCCC1P(C1CCCCC1)C1CCCCC1 WLPUWLXVBWGYMZ-UHFFFAOYSA-N 0.000 description 1
- RXJKFRMDXUJTEX-UHFFFAOYSA-N triethylphosphine Chemical compound CCP(CC)CC RXJKFRMDXUJTEX-UHFFFAOYSA-N 0.000 description 1
- 125000000876 trifluoromethoxy group Chemical group FC(F)(F)O* 0.000 description 1
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 1
- IGNTWNVBGLNYDV-UHFFFAOYSA-N triisopropylphosphine Chemical compound CC(C)P(C(C)C)C(C)C IGNTWNVBGLNYDV-UHFFFAOYSA-N 0.000 description 1
- ITHPEWAHFNDNIO-UHFFFAOYSA-N triphosphane Chemical compound PPP ITHPEWAHFNDNIO-UHFFFAOYSA-N 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
Landscapes
- Electroluminescent Light Sources (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
本発明は、新規なベンゾ［ｃ］フルオレン誘導体、並びにその誘導体を利用した有機エレクトロルミネッセンス（ＥＬ）素子に関するものである。本発明における新規なベンゾ［ｃ］フルオレン誘導体は、感光材料、有機光導電材料として使用でき、具体的には、平面光源や表示に使用される有機ＥＬ素子若しくは電子写真感光体等の正孔輸送材料、正孔注入材料及び発光材料として非常に有用である。 The present invention relates to a novel benzo [c] fluorene derivative and an organic electroluminescence (EL) device using the derivative. The novel benzo [c] fluorene derivative in the present invention can be used as a photosensitive material and an organic photoconductive material. Specifically, hole transport such as an organic EL device or an electrophotographic photosensitive member used for a planar light source or display. It is very useful as a material, a hole injection material and a light emitting material.
有機ＥＬ素子は、次世代の薄型平面ディスプレイとして現在盛んに研究されており、一部では携帯電話のサブディスプレイ等への実用化も始まっている。従来、有機ＥＬ素子は、液晶等の薄型平面ディスプレイと比較して、低消費電力であるとの特徴が期待されてきたが、現状、その特徴を十分引き出せているとは言い難く、さらなる低消費電力化に向けた改良検討が活発に行われている。 Organic EL elements are currently being actively researched as next-generation thin flat displays, and some have been put into practical use as sub-displays for mobile phones. Conventionally, organic EL elements have been expected to have low power consumption compared to thin flat displays such as liquid crystals. However, it is difficult to say that the characteristics can be fully exploited at the present time. Improvement studies for electric power are being actively conducted.
一般に有機ＥＬ素子は、陽極と陰極との間に、正孔輸送材料、発光材料及び電子輸送材料を積層させた構造であるが、現在では上述した低消費電力化、さらには長寿命化を達成させるため、正孔注入材料、電子注入材料を、それぞれ陽極と正孔輸送材料、陰極と電子輸送材料の間に挿入した構造が主流となっている。 In general, an organic EL element has a structure in which a hole transport material, a light emitting material, and an electron transport material are laminated between an anode and a cathode, but at the present time, the above-described low power consumption and long life are achieved. Therefore, a structure in which a hole injecting material and an electron injecting material are inserted between an anode and a hole transporting material and a cathode and an electron transporting material, respectively, has become the mainstream.
正孔注入材料としては、例えば、４，４’，４”−トリス（Ｎ，Ｎ−フェニル−ｍ−トリルアミノ）トリフェニルアミン［ｍ−ＭＴＤＡＴＡ］、４，４’，４”−トリス（Ｎ，Ｎ−（２−ナフチル）フェニルアミノ）トリフェニルアミン［２−ＴＮＡＴＡ］、４，４’，４”−トリス（Ｎ，Ｎ−（１−ナフチル）フェニルアミノ）トリフェニルアミン［１−ＴＮＡＴＡ］、４，４’，４”−トリス（Ｎ，Ｎ−（２−ナフチル）−ｍ−トリルアミノ）トリフェニルアミン［２−ＭＴＮＡＴＡ］等のスターバースト系アミン材料（例えば、特許文献１〜３参照）、銅フタロシアニン［ＣｕＰｃ］等（例えば、特許文献４参照）が広く用いられている。 As a hole injection material, for example, 4,4 ′, 4 ″ -tris (N, N-phenyl-m-tolylamino) triphenylamine [m-MTDATA], 4,4 ′, 4 ″ -tris (N, N- (2-naphthyl) phenylamino) triphenylamine [2-TNATA], 4,4 ′, 4 ″ -tris (N, N- (1-naphthyl) phenylamino) triphenylamine [1-TNATA], Starburst amine materials such as 4,4 ′, 4 ″ -tris (N, N- (2-naphthyl) -m-tolylamino) triphenylamine [2-MTNATA] (see, for example, Patent Documents 1 to 3), Copper phthalocyanine [CuPc] or the like (for example, see Patent Document 4) is widely used.
しかし、これらの材料は、低消費電力や耐久性の観点から、実用上十分満足できるものではない。例えば、ｍ−ＭＴＤＡＴＡ、１−ＴＮＡＴＡ等のスターバースト系アミン材料は、低消費電力の観点から十分ではなく、またガラス転移温度が１１０℃以下と低いため、素子寿命の観点からも耐久性に劣るものである。一方、ＣｕＰｃは安価で且つ安定な材料として有用であるが、低消費電力の特性には課題がある。 However, these materials are not sufficiently satisfactory for practical use from the viewpoint of low power consumption and durability. For example, starburst amine materials such as m-MTDATA and 1-TNATA are not sufficient from the viewpoint of low power consumption, and the glass transition temperature is as low as 110 ° C. or lower, so that the durability is also low from the viewpoint of device life. Is. On the other hand, CuPc is useful as an inexpensive and stable material, but there is a problem in the characteristics of low power consumption.
一方、ベンゾフルオレン骨格を有する有機ＥＬ素子が提案されている（例えば、特許文献５参照）。しかし、本先行文献には、ベンゾフルオレニル基にアミノ基が直接結合した化合物は開示されておらず、さらに本先行文献では、ベンゾフルオレニル基を有するポリマー材料が発光材料として有用であるとの記載はあるが、正孔注入材料への適用に関しては何ら言及されていない。 On the other hand, an organic EL element having a benzofluorene skeleton has been proposed (see, for example, Patent Document 5). However, this prior document does not disclose a compound in which an amino group is directly bonded to a benzofluorenyl group. Further, in this prior document, a polymer material having a benzofluorenyl group is useful as a light emitting material. However, no mention is made regarding application to a hole injection material.
上記背景に鑑み、本発明は、有機ＥＬ素子の低駆動電圧化や高電力効率化に有用な新規誘導体、並びにそれを用いた有機ＥＬ素子を提供することを目的とするものである。 In view of the above background, an object of the present invention is to provide a novel derivative useful for lowering the driving voltage and higher power efficiency of an organic EL element, and an organic EL element using the same.
本発明者らは鋭意検討した結果、一般式（１）で表される新規なベンゾ［ｃ］フルオレン誘導体が、前記目的を満足することを見出し、本発明を完成させるに至った。即ち、本発明は、一般式（１）で表されるベンゾ［ｃ］フルオレン誘導体及びその用途に関するものである。 As a result of intensive studies, the present inventors have found that the novel benzo [c] fluorene derivative represented by the general formula (1) satisfies the above object, and has completed the present invention. That is, the present invention relates to a benzo [c] fluorene derivative represented by the general formula (1) and its use.
以下、本発明を詳細に説明する。
Hereinafter, the present invention will be described in detail.
本発明の一般式（１）で表されるベンゾ［ｃ］フルオレン誘導体は新規化合物であり、一般式（１）において、Ｒ１及びＲ２は各々同一または異なっていてもよく、水素原子、炭素数１〜１８の直鎖，分岐若しくは環状のアルキル基、炭素数１〜１８の直鎖，分岐若しくは環状のアルコキシ基、炭素数６〜２４のアリール基若しくはアリールオキシ基、またはハロゲン原子を表す。 The benzo [c] fluorene derivative represented by the general formula (1) of the present invention is a novel compound. In the general formula (1), R 1 and R 2 may be the same or different from each other, and may be a hydrogen atom, carbon A linear, branched or cyclic alkyl group having 1 to 18 carbon atoms, a linear, branched or cyclic alkoxy group having 1 to 18 carbon atoms, an aryl group or aryloxy group having 6 to 24 carbon atoms, or a halogen atom.
Ｒ１及びＲ２における炭素数１〜１８の直鎖，分岐若しくは環状のアルキル基とは、具体的にはメチル基、エチル基、プロピル基、イソプロピル基、ブチル基、ｓｅｃ−ブチル基、ｔｅｒｔ−ブチル基、ペンチル基、ヘキシル基、ヘプチル基、オクチル基、ステアリル基、トリクロロメチル基、トリフルオロメチル基、シクロプロピル基、シクロヘキシル基、１，３−シクロヘキサジエニル基、２−シクロペンテン−１−イル基等を例示することができる。 Specific examples of the linear, branched or cyclic alkyl group having 1 to 18 carbon atoms in R 1 and R 2 include methyl group, ethyl group, propyl group, isopropyl group, butyl group, sec-butyl group, tert- Butyl, pentyl, hexyl, heptyl, octyl, stearyl, trichloromethyl, trifluoromethyl, cyclopropyl, cyclohexyl, 1,3-cyclohexadienyl, 2-cyclopenten-1-yl Examples include groups.
Ｒ１及びＲ２における炭素数１〜１８の直鎖，分岐若しくは環状のアルコキシ基とは、具体的にはメトキシ基、エトキシ基、プロポキシ基、イソプロポキシ基、ｎ−ブトキシ基、ｓｅｃ−ブトキシ基、ｔｅｒｔ−ブトキシ基、ペンチルオキシ基、ヘキシルオキシ基、ステアリルオキシ基、トリフルオロメトキシ基等を例示することができる。 Specific examples of the linear, branched, or cyclic alkoxy group having 1 to 18 carbon atoms in R 1 and R 2 include a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, an n-butoxy group, and a sec-butoxy group. Tert-butoxy group, pentyloxy group, hexyloxy group, stearyloxy group, trifluoromethoxy group and the like.
Ｒ１及びＲ２における炭素数６〜２４のアリール基とは、置換基を有していてもよい炭素数６〜２４のアリール基のことであり、具体的にはフェニル基、４−メチルフェニル基、３−メチルフェニル基、２−メチルフェニル基、４−エチルフェニル基、３−エチルフェニル基、２−エチルフェニル基、４−ｎ−プロピルフェニル基、４−ｎ−ブチルフェニル基、４−イソブチルフェニル基、４−ｔｅｒｔ−ブチルフェニル基、４−シクロペンチルフェニル基、４−シクロヘキシルフェニル基、２，４−ジメチルフェニル基、３，５−ジメチルフェニル基、３，４−ジメチルフェニル基、１−ビフェニル基、１−ナフチル基、２−ナフチル基、９−フェナントリル基、９，９−ジアルキル−フルオレン−２−イル基、９，９−ジ−トリフルオロメチル−フルオレン−２−イル基等を例示することができる。 The aryl group having 6 to 24 carbon atoms in R 1 and R 2 is an aryl group having 6 to 24 carbon atoms which may have a substituent, specifically, a phenyl group, 4-methylphenyl. Group, 3-methylphenyl group, 2-methylphenyl group, 4-ethylphenyl group, 3-ethylphenyl group, 2-ethylphenyl group, 4-n-propylphenyl group, 4-n-butylphenyl group, 4- Isobutylphenyl group, 4-tert-butylphenyl group, 4-cyclopentylphenyl group, 4-cyclohexylphenyl group, 2,4-dimethylphenyl group, 3,5-dimethylphenyl group, 3,4-dimethylphenyl group, 1- Biphenyl group, 1-naphthyl group, 2-naphthyl group, 9-phenanthryl group, 9,9-dialkyl-fluoren-2-yl group, 9,9-di-trifluoro It can be exemplified a fluorene-2-yl group and the like - methyl.
また、Ｒ１及びＲ２における炭素数６〜２４のアリールオキシ基とは、置換基を有していてもよい炭素数６〜２４のアリールオキシ基のことであり、具体的にはフェノキシ基、ｐ−ｔｅｒｔ−ブチルフェノキシ基、３−フルオロフェノキシ基、４−フルオロフェノキシ基等を例示することができる。 Moreover, the C6-C24 aryloxy group in R < 1 > and R < 2 > is the C6-C24 aryloxy group which may have a substituent, specifically, a phenoxy group, Examples thereof include a p-tert-butylphenoxy group, a 3-fluorophenoxy group, and a 4-fluorophenoxy group.
Ｒ１及びＲ２におけるハロゲン原子としては、弗素、塩素、臭素、またはヨウ素原子が例示できる。 Examples of the halogen atom in R 1 and R 2 include a fluorine, chlorine, bromine, or iodine atom.
なお、Ｒ１及びＲ２の具体例として上述した置換基は、互いに結合して環を形成してもよい。 The substituents described above as specific examples of R 1 and R 2 may be bonded to each other to form a ring.
一般式（１）において、Ａｒ１は各々独立して、置換若しくは無置換のアリール基またはヘテロアリール基を表し、それらに結合している窒素原子と共に含窒素複素環を形成してもよい基を表す。 In General Formula (1), each Ar 1 independently represents a substituted or unsubstituted aryl group or heteroaryl group, and a group that may form a nitrogen-containing heterocycle together with the nitrogen atom bonded thereto. Represent.
Ａｒ１における置換若しくは無置換のアリール基とは、置換基を有していてもよい炭素数６〜２４のアリール基のことであり、具体的にはフェニル基、１−ナフチル基、２−ナフチル基、２−アントリル基、９−アントリル基、２−フルオレニル基、フェナントリル基、ピレニル基、クリセニル基、ペリレニル基、ピセニル基、４−メチルフェニル基、３−メチルフェニル基、２−メチルフェニル基、４−エチルフェニル基、３−エチルフェニル基、２−エチルフェニル基、４−ｎ−プロピルフェニル基、４−イソプロピルフェニル基、２−イソプロピルフェニル基、４−ｎ−ブチルフェニル基、４−イソブチルフェニル基、４−ｓｅｃ−ブチルフェニル基、２−ｓｅｃ−ブチルフェニル基、４−ｔｅｒｔ−ブチルフェニル基、３−ｔｅｒｔ−ブチルフェニル基、２−ｔｅｒｔ−ブチルフェニル基、４−ｎ−ペンチルフェニル基、４−イソペンチルフェニル基、２−ネオペンチルフェニル基、４−ｔｅｒｔ−ペンチルフェニル基、４−ｎ−ヘキシルフェニル基、４−（２’−エチルブチル）フェニル基、４−ｎ−ヘプチルフェニル基、４−ｎ−オクチルフェニル基、４−（２’−エチルヘキシル）フェニル基、４−ｔｅｒｔ−オクチルフェニル基、４−ｎ−デシルフェニル基、４−ｎ−ドデシルフェニル基、４−ｎ−テトラデシルフェニル基、４−シクロペンチルフェニル基、４−シクロヘキシルフェニル基、４−（４’−メチルシクロヘキシル）フェニル基、４−（４’−ｔｅｒｔ−ブチルシクロヘキシル）フェニル基、３−シクロヘキシルフェニル基、２−シクロヘキシルフェニル基、４−エチル−１−ナフチル基、６−ｎ−ブチル−２−ナフチル基、２，４−ジメチルフェニル基、２，５−ジメチルフェニル基、３，４−ジメチルフェニル基、３，５−ジメチルフェニル基、２，６−ジメチルフェニル基、２，４−ジエチルフェニル基、２，３，５−トリメチルフェニル基、２，３，６−トリメチルフェニル基、３，４，５−トリメチルフェニル基、２，６−ジエチルフェニル基、２，５−ジイソプロピルフェニル基、２，６−ジイソブチルフェニル基、２，４−ジ−ｔｅｒｔ−ブチルフェニル基、２，５−ジ−ｔｅｒｔ−ブチルフェニル基、４，６−ジ−ｔｅｒｔ−ブチル−２−メチルフェニル基、５−ｔｅｒｔ−ブチル−２−メチルフェニル基、４−ｔｅｒｔ−ブチル−２，６−ジメチルフェニル基、９−メチル−２−フルオレニル基、９−エチル−２−フルオレニル基、９−ｎ−ヘキシル−２−フルオレニル基、９，９−ジメチル−２−フルオレニル基、９，９−ジエチル−２−フルオレニル基、９，９−ジ−ｎ−プロピル−２−フルオレニル基、４−メトキシフェニル基、３−メトキシフェニル基、２−メトキシフェニル基、４−エトキシフェニル基、３−エトキシフェニル基、２−エトキシフェニル基、４−ｎ−プロポキシフェニル基、３−ｎ−プロポキシフェニル基、４−イソプロポキシフェニル基、２−イソプロポキシフェニル基、４−ｎ−ブトキシフェニル基、４−イソブトキシフェニル基、２−ｓｅｃ−ブトキシフェニル基、４−ｎ−ペンチルオキシフェニル基、４−イソペンチルオキシフェニル基、２−イソペンチルオキシフェニル基、４−ネオペンチルオキシフェニル基、２−ネオペンチルオキシフェニル基、４−ｎ−ヘキシルオキシフェニル基、２−（２’−エチルブチル）オキシフェニル基、４−ｎ−オクチルオキシフェニル基、４−ｎ−デシルオキシフェニル基、４−ｎ−ドデシルオキシフェニル基、４−ｎ−テトラデシルオキシフェニル基、４−シクロヘキシルオキシフェニル基、２−シクロヘキシルオキシフェニル基、２−メトキシ−１−ナフチル基、４−メトキシ−１−ナフチル基、４−ｎ−ブトキシ−１−ナフチル基、５−エトキシ−１−ナフチル基、６−メトキシ−２−ナフチル基、６−エトキシ−２−ナフチル基、６−ｎ−ブトキシ−２−ナフチル基、６−ｎ−ヘキシルオキシ−２−ナフチル基、７−メトキシ−２−ナフチル基、７−ｎ−ブトキシ−２−ナフチル基、２−メチル−４−メトキシフェニル基、２−メチル−５−メトキシフェニル基、３−メチル−４−メトキシフェニル基、３−メチル−５−メトキシフェニル基、３−エチル−５−メトキシフェニル基、２−メトキシ−４−メチルフェニル基、３−メトキシ−４−メチルフェニル基、２，４−ジメトキシフェニル基、２，５−ジメトキシフェニル基、２，６−ジメトキシフェニル基、３，４−ジメトキシフェニル基、３，５−ジメトキシフェニル基、３，５−ジエトキシフェニル基、３，５−ジ−ｎ−ブトキシフェニル基、２−メトキシ−４−エトキシフェニル基、２−メトキシ−６−エトキシフェニル基、３，４，５−トリメトキシフェニル基、４−ビフェニリル基、３−ビフェニリル基、２−ビフェニリル基、４−（４’−メチルフェニル）フェニル基、４−（３’−メチルフェニル）フェニル基、４−（４’−メトキシフェニル）フェニル基、４−（４’−ｎ−ブトキシフェニル）フェニル基、２−（２’−メトキシフェニル）フェニル基、４−（４’−クロロフェニル）フェニル基、３−メチル−４−フェニルフェニル基、３−メトキシ−４−フェニルフェニル基、ターフェニル基、３，５−ジフェニルフェニル基、１０−フェニルアントリル基、１０−（３，５−ジフェニルフェニル）−９−アントリル基、９−フェニル−２−フルオレニル基、４−フルオロフェニル基、３−フルオロフェニル基、２−フルオロフェニル基、４−クロロフェニル基、３−クロロフェニル基、２−クロロフェニル基、４−ブロモフェニル基、２−ブロモフェニル基、４−クロロ−１−ナフチル基、４−クロロ−２−ナフチル基、６−ブロモ−２−ナフチル基、２，３−ジフルオロフェニル基、２，４−ジフルオロフェニル基、２，５−ジフルオロフェニル基、２，６−ジフルオロフェニル基、３，４−ジフルオロフェニル基、３，５−ジフルオロフェニル基、２，３−ジクロロフェニル基、２，４−ジクロロフェニル基、２，５−ジクロロフェニル基、３，４−ジクロロフェニル基、３，５−ジクロロフェニル基、２，５−ジブロモフェニル基、２，４，６−トリクロロフェニル基、２，４−ジクロロ−１−ナフチル基、１，６−ジクロロ−２−ナフチル基、２−フルオロ−４−メチルフェニル基、２−フルオロ−５−メチルフェニル基、３−フルオロ−２−メチルフェニル基、３−フルオロ−４−メチルフェニル基、２−メチル−４−フルオロフェニル基、２−メチル−５−フルオロフェニル基、３−メチル−４−フルオロフェニル基、２−クロロ−４−メチルフェニル基、２−クロロ−５−メチルフェニル基、２−クロロ−６−メチルフェニル基、２−メチル−３−クロロフェニル基、２−メチル−４−クロロフェニル基、３−クロロ−４−メチルフェニル基、３−メチル−４−クロロフェニル基、２−クロロ−４，６−ジメチルフェニル基、２−メトキシ−４−フルオロフェニル基、２−フルオロ−４−メトキシフェニル基、２−フルオロ−４−エトキシフェニル基、２−フルオロ−６−メトキシフェニル基、３−フルオロ−４−エトキシフェニル基、３−クロロ−４−メトキシフェニル基、２−メトキシ−５−クロロフェニル基、３−メトキシ−６−クロロフェニル基、５−クロロ−２，４−ジメトキシフェニル基等を例示することができる。 The substituted or unsubstituted aryl group in Ar 1 is an aryl group having 6 to 24 carbon atoms which may have a substituent, and specifically includes a phenyl group, 1-naphthyl group, 2-naphthyl group. Group, 2-anthryl group, 9-anthryl group, 2-fluorenyl group, phenanthryl group, pyrenyl group, chrysenyl group, perylenyl group, picenyl group, 4-methylphenyl group, 3-methylphenyl group, 2-methylphenyl group, 4-ethylphenyl group, 3-ethylphenyl group, 2-ethylphenyl group, 4-n-propylphenyl group, 4-isopropylphenyl group, 2-isopropylphenyl group, 4-n-butylphenyl group, 4-isobutylphenyl Group, 4-sec-butylphenyl group, 2-sec-butylphenyl group, 4-tert-butylphenyl group, 3-tert -Butylphenyl group, 2-tert-butylphenyl group, 4-n-pentylphenyl group, 4-isopentylphenyl group, 2-neopentylphenyl group, 4-tert-pentylphenyl group, 4-n-hexylphenyl group 4- (2′-ethylbutyl) phenyl group, 4-n-heptylphenyl group, 4-n-octylphenyl group, 4- (2′-ethylhexyl) phenyl group, 4-tert-octylphenyl group, 4-n -Decylphenyl group, 4-n-dodecylphenyl group, 4-n-tetradecylphenyl group, 4-cyclopentylphenyl group, 4-cyclohexylphenyl group, 4- (4'-methylcyclohexyl) phenyl group, 4- (4 '-Tert-butylcyclohexyl) phenyl group, 3-cyclohexylphenyl group, 2-cyclohexylphenyl group 4-ethyl-1-naphthyl group, 6-n-butyl-2-naphthyl group, 2,4-dimethylphenyl group, 2,5-dimethylphenyl group, 3,4-dimethylphenyl group, 3,5-dimethyl Phenyl group, 2,6-dimethylphenyl group, 2,4-diethylphenyl group, 2,3,5-trimethylphenyl group, 2,3,6-trimethylphenyl group, 3,4,5-trimethylphenyl group, 2 , 6-diethylphenyl group, 2,5-diisopropylphenyl group, 2,6-diisobutylphenyl group, 2,4-di-tert-butylphenyl group, 2,5-di-tert-butylphenyl group, 4,6 -Di-tert-butyl-2-methylphenyl group, 5-tert-butyl-2-methylphenyl group, 4-tert-butyl-2,6-dimethylphenyl group, 9-methyl-2 Fluorenyl group, 9-ethyl-2-fluorenyl group, 9-n-hexyl-2-fluorenyl group, 9,9-dimethyl-2-fluorenyl group, 9,9-diethyl-2-fluorenyl group, 9,9-di -N-propyl-2-fluorenyl group, 4-methoxyphenyl group, 3-methoxyphenyl group, 2-methoxyphenyl group, 4-ethoxyphenyl group, 3-ethoxyphenyl group, 2-ethoxyphenyl group, 4-n- Propoxyphenyl group, 3-n-propoxyphenyl group, 4-isopropoxyphenyl group, 2-isopropoxyphenyl group, 4-n-butoxyphenyl group, 4-isobutoxyphenyl group, 2-sec-butoxyphenyl group, 4 -N-pentyloxyphenyl group, 4-isopentyloxyphenyl group, 2-isopentyloxyphenyl group, 4 Neopentyloxyphenyl group, 2-neopentyloxyphenyl group, 4-n-hexyloxyphenyl group, 2- (2′-ethylbutyl) oxyphenyl group, 4-n-octyloxyphenyl group, 4-n-decyloxy Phenyl group, 4-n-dodecyloxyphenyl group, 4-n-tetradecyloxyphenyl group, 4-cyclohexyloxyphenyl group, 2-cyclohexyloxyphenyl group, 2-methoxy-1-naphthyl group, 4-methoxy-1 -Naphtyl group, 4-n-butoxy-1-naphthyl group, 5-ethoxy-1-naphthyl group, 6-methoxy-2-naphthyl group, 6-ethoxy-2-naphthyl group, 6-n-butoxy-2- Naphthyl group, 6-n-hexyloxy-2-naphthyl group, 7-methoxy-2-naphthyl group, 7-n-butoxy-2-naphth Group, 2-methyl-4-methoxyphenyl group, 2-methyl-5-methoxyphenyl group, 3-methyl-4-methoxyphenyl group, 3-methyl-5-methoxyphenyl group, 3-ethyl-5-methoxy group Phenyl group, 2-methoxy-4-methylphenyl group, 3-methoxy-4-methylphenyl group, 2,4-dimethoxyphenyl group, 2,5-dimethoxyphenyl group, 2,6-dimethoxyphenyl group, 3,4 -Dimethoxyphenyl group, 3,5-dimethoxyphenyl group, 3,5-diethoxyphenyl group, 3,5-di-n-butoxyphenyl group, 2-methoxy-4-ethoxyphenyl group, 2-methoxy-6- Ethoxyphenyl group, 3,4,5-trimethoxyphenyl group, 4-biphenylyl group, 3-biphenylyl group, 2-biphenylyl group, 4- (4′-methylphenyl) Nyl) phenyl group, 4- (3′-methylphenyl) phenyl group, 4- (4′-methoxyphenyl) phenyl group, 4- (4′-n-butoxyphenyl) phenyl group, 2- (2′-methoxy) Phenyl) phenyl group, 4- (4'-chlorophenyl) phenyl group, 3-methyl-4-phenylphenyl group, 3-methoxy-4-phenylphenyl group, terphenyl group, 3,5-diphenylphenyl group, 10- Phenylanthryl group, 10- (3,5-diphenylphenyl) -9-anthryl group, 9-phenyl-2-fluorenyl group, 4-fluorophenyl group, 3-fluorophenyl group, 2-fluorophenyl group, 4- Chlorophenyl group, 3-chlorophenyl group, 2-chlorophenyl group, 4-bromophenyl group, 2-bromophenyl group, 4-chloro-1-naphthyl 4-chloro-2-naphthyl group, 6-bromo-2-naphthyl group, 2,3-difluorophenyl group, 2,4-difluorophenyl group, 2,5-difluorophenyl group, 2,6-difluorophenyl group 3,4-difluorophenyl group, 3,5-difluorophenyl group, 2,3-dichlorophenyl group, 2,4-dichlorophenyl group, 2,5-dichlorophenyl group, 3,4-dichlorophenyl group, 3,5-dichlorophenyl Group, 2,5-dibromophenyl group, 2,4,6-trichlorophenyl group, 2,4-dichloro-1-naphthyl group, 1,6-dichloro-2-naphthyl group, 2-fluoro-4-methylphenyl Group, 2-fluoro-5-methylphenyl group, 3-fluoro-2-methylphenyl group, 3-fluoro-4-methylphenyl group, 2-methyl- -Fluorophenyl group, 2-methyl-5-fluorophenyl group, 3-methyl-4-fluorophenyl group, 2-chloro-4-methylphenyl group, 2-chloro-5-methylphenyl group, 2-chloro-6 -Methylphenyl group, 2-methyl-3-chlorophenyl group, 2-methyl-4-chlorophenyl group, 3-chloro-4-methylphenyl group, 3-methyl-4-chlorophenyl group, 2-chloro-4,6- Dimethylphenyl group, 2-methoxy-4-fluorophenyl group, 2-fluoro-4-methoxyphenyl group, 2-fluoro-4-ethoxyphenyl group, 2-fluoro-6-methoxyphenyl group, 3-fluoro-4- Ethoxyphenyl group, 3-chloro-4-methoxyphenyl group, 2-methoxy-5-chlorophenyl group, 3-methoxy-6-chlorophenyl Group, 5-chloro-2,4-dimethoxyphenyl group and the like.
Ａｒ１における置換若しくは無置換のヘテロアリール基とは、置換基を有していてもよい炭素数６〜２４の酸素原子、窒素原子及び硫黄原子のうちから少なくとも一つのヘテロ原子を含有するヘテロアリール基のことであり、具体的には４−キノリル基、４−ピリジル基、３−ピリジル基、２−ピリジル基、３−フリル基、２−フリル基、３−チエニル基、２−チエニル基、２−オキサゾリル基、２−チアゾリル基、２−ベンゾオキサゾリル基、２−ベンゾチアゾリル基、２−ベンゾイミダゾリル基などを例示することができる。 The substituted or unsubstituted heteroaryl group in Ar 1 is a heteroaryl containing at least one heteroatom among oxygen atoms, nitrogen atoms and sulfur atoms having 6 to 24 carbon atoms which may have a substituent. Specifically, 4-quinolyl group, 4-pyridyl group, 3-pyridyl group, 2-pyridyl group, 3-furyl group, 2-furyl group, 3-thienyl group, 2-thienyl group, Examples thereof include a 2-oxazolyl group, a 2-thiazolyl group, a 2-benzoxazolyl group, a 2-benzothiazolyl group, and a 2-benzimidazolyl group.
また、一般式（１）で表されるベンゾ［ｃ］フルオレン誘導体において、各々のＡｒ１に結合している窒素原子と共に含窒素複素環を形成してもよく、置換若しくは無置換のＮ−カルバゾリイル基、Ｎ−フェノキサジニイル基、またはＮ−フェノチアジニイル基を形成してもよい。含窒素複素環は、置換基として例えば、ハロゲン原子、炭素数１〜１０のアルキル基若しくはアルコキシ基、または炭素数６〜１０のアリール基が挙げられ、単置換または多置換されていてもよい。これらの中で好ましくは、無置換の、またはハロゲン原子、炭素数１〜４のアルキル基若しくはアルコキシ基、または炭素数６〜１０のアリール基で単置換若しくは多置換されたＮ−カルバゾリイル基、Ｎ−フェノキサジニイル基、またはＮ−フェノチアジニイル基であり、より好ましくは、無置換のＮ−カルバゾリイル基、Ｎ−フェノキサジニイル基、またはＮ−フェノチアジニイル基である。置換されたＮ−カルバゾリイル基、Ｎ−フェノキサジニイル基、またはＮ−フェノチアジニイル基の具体例としては、例えば、２−メチル−Ｎ−カルバゾリイル基、３−メチル−Ｎ−カルバゾリイル基、４−メチル−Ｎ−カルバゾリイル基、３−ｎ−ブチル−Ｎ−カルバゾリイル基、３−ｎ−ヘキシル−Ｎ−カルバゾリイル基、３−ｎ−オクチル−Ｎ−カルバゾリイル基、３−ｎ−デシル−Ｎ−カルバゾリイル基、３，６−ジメチル−Ｎ−カルバゾリイル基、２−メトキシ−Ｎ−カルバゾリイル基、３−メトキシ−Ｎ−カルバゾリイル基、３−エトキシ−Ｎ−カルバゾリイル基、３−イソプロポキシ−Ｎ−カルバゾリイル基、３−ｎ−ブトキシ−Ｎ−カルバゾリイル基、３−ｎ−オクチルオキシ−Ｎ−カルバゾリイル基、３−ｎ−デシルオキシ−Ｎ−カルバゾリイル基、３−フェニル−Ｎ−カルバゾリイル基、３−（４’−メチルフェニル）−Ｎ−カルバゾリイル基、３−（４’−ｔｅｒｔ−ブチルフェニル）−Ｎ−カルバゾリイル基、３−クロロ−Ｎ−カルバゾリイル基、２−メチル−Ｎ−フェノチアジニイル基などを例示することができる。 In the benzo [c] fluorene derivative represented by the general formula (1), a nitrogen-containing heterocyclic ring may be formed together with the nitrogen atom bonded to each Ar 1 , and a substituted or unsubstituted N-carbazolyl A group, an N-phenoxazinyl group, or an N-phenothiazinyl group may be formed. In the nitrogen-containing heterocycle, examples of the substituent include a halogen atom, an alkyl group having 1 to 10 carbon atoms or an alkoxy group, and an aryl group having 6 to 10 carbon atoms, and may be mono-substituted or poly-substituted. Among these, an N-carbazolyl group which is unsubstituted or monosubstituted or polysubstituted by a halogen atom, an alkyl group or alkoxy group having 1 to 4 carbon atoms, or an aryl group having 6 to 10 carbon atoms, -A phenoxazinyl group or an N-phenothiazinyl group, more preferably an unsubstituted N-carbazolyl group, an N-phenoxazinyl group, or an N-phenothiadinyl group. Specific examples of the substituted N-carbazolyl group, N-phenoxazinyl group, or N-phenothiazinyl group include, for example, 2-methyl-N-carbazolyl group, 3-methyl-N-carbazolyl group, 4 -Methyl-N-carbazolyl group, 3-n-butyl-N-carbazolyl group, 3-n-hexyl-N-carbazolyl group, 3-n-octyl-N-carbazolyl group, 3-n-decyl-N-carbazolyl group Group, 3,6-dimethyl-N-carbazolyl group, 2-methoxy-N-carbazolyl group, 3-methoxy-N-carbazolyl group, 3-ethoxy-N-carbazolyl group, 3-isopropoxy-N-carbazolyl group, 3-n-butoxy-N-carbazolyl group, 3-n-octyloxy-N-carbazolyl group, 3-n-decyloxy group -N-carbazolyl group, 3-phenyl-N-carbazolyl group, 3- (4'-methylphenyl) -N-carbazolyl group, 3- (4'-tert-butylphenyl) -N-carbazolyl group, 3-chloro -N-carbazolyl group, 2-methyl-N-phenothiazinyl group and the like can be exemplified.
Ａｒ２は各々独立して、置換若しくは無置換のアリーレン基またはヘテロアリーレン基を表し、具体的には置換若しくは無置換のフェニレン基、ナフチレン基、ビフェニリレン基、ターフェニリレン基、アントリレン基、フルオレニレン基、またはピリジレン基を例示することができ、好ましくは、フェニレン基、ナフチレン基、ビフェニリレン基、またはアントリレン基である。
Ar 2 are each independently a substituted or represents unsubstituted arylene group or a heteroarylene group, specifically a substituted or unsubstituted phenylene group, naphthyl alkylene group, Bifeniri alkylene group, Tafeniri alkylene group, Antori alkylene group , it can be exemplified fluorenyl alkylene group or pyrid alkylene group, preferably a phenylene group, naphthyl alkylene group, Bifeniri alkylene group or Antori alkylene group.
なお、一般式（１）の好ましい具体例を以下に例示するが、本発明の化合物はこれらに限定されるものではない。 In addition, although the preferable specific example of General formula (1) is illustrated below, the compound of this invention is not limited to these.
で表されるハロベンゾ［ｃ］フルオレン化合物と下記一般式（４）
A halobenzo [c] fluorene compound represented by the following general formula (4)
で表されるアミン化合物とを塩基及びパラジウム触媒の存在下に、反応させることにより容易に合成することができる。
It can be easily synthesized by reacting with an amine compound represented by the above in the presence of a base and a palladium catalyst.
本発明において使用される塩基としては、無機塩基及び／または有機塩基から選択すればよく、特に限定するものではないが、より好ましくは、ナトリウムメトキシド、ナトリウムエトキシド、カリウムメトキシド、カリウムエトキシド、リチウム−ｔｅｒｔ−ブトキシド、ナトリウム−ｔｅｒｔ−ブトキシド、カリウム−ｔｅｒｔ−ブトキシド等のようなアルカリ金属アルコキシドであり、それらは反応場にそのまま加えても、またアルカリ金属、水素化アルカリ金属及び水酸化アルカリ金属とアルコールからその場で調製して反応場に供してもよい。 The base used in the present invention may be selected from inorganic bases and / or organic bases, and is not particularly limited, but more preferably sodium methoxide, sodium ethoxide, potassium methoxide, potassium ethoxide. Alkali metal alkoxides such as lithium-tert-butoxide, sodium-tert-butoxide, potassium-tert-butoxide, etc., which can be added to the reaction field as they are, or alkali metals, alkali metal hydrides and alkali hydroxides. It may be prepared in situ from metal and alcohol and used in the reaction field.
使用される塩基の量は、反応で生成するハロゲン化水素に対し、０．５倍モル以上使用するのが好ましい。塩基の量が０．５倍モル未満では、ベンゾ［ｃ］フルオレン誘導体の収率が低くなる場合がある。また、塩基を大過剰に加えてもベンゾ［ｃ］フルオレン誘導体の収率に変化はないが、反応終了後の後処理操作が煩雑になることから、より好ましい塩基の量は、１〜５倍モルの範囲である。 The amount of the base used is preferably 0.5 moles or more based on the hydrogen halide produced in the reaction. If the amount of the base is less than 0.5 times mol, the yield of the benzo [c] fluorene derivative may be lowered. Moreover, even if a base is added in a large excess, the yield of the benzo [c] fluorene derivative does not change, but the post-treatment operation after the completion of the reaction becomes complicated, and therefore the more preferable amount of the base is 1 to 5 times. The range of moles.
また、本発明の方法において使用されるパラジウム触媒は、特に限定するものではないが、例えば、ヘキサクロロパラジウム（ＩＶ）酸ナトリウム四水和物、ヘキサクロロパラジウム（ＩＶ）酸カリウム等の４価パラジウム化合物類、塩化パラジウム（ＩＩ）、臭化パラジウム（ＩＩ）、酢酸パラジウム（ＩＩ）、パラジウム（ＩＩ）アセチルアセトナート、ジクロロビス（ベンゾニトリル）パラジウム（ＩＩ）、ジクロロビス（アセトニトリル）パラジウム（ＩＩ）、ジクロロビス（トリフェニルホスフィン）パラジウム（ＩＩ）、ジクロロテトラアンミンパラジウム（ＩＩ）、ジクロロ（シクロオクタ−１，５−ジエン）パラジウム（ＩＩ）、パラジウム（ＩＩ）トリフルオロアセテート等の２価パラジウム化合物類、トリス（ジベンジリデンアセトン）二パラジウム（０）、トリス（ジベンジリデンアセトン）二パラジウム（０）クロロホルム錯体、テトラキス（トリフェニルホスフィン）パラジウム（０）等の０価パラジウム化合物類等が挙げられる。 Further, the palladium catalyst used in the method of the present invention is not particularly limited. For example, tetravalent palladium compounds such as sodium hexachloropalladium (IV) acid tetrahydrate, potassium hexachloropalladium (IV) acid, etc. , Palladium (II) chloride, palladium (II) bromide, palladium (II) acetate, palladium (II) acetylacetonate, dichlorobis (benzonitrile) palladium (II), dichlorobis (acetonitrile) palladium (II), dichlorobis (tri Divalent palladium compounds such as phenylphosphine) palladium (II), dichlorotetraamminepalladium (II), dichloro (cycloocta-1,5-diene) palladium (II), palladium (II) trifluoroacetate, tris (dibenzi Den acetone) dipalladium (0), tris (dibenzylideneacetone) dipalladium (0) chloroform complex, tetrakis (triphenylphosphine) palladium (0) 0-valent palladium compounds such as and the like.
パラジウム化合物の使用量は、特に限定するものではないが、上記一般式（３）で表されるハロベンゾ［ｃ］フルオレン化合物１モルに対しパラジウム換算で、通常０．０００００１〜２０モル％の範囲である。パラジウム化合物が上記範囲内であれば、高い選択率でベンゾ［ｃ］フルオレン誘導体を合成することができるが、活性をさらに向上させるため、また高価なパラジウム化合物を使用することからも、より好ましいパラジウム化合物の使用量は、ハロベンゾ［ｃ］フルオレン化合物１モルに対し、パラジウム換算で０．０００１〜５モル％の範囲である。 Although the usage-amount of a palladium compound is not specifically limited, It is 0.000001-20 mol% normally in conversion of palladium with respect to 1 mol of halobenzo [c] fluorene compounds represented by the said General formula (3). is there. If the palladium compound is within the above range, a benzo [c] fluorene derivative can be synthesized with high selectivity. However, more preferable palladium is used because the activity is further improved and an expensive palladium compound is used. The usage-amount of a compound is the range of 0.0001-5 mol% in conversion of palladium with respect to 1 mol of halobenzo [c] fluorene compounds.
本発明の方法において使用されるパラジウム触媒に関して、三級ホスフィンを触媒配位子として併用すると、さらに効率的に反応を進行させることができる。本発明の方法において、パラジウム触媒と組み合わせて使用される三級ホスフィンとしては、特に限定されるものではなく、例えば、トリエチルホスフィン、トリシクロヘキシルホスフィン、トリイソプロピルホスフィン、トリ−ｎ−ブチルホスフィン、トリ−ｉｓｏ−ブチルホスフィン、トリ−ｓｅｃ−ブチルホスフィン、トリ−ｔｅｒｔ−ブチルホスフィン等のトリアルキルホスフィン類が挙げられるが、これらのうち、アリールアミン誘導体の選択性を向上させるためには、トリ−ｔｅｒｔ−ブチルホスフィンがより好ましい。 With regard to the palladium catalyst used in the method of the present invention, when tertiary phosphine is used in combination as a catalyst ligand, the reaction can proceed more efficiently. In the method of the present invention, the tertiary phosphine used in combination with the palladium catalyst is not particularly limited, and examples thereof include triethylphosphine, tricyclohexylphosphine, triisopropylphosphine, tri-n-butylphosphine, tri-phosphine. Trialkyl phosphines such as iso-butyl phosphine, tri-sec-butyl phosphine, tri-tert-butyl phosphine and the like can be mentioned. Among these, tri-tert-tert- Butylphosphine is more preferred.
本発明において、三級ホスフィンの使用量は、パラジウム触媒に対して、通常０．０１〜１００００倍モルの範囲である。三級ホスフィンの使用量が上記の範囲内であれば、ベンゾ［ｃ］フルオレン誘導体の選択率に変化はないが、活性をさらに向上させるため、また高価な三級ホスフィンを使用することからも、より好ましい三級ホスフィンの使用量は、パラジウム触媒に対して０．１〜１０倍モルの範囲である。 In this invention, the usage-amount of a tertiary phosphine is the range of 0.01-10000 times mole normally with respect to a palladium catalyst. If the amount of tertiary phosphine used is within the above range, the selectivity of the benzo [c] fluorene derivative does not change, but in order to further improve the activity, and from using expensive tertiary phosphine, A more preferable amount of the tertiary phosphine used is in the range of 0.1 to 10 times mol with respect to the palladium catalyst.
本発明においては、通常、パラジウム化合物と三級ホスフィンを組み合わせたものを触媒として機能させる。添加方法としては、反応系にそれぞれ単独で加えても、予め錯体の形に調製して添加してもよい。 In the present invention, a combination of a palladium compound and a tertiary phosphine is usually allowed to function as a catalyst. As an addition method, each may be added alone to the reaction system, or may be prepared in the form of a complex and added in advance.
本発明における反応は、通常、不活性溶媒存在下で行う。使用される溶媒としては、本反応を著しく阻害しない溶媒であればよく、特に限定するものではないが、ベンゼン、トルエン、キシレン等の芳香族系有機溶媒や、ジエチルエーテル、テトラハイドロフラン、ジオキサンなどのエーテル系有機溶媒、アセトニトリル、ジメチルホルムアミド、ジメチルスルホキシド、ヘキサメチルホスホルトリアミド等を挙げることができる。これらのうちより好ましくは、ベンゼン、トルエン、キシレン等の芳香族系有機溶媒である。 The reaction in the present invention is usually performed in the presence of an inert solvent. The solvent used is not particularly limited as long as it does not significantly inhibit this reaction, but is not limited to aromatic organic solvents such as benzene, toluene, xylene, diethyl ether, tetrahydrofuran, dioxane, etc. And ether-based organic solvents, acetonitrile, dimethylformamide, dimethyl sulfoxide, hexamethylphosphortriamide and the like. Of these, aromatic organic solvents such as benzene, toluene and xylene are more preferable.
本発明は、常圧下、窒素、アルゴン等の不活性ガス雰囲気下で行うことも、また加圧下で行うこともできる。 The present invention can be carried out under normal pressure, under an inert gas atmosphere such as nitrogen or argon, or under pressure.
本発明は、反応温度２０〜３００℃の範囲で行われるが、より好ましくは５０〜２００℃の範囲である。 Although this invention is performed in the range of reaction temperature 20-300 degreeC, More preferably, it is the range of 50-200 degreeC.
本発明において反応時間は、ハロベンゾ［ｃ］フルオレン化合物、アミン化合物、塩基、パラジウム触媒の量及び反応温度等の条件によって一定しないが、数分〜７２時間の範囲から選択すればよい。 In the present invention, the reaction time is not constant depending on conditions such as the amount of halobenzo [c] fluorene compound, amine compound, base, palladium catalyst and reaction temperature, but may be selected from a range of several minutes to 72 hours.
本発明者らは、上述したベンゾ［ｃ］フルオレン誘導体を有機ＥＬ素子に用いた場合、従来材料に比べて非常に高い特性を示す有機ＥＬ素子が得られることを見出した。具体的な特性としては、低駆動電圧や高電力効率等が挙げられる。従って、本発明は有機ＥＬ素子に関しても包含している。本発明の有機ＥＬ素子は、一対の電極間に複数の化合物を積層してなる多層構造を有している。本発明の有機ＥＬ素子においては、これら複数層のうち発光層、正孔輸送層、正孔注入層の少なくとも一つの層が一般式（１）で表される化合物で構成されていることを必須とする。特に、一般式（１）で表される化合物を正孔注入層に用いることが好ましい。 The present inventors have found that when the above-described benzo [c] fluorene derivative is used in an organic EL element, an organic EL element exhibiting extremely high characteristics as compared with conventional materials can be obtained. Specific characteristics include low drive voltage and high power efficiency. Therefore, the present invention also includes an organic EL element. The organic EL device of the present invention has a multilayer structure in which a plurality of compounds are laminated between a pair of electrodes. In the organic EL device of the present invention, it is essential that at least one of the light emitting layer, the hole transport layer, and the hole injection layer among the plurality of layers is composed of the compound represented by the general formula (1). And In particular, the compound represented by the general formula (1) is preferably used for the hole injection layer.
本発明による一般式（１）で表される新規なベンゾ［ｃ］フルオレン誘導体を用いれば、低駆動電圧及び高電力効率が達成可能な有機ＥＬ素子が提供可能となる。さらに、本発明のベンゾ［ｃ］フルオレン誘導体は、有機ＥＬ素子のみならず、電子写真感光体、光電変換素子、太陽電池またはイメージセンサ等の有機光伝導材料の分野への応用も期待できる。 If the novel benzo [c] fluorene derivative represented by the general formula (1) according to the present invention is used, an organic EL element capable of achieving a low driving voltage and high power efficiency can be provided. Furthermore, the benzo [c] fluorene derivative of the present invention can be expected to be applied not only to organic EL devices but also to organic photoconductive materials such as electrophotographic photoreceptors, photoelectric conversion devices, solar cells, and image sensors.
以下、本発明を実施例に基づき、さらに詳細に説明するが、本発明はこれら実施例に何ら限定されるものではない。 EXAMPLES Hereinafter, although this invention is demonstrated further in detail based on an Example, this invention is not limited to these Examples at all.
なお、本実施例で用いた分析機器及び測定方法を以下に列記する。 The analytical instruments and measurement methods used in this example are listed below.
［元素分析］
元素分析計：パーキンエルマー全自動元素分析装置 ２４００ＩＩ
酸素フラスコ燃焼−ＩＣ測定法：東ソー製 イオンクロマトグラフ ＩＣ−２００１
［質量分析］
質量分析装置：日立製作所製 Ｍ−８０Ｂ
測定方法：ＦＤ−ＭＳ分析
［ＮＭＲ測定］
ＮＭＲ測定装置：ＶＡＲＩＡＮ Ｇｅｍｉｎｉ−２００
［ガラス転移温度測定］
測定装置：マックサイエンス製 ＤＳＣ−３１００
測定方法：標準試料＝Ａｌ２Ｏ３ ５．０ｍｇ、昇温速度＝１０℃／分（窒素雰囲気）
合成例１ 中間体１ａの合成
[Elemental analysis]
Element analyzer: Perkin Elmer fully automatic element analyzer 2400II
Oxygen flask combustion-IC measurement method: Tosoh ion chromatography IC-2001
[Mass spectrometry]
Mass spectrometer: M-80B manufactured by Hitachi, Ltd.
Measuring method: FD-MS analysis [NMR measurement]
NMR measuring apparatus: VARIAN Gemini-200
[Glass transition temperature measurement]
Measuring device: DSC-3100 manufactured by Mac Science
Measuring method: standard sample = Al 2 O 3 5.0 mg, temperature rising rate = 10 ° C./min (nitrogen atmosphere)
Synthesis Example 1 Synthesis of Intermediate 1a
攪拌装置を備えた３Ｌフラスコ中に、ｏ−ブロモ安息香酸エチル［アルドリッチ製］６６．６ｇ（０．２９ｍｏｌ）、１−ナフチルボロン酸［アルドリッチ製］５０．０ｇ（０．２９ｍｏｌ）、テトラキス（トリフェニルホスフィン）パラジウム［Ｐｄ（ＰＰｈ３）４；和光純薬製］３．３ｇ（２．９ｍｍｏｌ）、ＴＨＦ［和光純薬製］１０００ｍＬ、炭酸ナトリウム［東京化成製］１４８．４ｇ（１．４０ｍｏｌ）、蒸留水６００．０ｇを仕込み、６５℃で１０時間攪拌した。反応終了後、反応液を室温まで戻して静置した後、副生塩及び過剰塩基を含んだ水層を分離した。得られた有機層を水、次いで飽和食塩水で洗浄分液した後、減圧濃縮に付してＴＨＦ溶媒を留去した。その結果、８０．１ｇの残渣（１ａ−１；収率＝１００％）を得た。なお、本残渣は精製することなく、次工程に用いた。
In a 3 L flask equipped with a stirrer, ethyl o-bromobenzoate [manufactured by Aldrich] 66.6 g (0.29 mol), 1-naphthylboronic acid [manufactured by Aldrich] 50.0 g (0.29 mol), tetrakis (tri Phenylphosphine) palladium [Pd (PPh 3 ) 4 ; manufactured by Wako Pure Chemical Industries, Ltd.] 3.3 g (2.9 mmol), THF [manufactured by Wako Pure Chemical Industries, Ltd.] 1000 mL, sodium carbonate [manufactured by Tokyo Chemical Industry] 148.4 g (1.40 mol) Then, 600.0 g of distilled water was charged and stirred at 65 ° C. for 10 hours. After completion of the reaction, the reaction solution was returned to room temperature and allowed to stand, and then an aqueous layer containing a by-product salt and an excess base was separated. The obtained organic layer was washed and separated with water and then with saturated brine, and then concentrated under reduced pressure to distill off the THF solvent. As a result, 80.1 g of a residue (1a-1; yield = 100%) was obtained. This residue was used in the next step without purification.
（第二工程：１ａ−２の合成）
窒素雰囲気下、攪拌装置を備えた２Ｌフラスコ中に、上記操作で得られた１ａ−１ ８０．０ｇ（０．２９ｍｏｌ）、ＴＨＦ［和光純薬製］３００ｍＬを仕込んだ。その後、ＭｅＭｇＢｒ［１．４Ｍ−ＴＨＦ溶液；関東化学製］４９０ｍＬ（０．６９ｍｏｌ）を反応液温が２０℃を超えないように、３時間かけて滴下した。その後、室温で１時間攪拌した。反応終了後、１０％塩化アンモニウム水溶液 ４００ｇ及びトルエン３００ｍＬを添加し、室温にて１時間攪拌して静置した後、副生塩を含んだ水層を分離した。さらに、１０％塩化アンモニウム水溶液で洗浄分液した後、減圧濃縮に付してＴＨＦ及びトルエン溶媒を留去した。その結果、７２．０ｇの残渣（１ａ−２；収率＝８７％）を得た。なお、本残渣は精製することなく、次工程に用いた。
(Second step: synthesis of 1a-2)
Under a nitrogen atmosphere, in a 2 L flask equipped with a stirrer, 80.0 g (0.29 mol) of 1a-1 obtained by the above operation and 300 mL of THF [manufactured by Wako Pure Chemical Industries, Ltd.] were charged. Thereafter, 490 mL (0.69 mol) of MeMgBr [1.4 M-THF solution; manufactured by Kanto Chemical Co., Ltd.] was added dropwise over 3 hours so that the reaction solution temperature did not exceed 20 ° C. Then, it stirred at room temperature for 1 hour. After completion of the reaction, 400 g of a 10% aqueous ammonium chloride solution and 300 mL of toluene were added, stirred at room temperature for 1 hour and allowed to stand, and then the aqueous layer containing by-product salt was separated. Furthermore, after washing and separating with a 10% aqueous ammonium chloride solution, the solution was concentrated under reduced pressure to distill off THF and the toluene solvent. As a result, 72.0 g of a residue (1a-2; yield = 87%) was obtained. This residue was used in the next step without purification.
（第三工程：１ａ−３の合成）
窒素雰囲気下、攪拌装置を備えた２Ｌフラスコ中に、上記操作で得られた１ａ−２ ７２．０ｇ（０．２７ｍｏｌ）、クロロホルム［キシダ化学製］１０００ｍＬを仕込んだ。その後、三フッ化ホウ素−エーテル錯体［アルドリッチ製］９７．０ｍＬ（０．３７ｍｏｌ）をクロロホルム１００ｍＬに溶解させた液を反応液温が２０℃を超えないように、２時間かけて滴下した。その後、室温で２時間攪拌した。反応終了後、蒸留水３００ｍＬを添加し、室温にて１時間攪拌して静置した後、水層を分離した。その後、減圧濃縮に付してクロロホルム溶媒を留去した。その結果、４８．０ｇの残渣（１ａ−３；収率＝６８％）を得た。さらに、本残渣をシリカゲルカラムクロマトグラフィーに付し、精製した１ａ−３ ４５．０ｇ（純度 ９９．５％）を得た。１Ｈ−ＮＭＲ測定により、１ａ−３（７，７−ジメチルベンゾ［ｃ］フルオレン）を同定した。
(Third step: synthesis of 1a-3)
Under a nitrogen atmosphere, 72.0 g (0.27 mol) of 1a-2 obtained by the above operation and 1000 mL of chloroform [manufactured by Kishida Chemical Co., Ltd.] were charged into a 2 L flask equipped with a stirrer. Thereafter, a solution obtained by dissolving 97.0 mL (0.37 mol) of boron trifluoride-ether complex [manufactured by Aldrich] in 100 mL of chloroform was added dropwise over 2 hours so that the reaction solution temperature did not exceed 20 ° C. Then, it stirred at room temperature for 2 hours. After completion of the reaction, 300 mL of distilled water was added, stirred at room temperature for 1 hour and allowed to stand, and then the aqueous layer was separated. Thereafter, the chloroform solvent was distilled off under reduced pressure. As a result, 48.0 g of a residue (1a-3; yield = 68%) was obtained. Furthermore, the residue was subjected to silica gel column chromatography to obtain 45.0 g (purity 99.5%) of purified 1a-3. 1a-3 (7,7-dimethylbenzo [c] fluorene) was identified by 1 H-NMR measurement.
１Ｈ−ＮＭＲ（ＣＤＣｌ３）：８．７６（ｄ，１Ｈ）， ８．３４（ｄ，１Ｈ）， ７．９５（ｄ，１Ｈ）， ７．８６（ｄ，１Ｈ）， ７．３６−７．６７（ｍ，６Ｈ）， １．５５（ｓ，６Ｈ）［ｐｐｍ］
（第四工程：１ａの合成）
攪拌装置を備えた１Ｌフラスコ中に、上記操作で得られた１ａ−３ ２４．４ｇ（１００ｍｍｏｌ）、ＤＭＦ［東京化成製］１００ｍＬを仕込んだ。その後、Ｎ−ブロモこはく酸イミド［和光純薬製］２３．１ｇ（１３０ｍｍｏｌ）をＤＭＦ［東京化成製］１００ｍＬに溶解させた溶液を、反応液温が３０℃を超えないように、５時間かけて添加した。その後、室温で１６時間攪拌した。反応終了後、蒸留水３００ｍＬを添加し、室温にて１時間攪拌した。さらに、この溶液中にトルエン［関東化学製］５００ｍＬを添加して、トルエン層に目的物を抽出し、分離したトルエン溶液を濃縮させると２５．９ｇの残渣（１ａ；収率＝８０％）が得られた。さらに、本残渣をシリカゲルカラムクロマトグラフィーに付し、精製した１ａ ２２．０ｇを得た（純度 ９９．７％）。１Ｈ−ＮＭＲ測定、質量分析及び元素分析の結果により、１ａを同定した。
1 H-NMR (CDCl 3 ): 8.76 (d, 1H), 8.34 (d, 1H), 7.95 (d, 1H), 7.86 (d, 1H), 7.36-7 .67 (m, 6H), 1.55 (s, 6H) [ppm]
(Fourth step: Synthesis of 1a)
In a 1 L flask equipped with a stirrer, 24.4 g (100 mmol) of 1a-3 obtained by the above operation and 100 mL of DMF [manufactured by Tokyo Chemical Industry] were charged. Thereafter, a solution prepared by dissolving 23.1 g (130 mmol) of N-bromosuccinimide [manufactured by Wako Pure Chemical Industries, Ltd.] in 100 mL of DMF [manufactured by Tokyo Chemical Industry] was added over 5 hours so that the reaction liquid temperature did not exceed 30 ° C. Added. Then, it stirred at room temperature for 16 hours. After completion of the reaction, 300 mL of distilled water was added and stirred at room temperature for 1 hour. Furthermore, 500 mL of toluene [manufactured by Kanto Chemical Co., Inc.] was added to this solution, and the target product was extracted into the toluene layer. When the separated toluene solution was concentrated, 25.9 g of residue (1a; yield = 80%) was obtained. Obtained. Furthermore, the residue was subjected to silica gel column chromatography to obtain 22.0 g of purified 1a (purity 99.7%). 1a was identified by the results of 1 H-NMR measurement, mass spectrometry, and elemental analysis.
１Ｈ−ＮＭＲ（ＣＤＣｌ３）：８．７６（ｄ，１Ｈ）， ８．３５（ｄｄ，２Ｈ）， ７．９２（ｓ，１Ｈ）， ７．２６−７．７０（ｍ，５Ｈ）， １．５４（ｓ，６Ｈ）［ｐｐｍ］
質量分析（ＦＤＭＳ）：３２３
元素分析（計算値）：Ｃ＝７０．６， Ｈ＝４．７， Ｂｒ＝２４．７
元素分析（実測値）：Ｃ＝７０．５， Ｈ＝４．６， Ｂｒ＝２４．７
合成例２ 中間体１ｂの合成
1 H-NMR (CDCl 3 ): 8.76 (d, 1H), 8.35 (dd, 2H), 7.92 (s, 1H), 7.26-7.70 (m, 5H), 1 .54 (s, 6H) [ppm]
Mass spectrometry (FDMS): 323
Elemental analysis (calculated values): C = 70.6, H = 4.7, Br = 24.7
Elemental analysis (actual measurement): C = 70.5, H = 4.6, Br = 24.7
Synthesis Example 2 Synthesis of Intermediate 1b
窒素雰囲気下、攪拌装置を備えた２Ｌフラスコ中に、合成例１と同様の操作で得られた１ａ−１ ８０．０ｇ（０．２９ｍｏｌ）、ＴＨＦ［和光純薬製］２００ｍＬを仕込んだ。その後、ＰｈＭｇＢｒ［２．０Ｍ−ＴＨＦ溶液；東京化成製］４００ｍＬ（０．８０ｍｏｌ）を反応液温が２０℃を超えないように、３時間かけて滴下した。その後、室温で１時間攪拌した。反応終了後、５％塩酸水溶液 ６００ｇ及びトルエン３００ｍＬを添加し、室温にて１時間攪拌して静置した後、副生塩を含んだ水層を分離した。さらに、５％塩酸水溶液及び水で洗浄分液した後、減圧濃縮に付してＴＨＦ及びトルエン溶媒を留去した。その結果、８４．１ｇの残渣（１ｂ−２；収率＝７５％）を得た。なお、本残渣は精製することなく、次工程に用いた。
In a 2 L flask equipped with a stirrer in a nitrogen atmosphere, 80.0 g (0.29 mol) of 1a-1 obtained by the same operation as in Synthesis Example 1 and 200 mL of THF [manufactured by Wako Pure Chemical Industries, Ltd.] were charged. Thereafter, PhMgBr [2.0 M-THF solution; manufactured by Tokyo Chemical Industry] 400 mL (0.80 mol) was added dropwise over 3 hours so that the reaction solution temperature did not exceed 20 ° C. Then, it stirred at room temperature for 1 hour. After completion of the reaction, 600 g of a 5% hydrochloric acid aqueous solution and 300 mL of toluene were added, stirred at room temperature for 1 hour and allowed to stand, and then the aqueous layer containing by-product salt was separated. Further, after washing and separating with a 5% hydrochloric acid aqueous solution and water, the solution was concentrated under reduced pressure to distill off the THF and toluene solvents. As a result, 84.1 g of residue (1b-2; yield = 75%) was obtained. This residue was used in the next step without purification.
（第二工程：１ｂ−３の合成）
窒素雰囲気下、攪拌装置を備えた２Ｌフラスコ中に、上記操作で得られた１ｂ−２ ８４．０ｇ（０．２７ｍｏｌ）、酢酸［キシダ化学製］３００ｍＬ、濃硫酸［関東化学製］３．０ｇ（０．０３ｍｏｌ）を仕込み、室温で２時間攪拌した。反応終了後、トルエン４００ｍＬ及び蒸留水３００ｍＬを添加し、室温にて１時間攪拌して静置した後、水層を分離した。その後、減圧濃縮に付して酢酸及びトルエン溶媒を留去した。その結果、６０．１ｇの残渣（１ｂ−３；収率＝６０％）を得た。さらに、本残渣をシリカゲルカラムクロマトグラフィーに付し、精製した１ｂ−３ ５９．６ｇ（純度 ９９．３％）を得た。１Ｈ−ＮＭＲ測定により、１ｂ−３（７，７−ジフェニルベンゾ［ｃ］フルオレン）を同定した。
(Second step: synthesis of 1b-3)
In a 2 L flask equipped with a stirrer under a nitrogen atmosphere, 84.0 g (0.27 mol) of 1b-2 obtained by the above operation, 300 mL of acetic acid [manufactured by Kishida Chemical], 3.0 g of concentrated sulfuric acid [manufactured by Kanto Chemical] (0.03 mol) was added and stirred at room temperature for 2 hours. After completion of the reaction, 400 mL of toluene and 300 mL of distilled water were added, and the mixture was stirred at room temperature for 1 hour and allowed to stand, and then the aqueous layer was separated. Then, acetic acid and toluene solvent were distilled off by concentrating under reduced pressure. As a result, 60.1 g of residue (1b-3; yield = 60%) was obtained. Furthermore, this residue was subjected to silica gel column chromatography to obtain 59.6 g (purity 99.3%) of purified 1b-3. 1b-3 (7,7-diphenylbenzo [c] fluorene) was identified by 1 H-NMR measurement.
１Ｈ−ＮＭＲ（ＣＤＣｌ３）：８．８０（ｄ，１Ｈ）， ８．３８（ｄ，１Ｈ）， ７．４６−７．８９（ｍ，７Ｈ）， ７．２１−７．３３（ｍ，１１Ｈ）［ｐｐｍ］
（第三工程：１ｂの合成）
攪拌装置を備えた１Ｌフラスコ中に、上記操作で得られた１ｂ−３ ３６．８ｇ（１００ｍｍｏｌ）、ＤＭＦ［東京化成製］１００ｍＬを仕込んだ。その後、Ｎ−ブロモこはく酸イミド［和光純薬製］２３．１ｇ（１３０ｍｍｏｌ）をＤＭＦ［東京化成製］１００ｍＬに溶解させた溶液を、反応液温が３０℃を超えないように、５時間かけて添加した。その後、室温で１６時間攪拌した。反応終了後、蒸留水３００ｍＬを添加し、室温にて１時間攪拌した。さらに、この溶液中にトルエン［関東化学製］５００ｍＬを添加して、トルエン層に目的物を抽出し、分離したトルエン溶液を濃縮させると４０．１ｇの残渣（１ｂ；収率＝８８％）が得られた。さらに、本残渣をシリカゲルカラムクロマトグラフィーに付し、精製した１ｂ ３５．６ｇを得た（純度 ９９．８％）。１Ｈ−ＮＭＲ測定、質量分析及び元素分析の結果により、１ｂを同定した。
1 H-NMR (CDCl 3 ): 8.80 (d, 1H), 8.38 (d, 1H), 7.46-7.89 (m, 7H), 7.21-7.33 (m, 11H) [ppm]
(Third step: synthesis of 1b)
In a 1 L flask equipped with a stirrer, 36.8 g (100 mmol) of 1b-3 obtained by the above operation and 100 mL of DMF [manufactured by Tokyo Chemical Industry] were charged. Thereafter, a solution prepared by dissolving 23.1 g (130 mmol) of N-bromosuccinimide [manufactured by Wako Pure Chemical Industries, Ltd.] in 100 mL of DMF [manufactured by Tokyo Chemical Industry] was added over 5 hours so that the reaction liquid temperature did not exceed 30 ° C. Added. Then, it stirred at room temperature for 16 hours. After completion of the reaction, 300 mL of distilled water was added and stirred at room temperature for 1 hour. Furthermore, 500 mL of toluene [manufactured by Kanto Chemical Co., Inc.] was added to this solution, the target product was extracted into the toluene layer, and when the separated toluene solution was concentrated, 40.1 g of residue (1b; yield = 88%) was obtained. Obtained. Furthermore, the residue was subjected to silica gel column chromatography to obtain 35.6 g of purified 1b (purity 99.8%). 1b was identified by the results of 1 H-NMR measurement, mass spectrometry, and elemental analysis.
１Ｈ−ＮＭＲ（ＣＤＣｌ３）：８．７１（ｄ，１Ｈ）， ８．４１（ｄ，１Ｈ）， ７．５３−７．９９（ｍ，５Ｈ）， ７．３０−７．４７（ｍ，１２Ｈ）［ｐｐｍ］
質量分析（ＦＤＭＳ）：４４７
元素分析（計算値）：Ｃ＝７７．９， Ｈ＝４．３， Ｂｒ＝１７．９
元素分析（実測値）：Ｃ＝７７．９， Ｈ＝４．２， Ｂｒ＝１７．８
合成例３ 中間体２ａの合成
1 H-NMR (CDCl 3 ): 8.71 (d, 1H), 8.41 (d, 1H), 7.53-7.99 (m, 5H), 7.30-7.47 (m, 12H) [ppm]
Mass spectrometry (FDMS): 447
Elemental analysis (calculated values): C = 77.9, H = 4.3, Br = 17.9
Elemental analysis (actual measurement): C = 77.9, H = 4.2, Br = 17.8
Synthesis Example 3 Synthesis of Intermediate 2a
窒素雰囲気下、攪拌装置を備えた１Ｌフラスコ中に、ｐ−ブロモクロロベンゼン［キシダ化学製］６７．１ｇ（０．３５ｍｏｌ）、ジフェニルアミン［和光純薬製］５９．３ｇ（０．３５ｍｏｌ）、ナトリウム−ｔｅｒｔ−ブトキシド［関東化学製］４０．４ｇ（０．４２ｍｏｌ）、ｏ−キシレン［キシダ化学製］５００．０ｇ、酢酸パラジウム［アルドリッチ製］４４．０ｍｇ（０．１９ｍｍｏｌ）、トリ−ｔｅｒｔ−ブチルホスフィン［アルドリッチ製］０．１４ｇ（０．６７ｍｍｏｌ）を添加し、１３０℃で２時間攪拌した。反応終了後、蒸留水２００ｍＬを添加し、室温にて０．５時間攪拌して静置した後、水層を分離した。さらに、飽和塩化ナトリウム水溶液、次いで飽和食塩水で洗浄分液した後、減圧濃縮に付してｏ−キシレン溶媒を留去した。さらに、得られた残渣を熱イソプロピルアルコールを用いて再結晶に付し、目的とする２ａ−１ ９３．２ｇを得た（収率＝９５％、純度 ９９．４％）。質量分析及び元素分析の結果により、２ａ−１を同定した。
In a 1 L flask equipped with a stirrer in a nitrogen atmosphere, p-bromochlorobenzene [manufactured by Kishida Chemical] 67.1 g (0.35 mol), diphenylamine [manufactured by Wako Pure Chemical Industries] 59.3 g (0.35 mol), sodium tert-Butoxide [manufactured by Kanto Kagaku] 40.4 g (0.42 mol), o-xylene [manufactured by Kishida Chemical] 500.0 g, palladium acetate [manufactured by Aldrich] 44.0 mg (0.19 mmol), tri-tert-butylphosphine [Aldrich] 0.14 g (0.67 mmol) was added and stirred at 130 ° C. for 2 hours. After completion of the reaction, 200 mL of distilled water was added and stirred at room temperature for 0.5 hours and allowed to stand, and then the aqueous layer was separated. Furthermore, after washing and separating with a saturated aqueous sodium chloride solution and then with a saturated saline solution, the o-xylene solvent was distilled off by concentration under reduced pressure. Furthermore, the obtained residue was subjected to recrystallization using hot isopropyl alcohol to obtain 93.2 g of the intended 2a-1 (yield = 95%, purity 99.4%). 2a-1 was identified by the results of mass spectrometry and elemental analysis.
質量分析（ＦＤＭＳ）：２７９
元素分析（計算値）：Ｃ＝７７．３， Ｈ＝５．０， Ｃｌ＝１２．７， Ｎ＝５．０
元素分析（実測値）：Ｃ＝７７．２， Ｈ＝５．１， Ｃｌ＝１２．７， Ｎ＝５．１
（第二工程：２ａ−２の合成）
窒素雰囲気下、攪拌装置を備えた３００ｍＬフラスコ中に、上記操作で得られた２ａ−１ ３０．８ｇ（１１０ｍｍｏｌ）、ベンジルアミン［和光純薬製］５．４ｇ（５０ｍｍｏｌ）、ナトリウム−ｔｅｒｔ−ブトキシド［関東化学製］１１．５ｇ（１２０ｍｍｏｌ）、ｏ−キシレン［キシダ化学製］１５０．０ｇ、酢酸パラジウム［アルドリッチ製］１１．０ｍｇ（０．０５ｍｍｏｌ）、トリ−ｔｅｒｔ−ブチルホスフィン［アルドリッチ製］４０．０ｍｇ（０．２０ｍｍｏｌ）を添加し、１３０℃で５時間攪拌した。反応終了後、蒸留水１００ｍＬを添加し、室温にて０．５時間攪拌して静置した後、水層を分離した。さらに、飽和塩化ナトリウム水溶液、次いで飽和食塩水で洗浄分液した後、減圧濃縮に付してｏ−キシレン溶媒を留去した。さらに、得られた残渣をシリカゲルカラムクロマログラフィーに付し、目的とする２ａ−２ ４８．３ｇを得た（収率＝７４％、純度 ９９．３％）。質量分析及び元素分析の結果により、２ａ−２を同定した。
Mass spectrometry (FDMS): 279
Elemental analysis (calculated values): C = 77.3, H = 5.0, Cl = 12.7, N = 5.0
Elemental analysis (actual measurement): C = 77.2, H = 5.1, Cl = 12.7, N = 5.1
(Second step: synthesis of 2a-2)
In a 300 mL flask equipped with a stirrer under a nitrogen atmosphere, 30.8 g (110 mmol) of 2a-1 obtained by the above operation, 5.4 g (50 mmol) of benzylamine [manufactured by Wako Pure Chemical Industries], sodium-tert-butoxide [Kanto Kagaku] 11.5 g (120 mmol), o-xylene [Kishida Chemical] 150.0 g, palladium acetate [Aldrich] 11.0 mg (0.05 mmol), tri-tert-butylphosphine [Aldrich] 40 0.0 mg (0.20 mmol) was added, and the mixture was stirred at 130 ° C. for 5 hours. After completion of the reaction, 100 mL of distilled water was added, stirred for 0.5 hours at room temperature and allowed to stand, and then the aqueous layer was separated. Furthermore, after washing and separating with a saturated aqueous sodium chloride solution and then with a saturated saline solution, the o-xylene solvent was distilled off by concentration under reduced pressure. Furthermore, the obtained residue was subjected to silica gel column chromatography to obtain 48.3 g of the intended 2a-2 (yield = 74%, purity 99.3%). 2a-2 was identified by the results of mass spectrometry and elemental analysis.
質量分析（ＦＤＭＳ）：５９３
元素分析（計算値）：Ｃ＝８７．０， Ｈ＝５．９， Ｎ＝７．１
元素分析（実測値）：Ｃ＝８７．２， Ｈ＝５．８， Ｎ＝７．１
（第三工程：２ａの合成）
攪拌装置を備えた３００ｍＬフラスコ中に、上記操作で得られた２ａ−２ ２３．８ｇ（４０ｍｍｏｌ）、１０％パラジウム−活性炭素［アルドリッチ製］４．８ｇ、ギ酸［東京化成製］９．２ｇ（２００ｍｍｏｌ）、トルエン［関東化学製］１００．０ｇ、水２５．０ｇを添加し、９０℃で１０時間攪拌した。反応終了後、水層を分離して得られた有機層を濃縮してトルエン溶媒を留去し、さらに、得られた残渣をシリカゲルカラムクロマログラフィーに付し、目的とする２ａ １７．１ｇを得た（収率＝８５％、純度 ９９．０％）。質量分析及び元素分析の結果により、２ａを同定した。
Mass spectrometry (FDMS): 593
Elemental analysis (calculated values): C = 87.0, H = 5.9, N = 7.1
Elemental analysis (actual measurement): C = 87.2, H = 5.8, N = 7.1
(Third step: Synthesis of 2a)
In a 300 mL flask equipped with a stirrer, 23.8 g (40 mmol) of 2a-2 obtained by the above operation, 4.8 g of 10% palladium-activated carbon [manufactured by Aldrich], 9.2 g of formic acid [manufactured by Tokyo Chemical Industry] ( 200 mmol), toluene [manufactured by Kanto Chemical Co., Inc.] 100.0 g, and water 25.0 g were added and stirred at 90 ° C. for 10 hours. After completion of the reaction, the organic layer obtained by separating the aqueous layer was concentrated to distill off the toluene solvent, and the resulting residue was subjected to silica gel column chromatography to obtain 17.1 g of the intended 2a. Obtained (yield = 85%, purity 99.0%). 2a was identified by the results of mass spectrometry and elemental analysis.
質量分析（ＦＤＭＳ）：５０３
元素分析（計算値）：Ｃ＝８５．９， Ｈ＝５．８， Ｎ＝８．３
元素分析（実測値）：Ｃ＝８５．６， Ｈ＝５．７， Ｎ＝８．２
合成例４ 中間体２ｂの合成
Mass spectrometry (FDMS): 503
Elemental analysis (calculated values): C = 85.9, H = 5.8, N = 8.3
Elemental analysis (actual measurement): C = 85.6, H = 5.7, N = 8.2
Synthesis Example 4 Synthesis of Intermediate 2b
窒素雰囲気下、攪拌装置を備えた１Ｌフラスコ中に、ｐ−ブロモクロロベンゼン［キシダ化学製］５７．４ｇ（０．３０ｍｏｌ）、１−ナフチルフェニルアミン［和光純薬製］６５．８ｇ（０．３０ｍｏｌ）、ナトリウム−ｔｅｒｔ−ブトキシド［関東化学製］３４．６ｇ（０．３６ｍｏｌ）、ｏ−キシレン［キシダ化学製］５００．０ｇ、酢酸パラジウム［アルドリッチ製］６９．５ｍｇ（０．３ｍｍｏｌ）、トリ−ｔｅｒｔ−ブチルホスフィン［アルドリッチ製］２４２．８ｍｇ（１．２ｍｍｏｌ）を添加し、１３０℃で２時間攪拌した。反応終了後、蒸留水１００ｍＬを添加し、室温にて０．５時間攪拌して静置した後、水層を分離した。さらに、飽和塩化ナトリウム水溶液、次いで飽和食塩水で洗浄分液した後、減圧濃縮に付してｏ−キシレン溶媒を留去した。さらに、得られた残渣をトルエンを用いて再結晶に付し、目的とする２ｂ−１ ９５．０ｇを得た（収率＝９６％、純度 ９９．９％）。質量分析及び元素分析の結果により、２ｂ−１を同定した。
In a 1 L flask equipped with a stirrer in a nitrogen atmosphere, 57.4 g (0.30 mol) of p-bromochlorobenzene [manufactured by Kishida Chemical], 65.8 g (0.30 mol) of 1-naphthylphenylamine [manufactured by Wako Pure Chemical Industries] ), Sodium-tert-butoxide [manufactured by Kanto Kagaku] 34.6 g (0.36 mol), o-xylene [manufactured by Kishida Chemical] 500.0 g, palladium acetate [manufactured by Aldrich] 69.5 mg (0.3 mmol), tri- 242.8 mg (1.2 mmol) of tert-butylphosphine [manufactured by Aldrich] was added, and the mixture was stirred at 130 ° C. for 2 hours. After completion of the reaction, 100 mL of distilled water was added, stirred for 0.5 hours at room temperature and allowed to stand, and then the aqueous layer was separated. Furthermore, after washing and separating with a saturated aqueous sodium chloride solution and then with a saturated saline solution, the o-xylene solvent was distilled off by concentration under reduced pressure. Furthermore, the obtained residue was subjected to recrystallization using toluene to obtain 95.0 g of the intended 2b-1 (yield = 96%, purity 99.9%). 2b-1 was identified by the results of mass spectrometry and elemental analysis.
質量分析（ＦＤＭＳ）：３２９
元素分析（計算値）：Ｃ＝８０．１， Ｈ＝４．９， Ｃｌ＝１０．８， Ｎ＝４．３
元素分析（実測値）：Ｃ＝８０．０， Ｈ＝４．８， Ｃｌ＝１０．６， Ｎ＝４．１
（第二工程：２ｂ−２の合成）
窒素雰囲気下、攪拌装置を備えた３００ｍＬフラスコ中に、上記操作で得られた２ｂ−１ ３６．３ｇ（１１０ｍｍｏｌ）、ベンジルアミン［和光純薬製］５．４ｇ（５０ｍｍｏｌ）、ナトリウム−ｔｅｒｔ−ブトキシド［関東化学製］１１．５ｇ（１２０ｍｍｏｌ）、ｏ−キシレン［キシダ化学製］１５０．０ｇ、酢酸パラジウム［アルドリッチ製］１１．０ｍｇ（０．０５ｍｍｏｌ）、トリ−ｔｅｒｔ−ブチルホスフィン［アルドリッチ製］４０．０ｍｇ（０．２０ｍｍｏｌ）を添加し、１３０℃で３時間攪拌した。反応終了後、蒸留水１００ｍＬを添加し、室温にて０．５時間攪拌して静置した後、水層を分離した。さらに、飽和塩化ナトリウム水溶液、次いで飽和食塩水で洗浄分液した後、減圧濃縮に付してｏ−キシレン溶媒を留去した。さらに、得られた残渣をシリカゲルカラムクロマログラフィーに付し、目的とする２ｂ−２ ５７．２ｇを得た（収率＝７５％、純度 ９９．１％）。質量分析及び元素分析の結果により、２ｂ−２を同定した。
Mass spectrometry (FDMS): 329
Elemental analysis (calculated values): C = 80.1, H = 4.9, Cl = 10.8, N = 4.3
Elemental analysis (actual measurement): C = 80.0, H = 4.8, Cl = 10.6, N = 4.1
(Second step: synthesis of 2b-2)
In a 300 mL flask equipped with a stirrer under a nitrogen atmosphere, 36.3 g (110 mmol) of 2b-1 obtained by the above operation, 5.4 g (50 mmol) of benzylamine [manufactured by Wako Pure Chemical Industries, Ltd.], sodium-tert-butoxide [Kanto Kagaku] 11.5 g (120 mmol), o-xylene [Kishida Chemical] 150.0 g, palladium acetate [Aldrich] 11.0 mg (0.05 mmol), tri-tert-butylphosphine [Aldrich] 40 0.0 mg (0.20 mmol) was added, and the mixture was stirred at 130 ° C. for 3 hours. After completion of the reaction, 100 mL of distilled water was added, stirred for 0.5 hours at room temperature and allowed to stand, and then the aqueous layer was separated. Furthermore, after washing and separating with a saturated aqueous sodium chloride solution and then with a saturated saline solution, the o-xylene solvent was distilled off by concentration under reduced pressure. Furthermore, the obtained residue was subjected to silica gel column chromatography to obtain 57.2 g of the intended 2b-2 (yield = 75%, purity 99.1%). 2b-2 was identified by the results of mass spectrometry and elemental analysis.
質量分析（ＦＤＭＳ）：６９３
元素分析（計算値）：Ｃ＝８８．３， Ｈ＝５．７， Ｎ＝６．１
元素分析（実測値）：Ｃ＝８８．３， Ｈ＝５．７， Ｎ＝６．０
（第三工程：２ｂの合成）
攪拌装置を備えた３００ｍＬフラスコ中に、上記操作で得られた２ｂ−２ ３４．７ｇ（５０ｍｍｏｌ）、１０％パラジウム−活性炭素［アルドリッチ製］５．６ｇ、ギ酸［東京化成製］１１．５ｇ（２５０ｍｍｏｌ）、トルエン［関東化学製］１５０．０ｇ、水３０．０ｇを添加し、８５℃で１５時間攪拌した。反応終了後、水層を分離して得られた有機層を濃縮してトルエン溶媒を留去し、さらに、得られた残渣をシリカゲルカラムクロマログラフィーに付し、目的とする２ｂ ２７．４ｇを得た（収率＝９０％、純度 ９９．３％）。質量分析及び元素分析の結果により、２ｂを同定した。
Mass spectrometry (FDMS): 693
Elemental analysis (calculated values): C = 88.3, H = 5.7, N = 6.1
Elemental analysis (actual measurement): C = 88.3, H = 5.7, N = 6.0
(Third step: Synthesis of 2b)
In a 300 mL flask equipped with a stirrer, 34.7 g (50 mmol) of 2b-2 obtained by the above operation, 5.6 g of 10% palladium-activated carbon [manufactured by Aldrich], 11.5 g of formic acid [manufactured by Tokyo Chemical Industry] ( 250 mmol), toluene [manufactured by Kanto Chemical Co., Inc.] 150.0 g, and water 30.0 g were added and stirred at 85 ° C. for 15 hours. After completion of the reaction, the organic layer obtained by separating the aqueous layer was concentrated to distill off the toluene solvent, and the resulting residue was subjected to silica gel column chromatography to obtain 27.4 g of the intended 2b. Obtained (yield = 90%, purity 99.3%). 2b was identified by the results of mass spectrometry and elemental analysis.
質量分析（ＦＤＭＳ）：６０３
元素分析（計算値）：Ｃ＝８７．５， Ｈ＝５．５， Ｎ＝７．０
元素分析（実測値）：Ｃ＝８７．６， Ｈ＝５．６， Ｎ＝６．９
実施例１ 化合物Ａ−１の合成
Mass spectrometry (FDMS): 603
Elemental analysis (calculated values): C = 87.5, H = 5.5, N = 7.0
Elemental analysis (actual measurement): C = 87.6, H = 5.6, N = 6.9
Example 1 Synthesis of Compound A-1
１Ｈ−ＮＭＲ（ＣＤＣｌ３）：８．７６（ｄ，１Ｈ）， ８．２０（ｄｄ，１Ｈ）， ７．０７−６５（ｍ，４４Ｈ）， １．５０（ｓ，６Ｈ）［ｐｐｍ］
質量分析（ＦＤＭＳ）：９１３
元素分析（計算値）：Ｃ＝８８．１， Ｈ＝５．７， Ｎ＝６．２
元素分析（実測値）：Ｃ＝８８．１， Ｈ＝５．９， Ｎ＝６．０
ガラス転移温度：１２８℃
実施例２ 化合物Ａ−２の合成
1 H-NMR (CDCl 3 ): 8.76 (d, 1H), 8.20 (dd, 1H), 7.07-65 (m, 44H), 1.50 (s, 6H) [ppm]
Mass spectrometry (FDMS): 913
Elemental analysis (calculated values): C = 88.1, H = 5.7, N = 6.2
Elemental analysis (actual measurement): C = 88.1, H = 5.9, N = 6.0
Glass transition temperature: 128 ° C
Example 2 Synthesis of Compound A-2
１Ｈ−ＮＭＲ（ＣＤＣｌ３）：８．７１（ｄ，１Ｈ）， ６．６５−８．２４（ｍ，４９Ｈ）， １．３４（ｓ，６Ｈ）［ｐｐｍ］
質量分析（ＦＤＭＳ）：１０１３
元素分析（計算値）：Ｃ＝８８．９， Ｈ＝５．６， Ｎ＝５．５
元素分析（実測値）：Ｃ＝８８．８， Ｈ＝５．８， Ｎ＝５．４
ガラス転移温度：１４０℃
実施例３ 化合物Ａ−２５の合成
1 H-NMR (CDCl 3 ): 8.71 (d, 1H), 6.65-8.24 (m, 49H), 1.34 (s, 6H) [ppm]
Mass spectrometry (FDMS): 1013
Elemental analysis (calculated values): C = 88.9, H = 5.6, N = 5.5
Elemental analysis (actual measurement): C = 88.8, H = 5.8, N = 5.4
Glass transition temperature: 140 ° C
Example 3 Synthesis of Compound A-25
１Ｈ−ＮＭＲ（ＣＤＣｌ３）：８．７４（ｄ，１Ｈ）， ８．１８（ｄｄ，１Ｈ）， ７．０１−８．１２（ｍ，５４Ｈ）［ｐｐｍ］
質量分析（ＦＤＭＳ）：１０３７
元素分析（計算値）：Ｃ＝８９．２， Ｈ＝５．４， Ｎ＝５．４
元素分析（実測値）：Ｃ＝８９．２， Ｈ＝５．３， Ｎ＝５．５
ガラス転移温度：１５３℃
実施例４ 化合物Ａ−２６の合成
1 H-NMR (CDCl 3 ): 8.74 (d, 1H), 8.18 (dd, 1H), 7.01-8.12 (m, 54H) [ppm]
Mass spectrometry (FDMS): 1037
Elemental analysis (calculated value): C = 89.2, H = 5.4, N = 5.4
Elemental analysis (actual measurement): C = 89.2, H = 5.3, N = 5.5
Glass transition temperature: 153 ° C
Example 4 Synthesis of Compound A-26
１Ｈ−ＮＭＲ（ＣＤＣｌ３）：８．７５（ｄ，１Ｈ）， ６．６０−８．３０（ｍ，５９Ｈ）［ｐｐｍ］
質量分析（ＦＤＭＳ）：１１３７
元素分析（計算値）：Ｃ＝８９．８， Ｈ＝５．３， Ｎ＝４．９
元素分析（実測値）：Ｃ＝８９．８， Ｈ＝５．４， Ｎ＝４．８
ガラス転移温度：１６８℃
実施例５ 有機ＥＬ素子の作製
厚さ１１０ｎｍのＩＴＯ透明電極を有するガラス基板をアセトン、イソプロピルアルコールで順次超音波洗浄し、次いでイソプロピルアルコールで煮沸洗浄した後、乾燥した。さらに、本基板をＵＶ／オゾン処理したものを透明導電性支持基板として使用した。本ＩＴＯ透明電極上に、実施例１で合成した化合物Ａ−１を真空蒸着法により３０ｎｍの膜厚で成膜し、正孔注入層を形成した。次に、α−ＮＰＤを真空蒸着法により２０ｎｍの膜厚で成膜し、正孔輸送層を形成した。次に、アルミニウムトリスキノリノール錯体（以下、Ａｌｑ３と略記する）を真空蒸着法により５０ｎｍの膜厚で成膜し、発光層兼電子輸送層を形成した。次に、陰極としてＭｇＡｇを１００ｎｍ、Ａｇを１０ｎｍ成膜して金属電極を形成した。
1 H-NMR (CDCl 3 ): 8.75 (d, 1H), 6.60-8.30 (m, 59H) [ppm]
Mass Spectrometry (FDMS): 1137
Elemental analysis (calculated value): C = 89.8, H = 5.3, N = 4.9
Elemental analysis (actual measurement): C = 89.8, H = 5.4, N = 4.8
Glass transition temperature: 168 ° C
Example 5 Production of Organic EL Element A glass substrate having an ITO transparent electrode having a thickness of 110 nm was sequentially ultrasonically washed with acetone and isopropyl alcohol, then boiled and washed with isopropyl alcohol, and then dried. Furthermore, what carried out UV / ozone processing of this board | substrate was used as a transparent conductive support substrate. On this ITO transparent electrode, the compound A-1 synthesized in Example 1 was formed into a film with a thickness of 30 nm by a vacuum vapor deposition method to form a hole injection layer. Next, α-NPD was formed into a film with a thickness of 20 nm by a vacuum evaporation method to form a hole transport layer. Next, an aluminum triskinolinol complex (hereinafter abbreviated as Alq 3 ) was formed into a film having a thickness of 50 nm by a vacuum deposition method, thereby forming a light emitting layer / electron transport layer. Next, a metal electrode was formed by forming a MgAg film of 100 nm and an Ag film of 10 nm as a cathode.
さらに、窒素雰囲気下、保護用ガラス基板を重ね、ＵＶ硬化樹脂で封止した。このようにして得られた素子に、ＩＴＯ電極を正極、ＭｇＡｇ−Ａｇ電極を負極にして、６．０Ｖの直流電圧を印加すると、７．５ｍＡ／ｃｍ２の電流密度が得られ、２３７ｃｄ／ｍ２の輝度で緑色の発光が得られた。電力効率は１．７ｌｍ／Ｗであった。結果を表１に示す。 Further, a protective glass substrate was stacked in a nitrogen atmosphere and sealed with a UV curable resin. When a direct current voltage of 6.0 V was applied to the device thus obtained with the ITO electrode as the positive electrode and the MgAg-Ag electrode as the negative electrode, a current density of 7.5 mA / cm 2 was obtained, and 237 cd / m 2 was obtained. Green light emission with a luminance of 2 was obtained. The power efficiency was 1.7 lm / W. The results are shown in Table 1.
実施例６〜８ 有機ＥＬ素子の作製
正孔注入層として、実施例１で合成した化合物Ａ−１の代わりに、表１に示した化合物を用いた以外は、実施例５に準じて同様に有機ＥＬ素子を作製した。電流密度７．５ｍＡ／ｃｍ２時における駆動電圧、輝度、電力効率の値を表１に併せて示す。
Examples 6 to 8 Preparation of organic EL device In the same manner as in Example 5, except that the compound shown in Table 1 was used instead of compound A-1 synthesized in Example 1 as the hole injection layer. An organic EL element was produced. The values of drive voltage, luminance, and power efficiency at a current density of 7.5 mA / cm 2 are also shown in Table 1.
比較例１〜２ 有機ＥＬ素子の作製
正孔注入層として、実施例１で合成した化合物Ａ−１の代わりに、ＭＴＤＡＴＡまたはＣｕＰｃを用いた以外は、実施例５に準じて同様に有機ＥＬ素子を作製した。電流密度７．５ｍＡ／ｃｍ２時における駆動電圧、輝度、電力効率の値を表１に併せて示す。
Comparative Examples 1 and 2 Preparation of Organic EL Element Similarly as Example 5, except that MTDATA or CuPc was used instead of Compound A-1 synthesized in Example 1 as the hole injection layer, the organic EL element was similarly prepared. Was made. The values of drive voltage, luminance, and power efficiency at a current density of 7.5 mA / cm 2 are also shown in Table 1.
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