JP5439711B2 - Benzofluorene compounds and uses thereof - Google Patents
Benzofluorene compounds and uses thereof Download PDFInfo
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- JP5439711B2 JP5439711B2 JP2007183926A JP2007183926A JP5439711B2 JP 5439711 B2 JP5439711 B2 JP 5439711B2 JP 2007183926 A JP2007183926 A JP 2007183926A JP 2007183926 A JP2007183926 A JP 2007183926A JP 5439711 B2 JP5439711 B2 JP 5439711B2
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- HKMTVMBEALTRRR-UHFFFAOYSA-N Benzo[a]fluorene Chemical class C1=CC=CC2=C3CC4=CC=CC=C4C3=CC=C21 HKMTVMBEALTRRR-UHFFFAOYSA-N 0.000 title description 4
- -1 benzofluorene compound Chemical class 0.000 claims description 216
- 125000004432 carbon atom Chemical group C* 0.000 claims description 25
- 150000001875 compounds Chemical class 0.000 claims description 22
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 claims description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- 230000005525 hole transport Effects 0.000 claims description 10
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 9
- 125000001424 substituent group Chemical group 0.000 claims description 9
- 238000002347 injection Methods 0.000 claims description 8
- 239000007924 injection Substances 0.000 claims description 8
- 235000010290 biphenyl Nutrition 0.000 claims description 7
- 239000004305 biphenyl Substances 0.000 claims description 7
- 125000006165 cyclic alkyl group Chemical group 0.000 claims description 7
- 229910052801 chlorine Inorganic materials 0.000 claims description 6
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 5
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Chemical compound BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 4
- 125000001624 naphthyl group Chemical group 0.000 claims description 4
- 125000001309 chloro group Chemical group Cl* 0.000 claims description 3
- 238000005401 electroluminescence Methods 0.000 claims description 3
- NIHNNTQXNPWCJQ-UHFFFAOYSA-N fluorene Chemical compound C1=CC=C2CC3=CC=CC=C3C2=C1 NIHNNTQXNPWCJQ-UHFFFAOYSA-N 0.000 claims description 3
- 229910052794 bromium Inorganic materials 0.000 claims description 2
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims 3
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 claims 2
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 claims 1
- 238000006467 substitution reaction Methods 0.000 claims 1
- 125000003944 tolyl group Chemical group 0.000 claims 1
- 239000000463 material Substances 0.000 description 34
- 125000003118 aryl group Chemical group 0.000 description 14
- 238000005160 1H NMR spectroscopy Methods 0.000 description 11
- 238000006243 chemical reaction Methods 0.000 description 11
- 238000005259 measurement Methods 0.000 description 11
- 229910052757 nitrogen Inorganic materials 0.000 description 10
- 239000010410 layer Substances 0.000 description 9
- 125000003277 amino group Chemical group 0.000 description 8
- 238000000151 deposition Methods 0.000 description 8
- 230000008021 deposition Effects 0.000 description 8
- 125000001072 heteroaryl group Chemical group 0.000 description 8
- 125000003545 alkoxy group Chemical group 0.000 description 7
- 230000015572 biosynthetic process Effects 0.000 description 7
- 238000000434 field desorption mass spectrometry Methods 0.000 description 7
- 125000005843 halogen group Chemical group 0.000 description 7
- 238000003786 synthesis reaction Methods 0.000 description 7
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 6
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 6
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 125000004122 cyclic group Chemical group 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 5
- 125000004104 aryloxy group Chemical group 0.000 description 5
- 238000000921 elemental analysis Methods 0.000 description 5
- 230000009477 glass transition Effects 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- IBHBKWKFFTZAHE-UHFFFAOYSA-N n-[4-[4-(n-naphthalen-1-ylanilino)phenyl]phenyl]-n-phenylnaphthalen-1-amine Chemical group 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 5
- 238000000746 purification Methods 0.000 description 5
- 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 4
- DJXDQKHSDQVEEW-UHFFFAOYSA-N 9-chloro-11,11-dimethylbenzo[a]fluorene Chemical compound C1=CC=CC2=C3C(C)(C)C4=CC(Cl)=CC=C4C3=CC=C21 DJXDQKHSDQVEEW-UHFFFAOYSA-N 0.000 description 4
- ZVBDFIKEPLCPMG-UHFFFAOYSA-N 9-chloro-7,7-dimethylbenzo[c]fluorene Chemical compound ClC=1C=CC=2C=3C4=C(C=CC3C(C2C1)(C)C)C=CC=C4 ZVBDFIKEPLCPMG-UHFFFAOYSA-N 0.000 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- 0 C*(C(C1C=C(C2(CCCC2)c2ccc(cccc3)c3c22)C2=CC1)c1ccccc1)c(cc1)ccc1N(c1ccccc1)c1ccc2-c3c(cccc4)c4ccc3C3(CCCC3)c2c1 Chemical compound C*(C(C1C=C(C2(CCCC2)c2ccc(cccc3)c3c22)C2=CC1)c1ccccc1)c(cc1)ccc1N(c1ccccc1)c1ccc2-c3c(cccc4)c4ccc3C3(CCCC3)c2c1 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 125000002490 anilino group Chemical group [H]N(*)C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 4
- 125000000319 biphenyl-4-yl group Chemical group [H]C1=C([H])C([H])=C([H])C([H])=C1C1=C([H])C([H])=C([*])C([H])=C1[H] 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 238000004140 cleaning Methods 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 239000012044 organic layer Substances 0.000 description 4
- 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 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000000460 chlorine Substances 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 125000003983 fluorenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3CC12)* 0.000 description 3
- 125000000040 m-tolyl group Chemical group [H]C1=C([H])C(*)=C([H])C(=C1[H])C([H])([H])[H] 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- VUIOUIWZVKVFCI-UHFFFAOYSA-N 1-(2-hydroxynaphthalen-1-yl)ethanone Chemical compound C1=CC=C2C(C(=O)C)=C(O)C=CC2=C1 VUIOUIWZVKVFCI-UHFFFAOYSA-N 0.000 description 2
- NGLCYRVNLMWYHK-UHFFFAOYSA-N 1-[2-(4-chlorophenyl)naphthalen-1-yl]ethanone Chemical compound C1=CC2=CC=CC=C2C(C(=O)C)=C1C1=CC=C(Cl)C=C1 NGLCYRVNLMWYHK-UHFFFAOYSA-N 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
- FDRNXKXKFNHNCA-UHFFFAOYSA-N 4-(4-anilinophenyl)-n-phenylaniline Chemical compound C=1C=C(C=2C=CC(NC=3C=CC=CC=3)=CC=2)C=CC=1NC1=CC=CC=C1 FDRNXKXKFNHNCA-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
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical group [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 2
- UWXOAHWTPGUUNU-UHFFFAOYSA-N 9-chloro-11-methyl-11h-benzo[a]fluorene Chemical compound C1=CC=CC2=C3C(C)C4=CC(Cl)=CC=C4C3=CC=C21 UWXOAHWTPGUUNU-UHFFFAOYSA-N 0.000 description 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 239000007983 Tris buffer Substances 0.000 description 2
- YLEIFZAVNWDOBM-ZTNXSLBXSA-N ac1l9hc7 Chemical compound C([C@H]12)C[C@@H](C([C@@H](O)CC3)(C)C)[C@@]43C[C@@]14CC[C@@]1(C)[C@@]2(C)C[C@@H]2O[C@]3(O)[C@H](O)C(C)(C)O[C@@H]3[C@@H](C)[C@H]12 YLEIFZAVNWDOBM-ZTNXSLBXSA-N 0.000 description 2
- HTZCNXWZYVXIMZ-UHFFFAOYSA-M benzyl(triethyl)azanium;chloride Chemical compound [Cl-].CC[N+](CC)(CC)CC1=CC=CC=C1 HTZCNXWZYVXIMZ-UHFFFAOYSA-M 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000003599 detergent Substances 0.000 description 2
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 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 2
- 238000009434 installation Methods 0.000 description 2
- 229910052740 iodine Inorganic materials 0.000 description 2
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 230000007935 neutral effect Effects 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
- 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 2
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 description 2
- 108091008695 photoreceptors Proteins 0.000 description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 238000010898 silica gel chromatography Methods 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- 239000004332 silver Substances 0.000 description 2
- MFRIHAYPQRLWNB-UHFFFAOYSA-N sodium tert-butoxide Chemical compound [Na+].CC(C)(C)[O-] MFRIHAYPQRLWNB-UHFFFAOYSA-N 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- TVIVIEFSHFOWTE-UHFFFAOYSA-K tri(quinolin-8-yloxy)alumane Chemical compound [Al+3].C1=CN=C2C([O-])=CC=CC2=C1.C1=CN=C2C([O-])=CC=CC2=C1.C1=CN=C2C([O-])=CC=CC2=C1 TVIVIEFSHFOWTE-UHFFFAOYSA-K 0.000 description 2
- WJKHJLXJJJATHN-UHFFFAOYSA-N triflic anhydride Chemical compound FC(F)(F)S(=O)(=O)OS(=O)(=O)C(F)(F)F WJKHJLXJJJATHN-UHFFFAOYSA-N 0.000 description 2
- 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 2
- 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 2
- 238000004506 ultrasonic cleaning Methods 0.000 description 2
- 238000001771 vacuum deposition Methods 0.000 description 2
- HBENZIXOGRCSQN-VQWWACLZSA-N (1S,2S,6R,14R,15R,16R)-5-(cyclopropylmethyl)-16-[(2S)-2-hydroxy-3,3-dimethylpentan-2-yl]-15-methoxy-13-oxa-5-azahexacyclo[13.2.2.12,8.01,6.02,14.012,20]icosa-8(20),9,11-trien-11-ol Chemical compound N1([C@@H]2CC=3C4=C(C(=CC=3)O)O[C@H]3[C@@]5(OC)CC[C@@]2([C@@]43CC1)C[C@@H]5[C@](C)(O)C(C)(C)CC)CC1CC1 HBENZIXOGRCSQN-VQWWACLZSA-N 0.000 description 1
- NAWXUBYGYWOOIX-SFHVURJKSA-N (2s)-2-[[4-[2-(2,4-diaminoquinazolin-6-yl)ethyl]benzoyl]amino]-4-methylidenepentanedioic acid Chemical compound C1=CC2=NC(N)=NC(N)=C2C=C1CCC1=CC=C(C(=O)N[C@@H](CC(=C)C(O)=O)C(O)=O)C=C1 NAWXUBYGYWOOIX-SFHVURJKSA-N 0.000 description 1
- CAYQIZIAYYNFCS-UHFFFAOYSA-N (4-chlorophenyl)boronic acid Chemical compound OB(O)C1=CC=C(Cl)C=C1 CAYQIZIAYYNFCS-UHFFFAOYSA-N 0.000 description 1
- JBGJVMVWYWUVOW-UHFFFAOYSA-N 1-(1-hydroxynaphthalen-2-yl)ethanone Chemical compound C1=CC=CC2=C(O)C(C(=O)C)=CC=C21 JBGJVMVWYWUVOW-UHFFFAOYSA-N 0.000 description 1
- UHXOHPVVEHBKKT-UHFFFAOYSA-N 1-(2,2-diphenylethenyl)-4-[4-(2,2-diphenylethenyl)phenyl]benzene Chemical compound C=1C=C(C=2C=CC(C=C(C=3C=CC=CC=3)C=3C=CC=CC=3)=CC=2)C=CC=1C=C(C=1C=CC=CC=1)C1=CC=CC=C1 UHXOHPVVEHBKKT-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
- 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
- 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 1
- 125000000339 4-pyridyl group Chemical group N1=C([H])C([H])=C([*])C([H])=C1[H] 0.000 description 1
- REEQYOKOKNXMAG-UHFFFAOYSA-N 9,9-dimethyl-2-phenylfluorene Chemical compound C1=C2C(C)(C)C3=CC=CC=C3C2=CC=C1C1=CC=CC=C1 REEQYOKOKNXMAG-UHFFFAOYSA-N 0.000 description 1
- RAPHUPWIHDYTKU-WXUKJITCSA-N 9-ethyl-3-[(e)-2-[4-[4-[(e)-2-(9-ethylcarbazol-3-yl)ethenyl]phenyl]phenyl]ethenyl]carbazole Chemical compound C1=CC=C2C3=CC(/C=C/C4=CC=C(C=C4)C4=CC=C(C=C4)/C=C/C=4C=C5C6=CC=CC=C6N(C5=CC=4)CC)=CC=C3N(CC)C2=C1 RAPHUPWIHDYTKU-WXUKJITCSA-N 0.000 description 1
- 229910015900 BF3 Inorganic materials 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
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- 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
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- 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
- PJANXHGTPQOBST-UHFFFAOYSA-N stilbene Chemical class C=1C=CC=CC=1C=CC1=CC=CC=C1 PJANXHGTPQOBST-UHFFFAOYSA-N 0.000 description 1
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Description
本発明は、新規なベンゾフルオレン化合物及びその用途、特に有機エレクトロルミネッセンス素子に関するものである。ベンゾフルオレン化合物は、感光材料、有機光導電材料として使用でき、更に具体的には、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、正孔注入材料及び発光材料として利用できる。 The present invention relates to a novel benzofluorene compound and its use, particularly to an organic electroluminescence device. Benzofluorene compounds can be used as photosensitive materials and organic photoconductive materials, and more specifically, hole transport, hole injection materials, and light emission of planar light sources and organic EL devices or electrophotographic photoreceptors used for display. Available as a material.
感光材料や正孔輸送材料として開発されている有機光導電材料は、低コスト、加工性が多様であり、また無公害性などの多くの利点があり、多くの化合物が提案されている。例えば、オキサジアゾール誘導体（例えば、特許文献１参照）、オキサゾール誘導体（例えば、特許文献２参照）、ヒドラゾン誘導体（例えば、特許文献３参照）、トリアリールピラゾリン誘導体（例えば、特許文献４，５参照）、アリールアミン誘導体（例えば、特許文献６，７参照）、スチルベン誘導体（例えば、特許文献８，９参照）等の材料が開示されている。 Organic photoconductive materials developed as photosensitive materials and hole transport materials have various advantages such as low cost, various processability, and non-polluting properties, and many compounds have been proposed. For example, oxadiazole derivatives (for example, see Patent Document 1), oxazole derivatives (for example, see Patent Document 2), hydrazone derivatives (for example, see Patent Document 3), triarylpyrazoline derivatives (for example, Patent Documents 4 and 5) Materials) such as arylamine derivatives (see, for example, Patent Documents 6 and 7), stilbene derivatives (see, for example, Patent Documents 8 and 9), and the like.
中でも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−（ｍ−トリル）フェニルアミノ］トリフェニルアミン（ＭＴＤＡＴＡ）等のスターバースト系材料、４，４’−ビス［Ｎ−（１−ナフチル）−Ｎ−フェニルアミノ］ビフェニル（α−ＮＰＤ）、４，４’−ビス［Ｎ−（ｍ−トリル）−Ｎ−フェニルアミノ］ビフェニル（ＴＰＤ）等のビフェニル系アリールアミン誘導体が、正孔輸送又は正孔注入材料として多く使用されている（例えば、非特許文献１，２参照）。 Among them, 4,4 ′, 4 ″ -tris [N, N- (1-naphthyl) phenylamino] triphenylamine (1-TNATA), 4,4 ′, 4 ″ -tris [N, N- (m-tolyl) ) Phenylamino] triphenylamine (MTDATA) and other starburst materials, 4,4′-bis [N- (1-naphthyl) -N-phenylamino] biphenyl (α-NPD), 4,4′-bis Biphenyl arylamine derivatives such as [N- (m-tolyl) -N-phenylamino] biphenyl (TPD) are often used as hole transport or hole injection materials (for example, Non-Patent Documents 1 and 2). reference).
更に、フルオレン骨格を部分構造として用いたアリールアミン化合物も提案されている（例えば、特許文献１０，１１参照）。 Furthermore, arylamine compounds using a fluorene skeleton as a partial structure have also been proposed (see, for example, Patent Documents 10 and 11).
また、本特許と同じベンゾフルオレン骨格を有する有機エレクトロルミネセンス材料も提案されているが（例えば、特許文献１２参照）、ベンゾフルオレニル基に直接アミノ基が結合した化合物の記載はない。加えて、特許文献１２において、特に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、正孔輸送材料及び正孔注入材料として有用であるとの記載はない。 In addition, an organic electroluminescent material having the same benzofluorene skeleton as in this patent has been proposed (see, for example, Patent Document 12), but there is no description of a compound in which an amino group is directly bonded to a benzofluorenyl group. In addition, in Patent Document 12, there is a description that a polymer material having a benzofluorenyl group is particularly useful as a light emitting material, but there is no description that it is useful as a hole transport material and a hole injection material. .
しかしながら、これらの材料は、安定性や耐久性に乏しいなどの難点を有しており、実用上十分満足できる材料であるとは言い難い。例えば、代表的材料であり、現状効率等で優れているＮＰＤは、ガラス転移温度が低いため、素子寿命の観点では有機エレクトロルミネセンス素子の突然死等の問題を包含しており、問題となっている。また、近年アクティブマトリクス駆動の有機エレクトロルミネセンス素子の実用化検討が活発化しているが、その際の要求特性は更なる低電圧駆動である。それについては、ＮＰＤでは十分満足できるものに至っていない。従って、更なる低電圧駆動並びに長寿命化を実現するための材料の開発が非常に望まれている。 However, these materials have difficulties such as poor stability and durability, and it is difficult to say that these materials are sufficiently satisfactory for practical use. For example, NPD, which is a representative material and excellent in current efficiency, has a low glass transition temperature, and thus includes problems such as sudden death of organic electroluminescent elements from the viewpoint of element lifetime, which is a problem. ing. In recent years, studies on the practical application of active matrix driving organic electroluminescence elements have become active, and the required characteristic at that time is further low voltage driving. NPD has not been satisfactory enough. Therefore, development of materials for realizing further low voltage driving and longer life is highly desired.
本発明の目的は、従来材料以上に低電圧駆動と長期耐久性を有する新規材料を提供することにある。更に詳しくは、有機ＥＬ素子等の正孔注入材料、正孔輸送材料及び発光材料に適した新規なベンゾフルオレン化合物を提供することにある。 An object of the present invention is to provide a novel material having lower voltage driving and longer-term durability than conventional materials. More specifically, it is to provide a novel benzofluorene compound suitable for a hole injection material such as an organic EL device, a hole transport material and a light emitting material.
本発明者らは鋭意検討した結果、一般式（１）で表されるベンゾフルオレン化合物が、効率及び耐久性の面で非常に優れていることを見出し、本発明を完成するに至った。即ち、本発明は、一般式（１）で表されるベンゾフルオレン化合物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 benzofluorene compound represented by the general formula (1) is very excellent in terms of efficiency and durability, and have completed the present invention. That is, this invention relates to the benzofluorene compound represented by General formula (1), and its use.
以下、本発明に関し詳細に説明する。
Hereinafter, the present invention will be described in detail.
一般式（１）で表されるベンゾフルオレン化合物において、Ｍは炭素数６〜４０の置換若しくは無置換のアリール基、又は炭素数５〜４０の置換若しくは無置換のヘテロアリール基である。アリール基の例としては、一置換、二置換若しくは三置換のベンゼン骨格、ビフェニル骨格、ターフェニル骨格、ナフタレン骨格、フルオレン骨格、スピロフルオレン骨格、ピレン骨格等が挙げられる。 In the benzofluorene compound represented by the general formula (1), M is a substituted or unsubstituted aryl group having 6 to 40 carbon atoms, or a substituted or unsubstituted heteroaryl group having 5 to 40 carbon atoms. Examples of the aryl group include a mono-substituted, di-substituted, or tri-substituted benzene skeleton, biphenyl skeleton, terphenyl skeleton, naphthalene skeleton, fluorene skeleton, spirofluorene skeleton, pyrene skeleton, and the like.
ヘテロアリール基の例としては一置換、二置換若しくは三置換のカルバゾール骨格、オキサゾール骨格、オキサジアゾール骨格、チアゾール骨格等が挙げられる。また、Ｍはメチル基、エチル基、プロピル基等のアルキル基、フッ素原子、塩素原子、ヨウ素原子、臭素原子等のハロゲン原子、メトキシ基、エトキシ基等のアルコキシ基、フェニル基、ナフチル基、ビフェニル基等のアリール基、ピリジル基、チエニル基、カルバゾイル基等のヘテロアリール基等の置換基を有していてもよい。 Examples of heteroaryl groups include mono-, di-, or tri-substituted carbazole skeletons, oxazole skeletons, oxadiazole skeletons, thiazole skeletons, and the like. M is an alkyl group such as a methyl group, an ethyl group or a propyl group, a halogen atom such as a fluorine atom, a chlorine atom, an iodine atom or a bromine atom, an alkoxy group such as a methoxy group or an ethoxy group, a phenyl group, a naphthyl group, or biphenyl. It may have a substituent such as an aryl group such as a group, a heteroaryl group such as a pyridyl group, a thienyl group, and a carbazoyl group.
中でも、Ｍが２置換のベンゼン骨格、ビフェニル骨格、フルオレン骨格、ターフェニル骨格、ナフタレン骨格、又はスピロフルオレン骨格である前記一般式（４）で表されるベンゾフルオレン化合物が、低電圧化を実現するための一つの要因である正孔移動度が高いという点で好ましい。 Among them, the benzofluorene compound represented by the general formula (4), in which M is a disubstituted benzene skeleton, biphenyl skeleton, fluorene skeleton, terphenyl skeleton, naphthalene skeleton, or spirofluorene skeleton, achieves low voltage. This is preferable in that the hole mobility, which is one of the factors, is high.
一般式（１）において、Ａｒ１〜Ａｒ４は各々独立して炭素数６〜４０の置換若しくは無置換のアリール基、又は炭素数５〜４０の置換若しくは無置換のヘテロアリール基である。但し、Ａｒ１〜Ａｒ４のうち少なくとも一つは、下記一般式（２）又は（３）で表される置換基である。 In General Formula (1), Ar 1 to Ar 4 are each independently a substituted or unsubstituted aryl group having 6 to 40 carbon atoms, or a substituted or unsubstituted heteroaryl group having 5 to 40 carbon atoms. However, at least one of Ar 1 to Ar 4 is a substituent represented by the following general formula (2) or (3).
Ａｒ１〜Ａｒ４における炭素数６〜４０の置換若しくは無置換のアリール基としては、具体的に例えば、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、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−フェニルフェニル基、３−フェニルフェニル基、２−フェニルフェニル基、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、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などを挙げることができるが、これらに限定されるものではない。
Specific examples of the substituted or unsubstituted aryl group having 6 to 40 carbon atoms in Ar 1 to Ar 4 include, for example, a phenyl group, 1-naphthyl group, 2-naphthyl group, 2-anthryl group, 9-anthryl group, 2-fluorenyl 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-isopentylph Nyl group, 2-neopentylphenyl group, 4-tert-pentylphenyl group, 4-n-hexylphenyl group, 4- (2′-ethylbutyl) phenyl group, 4-n-heptylphenyl group, 4-n-octyl Phenyl group, 4- (2′-ethylhexyl) phenyl group, 4-tert-octylphenyl group, 4-n-decylphenyl group, 4-n-dodecylphenyl group, 4-n-tetradecylphenyl group, 4-cyclopentyl Phenyl 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- Methylphenyl group, 3,4-dimethylphenyl group, 3,5-dimethylphenyl 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-di Tyl-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-neo Pentyloxyphenyl group, 2-neopentyloxyphenyl group, 4-n-hexyloxyphenyl group, 2- (2′-ethylbutyl) oxyphenyl group, 4-n-octyloxyphenyl group, 4-n-decyloxyphenyl group, 4-n-dodecyloxyphenyl group, 4-n-tetradecyloxyphenyl group, 4 -Cyclohexyloxyphenyl group, 2-cyclohexyloxyphenyl group, 2-methoxy-1-naphthyl group, 4-methoxy-1-naphthyl 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-naphthyl group, 2-methyl-4-methoxyphenyl group, 2-methyl-5-methoxyphenyl group, 3-methyl-4-meth Xiphenyl group, 3-methyl-5-methoxyphenyl group, 3-ethyl-5-methoxyphenyl 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-phenylphenyl group, 3-phenylphenyl group, 2-phenyl Phenyl group, 4- (4′-methylphenyl) phenyl group, 4- (3′-methylphenyl) phenyl group, 4- (4′-methoxyphenyl) An phenyl group, a 4- (4′-n-butoxyphenyl) phenyl group, a 2- (2′-methoxyphenyl) phenyl group, a 4- (4′-chlorophenyl) phenyl group, a 3-methyl-4-phenylphenyl group, 3-methoxy-4-phenylphenyl 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 group, 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-4-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-chloro Rophenyl 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-fluoro Phenyl group, 2-fluoro-4-methoxyphenyl group, 2-fluoro-4-ethoxyphenyl group, 2-fluoro-6-methoxyphenyl group, 3-fluoro-4-ethoxyphenyl group, 3-chloro-4-methoxy A phenyl group, a 2-methoxy-5-chlorophenyl group, a 3-methoxy-6-chlorophenyl group, a 5-chloro-2,4-dimethoxyphenyl group, and the like can be given, but the invention is not limited thereto.
Ａｒ１〜Ａｒ４における炭素数５〜４０の置換若しくは無置換のヘテロアリール基としては、酸素原子、窒素原子及び硫黄原子から選ばれる少なくとも一つのヘテロ原子を含有する芳香環基であり、例えば、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の複素環基を挙げることができるが、これらに限定されるものではない。 The substituted or unsubstituted heteroaryl group having 5 to 40 carbon atoms in Ar 1 to Ar 4 is an aromatic ring group containing at least one hetero atom selected from an oxygen atom, a nitrogen atom and a sulfur atom. 4-quinolyl group, 4-pyridyl group, 3-pyridyl group, 2-pyridyl group, 3-furyl group, 2-furyl group, 3-thienyl group, 2-thienyl group, 2-oxazolyl group, 2-thiazolyl group, Examples of the heterocyclic group include, but are not limited to, a 2-benzoxazolyl group, a 2-benzothiazolyl group, and a 2-benzimidazolyl group.
一般式（２）又は（３）において、Ｒ１〜Ｒ４は各々独立して水素原子、ハロゲン原子、置換若しくは無置換のアミノ基、直鎖，分岐若しくは環状のアルキル基、直鎖，分岐若しくは環状のアルコキシ基、炭素数６〜４０の置換若しくは無置換のアリール基、又は炭素数６〜４０の置換若しくは無置換のアリールオキシ基である。なお、Ｒ１とＲ２は互いに結合して環を形成してもよい。 In the general formula (2) or (3), R 1 to R 4 are each independently a hydrogen atom, a halogen atom, a substituted or unsubstituted amino group, a linear, branched or cyclic alkyl group, a linear, branched or A cyclic alkoxy group, a substituted or unsubstituted aryl group having 6 to 40 carbon atoms, or a substituted or unsubstituted aryloxy group having 6 to 40 carbon atoms. R 1 and R 2 may be bonded to each other to form a ring.
Ｒ１〜Ｒ４における直鎖，分岐若しくは環状のアルキル基としては、炭素数１〜１８の直鎖，分岐若しくは環状のアルキル基が挙げられ、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−イル基等を挙げることができる。 Examples of the linear, branched or cyclic alkyl group in R 1 to R 4 include a linear, branched or cyclic alkyl group having 1 to 18 carbon atoms, and specifically include a methyl group, an ethyl group, and a propyl group. , Isopropyl group, butyl group, sec-butyl group, tert-butyl group, pentyl group, hexyl group, heptyl group, octyl group, stearyl group, trichloromethyl group, trifluoromethyl group, cyclopropyl group, cyclohexyl group, 1, A 3-cyclohexadienyl group, a 2-cyclopenten-1-yl group, and the like can be given.
Ｒ１〜Ｒ４における直鎖，分岐若しくは環状のアルコキシ基としては、炭素数１〜１８の直鎖，分岐若しくは環状のアルコキシ基が挙げられ、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。 Examples of the linear, branched or cyclic alkoxy group in R 1 to R 4 include a linear, branched or cyclic alkoxy group having 1 to 18 carbon atoms, specifically, a methoxy group, an ethoxy group, a propoxy group, Illustrative examples include isopropoxy group, n-butoxy group, sec-butoxy group, tert-butoxy group, pentyloxy group, hexyloxy group, stearyloxy group, trifluoromethoxy group and the like.
Ｒ１〜Ｒ４における炭素数６〜４０の置換若しくは無置換のアリール基としては、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、４−（１−ナフチル）フェニル基、４−（９−アントリル）フェニル基、４−（１０−フェニル−９−アントリル）フェニル基、４−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−アントリル基、１０−フェニル−９−アントリル基、１０−ビフェニル−９−アントリル基、９，９−ジメチル−フルオレン−２−イル基、７−フェニル−９，９−ジメチル−フルオレン−２−イル基等の他、前記Ａｒ１〜Ａｒ４で例示した置換基を挙げることもできる。 Specific examples of the substituted or unsubstituted aryl group having 6 to 40 carbon atoms in R 1 to R 4 include a phenyl group, a 4-methylphenyl group, a 3-methylphenyl group, a 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, 4- (1-naphthyl) phenyl group, 4- (9-anthryl) phenyl Group, 4- (10-phenyl-9-anthryl) phenyl group, 4-biphenyl group, 1-naphthyl group, 2-naphthyl group, 9-phenane Ryl group, 9-anthryl group, 10-phenyl-9-anthryl group, 10-biphenyl-9-anthryl group, 9,9-dimethyl-fluoren-2-yl group, 7-phenyl-9,9-dimethyl-fluorene In addition to the -2-yl group and the like, the substituents exemplified for Ar 1 to Ar 4 can also be exemplified.
また、Ｒ１〜Ｒ４における炭素数６〜４０の置換若しくは無置換のアリールオキシ基としては、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挙げることができる。 Specific examples of substituted or unsubstituted aryloxy groups having 6 to 40 carbon atoms in R 1 to R 4 include phenoxy group, p-tert-butylphenoxy group, 3-fluorophenoxy group, 4-fluoro group. Phenoxy group etc. can be mentioned.
Ｒ１〜Ｒ４におけるハロゲン原子としては、フッ素、塩素、臭素又はヨウ素原子が挙げられる。 Examples of the halogen atom for R 1 to R 4 include a fluorine, chlorine, bromine or iodine atom.
Ｒ１〜Ｒ４における置換若しくは無置換のアミノ基としては、メチルアミノ基、エチルアミノ基、フェニルアミノ基、ｍ−トリルアミノ基、ｐ−トリルアミノ基、１−ナフチルアミノ基、２−ナフチルアミノ基、４−ビフェニルアミノ基等のモノ置換アミノ基、ジメチルアミノ基、ジエチルアミノ基、ジプロピルアミノ基、ジブチルアミノ基、ジフェニルアミノ基、ジ（ｍ−トリル）アミノ基、ジ（ｐ−トリル）アミノ基、Ｎ−（ｍ−トリル）フェニルアミノ基、Ｎ−（ｐ−トリル）フェニルアミノ基、Ｎ−（１−ナフチル）フェニルアミノ基、Ｎ−（２−ナフチル）フェニルアミノ基、Ｎ−（４−ビフェニル）フェニルアミノ基、ジ（４−ビフェニル）アミノ基、ジ（２−ナフチル）アミノ基、ビス（アセトキシメチル）アミノ基、ビス（アセトキシエチル）アミノ基、ビス（アセトキシプロピル）アミノ基、ビス（アセトキシブチル）アミノ基、ジベンジルアミノ基等を例示することができるが、上記置換基に限定されるものではない。 Examples of the substituted or unsubstituted amino group in R 1 to R 4 include a methylamino group, an ethylamino group, a phenylamino group, an m-tolylamino group, a p-tolylamino group, a 1-naphthylamino group, a 2-naphthylamino group, Mono-substituted amino group such as 4-biphenylamino group, dimethylamino group, diethylamino group, dipropylamino group, dibutylamino group, diphenylamino group, di (m-tolyl) amino group, di (p-tolyl) amino group, N- (m-tolyl) phenylamino group, N- (p-tolyl) phenylamino group, N- (1-naphthyl) phenylamino group, N- (2-naphthyl) phenylamino group, N- (4-biphenyl) ) Phenylamino group, di (4-biphenyl) amino group, di (2-naphthyl) amino group, bis (acetoxymethyl) amino group, bis Acetoxyethyl) amino group, bis (acetoxypropyl) amino group, bis (acetoxybutyl) amino group, can be exemplified dibenzylamino group and the like, but is not limited to the above substituents.
本発明の好ましい具体例としては、上記一般式（１）において、ｐが１、Ｍが２置換のビフェニル骨格又はターフェニル骨格であるベンゾフルオレン化合物である。より好ましくは、Ｍが２置換のビフェニル骨格である上記一般式（４）で表されるベンゾフルオレン化合物である。 A preferred specific example of the present invention is a benzofluorene compound in which p is 1 and M is a disubstituted biphenyl skeleton or terphenyl skeleton in the general formula (1). More preferably, it is a benzofluorene compound represented by the above general formula (4), wherein M is a disubstituted biphenyl skeleton.
更に好ましい具体例としては、上記一般式（４）において、Ａｒ１又はＡｒ２のいずれかとＡｒ３又はＡｒ４のいずれかが上記一般式（２）又は（３）で表される基であるベンゾフルオレン化合物である。より好ましくは、上記一般式（４）において、Ａｒ１＝Ａｒ３、Ａｒ２＝Ａｒ４を満たし、Ａｒ１又はＡｒ２のいずれかが上記一般式（２）又は（３）であるベンゾフルオレン化合物である。 As a more preferable specific example, in the above general formula (4), either Ar 1 or Ar 2 and Ar 3 or Ar 4 are groups represented by the above general formula (2) or (3). It is a fluorene compound. More preferably, in the above general formula (4), Ar 1 = Ar 3 , Ar 2 = Ar 4 is satisfied, and either Ar 1 or Ar 2 is the above general formula (2) or (3) It is.
また、上記一般式（２）又は（３）において、Ｒ１とＲ２は互いに結合して環を形成してもよい。具体的には、下記一般式（５）又は（６）で表されるベンゾフルオレン化合物が挙げられ、特に、この化合物は素子の効率及び耐久性の面で好ましい。 In the general formula (2) or (3), R 1 and R 2 may be bonded to each other to form a ring. Specific examples include benzofluorene compounds represented by the following general formula (5) or (6). Particularly, this compound is preferable in terms of efficiency and durability of the device.
以下に好ましい化合物を例示するが、これらの化合物に限定されるものではない。
Preferred compounds are illustrated below, but are not limited to these compounds.
また、一般式（７）又は（８）で表される化合物と、市販のＮ，Ｎ’−ジフェニルベンジジンとの組み合わせでも、上記と同一の化合物を合成することができる。
Further, the same compound as described above can be synthesized also by a combination of the compound represented by the general formula (7) or (8) and commercially available N, N′-diphenylbenzidine.
本発明のベンゾフルオレン化合物は、従来の材料以上に駆動電圧の改善と高い電力効率が期待される。更に高いガラス転移温度を有するため素子寿命の改善も期待できる。従って、有機ＥＬ素子若しくは電子写真感光体等の正孔注入材料、正孔輸送材料又は発光材料としてのみでなく、光電変換素子、太陽電池、イメージセンサー等の有機光導電材料の分野にも応用できる。 The benzofluorene compound of the present invention is expected to have improved driving voltage and higher power efficiency than conventional materials. Furthermore, since it has a high glass transition temperature, an improvement in device life can be expected. Therefore, it can be applied not only as a hole injection material, a hole transport material or a light emitting material such as an organic EL element or an electrophotographic photosensitive member, but also in a field of an organic photoconductive material such as a photoelectric conversion element, a solar cell or an image sensor .
本発明による上記一般式（１）で表されるベンゾフルオレン化合物は、従来の材料以上に低電圧駆動と高い電力効率、更に高いガラス転移温度を有するため素子寿命の改善が期待できる。そのため、有機ＥＬ素子若しくは電子写真感光体等の正孔輸送材料又は発光材料等として利用できる。 Since the benzofluorene compound represented by the above general formula (1) according to the present invention has lower voltage driving, higher power efficiency and higher glass transition temperature than conventional materials, it can be expected to improve the device life. Therefore, it can be used as a hole transport material such as an organic EL element or an electrophotographic photoreceptor, or a light emitting material.
以下、本発明を実施例に基づき、更に詳細に説明する。 Hereinafter, the present invention will be described in more detail based on examples.
なお、実施例で得られた化合物の同定は、１Ｈ−ＮＭＲ測定、１３Ｃ−ＮＭＲ測定、元素分析及びＦＤＭＳ測定により行った。 The compounds obtained in the examples were identified by 1 H-NMR measurement, 13 C-NMR measurement, elemental analysis, and FDMS measurement.
１Ｈ−ＮＭＲ測定，１３Ｃ−ＮＭＲ測定は、バリアン社製 Ｇｅｍｉｎｉ２００を使用して実施した。 1 H-NMR measurement and 13 C-NMR measurement were performed using Gemini 200 manufactured by Varian.
元素分析は、パーキンエルマー社製 全自動元素分析装置 ２４００ＩＩを使用して実施した。 Elemental analysis was carried out using a fully automatic elemental analyzer 2400II manufactured by PerkinElmer.
ＦＤＭＳ測定は、日立製作所製 Ｍ−８０Ｂを使用して実施した。 The FDMS measurement was carried out using M-80B manufactured by Hitachi, Ltd.
合成例１ （化合物２ａの合成［下記（１２）式参照］）
３００ｍｌナス型フラスコに、２’−ヒドロキシ−１’−アセトナフトン １８．６ｇ（１００ｍｍｏｌ）、ジクロロメタン１００ｍｌ、ピリジン３９．６ｇ（５００ｍｍｏｌ）を加え、反応液を５℃以下に冷却した。トリフルオロメタンスルホン酸無水物３１．０ｇ（１１０ｍｍｏｌ）を反応温度が５℃を超えないように滴下した後、室温下一晩攪拌した。反応液に水を加えて分層した。有機層は、３．５％塩酸水溶液および水で洗浄後、無水硫酸マグネシウムにて乾燥し、濃縮して１’−アセトナフトン−２’−トリフルオロメタンスルフォネート ３２．７ｇを微黄色油状物として単離した。なお、生成物は精製せずに、そのまま次の反応に用いた。
Synthesis Example 1 (Synthesis of Compound 2a [Refer to Formula (12) below))
To a 300 ml eggplant-shaped flask, 18.6 g (100 mmol) of 2′-hydroxy-1′-acetonaphthone, 100 ml of dichloromethane and 39.6 g (500 mmol) of pyridine were added, and the reaction solution was cooled to 5 ° C. or lower. 31.0 g (110 mmol) of trifluoromethanesulfonic anhydride was added dropwise so that the reaction temperature did not exceed 5 ° C., and the mixture was stirred overnight at room temperature. Water was added to the reaction solution to separate the layers. The organic layer was washed with 3.5% aqueous hydrochloric acid and water, dried over anhydrous magnesium sulfate, and concentrated to give 32.7 g of 1′-acetonaphthone-2′-trifluoromethanesulfonate as a slightly yellow oil. Released. The product was directly used in the next reaction without purification.
次に、５００ｍｌナス型フラスコに、得られた１’−アセトナフトン−２’−トリフルオロメタンスルフォネート １５．１ｇ（４７．５ｍｍｏｌ）、４−クロロフェニルボロン酸（９５％品）７．８ｇ（５０．０ｍｍｏｌ）、テトラキス（トリフェニルホスフィン）パラジウム５４９ｍｇ（０．４７５ｍｍｏｌ）、２０重量％の炭酸ナトリウム水溶液１００．７ｇ及びテトラヒドロフラン２５０ｍｌを加え、６０℃で一晩加熱攪拌した。室温まで冷却後、分層した。得られた有機層は、水による洗浄、無水硫酸マグネシウムによる乾燥処理の後、濃縮して淡黄色の結晶１２．４ｇが得られた。１Ｈ−ＮＭＲ測定により目的物の２’−（４−クロロフェニル）−１’−アセトナフトンであることを確認し、生成物は精製せずに、そのまま次の反応に用いた。 Next, in a 500 ml eggplant-shaped flask, 15.1 g (47.5 mmol) of 1′-acetonaphthone-2′-trifluoromethanesulfonate and 7.8 g of 4-chlorophenylboronic acid (95% product) were obtained. 0 mmol), 549 mg (0.475 mmol) of tetrakis (triphenylphosphine) palladium, 100.7 g of a 20 wt% aqueous sodium carbonate solution and 250 ml of tetrahydrofuran were added, and the mixture was heated and stirred overnight at 60 ° C. After cooling to room temperature, the layers were separated. The obtained organic layer was washed with water, dried with anhydrous magnesium sulfate, and concentrated to obtain 12.4 g of pale yellow crystals. It was confirmed by 1 H-NMR measurement that it was the target product, 2 ′-(4-chlorophenyl) -1′-acetonaphthone, and the product was directly used in the next reaction without purification.
１Ｈ−ＮＭＲ（２００ＭＨｚ、ＣＤＣｌ３）：２．１２（３Ｈ，ｓ）、７．３３−７．６５（７Ｈ，ｍ）、７．７８−８．０１（３Ｈ，ｍ）
１３Ｃ−ＮＭＲ（５０ＭＨｚ、ＣＤＣｌ３）：３２．９, １２４．７, １２６．５，１２７．１, １２７．６, １２８．３, １２８．８, １２８．９，１２９．５, １３０．６, １３２．６, １３４．３, １３４．４, １３８．４, １３８．７, ２０７．１
次に、３００ｍｌナス型フラスコに、先に得られた２’−（４−クロロフェニル）−１’−アセトナフトン ９．８ｇ（３５ｍｍｏｌ）、テトラヒドロフラン７０ｍｌ、エタノール７０ｍｌを加えた。溶解した後、水素化ホウ素ナトリウム６．６ｇ（１７５ｍｍｏｌ）を加え、室温にて８時間攪拌した。
1 H-NMR (200 MHz, CDCl 3 ): 2.12 (3H, s), 7.33-7.65 (7H, m), 7.78-8.01 (3H, m)
13 C-NMR (50 MHz, CDCl 3 ): 32.9, 124.7, 126.5, 127.1, 127.6, 128.3, 128.8, 128.9, 129.5, 130.6 132.6, 134.3, 134.4, 138.4, 138.7, 207.1.
Next, 9.8 g (35 mmol) of 2 ′-(4-chlorophenyl) -1′-acetonaphthone obtained previously, 70 ml of tetrahydrofuran, and 70 ml of ethanol were added to a 300 ml eggplant-shaped flask. After dissolution, 6.6 g (175 mmol) of sodium borohydride was added and stirred at room temperature for 8 hours.
１０％塩化アンモニウム水溶液１００ｇを発泡に注意しつつ添加した後、減圧濃縮した。残渣をトルエン２００ｍｌで抽出し、水による洗浄、無水硫酸マグネシウムによる乾燥処理の後、濃縮して淡黄色の結晶９．４ｇが得られた。１Ｈ−ＮＭＲ測定により目的物の１−（１−ヒドロキシ）エチル−２−（４−クロロフェニル）ナフタレンであることを確認し、生成物は精製せずに、そのまま次の反応に用いた。 After adding 100 g of 10% ammonium chloride aqueous solution while paying attention to foaming, the solution was concentrated under reduced pressure. The residue was extracted with 200 ml of toluene, washed with water, dried with anhydrous magnesium sulfate, and concentrated to obtain 9.4 g of pale yellow crystals. The product was confirmed to be 1- (1-hydroxy) ethyl-2- (4-chlorophenyl) naphthalene as a target product by 1 H-NMR measurement, and the product was directly used in the next reaction without purification.
１Ｈ−ＮＭＲ（２００ＭＨｚ、ＣＤＣｌ３）：１．７１（３Ｈ，ｄ，Ｊ＝７．０Ｈｚ）、２．０５（１Ｈ，ｂｒ−ｓ）、５．３５（１Ｈ，ｑ，Ｊ＝７．０Ｈｚ）、７．１６−７．６３（７Ｈ，ｍ）、７．６９−７．９５（２Ｈ，ｍ）、８．７６−８．９３（１Ｈ，ｂｒ−ｄ）
１３Ｃ−ＮＭＲ（５０ＭＨｚ、ＣＤＣｌ３）：２３．９, ６８．９, １２５．８，１２５．９, １２７．０, １２７．８, １２７．９, １２８．４, １２８．８, １３０．４, １３０．８, １３３．２, １３４．２, １３６．９, １３７．１, １４０．６
次に、１００ｍｌナス型フラスコに、先に得られた１−（１−ヒドロキシ）エチル−２−（４−クロロフェニル）ナフタレン ２．８ｇ（１０ｍｍｏｌ）、クロロホルム２０ｍｌを加えた。０℃に冷却した後、三フッ化ホウ素・ジエチルエーテラート１．８５ｇ（１３ｍｍｏｌ）を滴下し、室温にて１時間攪拌した。
1 H-NMR (200 MHz, CDCl 3 ): 1.71 (3H, d, J = 7.0 Hz), 2.05 (1H, br-s), 5.35 (1H, q, J = 7.0 Hz) ), 7.16-7.63 (7H, m), 7.69-7.95 (2H, m), 8.76-8.93 (1H, br-d)
13 C-NMR (50 MHz, CDCl 3 ): 23.9, 68.9, 125.8, 125.9, 127.0, 127.8, 127.9, 128.4, 128.8, 130.4 , 130.8, 133.2, 134.2, 136.9, 137.1, 140.6
Next, 2.8 g (10 mmol) of 1- (1-hydroxy) ethyl-2- (4-chlorophenyl) naphthalene obtained previously and 20 ml of chloroform were added to a 100 ml eggplant-shaped flask. After cooling to 0 ° C., 1.85 g (13 mmol) of boron trifluoride / diethyl etherate was added dropwise, and the mixture was stirred at room temperature for 1 hour.
水２０ｇを添加し反応を終了した後、有機層を水による洗浄、無水硫酸マグネシウムによる乾燥処理した後、濃縮して淡黄色の固体２．７ｇが得られた。１Ｈ−ＮＭＲ測定により目的物の９−クロロ−１１−メチル−１１Ｈ−ベンゾ［ａ］フルオレン（化合物１ａ）であることを確認し、生成物は精製せずに、そのまま次の反応に用いた。 After completion of the reaction by adding 20 g of water, the organic layer was washed with water, dried with anhydrous magnesium sulfate, and then concentrated to obtain 2.7 g of a pale yellow solid. The product was confirmed to be 9-chloro-11-methyl-11H-benzo [a] fluorene (compound 1a) by 1 H-NMR measurement, and the product was used in the next reaction without purification. .
１Ｈ−ＮＭＲ（２００ＭＨｚ、ＣＤＣｌ３）：１．６６（３Ｈ，ｄ，Ｊ＝７．２Ｈｚ）、４．３３（１Ｈ，ｑ，Ｊ＝７．２Ｈｚ）、７．３２−７．６５（５Ｈ，ｍ）、７．７０（１Ｈ，ｄ，Ｊ＝８．１Ｈｚ）、７．８０−８．０１（３Ｈ，ｍ）、８．０６（１Ｈ，ｄ，Ｊ＝８．０Ｈｚ）
得られた９−クロロ−１１−メチル−１１Ｈ−ベンゾ［ａ］フルオレン ２．７ｇ（１０ｍｍｏｌ）、ベンジルトリエチルアンモニウムクロリド２．３ｇ（１０ｍｍｏｌ）、ヨウ化メチル４．３ｇ（３０ｍｍｏｌ）をジメチルスルホキシド２０ｍｌに溶解し、０℃に冷却後、４８％水酸化ナトリウム水溶液 １．２ｇ（３０ｍｍｏｌ）を攪拌しながら滴下した。室温にて１時間攪拌後、トルエン５０ｍｌを加えてから、有機層を水にて洗浄した。硫酸マグネシウムによる乾燥の後、抽出液を濃縮して淡黄色の結晶を得た。シリカゲルカラムクロマトグラフィーに付し（溶出液：ヘキサン）、９−クロロ−１１，１１−ジメチル−１１Ｈ−ベンゾ［ａ］フルオレン（化合物２ａ）を白色結晶として２．０ｇ単離した（収率７２％）。
1 H-NMR (200 MHz, CDCl 3 ): 1.66 (3H, d, J = 7.2 Hz), 4.33 (1H, q, J = 7.2 Hz), 7.32-7.65 (5H M), 7.70 (1H, d, J = 8.1 Hz), 7.80-8.01 (3H, m), 8.06 (1H, d, J = 8.0 Hz)
2.7 g (10 mmol) of 9-chloro-11-methyl-11H-benzo [a] fluorene obtained, 2.3 g (10 mmol) of benzyltriethylammonium chloride, and 4.3 g (30 mmol) of methyl iodide in 20 ml of dimethyl sulfoxide. After dissolving and cooling to 0 ° C., 1.2 g (30 mmol) of 48% aqueous sodium hydroxide solution was added dropwise with stirring. After stirring at room temperature for 1 hour, 50 ml of toluene was added, and the organic layer was washed with water. After drying with magnesium sulfate, the extract was concentrated to obtain pale yellow crystals. The product was subjected to silica gel column chromatography (eluent: hexane), and 2.0 g of 9-chloro-11,11-dimethyl-11H-benzo [a] fluorene (compound 2a) was isolated as white crystals (yield 72%). ).
１Ｈ−ＮＭＲ（２００ＭＨｚ、ＣＤＣｌ３）：１．７３（６Ｈ，ｓ）、７．２１−７．６６（５Ｈ，ｍ）、７．６９（１Ｈ，ｄ，Ｊ＝７．８Ｈｚ）、７．８０−７．９９（３Ｈ，ｍ）、８．１９（１Ｈ，ｄ，Ｊ＝８．３Ｈｚ）
１３Ｃ−ＮＭＲ（５０ＭＨｚ、ＣＤＣｌ３）：２６．３, ４８．８, １１８．６,１２０．６, １２２．８, １２４．０, １２５．０, １２６．２, １２７．２, １２８．７, １３０．０, １３２．７, １３４．０,１３５．６, １３７．８， １４７．１， １５７．０
1 H-NMR (200 MHz, CDCl 3 ): 1.73 (6H, s), 7.21-7.66 (5H, m), 7.69 (1H, d, J = 7.8 Hz), 7. 80-7.99 (3H, m), 8.19 (1H, d, J = 8.3 Hz)
13 C-NMR (50 MHz, CDCl 3 ): 26.3, 48.8, 118.6, 120.6, 122.8, 124.0, 125.0, 126.2, 127.2, 128.7 , 130.0, 132.7, 134.0, 135.6, 137.8, 147.1, 157.0
２’−ヒドロキシ−１’−アセトナフトンの代わりに１’−ヒドロキシ−２’−アセトナフトンを用い、下記反応式（１３）に従い、合成例１と同じ反応条件により、目的とする９−クロロ−７，７−ジメチル−７Ｈ−ベンゾ［ｃ］フルオレン（１ｂ）を合成した。
1′-hydroxy-2′-acetonaphthone is used instead of 2′-hydroxy-1′-acetonaphthone, and according to the following reaction formula (13), the target 9-chloro-7, 7-dimethyl-7H-benzo [c] fluorene (1b) was synthesized.
元素分析（計算値）：Ｃ；８１．９％，Ｈ；５．４％，Ｃｌ；１２．７％
（実測値）：Ｃ；８１．８％，Ｈ；５．４％，Ｃｌ；１２．８％
ＦＤＭＳ：ｍ／ｚ＝２７８
Elemental analysis (calculated value): C; 81.9%, H; 5.4%, Cl; 12.7%
(Measured value): C; 81.8%, H; 5.4%, Cl; 12.8%
FDMS: m / z = 278
１００ｍｌナス型フラスコに、９−クロロ−１１，１１−ジメチル−１１Ｈ−ベンゾ［ａ］フルオレン ７３６ｍｇ（２．６４ｍｍｏｌ）、Ｎ，Ｎ’−ジフェニルベンジジン ４０４ｍｇ（１．２ｍｍｏｌ）、ナトリウム−ｔｅｒｔ−ブトキシド ４６１ｍｇをキシレン４０ｍｌに懸濁させ、窒素で系内を置換した。更に、窒素雰囲気下、酢酸パラジウム２．２５ｍｇ及びトリ−ｔｅｒｔ−ブチルホスフィン ７ｍｇを添加し、１２５℃に加熱した。所定温度で１５時間熟成した後、反応液を室温まで冷却した。水２０ｍｌを添加後、ジクロロメタンで抽出を行い、有機相を水洗後に濃縮した。シリカゲルカラムクロマトグラフィーにて精製し、薄黄土色の粉体化合物（Ｆ１）を９７４ｍｇ得た（収率９９％）。
In a 100 ml eggplant type flask, 736 mg (2.64 mmol) of 9-chloro-11,11-dimethyl-11H-benzo [a] fluorene, 404 mg (1.2 mmol) of N, N′-diphenylbenzidine, 461 mg of sodium tert-butoxide Was suspended in 40 ml of xylene, and the inside of the system was replaced with nitrogen. Furthermore, 2.25 mg of palladium acetate and 7 mg of tri-tert-butylphosphine were added under a nitrogen atmosphere and heated to 125 ° C. After aging at a predetermined temperature for 15 hours, the reaction solution was cooled to room temperature. After adding 20 ml of water, extraction was performed with dichloromethane, and the organic phase was washed with water and concentrated. Purification by silica gel column chromatography gave 974 mg of a light ocher powder compound (F1) (yield 99%).
同定は、ＦＤＭＳ測定および１Ｈ−ＮＭＲ測定により行った。 Identification was performed by FDMS measurement and 1 H-NMR measurement.
ＦＤＭＳ：ｍ／ｚ＝８２０
１Ｈ−ＮＭＲ（２００ＭＨｚ、ＣＤＣｌ３）：１．６８（１２Ｈ，ｓ）、６．９８−７．７５（３６Ｈ，ｍ）、７．８５（４Ｈ，ｓ）、７．９５（２Ｈ，ｄ，Ｊ＝８．０Ｈｚ）、８．１８（２Ｈ，ｄ，Ｊ＝８．０Ｈｚ）
化合物（Ｆ１）のガラス転移温度は１５４℃であり、従来材料である４，４’−ビス［Ｎ−（１−ナフチル）−Ｎ−フェニルアミノ］ビフェニル、２，７−ビス［Ｎ−（１−ナフチル）−Ｎ−フェニルアミノ］−９，９’−ジメチルフルオレン、Ｎ，Ｎ’−ジ［２−（９，９−ジメチルフルオレニル）］−Ｎ，Ｎ’−ジ（４−ビフェニル）ベンジジン等のガラス転移温度（各々、９６℃、１１０℃、１２０℃）より約３０℃以上高かった。
FDMS: m / z = 820
1 H-NMR (200 MHz, CDCl 3 ): 1.68 (12H, s), 6.98-7.75 (36H, m), 7.85 (4H, s), 7.95 (2H, d, J = 8.0 Hz), 8.18 (2H, d, J = 8.0 Hz)
Compound (F1) has a glass transition temperature of 154 ° C. and is a conventional material of 4,4′-bis [N- (1-naphthyl) -N-phenylamino] biphenyl, 2,7-bis [N- (1 -Naphthyl) -N-phenylamino] -9,9'-dimethylfluorene, N, N'-di [2- (9,9-dimethylfluorenyl)]-N, N'-di (4-biphenyl) It was about 30 ° C. or higher than the glass transition temperatures of benzidine and the like (96 ° C., 110 ° C., and 120 ° C., respectively).
実施例２ （化合物Ａ１の合成）
９−クロロ−１１，１１−ジメチル−１１Ｈ−ベンゾ［ａ］フルオレン（２ａ）の代わりに合成例２で得られた９−クロロ−７，７−ジメチル−７Ｈ−ベンゾ［ｃ］フルオレン（１ｂ）７３０ｍｇを用いて実施例１と同様な操作を行い、化合物Ａ１を９４６ｍｇ得た。
Example 2 (Synthesis of Compound A1)
9-chloro-7,7-dimethyl-7H-benzo [c] fluorene (1b) obtained in Synthesis Example 2 instead of 9-chloro-11,11-dimethyl-11H-benzo [a] fluorene (2a) The same operation as in Example 1 was carried out using 730 mg to obtain 946 mg of Compound A1.
同定は、元素分析、ＦＤＭＳにより行った。 Identification was performed by elemental analysis and FDMS.
元素分析（計算値）：Ｃ；９０．７％，Ｈ；５．９％，Ｎ；８．４％
（実測値）：Ｃ；９０．７％，Ｈ；５．８％，Ｎ；８．５％
ＦＤＭＳ：ｍ／ｚ＝８２０
実施例３ （素子作製）
厚さ１１０ｎｍのＩＴＯ透明電極（陽極）を積層したガラス基板を中性洗剤、純水及びアセトンにより超音波洗浄し、その後イソプロピルアルコールによる沸騰洗浄を行なった。さらに紫外線オゾン洗浄を行ない、真空蒸着装置へ設置後１×１０−４Ｐａになるまで、真空ポンプにて排気した。ＩＴＯ透明電極上に銅フタロシアニンを蒸着速度０．３ｎｍ／秒で蒸着し、２０ｎｍの正孔注入層とした。引き続き、化合物（Ｆ１）を蒸着速度０．３ｎｍ／秒で３０ｎｍ蒸着して正孔輸送層とし、続いてトリス（８−キノリノラート）アルミニウムを蒸着速度０．３ｎｍ／秒で５０ｎｍ蒸着して発光層とした。続いて銀とマグネシウムを蒸着速度０．３３ｎｍ／秒で１００ｎｍの厚さに共蒸着（重量比１０：１）し、更に銀を蒸着速度０．２ｎｍ／秒で１０ｎｍ蒸着して陰極とし、有機ＥＬ素子を作製した。
Elemental analysis (calculated value): C; 90.7%, H; 5.9%, N; 8.4%
(Measured value): C; 90.7%, H; 5.8%, N; 8.5%
FDMS: m / z = 820
Example 3 (Element fabrication)
A glass substrate on which an ITO transparent electrode (anode) having a thickness of 110 nm was laminated was subjected to ultrasonic cleaning with a neutral detergent, pure water and acetone, and then subjected to boiling cleaning with isopropyl alcohol. Furthermore, ultraviolet ozone cleaning was performed, and after evacuation with a vacuum pump until 1 × 10 −4 Pa was obtained after installation in a vacuum deposition apparatus. Copper phthalocyanine was deposited on the ITO transparent electrode at a deposition rate of 0.3 nm / second to form a 20 nm hole injection layer. Subsequently, compound (F1) was deposited at a deposition rate of 0.3 nm / second to 30 nm to form a hole transport layer, and then tris (8-quinolinolato) aluminum was deposited at a deposition rate of 0.3 nm / second to 50 nm to form a light emitting layer. did. Subsequently, silver and magnesium were co-deposited to a thickness of 100 nm at a deposition rate of 0.33 nm / second (weight ratio 10: 1), and silver was further deposited to a thickness of 10 nm at a deposition rate of 0.2 nm / second to form a cathode. An element was produced.
電流密度１０ｍＡ／ｃｍ２，２０ｍＡ／ｃｍ２時の輝度、駆動電圧、電流効率、電力効率を表１に示す。 Table 1 shows the luminance, driving voltage, current efficiency, and power efficiency at a current density of 10 mA / cm 2 and 20 mA / cm 2 .
実施例４ （素子作製）
化合物（Ｆ１）の代わりに化合物（Ａ１）を用いて、実施例３と同様な素子を作製した。電流密度２０ｍＡ／ｃｍ２時の輝度、駆動電圧、電流効率、電力効率を表１に示す。
Example 4 (Device fabrication)
A device similar to that of Example 3 was fabricated using the compound (A1) instead of the compound (F1). Table 1 shows the luminance, drive voltage, current efficiency, and power efficiency at a current density of 20 mA / cm 2 .
比較例１ （素子作製）
化合物（Ｆ１）をα−ＮＰＤに変更した以外は、実施例２と同様の素子を作製した。
Comparative Example 1 (Element fabrication)
A device was produced in the same manner as in Example 2 except that the compound (F1) was changed to α-NPD.
電流密度１０ｍＡ／ｃｍ２，２０ｍＡ／ｃｍ２時の輝度、駆動電圧、電流効率、電力効率を表１に示す。 Table 1 shows the luminance, driving voltage, current efficiency, and power efficiency at a current density of 10 mA / cm 2 and 20 mA / cm 2 .
厚さ１１０ｎｍのＩＴＯ透明電極（陽極）を積層したガラス基板を中性洗剤、純水及びアセトンにより超音波洗浄し、その後イソプロピルアルコールによる沸騰洗浄を行なった。さらに紫外線オゾン洗浄を行ない、真空蒸着装置へ設置後１×１０−４Ｐａになるまで、真空ポンプにて排気した。ＩＴＯ透明電極上に銅フタロシアニンを蒸着速度０．３ｎｍ／秒で蒸着し、２０ｎｍの正孔注入層とした。引き続き、化合物（Ｆ１）を蒸着速度０．３ｎｍ／秒で５０ｎｍ蒸着して正孔輸送層とし、続いてＢＣｚＶＢｉ、ＤＰＶＢｉをそれぞれ青色ドーパント（４ｍｏｌ％）、青色ホスト材料とし、蒸着速度０．３ｎｍ／秒で４０ｎｍ蒸着して発光層とした。続いてトリス（８−キノリノラート）アルミニウムを蒸着速度０．３ｎｍ／秒で２０ｎｍ蒸着して電子輸送層とした。続いてＬｉＦ、アルミニウムを各々０．５ｎｍ、１００ｎｍの厚さに蒸着して陰極とし、有機ＥＬ素子を作製した。
A glass substrate on which an ITO transparent electrode (anode) having a thickness of 110 nm was laminated was subjected to ultrasonic cleaning with a neutral detergent, pure water and acetone, and then subjected to boiling cleaning with isopropyl alcohol. Furthermore, ultraviolet ozone cleaning was performed, and after evacuation with a vacuum pump until 1 × 10 −4 Pa was obtained after installation in a vacuum deposition apparatus. Copper phthalocyanine was deposited on the ITO transparent electrode at a deposition rate of 0.3 nm / second to form a 20 nm hole injection layer. Subsequently, the compound (F1) was vapor-deposited at a deposition rate of 0.3 nm / second to 50 nm to form a hole transport layer, followed by BCzVBi and DPVBi as a blue dopant (4 mol%) and a blue host material, respectively. The light-emitting layer was deposited by 40 nm in seconds. Subsequently, tris (8-quinolinolato) aluminum was deposited to a thickness of 20 nm at a deposition rate of 0.3 nm / second to form an electron transport layer. Subsequently, LiF and aluminum were vapor-deposited to a thickness of 0.5 nm and 100 nm, respectively, to form a cathode, thereby producing an organic EL element.
電流密度２０ｍＡ／ｃｍ２時の輝度、駆動電圧、電流効率、電力効率、素子寿命（輝度半減寿命）を表２に示す。 Table 2 shows the luminance, driving voltage, current efficiency, power efficiency, and element lifetime (luminance half-life) at a current density of 20 mA / cm 2 .
化合物（Ｆ１）をα−ＮＰＤに変更した以外は、実施例５と同様な素子を作製した。
A device similar to that of Example 5 was produced, except that the compound (F1) was changed to α-NPD.
電流密度２０ｍＡ／ｃｍ２時の輝度、駆動電圧、電流効率、電力効率、素子寿命（輝度半減寿命）を表２に示す。 Table 2 shows the luminance, driving voltage, current efficiency, power efficiency, and element lifetime (luminance half-life) at a current density of 20 mA / cm 2 .
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