JP2008050337A - Benzofluorene compound and use thereof - Google Patents
Benzofluorene compound and use thereof Download PDFInfo
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- JP2008050337A JP2008050337A JP2007010813A JP2007010813A JP2008050337A JP 2008050337 A JP2008050337 A JP 2008050337A JP 2007010813 A JP2007010813 A JP 2007010813A JP 2007010813 A JP2007010813 A JP 2007010813A JP 2008050337 A JP2008050337 A JP 2008050337A
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- -1 Benzofluorene compound Chemical class 0.000 title claims abstract description 223
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 50
- 125000003118 aryl group Chemical group 0.000 claims abstract description 27
- 125000001072 heteroaryl group Chemical group 0.000 claims abstract description 16
- 125000001424 substituent group Chemical group 0.000 claims abstract description 10
- 125000003983 fluorenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3CC12)* 0.000 claims abstract description 5
- 150000001875 compounds Chemical class 0.000 claims description 37
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical group C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 claims description 16
- 125000003277 amino group Chemical group 0.000 claims description 13
- 125000003545 alkoxy group Chemical group 0.000 claims description 12
- 125000005843 halogen group Chemical group 0.000 claims description 12
- 230000005525 hole transport Effects 0.000 claims description 12
- 125000006165 cyclic alkyl group Chemical group 0.000 claims description 11
- 125000004122 cyclic group Chemical group 0.000 claims description 11
- 125000004104 aryloxy group Chemical group 0.000 claims description 10
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 8
- 229910052799 carbon Inorganic materials 0.000 claims description 8
- 239000004305 biphenyl Chemical group 0.000 claims description 7
- 235000010290 biphenyl Nutrition 0.000 claims description 7
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Chemical compound BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 6
- 238000002347 injection Methods 0.000 claims description 6
- 239000007924 injection Substances 0.000 claims description 6
- FRIJWEQBTIZQMD-UHFFFAOYSA-N 11H-benzo[c]fluorene Natural products C1=CC2=CC=CC=C2C2=C1CC1=CC=CC=C12 FRIJWEQBTIZQMD-UHFFFAOYSA-N 0.000 claims description 5
- 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 claims description 4
- 229910052794 bromium Inorganic materials 0.000 claims description 4
- 238000005401 electroluminescence Methods 0.000 claims description 4
- 125000001624 naphthyl group Chemical group 0.000 claims description 4
- 125000002947 alkylene group Chemical group 0.000 claims description 3
- 125000000732 arylene group Chemical group 0.000 claims description 3
- 229910052801 chlorine Inorganic materials 0.000 claims description 3
- 125000001309 chloro group Chemical group Cl* 0.000 claims description 2
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 37
- 230000009477 glass transition Effects 0.000 abstract description 8
- 230000007774 longterm Effects 0.000 abstract 1
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 84
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 42
- 238000005259 measurement Methods 0.000 description 35
- 238000005160 1H NMR spectroscopy Methods 0.000 description 31
- 238000006243 chemical reaction Methods 0.000 description 31
- 239000000243 solution Substances 0.000 description 31
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 31
- 230000015572 biosynthetic process Effects 0.000 description 24
- 238000003786 synthesis reaction Methods 0.000 description 24
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 23
- 239000012044 organic layer Substances 0.000 description 22
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 21
- 238000000434 field desorption mass spectrometry Methods 0.000 description 21
- 239000002904 solvent Substances 0.000 description 20
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 15
- 229910052757 nitrogen Inorganic materials 0.000 description 15
- 239000013078 crystal Substances 0.000 description 14
- 238000010898 silica gel chromatography Methods 0.000 description 14
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 12
- 239000000203 mixture Substances 0.000 description 12
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical class O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 12
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 11
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 10
- MFRIHAYPQRLWNB-UHFFFAOYSA-N sodium tert-butoxide Chemical compound [Na+].CC(C)(C)[O-] MFRIHAYPQRLWNB-UHFFFAOYSA-N 0.000 description 10
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 235000002597 Solanum melongena Nutrition 0.000 description 8
- 244000061458 Solanum melongena Species 0.000 description 8
- 238000001816 cooling Methods 0.000 description 8
- 239000012299 nitrogen atmosphere Substances 0.000 description 8
- 238000000605 extraction Methods 0.000 description 7
- 238000000746 purification Methods 0.000 description 7
- 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 7
- 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 6
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 6
- UAOMVDZJSHZZME-UHFFFAOYSA-N diisopropylamine Chemical compound CC(C)NC(C)C UAOMVDZJSHZZME-UHFFFAOYSA-N 0.000 description 6
- 239000010410 layer Substances 0.000 description 6
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 6
- 235000019341 magnesium sulphate Nutrition 0.000 description 6
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 6
- 239000000758 substrate Substances 0.000 description 6
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 5
- 238000002844 melting Methods 0.000 description 5
- 230000008018 melting Effects 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- 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 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 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
- HTZCNXWZYVXIMZ-UHFFFAOYSA-M benzyl(triethyl)azanium;chloride Chemical compound [Cl-].CC[N+](CC)(CC)CC1=CC=CC=C1 HTZCNXWZYVXIMZ-UHFFFAOYSA-M 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
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- 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 4
- 238000001953 recrystallisation Methods 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- FANCTJAFZSYTIS-IQUVVAJASA-N (1r,3s,5z)-5-[(2e)-2-[(1r,3as,7ar)-7a-methyl-1-[(2r)-4-(phenylsulfonimidoyl)butan-2-yl]-2,3,3a,5,6,7-hexahydro-1h-inden-4-ylidene]ethylidene]-4-methylidenecyclohexane-1,3-diol Chemical compound C([C@@H](C)[C@@H]1[C@]2(CCCC(/[C@@H]2CC1)=C\C=C\1C([C@@H](O)C[C@H](O)C/1)=C)C)CS(=N)(=O)C1=CC=CC=C1 FANCTJAFZSYTIS-IQUVVAJASA-N 0.000 description 3
- SHAHPWSYJFYMRX-GDLCADMTSA-N (2S)-2-(4-{[(1R,2S)-2-hydroxycyclopentyl]methyl}phenyl)propanoic acid Chemical compound C1=CC([C@@H](C(O)=O)C)=CC=C1C[C@@H]1[C@@H](O)CCC1 SHAHPWSYJFYMRX-GDLCADMTSA-N 0.000 description 3
- VIMMECPCYZXUCI-MIMFYIINSA-N (4s,6r)-6-[(1e)-4,4-bis(4-fluorophenyl)-3-(1-methyltetrazol-5-yl)buta-1,3-dienyl]-4-hydroxyoxan-2-one Chemical compound CN1N=NN=C1C(\C=C\[C@@H]1OC(=O)C[C@@H](O)C1)=C(C=1C=CC(F)=CC=1)C1=CC=C(F)C=C1 VIMMECPCYZXUCI-MIMFYIINSA-N 0.000 description 3
- UMFMSMTZMLZPLT-UHFFFAOYSA-N 7-methyl-7h-benzo[c]fluorene Chemical compound C1=CC2=CC=CC=C2C2=C1C(C)C1=CC=CC=C12 UMFMSMTZMLZPLT-UHFFFAOYSA-N 0.000 description 3
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical group [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 3
- HKMTVMBEALTRRR-UHFFFAOYSA-N Benzo[a]fluorene Chemical class C1=CC=CC2=C3CC4=CC=CC=C4C3=CC=C21 HKMTVMBEALTRRR-UHFFFAOYSA-N 0.000 description 3
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 3
- 0 CN(*[Al]C)c(cc1)ccc1-c(cc1)ccc1N(*)[Al](C)* Chemical compound CN(*[Al]C)c(cc1)ccc1-c(cc1)ccc1N(*)[Al](C)* 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- TZYWCYJVHRLUCT-VABKMULXSA-N N-benzyloxycarbonyl-L-leucyl-L-leucyl-L-leucinal Chemical compound CC(C)C[C@@H](C=O)NC(=O)[C@H](CC(C)C)NC(=O)[C@H](CC(C)C)NC(=O)OCC1=CC=CC=C1 TZYWCYJVHRLUCT-VABKMULXSA-N 0.000 description 3
- 230000032683 aging Effects 0.000 description 3
- SRVFFFJZQVENJC-IHRRRGAJSA-N aloxistatin Chemical compound CCOC(=O)[C@H]1O[C@@H]1C(=O)N[C@@H](CC(C)C)C(=O)NCCC(C)C SRVFFFJZQVENJC-IHRRRGAJSA-N 0.000 description 3
- 235000019270 ammonium chloride Nutrition 0.000 description 3
- OSVHLUXLWQLPIY-KBAYOESNSA-N butyl 2-[(6aR,9R,10aR)-1-hydroxy-9-(hydroxymethyl)-6,6-dimethyl-6a,7,8,9,10,10a-hexahydrobenzo[c]chromen-3-yl]-2-methylpropanoate Chemical compound C(CCC)OC(C(C)(C)C1=CC(=C2[C@H]3[C@H](C(OC2=C1)(C)C)CC[C@H](C3)CO)O)=O OSVHLUXLWQLPIY-KBAYOESNSA-N 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 229910052740 iodine Inorganic materials 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
- 239000003921 oil Substances 0.000 description 3
- 235000019198 oils Nutrition 0.000 description 3
- 239000012074 organic phase Substances 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 238000001771 vacuum deposition Methods 0.000 description 3
- 238000007740 vapor deposition Methods 0.000 description 3
- 239000008096 xylene Substances 0.000 description 3
- 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 2
- LJIOTBMDLVHTBO-CUYJMHBOSA-N (2s)-2-amino-n-[(1r,2r)-1-cyano-2-[4-[4-(4-methylpiperazin-1-yl)sulfonylphenyl]phenyl]cyclopropyl]butanamide Chemical compound CC[C@H](N)C(=O)N[C@]1(C#N)C[C@@H]1C1=CC=C(C=2C=CC(=CC=2)S(=O)(=O)N2CCN(C)CC2)C=C1 LJIOTBMDLVHTBO-CUYJMHBOSA-N 0.000 description 2
- FRJJJAKBRKABFA-TYFAACHXSA-N (4r,6s)-6-[(e)-2-[6-chloro-4-(4-fluorophenyl)-2-propan-2-ylquinolin-3-yl]ethenyl]-4-hydroxyoxan-2-one Chemical compound C(\[C@H]1OC(=O)C[C@H](O)C1)=C/C=1C(C(C)C)=NC2=CC=C(Cl)C=C2C=1C1=CC=C(F)C=C1 FRJJJAKBRKABFA-TYFAACHXSA-N 0.000 description 2
- IGVKWAAPMVVTFX-BUHFOSPRSA-N (e)-octadec-5-en-7,9-diynoic acid Chemical compound CCCCCCCCC#CC#C\C=C\CCCC(O)=O IGVKWAAPMVVTFX-BUHFOSPRSA-N 0.000 description 2
- GPYDMVZCPRONLW-UHFFFAOYSA-N 1-iodo-4-(4-iodophenyl)benzene Chemical group C1=CC(I)=CC=C1C1=CC=C(I)C=C1 GPYDMVZCPRONLW-UHFFFAOYSA-N 0.000 description 2
- STJQFERWDGKJOK-UHFFFAOYSA-N 2-naphthalen-1-ylbenzaldehyde Chemical compound O=CC1=CC=CC=C1C1=CC=CC2=CC=CC=C12 STJQFERWDGKJOK-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
- 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
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 2
- 229910015900 BF3 Inorganic materials 0.000 description 2
- ZHNUHDYFZUAESO-UHFFFAOYSA-N Formamide Chemical compound NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 description 2
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-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
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 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
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- HFACYLZERDEVSX-UHFFFAOYSA-N benzidine Chemical compound C1=CC(N)=CC=C1C1=CC=C(N)C=C1 HFACYLZERDEVSX-UHFFFAOYSA-N 0.000 description 2
- JPHKHHXWFNVDKL-UHFFFAOYSA-N benzo[c]fluoren-1-one Chemical compound C1=CC=C2C3=C4C(=O)C=CC=C4C=CC3=CC2=C1 JPHKHHXWFNVDKL-UHFFFAOYSA-N 0.000 description 2
- ILAHWRKJUDSMFH-UHFFFAOYSA-N boron tribromide Chemical compound BrB(Br)Br ILAHWRKJUDSMFH-UHFFFAOYSA-N 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 238000000151 deposition Methods 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- SWXVUIWOUIDPGS-UHFFFAOYSA-N diacetone alcohol Natural products CC(=O)CC(C)(C)O SWXVUIWOUIDPGS-UHFFFAOYSA-N 0.000 description 2
- 229940043279 diisopropylamine Drugs 0.000 description 2
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 2
- XNJXHWJUGDADMZ-UHFFFAOYSA-N ethyl 2-(6-bromonaphthalen-2-yl)benzoate Chemical compound CCOC(=O)C1=CC=CC=C1C1=CC=C(C=C(Br)C=C2)C2=C1 XNJXHWJUGDADMZ-UHFFFAOYSA-N 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 229910052731 fluorine Inorganic materials 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
- ZCSHNCUQKCANBX-UHFFFAOYSA-N lithium diisopropylamide Chemical compound [Li+].CC(C)[N-]C(C)C ZCSHNCUQKCANBX-UHFFFAOYSA-N 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 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
- GVOISEJVFFIGQE-YCZSINBZSA-N n-[(1r,2s,5r)-5-[methyl(propan-2-yl)amino]-2-[(3s)-2-oxo-3-[[6-(trifluoromethyl)quinazolin-4-yl]amino]pyrrolidin-1-yl]cyclohexyl]acetamide Chemical compound CC(=O)N[C@@H]1C[C@H](N(C)C(C)C)CC[C@@H]1N1C(=O)[C@@H](NC=2C3=CC(=CC=C3N=CN=2)C(F)(F)F)CC1 GVOISEJVFFIGQE-YCZSINBZSA-N 0.000 description 2
- HUMMCEUVDBVXTQ-UHFFFAOYSA-N naphthalen-1-ylboronic acid Chemical compound C1=CC=C2C(B(O)O)=CC=CC2=C1 HUMMCEUVDBVXTQ-UHFFFAOYSA-N 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
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- 125000003261 o-tolyl group Chemical group [H]C1=C([H])C(*)=C(C([H])=C1[H])C([H])([H])[H] 0.000 description 2
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- 235000019345 sodium thiosulphate Nutrition 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
- PJANXHGTPQOBST-UHFFFAOYSA-N stilbene Chemical class C=1C=CC=CC=1C=CC1=CC=CC=C1 PJANXHGTPQOBST-UHFFFAOYSA-N 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 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
- 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
- 125000001544 thienyl group Chemical group 0.000 description 1
- 125000003866 trichloromethyl group Chemical group ClC(Cl)(Cl)* 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
- 125000003258 trimethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 1
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- H05B33/00—Electroluminescent light sources
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Abstract
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ホスト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. Can be used as a host 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、代表的正孔輸送材料であり、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 hole transport material and excellent in current efficiency, has a low glass transition temperature, and thus includes problems such as sudden death of an organic electroluminescence element from the viewpoint of element lifetime, It is a problem. 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, realizes 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であり、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.
上記一般式（５）又は（６）で表されるベンゾフルオレン化合物において、Ｒ７，Ｒ８，Ｒ１１，Ｒ１２は、上記一般式（２）又は（３）で表されるＲ１〜Ｒ４と同一の置換基が挙げられる。Ｒ９，Ｒ１０としては、メチレン基、エチレン基、トリメチレン基、テトラエチレン基等のアルキレン基、フェニレン基、ナフチレン基等のアリーレン基が挙げられる。Ａｒ５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、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としては、上記一般式（１）で表されるＭと同一の置換基が挙げられる。
In the benzofluorene compound represented by the general formula (5) or (6), R 7 , R 8 , R 11 and R 12 are R 1 to R represented by the general formula (2) or (3). 4 and the same substituents. Examples of R 9 and R 10 include alkylene groups such as methylene group, ethylene group, trimethylene group and tetraethylene group, and arylene groups such as phenylene group and naphthylene group. The substituted or unsubstituted aryl group having 6 to 40 carbon atoms or the substituted or unsubstituted heteroaryl group having 5 to 40 carbon atoms in Ar 5 is the same substitution as M represented by the general formula (1). Groups.
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.
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測定及びＦＤＭＳ測定により行った。 In addition, the identification of the compound obtained in the Example was performed by 1 H-NMR measurement, 13 C-NMR measurement, and FDMS measurement.
１Ｈ−ＮＭＲ測定、１３Ｃ−ＮＭＲ測定及びＦＤＭＳ測定は、各々バリアン社製 Ｇｅｍｉｎｉ２００、日立製作所製 Ｍ−８０Ｂを使用して実施した。 1 H-NMR measurement, 13 C-NMR measurement, and FDMS measurement were performed using Gemini 200 manufactured by Varian and M-80B manufactured by Hitachi, Ltd., respectively.
合成例１ （化合物１ａの合成［下記（１２）式参照］）
３００ｍｌナス型フラスコに、ジイソプロピルアミン４６．０ｇ（４５５ｍｍｏｌ）、ジクロロメタン１５０ｍｌを加え、反応液を５℃以下に冷却した。２−ブロモベンゾイルクロリド ２５ｇ（１１４ｍｍｏｌ）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。反応液を常圧濃縮し、ジクロロメタン又は過剰のジイソプロピルアミンを留去した後、トルエン及び水を加えて抽出した。有機層は、飽和食塩水で洗浄後、無水硫酸マグネシウムにて乾燥し、濃縮して２−ブロモ−Ｎ，Ｎ’−ジイソプロピルベンズアミドを無色結晶として単離した。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 1a [Refer to Formula (12) below))
To a 300 ml eggplant type flask, 46.0 g (455 mmol) of diisopropylamine and 150 ml of dichloromethane were added, and the reaction solution was cooled to 5 ° C. or lower. 25 g (114 mmol) of 2-bromobenzoyl chloride was added dropwise so that the reaction temperature did not exceed 5 ° C., and the mixture was stirred overnight at room temperature. The reaction solution was concentrated at normal pressure, and dichloromethane or excess diisopropylamine was distilled off, followed by extraction with toluene and water. The organic layer was washed with saturated brine, dried over anhydrous magnesium sulfate, and concentrated to isolate 2-bromo-N, N′-diisopropylbenzamide as colorless crystals. The product was directly used in the next reaction without purification.
次に、２００ｍｌナス型フラスコに、得られた２−ブロモ−Ｎ，Ｎ’−ジイソプロピルベンズアミド ７．５ｇ（２６．３ｍｍｏｌ）、１−ナフチルボロン酸 ５．１ｇ（２９．１ｍｍｏｌ）、テトラキス（トリフェニルホスフィン）パラジウム１５０ｍｇ（０．１３ｍｍｏｌ）、２０重量％の炭酸ナトリウム水溶液３８．５ｇ及びテトラヒドロフラン６０ｍｌを加え、還流下一晩過熱攪拌した。室温まで冷却後、水を加え抽出した。得られた有機層は、飽和食塩水による洗浄、無水硫酸マグネシウムによる乾燥処理の後、濃縮し淡褐色の結晶が得られた。更に、シリカゲルクロマトグラフィー（溶媒：ヘキサン／トルエン）を用いて精製し、無色の結晶７．１ｇ（収率８２％）を単離した。１Ｈ−ＮＭＲ測定により目的物であることを確認した。 Next, in a 200 ml eggplant type flask, 7.5 g (26.3 mmol) of 2-bromo-N, N′-diisopropylbenzamide obtained, 5.1 g (29.1 mmol) of 1-naphthylboronic acid, tetrakis (triphenyl) Phosphine) palladium (150 mg, 0.13 mmol), 20 wt% aqueous sodium carbonate solution (38.5 g) and tetrahydrofuran (60 ml) were added, and the mixture was stirred overnight under reflux. After cooling to room temperature, water was added for extraction. The obtained organic layer was washed with saturated brine, dried with anhydrous magnesium sulfate, and then concentrated to obtain pale brown crystals. Further, purification was performed using silica gel chromatography (solvent: hexane / toluene) to isolate 7.1 g of colorless crystals (yield 82%). It was confirmed to be the target product by 1 H-NMR measurement.
次に、２００ｍｌナス型フラスコに、先に得られた２−（１−ナフチル）−Ｎ，Ｎ’−ジイソプロピルベンズアミド ４．０ｇ（１２ｍｍｏｌ）、テトラヒドロフラン３０ｍｌを加えた。溶解した後、反応液を−７８℃まで冷却し、リチウムジイソプロピルアミド（１．５Ｍ シクロヘキサン溶液）１６ｍｌを滴下した。 Next, 4.0 g (12 mmol) of 2- (1-naphthyl) -N, N′-diisopropylbenzamide obtained earlier and 30 ml of tetrahydrofuran were added to a 200 ml eggplant-shaped flask. After dissolution, the reaction solution was cooled to −78 ° C., and 16 ml of lithium diisopropylamide (1.5 M cyclohexane solution) was added dropwise.
滴下終了後、温度を保持しながら３時間攪拌し、更に室温下で一晩攪拌した。 After completion of dropping, the mixture was stirred for 3 hours while maintaining the temperature, and further stirred overnight at room temperature.
常法処理の後、シリカゲルクロマトグラフィー（溶媒：ヘキサン／トルエン）により無色の結晶１．５ｇ（収率５４％）を化合物１ａとして単離した。融点は１５８−１６０℃であり、文献値（Ｊ．Ｏｒｇ．Ｃｈｅｍ．，５６，５，１６８３（１９９１））と一致したことから、ベンゾ［ｃ］フルオレノンと同定した。 After ordinary treatment, 1.5 g (yield 54%) of colorless crystals was isolated as compound 1a by silica gel chromatography (solvent: hexane / toluene). The melting point was 158-160 ° C., which was consistent with literature values (J. Org. Chem., 56, 5, 1683 (1991)), and thus identified as benzo [c] fluorenone.
次に、ベンゾ［ｃ］フルオレノン３．０ｇ（１３ｍｍｏｌ）、９８％ヒドラジン１．６ｇ、水酸化ナトリウム２．３５ｇ、ジエチレングリコール４０ｍｌを２００ｍｌナス型フラスコに加え、１６０℃で１８時間加熱攪拌した。反応液を室温まで冷却後、クロロホルムにて抽出した。硫酸マグネシウムにて乾燥後、濃縮し濃褐色の結晶を得た。更に、シリカゲルクロマトグラフィー（溶媒：ヘキサン／トルエン）により精製し、無色の結晶を２．４ｇ単離した（収率８５％）。 Next, 3.0 g (13 mmol) of benzo [c] fluorenone, 1.6 g of 98% hydrazine, 2.35 g of sodium hydroxide, and 40 ml of diethylene glycol were added to a 200 ml eggplant type flask, and the mixture was heated and stirred at 160 ° C. for 18 hours. The reaction solution was cooled to room temperature and extracted with chloroform. The extract was dried over magnesium sulfate and concentrated to give dark brown crystals. Further, the product was purified by silica gel chromatography (solvent: hexane / toluene) to isolate 2.4 g of colorless crystals (yield 85%).
１Ｈ−ＮＭＲ測定及びＦＤＭＳ測定によりベンゾ［ｃ］フルオレンであることを確認した。 1 H-NMR measurement and FDMS measurement confirmed that it was benzo [c] fluorene.
得られたベンゾ［ｃ］フルオレン５ｇ（２３．１ｍｍｏｌ）をクロロホルム３０ｍｌに溶解し、少量のヨウ素を加えてから、臭素３．７ｇ（２３．１ｍｍｏｌ）を攪拌しながら室温下で滴下した。反応終了後、チオ硫酸ナトリウムにて過剰の臭素を中和してから、クロロホルムにて抽出した。飽和食塩水にて洗浄、硫酸マグネシウムによる乾燥の後、抽出液を濃縮し淡黄色の結晶を得た。トルエンにて再結晶し、化合物２ａを無色結晶として５．４ｇ単離した（収率７９％）。 5 g (23.1 mmol) of the obtained benzo [c] fluorene was dissolved in 30 ml of chloroform, a small amount of iodine was added, and 3.7 g (23.1 mmol) of bromine was added dropwise at room temperature with stirring. After completion of the reaction, excess bromine was neutralized with sodium thiosulfate and extracted with chloroform. After washing with saturated brine and drying over magnesium sulfate, the extract was concentrated to give pale yellow crystals. Recrystallization from toluene isolated 5.4 g of Compound 2a as colorless crystals (yield 79%).
２００ｍｌナス型フラスコに、２−ブロモベンズアルデヒド ６．４５ｇ（３４．９ｍｍｏｌ）、１−ナフチルボロン酸 ５．０ｇ（２９．１ｍｍｏｌ）、テトラキス（トリフェニルホスフィン）パラジウム ０．１５ｇ、テトラヒドロフラン６０ｍｌ、炭酸カリウム１０ｇ（７３ｍｍｏｌ）、水２０ｍｌを加え、一晩加熱還流した。飽和塩化アンモニウム水溶液及び飽和食塩水による洗浄、無水硫酸マグネシウムによる乾燥の後、抽出液を濃縮し黄色の結晶を得た。シリカゲルクロマトグラフィー（溶媒：ヘキサン／トルエン）により精製し、２−（１−ナフチル）ベンズアルデヒドを５．４ｇ得た（収率８１％）。
In a 200 ml eggplant-shaped flask, 6.45 g (34.9 mmol) of 2-bromobenzaldehyde, 5.0 g (29.1 mmol) of 1-naphthylboronic acid, 0.15 g of tetrakis (triphenylphosphine) palladium, 60 ml of tetrahydrofuran, 10 g of potassium carbonate (73 mmol) and 20 ml of water were added and heated to reflux overnight. After washing with a saturated aqueous ammonium chloride solution and saturated brine, and drying with anhydrous magnesium sulfate, the extract was concentrated to obtain yellow crystals. Purification by silica gel chromatography (solvent: hexane / toluene) gave 5.4 g of 2- (1-naphthyl) benzaldehyde (yield 81%).
同定は、１Ｈ−ＮＭＲ測定により行った。 Identification was performed by 1 H-NMR measurement.
１Ｈ−ＮＭＲ（ＣＤＣｌ３）；９．６３（ｓ，１Ｈ）、８．１２（ｄ，１Ｈ）、７．９４（ｄ，２Ｈ）、７．４０−７．７１（ｍ，８Ｈ）
次に、２００ｍｌナス型フラスコに、２−（１−ナフチル）ベンズアルデヒド ８．０ｇ（３４．４ｍｍｏｌ）とテトラヒドロフラン５０ｍｌを加えた後、反応液の温度を−３０℃以下に冷却した、その後、メチルマグネシウムクロリド（１．４ｍｏｌ／ｌのトルエン／テトラヒドロフラン溶液）３８ｍｌを滴下した。更に、−５〜０℃で１時間、室温で一晩攪拌し、１Ｎ塩酸水溶液６０ｍｌを滴下して反応を終了させた。テトラヒドロフランを加え、抽出して得られた有機層は、水、飽和食塩水により洗浄し、硫酸マグネシウムで乾燥した。溶媒を留去した後、ヘキサンで再結晶し、化合物３ａを７．６８ｇ（１００％純度として収率９０％、無色結晶、融点１１６〜１１８℃）得た。
1 H-NMR (CDCl 3 ); 9.63 (s, 1H), 8.12 (d, 1H), 7.94 (d, 2H), 7.40-7.71 (m, 8H)
Next, after adding 8.0 g (34.4 mmol) of 2- (1-naphthyl) benzaldehyde and 50 ml of tetrahydrofuran to a 200 ml eggplant type flask, the temperature of the reaction solution was cooled to −30 ° C. or less, and then methyl magnesium 38 ml of chloride (1.4 mol / l toluene / tetrahydrofuran solution) was added dropwise. Further, the mixture was stirred at −5 to 0 ° C. for 1 hour and at room temperature overnight, and 60 ml of 1N hydrochloric acid aqueous solution was added dropwise to complete the reaction. The organic layer obtained by adding tetrahydrofuran and extracting was washed with water and saturated brine, and dried over magnesium sulfate. After the solvent was distilled off, the residue was recrystallized with hexane to obtain 7.68 g of Compound 3a (100% purity, yield 90%, colorless crystals, melting point 116 to 118 ° C.).
なお、１Ｈ−ＮＭＲ測定により、化合物３ａは異性体の混合物であることが分かった。 In addition, < 1 > H-NMR measurement showed that Compound 3a was a mixture of isomers.
次に、２００ｍｌナス型フラスコに、上記で得られた化合物３ａ ６．０ｇ（２４．２ｍｍｏｌ）、クロロホルム６０ｍｌを加えた後、三フッ化ホウ素エーテル錯体７．４ｇ（５２．３ｍｍｏｌ）を５０℃で滴下した。更に同温度で５時間反応させた。水８０ｍｌを加え、有機層を抽出した。有機層は水１００ｍｌで３回洗浄し、更に飽和食塩水で洗浄した。硫酸マグネシウムで乾燥後、溶媒を留去し、クルードの７−メチル−ベンゾ［ｃ］フルオレンを得た。更に、シリカゲルクロマトグラフィー（溶媒：ヘキサン／トルエン）で精製し、７−メチル−ベンゾ［ｃ］フルオレンを無色結晶として３．３４ｇ得た（収率６０％、融点８１〜８３℃）。 Next, after adding 6.0 g (24.2 mmol) of the compound 3a obtained above and 60 ml of chloroform to a 200 ml eggplant type flask, 7.4 g (52.3 mmol) of boron trifluoride ether complex was added at 50 ° C. It was dripped. Furthermore, it was made to react at the same temperature for 5 hours. 80 ml of water was added and the organic layer was extracted. The organic layer was washed 3 times with 100 ml of water and further washed with saturated brine. After drying with magnesium sulfate, the solvent was distilled off to obtain crude 7-methyl-benzo [c] fluorene. Further, the residue was purified by silica gel chromatography (solvent: hexane / toluene) to obtain 3.34 g of 7-methyl-benzo [c] fluorene as colorless crystals (yield 60%, melting point 81-83 ° C.).
同定は、１Ｈ−ＮＭＲ測定により行った。 Identification was performed by 1 H-NMR measurement.
１Ｈ−ＮＭＲ（ＣＤＣｌ３）；８．７７（ｄ，１Ｈ）、８．３７（ｄ，１Ｈ）、７．９７（ｄ，１Ｈ）、７．８５（ｄ，１Ｈ）、７．２６−７．７０（ｍ，６Ｈ）、４．０２（１Ｈ，ｑ）、１．５９（ｄ，３Ｈ）
２００ｍｌナス型フラスコに、７−メチル−ベンゾ［ｃ］フルオレン ３．３ｇ（１４．５ｍｍｏｌ）、ジメチルスルホキシド７０ｍｌ、４５％水酸化ナトリウム水溶液５．５ｇ、ベンジルトリエチルアンモニウムクロリド３．２９ｇ（１４．４ｍｍｏｌ）を加えた。５０℃でヨウ化メチル４．２０ｇ（２９．６ｍｍｏｌ）を滴下し、その後、同温度で一晩加熱攪拌した。室温まで冷却後、トルエン１００ｍｌ、水５０ｍｌを加えて抽出した。水、飽和食塩水により洗浄後、硫酸マグネシウムにより乾燥した。得られた有機層を濃縮することで、淡褐色の結晶を得た。更に、シリカゲルクロマトグラフィー（溶媒：ヘキサン／トルエン）により精製することで、目的とする化合物４ａを収率７７％で得た。
1 H-NMR (CDCl 3 ); 8.77 (d, 1H), 8.37 (d, 1H), 7.97 (d, 1H), 7.85 (d, 1H), 7.26-7 .70 (m, 6H), 4.02 (1H, q), 1.59 (d, 3H)
In a 200 ml eggplant-shaped flask, 3.3 g (14.5 mmol) of 7-methyl-benzo [c] fluorene, 70 ml of dimethyl sulfoxide, 5.5 g of 45% aqueous sodium hydroxide, 3.29 g (14.4 mmol) of benzyltriethylammonium chloride Was added. Methyl iodide (4.20 g, 29.6 mmol) was added dropwise at 50 ° C., and then the mixture was heated and stirred overnight at the same temperature. After cooling to room temperature, 100 ml of toluene and 50 ml of water were added for extraction. The extract was washed with water and saturated brine, and dried over magnesium sulfate. By concentrating the obtained organic layer, pale brown crystals were obtained. Further, purification by silica gel chromatography (solvent: hexane / toluene) gave the target compound 4a in a yield of 77%.
同定は、１Ｈ−ＮＭＲ測定、ＦＤＭＳ測定により行った。 Identification was performed by 1 H-NMR measurement and FDMS 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）
ＦＤＭＳ；２４４
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)
FDMS; 244
１００ｍｌナス型フラスコに、合成例２で得られた化合物４ａ ２．２０ｇ（９．０２ｍｍｏｌ）とジメチルホルムアミド１５ｍｌを加え、室温下、Ｎ−ブロモスクシンイミド（ＮＢＳ）１．６５ｇ（９．２８ｍｍｏｌ）のジメチルホルムアミド溶液を滴下し、一晩攪拌した。次に、反応液にトルエン５０ｍｌ及び水３０ｍｌを加え、有機層を抽出した。常法処理の後、反応液を濃縮し、淡褐色の結晶を得た。メタノールで再結晶し、２．５５ｇの無色の結晶を得た（収率８８％、融点１０５〜１０７℃）。
To a 100 ml eggplant-shaped flask were added 2.20 g (9.02 mmol) of compound 4a obtained in Synthesis Example 2 and 15 ml of dimethylformamide, and 1.65 g (9.28 mmol) of dimethyl dimethyl succinimide (NBS) at room temperature. Formamide solution was added dropwise and stirred overnight. Next, 50 ml of toluene and 30 ml of water were added to the reaction solution, and the organic layer was extracted. After the usual treatment, the reaction solution was concentrated to obtain light brown crystals. Recrystallization from methanol gave 2.55 g of colorless crystals (yield 88%, melting point 105-107 ° C.).
同定は、１Ｈ−ＮＭＲ測定により行った。 Identification was performed by 1 H-NMR measurement.
１Ｈ−ＮＭＲ（ＣＤＣｌ３）；８．７６（ｄ，１Ｈ）、８．３４−８．４１（ｄｄ，２Ｈ）、７．９３（ｓ，１Ｈ）、７．３８−７．７０（ｍ，５Ｈ）、１．５４（ｓ，６Ｈ） 1 H-NMR (CDCl 3 ); 8.76 (d, 1H), 8.34-8.41 (dd, 2H), 7.93 (s, 1H), 7.38-7.70 (m, 5H), 1.54 (s, 6H)
３００ｍｌナス型フラスコに、合成例１で得られた化合物２ａ （５−ブロモ−７Ｈ−ベンゾ［ｃ］フルオレン） １０ｇ（３３．９ｍｍｏｌ）、ジメチルスルホキシド８０ｍｌ、ベンジルトリエチルアンモニウムクロリド１．１５ｇ（６．２ｍｍｏｌ）、５０％水酸化ナトリウム１５ｇ（１８７ｍｍｏｌ）を加えた。室温下で、１，４−ジブロモブタン ７．３９ｇ（３４．２ｍｍｏｌ）とジメチルスルホキシド２０ｍｌの混合液を滴下し、同温度で２時間、更に８０℃で５時間攪拌した。
In a 300 ml eggplant type flask, 10 g (33.9 mmol) of compound 2a (5-bromo-7H-benzo [c] fluorene) obtained in Synthesis Example 1, 80 ml of dimethyl sulfoxide, 1.15 g (6.2 mmol) of benzyltriethylammonium chloride. ), 15 g (187 mmol) of 50% sodium hydroxide was added. A mixed solution of 7.39 g (34.2 mmol) of 1,4-dibromobutane and 20 ml of dimethyl sulfoxide was added dropwise at room temperature, followed by stirring at the same temperature for 2 hours and further at 80 ° C. for 5 hours.
水７０ｍｌを加えた後、トルエン１００ｍｌを加え抽出した。水、飽和食塩水による洗浄の後、有機層は無水硫酸マグネシウムにより乾燥した。トルエンを留去させた後、淡黄色の粘調油状物を１０．１ｇ得た（収率８５％）。 After adding 70 ml of water, 100 ml of toluene was added for extraction. After washing with water and saturated brine, the organic layer was dried over anhydrous magnesium sulfate. After distilling off the toluene, 10.1 g of a pale yellow viscous oil was obtained (yield 85%).
同定は、１Ｈ−ＮＭＲ測定、１３Ｃ−ＮＭＲ測定により行った。 Identification was performed by 1 H-NMR measurement and 13 C-NMR measurement.
１Ｈ−ＮＭＲ（ＣＤＣｌ３）；２．１７(ｂｒ−ｓ，８Ｈ)、７．３２−７．６７（ｍ，５Ｈ）、７．９１（ｓ，１Ｈ）、８．２９（ｄ，１Ｈ）、８．３７（ｄ，１Ｈ）、８．７４（ｄ，１Ｈ）
１３Ｃ−ＮＭＲ（ＣＤＣｌ３）；２７．６， ３９．２， ５７．５， １２２．７， １２２．８， １２４．１， １２５．７， １２６．２， １２６．９， １２７．０， １２７．３， １３０．３， １３１．２， １３３．５， １３９．６， １５３．２， １５５．６
1 H-NMR (CDCl 3 ); 2.17 (br-s, 8H), 7.32-7.67 (m, 5H), 7.91 (s, 1H), 8.29 (d, 1H) 8.37 (d, 1H), 8.74 (d, 1H)
13 C-NMR (CDCl 3 ); 27.6, 39.2, 57.5, 122.7, 122.8, 124.1, 125.7, 126.2, 126.9, 127.0, 127 .3, 130.3, 131.2, 133.5, 139.6, 153.2, 155.6
５００ｍｌナス型フラスコに、２−ブロモ安息香酸エチル ９．１６ｇ（４０．０ｍｍｏｌ）、６−メトキシナフタレンボロン酸 ８．８９ｇ（４４．０ｍｍｏｌ）、テトラヒドロフラン３００ｍｌ及び２０％炭酸ナトリウム水溶液９４ｇを加えた。窒素気流下、テトラキス（トリフェニルホスフィン）パラジウム０．４６ｇを添加して一晩加熱還流した。飽和塩化アンモニウム水溶液及び飽和食塩水による洗浄、無水硫酸マグネシウムによる乾燥の後、抽出液を濃縮し薄褐色の油状物を得た。シリカゲルクロマトグラフィー（溶媒：ヘキサン／酢酸エチル）により精製し、化合物１ｂ（無色油状物）を１０．５２ｇ得た（収率８６％）。
To a 500 ml eggplant-shaped flask, 9.16 g (40.0 mmol) of ethyl 2-bromobenzoate, 8.89 g (44.0 mmol) of 6-methoxynaphthaleneboronic acid, 300 ml of tetrahydrofuran and 94 g of 20% aqueous sodium carbonate solution were added. Under a nitrogen stream, 0.46 g of tetrakis (triphenylphosphine) palladium was added and heated to reflux overnight. After washing with saturated aqueous ammonium chloride and saturated brine, and drying over anhydrous magnesium sulfate, the extract was concentrated to give a light brown oil. Purification by silica gel chromatography (solvent: hexane / ethyl acetate) gave 10.52 g of Compound 1b (colorless oil) (yield 86%).
同定は、１Ｈ−ＮＭＲ測定、１３Ｃ−ＮＭＲ測定により行った。 Identification was performed by 1 H-NMR measurement and 13 C-NMR measurement.
１Ｈ−ＮＭＲ（ＣＤＣｌ３）；０．８９（ｔ，３Ｈ，Ｊ＝７．２Ｈｚ）、３．９３（ｓ，３Ｈ）、４．０６（ｑ，２Ｈ，Ｊ＝７．２Ｈｚ）、７．１１−７．２０（ｍ，２Ｈ）、７．３６−７．５９（ｍ，４Ｈ）、７．６９−７．７８（ｍ，３Ｈ）、７．８５（ｄ，１Ｈ，Ｊ＝７．４Ｈｚ）
１３Ｃ−ＮＭＲ（ＣＤＣｌ３）；１３．８， ５５．４， ６１．０， １０５．６， １１９．０， １２６．２， １２６．７， １２７．０， １２７．５， １２８．７， １２９．５， １２９．７， １３０．９， １３１．１， １３１．４， １３３．６， １３６．７， １４２．３， １５７．７， １６８．９
1 H-NMR (CDCl 3 ); 0.89 (t, 3H, J = 7.2 Hz), 3.93 (s, 3H), 4.06 (q, 2H, J = 7.2 Hz), 7. 11-7.20 (m, 2H), 7.36-7.59 (m, 4H), 7.69-7.78 (m, 3H), 7.85 (d, 1H, J = 7.4 Hz) )
13 C-NMR (CDCl 3 ); 13.8, 55.4, 61.0, 105.6, 119.0, 126.2, 126.7, 127.0, 127.5, 128.7, 129 .5, 129.7, 130.9, 131.1, 131.4, 133.6, 136.7, 142.3, 157.7, 168.9
次に、１００ｍｌナス型フラスコに、上記で得られた化合物２ｂ ３．３６ｇ（１１．５ｍｍｏｌ）、クロロホルム６０ｍｌを加えた後、三フッ化ホウ素エーテル錯体２．１２ｇ（１５．０ｍｍｏｌ）を５０℃で滴下した。更に同温度で２時間反応させた。室温に冷却後水３０ｍｌを加えた。分層後、有機層は水１５０ｍｌで洗浄し、溶媒を留去した。残渣はシリカゲルクロマトグラフィー（溶媒：ヘキサン／トルエン）で精製し、化合物３ｂを無色固体として２．１７ｇ（収率６８．８％）得た。 Next, after adding 3.36 g (11.5 mmol) of the compound 2b obtained above and 60 ml of chloroform to a 100 ml eggplant-shaped flask, 2.12 g (15.0 mmol) of boron trifluoride ether complex was added at 50 ° C. It was dripped. The reaction was further continued at the same temperature for 2 hours. After cooling to room temperature, 30 ml of water was added. After separation, the organic layer was washed with 150 ml of water and the solvent was distilled off. The residue was purified by silica gel chromatography (solvent: hexane / toluene) to obtain 2.17 g (yield 68.8%) of compound 3b as a colorless solid.
なお、化合物２ｂ、３ｂの同定は、１Ｈ−ＮＭＲ測定、１３Ｃ−ＮＭＲ測定により行った。 The compounds 2b and 3b were identified by 1 H-NMR measurement and 13 C-NMR measurement.
＜化合物２ｂ＞
１Ｈ−ＮＭＲ（ＣＤＣｌ３）；１．４７（ｓ，６Ｈ）、１．９０（ｂｒ−ｓ，１Ｈ）、３．９２（ｓ，３Ｈ）、７．０２−７．４８（ｍ，６Ｈ）、７．６０−７．７９（ｍ，４Ｈ）
１３Ｃ−ＮＭＲ（ＣＤＣｌ３）；３２．７， ５５．４， ７４．１， １０５．７， １１９．３， １２５．８， １２６．０， １２６．１， １２７．４， １２７．７， １２８．２， １２８．７， １２９．４， １３２．５， １３３．４， １３９．０， １３９．９， １４６．４， １５７．８
＜化合物３ｂ＞
１Ｈ−ＮＭＲ（ＣＤＣｌ３）；１．７０（ｓ，６Ｈ）、３．８９（ｓ，３Ｈ）、７．１９−７．２８（ｍ，２Ｈ）、７．２８−７．３８（ｍ，２Ｈ）、７．４２−７．５１（ｍ，１Ｈ）、７．６８−７．７８（ｄ，２Ｈ）、７．８４（ｄ，１Ｈ，Ｊ＝８．６Ｈｚ）、８．１２（ｄ，１Ｈ，Ｊ＝９．８Ｈｚ）
１３Ｃ−ＮＭＲ（ＣＤＣｌ３）；２６．６， ４８．６， ５５．４， １０７．９， １１８．７， １１９．４， １２２．１， １２５．３， １２５．６， １２６．６， １２６．９， １２７．３， １３４．８， １３５．３， １３９．５， １４７．６， １５５．０， １５６．７
<Compound 2b>
1 H-NMR (CDCl 3 ); 1.47 (s, 6H), 1.90 (br-s, 1H), 3.92 (s, 3H), 7.02-7.48 (m, 6H) 7.60-7.79 (m, 4H)
13 C-NMR (CDCl 3 ); 32.7, 55.4, 74.1, 105.7, 119.3, 125.8, 126.0, 126.1, 127.4, 127.7, 128 .2, 128.7, 129.4, 132.5, 133.4, 139.0, 139.9, 146.4, 157.8
<Compound 3b>
1 H-NMR (CDCl 3 ); 1.70 (s, 6H), 3.89 (s, 3H), 7.19-7.28 (m, 2H), 7.28-7.38 (m, 2H), 7.42-7.51 (m, 1H), 7.68-7.78 (d, 2H), 7.84 (d, 1H, J = 8.6 Hz), 8.12 (d, 1H, J = 9.8Hz)
13 C-NMR (CDCl 3 ); 26.6, 48.6, 55.4, 107.9, 118.7, 119.4, 122.1, 125.3, 125.6, 126.6, 126 .9, 127.3, 134.8, 135.3, 139.5, 147.6, 155.0, 156.7
４ｂは、更に、常法によりピリジン及びトリフルオロメタンスルホン酸無水物と反応させることにより、化合物５ｂを３．０ｇ得た（収率９９％）。 4b was further reacted with pyridine and trifluoromethanesulfonic anhydride by a conventional method to obtain 3.0 g of Compound 5b (yield 99%).
生成物の同定は、１Ｈ−ＮＭＲ測定、１３Ｃ−ＮＭＲ測定、ＦＤＭＳ測定により行った。 The product was identified by 1 H-NMR measurement, 13 C-NMR measurement, and FDMS measurement.
＜化合物４ｂ＞
１Ｈ−ＮＭＲ（ＣＤＣｌ３）；１．７０（ｓ，６Ｈ）、５．５０（ｂｒ−ｓ，１Ｈ）、７．１２−７．４３（ｍ，４Ｈ）、７．４３−７．６０（ｍ，１Ｈ）、７．６０−７．９０（ｍ，３Ｈ）、８．１２（ｄ，１Ｈ，Ｊ＝８．８Ｈｚ）
１３Ｃ−ＮＭＲ（ＣＤＣｌ３）；２６．６， ４８．５， １１１．５， １１７．７， １１９．３， １１９．５， １２２．１， １２５．２， １２５．９， １２６．５， １２８．８， １２６．９， １３４．７， １３５．３， １３９．４， １４７．６， １５２．５， １５４．９
＜化合物５ｂ＞
１Ｈ−ＮＭＲ（ＣＤＣｌ３）；１．７４（ｓ，６Ｈ）、７．３６−７．５９（ｍ，４Ｈ）、７．７８−７．９６（ｍ，３Ｈ）、８．０２（ｄ，１Ｈ，Ｊ＝８．６Ｈｚ）、８．１２（ｄ，１Ｈ，Ｊ＝９．２Ｈｚ）
ＦＤＭＳ；３９２
<Compound 4b>
1 H-NMR (CDCl 3 ); 1.70 (s, 6H), 5.50 (br-s, 1H), 7.12-7.43 (m, 4H), 7.43-7.60 ( m, 1H), 7.60-7.90 (m, 3H), 8.12 (d, 1H, J = 8.8 Hz)
13 C-NMR (CDCl 3 ); 26.6, 48.5, 111.5, 117.7, 119.3, 119.5, 122.1, 125.2, 125.9, 126.5, 128 .8, 126.9, 134.7, 135.3, 139.4, 147.6, 152.5, 154.9
<Compound 5b>
1 H-NMR (CDCl 3 ); 1.74 (s, 6H), 7.36-7.59 (m, 4H), 7.78-7.96 (m, 3H), 8.02 (d, 1H, J = 8.6 Hz), 8.12 (d, 1H, J = 9.2 Hz)
FDMS; 392
１００ｍｌナス型フラスコに、１−（２−（エトキシカルボニル）フェニル）−ナフタレン １．００ｇ（３．６２ｍｍｏｌ）、テトラヒドロフラン１０ｍｌを窒素雰囲気下加えた。反応液を５０℃まで昇温し、フェニルマグネシウムブロミドのテトラヒドロフラン溶液（２ｍｏｌ／ｌ）７．２ｍｌを３０分かけて滴下し、同温度で１８時間攪拌した。室温まで冷却後、氷水で冷却しながら純水２０ｍｌを滴下した後、トルエン３０ｍｌで有機層を抽出した。更に、有機層は、純水、飽和食塩水で洗浄し、無水硫酸マグネシウムで乾燥した。得られた有機層を濃縮することにより、化合物７ａを黄色油状物として１．４６ｇ単離した。
To a 100 ml eggplant-shaped flask, 1.00 g (3.62 mmol) of 1- (2- (ethoxycarbonyl) phenyl) -naphthalene and 10 ml of tetrahydrofuran were added under a nitrogen atmosphere. The reaction solution was heated to 50 ° C., 7.2 ml of a phenylmagnesium bromide tetrahydrofuran solution (2 mol / l) was added dropwise over 30 minutes, and the mixture was stirred at the same temperature for 18 hours. After cooling to room temperature, 20 ml of pure water was added dropwise while cooling with ice water, and then the organic layer was extracted with 30 ml of toluene. Furthermore, the organic layer was washed with pure water and saturated brine, and dried over anhydrous magnesium sulfate. By concentrating the obtained organic layer, 1.46 g of compound 7a was isolated as a yellow oil.
引続き、１００ｍｌナス型フラスコに、７ａを１．４５ｇ、酢酸２５ｍｌを加えた後、濃硫酸を数滴添加し、室温下１８時間攪拌した。その後、反応液を分液ロートに移し、トルエン３０ｍｌ、純水２０ｍｌを加え、有機層を抽出した。更に、有機層は、純水で中性になるまで洗浄した。飽和食塩水で洗浄した後、無水硫酸マグネシウムで乾燥した。濃縮後、得られた残渣は、シリカゲルクロマトグラフィー（溶媒：ヘキサン／トルエン）により精製することで、化合物８ａを淡黄色粉末として０．８１ｇ単離した（収率６１％）。 Subsequently, 1.45 g of 7a and 25 ml of acetic acid were added to a 100 ml eggplant-shaped flask, and then several drops of concentrated sulfuric acid were added, followed by stirring at room temperature for 18 hours. Thereafter, the reaction solution was transferred to a separatory funnel, 30 ml of toluene and 20 ml of pure water were added, and the organic layer was extracted. Further, the organic layer was washed with pure water until neutral. The extract was washed with saturated brine and dried over anhydrous magnesium sulfate. After concentration, the obtained residue was purified by silica gel chromatography (solvent: hexane / toluene) to isolate 0.81 g of compound 8a as a pale yellow powder (yield 61%).
同定は、１Ｈ−ＮＭＲ測定、ＦＤＭＳ測定により行った。 Identification was performed by 1 H-NMR measurement and FDMS measurement.
１Ｈ−ＮＭＲ（ＣＤＣｌ３）；７．２１−７．３３（ｍ，１１Ｈ）、７．４６−７．８９（ｍ，７Ｈ）、８．３６−８．４０（ｄ，１Ｈ）、８．７７−８．８１（ｄ，１Ｈ）
ＦＤＭＳ；３６８
次に、化合物８ａを合成例３に従い臭素化することにより、化合物９ａを単離した。
1 H-NMR (CDCl 3 ); 7.21-7.33 (m, 11H), 7.46-7.89 (m, 7H), 8.36-8.40 (d, 1H), 8. 77-8.81 (d, 1H)
FDMS; 368
Next, compound 9a was isolated by brominating compound 8a according to Synthesis Example 3.
同定は、ＦＤＭＳ測定により行った。 Identification was performed by FDMS measurement.
ＦＤＭＳ；４４６ FDMS; 446
３００ｍｌナス型フラスコに、２−ブロモ−６−（２−（エトキシカルボニル）フェニル）ナフタレン （６ｂ）１２ｇ（３３．８ｍｍｏｌ）、脱水テトラヒドロフラン１２０ｍｌを仕込み、室温下、フェニルマグネシウムブロミドのテトラヒドロフラン溶液（２ｍｏｌ／ｌ）を６０ｍｌ滴下した。滴下終了後、更に５０℃で一晩加熱攪拌した。反応液を室温まで冷却し、１０％塩化アンモニウム水溶液１００ｇを加えて反応を終了した。有機層は純水５０ｇで３回洗浄し、更に硫酸マグネシウムで乾燥した。有機層を濾過・濃縮することで、化合物７ｂをオレンジ色油状物として１７．３ｇ得た。７ｂはそのまま次の工程に用いた。
A 300 ml eggplant-shaped flask was charged with 12 g (33.8 mmol) of 2-bromo-6- (2- (ethoxycarbonyl) phenyl) naphthalene (6b) and 120 ml of dehydrated tetrahydrofuran, and a tetrahydrofuran solution of phenylmagnesium bromide (2 mol / mol) at room temperature. 60 ml of 1) was added dropwise. After completion of the dropwise addition, the mixture was further heated and stirred overnight at 50 ° C. The reaction solution was cooled to room temperature, and 100 g of 10% aqueous ammonium chloride solution was added to complete the reaction. The organic layer was washed 3 times with 50 g of pure water and further dried over magnesium sulfate. The organic layer was filtered and concentrated to obtain 17.3 g of Compound 7b as an orange oil. 7b was directly used in the next step.
１００ｍｌナス型フラスコに、上記で得られた７ｂ ３．４６ｇ（６．７６ｍｍｏｌ）と酢酸１４ｍｌを仕込んだ後、室温下一晩攪拌した。その後、反応液を分液ロートに移し、トルエン５０ｍｌ、純水５０ｍｌを加え、有機層を抽出した。更に、有機層は純水で中性になるまで洗浄した。飽和食塩水で洗浄した後、無水硫酸マグネシウムで乾燥した。濃縮後、得られた残渣は、シリカゲルクロマトグラフィー（溶媒：ヘキサン／トルエン）により精製することで、化合物８ｂを白色粉末として１．３ｇ単離した（収率４２％）。 A 100 ml eggplant-shaped flask was charged with 3.46 g (6.76 mmol) of 7b obtained above and 14 ml of acetic acid, and stirred overnight at room temperature. Thereafter, the reaction solution was transferred to a separating funnel, and 50 ml of toluene and 50 ml of pure water were added to extract the organic layer. Further, the organic layer was washed with pure water until neutral. The extract was washed with saturated brine and dried over anhydrous magnesium sulfate. After concentration, the obtained residue was purified by silica gel chromatography (solvent: hexane / toluene) to isolate 1.3 g of compound 8b as a white powder (yield 42%).
同定は、１Ｈ−ＮＭＲ測定、ＦＤＭＳ測定により行った。 Identification was performed by 1 H-NMR measurement and FDMS measurement.
１Ｈ−ＮＭＲ（ＣＤＣｌ３）；８．０２（ｄ，２Ｈ）、７．８１−７．８８（ｍ，２Ｈ）、７．６０（ｄ，１Ｈ）、７．１８−７．４６（ｍ，１４Ｈ）
ＦＤＭＳ；４４６
1 H-NMR (CDCl 3 ); 8.02 (d, 2H), 7.81-7.88 (m, 2H), 7.60 (d, 1H), 7.18-7.46 (m, 14H)
FDMS; 446
１００ｍｌナス型フラスコを用い、合成例３で得られた化合物５ａ ２ｇ（６．２ｍｍｏｌ）、アニリン０．５８ｇ（６．２ｍｍｏｌ）、ナトリウム−ｔｅｒｔ−ブトキシド ０．８３ｇ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、酢酸パラジム３ｍｇ及びトリ−ｔｅｒｔ−ブチルホスフィン ８ｍｇを添加し、１２５℃に加熱した。所定温度で２０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、抽出を行い、有機相を濃縮した。得られた濃縮物は、精製せずにそのまま次工程に使用した。
Using a 100 ml eggplant type flask, 2 g (6.2 mmol) of the compound 5a obtained in Synthesis Example 3, 0.58 g (6.2 mmol) of aniline, 0.83 g of sodium tert-butoxide were suspended in 40 ml of xylene, and nitrogen was added. The inside of the system was replaced with. Furthermore, under a nitrogen atmosphere, 3 mg of paradymium acetate and 8 mg of tri-tert-butylphosphine were added and heated to 125 ° C. After aging at a predetermined temperature for 20 hours, the reaction solution was cooled to room temperature. Extraction was performed after adding 20 ml of water, and the organic phase was concentrated. The obtained concentrate was directly used in the next step without purification.
次に、２００ｍｌナス型フラスコを用い、４，４’−ジヨードビフェニル ３．０ｇ（７．４ｍｍｏｌ）、先に得られた５−フェニルアミノ−７，７−ジメチル−７Ｈ−ベンゾ［ｃ］フルオレン ５．１ｇ（１５．２ｍｍｏｌ）、ナトリウム−ｔｅｒｔ−ブトキシド １．７ｇ（１７．７ｍｍｏｌ）をキシレン５０ｍｌに懸濁させ、窒素で系内を置換した。更に、窒素雰囲気下、酢酸パラジム３ｍｇ及びトリ−ｔｅｒｔ−ブチルホスフィン ８ｍｇを添加し、１２５℃に加熱した。所定温度で２０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、抽出を行い、有機相を濃縮した。トルエンにて再結晶し、化合物（Ａ１）を４．９８ｇ得た（収率８２％）。 Next, using a 200 ml eggplant type flask, 3.0 g (7.4 mmol) of 4,4′-diiodobiphenyl and 5-phenylamino-7,7-dimethyl-7H-benzo [c] fluorene obtained earlier 5.1 g (15.2 mmol) and sodium tert-butoxide 1.7 g (17.7 mmol) were suspended in 50 ml of xylene, and the system was replaced with nitrogen. Furthermore, under a nitrogen atmosphere, 3 mg of paradymium acetate and 8 mg of tri-tert-butylphosphine were added and heated to 125 ° C. After aging at a predetermined temperature for 20 hours, the reaction solution was cooled to room temperature. Extraction was performed after adding 20 ml of water, and the organic phase was concentrated. Recrystallization from toluene gave 4.98 g of compound (A1) (yield 82%).
化合物（Ａ１）のガラス転移温度は１６２℃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４０℃以上高かった。 Compound (A1) has a glass transition temperature of 162 ° 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) About 40 ° 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（Ｂ３）の合成）
化合物５ａの代わりに、合成例４で合成した化合物６ａを用いて、実施例１と同様な操作を行い、化合物（Ｂ３）を５．０ｇ単離した（収率７８％）。
Example 2 (Synthesis of Compound (B3))
Using Compound 6a synthesized in Synthesis Example 4 instead of Compound 5a, the same operation as in Example 1 was performed to isolate 5.0 g of Compound (B3) (yield 78%).
実施例３ （化合物（Ｆ１）の合成）
３００ｍｌナス型フラスコに、アニリン８９４ｍｇ（９．６ｍｍｏｌ）、ナトリウム−ｔｅｒｔ−ブトキシド ９２３ｍｇ（９．６ｍｍｏｌ）、トリス（ジベンジリデンアセトン）ジパラジウム４４ｍｇ（０．０４８ｍｍｏｌ）、ビス（ジフェニルホスフィノ）フェロセン１６０ｍｇ（０．２８８ｍｍｏｌ）、トルエン１３０ｍｌを窒素雰囲気下加えた。反応液を８０℃に加熱した後、合成例５で合成した化合物５ｂ ２．５１ｇ（６．４ｍｍｏｌ）のトルエン（３０ｍｌ）溶液を３０分かけて滴下し、同温で一晩攪拌した。室温に冷却後、水２００ｍｌを加え反応を終了させた。分層後の有機層は、更に水６００ｍｌで洗浄し、無水硫酸マグネシウム処理後、溶媒を留去した。残渣をシリカゲルクロマトグラフィー（溶媒：ヘキサン／トルエン）により精製し、目的とする二級アミンを微紫色固体として１．７６ｇ得た（収率８１％）。
Example 3 (Synthesis of Compound (F1))
In a 300 ml eggplant-shaped flask, 894 mg (9.6 mmol) of aniline, 923 mg (9.6 mmol) of sodium-tert-butoxide, 44 mg (0.048 mmol) of tris (dibenzylideneacetone) dipalladium, 160 mg of bis (diphenylphosphino) ferrocene 0.288 mmol) and 130 ml of toluene were added under a nitrogen atmosphere. After heating the reaction solution to 80 ° C., a toluene (30 ml) solution of 2.51 g (6.4 mmol) of compound 5b synthesized in Synthesis Example 5 was added dropwise over 30 minutes, and the mixture was stirred overnight at the same temperature. After cooling to room temperature, 200 ml of water was added to terminate the reaction. The separated organic layer was further washed with 600 ml of water, treated with anhydrous magnesium sulfate, and then the solvent was distilled off. The residue was purified by silica gel chromatography (solvent: hexane / toluene) to obtain 1.76 g of the desired secondary amine as a slightly purple solid (yield 81%).
化合物の同定は、１Ｈ−ＮＭＲ測定、ＦＤＭＳ測定により行った。 The compound was identified by 1 H-NMR measurement and FDMS measurement.
１Ｈ−ＮＭＲ（ＣＤＣｌ３）；１．７４（ｓ，６Ｈ）、５．８８（ｂｒ−ｓ，１Ｈ）、６．９４−７．０４（ｍ，１Ｈ）、７．１２−７．４０（ｍ，７Ｈ）、７．４２−７．５８（ｍ，２Ｈ）、７．６２−７．８６（ｍ，３Ｈ）、８．１２（ｄ，１Ｈ，Ｊ＝９．２Ｈｚ）
ＦＤＭＳ；３３５
次に、１００ｍｌナス型フラスコに、上記二級アミン１．７６ｇ（５．２５ｍｍｏｌ）、４，４’−ジヨードビフェニル １．０２ｇ（２．５ｍｍｏｌ）、ナトリウム−ｔｅｒｔ−ブトキシド ５０５ｍｇ（５．２５ｍｍｏｌ）、酢酸パラジウム１１．８ｍｇ（０．０５３ｍｍｏｌ）、オルトキシレン６０ｍｌを窒素雰囲気下加えた。この反応液に、トリ（ｔｅｒｔ−ブチル）ホスフィン（０．２１ｍｍｏｌ）トルエン溶液０．２１ｍｌを滴下後、反応液を１２０℃に加熱した。２時間後、室温まで冷却し、水２００ｍｌを加え反応を終了させた。分層後の有機層は、更に水６００ｍｌで洗浄し、無水硫酸マグネシウム処理後、溶媒を留去した。残渣をシリカゲルクロマトグラフィー（溶媒：ヘキサン／トルエン）により精製し、化合物（Ｆ１）を微黄色固体として１．８９ｇ得た（収率９２％、融点＝２９２℃）。
1 H-NMR (CDCl 3 ); 1.74 (s, 6H), 5.88 (br-s, 1H), 6.94-7.04 (m, 1H), 7.12-7.40 ( m, 7H), 7.42-7.58 (m, 2H), 7.62-7.86 (m, 3H), 8.12 (d, 1H, J = 9.2 Hz)
FDMS; 335
Next, in a 100 ml eggplant-shaped flask, 1.76 g (5.25 mmol) of the secondary amine, 1.02 g (2.5 mmol) of 4,4′-diiodobiphenyl, and 505 mg (5.25 mmol) of sodium tert-butoxide. Then, 11.8 mg (0.053 mmol) of palladium acetate and 60 ml of orthoxylene were added under a nitrogen atmosphere. To this reaction solution, 0.21 ml of a tri (tert-butyl) phosphine (0.21 mmol) toluene solution was added dropwise, and then the reaction solution was heated to 120 ° C. After 2 hours, the mixture was cooled to room temperature, and 200 ml of water was added to complete the reaction. The separated organic layer was further washed with 600 ml of water, treated with anhydrous magnesium sulfate, and then the solvent was distilled off. The residue was purified by silica gel chromatography (solvent: hexane / toluene) to obtain 1.89 g of compound (F1) as a slightly yellow solid (yield 92%, melting point = 292 ° C.).
化合物の同定は、１Ｈ−ＮＭＲ測定、ＦＤＭＳ測定により行った。 The compound was identified by 1 H-NMR measurement and FDMS measurement.
１Ｈ−ＮＭＲ（ＣＤＣｌ３）；１．７２（ｓ，１２Ｈ）、７．００−７．１２（ｂｒ−ｔ，２Ｈ）、７．１２−７．６８（ｍ，２８Ｈ）、７．７０−７．８６（ｍ，４Ｈ）、８．１０（ｄ，２Ｈ，Ｊ＝９．２Ｈｚ）
ＦＤＭＳ；８２０
なお、化合物（Ｆ１）のガラス転移温度は１７２℃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５０℃以上高かった。
1 H-NMR (CDCl 3 ); 1.72 (s, 12H), 7.00-7.12 (br-t, 2H), 7.12-7.68 (m, 28H), 7.70- 7.86 (m, 4H), 8.10 (d, 2H, J = 9.2 Hz)
FDMS; 820
Compound (F1) has a glass transition temperature of 172 ° 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- About 50 ° C. higher than the glass transition temperatures of biphenyl) benzidine and the like (96 ° C., 110 ° C., 120 ° C., respectively).
実施例４ （化合物（Ｂ２）の合成）
合成例６で得られた化合物９ａ ３．３１ｇ（７．４３ｍｍｏｌ）、４，４’−ジフェニルベンジジン １．２２ｇ（３．６３ｍｍｏｌ）、ナトリウム−ｔｅｒｔ−ブトキシド ０．８４ｇをキシレン２５ｍｌ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８ｍｇ及びトリ−ｔｅｒｔ−ブチルホスフィン ３２ｍｇを添加し、１２５℃に加熱した。所定温度で２０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、抽出を行い、有機相を濃縮した。トルエンにて再結晶し、化合物（Ｂ２）を黄色粉末として２．３６ｇ得た（収率６１％）。
Example 4 (Synthesis of Compound (B2))
Compound 31a obtained in Synthesis Example 6 3.31 g (7.43 mmol), 4,4′-diphenylbenzidine 1.22 g (3.63 mmol), sodium tert-butoxide 0.84 g were suspended in xylene 25 ml, The system was replaced with nitrogen. Furthermore, 8 mg of palladium acetate and 32 mg of tri-tert-butylphosphine were added under a nitrogen atmosphere and heated to 125 ° C. After aging at a predetermined temperature for 20 hours, the reaction solution was cooled to room temperature. Extraction was performed after adding 20 ml of water, and the organic phase was concentrated. Recrystallization from toluene gave 2.36 g of compound (B2) as a yellow powder (yield 61%).
同定は、ＦＤＭＳ測定により行った。 Identification was performed by FDMS measurement.
ＦＤＭＳ；１０６８
実施例５ （化合物（Ｆ６）の合成）
化合物９ａの代わりに、合成例７で得られた化合物８ｂを用いて実施例４と同様の反応を行い、化合物（Ｆ６）を合成した。
FDMS; 1068
Example 5 (Synthesis of Compound (F6))
The compound (F6) was synthesized by performing the same reaction as in Example 4 using the compound 8b obtained in Synthesis Example 7 instead of the compound 9a.
同定は、ＦＤＭＳ測定により行った。 Identification was performed by FDMS measurement.
ＦＤＭＳ；１０６８
実施例６ （素子作製）
厚さ１３０ｎｍ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。更に、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。ＩＴＯ透明電極上に、銅フタロシアニンを真空蒸着法により２５ｎｍの膜厚で成膜した。次に、化合物（Ａ１）を真空蒸着法により４５ｎｍ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を真空蒸着法により６０ｎｍの膜厚で成膜し、電子輸送層を形成した。なお、上記有機化合物の蒸着条件は、真空度１．０×１０−４Ｐａ、成膜速度０．３ｎｍ／秒の同一条件で成膜した。
FDMS; 1068
Example 6 (Element fabrication)
A glass substrate having an ITO transparent electrode having a thickness of 130 nm was ultrasonically washed successively with acetone and isopropyl alcohol, then boiled and washed with isopropyl alcohol, and then dried. Furthermore, what was UV / ozone treated was used as a transparent conductive support substrate. On the ITO transparent electrode, copper phthalocyanine was formed into a film with a thickness of 25 nm by vacuum deposition. Next, the compound (A1) was formed into a film with a thickness of 45 nm by a vacuum vapor deposition method to form a hole transport layer. Next, an aluminum triskinolinol complex was formed into a film with a thickness of 60 nm by a vacuum vapor deposition method to form an electron transport layer. The organic compound was deposited under the same conditions of a vacuum degree of 1.0 × 10 −4 Pa and a deposition rate of 0.3 nm / second.
次に、陰極としてＬｉＦを０．５ｎｍ、Ａｌを１００ｎｍ蒸着し、金属電極を形成した。 Next, LiF was deposited to 0.5 nm and Al was deposited to 100 nm as a cathode to form a metal electrode.
更に、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、ＬｉＦ−Ａｌ電極を負極にして、４．５Ｖの直流電圧を印加すると７．５ｍＡ／ｃｍ２の電流密度が得られ、４０１ｃｄ／ｍ２の輝度で緑色の発光が観測された。 Further, a protective glass substrate was stacked in a nitrogen atmosphere and sealed with a UV curable resin. When a direct current voltage of 4.5 V was applied to the device obtained in this manner with the ITO electrode as the positive electrode and the LiF-Al electrode as the negative electrode, a current density of 7.5 mA / cm 2 was obtained, and 401 cd / m 2 Green light emission was observed at a brightness of.
比較例１〜２
化合物（Ａ１）の代わりに、ＮＰＤ、又は２，７−ビス（ナフチルフェニルアミノ）−９，９−ジメチルフルオレンを用い、実施例６に準じて素子を作成した。
Comparative Examples 1-2
A device was prepared according to Example 6 using NPD or 2,7-bis (naphthylphenylamino) -9,9-dimethylfluorene instead of the compound (A1).
電流密度７．５ｍＡ／ｃｍ２時の効率及び寿命に関する評価結果を表１に示す。 Table 1 shows the evaluation results regarding the efficiency and lifetime at a current density of 7.5 mA / cm 2 .
化合物（Ａ１）の代わりに、化合物（Ｆ１）を正孔輸送層に用い、実施例６と同様な操作を行い、有機ＥＬ素子を作製した。定電流密度＝２０ｍＡ／ｃｍ２の条件下測定すると、駆動電圧＝５．６７Ｖ、電流効率＝４．５ｃｄ／Ａ、電力効率＝２．５ｌｍ／Ｗの値を示した。評価結果を表２に示す。
Instead of the compound (A1), the compound (F1) was used for the hole transport layer, and the same operation as in Example 6 was performed to produce an organic EL device. When measured under the condition of constant current density = 20 mA / cm 2 , values of driving voltage = 5.67 V, current efficiency = 4.5 cd / A, and power efficiency = 2.5 lm / W were shown. The evaluation results are shown in Table 2.
実施例８
化合物（Ｆ１）を化合物（Ａ１）に変更した以外は、実施例７と同様な素子を作成した。２０ｍＡ／ｃｍ２の定電流密度条件下で駆動させた際の値を表２に示す。
Example 8
A device was prepared in the same manner as in Example 7 except that the compound (F1) was changed to the compound (A1). Table 2 shows values when driven under a constant current density condition of 20 mA / cm 2 .
比較例３
化合物（Ｆ１）をＮＰＤに変更した以外は、実施例７と同様な素子を作成した。２０ｍＡ／ｃｍ２の定電流密度条件下で駆動させた際の値を表２に示す。
Comparative Example 3
A device was prepared in the same manner as in Example 7 except that the compound (F1) was changed to NPD. Table 2 shows values when driven under a constant current density condition of 20 mA / cm 2 .
厚さ１３０ｎｍ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。更に、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。ＩＴＯ透明電極上に、銅フタロシアニンを真空蒸着法により２５ｎｍの膜厚で成膜した。次に、化合物（Ａ１）を真空蒸着法により４５ｎｍの膜厚で成膜し、正孔輸送層を形成した。次に、ＴＢＡＤＮをホスト材、ＴＢＰｅをドーパント材として、重量比＝９９：１で共蒸着し、４０ｎｍの膜厚を形成した。次に、アルミニウムトリスキノリノール錯体を真空蒸着法により２０ｎｍの膜厚で成膜し、電子輸送層を形成した。なお、上記有機化合物の蒸着条件は、真空度１．０×１０−４Ｐａ、成膜速度０．３ｎｍ／秒の同一条件で成膜した。
A glass substrate having an ITO transparent electrode having a thickness of 130 nm was ultrasonically washed successively with acetone and isopropyl alcohol, then boiled and washed with isopropyl alcohol, and then dried. Furthermore, what was UV / ozone treated was used as a transparent conductive support substrate. On the ITO transparent electrode, copper phthalocyanine was formed into a film with a thickness of 25 nm by vacuum deposition. Next, the compound (A1) was formed into a film with a thickness of 45 nm by a vacuum vapor deposition method to form a hole transport layer. Next, TBADN was used as a host material and TBPe was used as a dopant material to perform co-evaporation at a weight ratio of 99: 1 to form a film thickness of 40 nm. Next, an aluminum triskinolinol complex was formed into a film with a thickness of 20 nm by a vacuum deposition method to form an electron transport layer. The organic compound was deposited under the same conditions of a vacuum degree of 1.0 × 10 −4 Pa and a deposition rate of 0.3 nm / second.
次に、陰極としてＬｉＦを０．５ｎｍ、Ａｌを１００ｎｍ蒸着し、金属電極を形成した。 Next, LiF was deposited to 0.5 nm and Al was deposited to 100 nm as a cathode to form a metal electrode.
更に、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、ＬｉＦ−Ａｌ電極を負極にして、２０ｍＡ／ｃｍ２の定電流密度条件下で駆動させた際の輝度、駆動電圧、電流効率、電力効率及び輝度半減寿命は、各々９４０ｃｄ／ｍ２、５．５１Ｖ、４．７ｃｄ／Ａ、２．７ｌｍ／Ｗ、４５０ｈｒであった。結果を表３に示す。 Further, a protective glass substrate was stacked in a nitrogen atmosphere and sealed with a UV curable resin. Luminance, drive voltage, current efficiency, and power efficiency when the device thus obtained was driven under a constant current density condition of 20 mA / cm 2 with the ITO electrode as the positive electrode and the LiF-Al electrode as the negative electrode. The luminance half-life was 940 cd / m 2 , 5.51 V, 4.7 cd / A, 2.7 lm / W, and 450 hr, respectively. The results are shown in Table 3.
化合物（Ａ１）を化合物（Ｆ１）に変更した以外は、実施例９と同様な素子を作成した。２０ｍＡ／ｃｍ２の定電流密度条件下で駆動させた際の値を表３に示す。
A device was prepared in the same manner as in Example 9 except that the compound (A1) was changed to the compound (F1). Table 3 shows values when driven under a constant current density condition of 20 mA / cm 2 .
実施例１１
化合物（Ａ１）を化合物（Ｆ６）に変更した以外は、実施例９と同様な素子を作成した。２０ｍＡ／ｃｍ２の定電流密度条件下で駆動させた際の値を表３に示す。
Example 11
A device was prepared in the same manner as in Example 9 except that the compound (A1) was changed to the compound (F6). Table 3 shows values when driven under a constant current density condition of 20 mA / cm 2 .
比較例４
化合物（Ａ１）をＮＰＤに変更した以外は、実施例９と同様な素子を作成した。２０ｍＡ／ｃｍ２の定電流密度条件下で駆動させた際の値を表３に示す。
Comparative Example 4
A device was prepared in the same manner as in Example 9 except that the compound (A1) was changed to NPD. Table 3 shows values when driven under a constant current density condition of 20 mA / cm 2 .
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