JP5754116B2 - Amine compound, production method thereof, and use thereof - Google Patents
Amine compound, production method thereof, and use thereof Download PDFInfo
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- JP5754116B2 JP5754116B2 JP2010264086A JP2010264086A JP5754116B2 JP 5754116 B2 JP5754116 B2 JP 5754116B2 JP 2010264086 A JP2010264086 A JP 2010264086A JP 2010264086 A JP2010264086 A JP 2010264086A JP 5754116 B2 JP5754116 B2 JP 5754116B2
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- -1 Amine compound Chemical class 0.000 title claims description 198
- 238000004519 manufacturing process Methods 0.000 title claims 3
- 150000001875 compounds Chemical class 0.000 claims description 149
- 238000006243 chemical reaction Methods 0.000 claims description 43
- 125000004432 carbon atom Chemical group C* 0.000 claims description 23
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 10
- 125000004122 cyclic group Chemical group 0.000 claims description 7
- 150000002941 palladium compounds Chemical class 0.000 claims description 7
- 125000003545 alkoxy group Chemical group 0.000 claims description 6
- 239000003377 acid catalyst Substances 0.000 claims description 5
- 125000006165 cyclic alkyl group Chemical group 0.000 claims description 5
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical group [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims description 3
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 3
- 229910052801 chlorine Inorganic materials 0.000 claims description 3
- 125000001309 chloro group Chemical group Cl* 0.000 claims description 3
- 239000001257 hydrogen Substances 0.000 claims description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 3
- 229910052740 iodine Inorganic materials 0.000 claims description 3
- 125000005951 trifluoromethanesulfonyloxy group Chemical group 0.000 claims description 3
- 239000003054 catalyst Substances 0.000 claims description 2
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 claims description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims 2
- 125000004429 atom Chemical group 0.000 claims 2
- 125000003944 tolyl group Chemical group 0.000 claims 2
- IAJOBQBIJHVGMQ-UHFFFAOYSA-N Phosphinothricin Natural products CP(O)(=O)CCC(N)C(O)=O IAJOBQBIJHVGMQ-UHFFFAOYSA-N 0.000 claims 1
- IAJOBQBIJHVGMQ-BYPYZUCNSA-N glufosinate-P Chemical compound CP(O)(=O)CC[C@H](N)C(O)=O IAJOBQBIJHVGMQ-BYPYZUCNSA-N 0.000 claims 1
- 239000000463 material Substances 0.000 description 51
- 239000000243 solution Substances 0.000 description 46
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 45
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 40
- 238000005160 1H NMR spectroscopy Methods 0.000 description 40
- 230000015572 biosynthetic process Effects 0.000 description 40
- 238000003786 synthesis reaction Methods 0.000 description 40
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 39
- 238000005401 electroluminescence Methods 0.000 description 35
- 239000000843 powder Substances 0.000 description 33
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 31
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 27
- 239000010410 layer Substances 0.000 description 25
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 22
- 239000012299 nitrogen atmosphere Substances 0.000 description 21
- 239000002904 solvent Substances 0.000 description 21
- 238000004458 analytical method Methods 0.000 description 20
- 239000000203 mixture Substances 0.000 description 18
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 17
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 15
- DMBHHRLKUKUOEG-UHFFFAOYSA-N diphenylamine Chemical compound C=1C=CC=CC=1NC1=CC=CC=C1 DMBHHRLKUKUOEG-UHFFFAOYSA-N 0.000 description 14
- 239000012044 organic layer Substances 0.000 description 14
- 238000001296 phosphorescence spectrum Methods 0.000 description 14
- YLQBMQCUIZJEEH-UHFFFAOYSA-N Furan Chemical group C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 12
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 12
- 230000005525 hole transport Effects 0.000 description 12
- 239000007787 solid Substances 0.000 description 12
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 11
- 238000002347 injection Methods 0.000 description 11
- 239000007924 injection Substances 0.000 description 11
- 230000009477 glass transition Effects 0.000 description 10
- 238000000034 method Methods 0.000 description 10
- 238000010898 silica gel chromatography Methods 0.000 description 10
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical class O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 10
- BWHDROKFUHTORW-UHFFFAOYSA-N tritert-butylphosphane Chemical compound CC(C)(C)P(C(C)(C)C)C(C)(C)C BWHDROKFUHTORW-UHFFFAOYSA-N 0.000 description 10
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 9
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 9
- 125000003118 aryl group Chemical group 0.000 description 9
- 238000000113 differential scanning calorimetry Methods 0.000 description 9
- 230000005281 excited state Effects 0.000 description 9
- 238000005259 measurement Methods 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 8
- 238000005576 amination reaction Methods 0.000 description 8
- NROKBHXJSPEDAR-UHFFFAOYSA-M potassium fluoride Chemical compound [F-].[K+] NROKBHXJSPEDAR-UHFFFAOYSA-M 0.000 description 8
- MFRIHAYPQRLWNB-UHFFFAOYSA-N sodium tert-butoxide Chemical compound [Na+].CC(C)(C)[O-] MFRIHAYPQRLWNB-UHFFFAOYSA-N 0.000 description 8
- 238000005406 washing Methods 0.000 description 8
- MEKOFIRRDATTAG-UHFFFAOYSA-N 2,2,5,8-tetramethyl-3,4-dihydrochromen-6-ol Chemical compound C1CC(C)(C)OC2=C1C(C)=C(O)C=C2C MEKOFIRRDATTAG-UHFFFAOYSA-N 0.000 description 7
- 238000011156 evaluation Methods 0.000 description 7
- YJVFFLUZDVXJQI-UHFFFAOYSA-L palladium(ii) acetate Chemical compound [Pd+2].CC([O-])=O.CC([O-])=O YJVFFLUZDVXJQI-UHFFFAOYSA-L 0.000 description 7
- 125000001424 substituent group Chemical group 0.000 description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-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
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 6
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 6
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 description 6
- 239000013078 crystal Substances 0.000 description 6
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 5
- 238000000151 deposition Methods 0.000 description 5
- 230000008021 deposition Effects 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
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 229910052763 palladium Inorganic materials 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- CYPYTURSJDMMMP-WVCUSYJESA-N (1e,4e)-1,5-diphenylpenta-1,4-dien-3-one;palladium Chemical compound [Pd].[Pd].C=1C=CC=CC=1\C=C\C(=O)\C=C\C1=CC=CC=C1.C=1C=CC=CC=1\C=C\C(=O)\C=C\C1=CC=CC=C1.C=1C=CC=CC=1\C=C\C(=O)\C=C\C1=CC=CC=C1 CYPYTURSJDMMMP-WVCUSYJESA-N 0.000 description 4
- UHKAJLSKXBADFT-UHFFFAOYSA-N 1,3-indandione Chemical compound C1=CC=C2C(=O)CC(=O)C2=C1 UHKAJLSKXBADFT-UHFFFAOYSA-N 0.000 description 4
- RHPVVNRNAHRJOQ-UHFFFAOYSA-N 4-methyl-n-(4-methylphenyl)aniline Chemical compound C1=CC(C)=CC=C1NC1=CC=C(C)C=C1 RHPVVNRNAHRJOQ-UHFFFAOYSA-N 0.000 description 4
- VFUDMQLBKNMONU-UHFFFAOYSA-N 9-[4-(4-carbazol-9-ylphenyl)phenyl]carbazole Chemical group C12=CC=CC=C2C2=CC=CC=C2N1C1=CC=C(C=2C=CC(=CC=2)N2C3=CC=CC=C3C3=CC=CC=C32)C=C1 VFUDMQLBKNMONU-UHFFFAOYSA-N 0.000 description 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- 125000000609 carbazolyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3NC12)* 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- 229940078552 o-xylene Drugs 0.000 description 4
- 239000003960 organic solvent Substances 0.000 description 4
- LXNAVEXFUKBNMK-UHFFFAOYSA-N palladium(II) acetate Substances [Pd].CC(O)=O.CC(O)=O LXNAVEXFUKBNMK-UHFFFAOYSA-N 0.000 description 4
- 239000011698 potassium fluoride Substances 0.000 description 4
- 235000003270 potassium fluoride Nutrition 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 239000000377 silicon dioxide Substances 0.000 description 4
- 239000012279 sodium borohydride Substances 0.000 description 4
- 229910000033 sodium borohydride Inorganic materials 0.000 description 4
- HJUGFYREWKUQJT-UHFFFAOYSA-N tetrabromomethane Chemical compound BrC(Br)(Br)Br HJUGFYREWKUQJT-UHFFFAOYSA-N 0.000 description 4
- 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 4
- 229910015900 BF3 Inorganic materials 0.000 description 3
- 239000007848 Bronsted acid Substances 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 229910052786 argon Inorganic materials 0.000 description 3
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 3
- 125000004104 aryloxy group Chemical group 0.000 description 3
- 239000002585 base Substances 0.000 description 3
- 238000009835 boiling Methods 0.000 description 3
- 239000007810 chemical reaction solvent Substances 0.000 description 3
- 125000001072 heteroaryl group Chemical group 0.000 description 3
- 125000005842 heteroatom Chemical group 0.000 description 3
- 238000004128 high performance liquid chromatography Methods 0.000 description 3
- 239000007791 liquid phase Substances 0.000 description 3
- 238000007363 ring formation reaction Methods 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 239000008096 xylene Substances 0.000 description 3
- 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 2
- 125000001637 1-naphthyl group Chemical group [H]C1=C([H])C([H])=C2C(*)=C([H])C([H])=C([H])C2=C1[H] 0.000 description 2
- 125000001622 2-naphthyl group Chemical group [H]C1=C([H])C([H])=C2C([H])=C(*)C([H])=C([H])C2=C1[H] 0.000 description 2
- 125000000590 4-methylphenyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)C([H])([H])[H] 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-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
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- 0 [B+][C@](C1)(I*)IC(*)CCC1C(C(C(*)(*)C(C)ICC)(C(*)([C@@](C)C1C)O)C1(*CC)O)=* Chemical compound [B+][C@](C1)(I*)IC(*)CCC1C(C(C(*)(*)C(C)ICC)(C(*)([C@@](C)C1C)O)C1(*CC)O)=* 0.000 description 2
- 235000011054 acetic acid Nutrition 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
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- YNHIGQDRGKUECZ-UHFFFAOYSA-L bis(triphenylphosphine)palladium(ii) dichloride Chemical compound [Cl-].[Cl-].[Pd+2].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 YNHIGQDRGKUECZ-UHFFFAOYSA-L 0.000 description 2
- FJDQFPXHSGXQBY-UHFFFAOYSA-L caesium carbonate Chemical compound [Cs+].[Cs+].[O-]C([O-])=O FJDQFPXHSGXQBY-UHFFFAOYSA-L 0.000 description 2
- 229910000024 caesium carbonate Inorganic materials 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 125000002676 chrysenyl group Chemical group C1(=CC=CC=2C3=CC=C4C=CC=CC4=C3C=CC12)* 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- 230000008034 disappearance Effects 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 125000003983 fluorenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3CC12)* 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- UEEXRMUCXBPYOV-UHFFFAOYSA-N iridium;2-phenylpyridine Chemical compound [Ir].C1=CC=CC=C1C1=CC=CC=N1.C1=CC=CC=C1C1=CC=CC=N1.C1=CC=CC=C1C1=CC=CC=N1 UEEXRMUCXBPYOV-UHFFFAOYSA-N 0.000 description 2
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 2
- 239000012280 lithium aluminium hydride Substances 0.000 description 2
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Chemical compound [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 description 2
- 125000000040 m-tolyl group Chemical group [H]C1=C([H])C(*)=C([H])C(=C1[H])C([H])([H])[H] 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 125000001624 naphthyl group Chemical group 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
- 125000002080 perylenyl group Chemical group C1(=CC=C2C=CC=C3C4=CC=CC5=CC=CC(C1=C23)=C45)* 0.000 description 2
- 125000005561 phenanthryl group Chemical group 0.000 description 2
- 125000001388 picenyl group Chemical group C1(=CC=CC2=CC=C3C4=CC=C5C=CC=CC5=C4C=CC3=C21)* 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 125000001725 pyrenyl group Chemical group 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000011973 solid acid Substances 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 2
- 238000001771 vacuum deposition Methods 0.000 description 2
- 238000007740 vapor deposition Methods 0.000 description 2
- VNDYJBBGRKZCSX-UHFFFAOYSA-L zinc bromide Chemical compound Br[Zn]Br VNDYJBBGRKZCSX-UHFFFAOYSA-L 0.000 description 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 2
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 1
- SLLDDDJWIRFAGU-UHFFFAOYSA-N 1,2-dichlorocycloocta-1,5-diene Chemical compound ClC1=C(Cl)CCC=CCC1 SLLDDDJWIRFAGU-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- IANQTJSKSUMEQM-UHFFFAOYSA-N 1-benzofuran Chemical group C1=CC=C2OC=CC2=C1 IANQTJSKSUMEQM-UHFFFAOYSA-N 0.000 description 1
- LZSYGJNFCREHMD-UHFFFAOYSA-N 1-bromo-2-(bromomethyl)benzene Chemical compound BrCC1=CC=CC=C1Br LZSYGJNFCREHMD-UHFFFAOYSA-N 0.000 description 1
- YLRBJYMANQKEAW-UHFFFAOYSA-N 1-bromo-4-(bromomethyl)benzene Chemical compound BrCC1=CC=C(Br)C=C1 YLRBJYMANQKEAW-UHFFFAOYSA-N 0.000 description 1
- STTGYIUESPWXOW-UHFFFAOYSA-N 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline Chemical compound C=12C=CC3=C(C=4C=CC=CC=4)C=C(C)N=C3C2=NC(C)=CC=1C1=CC=CC=C1 STTGYIUESPWXOW-UHFFFAOYSA-N 0.000 description 1
- IXHWGNYCZPISET-UHFFFAOYSA-N 2-[4-(dicyanomethylidene)-2,3,5,6-tetrafluorocyclohexa-2,5-dien-1-ylidene]propanedinitrile Chemical compound FC1=C(F)C(=C(C#N)C#N)C(F)=C(F)C1=C(C#N)C#N IXHWGNYCZPISET-UHFFFAOYSA-N 0.000 description 1
- ZFFBIQMNKOJDJE-UHFFFAOYSA-N 2-bromo-1,2-diphenylethanone Chemical compound C=1C=CC=CC=1C(Br)C(=O)C1=CC=CC=C1 ZFFBIQMNKOJDJE-UHFFFAOYSA-N 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
- JWUJQDFVADABEY-UHFFFAOYSA-N 2-methyltetrahydrofuran Chemical compound CC1CCCO1 JWUJQDFVADABEY-UHFFFAOYSA-N 0.000 description 1
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- PUGUQINMNYINPK-UHFFFAOYSA-N tert-butyl 4-(2-chloroacetyl)piperazine-1-carboxylate Chemical compound CC(C)(C)OC(=O)N1CCN(C(=O)CCl)CC1 PUGUQINMNYINPK-UHFFFAOYSA-N 0.000 description 1
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- ZGNPLWZYVAFUNZ-UHFFFAOYSA-N tert-butylphosphane Chemical compound CC(C)(C)P ZGNPLWZYVAFUNZ-UHFFFAOYSA-N 0.000 description 1
- PCCVSPMFGIFTHU-UHFFFAOYSA-N tetracyanoquinodimethane Chemical compound N#CC(C#N)=C1C=CC(=C(C#N)C#N)C=C1 PCCVSPMFGIFTHU-UHFFFAOYSA-N 0.000 description 1
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- JMXKSZRRTHPKDL-UHFFFAOYSA-N titanium ethoxide Chemical compound [Ti+4].CC[O-].CC[O-].CC[O-].CC[O-] JMXKSZRRTHPKDL-UHFFFAOYSA-N 0.000 description 1
- UBZYKBZMAMTNKW-UHFFFAOYSA-J titanium tetrabromide Chemical compound Br[Ti](Br)(Br)Br UBZYKBZMAMTNKW-UHFFFAOYSA-J 0.000 description 1
- 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 1
- FEONEKOZSGPOFN-UHFFFAOYSA-K tribromoiron Chemical compound Br[Fe](Br)Br FEONEKOZSGPOFN-UHFFFAOYSA-K 0.000 description 1
- TUQOTMZNTHZOKS-UHFFFAOYSA-N tributylphosphine Chemical compound CCCCP(CCCC)CCCC TUQOTMZNTHZOKS-UHFFFAOYSA-N 0.000 description 1
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- WLPUWLXVBWGYMZ-UHFFFAOYSA-N tricyclohexylphosphine Chemical compound C1CCCCC1P(C1CCCCC1)C1CCCCC1 WLPUWLXVBWGYMZ-UHFFFAOYSA-N 0.000 description 1
- RXJKFRMDXUJTEX-UHFFFAOYSA-N triethylphosphine Chemical compound CCP(CC)CC RXJKFRMDXUJTEX-UHFFFAOYSA-N 0.000 description 1
- ITMCEJHCFYSIIV-UHFFFAOYSA-N triflic acid Chemical compound OS(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-N 0.000 description 1
- 125000000876 trifluoromethoxy group Chemical group FC(F)(F)O* 0.000 description 1
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 1
- 125000005580 triphenylene group Chemical group 0.000 description 1
- 125000003960 triphenylenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3C3=CC=CC=C3C12)* 0.000 description 1
- 238000004506 ultrasonic cleaning Methods 0.000 description 1
- 238000000825 ultraviolet detection Methods 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
- 229940102001 zinc bromide Drugs 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
- 235000005074 zinc chloride Nutrition 0.000 description 1
- 150000003752 zinc compounds Chemical class 0.000 description 1
- 150000003755 zirconium compounds Chemical class 0.000 description 1
- DUNKXUFBGCUVQW-UHFFFAOYSA-J zirconium tetrachloride Chemical compound Cl[Zr](Cl)(Cl)Cl DUNKXUFBGCUVQW-UHFFFAOYSA-J 0.000 description 1
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- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Electroluminescent Light Sources (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
本発明は、新規なアミン化合物及びそれを用いた有機エレクトロルミネッセンス(EL)素子に関するものである。本発明におけるアミン化合物は、感光材料、有機光導電材料として使用でき、具体的には、平面光源や表示に使用される有機EL素子若しくは電子写真感光体等の正孔輸送材料、正孔注入材料及び発光材料として有用である。特に、本発明のアミン化合物は、燐光材料を用いた有機EL素子に対して非常に有用である。 The present invention relates to a novel amine compound and an organic electroluminescence (EL) device using the same. The amine compound in the present invention can be used as a photosensitive material or an organic photoconductive material. Specifically, a hole transport material such as an organic EL device or an electrophotographic photosensitive member used for a flat light source or a display, or a hole injection material. And it is useful as a luminescent material. In particular, the amine compound of the present invention is very useful for an organic EL device using a phosphorescent material.
有機EL素子は、次世代の薄型平面ディスプレイとして現在盛んに研究されており、既に携帯電話のディスプレイやテレビ等への実用化も始まっている。しかし、有機EL素子をさらに広く普及させるために、素子の発光効率を一層向上させることが求められている。 Organic EL devices are currently being actively researched as next-generation thin flat displays, and have already been put into practical use in mobile phone displays and televisions. However, in order to further spread the organic EL element, it is required to further improve the light emission efficiency of the element.
有機EL素子の一般的な発光メカニズムは、両電極から電子及び正孔が注入されると、それらが対電極に向かい、発光層で再結合して励起子を生成し、その励起子の励起状態が基底状態に戻るときに発光が生じるものである。この励起状態には、電子スピンの向きが反平行である一重項励起状態と、電子スピンの向きが平行となる三重項励起状態とがあるが、現在普及している有機EL素子は、一重項励起状態のみが関与する蛍光発光が主流となっている。しかし、単純な量子力学的推論から、電子と正孔の再結合により生成する一重項励起状態と三重項励起状態の生成比率は1:3であるため、蛍光を利用した有機EL素子の場合には内部量子効率の最大値は25%となる。つまり、励起状態の75%は発光に使用されないことになる。また、有機EL素子外部への光取り出し効率は、高々20%程度であるため、蛍光を利用した有機EL素子においては、その外部量子効率は25%×20%となり、最大5%程度と見積もられる。 The general light emission mechanism of organic EL devices is that when electrons and holes are injected from both electrodes, they go to the counter electrode and recombine in the light emitting layer to generate excitons. Light emission occurs when the light returns to the ground state. In this excited state, there are a singlet excited state in which the direction of electron spin is antiparallel and a triplet excited state in which the direction of electron spin is parallel. Fluorescence emission involving only the excited state is the mainstream. However, from the simple quantum mechanical reasoning, the generation ratio of singlet excited state and triplet excited state generated by recombination of electrons and holes is 1: 3. Therefore, in the case of an organic EL element using fluorescence. The maximum value of the internal quantum efficiency is 25%. That is, 75% of the excited state is not used for light emission. In addition, since the light extraction efficiency to the outside of the organic EL element is about 20% at most, in the organic EL element using fluorescence, the external quantum efficiency is 25% × 20%, which is estimated to be about 5% at the maximum. .
このため、外部量子効率をさらに向上させるためには、励起状態のうちの75%を占める三重項励起状態からの発光、すなわち燐光も利用する必要がある。この利用が可能となれば、外部量子効率を最大20%まで向上させることができる。このような背景から、近年では燐光材料を用いた有機EL素子の開発が活発化している。 For this reason, in order to further improve the external quantum efficiency, it is necessary to use light emission from a triplet excited state that occupies 75% of the excited state, that is, phosphorescence. If this utilization becomes possible, the external quantum efficiency can be improved up to 20%. Against this background, in recent years, development of organic EL elements using phosphorescent materials has been activated.
ところで、燐光材料を用いた有機EL素子では、発光層と隣接する層に用いる材料は、蛍光材料に比べて高い三重項準位(T1)を有することが求められる。一方、蛍光材料を利用した有機EL素子において従来使用されてきた周知の材料の三重項準位は十分とは言い難い。例えば、正孔輸送材料として良く知られている、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)の三重項準位は、2.3eV程度と低いため、2.3eV以上の三重項準位を有する燐光材料と組み合わせた場合には、励起エネルギーを十分に閉じ込められず、効率の低下を招いてしまう。 By the way, in an organic EL element using a phosphorescent material, a material used for a layer adjacent to the light emitting layer is required to have a higher triplet level (T1) than a fluorescent material. On the other hand, it is difficult to say that triplet levels of known materials conventionally used in organic EL elements using fluorescent materials are sufficient. For example, the triplet level of 4,4′-bis [N- (1-naphthyl) -N-phenylamino] biphenyl (α-NPD), which is well known as a hole transport material, is about 2.3 eV. Therefore, when combined with a phosphorescent material having a triplet level of 2.3 eV or higher, excitation energy cannot be sufficiently confined, resulting in a decrease in efficiency.
さらに、三重項準位を向上させるために、材料中にカルバゾール基などの骨格を導入する方法も試みられている。例えば、カルバゾール骨格を有する化合物として、4,4’−ビス(N−カルバゾリル)ビフェニル(CBP)が挙げられるが(例えば、非特許文献1参照)、その三重項準位は2.6eV程度であり、十分なレベルとは言い難いものである。 Furthermore, in order to improve the triplet level, a method of introducing a skeleton such as a carbazole group into the material has been attempted. For example, a compound having a carbazole skeleton includes 4,4′-bis (N-carbazolyl) biphenyl (CBP) (see, for example, Non-Patent Document 1), but the triplet level is about 2.6 eV. It's hard to say that the level is sufficient.
本発明の目的は、従来材料以上に高い効率を発現する有機EL用材料、特に燐光材料を用いた有機EL素子において非常に有用である材料を提供することにある。さらに詳しくは、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材料を提供することにある。 An object of the present invention is to provide an organic EL material that exhibits higher efficiency than conventional materials, particularly a material that is very useful in an organic EL element using a phosphorescent material. More specifically, it is to provide a novel material suitable for a hole injection material such as an organic EL element, 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)で表されるアミン化合物が、従来周知の材料に比べて高い三重項準位を有することを見出した。即ち本発明は、一般式(1)で表されるアミ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 amine compound represented by the general formula (1) has a higher triplet level than a conventionally known material. That is, the present invention relates to an amine compound represented by the general formula (1) and its use.
以下、本発明を詳細に説明する。
Hereinafter, the present invention will be described in detail.
本発明の一般式(1)で表されるアミン化合物において、環A、環B及び環Cは各々独立してヘテロ原子を含んでもよい芳香環を表す。以下に限定されるものではないが、具体的には、ベンゼン環、ナフタレン環、アントラセン環、トリフェニレン環、フルオレン環、ピリジン環、ピラジン環、キノリン環、ピロール環、インドール環、カルバゾール環、フラン環、ベンゾフラン環、ジベンゾフラン環等を例示することができる。 In the amine compound represented by the general formula (1) of the present invention, ring A, ring B and ring C each independently represent an aromatic ring which may contain a hetero atom. Specific examples include, but are not limited to, benzene ring, naphthalene ring, anthracene ring, triphenylene ring, fluorene ring, pyridine ring, pyrazine ring, quinoline ring, pyrrole ring, indole ring, carbazole ring, furan ring. Benzofuran ring, dibenzofuran ring and the like.
本発明の一般式(1)で表されるアミン化合物において、R1、R2、R3、R4、R5、R6、R7、R8及びR9は各々独立して水素原子、炭素数1〜18の直鎖、分岐若しくは環状のアルキル基、炭素数1〜18の直鎖、分岐若しくは環状のアルコキシ基、炭素数6〜24のアリール基、又は炭素数6〜24のアリールオキシ基を表す。炭素数1〜18の直鎖、分岐若しくは環状のアルキル基としては、以下に限定されるものではないが、具体的には、メチル基、エチル基、プロピル基、イソプロピル基、ブチル基、sec−ブチル基、tert−ブチル基、ペンチル基、ヘキシル基、ヘプチル基、オクチル基、ステアリル基、トリクロロメチル基、トリフルオロメチル基、シクロプロピル基、シクロヘキシル基、1,3−シクロヘキサジエニル基、2−シクロペンテン−1−イル基等を例示することができる。 In the amine compound represented by the general formula (1) of the present invention, R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 and R 9 are each independently a hydrogen atom, A linear, branched or cyclic alkyl group having 1 to 18 carbon atoms, a linear, branched or cyclic alkoxy group having 1 to 18 carbon atoms, an aryl group having 6 to 24 carbon atoms, or an aryloxy group having 6 to 24 carbon atoms Represents a group. Examples of the linear, branched or cyclic alkyl group having 1 to 18 carbon atoms include, but are not limited to, methyl group, ethyl group, propyl group, isopropyl group, butyl group, sec- Butyl, tert-butyl, pentyl, hexyl, heptyl, octyl, stearyl, trichloromethyl, trifluoromethyl, cyclopropyl, cyclohexyl, 1,3-cyclohexadienyl, 2- A cyclopenten-1-yl group etc. can be illustrated.
炭素数1〜18の直鎖、分岐若しくは環状のアルコキシ基としては、以下に限定されるものではないが、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。 The linear, branched or cyclic alkoxy group having 1 to 18 carbon atoms is not limited to the following, and specifically includes a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, and an n-butoxy group. , Sec-butoxy group, tert-butoxy group, pentyloxy group, hexyloxy group, stearyloxy group, trifluoromethoxy group and the like.
炭素数6〜24のアリール基としては、以下に限定されるものではないが、具体的には、フェニル基、4−メチルフェニル基、3−メチルフェニル基、2−メチルフェニル基、4−エチルフェニル基、3−エチルフェニル基、2−エチルフェニル基、4−n−プロピルフェニル基、4−n−ブチルフェニル基、4−イソブチルフェニル基、4−tert−ブチルフェニル基、4−シクロペンチルフェニル基、4−シクロヘキシルフェニル基、2,4−ジメチルフェニル基、3,5−ジメチルフェニル基、3,4−ジメチルフェニル基、1−ビフェニル基、1−ナフチル基、2−ナフチル基、9−フェナントリル基、9,9−ジアルキル−フルオレン−2−イル基、9,9−ジ−トリフルオロメチル−フルオレン−2−イル基等を例示することができる。 Examples of the aryl group having 6 to 24 carbon atoms include, but are not limited to, phenyl group, 4-methylphenyl group, 3-methylphenyl group, 2-methylphenyl group, 4-ethyl. Phenyl group, 3-ethylphenyl group, 2-ethylphenyl group, 4-n-propylphenyl group, 4-n-butylphenyl group, 4-isobutylphenyl group, 4-tert-butylphenyl group, 4-cyclopentylphenyl group 4-cyclohexylphenyl group, 2,4-dimethylphenyl group, 3,5-dimethylphenyl group, 3,4-dimethylphenyl group, 1-biphenyl group, 1-naphthyl group, 2-naphthyl group, 9-phenanthryl group , 9,9-dialkyl-fluoren-2-yl group, 9,9-di-trifluoromethyl-fluoren-2-yl group, etc. It can be.
炭素数6〜24のアリールオキシ基としては、以下に限定されるものではないが、具体的には、フェノキシ基、p−tert−ブチルフェノキシ基、3−フルオロフェノキシ基、4−フルオロフェノキシ基等を例示することができる。 Examples of the aryloxy group having 6 to 24 carbon atoms include, but are not limited to, phenoxy group, p-tert-butylphenoxy group, 3-fluorophenoxy group, 4-fluorophenoxy group, and the like. Can be illustrated.
なお、R3又はR4とR5又はR6は、お互いに結合して環を形成することができる。 R 3 or R 4 and R 5 or R 6 can be bonded to each other to form a ring.
本発明の一般式(1)で表されるアミン化合物において、Ar1、Ar2、Ar3及びAr4は各々独立して炭素数6〜40の置換基を有してもよいアリール基、又は炭素数5〜40の置換基を有してもよいヘテロアリール基を表す。炭素数6〜40の置換基を有してもよいアリール基としては、以下に限定されるものではないが、具体的には、置換基を有してもよいフェニル基、ナフチル基、ビフェニリル基、ターフェニル基、ビフェニレニル基、アントリル基、トリフェニレニル基、フルオレニル基、ベンゾフルオレニル基、フェナントリル基、ピレニル基、クリセニル基、ペリレニル基、ピセニル基等を例示することができ、さらに具体的には、フェニル基、1−ナフチル基、2−ナフチル基、2−アントリル基、9−アントリル基、2−フルオレニル基、フェナントリル基、ピレニル基、クリセニル基、ペリレニル基、ピセニル基、4−メチルフェニル基、3−メチルフェニル基、2−メチルフェニル基、4−エチルフェニル基、3−エチルフェニル基、2−エチルフェニル基、4−n−プロピルフェニル基、4−イソプロピルフェニル基、2−イソプロピルフェニル基、4−n−ブチルフェニル基、4−イソブチルフェニル基、4−sec−ブチルフェニル基、2−sec−ブチルフェニル基、4−tert−ブチルフェニル基、3−tert−ブチルフェニル基、2−tert−ブチルフェニル基、4−n−ペンチルフェニル基、4−イソペンチルフェニル基、2−ネオペンチルフェニル基、4−tert−ペンチルフェニル基、4−n−ヘキシルフェニル基、4−(2’−エチルブチル)フェニル基、4−n−ヘプチルフェニル基、4−n−オクチルフェニル基、4−(2’−エチルヘキシル)フェニル基、4−tert−オクチルフェニル基、4−n−デシルフェニル基、4−n−ドデシルフェニル基、4−n−テトラデシルフェニル基、4−シクロペンチルフェニル基、4−シクロヘキシルフェニル基、4−(4’−メチルシクロヘキシル)フェニル基、4−(4’−tert−ブチルシクロヘキシル)フェニル基、3−シクロヘキシルフェニル基、2−シクロヘキシルフェニル基、4−エチル−1−ナフチル基、6−n−ブチル−2−ナフチル基、2,4−ジメチルフェニル基、2,5−ジメチルフェニル基、3,4−ジメチルフェニル基、3,5−ジメチルフェニル基、2,6−ジメチルフェニル基、2,4−ジエチルフェニル基、2,3,5−トリメチルフェニル基、2,3,6−トリメチルフェニル基、3,4,5−トリメチルフェニル基、2,6−ジエチルフェニル基、2,5−ジイソプロピルフェニル基、2,6−ジイソブチルフェニル基、2,4−ジ−tert−ブチルフェニル基、2,5−ジ−tert−ブチルフェニル基、4,6−ジ−tert−ブチル−2−メチルフェニル基、5−tert−ブチル−2−メチルフェニル基、4−tert−ブチル−2,6−ジメチルフェニル基、9−メチル−2−フルオレニル基、9−エチル−2−フルオレニル基、9−n−ヘキシル−2−フルオレニル基、9,9−ジメチル−2−フルオレニル基、9,9−ジエチル−2−フルオレニル基、9,9−ジ−n−プロピル−2−フルオレニル基、4−メトキシフェニル基、3−メトキシフェニル基、2−メトキシフェニル基、4−エトキシフェニル基、3−エトキシフェニル基、2−エトキシフェニル基、4−n−プロポキシフェニル基、3−n−プロポキシフェニル基、4−イソプロポキシフェニル基、2−イソプロポキシフェニル基、4−n−ブトキシフェニル基、4−イソブトキシフェニル基、2−sec−ブトキシフェニル基、4−n−ペンチルオキシフェニル基、4−イソペンチルオキシフェニル基、2−イソペンチルオキシフェニル基、4−ネオペンチルオキシフェニル基、2−ネオペンチルオキシフェニル基、4−n−ヘキシルオキシフェニル基、2−(2’−エチルブチル)オキシフェニル基、4−n−オクチルオキシフェニル基、4−n−デシルオキシフェニル基、4−n−ドデシルオキシフェニル基、4−n−テトラデシルオキシフェニル基、4−シクロヘキシルオキシフェニル基、2−シクロヘキシルオキシフェニル基、2−メトキシ−1−ナフチル基、4−メトキシ−1−ナフチル基、4−n−ブトキシ−1−ナフチル基、5−エトキシ−1−ナフチル基、6−メトキシ−2−ナフチル基、6−エトキシ−2−ナフチル基、6−n−ブトキシ−2−ナフチル基、6−n−ヘキシルオキシ−2−ナフチル基、7−メトキシ−2−ナフチル基、7−n−ブトキシ−2−ナフチル基、2−メチル−4−メトキシフェニル基、2−メチル−5−メトキシフェニル基、3−メチル−4−メトキシフェニル基、3−メチル−5−メトキシフェニル基、3−エチル−5−メトキシフェニル基、2−メトキシ−4−メチルフェニル基、3−メトキシ−4−メチルフェニル基、2,4−ジメトキシフェニル基、2,5−ジメトキシフェニル基、2,6−ジメトキシフェニル基、3,4−ジメトキシフェニル基、3,5−ジメトキシフェニル基、3,5−ジエトキシフェニル基、3,5−ジ−n−ブトキシフェニル基、2−メトキシ−4−エトキシフェニル基、2−メトキシ−6−エトキシフェニル基、3,4,5−トリメトキシフェニル基、4−ビフェニリル基、3−ビフェニリル基、2−ビフェニリル基、4−(4’−メチルフェニル)フェニル基、4−(3’−メチルフェニル)フェニル基、4−(4’−メトキシフェニル)フェニル基、4−(4’−n−ブトキシフェニル)フェニル基、2−(2’−メトキシフェニル)フェニル基、3−メチル−4−フェニルフェニル基、3−メトキシ−4−フェニルフェニル基、ターフェニル基、3,5−ジフェニルフェニル基、10−フェニルアントリル基、10−(3,5−ジフェニルフェニル)−9−アントリル基、9−フェニル−2−フルオレニル基等を例示することができる。また、炭素数5〜40の置換基を有してもよいヘテロアリール基としては、以下に限定されるものではないが、具体的には、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族基であり、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等の複素環基を例示することができる。なお、Ar1とAr2、及びAr3とAr4は互いに結合して環を形成することができる。Ar1とAr2、及びAr3とAr4が形成する環としては、以下に限定されるものではないが、具体的には、カルバゾール環、フェノチアジン環、フェノキサジン環等を例示することができる。 In the amine compound represented by the general formula (1) of the present invention, Ar 1 , Ar 2 , Ar 3 and Ar 4 are each independently an aryl group which may have a substituent having 6 to 40 carbon atoms, or The heteroaryl group which may have a C5-C40 substituent may be represented. The aryl group which may have a substituent having 6 to 40 carbon atoms is not limited to the following, and specifically, a phenyl group, a naphthyl group, or a biphenylyl group which may have a substituent. Terphenyl group, biphenylenyl group, anthryl group, triphenylenyl group, fluorenyl group, benzofluorenyl group, phenanthryl group, pyrenyl group, chrysenyl group, perylenyl group, picenyl group, etc. , Phenyl group, 1-naphthyl group, 2-naphthyl group, 2-anthryl group, 9-anthryl group, 2-fluorenyl group, phenanthryl group, pyrenyl group, chrysenyl group, perylenyl group, picenyl group, 4-methylphenyl group, 3-methylphenyl group, 2-methylphenyl group, 4-ethylphenyl group, 3-ethylphenyl group, 2-ethyl Enyl group, 4-n-propylphenyl group, 4-isopropylphenyl group, 2-isopropylphenyl group, 4-n-butylphenyl group, 4-isobutylphenyl group, 4-sec-butylphenyl group, 2-sec-butyl Phenyl group, 4-tert-butylphenyl group, 3-tert-butylphenyl group, 2-tert-butylphenyl group, 4-n-pentylphenyl group, 4-isopentylphenyl group, 2-neopentylphenyl group, 4 -Tert-pentylphenyl group, 4-n-hexylphenyl group, 4- (2'-ethylbutyl) phenyl group, 4-n-heptylphenyl group, 4-n-octylphenyl group, 4- (2'-ethylhexyl) Phenyl group, 4-tert-octylphenyl group, 4-n-decylphenyl group, 4-n-dodecylphenyl group 4-n-tetradecylphenyl group, 4-cyclopentylphenyl group, 4-cyclohexylphenyl group, 4- (4′-methylcyclohexyl) phenyl group, 4- (4′-tert-butylcyclohexyl) phenyl group, 3- Cyclohexylphenyl group, 2-cyclohexylphenyl group, 4-ethyl-1-naphthyl group, 6-n-butyl-2-naphthyl group, 2,4-dimethylphenyl group, 2,5-dimethylphenyl group, 3,4- Dimethylphenyl group, 3,5-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-diisobutyl Phenyl 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-dimethyl-2-fluorenyl group, 9,9-diethyl-2-fluorenyl group, 9,9-di-n-propyl-2-fluorenyl group, 4-methoxyphenyl group, 3-methoxyphenyl group, 2-methoxy Phenyl 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-isopentyloxy Phenyl group, 2-isopentyloxyphenyl group, 4-neopentyloxyphenyl group, 2-neopentyloxyphenyl group, 4-n-hexyloxyphenyl group, 2- (2′-ethylbutyl) oxyphenyl group, 4- n-octyloxyphenyl group, 4-n-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-methoxyphenyl 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- Biphenylyl group, 3-biphenylyl group, 2-biphenylyl group, 4- (4′-methylphenyl) phenyl group, 4- (3′-methylphenyl) phenyl group, 4- (4′-methoxyphenyl) phenyl group, 4 -(4'-n-butoxyphenyl) phenyl group, 2- (2'-methoxyphenyl) phenyl group, 3-methyl-4-phenylphenyl group, 3-methoxy-4-phenylphenyl group, terphenyl group, 3 , 5-diphenylphenyl group, 10-phenylanthryl group, 10- (3,5-diphenylphenyl) -9-anthryl group, 9-phenyl-2-fluoreni And the like. Further, the heteroaryl group which may have a substituent having 5 to 40 carbon atoms is not limited to the following, but specifically, at least one selected from an oxygen atom, a nitrogen atom and a sulfur atom. Aromatic groups containing two heteroatoms, such as 4-quinolyl, 4-pyridyl, 3-pyridyl, 2-pyridyl, 3-furyl, 2-furyl, 3-thienyl, 2 Examples include heterocyclic groups such as -thienyl group, 2-oxazolyl group, 2-thiazolyl group, 2-benzoxazolyl group, 2-benzothiazolyl group, 2-benzoimidazolyl group. Ar 1 and Ar 2 , and Ar 3 and Ar 4 can be bonded to each other to form a ring. The ring formed by Ar 1 and Ar 2 and Ar 3 and Ar 4 is not limited to the following, but specific examples include a carbazole ring, a phenothiazine ring, a phenoxazine ring, and the like. .
また、上記一般式(1)で表されるアミン化合物の好ましい具体例として、下記一般式(2)で表されるアミン化合物を挙げることができる。 Moreover, the amine compound represented by following General formula (2) can be mentioned as a preferable specific example of the amine compound represented by the said General formula (1).
本発明の一般式(1)で表されるアミン化合物の中間体であるトリキナン化合物(3)は、下記一般式(4)で表される化合物を環化することで合成することが出来る。 The triquinane compound (3), which is an intermediate of the amine compound represented by the general formula (1) of the present invention, can be synthesized by cyclizing the compound represented by the following general formula (4).
化合物(4)は、公知の方法によって合成することができる(例えば、非特許文献2〜4参照)。
A compound (4) is compoundable by a well-known method (for example, refer nonpatent literature 2-4).
酸触媒としては、特に限定されるものではないが、塩化鉄(III)、臭化鉄(III)等の鉄化合物、塩化亜鉛、臭化亜鉛等の亜鉛化合物、塩化ジルコニウム等のジルコニウム化合物、塩化チタン、臭化チタン、チタニウムエトキシド等のチタン化合物、塩化アルミニウム、臭化アルミニウム等のアルミニウム化合物、三フッ化ボロン、三フッ化ボロン・エーテル錯体、三フッ化ボロン・酢酸錯体、三臭化ボロン等のボロン化合物、塩化スカンジウム、塩化ランタン等のランタノイド金属塩等のルイス酸、硫酸、塩酸、燐酸、ポリ燐酸、p−トルエンスルホン酸、トリフルオロメタンスルホン酸等のブレンステッド酸、ニオブ酸、シリカアルミナ、シリカチタニア、シリカジルコニア、チタニアジルコニア、リン酸アルミニウム、オルトリン酸アルミニウム系触媒、リン酸鉄、硫酸アルミニウム、硫酸イオン担持ジルコニア、硫酸イオン担持チタニア、五フッ化アンチモン担持シリカアルミナ、酸性白土、カオリン、モンモリロナイト、フッ化スルホン樹脂、ゼオライト、強酸性陽イオン交換樹脂、ヘテロポリ酸塩等の固体酸が挙げられる。このうちブレンステッド酸が好ましく、特に好ましくは硫酸である。 The acid catalyst is not particularly limited, but iron compounds such as iron (III) chloride and iron (III) bromide, zinc compounds such as zinc chloride and zinc bromide, zirconium compounds such as zirconium chloride, and chlorides. Titanium compounds such as titanium, titanium bromide and titanium ethoxide, aluminum compounds such as aluminum chloride and aluminum bromide, boron trifluoride, boron trifluoride / ether complex, boron trifluoride / acetic acid complex, boron tribromide Boron compounds such as lanthanoid metal salts such as scandium chloride and lanthanum chloride, Bronsted acids such as sulfuric acid, hydrochloric acid, phosphoric acid, polyphosphoric acid, p-toluenesulfonic acid, trifluoromethanesulfonic acid, niobic acid, silica alumina , Silica titania, silica zirconia, titania zirconia, aluminum phosphate, ortho Aluminum acid catalyst, iron phosphate, aluminum sulfate, sulfate ion supported zirconia, sulfate ion supported titania, antimony pentafluoride supported silica alumina, acid clay, kaolin, montmorillonite, fluorinated sulfone resin, zeolite, strongly acidic cation exchange resin And solid acids such as heteropolyacid salts. Of these, Bronsted acid is preferable, and sulfuric acid is particularly preferable.
ルイス酸またはブレンステッド酸の使用量は、特に限定されないが、上記一般式(4)で表されるジオール化合物の1モルに対して、通常、0.5〜20倍モルであり、好ましくは2〜10倍モルの範囲である。 The amount of Lewis acid or Bronsted acid used is not particularly limited, but is usually 0.5 to 20 times mol, preferably 2 with respect to 1 mol of the diol compound represented by the general formula (4). It is the range of 10 times mole.
固体酸の使用量は、特に限定するものではないが、原料である上記一般式(4)で表されるジオール化合物の使用量に対し、通常0.01〜20重量%の範囲であり、好ましくは0.1〜10重量%の範囲である。 The amount of the solid acid used is not particularly limited, but is usually in the range of 0.01 to 20% by weight with respect to the amount of the diol compound represented by the general formula (4) as a raw material. Is in the range of 0.1 to 10% by weight.
本発明における環化反応は液相で行うことも出来るし、気相で行うことも出来るが、液相反応が好ましい。また、反応は回分式、連続式または固定床流通式でも実施することが出来る。 The cyclization reaction in the present invention can be carried out in the liquid phase or in the gas phase, but the liquid phase reaction is preferred. The reaction can also be carried out in a batch, continuous or fixed bed flow system.
液相での環化反応は、有機溶媒中で実施される。有機溶媒は、反応を阻害しないものであれば特に制限はないが、通常、蟻酸、酢酸、プロピオン酸などのプロトン酸溶媒、ジクロロメタン、クロロホルム、四塩化炭素等のハロゲン系溶媒、ベンゼン、トルエン、キシレン、メシチレン等の芳香族炭化水素溶媒を好ましく用いることが出来る。 The cyclization reaction in the liquid phase is carried out in an organic solvent. The organic solvent is not particularly limited as long as it does not inhibit the reaction, but is usually a protonic acid solvent such as formic acid, acetic acid, propionic acid, a halogen-based solvent such as dichloromethane, chloroform, carbon tetrachloride, benzene, toluene, xylene. An aromatic hydrocarbon solvent such as mesitylene can be preferably used.
上記環化反応は、常圧下、窒素、アルゴン等の不活性ガス雰囲気下で行うことができ、加圧下で行うこともできる。尚、反応は、−10〜300℃の温度範囲で行われるが、より好ましくは0〜200℃の温度範囲である。 The cyclization reaction can be performed under an atmospheric pressure, an inert gas atmosphere such as nitrogen or argon, or can be performed under pressure. In addition, although reaction is performed in the temperature range of -10-300 degreeC, More preferably, it is a temperature range of 0-200 degreeC.
反応に要する時間は、使用する上記化合物(4)及び酸触媒の量、反応温度等によって変動するため、必ずしも限定されないが、例えば、1〜40時間である。 The time required for the reaction varies depending on the amount of the compound (4) and acid catalyst used, the reaction temperature, and the like, and is not necessarily limited, but is, for example, 1 to 40 hours.
このようにして得られるトリキナン化合物(3)は本発明の有機EL用材料の中間体としてだけでなく、太陽電池等の電子材料中間体、超分子構築用の中間体、医農薬中間体としての利用が期待出来る。 The thus obtained triquinane compound (3) is used not only as an intermediate of the organic EL material of the present invention, but also as an intermediate for electronic materials such as solar cells, an intermediate for supramolecular construction, and an intermediate for medical and agricultural chemicals. Can be used.
本発明の一般式(1)で表されるアミン化合物は、下記一般式(5)及び(6)で表されるアミン化合物を用い、公知の方法(例えば、非特許文献5参照)で、トリキナン化合物(3)をアミノ化することによって、効率良く合成することが出来る。このとき、化合物(5)と(6)は異なっても良いし、同じであっても良い。反応から得られる一般式(1)で表されるアミン化合物は、単一構造の場合もあるが、化合物(5)と化合物(6)が異なる場合、これらに対応した混合物として得ることも出来る。 The amine compound represented by the general formula (1) of the present invention is an amine compound represented by the following general formulas (5) and (6), and is a triquinane by a known method (for example, see Non-Patent Document 5). The compound (3) can be efficiently synthesized by amination. At this time, the compounds (5) and (6) may be different or the same. The amine compound represented by the general formula (1) obtained from the reaction may have a single structure, but when the compound (5) and the compound (6) are different, they can be obtained as a mixture corresponding to them.
一般式(1)で表されるアミン化合物は、具体的には、以下に挙げるルートで製造することが出来る。
Specifically, the amine compound represented by the general formula (1) can be produced by the following route.
ルートA:化合物(3)、化合物(5)及び化合物(6)を混合し、反応させて化合物(1)を得るルート。 Route A: A route in which compound (3), compound (5) and compound (6) are mixed and reacted to obtain compound (1).
ルートB:化合物(3)と化合物(5)の反応生成物のうち、1対1で反応した成分を単離精製し、この単離生成物に化合物(6)を反応させて化合物(1)を得るルート。 Route B: Among the reaction products of the compound (3) and the compound (5), the components reacted in a one-to-one relationship are isolated and purified, and the compound (6) is reacted with the isolated product to react with the compound (1). Get route.
ルートC:化合物(3)と化合物(6)の反応生成物のうち、1対1で反応した成分を単離精製し、この単離生成物に化合物(5)を反応させて化合物(1)を得るルート。 Route C: Among the reaction products of the compound (3) and the compound (6), the components reacted in a one-to-one manner are isolated and purified, and the compound (5) is reacted with the isolated product to give the compound (1) Get route.
ルートD:化合物(3)と化合物(5)を反応させ、得られた生成物に、直接化合物(6)を反応させて化合物(1)を得るルート。 Route D: a route in which compound (3) and compound (5) are reacted, and the resulting product is directly reacted with compound (6) to obtain compound (1).
ルートE:化合物(3)と化合物(6)を反応させ、得られた生成物に、直接化合物(5)を反応させて化合物(1)を得るルート。 Route E: Route in which compound (3) and compound (6) are reacted, and the resulting product is directly reacted with compound (5) to obtain compound (1).
上記いずれかのルートで得られる最終生成物から、未反応原料及び不要副生物をカラムクロマトグラフィー等で除去することによって、本願発明である有機EL材料に適したアミン化合物(1)を得ることが出来る。 An amine compound (1) suitable for the organic EL material of the present invention can be obtained by removing unreacted raw materials and unnecessary by-products from the final product obtained by any one of the above routes by column chromatography or the like. I can do it.
化合物(5)と化合物(6)が同一の場合又はルートB若しくはルートCでアミノ化を行った場合、高純度の化合物(1)を得ることが出来る。一方、ルートA、ルートD又はルートEの場合、アミン化合物(1)は用いた原料化合物に対応した混合物となる。 When the compound (5) and the compound (6) are the same or when amination is performed by the route B or route C, the compound (1) with high purity can be obtained. On the other hand, in the case of Route A, Route D or Route E, the amine compound (1) is a mixture corresponding to the raw material compound used.
本アミノ化反応における化合物(5)及び(6)の使用量は、いずれも、化合物(3)1モルに対し1〜1.2倍モルが好ましい。 As for the usage-amount of the compounds (5) and (6) in this amination reaction, 1-1.2 times mole is preferable with respect to 1 mol of compound (3) all.
本アミノ化反応は、パラジウム化合物、トリアルキルホスフィン類及び塩基の存在下、有機溶媒中で実施することが出来る。 This amination reaction can be carried out in an organic solvent in the presence of a palladium compound, a trialkylphosphine and a base.
パラジウム化合物としては、特に限定されないが、具体例として、塩化パラジウム(II)、臭化パラジウム(II)、酢酸パラジウム(II)、パラジウム(II)アセチルアセトナート、ジクロロビス(ベンゾニトリル)パラジウム(II)、ジクロロビス(アセトニトリル)パラジウム(II)、ジクロロビス(トリフェニルホスフィン)パラジウム(II)、ジクロロテトラアンミンパラジウム(II)、ジクロロ(シクロオクタ−1,5−ジエン)パラジウム(II)、パラジウム(II)トリフルオロアセテート等の2価パラジウム化合物、トリス(ジベンジリデンアセトン)二パラジウム(0)、トリス(ジベンジリデンアセトン)二パラジウム(0)クロロホルム錯体、テトラキス(トリフェニルホスフィン)パラジウム(0)、パラジウム−カーボン等の0価パラジウム化合物を挙げることができる。これらのうち特に好ましくは、酢酸パラジウム(II)又はトリス(ジベンジリデンアセトン)二パラジウム(0)である。パラジウム化合物の使用量は、特に限定するものではないが、上記一般式(5)及び(6)で表されるアミンに対し、パラジウム換算で0.001〜10モル%であり、より好ましくは、パラジウム換算で0.005〜5モル%である。0.001〜10モル%の範囲であれば、十分な触媒活性が得られる上、経済的にも好ましい。 Although it does not specifically limit as a palladium compound, As a specific example, palladium chloride (II), palladium bromide (II), palladium acetate (II), palladium (II) acetylacetonate, dichlorobis (benzonitrile) palladium (II) , Dichlorobis (acetonitrile) palladium (II), dichlorobis (triphenylphosphine) palladium (II), dichlorotetraamminepalladium (II), dichloro (cycloocta-1,5-diene) palladium (II), palladium (II) trifluoroacetate Divalent palladium compounds such as tris (dibenzylideneacetone) dipalladium (0), tris (dibenzylideneacetone) dipalladium (0) chloroform complex, tetrakis (triphenylphosphine) palladium ( ), Palladium - can be mentioned 0-valent palladium compounds such as carbon. Of these, palladium (II) acetate or tris (dibenzylideneacetone) dipalladium (0) is particularly preferable. Although the usage-amount of a palladium compound is not specifically limited, It is 0.001-10 mol% in conversion of palladium with respect to the amine represented by the said General formula (5) and (6), More preferably, It is 0.005 to 5 mol% in terms of palladium. If it is in the range of 0.001 to 10 mol%, sufficient catalytic activity can be obtained and economically preferable.
また、パラジウムの配位子として使用されるトリアルキルホスフィン類の具体例としては、特に限定されないが、トリエチルホスフィン、トリ−n−ブチルホスフィン、n−ブチル−ジ(1−アダマンチル)ホスフィン、トリ−tert−ブチルホスフィン、トリシクロヘキシルホスフィンなどが挙げられるが、反応性の良さから特にトリ−tert−ブチルホスフィンが好適に用いられる。トリアルキルホスフィンの使用量は、特に限定されないが、パラジウム金属1モルに対し、0.5〜5倍モル、好ましくは1〜4倍モルの範囲が選ばれる。ここで、1〜4倍モルの範囲であれば、十分な触媒活性が得られる上、経済的にも好ましい。
本アミノ化反応において、使用される塩基としては、有機塩基及び無機塩基からなる群より選択することが出来る。具体例として、特に限定されないが、水素化ナトリウム、水素化カリウム、水素化リチウム、ナトリウムアミド、カリウムアミド、リチウムアミド、炭酸カリウム、炭酸ナトリウム、炭酸リチウム、炭酸ルビジウム、炭酸セシウム、炭酸水素カリウム、炭酸水素ナトリウム、ナトリウム金属、カリウム金属、リチウム金属、メトキシナトリウム、メトキシカリウム、エトキシナトリウム、エトキシカリウム、エトキシリチウム、tert−ブトキシリチウム、tert−ブトキシナトリウム、tert−ブトキシカリウム等が挙げられる。これらのうち、tert−ブトキシナトリウムが好適に用いられる。これらの塩基の使用量は、特に限定されないが、一般式(3)で表される化合物1モルに対し、1〜5倍モルである。
また、本アミノ化反応は、通常、反応溶媒中で実施される。反応溶媒は、反応を阻害しないものであれば特に限定されないが、具体例として、ベンゼン、トルエン、キシレン等の芳香族炭化水素溶媒、ジエチルエーテル、テトラヒドロフラン、ジオキサン等のエーテル溶媒、アセトニトリル、ジメチルホルムアミド、ジメチルスルホキシド、ヘキサメチルホスホトリアミド等が挙げられる。これらのうち、ベンゼン、トルエン、キシレン等の芳香族炭化水素溶媒が好適に用いられる。ここで、溶媒は、単一または混合溶媒として用いることも出来る。反応溶媒の使用量は、特に限定されないが、一般式(3)で表される化合物に対し、2〜20重量比である。
Specific examples of trialkylphosphines used as a ligand for palladium are not particularly limited, but include triethylphosphine, tri-n-butylphosphine, n-butyl-di (1-adamantyl) phosphine, tri- Examples thereof include tert-butylphosphine and tricyclohexylphosphine, and tri-tert-butylphosphine is particularly preferably used because of its good reactivity. Although the usage-amount of a trialkylphosphine is not specifically limited, The range of 0.5-5 times mole with respect to 1 mol of palladium metals, Preferably it is 1-4 times mole. Here, if it is the range of 1-4 times mole, sufficient catalyst activity will be obtained and it is economically preferable.
In this amination reaction, the base used can be selected from the group consisting of organic bases and inorganic bases. Specific examples include, but are not limited to, sodium hydride, potassium hydride, lithium hydride, sodium amide, potassium amide, lithium amide, potassium carbonate, sodium carbonate, lithium carbonate, rubidium carbonate, cesium carbonate, potassium bicarbonate, carbonate Sodium hydrogen, sodium metal, potassium metal, lithium metal, methoxy sodium, methoxy potassium, ethoxy sodium, ethoxy potassium, ethoxy lithium, tert-butoxy lithium, tert-butoxy sodium, tert-butoxy potassium and the like can be mentioned. Of these, tert-butoxy sodium is preferably used. Although the usage-amount of these bases is not specifically limited, It is 1-5 times mole with respect to 1 mol of compounds represented by General formula (3).
Moreover, this amination reaction is normally implemented in a reaction solvent. The reaction solvent is not particularly limited as long as it does not inhibit the reaction. Specific examples include aromatic hydrocarbon solvents such as benzene, toluene and xylene, ether solvents such as diethyl ether, tetrahydrofuran and dioxane, acetonitrile, dimethylformamide, Examples thereof include dimethyl sulfoxide and hexamethylphosphotriamide. Of these, aromatic hydrocarbon solvents such as benzene, toluene and xylene are preferably used. Here, the solvent may be used as a single solvent or a mixed solvent. Although the usage-amount of a reaction solvent is not specifically limited, It is 2-20 weight ratio with respect to the compound represented by General formula (3).
また本アミノ化反応は、通常、常圧下、窒素、アルゴン等の不活性ガス雰囲気下で実施されるが、加圧条件下で実施することも出来る。反応は、20〜300℃の温度範囲で実施されるが、より好ましくは50〜200℃の温度範囲である。 The amination reaction is usually carried out under normal pressure and an inert gas atmosphere such as nitrogen or argon, but can also be carried out under pressurized conditions. The reaction is carried out in the temperature range of 20 to 300 ° C, more preferably in the temperature range of 50 to 200 ° C.
反応時間は、反応温度、使用する上記化合物(3)、(5)、(6)及びパラジウム化合物の量により異なるため、特に限定されないが、例えば、数分〜72時間である。 The reaction time varies depending on the reaction temperature, the amount of the compounds (3), (5), (6) and the palladium compound used, and is not particularly limited, but is, for example, several minutes to 72 hours.
特に、前記一般式(1)で表されるアミン化合物は正孔輸送能に優れることから、正孔輸送層及び/又は正孔注入層として使用した際に、有機EL素子の低駆動電圧化、高発光効率化及び耐久性の向上を実現することができる。 In particular, since the amine compound represented by the general formula (1) is excellent in hole transport ability, when used as a hole transport layer and / or a hole injection layer, the driving voltage of the organic EL device is reduced, High luminous efficiency and improved durability can be realized.
前記一般式(1)で表されるアミン化合物を有機EL素子の正孔注入層及び/又は正孔輸送層として使用する際の発光層には、従来から使用されている公知の発光材料を使用することができる。発光層は1種類の発光材料のみで形成されていても、ホスト材料中に1種類以上の発光材料がドープされていてもよい。 For the light emitting layer when the amine compound represented by the general formula (1) is used as a hole injection layer and / or a hole transport layer of an organic EL device, a conventionally known light emitting material is used. can do. The light emitting layer may be formed of only one kind of light emitting material, or one or more kinds of light emitting materials may be doped in the host material.
近年、高い発光効率を実現できることから、発光材料として燐光材料を使用した有機EL素子が注目されているが、前記一般式(1)で表されるアミン化合物は燐光材料とも組み合わせて使用することができる。 In recent years, an organic EL element using a phosphorescent material as a light emitting material has attracted attention because it can realize high luminous efficiency. However, the amine compound represented by the general formula (1) may be used in combination with a phosphorescent material. it can.
前記一般式(1)で表されるアミン化合物からなる正孔注入層及び/又は正孔輸送層を形成する際には、必要に応じて2種類以上の材料を含有若しくは積層させてもよく、例えば、酸化モリブデン等の酸化物、7,7,8,8−テトラシアノキノジメタン、2,3,5,6−テトラフルオロ−7,7,8,8−テトラシアノキノジメタン、ヘキサシアノヘキサアザトリフェニレン等の公知の電子受容性材料を含有若しくは積層させてもよい。 When forming the hole injection layer and / or hole transport layer made of the amine compound represented by the general formula (1), two or more kinds of materials may be contained or laminated as necessary. For example, oxides such as molybdenum oxide, 7,7,8,8-tetracyanoquinodimethane, 2,3,5,6-tetrafluoro-7,7,8,8-tetracyanoquinodimethane, hexacyanohexahexa A known electron-accepting material such as azatriphenylene may be contained or laminated.
前記一般式(1)で表されるアミン化合物を有機EL素子の発光層として使用する場合には、アミン化合物を単独で使用、公知の発光ホスト材料にドープして使用、又は公知の蛍光若しくは燐光材料をドープして使用することができる。 When the amine compound represented by the general formula (1) is used as the light emitting layer of the organic EL device, the amine compound is used alone, doped into a known light emitting host material, or known fluorescent or phosphorescent. It can be used by doping the material.
前記一般式(1)で表されるアミン化合物を含有する正孔注入層、正孔輸送層又は発光層を形成する方法としては、例えば真空蒸着法、スピンコート法、キャスト法等の公知の方法を適用することができる。 As a method for forming a hole injection layer, a hole transport layer or a light emitting layer containing the amine compound represented by the general formula (1), for example, a known method such as a vacuum deposition method, a spin coating method, a casting method or the like Can be applied.
本発明による一般式(1)で表されるアミン化合物は、従来の材料以上に高い三重項準位を有するため、有機EL素子、特に燐光材料を用いた有機EL素子において高い外部量子効率を発現させることが可能となる。 Since the amine compound represented by the general formula (1) according to the present invention has a triplet level higher than that of conventional materials, it exhibits high external quantum efficiency in organic EL elements, particularly organic EL elements using phosphorescent materials. It becomes possible to make it.
以下、本発明を実施例に基づき、さらに詳細に説明するが、本発明はこれら実施例に何ら限定されるものではない。 EXAMPLES Hereinafter, although this invention is demonstrated further in detail based on an Example, this invention is not limited to these Examples at all.
なお、本実施例で用いた分析機器及び測定方法を以下に列記する。 The analytical instruments and measurement methods used in this example are listed below.
[材料純度測定(HPLC分析)]
測定装置:東ソー製 マルチステーションLC−8020
測定方法:カラム Inertsil ODS−3V(4.6mmΦ×250mm)
検出器 UV検出(波長 254nm)
溶離液 メタノール/テトラヒドロフラン=9/1(v/v比)
[燐光スペクトル測定]
測定装置:日本分光株式会社製 分光蛍光光度計FP−6500
[NMR測定]
測定装置:バリアン社製 Gemini200
[有機EL素子の電流−電圧特性及び発光特性]
測定装置:ケースレーインスツルメンツ社製 ソースメータ(2400)
TOPCON社製 輝度計LUMINANCE METER(BM−9)
[ガラス転移温度測定]
測定装置:マックサイエンス社製 DSC−3100
測定方法:窒素気流下、昇温速度10℃/分で測定
[Material purity measurement (HPLC analysis)]
Measuring device: Tosoh Multi Station LC-8020
Measuring method: Column Inertsil ODS-3V (4.6 mmΦ × 250 mm)
Detector UV detection (wavelength 254nm)
Eluent Methanol / Tetrahydrofuran = 9/1 (v / v ratio)
[Phosphorescence spectrum measurement]
Measuring device: JASCO Corporation spectrofluorimeter FP-6500
[NMR measurement]
Measuring device: Gemini200 manufactured by Varian
[Current-voltage characteristics and light emission characteristics of organic EL elements]
Measuring device: Keithley Instruments source meter (2400)
Luminance meter LUMINANCE METER (BM-9) made by TOPCON
[Glass transition temperature measurement]
Measuring device: DSC-3100 manufactured by Mac Science
Measuring method: Measured at a heating rate of 10 ° C / min under a nitrogen stream
窒素雰囲気下、攪拌装置を備えた1L3つ口フラスコ中に、1,3−インダンジオン 21.2g(144mmol)、アセトニトリル 250mL、フッ化カリウム 42.0g(723mmol)を加え、室温で10分間攪拌した。この溶液に、p−ブロモベンジルブロミド 72.6g(290mmol)をアセトニトリル 250mLに溶解させた溶液を、90分かけて滴下した。滴下終了後、さらに室温で7時間攪拌した。反応終了後、純水 600mLを添加し、室温で1時間攪拌した。析出した黄色粉末をろ取し、純水 500mLで洗浄した。さらに、得られた黄色粉末をエタノールで再結晶精製し、淡黄色粉末 62.1gを得た(収率 89%、純度 99.8%)。1H−NMR及び13C−NMR分析から、得られた淡黄色粉末は目的の化合物(B−1)であることを確認した。
1H−NMR(CDCl3)δ(ppm)=3.18(s 4H), 6.83〜6.87(d 4H),7.12〜7.16(d 4H), 7.56〜7.68(m 4H)
13C−NMR(CDCl3)δ(ppm)=40.69, 61.64, 120.90, 122.55, 131.17, 131.52, 134.08, 135.64, 142.45, 202.84
合成例2 化合物(B−2)の合成
窒素雰囲気下、攪拌装置を備えた1L3つ口フラスコ中に、化合物(B−1) 15.0g(31.0mmol)、テトラヒドロフラン 150mL、メタノール 150mLを加え、室温で10分間攪拌した。この溶液に、水素化ホウ素ナトリウム 8.8g(233mmol)を1時間かけてゆっくりと加え、さらに室温で1時間攪拌した。反応終了後、反応容器を0℃に冷却し、10%塩化水素水溶液 75mLをゆっくりと加えた。純水 250mLを添加し、ジクロロメタン 300mLで抽出した。得られた有機層を純水 500mL、次いで飽和食塩水で洗浄分液し、無水硫酸マグネシウムで乾燥した。その後、減圧濃縮して溶媒を留去し、黄色オイル 14.9gを得た(収率 99%、純度 99.6%)。得られた黄色オイルをイソプロパノール/テトラヒドロフランの混合溶液で再結晶し、白色結晶として一方のジアステレオマーを単離した。1H−NMR及び13C−NMR分析から、得られた白色結晶は目的の化合物(B−2)であることを確認した。
1 H-NMR (CDCl 3 ) δ (ppm) = 3.18 (s 4H), 6.83 to 6.87 (d 4H), 7.12 to 7.16 (d 4H), 7.56 to 7 .68 (m 4H)
13 C-NMR (CDCl 3 ) δ (ppm) = 40.69, 61.64, 120.90, 122.55, 131.17, 131.52, 134.08, 135.64, 142.45, 202 .84
Synthesis Example 2 Synthesis of Compound (B-2) In a 1 L three-necked flask equipped with a stirrer in a nitrogen atmosphere, 15.0 g (31.0 mmol) of compound (B-1), 150 mL of tetrahydrofuran, and 150 mL of methanol were added. Stir at room temperature for 10 minutes. To this solution, 8.8 g (233 mmol) of sodium borohydride was slowly added over 1 hour, and further stirred at room temperature for 1 hour. After completion of the reaction, the reaction vessel was cooled to 0 ° C., and 75 mL of 10% aqueous hydrogen chloride solution was slowly added. 250 mL of pure water was added and extracted with 300 mL of dichloromethane. The obtained organic layer was washed and separated with 500 mL of pure water and then with saturated brine, and dried over anhydrous magnesium sulfate. Thereafter, the solvent was distilled off under reduced pressure to obtain 14.9 g of a yellow oil (yield 99%, purity 99.6%). The resulting yellow oil was recrystallized with a mixed solution of isopropanol / tetrahydrofuran to isolate one diastereomer as white crystals. From the 1 H-NMR and 13 C-NMR analyses, it was confirmed that the obtained white crystals were the target compound (B-2).
1H−NMR(CDCl3)δ(ppm)=1.46〜1.49(d 2H), 2.89(s 4H), 5.10〜5.13(d 2H), 7.04〜7.35(m 12H)
13C−NMR(CDCl3)δ(ppm)=37.16, 55.91, 78.82, 120.11, 124.16, 128.79, 131.13, 132.16, 137.71, 142.80
実施例1 化合物(B−3)の合成
窒素雰囲気下、攪拌装置を備えた500mL3つ口フラスコ中に、硫酸 4.0g(41mmol)、ジクロロメタン 200mLを加え、室温で5分間攪拌した。この溶液に、化合物(B−2) 10g(29mmol)をジクロロメタン 70mLに溶解させた溶液を、1時間かけて滴下した。滴下終了後、さらに45℃で20時間攪拌した。反応終了後、純水 200mLを添加して洗浄分液した。さらに、飽和食塩水で洗浄分液した後、得られた有機層を減圧濃縮して溶媒を留去した。さらに、得られた残渣をシリカゲルカラムクロマトグラフィーで精製し、トルエンで再結晶することにより、白色固体 7.1gを得た(収率 77%、純度 99.9%)。1H−NMR及び13C−NMR分析から、得られた白色固体は目的の化合物(B−3)であることを確認した。
1 H-NMR (CDCl 3 ) δ (ppm) = 1.46 to 1.49 (d 2H), 2.89 (s 4H), 5.10 to 5.13 (d 2H), 7.04 to 7 .35 (m 12H)
13 C-NMR (CDCl 3 ) δ (ppm) = 37.16, 55.91, 78.82, 120.11, 124.16, 128.79, 131.13, 132.16, 137.71, 142 .80
Example 1 Synthesis of Compound (B-3) Under a nitrogen atmosphere, 4.0 g (41 mmol) of sulfuric acid and 200 mL of dichloromethane were added to a 500 mL three-necked flask equipped with a stirrer, and stirred at room temperature for 5 minutes. A solution prepared by dissolving 10 g (29 mmol) of the compound (B-2) in 70 mL of dichloromethane was added dropwise to this solution over 1 hour. After completion of dropping, the mixture was further stirred at 45 ° C. for 20 hours. After completion of the reaction, 200 mL of pure water was added and the solution was separated. Further, after washing and separating with saturated brine, the obtained organic layer was concentrated under reduced pressure to distill off the solvent. Furthermore, the obtained residue was purified by silica gel column chromatography and recrystallized from toluene to obtain 7.1 g of a white solid (yield 77%, purity 99.9%). From 1 H-NMR and 13 C-NMR analysis, it was confirmed that the obtained white solid was the target compound (B-3).
1H−NMR(CDCl3)δ(ppm)=3.03〜3.30(4H), 4.40(s 2H), 7.02〜7.06(d 2H), 7.19〜7.36(m 6H), 7.48(s 2H)
13C−NMR(CDCl3)δ(ppm)=43.71, 61.77, 63.73, 120.53, 124.56, 126.39, 127.77, 130.13, 141.37, 143.20, 145.95
実施例2 化合物(A−1)の合成
窒素雰囲気下、攪拌装置を備えた100mL4つ口フラスコ中に、化合物(B−3) 0.70g(1.5mmol)、ジフェニルアミン 0.58g(3.41mmol)、炭酸セシウム 1.51g(4.64mmol)、酢酸パラジウム(II) 7mg(0.03mmol)、トリ−tert−ブチルホスフィン 20mg(0.1mmol)、o−キシレン 10mLを加え、120℃で15時間攪拌した。反応終了後、純水 30mL、トルエン 30mLを添加して洗浄分液した。さらに、純水 30mL、次いで飽和食塩水で洗浄分液した後、得られた有機層を減圧濃縮して溶媒を留去した。さらに、得られた残渣をシリカゲルカラムクロマトグラフィーで精製し、白色固体 0.72gを得た(収率 74%、純度 99.6%)。1H−NMR及び13C−NMR分析から、得られた白色固体は目的の化合物(A−1)であることを確認した。DSC分析から、化合物(A−1)のガラス転移温度は120℃であった。
1 H-NMR (CDCl 3 ) δ (ppm) = 3.03 to 3.30 (4H), 4.40 (s 2H), 7.02 to 7.06 (d 2H), 7.19 to 7. 36 (m 6H), 7.48 (s 2H)
13 C-NMR (CDCl 3 ) δ (ppm) = 43.71, 61.77, 63.73, 120.53, 124.56, 126.39, 127.77, 130.13, 141.37, 143 .20, 145.95
Example 2 Synthesis of Compound (A-1) In a 100 mL four-necked flask equipped with a stirrer in a nitrogen atmosphere, 0.70 g (1.5 mmol) of compound (B-3), 0.58 g (3.41 mmol) of diphenylamine ), 1.51 g (4.64 mmol) of cesium carbonate, 7 mg (0.03 mmol) of palladium (II) acetate, 20 mg (0.1 mmol) of tri-tert-butylphosphine, and 10 mL of o-xylene, and added at 120 ° C. for 15 hours. Stir. After completion of the reaction, 30 mL of pure water and 30 mL of toluene were added to separate the solution. Furthermore, after washing and separating with 30 mL of pure water and then with saturated saline, the obtained organic layer was concentrated under reduced pressure to distill off the solvent. Furthermore, the obtained residue was purified by silica gel column chromatography to obtain 0.72 g of a white solid (yield 74%, purity 99.6%). From 1 H-NMR and 13 C-NMR analysis, it was confirmed that the obtained white solid was the target compound (A-1). From the DSC analysis, the glass transition temperature of the compound (A-1) was 120 ° C.
1H−NMR(CDCl3)δ(ppm)=3.09〜3.38(4H), 4.40(s 2H), 6.86〜7.26(m 30H)
13C−NMR(CDCl3)δ(ppm)=44.59, 62.50, 63.25, 120.99, 122.22, 123.65, 123.92, 124.38, 125.29, 127.20, 129.05, 137.42, 144.01, 145.14, 146.74, 148.00
実施例3 化合物(A−4)の合成
実施例2において、ジフェニルアミンの代わりにジ−p−トリルアミンを0.64g(3.24mmol)用いた以外は同様の実験操作を行って、白色固体を0.74g得た(収率 70%、純度 99.4%)。1H−NMR及び13C−NMR分析から、得られた白色固体は目的の化合物(A−4)であることを確認した。DSC分析から、化合物(A−4)のガラス転移温度は124℃であった。
1 H-NMR (CDCl 3 ) δ (ppm) = 3.09 to 3.38 (4H), 4.40 (s 2H), 6.86 to 7.26 (m 30H)
13 C-NMR (CDCl 3 ) δ (ppm) = 44.59, 62.50, 63.25, 120.99, 122.22, 123.65, 123.92, 124.38, 125.29, 127 .20, 129.05, 137.42, 144.01, 145.14, 146.74, 148.00
Example 3 Synthesis of Compound (A-4) In Example 2, the same experimental operation was performed except that 0.64 g (3.24 mmol) of di-p-tolylamine was used instead of diphenylamine, and a white solid was reduced to 0. 0.74 g was obtained (yield 70%, purity 99.4%). From 1 H-NMR and 13 C-NMR analysis, it was confirmed that the obtained white solid was the target compound (A-4). From the DSC analysis, the glass transition temperature of the compound (A-4) was 124 ° C.
1H−NMR(CDCl3)δ(ppm)=2.30(s 12H), 3.07〜3.36(4H), 4.38(s 2H), 6.80〜7.25(m 26H)
13C−NMR(CDCl3)δ(ppm)=20.88, 44.59, 62.54, 63.29, 119.95, 122.91, 123.86, 124.40, 125.09, 127.11, 129.65, 131.68, 136.52, 144.10, 144.96, 145.69, 147.14
実施例4 化合物(A−5)の合成
実施例2において、ジフェニルアミンの代わりにN−(4−ビフェニリル)アニリンを0.80g(3.24mmol)用いた以外は同様の実験操作を行って、白色粉末を0.98g得た(収率 84%、純度 99.2%)。1H−NMR及び13C−NMR分析から、得られた白色固体は目的の化合物(A−5)であることを確認した。DSC分析から、化合物(A−5)のガラス転移温度は136℃であった。
1 H-NMR (CDCl 3 ) δ (ppm) = 2.30 (s 12H), 3.07 to 3.36 (4H), 4.38 (s 2H), 6.80 to 7.25 (m 26H )
13 C-NMR (CDCl 3 ) δ (ppm) = 20.88, 44.59, 62.54, 63.29, 119.95, 122.91, 123.86, 124.40, 125.09, 127 .11, 129.65, 131.68, 136.52, 144.10, 144.96, 145.69, 147.14
Example 4 Synthesis of Compound (A-5)
In Example 2, the same experimental operation was performed except that 0.80 g (3.24 mmol) of N- (4-biphenylyl) aniline was used instead of diphenylamine, to obtain 0.98 g of white powder (yield 84). %, Purity 99.2%). From 1 H-NMR and 13 C-NMR analysis, it was confirmed that the obtained white solid was the target compound (A-5). From the DSC analysis, the glass transition temperature of compound (A-5) was 136 ° C.
1H−NMR(CDCl3)δ(ppm)=3.11〜3.40(4H), 4.42(s 2H), 6.91〜7.60(m 38H)
13C−NMR(CDCl3)δ(ppm)=44.63, 62.53, 63.29, 121.19, 122.53, 123.39, 123.97, 124.14, 124.43, 125.40, 126.57, 126.70, 127.27, 127.62, 128.70, 129.14, 134.63, 137.67, 140.66, 144.01, 145.22, 146.57, 147.34, 147.83
1 H-NMR (CDCl 3 ) δ (ppm) = 3.11 to 3.40 (4H), 4.42 (s 2H), 6.91 to 7.60 (m 38H)
13 C-NMR (CDCl 3 ) δ (ppm) = 44.63, 62.53, 63.29, 121.19, 122.53, 123.39, 123.97, 124.14, 124.43, 125 .40, 126.57, 126.70, 127.27, 127.62, 128.70, 129.14, 134.63, 137.67, 140.66, 144.01, 145.22, 146.57 , 147.34, 147.83
窒素雰囲気下、攪拌装置を備えた1L3つ口フラスコ中に、1,3−インダンジオン 14.7g(100mmol)、アセトニトリル 300mL、フッ化カリウム 29.2g(502mmol)を加え、室温で10分間攪拌した。この溶液に、o−ブロモベンジルブロミド 50.6g(202mmol)をアセトニトリル 120mLに溶解させた溶液を、40分かけて滴下した。滴下終了後、さらに室温で15時間攪拌した。反応終了後、純水 1000mLを添加し、室温で1時間攪拌した。析出した黄色粉末をろ取し、純水 500mLで洗浄した。さらに、得られた黄色粉末をエタノールで再結晶精製し、淡肌色粉末 42.3gを得た(収率 87%、純度 99.9%)。1H−NMR及び13C−NMR分析から、得られた淡黄色粉末は目的の化合物(C−1)であることを確認した。
1H−NMR(CDCl3)δ(ppm)=3.51(s 4H), 6.87〜7.09(m 4H),7.39〜7.43(4H), 7.64〜7.82(m 4H)
13C−NMR(CDCl3)δ(ppm)=39.67, 59.92, 122.97, 125.66, 126.92, 128.42, 131.32, 133.13, 135.22, 135.40, 142.14, 201.56
合成例4 化合物(C−2)の合成
窒素雰囲気下、攪拌装置を備えた1L3つ口フラスコ中に、化合物(C−1) 42.2g(87.2mmol)、テトラヒドロフラン 230mL、メタノール 230mLを加え、室温で10分間攪拌した。この溶液に、水素化ホウ素ナトリウム 16.5g(436mmol)を1時間30分かけてゆっくりと加え、さらに室温で1時間攪拌した。反応終了後、反応容器を0℃に冷却し、10%塩化水素水溶液 100mLをゆっくりと加えた。純水 150mLを添加し、ジクロロメタン 300mLで抽出した。得られた有機層を純水 300mL、次いで飽和食塩水で洗浄分液し、無水硫酸マグネシウムで乾燥した。その後、減圧濃縮して溶媒を留去し、白色粉末 42.4gを得た(収率 99%、純度 99.5%)。1H−NMR及び13C−NMR分析から、得られた白色粉末は目的の化合物(C−2)であることを確認した。
1 H-NMR (CDCl 3 ) δ (ppm) = 3.51 (s 4H), 6.87 to 7.09 (m 4H), 7.39 to 7.43 (4H), 7.64 to 7. 82 (m 4H)
13 C-NMR (CDCl 3 ) δ (ppm) = 39.67, 59.92, 122.97, 125.66, 126.92, 128.42, 131.32, 133.13, 135.22, 135 .40, 142.14, 201.56
Synthesis Example 4 Synthesis of Compound (C-2) In a 1 L three-necked flask equipped with a stirrer under a nitrogen atmosphere, 42.2 g (87.2 mmol) of Compound (C-1), 230 mL of tetrahydrofuran, and 230 mL of methanol were added. Stir at room temperature for 10 minutes. To this solution, 16.5 g (436 mmol) of sodium borohydride was slowly added over 1 hour 30 minutes, and further stirred at room temperature for 1 hour. After completion of the reaction, the reaction vessel was cooled to 0 ° C., and 100 mL of 10% aqueous hydrogen chloride solution was slowly added. 150 mL of pure water was added and extracted with 300 mL of dichloromethane. The obtained organic layer was washed and separated with 300 mL of pure water and then with saturated brine, and dried over anhydrous magnesium sulfate. Thereafter, the solvent was distilled off under reduced pressure to obtain 42.4 g of a white powder (yield 99%, purity 99.5%). From 1 H-NMR and 13 C-NMR analysis, it was confirmed that the obtained white powder was the target compound (C-2).
1H−NMR(CDCl3)δ(ppm)=2.15〜2.18(d 2H), 3.21〜3.39(4H), 5.34〜5.36(d 2H), 6.86〜7.07(m 8H), 7.34〜7.44(m 4H)
13C−NMR(CDCl3)δ(ppm)=36.66, 58.36, 78.38, 123.68, 125.75, 126.78, 127.42, 128.30, 132.54, 133.00, 138.64, 143.29
実施例5 化合物(C−3)の合成
窒素雰囲気下、攪拌装置を備えた1L3つ口フラスコ中に、硫酸 29.8g(304mmol)、ジクロロメタン 400mLを加え、室温で10分間攪拌した。この溶液に、化合物(C−2) 42.4g(86.8mmol)をジクロロメタン 220mLに溶解させた溶液を、1時間30分かけて滴下した。滴下終了後、さらに45℃で17時間攪拌した。反応終了後、蒸留水 400mLを添加して洗浄分液した。さらに、飽和食塩水で洗浄分液した後、得られた有機層を減圧濃縮して溶媒を留去した。さらに、得られた残渣をシリカゲルカラムクロマトグラフィーで精製し、トルエンで再結晶することにより、白色粉末 11.0gを得た(収率 28%、純度 99.9%)。1H−NMR及び13C−NMR分析から、得られた白色固体は目的の化合物(C−3)であることを確認した。
1 H-NMR (CDCl 3 ) δ (ppm) = 2.15 to 2.18 (d 2H), 3.21 to 3.39 (4H), 5.34 to 5.36 (d 2H), 86-7.07 (m 8H), 7.34-7.44 (m 4H)
13 C-NMR (CDCl 3 ) δ (ppm) = 36.66, 58.36, 78.38, 123.68, 125.75, 126.78, 127.42, 128.30, 132.54, 133 .00, 138.64, 143.29
Example 5 Synthesis of Compound (C-3) In a nitrogen atmosphere, 29.8 g (304 mmol) of sulfuric acid and 400 mL of dichloromethane were added to a 1 L three-necked flask equipped with a stirrer and stirred at room temperature for 10 minutes. A solution prepared by dissolving 42.4 g (86.8 mmol) of compound (C-2) in 220 mL of dichloromethane was added dropwise to this solution over 1 hour and 30 minutes. After completion of dropping, the mixture was further stirred at 45 ° C. for 17 hours. After completion of the reaction, 400 mL of distilled water was added and the solution was separated. Further, after washing and separating with saturated brine, the obtained organic layer was concentrated under reduced pressure to distill off the solvent. Furthermore, the obtained residue was purified by silica gel column chromatography and recrystallized from toluene to obtain 11.0 g of a white powder (yield 28%, purity 99.9%). From 1 H-NMR and 13 C-NMR analysis, it was confirmed that the obtained white solid was the target compound (C-3).
1H−NMR(CDCl3)δ(ppm)=3.17〜3.44(4H), 4.58(s 2H), 7.04〜7.36(m 10H)
13C−NMR(CDCl3)δ(ppm)=46.04, 60.76, 63.31, 120.11, 123.39, 124.45, 127.64, 128.75, 130.18, 142.73, 143.48, 145.47
実施例6 化合物(A−21)の合成
窒素雰囲気下、攪拌装置を備えた100mL4つ口フラスコ中に、化合物(C−3) 2.00g(4.42mmol)、ジフェニルアミン 1.57g(9.38mmol)、ナトリウム−tert−ブトキシド 1.02g(10.6mmol)、酢酸パラジウム(II) 20mg(0.089mmol)、トリ−tert−ブチルホスフィン 70mg(0.35mmol)、o−キシレン 30mLを加え、120℃で3時間攪拌した。反応終了後、蒸留水 50mL、トルエン 50mLを添加して洗浄分液した。さらに、純水 50mL、次いで飽和食塩水で洗浄分液した後、得られた有機層を減圧濃縮して溶媒を留去した。さらに、得られた残渣をシリカゲルカラムクロマトグラフィーで精製し、白色粉末 2.34gを得た(収率 84%、純度 98.7%)。1H−NMR及び13C−NMR分析から、得られた白色固体は目的の化合物(A−21)であることを確認した。DSC分析から、化合物(A−21)のガラス転移温度は113℃であった。
1 H-NMR (CDCl 3 ) δ (ppm) = 3.17 to 3.44 (4H), 4.58 (s 2H), 7.04 to 7.36 (m 10H)
13 C-NMR (CDCl 3 ) δ (ppm) = 46.04, 60.76, 63.31, 120.11, 123.39, 124.45, 127.64, 128.75, 130.18, 142 .73, 143.48, 145.47
Example 6 Synthesis of Compound (A-21) In a 100 mL four-necked flask equipped with a stirrer under a nitrogen atmosphere, 2.00 g (4.42 mmol) of compound (C-3), 1.57 g (9.38 mmol) of diphenylamine. ), Sodium tert-butoxide 1.02 g (10.6 mmol), palladium acetate (II) 20 mg (0.089 mmol), tri-tert-butylphosphine 70 mg (0.35 mmol), o-xylene 30 mL, and 120 ° C. For 3 hours. After completion of the reaction, 50 mL of distilled water and 50 mL of toluene were added to separate the solution. Further, after washing and separating with 50 mL of pure water and then with saturated saline, the obtained organic layer was concentrated under reduced pressure to distill off the solvent. Furthermore, the obtained residue was purified by silica gel column chromatography to obtain 2.34 g of a white powder (yield 84%, purity 98.7%). From 1 H-NMR and 13 C-NMR analysis, it was confirmed that the obtained white solid was the target compound (A-21). From the DSC analysis, the glass transition temperature of the compound (A-21) was 113 ° C.
1H−NMR(CDCl3)δ(ppm)=2.27〜2.83(4H), 4.30(s 2H), 6.89〜7.41(m 30H)
13C−NMR(CDCl3)δ(ppm)=42.87, 62.06, 62.39, 121.06, 121.80, 122.38, 124.54, 125.73, 127.27, 128.28, 128.97, 139.25, 143.20, 143.95, 145.99, 147.14
実施例7 化合物(A−22)の合成
実施例6において、ジフェニルアミンの代わりにジ−p−トリルアミンを1.76g(8.92mmol)用いた以外は同様の実験操作を行って、白色粉末を2.70g得た(収率 97%、純度 98.8%)。1H−NMR及び13C−NMR分析から、得られた白色固体は目的の化合物(A−22)であることを確認した。DSC分析から、化合物(A−22)のガラス転移温度は117℃であった。
1 H-NMR (CDCl 3 ) δ (ppm) = 2.27 to 2.83 (4H), 4.30 (s 2H), 6.89 to 7.41 (m 30H)
13 C-NMR (CDCl 3 ) δ (ppm) = 42.87, 62.06, 62.39, 121.06, 121.80, 122.38, 124.54, 125.73, 127.27, 128 .28, 128.97, 139.25, 143.20, 143.95, 145.99, 147.14
Example 7 Synthesis of Compound (A-22) In Example 6, the same experimental operation was carried out except that 1.76 g (8.92 mmol) of di-p-tolylamine was used instead of diphenylamine. .70 g was obtained (yield 97%, purity 98.8%). From 1 H-NMR and 13 C-NMR analysis, it was confirmed that the obtained white solid was the target compound (A-22). From the DSC analysis, the glass transition temperature of compound (A-22) was 117 ° C.
1H−NMR(CDCl3)δ(ppm)=2.26(s 12H), 2.38〜2.84(4H), 4.30(s 2H), 6.77〜7.39(m 26H)
13C−NMR(CDCl3)δ(ppm)=20.88, 42.95, 62.15, 62.45, 120.55, 122.51, 124.54, 125.31, 127.22, 128.13, 129.52, 131.06, 138.90, 143.53, 144.14, 145.03, 145.95
実施例8 化合物(A−26)の合成
実施例6において、ジフェニルアミンの代わりにp−メトキシフェニルフェニルアミンを1.78g(8.93mmol)用いた以外は同様の実験操作を行って、白色粉末を2.98g得た(収率 98%、純度 99.6%)。1H−NMR及び13C−NMR分析から、得られた白色固体は目的の化合物(A−26)であることを確認した。DSC分析から、化合物(A−26)のガラス転移温度は102℃であった。
1 H-NMR (CDCl 3 ) δ (ppm) = 2.26 (s 12H), 2.38 to 2.84 (4H), 4.30 (s 2H), 6.77 to 7.39 (m 26H )
13 C-NMR (CDCl 3 ) δ (ppm) = 20.88, 42.95, 62.15, 62.45, 120.55, 122.51, 124.54, 125.31, 127.22, 128 .13, 129.52, 131.06, 138.90, 143.53, 144.14, 145.03, 145.95
Example 8 Synthesis of Compound (A-26) A white powder was prepared in the same manner as in Example 6, except that 1.78 g (8.93 mmol) of p-methoxyphenylphenylamine was used instead of diphenylamine. 2.98 g was obtained (yield 98%, purity 99.6%). From 1 H-NMR and 13 C-NMR analysis, it was confirmed that the obtained white solid was the target compound (A-26). From the DSC analysis, the glass transition temperature of the compound (A-26) was 102 ° C.
1H−NMR(CDCl3)δ(ppm)=2.35〜2.85(4H), 3.78(s 6H),4.31(s 2H), 6.73〜7.40(m 28H)
13C−NMR(CDCl3)δ(ppm)=43.07, 55.51, 62.14, 62.32, 114.43, 120.61, 124.52, 125.13, 125.66, 127.22, 128.15, 128.85, 138.68, 140.38, 143.49, 144.03, 145.93, 147.78, 155.40
実施例9 化合物(A−27)の合成
実施例6において、ジフェニルアミンの代わりにジ−p−メトキシフェニルアミンを2.05g(8.94mmol)用いた以外は同様の実験操作を行って、白色粉末を2.32g得た(収率 70%、純度 99.1%)。1H−NMR及び13C−NMR分析から、得られた白色固体は目的の化合物(A−27)であることを確認した。DSC分析から、化合物(A−27)のガラス転移温度は105℃であった。
1 H-NMR (CDCl 3 ) δ (ppm) = 2.35 to 2.85 (4H), 3.78 (s 6H), 4.31 (s 2H), 6.73 to 7.40 (m 28H )
13 C-NMR (CDCl 3 ) δ (ppm) = 43.07, 55.51, 62.14, 62.32, 114.43, 120.61, 124.52, 125.13, 125.66, 127 .22, 128.15, 128.85, 138.68, 140.38, 143.49, 144.03, 145.93, 147.78, 155.40
Example 9 Synthesis of Compound (A-27)
In Example 6, the same experimental operation was performed except that 2.05 g (8.94 mmol) of di-p-methoxyphenylamine was used instead of diphenylamine, to obtain 2.32 g of a white powder (yield 70%). , Purity 99.1%). From 1 H-NMR and 13 C-NMR analysis, it was confirmed that the obtained white solid was the target compound (A-27). From the DSC analysis, the glass transition temperature of compound (A-27) was 105 ° C.
1H−NMR(CDCl3)δ(ppm)=2.38〜2.81(4H), 3.76(s 12H),4.28(s 2H), 6.70〜7.39(m 26H)
13C−NMR(CDCl3)δ(ppm)=43.28, 55.53, 62.23, 114.31, 119.78, 124.12, 124.49, 127.12, 127.97, 137.78, 141.39, 144.12, 145.95, 154.63
1 H-NMR (CDCl 3 ) δ (ppm) = 2.38 to 2.81 (4H), 3.76 (s 12H), 4.28 (s 2H), 6.70 to 7.39 (m 26H )
13 C-NMR (CDCl 3 ) δ (ppm) = 43.28, 55.53, 62.23, 114.31, 119.78, 124.12, 124.49, 127.12, 127.97, 137 78, 141.39, 144.12, 145.95, 154.63
窒素雰囲気下、攪拌装置を備えた500mL4つ口フラスコ中に、3−クロロ−2−メチル安息香酸 8.12g(47.6mmol)、テトラヒドロフラン 100mLを加え、反応容器を−78℃に冷却した。この溶液に、リチウムアルミニウムヒドリド溶液 100mL(アルドリッチ製 1.0Mテトラヒドロフラン溶液)を30分かけて滴下した。滴下終了後、−78℃で1時間攪拌し、さらに室温に戻して5時間攪拌した。反応終了後、反応容器を0℃に冷却し、3.5%塩化水素水溶液を注意深く滴下した。純水 300mLを添加し、トルエン 500mLで抽出した。得られた有機層を飽和食塩水で洗浄分液し、無水硫酸マグネシウムで乾燥した。その後、減圧濃縮して溶媒を留去し、白色粉末 6.92gを得た(収率 93%、純度 95.5%)。1H−NMR及び13C−NMR分析から、得られた淡黄色粉末は目的の化合物(D−1)であることを確認した。
1H−NMR(CDCl3)δ(ppm)=2.30(s 1H), 2.44(s 3H), 4.75(s 2H), 7.15〜7.41(m 3H)
13C−NMR(CDCl3)δ(ppm)=15.35, 63.78, 125.97, 126.68, 128.64, 134.08, 135.03, 140.46
合成例6 化合物(D−2)の合成
窒素雰囲気下、攪拌装置を備えた500mL4つ口フラスコ中に、化合物(D−1) 6.82g(43.5mmol)、トリフェニルホスフィン 12.6g(47.9mmol)、ジエチルエーテル 40mLを加え、室温で5分間攪拌した。この溶液に、四臭化炭素 15.2g(45.7mmol)をジエチルエーテル 20mLに溶解させた溶液を20分かけて滴下し、さらに室温で1時間攪拌した。反応終了後、反応液をろ過した。得られたろ液をシリカゲルカラムクロマトグラフィーで精製した。更に減圧蒸留して低沸不純物を除去し、無色透明オイル 7.93gを得た(収率 83%、純度 97.1%)。1H−NMR及び13C−NMR分析から、得られた無色透明オイルは目的の化合物(D−2)であることを確認した。
1 H-NMR (CDCl 3 ) δ (ppm) = 2.30 (s 1H), 2.44 (s 3H), 4.75 (s 2H), 7.15 to 7.41 (m 3H)
13 C-NMR (CDCl 3 ) δ (ppm) = 15.35, 63.78, 125.97, 126.68, 128.64, 134.08, 135.03, 140.46
Synthesis Example 6 Synthesis of Compound (D-2) In a 500 mL four-necked flask equipped with a stirrer in a nitrogen atmosphere, compound (D-1) 6.82 g (43.5 mmol), triphenylphosphine 12.6 g (47) 0.9 mmol) and diethyl ether (40 mL) were added, and the mixture was stirred at room temperature for 5 minutes. To this solution, a solution of 15.2 g (45.7 mmol) of carbon tetrabromide dissolved in 20 mL of diethyl ether was added dropwise over 20 minutes, and the mixture was further stirred at room temperature for 1 hour. After completion of the reaction, the reaction solution was filtered. The obtained filtrate was purified by silica gel column chromatography. Further, low-boiling impurities were removed by distillation under reduced pressure to obtain 7.93 g of a colorless transparent oil (yield 83%, purity 97.1%). From the 1 H-NMR and 13 C-NMR analyses, it was confirmed that the obtained colorless transparent oil was the target compound (D-2).
1H−NMR(CDCl3)δ(ppm)=2.44(s 3H), 4.50(s 2H), 7.05〜7.35(m 3H)
13C−NMR(CDCl3)δ(ppm)=15.79, 32.32, 126.89, 128.44, 129.80, 135.36, 135.49, 137.62
合成例7 化合物(D−3)の合成
窒素雰囲気下、攪拌装置を備えた300mL3つ口フラスコ中に、1,3−インダンジオン 2.40g(16.4mmol)、アセトニトリル 40mL、フッ化カリウム 4.77g(82.1mmol)を加え、室温で10分間攪拌した。この溶液に、化合物(D−2) 7.93g(36.1mmol)をアセトニトリル 30mLに溶解させた溶液を、15分かけて滴下した。滴下終了後、さらに室温で15時間攪拌した。反応終了後、純水 200mLを添加し、室温で1時間攪拌した。析出した黄色粉末をろ取し、純水 100mLで洗浄した。さらに、得られた黄色粉末をエタノールで再結晶精製し、肌色粉末 5.40gを得た(収率 78%、純度 97.0%)。この肌色粉末を、化合物(D−3)として次工程(合成例8)へ用いた。
1 H-NMR (CDCl 3 ) δ (ppm) = 2.44 (s 3H), 4.50 (s 2H), 7.05 to 7.35 (m 3H)
13 C-NMR (CDCl 3 ) δ (ppm) = 15.79, 32.32, 126.89, 128.44, 129.80, 135.36, 135.49, 137.62
Synthesis Example 7 Synthesis of Compound (D-3) In a 300 mL three-neck flask equipped with a stirrer under a nitrogen atmosphere, 2.40 g (16.4 mmol) of 1,3-indandione, 40 mL of acetonitrile, potassium fluoride 4. 77 g (82.1 mmol) was added and stirred at room temperature for 10 minutes. To this solution, a solution prepared by dissolving 7.93 g (36.1 mmol) of compound (D-2) in 30 mL of acetonitrile was dropped over 15 minutes. After completion of dropping, the mixture was further stirred at room temperature for 15 hours. After completion of the reaction, 200 mL of pure water was added and stirred at room temperature for 1 hour. The precipitated yellow powder was collected by filtration and washed with 100 mL of pure water. Furthermore, the obtained yellow powder was recrystallized and purified with ethanol to obtain 5.40 g of a flesh-colored powder (yield 78%, purity 97.0%). This skin color powder was used as the compound (D-3) in the next step (Synthesis Example 8).
合成例8 化合物(D−4)の合成
窒素雰囲気下、攪拌装置を備えた300mL4つ口フラスコ中に、化合物(D−3) 4.3g(10.2mmol)、テトラヒドロフラン 35mL、メタノール 35mLを加え、反応容器を0℃に冷却した。この溶液に、水素化ホウ素ナトリウム 3.92g(104mmol)を1時間30分かけてゆっくりと加え、さらに室温で1時間攪拌し、HPLC分析にて原料消失を確認した。反応容器を0℃に冷却し、10%塩化水素水溶液 30mLをゆっくりと加えた。純水 50mLを添加し、ジクロロメタン 120mLで抽出した。得られた有機層を純水 100mL、次いで飽和食塩水で洗浄分液し、無水硫酸マグネシウムで乾燥した。その後、減圧濃縮して溶媒を留去し、淡桃色粉末 4.35gを得た(収率 99%、純度 96.0%)。この淡桃色粉末を、化合物(D−4)として次工程(実施例10)へ用いた。
Synthesis Example 8 Synthesis of Compound (D-4) In a 300 mL four-necked flask equipped with a stirrer in a nitrogen atmosphere, 4.3 g (10.2 mmol) of Compound (D-3), 35 mL of tetrahydrofuran, and 35 mL of methanol were added. The reaction vessel was cooled to 0 ° C. To this solution, 3.92 g (104 mmol) of sodium borohydride was slowly added over 1 hour and 30 minutes, further stirred at room temperature for 1 hour, and disappearance of raw materials was confirmed by HPLC analysis. The reaction vessel was cooled to 0 ° C., and 30 mL of 10% aqueous hydrogen chloride solution was slowly added. 50 mL of pure water was added and extracted with 120 mL of dichloromethane. The obtained organic layer was washed and separated with 100 mL of pure water and then with saturated brine, and dried over anhydrous magnesium sulfate. Then, it concentrated under reduced pressure and the solvent was distilled off and 4.35g of pale pink powder was obtained (yield 99%, purity 96.0%). This pale pink powder was used as the compound (D-4) in the next step (Example 10).
実施例10 化合物(D−5)の合成
窒素雰囲気下、攪拌装置を備えた300mL3つ口フラスコ中に、硫酸 3.0g(31mmol)、ジクロロメタン 100mLを加え、室温で10分間攪拌した。この溶液に、化合物(D−4) 4.35g(10.1mmol)をジクロロメタン 10mLに溶解させた溶液を、20分かけて滴下した。滴下終了後、さらに45℃で15時間攪拌した。反応終了後、純水 150mL ジクロロメタン100mLを添加して洗浄分液した。さらに、飽和食塩水で洗浄分液した後、得られた有機層を減圧濃縮して溶媒を留去した。さらに、得られた残渣をシリカゲルカラムクロマトグラフィーで精製し、トルエンで再結晶することにより、淡黄色結晶 1.26gを得た(収率 32%、純度 99.0%)。1H−NMR及び13C−NMR分析から、得られた淡黄色結晶は目的の化合物(D−5)であることを確認した。
Example 10 Synthesis of Compound (D-5) In a 300 mL three-necked flask equipped with a stirrer under a nitrogen atmosphere, 3.0 g (31 mmol) of sulfuric acid and 100 mL of dichloromethane were added and stirred at room temperature for 10 minutes. A solution prepared by dissolving 4.35 g (10.1 mmol) of the compound (D-4) in 10 mL of dichloromethane was added dropwise to this solution over 20 minutes. After completion of dropping, the mixture was further stirred at 45 ° C. for 15 hours. After completion of the reaction, 150 mL of pure water and 100 mL of dichloromethane were added and washed to separate. Further, after washing and separating with saturated brine, the obtained organic layer was concentrated under reduced pressure to distill off the solvent. Furthermore, the obtained residue was purified by silica gel column chromatography and recrystallized from toluene to obtain 1.26 g of pale yellow crystals (yield 32%, purity 99.0%). From the 1 H-NMR and 13 C-NMR analyses, it was confirmed that the obtained pale yellow crystals were the target compound (D-5).
1H−NMR(CDCl3)δ(ppm)=2.26(s 6H), 3.09〜3.38(4H), 4.44(s 2H), 7.12〜7.34(m 8H)
13C−NMR(CDCl3)δ(ppm)=16.69, 44.32, 62.32, 62.67, 122.69, 124.34, 127.47, 127.84, 132.11, 132.91, 142.03, 143.15, 143.64
実施例11 化合物(A−34)の合成
窒素雰囲気下、攪拌装置を備えた100mL4つ口フラスコ中に、化合物(D−5) 0.61g(1.56mmol)、ジ−p−トリルアミン 0.63g(3.19mmol)、ナトリウム−tert−ブトキシド 0.36g(3.74mmol)、酢酸パラジウム(II) 7mg(0.031mmol)、トリ−tert−ブチルホスフィン 25mg(0.12mmol)、o−キシレン 15mLを加え、120℃で15時間攪拌した。反応終了後、純水 30mL、トルエン 15mLを添加して洗浄分液した。さらに、純水 30mL、次いで飽和食塩水で洗浄分液した後、得られた有機層を減圧濃縮して溶媒を留去した。さらに、得られた残渣をシリカゲルカラムクロマトグラフィーで精製し、白色粉末 0.86gを得た(収率 77%、純度 99.0%)。1H−NMR及び13C−NMR分析から、得られた白色粉末は目的の化合物(A−34)であることを確認した。DSC分析から、化合物(A−34)のガラス転移温度は147℃であった。
1 H-NMR (CDCl 3 ) δ (ppm) = 2.26 (s 6H), 3.09 to 3.38 (4H), 4.44 (s 2H), 7.12 to 7.34 (m 8H )
13 C-NMR (CDCl 3 ) δ (ppm) = 16.69, 44.32, 62.32, 62.67, 122.69, 124.34, 127.47, 127.84, 132.11, 132 .91, 142.03, 143.15, 143.64
Example 11 Synthesis of Compound (A-34) In a 100 mL four-necked flask equipped with a stirrer under a nitrogen atmosphere, 0.61 g (1.56 mmol) of compound (D-5), 0.63 g of di-p-tolylamine (3.19 mmol), sodium tert-butoxide 0.36 g (3.74 mmol), palladium (II) acetate 7 mg (0.031 mmol), tri-tert-butylphosphine 25 mg (0.12 mmol), o-xylene 15 mL. In addition, the mixture was stirred at 120 ° C. for 15 hours. After completion of the reaction, 30 mL of pure water and 15 mL of toluene were added to separate the solution. Furthermore, after washing and separating with 30 mL of pure water and then with saturated saline, the obtained organic layer was concentrated under reduced pressure to distill off the solvent. Furthermore, the obtained residue was purified by silica gel column chromatography to obtain 0.86 g of white powder (yield 77%, purity 99.0%). From 1 H-NMR and 13 C-NMR analysis, it was confirmed that the obtained white powder was the target compound (A-34). From the DSC analysis, the glass transition temperature of compound (A-34) was 147 ° C.
1H−NMR(CDCl3)δ(ppm)=1.93(s 6H), 2.26(s 12H), 3.08〜3.39(4H), 4.52(s 2H), 6.81〜7.42(m 24H)
13C−NMR(CDCl3)δ(ppm)=15.22, 20.75, 44.80, 62.45, 62.85, 121.34, 122.69, 124.51, 127.25, 128.31, 129.45, 130.26, 132.38, 140.99, 143.46, 144.41, 144.45, 145.51
1 H-NMR (CDCl 3 ) δ (ppm) = 1.93 (s 6H), 2.26 (s 12H), 3.08 to 3.39 (4H), 4.52 (s 2H), 81 to 7.42 (m 24H)
13 C-NMR (CDCl 3 ) δ (ppm) = 15.22, 20.75, 44.80, 62.45, 62.85, 121.34, 122.69, 124.51, 127.25, 128 .31, 129.45, 130.26, 132.38, 140.99, 143.46, 144.41, 144.45, 145.51
窒素雰囲気下、攪拌装置を備えた500mL4つ口フラスコ中に、5−クロロ−2−メチル安息香酸 8.12g(47.6mmol)、テトラヒドロフラン 100mLを加え、反応容器を−78℃に冷却した。この溶液に、リチウムアルミニウムヒドリド溶液 100mL(アルドリッチ製 1.0Mテトラヒドロフラン溶液)を30分かけて滴下した。滴下終了後、−78℃で1時間攪拌し、さらに室温に戻して5時間攪拌した。反応終了後、反応容器を0℃に冷却し、3.5%塩化水素水溶液を注意深く滴下した。純水 300mLを添加し、トルエン 500mLで抽出した。得られた有機層を飽和食塩水で洗浄分液し、無水硫酸マグネシウムで乾燥した。その後、減圧濃縮して溶媒を留去し、淡黄色オイル 7.30gを得た(収率 98%、純度 98.3%)。この淡黄色オイルを化合物(E−1)として次工程(合成例10)に用いた。
合成例10 化合物(E−2)の合成
窒素雰囲気下、攪拌装置を備えた500mL4つ口フラスコ中に、化合物(E−1) 7.30g(46.6mmol)、トリフェニルホスフィン 13.5g(51.5mmol)、ジエチルエーテル 70mLを加え、室温で5分間攪拌した。この溶液に、四臭化炭素 16.2g(48.8mmol)をジエチルエーテル 20mLに溶解させた溶液を20分かけて滴下し、さらに室温で1時間攪拌した。反応終了後、反応液をろ過した。得られたろ液をシリカゲルカラムクロマトグラフィーで精製した。更に減圧蒸留して低沸不純物を除去し、淡黄色オイル 10.0gを得た(収率 98%、純度 98.8%)。1H−NMR及び13C−NMR分析から、得られた淡黄色オイルは目的の化合物(E−2)であることを確認した。
Synthesis Example 10 Synthesis of Compound (E-2) In a 500 mL four-necked flask equipped with a stirrer in a nitrogen atmosphere, 7.30 g (46.6 mmol) of compound (E-1), 13.5 g of triphenylphosphine (51 0.5 mmol) and 70 mL of diethyl ether were added and stirred at room temperature for 5 minutes. To this solution, a solution of 16.2 g (48.8 mmol) of carbon tetrabromide dissolved in 20 mL of diethyl ether was added dropwise over 20 minutes, and the mixture was further stirred at room temperature for 1 hour. After completion of the reaction, the reaction solution was filtered. The obtained filtrate was purified by silica gel column chromatography. Further, low-boiling impurities were removed by distillation under reduced pressure to obtain 10.0 g of a pale yellow oil (yield 98%, purity 98.8%). From the 1 H-NMR and 13 C-NMR analyses, it was confirmed that the obtained pale yellow oil was the target compound (E-2).
1H−NMR(CDCl3)δ(ppm)=2.37(s 3H), 4.43(s 2H), 7.08〜7.30(m 3H)
13C−NMR(CDCl3)δ(ppm)=18.33, 31.12, 128.79, 129.69, 131.63, 132.03, 135.53, 137.32
合成例11 化合物(E−3)の合成
窒素雰囲気下、攪拌装置を備えた300mL3つ口フラスコ中に、1,3−インダンジオン 2.90g(19.8mmol)、アセトニトリル 100mL、フッ化カリウム 5.80g(100mmol)を加え、室温で10分間攪拌した。この溶液に、化合物(E−2) 9.13g(41.6mmol)をアセトニトリル 10mLに溶解させた溶液を、15分かけて滴下した。滴下終了後、さらに室温で15時間攪拌した。反応終了後、純水 200mLを添加し、室温で1時間攪拌した。析出した肌色粉末をろ取し、純水 100mLで洗浄した。さらに、得られた肌色粉末をエタノールで再結晶精製し、白色粉末 4.90gを得た(収率 58%、純度 95.3%)。この白色粉末を化合物(E−3)として次工程(合成例12)に用いた。
1 H-NMR (CDCl 3 ) δ (ppm) = 2.37 (s 3H), 4.43 (s 2H), 7.08 to 7.30 (m 3H)
13 C-NMR (CDCl 3 ) δ (ppm) = 18.33, 31.12, 128.79, 129.69, 131.63, 132.03, 135.53, 137.32.
Synthesis Example 11 Synthesis of Compound (E-3) In a 300 mL three-necked flask equipped with a stirrer under a nitrogen atmosphere, 2.90 g (19.8 mmol) of 1,3-indandione, 100 mL of acetonitrile, potassium fluoride 5. 80 g (100 mmol) was added and stirred at room temperature for 10 minutes. A solution prepared by dissolving 9.13 g (41.6 mmol) of compound (E-2) in 10 mL of acetonitrile was added dropwise to this solution over 15 minutes. After completion of dropping, the mixture was further stirred at room temperature for 15 hours. After completion of the reaction, 200 mL of pure water was added and stirred at room temperature for 1 hour. The precipitated flesh-colored powder was collected by filtration and washed with 100 mL of pure water. Furthermore, the obtained flesh-colored powder was recrystallized and purified with ethanol to obtain 4.90 g of a white powder (yield 58%, purity 95.3%). This white powder was used as the compound (E-3) in the next step (Synthesis Example 12).
合成例12 化合物(E−4)の合成
窒素雰囲気下、攪拌装置を備えた300mL4つ口フラスコ中に、化合物(E−3) 4.90g(11.6mmol)、テトラヒドロフラン 40mL、メタノール 40mLを加え、反応容器を0℃に冷却した。この溶液に、水素化ホウ素ナトリウム 3.20g(84.6mmol)を1時間30分かけてゆっくりと加え、さらに室温で1時間攪拌し、HPLC分析にて原料消失を確認した。反応容器を0℃に冷却し、10%塩化水素水溶液 30mLをゆっくりと加えた。純水 50mLを添加し、ジクロロメタン 150mLで抽出した。得られた有機層を純水 100mL、次いで飽和食塩水で洗浄分液し、無水硫酸マグネシウムで乾燥した。その後、減圧濃縮して溶媒を留去し、白色粉末 4.94gを得た(収率 99%、純度 96.4%)。この白色粉末を化合物(E−4)として次工程(実施例12)に用いた。
Synthesis Example 12 Synthesis of Compound (E-4) In a 300 mL four-necked flask equipped with a stirrer in a nitrogen atmosphere, 4.90 g (11.6 mmol) of compound (E-3), 40 mL of tetrahydrofuran, and 40 mL of methanol were added. The reaction vessel was cooled to 0 ° C. To this solution, 3.20 g (84.6 mmol) of sodium borohydride was slowly added over 1 hour and 30 minutes, and further stirred at room temperature for 1 hour, and disappearance of raw materials was confirmed by HPLC analysis. The reaction vessel was cooled to 0 ° C., and 30 mL of 10% aqueous hydrogen chloride solution was slowly added. 50 mL of pure water was added and extracted with 150 mL of dichloromethane. The obtained organic layer was washed and separated with 100 mL of pure water and then with saturated brine, and dried over anhydrous magnesium sulfate. Then, it concentrated under reduced pressure and the solvent was distilled off and 4.94g of white powder was obtained (yield 99%, purity 96.4%). This white powder was used as the compound (E-4) in the next step (Example 12).
実施例12 化合物(E−5)の合成
窒素雰囲気下、攪拌装置を備えた200mL3つ口フラスコ中に、硫酸 5.69g(58.0mmol)、ジクロロメタン 120mLを加え、室温で10分間攪拌した。この溶液に、化合物(E−4) 4.94g(11.6mmol)をジクロロメタン 10mLに溶解させた溶液を、20分かけて滴下した。滴下終了後、さらに45℃で15時間攪拌した。反応終了後、純水 150mL ジクロロメタン100mLを添加して洗浄分液した。さらに、飽和食塩水で洗浄分液した後、得られた有機層を減圧濃縮して溶媒を留去した。さらに、得られた残渣をシリカゲルカラムクロマトグラフィーで精製し、トルエンで再結晶することにより、白色結晶 0.77gを得た(収率 17%、純度 99.9%)。1H−NMR及び13C−NMR分析から、得られた白色結晶は目的の化合物(E−5)であることを確認した。
Example 12 Synthesis of Compound (E-5) In a nitrogen atmosphere, 5.69 g (58.0 mmol) of sulfuric acid and 120 mL of dichloromethane were added to a 200 mL three-necked flask equipped with a stirrer, and the mixture was stirred at room temperature for 10 minutes. A solution prepared by dissolving 4.94 g (11.6 mmol) of the compound (E-4) in 10 mL of dichloromethane was added dropwise to this solution over 20 minutes. After completion of dropping, the mixture was further stirred at 45 ° C. for 15 hours. After completion of the reaction, 150 mL of pure water and 100 mL of dichloromethane were added and washed to separate. Further, after washing and separating with saturated brine, the obtained organic layer was concentrated under reduced pressure to distill off the solvent. Furthermore, the obtained residue was purified by silica gel column chromatography and recrystallized from toluene to obtain 0.77 g of white crystals (yield 17%, purity 99.9%). From the 1 H-NMR and 13 C-NMR analysis, it was confirmed that the obtained white crystals were the target compound (E-5).
1H−NMR(CDCl3)δ(ppm)=2.19(s 6H), 2.92〜3.30(4H), 4.67(s 2H), 6.93〜7.20(m 6H), 7.68〜7.73(m 2H)
13C−NMR(CDCl3)δ(ppm)=18.85, 42.67, 61.59, 62.83, 126.98, 127.03, 127.73, 128.66, 129.50, 132.71, 140.73, 142.82, 143.90
実施例13 化合物(A−38)の合成
窒素雰囲気下、攪拌装置を備えた100mL4つ口フラスコ中に、化合物(E−5) 0.61g(1.56mmol)、ジ−p−トリルアミン 0.63g(3.19mmol)、ナトリウム−tert−ブトキシド 0.36g(3.74mmol)、酢酸パラジウム(II) 7mg(0.031mmol)、トリ−tert−ブチルホスフィン 25mg(0.12mmol)、o−キシレン 15mLを加え、120℃で15時間攪拌した。反応終了後、純水 30mL、トルエン 15mLを添加して洗浄分液した。さらに、純水 30mL、次いで飽和食塩水で洗浄分液した後、得られた有機層を減圧濃縮して溶媒を留去した。さらに、得られた残渣をシリカゲルカラムクロマトグラフィーで精製し、白色粉末 0.59gを得た(収率 53%、純度 99.8%)。1H−NMR及び13C−NMR分析から、得られた白色粉末は目的の化合物(A−38)であることを確認した。DSC分析から、化合物(A−38)のガラス転移温度は149℃であった。
1 H-NMR (CDCl 3 ) δ (ppm) = 2.19 (s 6H), 2.92 to 3.30 (4H), 4.67 (s 2H), 6.93 to 7.20 (m 6H ), 7.68-7.73 (m 2H)
13 C-NMR (CDCl 3 ) δ (ppm) = 18.85, 42.67, 61.59, 62.83, 126.98, 127.03, 127.73, 128.66, 129.50, 132 .71, 140.73, 142.82, 143.90
Example 13 Synthesis of Compound (A-38) In a 100 mL four-necked flask equipped with a stirrer under a nitrogen atmosphere, 0.61 g (1.56 mmol) of compound (E-5), 0.63 g of di-p-tolylamine (3.19 mmol), sodium tert-butoxide 0.36 g (3.74 mmol), palladium (II) acetate 7 mg (0.031 mmol), tri-tert-butylphosphine 25 mg (0.12 mmol), o-xylene 15 mL. In addition, the mixture was stirred at 120 ° C. for 15 hours. After completion of the reaction, 30 mL of pure water and 15 mL of toluene were added to separate the solution. Furthermore, after washing and separating with 30 mL of pure water and then with saturated saline, the obtained organic layer was concentrated under reduced pressure to distill off the solvent. Furthermore, the obtained residue was purified by silica gel column chromatography to obtain 0.59 g of a white powder (yield 53%, purity 99.8%). From the 1 H-NMR and 13 C-NMR analyses, it was confirmed that the obtained white powder was the target compound (A-38). From the DSC analysis, the glass transition temperature of compound (A-38) was 149 ° C.
1H−NMR(CDCl3)δ(ppm)=2.11(s 6H), 2.26(s 12H), 2.79〜3.00(4H), 3.90(s 2H), 6.71〜7.00(m 22H), 7.38〜7.42(m 2H)
13C−NMR(CDCl3)δ(ppm)=18.74, 20.77, 43.22, 61.15, 61.29, 122.25, 125.71, 125.93, 126.78, 129.21, 129.49, 130.04, 130.86, 139.76, 142.14, 143.79, 143.88, 145.11
実施例14 化合物(A−1)の三重項準位の測定
サンプルチューブ内で、化合物(A−1) 1mgと2−メチルテトラヒドロフラン 1mLをよく混合し、均一な溶液を調製した。この溶液をアルゴンガスで10分間バブリングすることによって脱気した後、このサンプルチューブを密栓することにより燐光スペクトル測定用サンプルとした。温度77K(液体窒素冷却下)で燐光スペクトルを測定したところ、得られた燐光スペクトルから算出された化合物(A−1)の三重項準位は、2.95eVであった。
1 H-NMR (CDCl 3 ) δ (ppm) = 2.11 (s 6H), 2.26 (s 12H), 2.79 to 3.00 (4H), 3.90 (s 2H), 71-7.00 (m 22H), 7.38-7.42 (m 2H)
13 C-NMR (CDCl 3 ) δ (ppm) = 18.74, 20.77, 43.22, 61.15, 61.29, 122.25, 125.71, 125.93, 126.78, 129 .21, 129.49, 130.04, 130.86, 139.76, 142.14, 143.79, 143.88, 145.11.
Example 14 Measurement of Triplet Level of Compound (A-1) In a sample tube, 1 mg of compound (A-1) and 1 mL of 2-methyltetrahydrofuran were mixed well to prepare a uniform solution. This solution was deaerated by bubbling with argon gas for 10 minutes, and then the sample tube was sealed to obtain a sample for phosphorescence spectrum measurement. When a phosphorescence spectrum was measured at a temperature of 77 K (under liquid nitrogen cooling), the triplet level of the compound (A-1) calculated from the obtained phosphorescence spectrum was 2.95 eV.
実施例15 化合物(A−4)の三重項準位の測定
実施例14において、化合物(A−1)の代わりに化合物(A−4)を用いた以外は同様の実験操作を行って燐光スペクトルを測定したところ、得られた燐光スペクトルから算出された化合物(A−4)の三重項準位は、2.93eVであった。
Example 15 Measurement of Triplet Level of Compound (A-4) A phosphorescence spectrum was obtained in the same manner as in Example 14 except that compound (A-4) was used instead of compound (A-1). Was measured, and the triplet level of the compound (A-4) calculated from the obtained phosphorescence spectrum was 2.93 eV.
実施例16 化合物(A−21)の三重項準位の測定
実施例14において、化合物(A−1)の代わりに化合物(A−21)を用いた以外は同様の実験操作を行って燐光スペクトルを測定したところ、得られた燐光スペクトルから算出された化合物(A−21)の三重項準位は、2.95eVであった。
Example 16 Measurement of Triplet Level of Compound (A-21) A phosphorescence spectrum was obtained by performing the same experimental procedure as in Example 14, except that compound (A-21) was used instead of compound (A-1). Was measured, and the triplet level of the compound (A-21) calculated from the obtained phosphorescence spectrum was 2.95 eV.
実施例17 化合物(A−22)の三重項準位の測定
実施例14において、化合物(A−1)の代わりに化合物(A−22)を用いた以外は同様の実験操作を行って燐光スペクトルを測定したところ、得られた燐光スペクトルから算出された化合物(A−22)の三重項準位は、2.94eVであった。
Example 17 Measurement of Triplet Level of Compound (A-22) A phosphorescence spectrum was obtained in the same manner as in Example 14 except that compound (A-22) was used instead of compound (A-1). Was measured, and the triplet level of the compound (A-22) calculated from the obtained phosphorescence spectrum was 2.94 eV.
実施例18 化合物(A−34)の三重項準位の測定
実施例14において、化合物(A−1)の代わりに化合物(A−34)を用いた以外は同様の実験操作を行って燐光スペクトルを測定したところ、得られた燐光スペクトルから算出された化合物(A−34)の三重項準位は、2.96eVであった。
Example 18 Measurement of Triplet Level of Compound (A-34) A phosphorescence spectrum was obtained in the same manner as in Example 14 except that compound (A-34) was used instead of compound (A-1). Was measured, and the triplet level of the compound (A-34) calculated from the obtained phosphorescence spectrum was 2.96 eV.
実施例19 化合物(A−38)の三重項準位の測定
実施例14において、化合物(A−1)の代わりに化合物(A−38)を用いた以外は同様の実験操作を行って燐光スペクトルを測定したところ、得られた燐光スペクトルから算出された化合物(A−38)の三重項準位は、2.93eVであった。
Example 19 Measurement of Triplet Level of Compound (A-38) A phosphorescence spectrum was obtained in the same manner as in Example 14 except that compound (A-38) was used instead of compound (A-1). Was measured, and the triplet level of the compound (A-38) calculated from the obtained phosphorescence spectrum was 2.93 eV.
実施例20 化合物(A−1)の素子評価
厚さ200nmのITO透明電極を積層したガラス基板を、アセトン及び純水による超音波洗浄、イソプロピルアルコールによる煮沸洗浄した後、乾燥した。さらに、UV/オゾン処理を行い、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。まず、ITO透明電極上にα−NPDを蒸着速度0.3nm/秒で蒸着し、20nmの正孔注入層とした。次に、化合物(A−1)を蒸着速度0.3nm/秒で蒸着し、30nmの正孔輸送層とした。次に、燐光ドーパント材料であるトリス(2−フェニルピリジン)イリジウム(Ir(ppy)3)とホスト材料である4,4’−ビス(N−カルバゾリル)ビフェニル(CBP)を重量比が1:11.5となるように蒸着速度0.25nm/秒で共蒸着し、20nmの発光層とした。次に、2,9−ジメチル−4,7−ジフェニル−1,10−フェナントロリン(BCP)を蒸着速度0.3nm/秒で蒸着し、10nmのエキシトシンブロック層とした。次に、トリス(8−キノリノラート)アルミニウム錯体を蒸着速度0.3nm/秒で蒸着し、30nmの電子輸送層とした。さらに、電子注入層としてフッ化リチウムを蒸着速度0.01nm/秒で0.5nm蒸着し、最後にアルミニウムを蒸着速度0.25nm/秒で100nm蒸着して陰極を形成した。窒素雰囲気下、封止用のガラス板をUV硬化樹脂で接着し、評価用の有機EL素子とした。このようにして得られた素子に、20mA/cm2の電流を印加し、駆動電圧及び外部量子効率を測定した。結果を表1に示す。
Example 20 Device Evaluation of Compound (A-1) A glass substrate on which an ITO transparent electrode having a thickness of 200 nm was laminated was subjected to ultrasonic cleaning with acetone and pure water and boiling cleaning with isopropyl alcohol, and then dried. Further, UV / ozone treatment was performed, and after evacuation with a vacuum pump until it was 1 × 10 −4 Pa after installation in a vacuum deposition apparatus. First, α-NPD was deposited on the ITO transparent electrode at a deposition rate of 0.3 nm / second to form a 20 nm hole injection layer. Next, the compound (A-1) was deposited at a deposition rate of 0.3 nm / second to form a 30 nm hole transport layer. Next, tris (2-phenylpyridine) iridium (Ir (ppy) 3 ) that is a phosphorescent dopant material and 4,4′-bis (N-carbazolyl) biphenyl (CBP) that is a host material have a weight ratio of 1:11. Co-deposited at a deposition rate of 0.25 nm / second to obtain a 20 nm light emitting layer. Next, 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline (BCP) was vapor-deposited at a vapor deposition rate of 0.3 nm / second to form a 10 nm excitocin block layer. Next, a tris (8-quinolinolato) aluminum complex was vapor-deposited at a vapor deposition rate of 0.3 nm / second to form a 30-nm electron transport layer. Further, lithium fluoride was deposited as an electron injection layer to a thickness of 0.5 nm at a deposition rate of 0.01 nm / second, and finally aluminum was deposited to a thickness of 100 nm at a deposition rate of 0.25 nm / second to form a cathode. In a nitrogen atmosphere, a sealing glass plate was bonded with a UV curable resin to obtain an organic EL element for evaluation. A current of 20 mA / cm 2 was applied to the device thus obtained, and driving voltage and external quantum efficiency were measured. The results are shown in Table 1.
実施例21 化合物(A−4)の素子評価
実施例20において、化合物(A−1)の代わりに化合物(A−4)を用いた以外は同様の実験操作を行って、有機EL素子を作製した。20mA/cm2の電流を印加し、駆動電圧及び外部量子効率を測定した。結果を表1に示す。
Example 21 Element Evaluation of Compound (A-4) In Example 20, an organic EL element was produced by performing the same experimental operation except that the compound (A-4) was used instead of the compound (A-1). did. A current of 20 mA / cm 2 was applied, and driving voltage and external quantum efficiency were measured. The results are shown in Table 1.
実施例22 化合物(A−22)の素子評価
実施例20において、化合物(A−1)の代わりに化合物(A−22)を用いた以外は同様の実験操作を行って、有機EL素子を作製した。20mA/cm2の電流を印加し、駆動電圧及び外部量子効率を測定した。結果を表1に示す。
Example 22 Device Evaluation of Compound (A-22) An organic EL device was produced in the same manner as in Example 20 except that compound (A-22) was used instead of compound (A-1). did. A current of 20 mA / cm 2 was applied, and driving voltage and external quantum efficiency were measured. The results are shown in Table 1.
実施例23 化合物(A−34)の素子評価
実施例20において、化合物(A−1)の代わりに化合物(A−34)を用いた以外は同様の実験操作を行って、有機EL素子を作製した。20mA/cm2の電流を印加し、駆動電圧及び外部量子効率を測定した。結果を表1に示す。
Example 23 Device Evaluation of Compound (A-34) An organic EL device was produced in the same manner as in Example 20 except that the compound (A-34) was used instead of the compound (A-1). did. A current of 20 mA / cm 2 was applied, and driving voltage and external quantum efficiency were measured. The results are shown in Table 1.
実施例24 化合物(A−38)の素子評価
実施例20において、化合物(A−1)の代わりに化合物(A−38)を用いた以外は同様の実験操作を行って、有機EL素子を作製した。20mA/cm2の電流を印加し、駆動電圧及び外部量子効率を測定した。結果を表1に示す。
Example 24 Device Evaluation of Compound (A-38) An organic EL device was produced in the same manner as in Example 20 except that the compound (A-38) was used instead of the compound (A-1). did. A current of 20 mA / cm 2 was applied, and driving voltage and external quantum efficiency were measured. The results are shown in Table 1.
比較例1 α−NPDの素子評価
実施例20において、化合物(A−1)の代わりにα−NPDを用いた以外は同様の実験操作を行って、有機EL素子を作製した。20mA/cm2の電流を印加し、駆動電圧及び外部量子効率を測定した。結果を表1に示す。
Comparative Example 1 Element Evaluation of α-NPD In Example 20, the same experimental operation was performed except that α-NPD was used instead of the compound (A-1), and an organic EL element was produced. A current of 20 mA / cm 2 was applied, and driving voltage and external quantum efficiency were measured. The results are shown in Table 1.
本発明のアミン化合物は、有機EL素子の正孔注入材料、正孔輸送材料又は発光層のホスト材料として利用可能であり、従来の材料以上に高い三重項準位を有するため、特に燐光材料を用いた有機EL素子において極めて有用な材料となることが期待される。さらには、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への分野にも応用可能である。 The amine compound of the present invention can be used as a hole injection material, a hole transport material or a light emitting layer host material of an organic EL device, and has a higher triplet level than a conventional material. It is expected to be an extremely useful material in the organic EL element used. Furthermore, 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 to an organic photoconductive material such as a photoelectric conversion element, a solar cell, and an image sensor. Applicable.
Claims (4)
数1〜18の直鎖、分岐若しくは環状のアルキル基、又は炭素数1〜18の直鎖、分岐若しくは環状のアルコキシ基を表す。なお、R3とR5はお互いに結合して環を形成しても良い。X1及びX2は各々独立して塩素原子、臭素原子、ヨウ素原子、又はトリフルオロメタンスルホニルオキシ基を表す。) A triquinane compound represented by the general formula (3).
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