CN116406530A - Organic light emitting device - Google Patents
Organic light emitting device Download PDFInfo
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- CN116406530A CN116406530A CN202280007495.3A CN202280007495A CN116406530A CN 116406530 A CN116406530 A CN 116406530A CN 202280007495 A CN202280007495 A CN 202280007495A CN 116406530 A CN116406530 A CN 116406530A
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- 150000001875 compounds Chemical class 0.000 claims description 985
- -1 dibenzofuranyl Chemical group 0.000 claims description 198
- UJOBWOGCFQCDNV-UHFFFAOYSA-N 9H-carbazole Chemical compound C1=CC=C2C3=CC=CC=C3NC2=C1 UJOBWOGCFQCDNV-UHFFFAOYSA-N 0.000 claims description 106
- 229910052805 deuterium Inorganic materials 0.000 claims description 45
- 239000000126 substance Substances 0.000 claims description 44
- YZCKVEUIGOORGS-OUBTZVSYSA-N Deuterium Chemical compound [2H] YZCKVEUIGOORGS-OUBTZVSYSA-N 0.000 claims description 42
- 125000003118 aryl group Chemical group 0.000 claims description 30
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 claims description 30
- 125000001072 heteroaryl group Chemical group 0.000 claims description 25
- 229910052760 oxygen Inorganic materials 0.000 claims description 19
- 125000001997 phenyl group Chemical class [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 18
- 229910052717 sulfur Inorganic materials 0.000 claims description 18
- 235000010290 biphenyl Nutrition 0.000 claims description 15
- 125000001624 naphthyl group Chemical group 0.000 claims description 15
- 125000005561 phenanthryl group Chemical group 0.000 claims description 15
- 239000004305 biphenyl Substances 0.000 claims description 14
- YJTKZCDBKVTVBY-UHFFFAOYSA-N 1,3-Diphenylbenzene Chemical group C1=CC=CC=C1C1=CC=CC(C=2C=CC=CC=2)=C1 YJTKZCDBKVTVBY-UHFFFAOYSA-N 0.000 claims description 13
- SLGBZMMZGDRARJ-UHFFFAOYSA-N Triphenylene Natural products C1=CC=C2C3=CC=CC=C3C3=CC=CC=C3C2=C1 SLGBZMMZGDRARJ-UHFFFAOYSA-N 0.000 claims description 10
- 125000000732 arylene group Chemical group 0.000 claims description 10
- 125000004988 dibenzothienyl group Chemical group C1(=CC=CC=2SC3=C(C21)C=CC=C3)* 0.000 claims description 10
- 125000003914 fluoranthenyl group Chemical group C1(=CC=C2C=CC=C3C4=CC=CC=C4C1=C23)* 0.000 claims description 10
- 125000005580 triphenylene group Chemical group 0.000 claims description 10
- 229910052739 hydrogen Inorganic materials 0.000 claims description 9
- 239000001257 hydrogen Substances 0.000 claims description 9
- 125000005878 benzonaphthofuranyl group Chemical group 0.000 claims description 8
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 7
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 7
- 125000005549 heteroarylene group Chemical group 0.000 claims description 4
- 150000003254 radicals Chemical class 0.000 claims description 4
- 125000005509 dibenzothiophenyl group Chemical group 0.000 claims description 3
- 125000003392 indanyl group Chemical group C1(CCC2=CC=CC=C12)* 0.000 claims description 3
- FBTOLQFRGURPJH-UHFFFAOYSA-N 1-phenyl-9h-carbazole Chemical compound C1=CC=CC=C1C1=CC=CC2=C1NC1=CC=CC=C12 FBTOLQFRGURPJH-UHFFFAOYSA-N 0.000 claims description 2
- 125000005605 benzo group Chemical group 0.000 claims description 2
- 150000002431 hydrogen Chemical group 0.000 claims description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 564
- 239000012044 organic layer Substances 0.000 description 516
- 239000000203 mixture Substances 0.000 description 507
- MXQOYLRVSVOCQT-UHFFFAOYSA-N palladium;tritert-butylphosphane Chemical compound [Pd].CC(C)(C)P(C(C)(C)C)C(C)(C)C.CC(C)(C)P(C(C)(C)C)C(C)(C)C MXQOYLRVSVOCQT-UHFFFAOYSA-N 0.000 description 475
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 382
- 238000006243 chemical reaction Methods 0.000 description 301
- 238000010898 silica gel chromatography Methods 0.000 description 283
- MFRIHAYPQRLWNB-UHFFFAOYSA-N sodium tert-butoxide Chemical compound [Na+].CC(C)(C)[O-] MFRIHAYPQRLWNB-UHFFFAOYSA-N 0.000 description 280
- 239000011541 reaction mixture Substances 0.000 description 271
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 269
- 239000000706 filtrate Substances 0.000 description 269
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 236
- 239000010410 layer Substances 0.000 description 218
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 204
- 230000015572 biosynthetic process Effects 0.000 description 158
- 238000003786 synthesis reaction Methods 0.000 description 158
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 142
- 239000002904 solvent Substances 0.000 description 142
- 239000008096 xylene Substances 0.000 description 142
- 229910052757 nitrogen Inorganic materials 0.000 description 119
- 229910000027 potassium carbonate Inorganic materials 0.000 description 102
- PBKONEOXTCPAFI-UHFFFAOYSA-N 1,2,4-trichlorobenzene Chemical compound ClC1=CC=C(Cl)C(Cl)=C1 PBKONEOXTCPAFI-UHFFFAOYSA-N 0.000 description 81
- XLYOFNOQVPJJNP-ZSJDYOACSA-N Heavy water Chemical compound [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 56
- WJKHJLXJJJATHN-UHFFFAOYSA-N triflic anhydride Chemical compound FC(F)(F)S(=O)(=O)OS(=O)(=O)C(F)(F)F WJKHJLXJJJATHN-UHFFFAOYSA-N 0.000 description 56
- YLQBMQCUIZJEEH-UHFFFAOYSA-N Furan Chemical compound C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 52
- 239000000243 solution Substances 0.000 description 33
- 239000000463 material Substances 0.000 description 29
- 239000011259 mixed solution Substances 0.000 description 27
- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical compound [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 description 26
- ZADPBFCGQRWHPN-UHFFFAOYSA-N boronic acid Chemical compound OBO ZADPBFCGQRWHPN-UHFFFAOYSA-N 0.000 description 24
- 238000002347 injection Methods 0.000 description 22
- 239000007924 injection Substances 0.000 description 22
- 238000005406 washing Methods 0.000 description 20
- 239000012299 nitrogen atmosphere Substances 0.000 description 19
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 18
- 229910052799 carbon Inorganic materials 0.000 description 18
- 230000000903 blocking effect Effects 0.000 description 16
- 239000011368 organic material Substances 0.000 description 15
- 238000010992 reflux Methods 0.000 description 15
- 125000001424 substituent group Chemical group 0.000 description 15
- UKSZBOKPHAQOMP-SVLSSHOZSA-N (1e,4e)-1,5-diphenylpenta-1,4-dien-3-one;palladium Chemical compound [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 UKSZBOKPHAQOMP-SVLSSHOZSA-N 0.000 description 14
- 150000001335 aliphatic alkanes Chemical class 0.000 description 14
- IPWKHHSGDUIRAH-UHFFFAOYSA-N bis(pinacolato)diboron Chemical compound O1C(C)(C)C(C)(C)OB1B1OC(C)(C)C(C)(C)O1 IPWKHHSGDUIRAH-UHFFFAOYSA-N 0.000 description 14
- HXITXNWTGFUOAU-UHFFFAOYSA-N phenylboronic acid Chemical compound OB(O)C1=CC=CC=C1 HXITXNWTGFUOAU-UHFFFAOYSA-N 0.000 description 14
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 description 14
- 230000032258 transport Effects 0.000 description 14
- WLPUWLXVBWGYMZ-UHFFFAOYSA-N tricyclohexylphosphine Chemical compound C1CCCCC1P(C1CCCCC1)C1CCCCC1 WLPUWLXVBWGYMZ-UHFFFAOYSA-N 0.000 description 14
- 239000000284 extract Substances 0.000 description 13
- 235000011056 potassium acetate Nutrition 0.000 description 13
- KPTRDYONBVUWPD-UHFFFAOYSA-N naphthalen-2-ylboronic acid Chemical compound C1=CC=CC2=CC(B(O)O)=CC=C21 KPTRDYONBVUWPD-UHFFFAOYSA-N 0.000 description 10
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 9
- 125000000217 alkyl group Chemical group 0.000 description 9
- JOFBTOVNZIUWPX-UHFFFAOYSA-N dibenzofuran-1-ylboronic acid Chemical compound O1C2=CC=CC=C2C2=C1C=CC=C2B(O)O JOFBTOVNZIUWPX-UHFFFAOYSA-N 0.000 description 8
- 230000005525 hole transport Effects 0.000 description 8
- 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 8
- 125000003342 alkenyl group Chemical group 0.000 description 7
- 125000000753 cycloalkyl group Chemical group 0.000 description 7
- 150000004982 aromatic amines Chemical class 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- 238000002360 preparation method Methods 0.000 description 6
- 238000006467 substitution reaction Methods 0.000 description 6
- 239000000758 substrate Substances 0.000 description 6
- HXITXNWTGFUOAU-RALIUCGRSA-N (2,3,4,5,6-pentadeuteriophenyl)boronic acid Chemical compound [2H]C1=C([2H])C([2H])=C(B(O)O)C([2H])=C1[2H] HXITXNWTGFUOAU-RALIUCGRSA-N 0.000 description 5
- 239000010406 cathode material Substances 0.000 description 5
- 239000002019 doping agent Substances 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 4
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 229910052782 aluminium Inorganic materials 0.000 description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 4
- 239000010405 anode material Substances 0.000 description 4
- 125000004432 carbon atom Chemical group C* 0.000 description 4
- 125000004185 ester group Chemical group 0.000 description 4
- IJHUAXLYGCBSEO-UHFFFAOYSA-N 1-bromo-4-chloro-2-phenylbenzene Chemical group ClC1=CC=C(Br)C(C=2C=CC=CC=2)=C1 IJHUAXLYGCBSEO-UHFFFAOYSA-N 0.000 description 3
- NHDODQWIKUYWMW-UHFFFAOYSA-N 1-bromo-4-chlorobenzene Chemical compound ClC1=CC=C(Br)C=C1 NHDODQWIKUYWMW-UHFFFAOYSA-N 0.000 description 3
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 3
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 description 3
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 3
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 3
- 125000002877 alkyl aryl group Chemical group 0.000 description 3
- 229910045601 alloy Inorganic materials 0.000 description 3
- 239000000956 alloy Substances 0.000 description 3
- 125000003710 aryl alkyl group Chemical group 0.000 description 3
- 125000001769 aryl amino group Chemical group 0.000 description 3
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 3
- 229910052794 bromium Inorganic materials 0.000 description 3
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 3
- 239000000460 chlorine Substances 0.000 description 3
- 229910052801 chlorine Inorganic materials 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 229920001940 conductive polymer Polymers 0.000 description 3
- 150000001975 deuterium Chemical class 0.000 description 3
- JRBPAEWTRLWTQC-UHFFFAOYSA-N dodecylamine Chemical compound CCCCCCCCCCCCN JRBPAEWTRLWTQC-UHFFFAOYSA-N 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 229910052733 gallium Inorganic materials 0.000 description 3
- 238000004770 highest occupied molecular orbital Methods 0.000 description 3
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 3
- 125000005462 imide group Chemical group 0.000 description 3
- 239000011777 magnesium Substances 0.000 description 3
- 229910052749 magnesium Inorganic materials 0.000 description 3
- 229910052709 silver Inorganic materials 0.000 description 3
- 239000004332 silver Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
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- XDPLWYUXKVCBFV-UHFFFAOYSA-N 1-bromo-3-(3-chlorophenyl)benzene Chemical group ClC1=CC=CC(C=2C=C(Br)C=CC=2)=C1 XDPLWYUXKVCBFV-UHFFFAOYSA-N 0.000 description 2
- HUHYFZSUBKNCJM-UHFFFAOYSA-N 1-bromo-3-(4-chlorophenyl)benzene Chemical group C1=CC(Cl)=CC=C1C1=CC=CC(Br)=C1 HUHYFZSUBKNCJM-UHFFFAOYSA-N 0.000 description 2
- SJLJTKRBBCLGPR-UHFFFAOYSA-N 1-bromo-3-chloro-5-phenylbenzene Chemical group ClC1=CC(Br)=CC(C=2C=CC=CC=2)=C1 SJLJTKRBBCLGPR-UHFFFAOYSA-N 0.000 description 2
- WMXVUHANYJZYHO-UHFFFAOYSA-N 1-bromo-4-(4-chlorophenyl)benzene Chemical group C1=CC(Cl)=CC=C1C1=CC=C(Br)C=C1 WMXVUHANYJZYHO-UHFFFAOYSA-N 0.000 description 2
- OGIRAIZAIKKTPL-UHFFFAOYSA-N 1-bromo-4-(4-chlorophenyl)naphthalene Chemical compound ClC1=CC=C(C=C1)C1=CC=C(Br)C2=C1C=CC=C2 OGIRAIZAIKKTPL-UHFFFAOYSA-N 0.000 description 2
- SHZRNNKKHUDHNF-UHFFFAOYSA-N 1-bromo-4-chlorodibenzofuran Chemical compound BrC1=CC=C(C=2OC3=C(C=21)C=CC=C3)Cl SHZRNNKKHUDHNF-UHFFFAOYSA-N 0.000 description 2
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- 125000005916 2-methylpentyl group Chemical group 0.000 description 2
- JWAZRIHNYRIHIV-UHFFFAOYSA-N 2-naphthol Chemical compound C1=CC=CC2=CC(O)=CC=C21 JWAZRIHNYRIHIV-UHFFFAOYSA-N 0.000 description 2
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- 239000005725 8-Hydroxyquinoline Substances 0.000 description 2
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- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
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- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 238000006069 Suzuki reaction reaction Methods 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- 125000003282 alkyl amino group Chemical group 0.000 description 2
- 150000001412 amines Chemical group 0.000 description 2
- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Chemical compound C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 description 2
- 125000005264 aryl amine group Chemical group 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 125000001309 chloro group Chemical group Cl* 0.000 description 2
- 238000000151 deposition Methods 0.000 description 2
- UZVGSSNIUNSOFA-UHFFFAOYSA-N dibenzofuran-1-carboxylic acid Chemical compound O1C2=CC=CC=C2C2=C1C=CC=C2C(=O)O UZVGSSNIUNSOFA-UHFFFAOYSA-N 0.000 description 2
- ZXHUJRZYLRVVNP-UHFFFAOYSA-N dibenzofuran-4-ylboronic acid Chemical compound C12=CC=CC=C2OC2=C1C=CC=C2B(O)O ZXHUJRZYLRVVNP-UHFFFAOYSA-N 0.000 description 2
- 125000003983 fluorenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3CC12)* 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 125000005843 halogen group Chemical group 0.000 description 2
- 150000002367 halogens Chemical group 0.000 description 2
- 125000005241 heteroarylamino group Chemical group 0.000 description 2
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Chemical compound [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 description 2
- 238000001840 matrix-assisted laser desorption--ionisation time-of-flight mass spectrometry Methods 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 125000002950 monocyclic group Chemical group 0.000 description 2
- 229910017464 nitrogen compound Inorganic materials 0.000 description 2
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- QWVGKYWNOKOFNN-UHFFFAOYSA-N o-cresol Chemical compound CC1=CC=CC=C1O QWVGKYWNOKOFNN-UHFFFAOYSA-N 0.000 description 2
- 125000002971 oxazolyl group Chemical group 0.000 description 2
- MPQXHAGKBWFSNV-UHFFFAOYSA-N oxidophosphanium Chemical group [PH3]=O MPQXHAGKBWFSNV-UHFFFAOYSA-N 0.000 description 2
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- 229910052763 palladium Inorganic materials 0.000 description 2
- UPYVSYVLGOADDG-UHFFFAOYSA-N phenanthren-3-ylboronic acid Chemical compound C1=CC=C2C3=CC(B(O)O)=CC=C3C=CC2=C1 UPYVSYVLGOADDG-UHFFFAOYSA-N 0.000 description 2
- 238000005240 physical vapour deposition Methods 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 229920000767 polyaniline Polymers 0.000 description 2
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- BBEAQIROQSPTKN-UHFFFAOYSA-N pyrene Chemical compound C1=CC=C2C=CC3=CC=CC4=CC=C1C2=C43 BBEAQIROQSPTKN-UHFFFAOYSA-N 0.000 description 2
- MCJGNVYPOGVAJF-UHFFFAOYSA-N quinolin-8-ol Chemical compound C1=CN=C2C(O)=CC=CC2=C1 MCJGNVYPOGVAJF-UHFFFAOYSA-N 0.000 description 2
- 230000004044 response Effects 0.000 description 2
- 125000003808 silyl group Chemical group [H][Si]([H])([H])[*] 0.000 description 2
- 239000010409 thin film Substances 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- 239000011787 zinc oxide Substances 0.000 description 2
- XPEIJWZLPWNNOK-UHFFFAOYSA-N (4-phenylphenyl)boronic acid Chemical compound C1=CC(B(O)O)=CC=C1C1=CC=CC=C1 XPEIJWZLPWNNOK-UHFFFAOYSA-N 0.000 description 1
- UWRZIZXBOLBCON-VOTSOKGWSA-N (e)-2-phenylethenamine Chemical compound N\C=C\C1=CC=CC=C1 UWRZIZXBOLBCON-VOTSOKGWSA-N 0.000 description 1
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical compound C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 description 1
- DFLSTCPTCSTCDT-UHFFFAOYSA-N 1-(4-bromophenyl)-4-chloronaphthalene Chemical compound ClC1=C2C=CC=CC2=C(C=C1)C1=CC=C(Br)C=C1 DFLSTCPTCSTCDT-UHFFFAOYSA-N 0.000 description 1
- JSVXIWLDFVOHBB-UHFFFAOYSA-N 1-bromo-2-(2-chlorophenyl)benzene Chemical group ClC1=CC=CC=C1C1=CC=CC=C1Br JSVXIWLDFVOHBB-UHFFFAOYSA-N 0.000 description 1
- CJBHNVDCKKHUFP-UHFFFAOYSA-N 1-bromo-2-(3-chlorophenyl)benzene Chemical group ClC1=CC=CC(C=2C(=CC=CC=2)Br)=C1 CJBHNVDCKKHUFP-UHFFFAOYSA-N 0.000 description 1
- QBELEDRHMPMKHP-UHFFFAOYSA-N 1-bromo-2-chlorobenzene Chemical compound ClC1=CC=CC=C1Br QBELEDRHMPMKHP-UHFFFAOYSA-N 0.000 description 1
- FSZBLBIVFQOJJR-UHFFFAOYSA-N 1-bromo-3-(2-chlorophenyl)benzene Chemical group ClC1=CC=CC=C1C1=CC=CC(Br)=C1 FSZBLBIVFQOJJR-UHFFFAOYSA-N 0.000 description 1
- JRGGUPZKKTVKOV-UHFFFAOYSA-N 1-bromo-3-chlorobenzene Chemical compound ClC1=CC=CC(Br)=C1 JRGGUPZKKTVKOV-UHFFFAOYSA-N 0.000 description 1
- WUGJECZACFHDFE-UHFFFAOYSA-N 1-bromo-4-chloronaphthalene Chemical compound C1=CC=C2C(Cl)=CC=C(Br)C2=C1 WUGJECZACFHDFE-UHFFFAOYSA-N 0.000 description 1
- 125000004973 1-butenyl group Chemical group C(=CCC)* 0.000 description 1
- 125000006218 1-ethylbutyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C([H])([H])[H] 0.000 description 1
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- 238000007650 screen-printing Methods 0.000 description 1
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- 125000003548 sec-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 238000004088 simulation Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 125000003003 spiro group Chemical group 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 238000010025 steaming Methods 0.000 description 1
- 125000005504 styryl group Chemical group 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 125000004434 sulfur atom Chemical group 0.000 description 1
- 229940042055 systemic antimycotics triazole derivative Drugs 0.000 description 1
- 238000010345 tape casting Methods 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- ILMRJRBKQSSXGY-UHFFFAOYSA-N tert-butyl(dimethyl)silicon Chemical group C[Si](C)C(C)(C)C ILMRJRBKQSSXGY-UHFFFAOYSA-N 0.000 description 1
- 125000001973 tert-pentyl group Chemical group [H]C([H])([H])C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 150000000000 tetracarboxylic acids Chemical class 0.000 description 1
- 125000001113 thiadiazolyl group Chemical group 0.000 description 1
- 125000000335 thiazolyl group Chemical group 0.000 description 1
- 125000001544 thienyl group Chemical group 0.000 description 1
- IBBLKSWSCDAPIF-UHFFFAOYSA-N thiopyran Chemical compound S1C=CC=C=C1 IBBLKSWSCDAPIF-UHFFFAOYSA-N 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 239000011135 tin Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 125000004306 triazinyl group Chemical group 0.000 description 1
- 150000003852 triazoles Chemical class 0.000 description 1
- 125000001425 triazolyl group Chemical group 0.000 description 1
- LALRXNPLTWZJIJ-UHFFFAOYSA-N triethylborane Chemical group CCB(CC)CC LALRXNPLTWZJIJ-UHFFFAOYSA-N 0.000 description 1
- WXRGABKACDFXMG-UHFFFAOYSA-N trimethylborane Chemical group CB(C)C WXRGABKACDFXMG-UHFFFAOYSA-N 0.000 description 1
- 125000000026 trimethylsilyl group Chemical group [H]C([H])([H])[Si]([*])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- MXSVLWZRHLXFKH-UHFFFAOYSA-N triphenylborane Chemical group C1=CC=CC=C1B(C=1C=CC=CC=1)C1=CC=CC=C1 MXSVLWZRHLXFKH-UHFFFAOYSA-N 0.000 description 1
- PXFBSZZEOWJJNL-UHFFFAOYSA-N triphenylen-2-ylboronic acid Chemical compound C1=CC=C2C3=CC(B(O)O)=CC=C3C3=CC=CC=C3C2=C1 PXFBSZZEOWJJNL-UHFFFAOYSA-N 0.000 description 1
- 238000001771 vacuum deposition Methods 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- NAWDYIZEMPQZHO-UHFFFAOYSA-N ytterbium Chemical compound [Yb] NAWDYIZEMPQZHO-UHFFFAOYSA-N 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 1
- YVTHLONGBIQYBO-UHFFFAOYSA-N zinc indium(3+) oxygen(2-) Chemical compound [O--].[Zn++].[In+3] YVTHLONGBIQYBO-UHFFFAOYSA-N 0.000 description 1
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- H10K85/60—Organic compounds having low molecular weight
- H10K85/649—Aromatic compounds comprising a hetero atom
- H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
- H10K85/6574—Polycyclic condensed heteroaromatic hydrocarbons comprising only oxygen in the heteroaromatic polycondensed ring system, e.g. cumarine dyes
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- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K50/00—Organic light-emitting devices
- H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
- H10K50/11—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers
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- H10K85/631—Amine compounds having at least two aryl rest on at least one amine-nitrogen atom, e.g. triphenylamine
- H10K85/636—Amine compounds having at least two aryl rest on at least one amine-nitrogen atom, e.g. triphenylamine comprising heteroaromatic hydrocarbons as substituents on the nitrogen atom
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Abstract
The present disclosure provides an organic light emitting device having improved driving voltage, efficiency, and lifetime.
Description
Technical Field
Cross Reference to Related Applications
The present application claims the benefits of korean patent application No. 10-2021-0096451 filed at the korean intellectual property office on 7 month 22 of 2021 and korean patent application No. 10-2022-0091091 filed at the korean intellectual property office on 7 month 22 of 2022, the contents of which are incorporated herein by reference in their entireties.
The present disclosure relates to organic light emitting devices having improved driving voltages, efficiencies, and lifetimes.
Background
In general, an organic light emitting phenomenon refers to a phenomenon in which electric energy is converted into light energy by using an organic material. An organic light emitting device using the organic light emitting phenomenon has characteristics such as a wide viewing angle, excellent contrast, a fast response time, excellent brightness, driving voltage, and response speed, and thus many researches have been conducted.
The organic light emitting device generally has a structure including an anode, a cathode, and an organic material layer interposed between the anode and the cathode. The organic material layer generally has a multi-layered structure including different materials to enhance efficiency and stability of the organic light emitting device, for example, the organic material layer may be formed of a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, an electron injection layer, and the like. In the structure of the organic light emitting device, if a voltage is applied between two electrodes, holes are injected from an anode into an organic material layer, and electrons are injected from a cathode into the organic material layer, and excitons are formed when the injected holes and electrons meet each other, and light is emitted when the excitons fall back to a ground state again.
There is a continuing need to develop organic materials for use in organic light emitting devices as described above.
[ Prior Art literature ]
[ patent literature ]
(patent document 1): korean unexamined patent publication No. 10-2000-0051826
Disclosure of Invention
Technical problem
It is an object of the present disclosure to provide an organic light emitting device with improved driving voltage, efficiency and lifetime.
Technical proposal
According to the present disclosure, the following organic light emitting device is provided:
the organic light emitting device includes:
an anode;
a cathode; and
a light-emitting layer interposed between the anode and the cathode,
wherein the light emitting layer includes a compound represented by the following chemical formula 1 and a compound represented by the following chemical formula 2:
[ chemical formula 1]
In the chemical formula 1, the chemical formula is shown in the drawing,
Ar 1 and Ar is a group 2 Each independently is a substituted or unsubstituted C 6-60 An aryl group; or substituted or unsubstituted C comprising any one or more selected from N, O and S 2-60 A heteroaryl group, which is a group,
L 1 is a single bond or any one selected from the group consisting of:
in the above group of the present invention,
d is deuterium, and the D is deuterium,
n1 to n3 and n5 are each independently integers from 0 to 4,
n4, n6 and n7 are each independently integers from 0 to 6,
L 2 and L 3 Each independently is a single bond; or C which is substituted or unsubstituted 6-60 An arylene group,
each R is 1 Independently hydrogen; deuterium; substituted or unsubstituted C 6-60 An aryl group; or substituted or unsubstituted C comprising any one or more selected from N, O and S 2-60 Heteroaryl, provided that at least one R 1 Deuterium, deuterium-substituted phenyl, substituted or unsubstituted C 10-60 Aryl, or substituted or unsubstituted C comprising any one or more selected from N, O and S 2-60 Heteroaryl group
a is an integer of 1 to 7,
wherein the compound represented by chemical formula 1 may not contain any deuterium or may contain at least one deuterium,
[ chemical formula 2]
In the chemical formula 2, the chemical formula is shown in the drawing,
a is a benzene ring or naphthalene ring condensed with an adjacent ring,
Ar 3 and Ar is a group 4 Each independently is a substituted or unsubstituted C 6-60 An aryl group; or substituted or unsubstituted C comprising any one or more selected from N, O and S 2-60 A heteroaryl group, which is a group,
L 4 is C substituted or unsubstituted 6-60 Arylene group
L 5 And L 6 Each independently is a single bond, substituted or unsubstituted C 6-60 Arylene, or substituted or unsubstituted C comprising any one or more selected from N, O and S 2-60 Heteroarylene group.
Advantageous effects
The above-described organic light emitting device includes the compound represented by chemical formula 1 and the compound represented by chemical formula 2 in the light emitting layer, and thus can improve efficiency, achieve a low driving voltage, and/or improve lifetime characteristics in the organic light emitting device.
Drawings
Fig. 1 shows an example of an organic light emitting device including a substrate 1, an anode 2, a light emitting layer 3, and a cathode 4.
Fig. 2 shows an example of an organic light emitting device including a substrate 1, an anode 2, a hole injection layer 5, a hole transport layer 6, an electron blocking layer 7, a light emitting layer 3, a hole blocking layer 8, an electron injection and transport layer 9, and a cathode 4.
Detailed Description
Hereinafter, embodiments of the present disclosure will be described in more detail to facilitate understanding of the present invention.
As used herein, a symbol
Or->
Meaning a bond to another substituent.
As used herein, the term "substituted or unsubstituted" means unsubstituted or substituted with one or more substituents selected from the group consisting of: deuterium; a halogen group; a nitrile group; a nitro group; a hydroxyl group; a carbonyl group; an ester group; an imide group; an amino group; a phosphine oxide group; an alkoxy group; an aryloxy group; alkylthio; arylthio; an alkylsulfonyl group; arylsulfonyl; a silyl group; a boron base; an alkyl group; cycloalkyl; alkenyl groups; an aryl group; an aralkyl group; aralkenyl; alkylaryl groups; an alkylamino group; an aralkylamine group; heteroaryl amine groups; an arylamine group; aryl phosphino; and heteroaryl groups comprising at least one of N, O and S atoms, or substituted with substituents that are unsubstituted or linked with two or more of the substituents exemplified above. For example, a "substituent in which two or more substituents are linked" may be a biphenyl group. That is, biphenyl may be aryl, or it may be interpreted as a substituent to which two phenyl groups are attached.
In the present disclosure, the carbon number of the carbonyl group is not particularly limited, but is preferably 1 to 40. Specifically, the carbonyl group may be a substituent having the following structural formula, but is not limited thereto.
In the present disclosure, the ester group may have a structure in which oxygen of the ester group may be substituted with a linear, branched, or cyclic alkyl group having 1 to 25 carbon atoms or an aryl group having 6 to 25 carbon atoms. Specifically, the ester group may be a substituent having the following structural formula, but is not limited thereto.
In the present disclosure, the carbon number of the imide group is not particularly limited, but is preferably 1 to 25.
Specifically, the imide group may be a substituent having the following structural formula, but is not limited thereto.
In the present disclosure, the silyl group specifically includes, but is not limited to, trimethylsilyl, triethylsilyl, t-butyldimethylsilyl, vinyldimethylsilyl, propyldimethylsilyl, triphenylsilyl, diphenylsilyl, phenylsilyl, and the like.
In the present disclosure, the boron group specifically includes trimethylboron group, triethylboron group, t-butyldimethylboroyl group, triphenylboron group, and phenylboron group, but is not limited thereto.
In the present disclosure, examples of halogen groups include fluorine, chlorine, bromine, or iodine.
In the present disclosure, the alkyl group may be straight or branched, and the carbon number thereof is not particularly limited, but is preferably 1 to 40. According to one embodiment, the alkyl group has a carbon number of 1 to 20. According to another embodiment, the alkyl group has a carbon number of 1 to 10. According to another embodiment, the alkyl group has a carbon number of 1 to 6. Specific examples of the alkyl group include, but are not limited to, methyl, ethyl, propyl, n-propyl, isopropyl, butyl, n-butyl, isobutyl, tert-butyl, sec-butyl, 1-methyl-butyl, 1-ethyl-butyl, pentyl, n-pentyl, isopentyl, neopentyl, tert-pentyl, hexyl, n-hexyl, 1-methylpentyl, 2-methylpentyl, 4-methyl-2-pentyl, 3-dimethylbutyl, 2-ethylbutyl, heptyl, n-heptyl, 1-methylhexyl, cyclopentylmethyl, cyclohexylmethyl, octyl, n-octyl, tert-octyl, 1-methylheptyl, 2-ethylhexyl, 2-propylpentyl, n-nonyl, 2-dimethylheptyl, 1-ethyl-propyl, 1-dimethyl-propyl, isohexyl, 2-methylpentyl, 4-methylhexyl, 5-methylhexyl and the like.
In the present disclosure, the alkenyl group may be straight or branched, and the carbon number thereof is not particularly limited, but is preferably 2 to 40. According to one embodiment, the alkenyl group has a carbon number of 2 to 20. According to another embodiment, the alkenyl group has a carbon number of 2 to 10. According to yet another embodiment, the alkenyl group has a carbon number of 2 to 6. Specific examples thereof include vinyl, 1-propenyl, isopropenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-pentenyl, 2-pentenyl, 3-methyl-1-butenyl, 1, 3-butadienyl, allyl, 1-phenylvinyl-1-yl, 2-diphenylvinyl-1-yl, 2-phenyl-2- (naphthalen-1-yl) vinyl-1-yl, 2-bis (diphenyl-1-yl) vinyl-1-yl, 
Radical, styryl, etc., but is not limited thereto.
In the present disclosure, the cycloalkyl group is not particularly limited, but the carbon number thereof is preferably 3 to 60. According to one embodiment, the cycloalkyl group has a carbon number of 3 to 30. According to another embodiment, the cycloalkyl group has a carbon number of 3 to 20. According to yet another embodiment, the cycloalkyl group has a carbon number of 3 to 6. Specific examples thereof include cyclopropyl, cyclobutyl, cyclopentyl, 3-methylcyclopentyl, 2, 3-dimethylcyclopentyl, cyclohexyl, 3-methylcyclohexyl, 4-methylcyclohexyl, 2, 3-dimethylcyclohexyl, 3,4, 5-trimethylcyclohexyl, 4-t-butylcyclohexyl, cycloheptyl, cyclooctyl and the like, but are not limited thereto.
In the present disclosure, the aryl group is not particularly limited, but the carbon number thereof is preferably 6 to 60, and it may be a monocyclic aryl group or a polycyclic aryl group. According to one embodiment, the aryl group has a carbon number of 6 to 30. According to one embodiment, the aryl group has a carbon number of 6 to 20. As the monocyclic aryl group, an aryl group may be phenyl, biphenyl, terphenyl, or the like, but is not limited thereto. Polycyclic aryl groups include naphthyl, anthryl, phenanthryl, pyrenyl,
Base, & gt>
A base, etc., but is not limited thereto.
In the present disclosure, the fluorenyl group may be substituted, and two substituents may be linked to each other to form a spiro structure. In the case where the fluorenyl group is substituted, it may be formed 
Etc. However, the structure is not limited thereto.
In the present disclosure, the heteroaryl group is a heteroaryl group including at least one of O, N, si and S as a heteroatom, and the carbon number thereof is not particularly limited, but is preferably 2 to 60. According to one exemplary embodiment of heteroaryl groups, the heteroaryl groups have 6 to 30 carbon atoms. According to one exemplary embodiment, the heteroaryl group has 6 to 20 carbon atoms. Examples of heteroaryl groups include thienyl, furyl, pyrrolyl, imidazolyl, thiazolyl,
Azolyl, (-) -and (II) radicals>
Diazolyl, triazolyl, pyridyl, bipyridyl, pyrimidinyl, triazinyl, acridinyl, pyridazinyl, pyrazinyl, quinolinyl, quinazolinyl, quinoxalinyl, phthalazinyl, pyridopyrimidinyl, pyridopyrazinyl, pyrazinopyrazinyl, isoquinolinyl, indolyl, carbazolyl, benzo->
Oxazolyl, benzimidazolyl, benzothiazolyl, benzocarbazolyl, benzothienyl, dibenzothiophenyl, benzofuranyl, phenanthrolinyl, and i ∈ ->
Oxazolyl, thiadiazolyl, phenothiazinyl, dibenzofuranyl, and the like, but are not limited thereto.
In the present disclosure, the aryl groups in the aralkyl group, the aralkenyl group, the alkylaryl group, and the arylamine group are the same as the examples of the above aryl groups. In the present disclosure, the alkyl groups in the aralkyl group, the alkylaryl group, and the alkylamino group are the same as the examples of the alkyl groups described above. In the present disclosure, the heteroaryl groups in the heteroaryl amines may be as described for heteroaryl groups above. In the present disclosure, alkenyl groups in aralkenyl groups are the same as the examples of alkenyl groups described above. In the present disclosure, the above description of aryl groups may be applied, except that arylene groups are divalent groups. In the present disclosure, the above description of heteroaryl groups may be applied, except that the heteroarylene group is a divalent group. In the present disclosure, the above description of aryl or cycloalkyl groups may be applied, except that the hydrocarbon ring is not a monovalent group but is formed by combining two substituents. In the present disclosure, the above description of heteroaryl groups may be applied, except that heteroaryl groups are not monovalent groups but are formed by combining two substituents.
In the present disclosure, the term "deuterated or deuterium-substituted" means that at least one available hydrogen in each formula is replaced with deuterium. In particular, "deuterium substituted" in the definition of each chemical formula or substituent means that at least one or more positions in the molecule to which hydrogen may be bonded are substituted with deuterium.
Furthermore, in the present disclosure, the term "deuterium substitution rate" means the percentage of the number of substituted deuterium relative to the total number of hydrogen that may be present in each formula.
Hereinafter, the present disclosure will be described in detail for each configuration.
Anode and cathode
The anode and cathode used in the present disclosure mean electrodes used in an organic light emitting device.
As the anode material, it is generally preferable to use a material having a large work function so that holes can be smoothly injected into the organic material layer. Specific examples of the anode material include: metals such as vanadium, chromium, copper, zinc, and gold, or alloys thereof; metal oxides such as zinc oxide, indium Tin Oxide (ITO), and Indium Zinc Oxide (IZO); a combination of a metal and an oxide,for example ZnO, al or SNO 2 Sb; conductive polymers, e.g. poly (3-methylthiophene), poly [3,4- (ethylene-1, 2-dioxythiophene) ](PEDOT), polypyrrole and polyaniline; etc., but is not limited thereto.
As the cathode material, it is generally preferable to use a material having a small work function so that electrons can be easily injected into the organic material layer. Specific examples of the cathode material include: metals such as magnesium, calcium, sodium, potassium, titanium, indium, yttrium, lithium, gadolinium, aluminum, silver, tin, and lead, or alloys thereof; multilayer structural materials, e.g. LiF/Al or LiO 2 Al; etc., but is not limited thereto.
Hole injection layer
The organic light emitting device according to the present disclosure may further include a hole injection layer on the anode, if necessary.
The hole injection layer is a layer for injecting holes from the electrode, and the hole injection material is preferably a compound of: it has a capability of transporting holes, and thus has an effect of injecting holes in an anode and an excellent hole injection effect to a light emitting layer or a light emitting material, prevents excitons generated in the light emitting layer from moving to an electron injection layer or an electron injection material, and is also excellent in a capability of forming a thin film. Further, it is preferable that the HOMO (highest occupied molecular orbital) of the hole injection material is between the work function of the anode material and the HOMO of the surrounding organic material layer.
Specific examples of the hole injection material include metalloporphyrin, oligothiophene, arylamine-based organic material, hexanitrile hexaazabenzophenanthrene-based organic material, quinacridone-based organic material, and the like
But not limited to, anthraquinone, polyaniline-based and polythiophene-based conductive polymers, etc.
Hole transport layer
The organic light emitting device according to the present disclosure may include a hole transport layer on the anode (or on the hole injection layer if present), if necessary.
The hole transporting layer is a layer that can receive holes from the anode or the hole injecting layer and transport the holes to the light emitting layer, and the hole transporting material is suitably a material having a large mobility to the holes, which can receive holes from the anode or the hole injecting layer and transfer the holes to the light emitting layer.
Specific examples of the hole transport material include an arylamine-based organic material, a conductive polymer, a block copolymer in which a conjugated moiety and a non-conjugated moiety are simultaneously present, and the like, but are not limited thereto.
Electron blocking layer
The organic light emitting device according to the present disclosure may include an electron blocking layer between the hole transport layer and the light emitting layer, if necessary. An electron blocking layer refers to a layer such as: which is formed on the hole transport layer and is preferably disposed in contact with the light emitting layer, and thus serves to control hole mobility, prevent excessive movement of electrons, and increase the possibility of hole-electron bonding, thereby improving the efficiency of the organic light emitting device. The electron blocking layer contains an electron blocking material, and as an example of such an electron blocking material, an arylamine-based organic material or the like can be used, but is not limited thereto.
Light-emitting layer
The light emitting layer used in the present disclosure is a layer that can emit light in the visible light region by combining holes and electrons transported from an anode and a cathode. Generally, the light emitting layer includes a host material and a dopant material, and in the present disclosure, the light emitting layer includes a compound represented by chemical formula 1 and a compound represented by chemical formula 2 as hosts.
The compound represented by chemical formula 1 may contain no deuterium or may contain at least one deuterium.
Preferably Ar 1 And Ar is a group 2 May each independently be a substituted or unsubstituted C 6-20 An aryl group; or substituted or unsubstituted C comprising any one or more selected from N, O and S 2-20 Heteroaryl groups.
More preferably Ar 1 And Ar is a group 2 Can each beIndependently is phenyl, biphenyl, terphenyl, naphthyl, phenanthryl, dibenzofuranyl, dibenzothienyl, or triphenylsilylphenyl, and Ar 1 And Ar is a group 2 Each independently unsubstituted or substituted with deuterium.
Most preferably Ar 1 And Ar is a group 2 May each independently be any one selected from the group consisting of:
preferably L 1 May be a single bond or any one selected from the group consisting of:
in the above group, n1 to n7 are as defined in chemical formula 1.
Preferably L 2 And L 3 May each independently be a single bond, or may be a substituted or unsubstituted C 6-20 Arylene groups.
More preferably L 2 And L 3 May each independently be a single bond, phenylene, biphenylene, or naphthalenediyl, and the hydrogens in the phenylene, biphenyldiyl, and naphthalenediyl may each independently be unsubstituted or substituted with deuterium.
In the present disclosure, a represents R 1 And when a is 2 or greater, two or more R 1 May be the same or different from each other.
Preferably, each R 1 Independently hydrogen; deuterium; substituted or unsubstituted C 6-20 An aryl group; or substituted or unsubstituted C comprising any one or more selected from N, O and S 2-20 Heteroaryl, provided that at least one R 1 Can be deuterium, phenyl substituted by deuterium, C substituted or unsubstituted 10-20 Aryl, or substituted or unsubstituted C comprising any one or more selected from N, O and S 2-20 Heteroaryl groups.
More preferably, each R 1 Independently is hydrogen, deuterium, phenyl, biphenyl, terphenyl, naphthyl, phenanthryl, triphenylene, fluoranthenyl, naphthylphenyl, phenylnaphthyl, indanyl, dibenzofuranyl, dibenzothienyl, benzonaphthofuranyl, or benzonaphthothienyl, provided that at least one R 1 Can be deuterium, deuterium-substituted phenyl, biphenyl, terphenyl, naphthyl, phenanthryl, triphenylene, fluoranthenyl, naphthylphenyl, phenylnaphthyl, dibenzofuranyl, dibenzothienyl, benzonaphthofuranyl, or benzonaphthothienyl, and
the hydrogens in biphenyl, terphenyl, naphthyl, phenanthryl, triphenylene, fluoranthenyl, naphthylphenyl, phenylnaphthyl, dibenzofuranyl, dibenzothienyl, benzonaphthofuranyl, and benzonaphthobenzothienyl may each independently be unsubstituted or substituted with deuterium.
Most preferably, each R 1 May be independently deuterium, deuterium-substituted phenyl, biphenyl, terphenyl, naphthyl, phenanthryl, triphenylene, fluoranthenyl, naphthylphenyl, phenylnaphthyl, indanyl, dibenzofuranyl, dibenzothienyl, benzonaphthofuranyl, or benzonaphthothienyl, and hydrogen in biphenyl, terphenyl, naphthyl, phenanthryl, triphenylene, fluoranthenyl, naphthylphenyl, phenylnaphthyl, dibenzofuranyl, dibenzothienyl, benzonaphthofuranyl, and benzonaphthothienyl may each independently be unsubstituted or substituted with deuterium.
Further, the compound represented by chemical formula 1 may not include deuterium or may include at least one deuterium.
As an example, when the compound includes deuterium, the deuterium substitution rate of the compound may be 1% to 100%. Specifically, the deuterium substitution rate of the compound may be 5% or more, 10% or more, 20% or more, 30% or more, 40% or more, 50% or more, 60% or more, 70% or more, 75% or more, 80% or more, or 90% or more, and less than 100%. The deuterium substitution rate of such compounds is calculated as the number of substituted deuterium relative to the total number of hydrogens that may be present in the formula, wherein the number of substituted deuterium may be obtained by MALDI-TOF MS (Matrix-Assisted Laser Desorption/Ionization Time-of-Flight Mass Spectrometer, matrix-assisted laser desorption/Ionization Time-of-flight mass spectrometry) analysis.
Representative examples of the compound represented by chemical formula 1 are as follows:
in the above compounds, the structural formula is represented by "[ structural formula ]]D n The "represented compound means a compound in which n hydrogens in the compound having the corresponding" structural formula "are substituted with deuterium.
As an example, a compound represented by chemical formula 1 (wherein a is 1, and R 1 Is C substituted or unsubstituted 6-60 An aryl group; or substituted or unsubstituted C comprising any one or more selected from N, O and S 2-60 Heteroaryl) can be prepared by the preparation method as shown in scheme 1 below, and other remaining compounds can be prepared in a similar manner.
In scheme 1, R 1 、Ar 1 、Ar 2 And L 1 To L 3 As defined in chemical formula 1, and X 1 And X 2 Each independently is halogen, and preferably X 1 And X 2 Each independently is chlorine or bromine.
Preferably, the compound represented by chemical formula 2 may be represented by any one of the following chemical formulas 2-1 to 2-4:
[ chemical formula 2-1]
[ chemical formula 2-2]
[ chemical formulas 2-3]
[ chemical formulas 2-4]
In chemical formulas 2-1 to 2-4,
Ar 3 、Ar 4 and L 4 To L 6 As defined in chemical formula 2.
Preferably Ar 3 And Ar is a group 4 Each independently is a substituted or unsubstituted C 6-20 Aryl, or substituted or unsubstituted C comprising any one or more selected from N, O and S 2-20 Heteroaryl groups.
More preferably Ar 3 And Ar is a group 4 Can be phenyl, biphenyl, terphenyl, tetrabiphenyl, triphenylmethylphenyl, triphenylsilylphenyl, naphthyl, phenanthryl, triphenylene, fluoranthenyl, and the like,
Radical, benzo [ c ]]Phenanthryl, carbazole, phenylcarbazole, dimethylfluorenyl, dibenzofuranyl, or dibenzothiophenyl.
Most preferably Ar 3 And Ar is a group 4 May each independently be any one selected from the group consisting of:
preferably L 4 May be substituted or unsubstituted C 6-60 Arylene groups.
More preferably L 4 Is phenylene, biphenyldiyl, terphenyldiyl, tetrabenzenediyl, naphthalenediyl, phenylnaphthalenediyl or phenylnaphthalenediyl substituted by one phenyl group.
Most preferably L 4 May be any one selected from the following:
preferably L 5 And L 6 Can each independently be a single bond, a substituted or unsubstituted C 6-20 Arylene, or substituted or unsubstituted C comprising any one or more selected from N, O and S 2-20 Heteroarylene group.
More preferably L 5 And L 6 May each independently be a single bond, phenylene, biphenyldiyl, naphthalenediyl, phenylnaphthalenediyl, or carbazolediyl.
Most preferably L 5 And L 6 May each independently be a single bond or any one selected from the group consisting of:
representative examples of the compound represented by chemical formula 2 are as follows:
in the above compounds, the structural formula is represented by "[ structural formula ]]D n The "represented compound means a compound in which n hydrogens in the compound having the corresponding" structural formula "are substituted with deuterium.
As an example, the compound represented by chemical formula 2 may be prepared by a preparation method as shown in the following reaction scheme 2, and other remaining compounds may be prepared in a similar manner.
In scheme 2, ar 3 、Ar 4 And L 4 To L 6 As defined in chemical formula 2, and X 'is halogen, and preferably, X' is chlorine or bromine.
Preferably, the weight ratio of the compound represented by chemical formula 1 to the compound represented by chemical formula 2 in the light emitting layer is 10:90 to 90:10, more preferably 20:80 to 80:20, 30:70 to 70:30, or 40:60 to 60:40.
Meanwhile, the light emitting layer may further include a dopant in addition to the host. The dopant material is not particularly limited as long as it is a material for an organic light emitting device. As examples, aromatic amine derivatives, styrene amine compounds, boron complexes, fluoranthene compounds, metal complexes, and the like can be mentioned. Specific examples of the aromatic amine derivative include substituted or unsubstituted fused aromatic ring derivatives having an arylamino group, examples of which include pyrene, anthracene having an arylamino group,
And bisindenopyrene, etc. The styrylamine compound is a compound in which at least one arylvinyl group is substituted in a substituted or unsubstituted arylamine, wherein one or two or more substituents selected from the group consisting of aryl, silyl, alkyl, cycloalkyl, and arylamino groups are substituted or unsubstituted. Specific examples thereof include, but are not limited to, styrylamine, styrylenediamine, styrylenetriamine, styrenetetramine, and the like. Further, examples of the metal complex include iridium complex, platinum complex, and the like, but are not limited thereto.
Preferably, the dopant material may be any one selected from the following, but is not limited thereto:
hole blocking layer
Organic, if necessary, according to the present disclosureThe light emitting device may include a hole blocking layer between the light emitting layer and an electron transport layer described later. The hole blocking layer refers to a layer of: which is formed on the light emitting layer and is preferably disposed in contact with the light emitting layer, and thus serves to control electron mobility, prevent excessive movement of holes, and increase the possibility of hole-electron bonding, thereby improving the efficiency of the organic light emitting device. The hole blocking layer contains a hole blocking material, and as an example of such a hole blocking material, a compound having an electron withdrawing group introduced therein, such as azine derivatives including triazine; triazole derivatives;
an diazole derivative; phenanthroline derivatives; phosphine oxide derivatives, but are not limited thereto.
Electron transport layer
The organic light emitting device according to the present disclosure may include an electron transport layer on the light emitting layer, if necessary.
The electron transporting layer is a layer that receives electrons from the cathode or an electron injecting layer formed on the cathode and transports the electrons to the light emitting layer, and suppresses transfer of holes from the light emitting layer, and the electron transporting material is suitably a material such as: which can well receive electrons from the cathode and transfer the electrons to the light emitting layer, and has a large electron mobility.
Specific examples of the electron transport material include: al complexes of 8-hydroxyquinoline; comprising Alq 3 Is a complex of (a) and (b); an organic radical compound; hydroxyflavone-metal complexes; etc., but is not limited thereto. The electron transport layer may be used with any desired cathode material as used according to conventional techniques. In particular, suitable examples of cathode materials are typical materials having a small work function, followed by an aluminum layer or a silver layer. Specific examples thereof include cesium, barium, calcium, ytterbium and samarium, in each case followed by an aluminum layer or a silver layer.
Electron injection layer
The organic light emitting device according to the present disclosure may further include an electron injection layer on the light emitting layer (or on the electron transport layer if present).
The electron injection layer is a layer that injects electrons from an electrode, and is preferably a compound that: it has an ability to transport electrons, has an effect of injecting electrons from a cathode and an excellent effect of injecting electrons into a light emitting layer or a light emitting material, prevents excitons generated by the light emitting layer from moving to a hole injecting layer, and is also excellent in an ability to form a thin film.
Specific examples of the electron injection layer include fluorenone, anthraquinone dimethane, diphenoquinone, thiopyran dioxide, 
Azole,/->
Diazole, triazole, imidazole, < >>
Tetracarboxylic acid, fluorenylmethane, anthrone, and the like, and derivatives thereof, metal complex compounds, nitrogen-containing 5-membered ring derivatives, and the like, but are not limited thereto.
Examples of the metal complex compound include, but are not limited to, lithium 8-hydroxyquinoline, zinc bis (8-hydroxyquinoline), copper bis (8-hydroxyquinoline), manganese bis (8-hydroxyquinoline), aluminum tris (2-methyl-8-hydroxyquinoline), gallium tris (8-hydroxyquinoline), beryllium bis (10-hydroxybenzo [ h ] quinoline), zinc bis (2-methyl-8-quinoline) chlorogallium, gallium bis (2-methyl-8-quinoline) (o-cresol), aluminum bis (2-methyl-8-quinoline) (1-naphthol), gallium bis (2-methyl-8-quinoline) (2-naphthol), and the like.
Meanwhile, in the present disclosure, the "electron injection and transport layer" is a layer performing the function of both the electron injection layer and the electron transport layer, and materials of the respective layers performing the function may be used alone or in combination, but are not limited thereto.
Organic light emitting device
Fig. 1 and 2 illustrate the structure of an organic light emitting device according to the present disclosure. Fig. 1 shows an example of an organic light emitting device including a substrate 1, an anode 2, a light emitting layer 3, and a cathode 4. Fig. 2 shows an example of an organic light emitting device including a substrate 1, an anode 2, a hole injection layer 5, a hole transport layer 6, an electron blocking layer 7, a light emitting layer 3, a hole blocking layer 8, an electron injection and transport layer 9, and a cathode 4.
The organic light emitting device according to the present disclosure may be manufactured by sequentially stacking the above-described structures. In this case, the organic light emitting device may be manufactured by: the above-described respective layers are formed on an anode by depositing a metal, a metal oxide having conductivity, or an alloy thereof on a substrate using a PVD (physical vapor deposition) method such as a sputtering method or an electron beam evaporation method to form an anode, and then a material that can function as a cathode is deposited thereon. In addition to such a method, the organic light emitting device may also be manufactured by sequentially depositing a cathode material to an anode material on a substrate in the reverse order of the above-described configuration (WO 2003/012690). In addition, the light emitting layer may be formed by subjecting the host and the dopant to a vacuum deposition method and a solution coating method. Herein, the solution coating method means spin coating, dip coating, knife coating, ink jet printing, screen printing, spray method, roll coating, etc., but is not limited thereto.
Meanwhile, the organic light emitting device according to the present disclosure may be a bottom emission device, a top emission device, or a double-sided light emitting device, and in particular, may be a bottom emission device requiring relatively high light emitting efficiency.
Hereinafter, preferred embodiments are presented to aid in understanding the present disclosure. The following examples are provided only for a better understanding of the present disclosure and are not intended to limit the disclosure.
Synthesis example 1-1
(2-chlorodibenzo [ b, d ] furan-1-yl) boronic acid (15 g,60.9 mmol) and compound Trz1 (26.7 g,63.9 mmol) are added to 300ml THF and the mixture is stirred and refluxed. Then, potassium carbonate (25.2 g,182.6 mmol) was dissolved in 76ml of water and added to the mixture, and the mixture was stirred well, followed by addition of bis (tri-t-butylphosphine) palladium (0) (0.3 g,0.6 mmol). After 3 hours of reaction, the reaction mixture was cooled to room temperature, and the organic layer and the aqueous layer were separated, and then the organic layer was distilled. It was dissolved again in chloroform, washed twice with water, then the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 24.5g of compound 1-1_p1. (yield: 69%, MS: [ m+h ] +=584).
Compound 1-1_P1 (15 g,25.7 mmol) and naphthalen-2-ylboronic acid (4.6 g,27 mmol) are added to 300ml THF and the mixture is stirred and refluxed. Then, potassium carbonate (10.6 g,77 mmol) was dissolved in 32ml of water and added to the mixture, and the mixture was sufficiently stirred, followed by addition of bis (tri-t-butylphosphine) palladium (0) (0.1 g,0.3 mmol). After 3 hours of reaction, the reaction mixture was cooled to room temperature, and the organic layer and the aqueous layer were separated, and then the organic layer was distilled. It was dissolved again in chloroform, washed twice with water, then the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 12.1g of compound 1-1. (yield: 70%, MS: [ M+H ] ] + ＝676)。
Synthesis examples 1 to 2
(2-chlorodibenzo [ b, d)]Furan-1-yl) boronic acid (15 g,60.9 mmol) and compound Trz2 (30.9 g,63.9 mmol) were added to 300ml THF and the mixture was stirred and refluxed. Potassium carbonate (25.2 g,182.6 mmol) was then dissolved in 76ml of water and added to the mixtureTo the mixture was stirred well, and bis (tri-t-butylphosphine) palladium (0) (0.3 g,0.6 mmol) was then added. After 2 hours of reaction, the reaction mixture was cooled to room temperature, and the organic layer and the aqueous layer were separated, and then the organic layer was distilled. It was dissolved again in chloroform, washed twice with water, then the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 26.5g of compound 1-2_p1. (yield: 67%, MS: [ M+H)] + ＝650)。
Compound 1-2_P1 (15 g,23.1 mmol) and dibenzo [ b, d]Furan-2-ylboronic acid (5.1 g,24.2 mmol) was added to 300ml THF and the mixture was stirred and refluxed. Then, potassium carbonate (9.6 g,69.2 mmol) was dissolved in 29ml of water and added to the mixture, and the mixture was stirred well, followed by addition of bis (tri-t-butylphosphine) palladium (0) (0.1 g,0.2 mmol). After 2 hours of reaction, the reaction mixture was cooled to room temperature, and the organic layer and the aqueous layer were separated, and then the organic layer was distilled. It was dissolved again in chloroform, washed twice with water, then the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 13.2g of compound 1-2. (yield: 73%, MS: [ M+H) ] + ＝782)。
Synthesis examples 1 to 3
(2-chlorodibenzo [ b, d)]Furan-1-yl) boronic acid (15 g,60.9 mmol) and compound Trz3 (27.1 g,63.9 mmol) were added to 300ml THF and the mixture was stirred and refluxed. Then, potassium carbonate (25.2 g,182.6 mmol) was dissolved in 76ml of water and added to the mixture, and the mixture was stirred well, then double was added(tri-t-butylphosphine) palladium (0) (0.3 g,0.6 mmol). After 4 hours of reaction, the reaction mixture was cooled to room temperature, and the organic layer and the aqueous layer were separated, and then the organic layer was distilled. It was dissolved again in chloroform, washed twice with water, then the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 23.3g of compound 1-3_p1. (yield: 66%, MS: [ M+H)] + ＝580)。
Compounds 1-3_P1 (15 g,25.4 mmol) and [1,1' -biphenyl]4-Ylboronic acid (5.3 g,26.7 mmol) was added to 300ml THF and the mixture was stirred and refluxed. Then, potassium carbonate (10.5 g,76.3 mmol) was dissolved in 32ml of water and added to the mixture, and the mixture was stirred well, followed by addition of bis (tri-t-butylphosphine) palladium (0) (0.1 g,0.3 mmol). After 5 hours of reaction, the reaction mixture was cooled to room temperature, and the organic layer and the aqueous layer were separated, and then the organic layer was distilled. It was dissolved again in chloroform, washed twice with water, then the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 13.5g of compounds 1 to 3. (yield: 75%, MS: [ M+H) ] + ＝708)。
Synthesis examples 1 to 4
(3-chlorodibenzo [ b, d)]Furan-1-yl) boronic acid (15 g,60.9 mmol) and compound Trz4 (28.4 g,63.9 mmol) were added to 300ml THF and the mixture was stirred and refluxed. Then, potassium carbonate (25.2 g,182.6 mmol) was dissolved in 76ml of water and added to the mixture, and the mixture was stirred well, followed by addition of bis (tri-t-butylphosphine) palladium (0) (0.3 g,0.6 mmol). After 3 hours of reactionAfter that, the reaction mixture was cooled to room temperature, and the organic layer and the aqueous layer were separated, and then the organic layer was distilled. It was dissolved again in chloroform, washed twice with water, then the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 27.4g of compound 1-4_p1. (yield: 74%, MS: [ M+H)] + ＝610)。
Compound 1-4_P1 (15 g,24.6 mmol) and naphthalen-2-ylboronic acid (4.4 g,25.8 mmol) are added to 300ml THF and the mixture is stirred and refluxed. Then, potassium carbonate (10.2 g,73.8 mmol) was dissolved in 31ml of water and added to the mixture, and the mixture was stirred well, followed by addition of bis (tri-t-butylphosphine) palladium (0) (0.1 g,0.2 mmol). After 5 hours of reaction, the reaction mixture was cooled to room temperature, and the organic layer and the aqueous layer were separated, and then the organic layer was distilled. It was dissolved again in chloroform, washed twice with water, then the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 11.2g of compounds 1 to 4. (yield: 65%, MS: [ M+H) ] + ＝702)。
Synthesis examples 1 to 5
(3-chlorodibenzo [ b, d)]Furan-1-yl) boronic acid (15 g,60.9 mmol) and compound Trz5 (17.1 g,63.9 mmol) were added to 300ml THF and the mixture was stirred and refluxed. Then, potassium carbonate (25.2 g,182.6 mmol) was dissolved in 76ml of water and added to the mixture, and the mixture was stirred well, followed by addition of bis (tri-t-butylphosphine) palladium (0) (0.3 g,0.6 mmol). After 3 hours of reaction, the reaction mixture was cooled to room temperature, and the organic layer and the aqueous layer were separatedThe organic layer was then distilled. It was dissolved again in chloroform, washed twice with water, then the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 18.7g of compound 1-5_p1. (yield: 71%, MS: [ M+H)] + ＝434)。
Compound 1-5_P1 (15 g,34.6 mmol) and fluoranthen-3-ylboronic acid (8.9 g,36.3 mmol) were added to 300ml THF and the mixture stirred and refluxed. Then, potassium carbonate (14.3 g,103.7 mmol) was dissolved in 43ml of water and added to the mixture, and the mixture was stirred well, followed by addition of bis (tri-t-butylphosphine) palladium (0) (0.2 g,0.3 mmol). After 4 hours of reaction, the reaction mixture was cooled to room temperature, and the organic layer and the aqueous layer were separated, and then the organic layer was distilled. It was dissolved again in chloroform, washed twice with water, then the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 14.9g of compounds 1 to 5. (yield: 72%, MS: [ M+H) ] + ＝600)。
Synthesis examples 1 to 6
Compound 1-5_P1 (15 g,34.6 mmol) and naphtho [2,3-b]Benzofuran-1-ylboronic acid (9.5 g,36.3 mmol) is added to 300ml THF and the mixture is stirred and refluxed. Then, potassium carbonate (14.3 g,103.7 mmol) was dissolved in 43ml of water and added to the mixture, and the mixture was stirred well, followed by addition of bis (tri-t-butylphosphine) palladium (0) (0.2 g,0.3 mmol). After 4 hours of reaction, the reaction mixture was cooled to room temperature, and the organic layer and the aqueous layer were separated, and then the organic layer was distilled. Dissolving in chloroform again, and using waterThe organic layer was then separated, anhydrous magnesium sulfate was added thereto, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 13.8g of compounds 1 to 6. (yield: 65%, MS: [ M+H)] + ＝616)。
Synthesis examples 1 to 7
(3-chlorodibenzo [ b, d)]Furan-1-yl) boronic acid (15 g,60.9 mmol) and compound Trz6 (32.9 g,63.9 mmol) were added to 300ml THF and the mixture was stirred and refluxed. Then, potassium carbonate (25.2 g,182.6 mmol) was dissolved in 76ml of water and added to the mixture, and the mixture was stirred well, followed by addition of bis (tri-t-butylphosphine) palladium (0) (0.3 g,0.6 mmol). After 4 hours of reaction, the reaction mixture was cooled to room temperature, and the organic layer and the aqueous layer were separated, and then the organic layer was distilled. It was dissolved again in chloroform, washed twice with water, then the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 27.4g of compound 1-7_p1. (yield: 71%, MS: [ M+H) ] + ＝636)。
Compound 1-7_P1 (15 g,23.6 mmol) and naphthalen-2-ylboronic acid (4.3 g,24.8 mmol) are added to 300ml THF and the mixture is stirred and refluxed. Then, potassium carbonate (9.8 g,70.7 mmol) was dissolved in 29ml of water and added to the mixture, and the mixture was stirred well, followed by addition of bis (tri-t-butylphosphine) palladium (0) (0.1 g,0.2 mmol). After 4 hours of reaction, the reaction mixture was cooled to room temperature, and the organic layer and the aqueous layer were separated, and then the organic layer was distilled. It was redissolved in chloroform, washed twice with water, and then the organic layer was separated, and anhydrous magnesium sulfate was added theretoStirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 11.5g of compounds 1 to 7. (yield: 67%, MS: [ M+H)] + ＝728)。
Synthesis examples 1 to 8
Trifluoromethanesulfonic anhydride (30.1 g,106.6 mmol) and deuterium oxide (10.7 g,532.8 mmol) were added at 0℃and stirred for 5 hours to prepare a solution. 1-bromo-4-chlorodibenzo [ b, d ] furan (15 g,53.3 mmol) was added to 120ml of 1,2, 4-trichlorobenzene and the mixture was stirred. Then, the prepared mixed solution of trifluoromethanesulfonic anhydride and deuterium oxide was slowly dropped into the mixed solution of 1-bromo-4-chlorodibenzo [ b, d ] furan and 1,2, 4-trichlorobenzene, and the mixture was stirred while heating to 140 ℃ and then maintaining the temperature. After 3 hours of reaction, the reaction mixture was cooled to room temperature, and the organic layer and the aqueous layer were separated. Then, the organic layer was neutralized with an aqueous potassium carbonate solution. After washing with water twice, the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 6.5g of compound sub1-1-1. (yield: 43%, MS: [ M+H ] +=283)
The compounds Sub1-1-1 (15 g,52.9 mmol) and bis (pinacolato) diboron (14.8 g,58.2 mmol) are added to 300ml of 1, 4-diboron
In an alkane, and the mixture was stirred under reflux. Then, potassium acetate (7.8 g,79.4 mmol) was added thereto, and the mixture was stirred well, followed by addition of bis (dibenzylideneacetone) palladium (0) (0.9 g,1.6 mmol) and tricyclohexylphosphine (0.9 g,3.2 mmol). After the reaction for 6 hours, the reaction mixture was cooled to room temperature, and the organic layer was separated using chloroform and water, and then distilled. It was dissolved again in chloroform, washed twice with water, and then the organic layer was separated. To this was added anhydrous magnesium sulfate,stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 10.8g of compound Sub1-1-2. (yield: 62%, MS: [ M+H)]+＝331)/>
Compound Sub1-1-2 (15 g,45.4 mmol) and compound Trz7 (28.1 g,47.6 mmol) were added to 300ml THF and the mixture was stirred and refluxed. Then, potassium carbonate (18.8 g,136.1 mmol) was dissolved in 56ml of water and added to the mixture, and the mixture was stirred well, followed by addition of bis (tri-t-butylphosphine) palladium (0) (0.2 g,0.5 mmol). After 2 hours of reaction, the reaction mixture was cooled to room temperature, and the organic layer and the aqueous layer were separated, and then the organic layer was distilled. It was dissolved again in chloroform, washed twice with water, then the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 23.3g of compound 1-8_p1. (yield: 72%, MS: [ M+H) ] + ＝714)。
Compound 1-8_P1 (15 g,21 mmol) and phenylboronic acid (2.7 g,22.1 mmol) were added to 300ml THF and the mixture was stirred and refluxed. Then, potassium carbonate (8.7 g,63 mmol) was dissolved in 26ml of water and added to the mixture, and the mixture was stirred well, followed by addition of bis (tri-t-butylphosphine) palladium (0) (0.1 g,0.2 mmol). After 5 hours of reaction, the reaction mixture was cooled to room temperature, and the organic layer and the aqueous layer were separated, and then the organic layer was distilled. It was dissolved again in chloroform, washed twice with water, then the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 10g of compounds 1 to 8. (yield: 63%,MS:[M+H] + ＝756)。
synthesis examples 1 to 9
Compound Sub1-1-2 (15 g,45.4 mmol) and compound Trz8 (29.6 g,47.6 mmol) were added to 300ml THF and the mixture was stirred and refluxed. Then, potassium carbonate (18.8 g,136.1 mmol) was dissolved in 56ml of water and added to the mixture, and the mixture was stirred well, followed by addition of bis (tri-t-butylphosphine) palladium (0) (0.2 g,0.5 mmol). After 5 hours of reaction, the reaction mixture was cooled to room temperature, and the organic layer and the aqueous layer were separated, and then the organic layer was distilled. It was dissolved again in chloroform, washed twice with water, then the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 25.3g of compound 1-9_p1. (yield: 75%, MS: [ M+H) ] + ＝744)。
Compound 1-9_P1 (15 g,20.2 mmol) and phenylboronic acid (2.6 g,21.2 mmol) were added to 300ml THF and the mixture was stirred and refluxed. Then, potassium carbonate (8.4 g,60.5 mmol) was dissolved in 25ml of water and added to the mixture, and the mixture was stirred well, followed by addition of bis (tri-t-butylphosphine) palladium (0) (0.1 g,0.2 mmol). After 5 hours of reaction, the reaction mixture was cooled to room temperature, and the organic layer and the aqueous layer were separated, and then the organic layer was distilled. It was dissolved again in chloroform, washed twice with water, then the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 11.1g of compounds 1 to 9. (yield: 70%, MS: [ M+H ]] + ＝786)。
Synthesis examples 1 to 10
Trifluoromethanesulfonic anhydride (60.1 g,213.1 mmol) and deuterium oxide (21.4 g,1065.6 mmol) were added at 0℃and stirred for 5 hours to prepare a solution. 1-bromo-4-chlorodibenzo [ b, d ]]Furan (15 g,53.3 mmol) was added to 120ml 1,2, 4-trichlorobenzene and the mixture was stirred. Then, the prepared mixed solution of trifluoromethanesulfonic anhydride and deuterium oxide is slowly dropped to 1-bromo-4-chlorodibenzo [ b, d ] ]In a mixed solution of furan and 1,2, 4-trichlorobenzene, and the mixture was stirred while being heated to 140 ℃ and then maintained at that temperature. After 10 hours of reaction, the reaction mixture was cooled to room temperature, and the organic layer and the aqueous layer were separated. Then, the organic layer was neutralized with an aqueous potassium carbonate solution. After washing with water twice, the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 5.3g of compound Sub1-2-1. (yield: 35%, MS: [ M+H)] + ＝285)
The compounds Sub1-2-1 (15 g,52.5 mmol) and bis (pinacolato) diboron (14.7 g,57.8 mmol) are added to 300ml of 1, 4-di
In an alkane, and the mixture was stirred under reflux. Then, potassium acetate (7.7 g,78.8 mmol) was added thereto, and the mixture was stirred well, followed by addition of bis (dibenzylideneacetone) palladium (0) (0.9 g,1.6 mmol) and tricyclohexylphosphine (0.9 g,3.2 mmol). After the reaction for 6 hours, the reaction mixture was cooled to room temperature, and the organic layer was separated using chloroform and water, and then distilled. It was dissolved again in chloroform, washed twice with water, and then the organic layer was separated. Anhydrous magnesium sulfate was added thereto, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 11g of compound Sub1-2-2. (yield: 63%, MS: [ M+H) ] + ＝333)/>
Compound Sub1-2-2 (15 g,45.1 mmol) and compound Trz9 (15.8 g,47.4 mmol) were added to 300ml THF and the mixture was stirred and refluxed. Then, potassium carbonate (18.7 g,135.3 mmol) was dissolved in 56ml of water and added to the mixture, and the mixture was stirred well, followed by addition of bis (tri-t-butylphosphine) palladium (0) (0.2 g,0.5 mmol). After 3 hours of reaction, the reaction mixture was cooled to room temperature, and the organic layer and the aqueous layer were separated, and then the organic layer was distilled. It was dissolved again in chloroform, washed twice with water, then the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 14.6g of compound 1-10_p1. (yield: 66%, MS: [ M+H)] + ＝493)。
Compound 1-10_P1 (15 g,30.4 mmol) and dibenzo [ b, d]Furan-1-ylboronic acid (6.8 g,31.9 mmol) is added to 300ml THF and the mixture is stirred and refluxed. Then, potassium carbonate (12.6 g,91.3 mmol) was dissolved in 38ml of water and added to the mixture, and the mixture was stirred well, followed by addition of bis (tri-t-butylphosphine) palladium (0) (0.2 g,0.3 mmol). After 2 hours of reaction, the reaction mixture was cooled to room temperature, and the organic layer and the aqueous layer were separated, and then the organic layer was distilled. It was dissolved again in chloroform, washed twice with water, then the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 13.3g of compounds 1 to 10. (yield: 70%, MS: [ M+H ] ] + ＝625)。
Synthesis examples 1 to 11
(3-chlorodibenzo [ b, d)]Furan-1-yl) boronic acid (15 g,60.9 mmol) and compound Trz10 (25.2 g,63.9 mmol) were added to 300ml THF and the mixture was stirred and refluxed. Then, potassium carbonate (25.2 g,182.6 mmol) was dissolved in 76ml of water and added to the mixture, and the mixture was stirred well, followed by addition of bis (tri-t-butylphosphine) palladium (0) (0.3 g,0.6 mmol). After 2 hours of reaction, the reaction mixture was cooled to room temperature, and the organic layer and the aqueous layer were separated, and then the organic layer was distilled. It was dissolved again in chloroform, washed twice with water, then the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 21.1g of compound 1-11_p1. (yield: 62%, MS: [ M+H)] + ＝560)。
Compound 1-11_P1 (15 g,26.8 mmol) and phenylboronic acid (3.4 g,28.1 mmol) were added to 300ml THF and the mixture was stirred and refluxed. Then, potassium carbonate (11.1 g,80.3 mmol) was dissolved in 33ml of water and added to the mixture, and the mixture was stirred well, followed by addition of bis (tri-t-butylphosphine) palladium (0) (0.1 g,0.3 mmol). After 2 hours of reaction, the reaction mixture was cooled to room temperature, and the organic layer and the aqueous layer were separated, and then the organic layer was distilled. It was dissolved again in chloroform, washed twice with water, then the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 11.8g of compound 1-11_p2. (yield: 73%, MS: [ M+H) ] + ＝602)。
Will be combined1-11_P2 (10 g,16.6 mmol), ptO 2 (1.1 g,5 mmol) and D 2 O (83 ml) was added to the shaker tube, and the tube was then sealed and heated at 250℃and 600psi for 12 hours. When the reaction was completed, chloroform was added, and the reaction solution was transferred to a separating funnel and extracted. The extract was subjected to MgSO 4 Dried and concentrated, and then the sample was purified by silica gel column chromatography to prepare 3.1g of compounds 1 to 11. (yield: 30%, MS [ M+H ]]+＝626)
Synthesis examples 1 to 12
(3-chlorodibenzo [ b, d)]Furan-1-yl) boronic acid (15 g,60.9 mmol) and compound Trz11 (23.5 g,63.9 mmol) were added to 300ml THF and the mixture was stirred and refluxed. Then, potassium carbonate (25.2 g,182.6 mmol) was dissolved in 76ml of water and added to the mixture, and the mixture was stirred well, followed by addition of bis (tri-t-butylphosphine) palladium (0) (0.3 g,0.6 mmol). After 2 hours of reaction, the reaction mixture was cooled to room temperature, and the organic layer and the aqueous layer were separated, and then the organic layer was distilled. It was dissolved again in chloroform, washed twice with water, then the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 23.4g of compound 1-12_p1. (yield: 72%, MS: [ M+H) ] + ＝534)。
Compounds 1-12_P1 (15 g,28.1 mmol) and dibenzo [ b, d]Thiophene-4-ylboronic acid (6.7 g,29.5 mmol) was added to 300ml THF and the mixture was stirred and refluxed. Then, potassium carbonate (11.6 g,84.3 mmol) was dissolved in 35ml of water and added to the mixture, and the mixture was stirred well, followed by addition of bis (tri-t-butylphosphine) palladium (0) (0.1 g,0.3 mmol). After 4 hours of reaction, the reaction mixture was cooled to a roomWarm and separate the organic and aqueous layers, then distill the organic layer. It was dissolved again in chloroform, washed twice with water, then the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 12.4g of compound 1-12_p2. (yield: 65%, MS: [ M+H)] + ＝682)。
Compound 1-12_P2 (10 g,14.7 mmol), ptO 2 (1 g,4.4 mmol) and D 2 O (73 ml) was added to the shaker tube, and the tube was then sealed and heated at 250℃and 600psi for 12 hours. When the reaction was completed, chloroform was added, and the reaction solution was transferred to a separating funnel and extracted. The extract was subjected to MgSO 4 Dried and concentrated, and then the sample was purified by silica gel column chromatography to prepare 5.1g of compounds 1 to 12. (yield: 49%, MS: [ M+H) ] + ＝706)
Synthesis examples 1 to 13
(4-chlorodibenzo [ b, d)]Furan-1-yl) boronic acid (15 g,60.9 mmol) and compound Trz12 (30 g,63.9 mmol) were added to 300ml THF and the mixture was stirred and refluxed. Then, potassium carbonate (25.2 g,182.6 mmol) was dissolved in 76ml of water and added to the mixture, and the mixture was stirred well, followed by addition of bis (tri-t-butylphosphine) palladium (0) (0.3 g,0.6 mmol). After 3 hours of reaction, the reaction mixture was cooled to room temperature, and the organic layer and the aqueous layer were separated, and then the organic layer was distilled. It was dissolved again in chloroform, washed twice with water, then the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 24.4g of compound 1-13_p1. (yield: 63%, MS: [ M+H)] + ＝636)。
Compound 1-13_P1 (15 g,23.6 mmol) and naphthalen-2-ylboronic acid (4.3 g,24.8 mmol) are added to 300ml THF and the mixture is stirred and refluxed. Then, potassium carbonate (9.8 g,70.7 mmol) was dissolved in 29ml of water and added to the mixture, and the mixture was stirred well, followed by addition of bis (tri-t-butylphosphine) palladium (0) (0.1 g,0.2 mmol). After 5 hours of reaction, the reaction mixture was cooled to room temperature, and the organic layer and the aqueous layer were separated, and then the organic layer was distilled. It was dissolved again in chloroform, washed twice with water, then the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 10.5g of compounds 1 to 13. (yield: 61%, MS: [ M+H) ] + ＝728)。
Synthesis examples 1 to 14
(4-chlorodibenzo [ b, d)]Furan-1-yl) boronic acid (15 g,60.9 mmol) and compound Trz13 (22 g,63.9 mmol) were added to 300ml THF and the mixture was stirred and refluxed. Then, potassium carbonate (25.2 g,182.6 mmol) was dissolved in 76ml of water and added to the mixture, and the mixture was stirred well, followed by addition of bis (tri-t-butylphosphine) palladium (0) (0.3 g,0.6 mmol). After 3 hours of reaction, the reaction mixture was cooled to room temperature, and the organic layer and the aqueous layer were separated, and then the organic layer was distilled. It was dissolved again in chloroform, washed twice with water, then the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 22.3g of compound 1-14_p1. (yield: 72%, MS: [ M+H)] + ＝510)。
Compound 1-14_P1 (15 g,29.4 mmol) and naphtho [2,3-b]Benzofuran-4-ylboronic acid (8.1 g,30.9 mmol) is added to 300ml THF and the mixture is stirred and refluxed. Then, potassium carbonate (12.2 g,88.2 mmol) was dissolved in 37ml of water and added to the mixture, and the mixture was stirred well, followed by addition of bis (tri-t-butylphosphine) palladium (0) (0.2 g,0.3 mmol). After 4 hours of reaction, the reaction mixture was cooled to room temperature, and the organic layer and the aqueous layer were separated, and then the organic layer was distilled. It was dissolved again in chloroform, washed twice with water, then the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 14.2g of compounds 1 to 14. (yield: 70%, MS: [ M+H ] ] + ＝692)。
Synthesis examples 1 to 15
(4-chlorodibenzo [ b, d)]Furan-1-yl) boronic acid (15 g,60.9 mmol) and compound Trz14 (26.1 g,63.9 mmol) were added to 300ml THF and the mixture was stirred and refluxed. Then, potassium carbonate (25.2 g,182.6 mmol) was dissolved in 76ml of water and added to the mixture, and the mixture was stirred well, followed by addition of bis (tri-t-butylphosphine) palladium (0) (0.3 g,0.6 mmol). After 2 hours of reaction, the reaction mixture was cooled to room temperature, and the organic layer and the aqueous layer were separated, and then the organic layer was distilled. It was dissolved again in chloroform, washed twice with water, then the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 24.8g of compound 1-15_p1. (yield: 71%, MS: [ M+H)] + ＝574)。
Compounds 1-15_P1 (15 g,26.1 mmol) and dibenzo [ b, d]Furan-1-ylboronic acid (5.8 g,27.4 mmol) is added to 300ml THF and the mixture is stirred and refluxed. Then, potassium carbonate (10.8 g,78.4 mmol) was dissolved in 33ml of water and added to the mixture, and the mixture was stirred well, followed by addition of bis (tri-t-butylphosphine) palladium (0) (0.1 g,0.3 mmol). After 3 hours of reaction, the reaction mixture was cooled to room temperature, and the organic layer and the aqueous layer were separated, and then the organic layer was distilled. It was dissolved again in chloroform, washed twice with water, then the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 11.1g of compounds 1 to 15. (yield: 60%, MS: [ M+H) ] + ＝706)。
Synthesis examples 1 to 16
Trifluoromethanesulfonic anhydride (45.1 g,159.8 mmol) and deuterium oxide (16 g,799.2 mmol) were added at 0℃and stirred for 5 hours to prepare a solution. 1-bromo-4-chlorodibenzo [ b, d ]]Furan (15 g,53.3 mmol) was added to 120ml 1,2, 4-trichlorobenzene and the mixture was stirred. Then, the prepared mixed solution of trifluoromethanesulfonic anhydride and deuterium oxide is slowly dropped to 1-bromo-4-chlorodibenzo [ b, d ]]In a mixed solution of furan and 1,2, 4-trichlorobenzene, and the mixture was stirred while being heated to 140 ℃ and then maintained at that temperature. After 7 hours of reaction, the reaction mixture was cooled to room temperature, and the organic layer and the aqueous layer were separated. Then, the organic layer was neutralized with an aqueous potassium carbonate solution. After washing with water twice, the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 5.6g of compound Sub1-3-1. (yield: 37%, MS: [ M+H)] + ＝284)
The compounds Sub1-3-1 (15 g,52.7 mmol) and bis (pinacolato) diboron (14.7 g,58 mmol) are added to 300ml of 1, 4-di
In an alkane, and the mixture was stirred under reflux. Then, potassium acetate (7.8 g,79.1 mmol) was added thereto, and the mixture was stirred well, followed by bis (dibenzylideneacetone) palladium (0) (0.9 g,1.6 mmol) and tricyclohexylphosphine (0.9 g,3.2 mmol). After the reaction for 6 hours, the reaction mixture was cooled to room temperature, and the organic layer was separated using chloroform and water, and then distilled. It was dissolved again in chloroform, washed twice with water, and then the organic layer was separated. Anhydrous magnesium sulfate was added thereto, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 10.1g of compound Sub1-3-2. (yield: 58%, MS: [ M+H) ] + ＝332)
Compound Sub1-3-2 (15 g,45.2 mmol) and compound Trz15 (17.7 g,47.5 mmol) were added to 300ml THF and the mixture was stirred and refluxed. Then, potassium carbonate (18.8 g,135.7 mmol) was dissolved in 56ml of water and added to the mixture, and the mixture was stirred well, followed by addition of bis (tri-t-butylphosphine) palladium (0) (0.2 g,0.5 mmol). After 2 hours of reaction, the reaction mixture was cooled to room temperature, and the organic layer and the aqueous layer were separated, and then the organic layer was distilled. It was dissolved again in chloroform, washed twice with water, then the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 15.4g of compound 1-16_p1. (yield: 63%, MS: [ M+H)] + ＝542)。
Compound 1-16_P1 (15 g,27.7 mmol) and (phenyl-d 5) boronic acid (3.7 g,29.1 mmol) were added to 300ml THF and the mixture was stirred and refluxed. Then, potassium carbonate (11.5 g,83 mmol) was dissolved in 34ml of water and added to the mixture, and the mixture was stirred well, followed by addition of bis (tri-t-butylphosphine) palladium (0) (0.1 g,0.3 mmol). After 3 hours of reaction, the reaction mixture was cooled to room temperature, and the organic layer and the aqueous layer were separated, and then the organic layer was distilled. It was dissolved again in chloroform, washed twice with water, then the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 11.9g of compounds 1 to 16. (yield: 73%, MS: [ M+H) ] + ＝589)。
Synthesis examples 1 to 17
(6-chlorodibenzo [ b, d)]Furan-1-yl) boronic acid (15 g,60.9 mmol) and compound Trz16 (23.5 g,63.9 mmol) were added to 300ml THF and the mixture was stirred and refluxed. Then, potassium carbonate (25.2 g,182.6 mmol) was dissolved in 76ml of water and added to the mixture, and the mixture was stirred well, followed by addition of bis (tri-t-butylphosphine) palladium (0) (0.3 g,0.6 mmol). After 2 hours of reaction, the reaction mixture was cooled to room temperature, and the organic layer and the aqueous layer were separated, and then the organic layer was distilled. It was dissolved again in chloroform, washed twice with water, then the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 23.4g of compound 1-17_p1. (yield: 72%, MS: [ M+H)] + ＝534)。
Compound 1-17_P1 (15 g,28.1 mmol) and naphthalen-2-ylboronAcid (5.1 g,29.5 mmol) was added to 300ml THF and the mixture was stirred and refluxed. Then, potassium carbonate (11.6 g,84.3 mmol) was dissolved in 35ml of water and added to the mixture, and the mixture was stirred well, followed by addition of bis (tri-t-butylphosphine) palladium (0) (0.1 g,0.3 mmol). After 3 hours of reaction, the reaction mixture was cooled to room temperature, and the organic layer and the aqueous layer were separated, and then the organic layer was distilled. It was dissolved again in chloroform, washed twice with water, then the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 12.5g of compounds 1 to 17. (yield: 71%, MS: [ M+H) ] + ＝626)。
Synthesis examples 1 to 18
(6-chlorodibenzo [ b, d)]Furan-1-yl) boronic acid (15 g,60.9 mmol) and compound Trz17 (29.7 g,63.9 mmol) were added to 300ml THF and the mixture was stirred and refluxed. Then, potassium carbonate (25.2 g,182.6 mmol) was dissolved in 76ml of water and added to the mixture, and the mixture was stirred well, followed by addition of bis (tri-t-butylphosphine) palladium (0) (0.3 g,0.6 mmol). After 5 hours of reaction, the reaction mixture was cooled to room temperature, and the organic layer and the aqueous layer were separated, and then the organic layer was distilled. It was dissolved again in chloroform, washed twice with water, then the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 24.6g of compound 1-18_p1. (yield: 69%, MS: [ M+H)] + ＝586)。
Compound 1-18_P1 (15 g,25.6 mmol) and naphthalen-2-ylboronic acid (4.6 g,26.9 mmol) are added to 300ml THF and the mixture is stirred and the mixture is taken upAnd (5) refluxing. Then, potassium carbonate (10.6 g,76.8 mmol) was dissolved in 32ml of water and added to the mixture, and the mixture was stirred well, followed by addition of bis (tri-t-butylphosphine) palladium (0) (0.1 g,0.3 mmol). After 2 hours of reaction, the reaction mixture was cooled to room temperature, and the organic layer and the aqueous layer were separated, and then the organic layer was distilled. It was dissolved again in chloroform, washed twice with water, then the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 10.9g of compounds 1 to 18. (yield: 63%, MS: [ M+H) ] + ＝678)。
Synthesis examples 1 to 19
(6-chlorodibenzo [ b, d)]Furan-1-yl) boronic acid (15 g,60.9 mmol) and compound Trz18 (31.2 g,63.9 mmol) were added to 300ml THF and the mixture was stirred and refluxed. Then, potassium carbonate (25.2 g,182.6 mmol) was dissolved in 76ml of water and added to the mixture, and the mixture was stirred well, followed by addition of bis (tri-t-butylphosphine) palladium (0) (0.3 g,0.6 mmol). After 3 hours of reaction, the reaction mixture was cooled to room temperature, and the organic layer and the aqueous layer were separated, and then the organic layer was distilled. It was dissolved again in chloroform, washed twice with water, then the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 24.5g of compound 1-19_p1. (yield: 66%, MS: [ M+H)] + ＝610)。
Compound 1-19_P1 (15 g,24.6 mmol) and naphthalen-2-ylboronic acid (4.4 g,25.8 mmol) are added to 300ml THF and the mixture is stirred and refluxed. Potassium carbonate (10.2 g,73.8 mmol) was then dissolved in 31ml waterAnd added to the mixture, and the mixture was stirred well, then bis (tri-t-butylphosphine) palladium (0) (0.1 g,0.2 mmol) was added. After 2 hours of reaction, the reaction mixture was cooled to room temperature, and the organic layer and the aqueous layer were separated, and then the organic layer was distilled. It was dissolved again in chloroform, washed twice with water, then the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 11.4g of compounds 1 to 19. (yield: 66%, MS: [ M+H) ] + ＝702)。
Synthesis examples 1 to 20
(6-chlorodibenzo [ b, d)]Furan-1-yl) boronic acid (15 g,60.9 mmol) and compound Trz19 (20.3 g,63.9 mmol) were added to 300ml THF and the mixture was stirred and refluxed. Then, potassium carbonate (25.2 g,182.6 mmol) was dissolved in 76ml of water and added to the mixture, and the mixture was stirred well, followed by addition of bis (tri-t-butylphosphine) palladium (0) (0.3 g,0.6 mmol). After 5 hours of reaction, the reaction mixture was cooled to room temperature, and the organic layer and the aqueous layer were separated, and then the organic layer was distilled. It was dissolved again in chloroform, washed twice with water, then the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 19.1g of compound 1-20_p1. (yield: 65%, MS: [ M+H)] + ＝484)。
Compound 1-20_P1 (15 g,31 mmol) and phenanthren-9-ylboronic acid (7.2 g,32.5 mmol) are added to 300ml THF and the mixture is stirred and refluxed. Then, potassium carbonate (12.9 g,93 mmol) was dissolved in 39ml of water and added to the mixture, and the mixture was stirred well and then addedBis (tri-t-butylphosphine) palladium (0) (0.2 g,0.3 mmol) was added. After 2 hours of reaction, the reaction mixture was cooled to room temperature, and the organic layer and the aqueous layer were separated, and then the organic layer was distilled. It was dissolved again in chloroform, washed twice with water, then the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 12g of compounds 1 to 20. (yield: 62%, MS: [ M+H) ] + ＝626)。
Synthesis examples 1 to 21
Trifluoromethanesulfonic anhydride (30.1 g,106.6 mmol) and deuterium oxide (10.7 g,532.8 mmol) were added at 0℃and stirred for 5 hours to prepare a solution. 1-bromo-6-chlorodibenzo [ b, d ]]Furan (15 g,53.3 mmol) was added to 120ml 1,2, 4-trichlorobenzene and the mixture was stirred. Then, the prepared mixed solution of trifluoromethanesulfonic anhydride and deuterium oxide is slowly dropped to 1-bromo-6-chlorodibenzo [ b, d ]]In a mixed solution of furan and 1,2, 4-trichlorobenzene, and the mixture was stirred while being heated to 140 ℃ and then maintained at that temperature. After 3 hours of reaction, the reaction mixture was cooled to room temperature, and the organic layer and the aqueous layer were separated. Then, the organic layer was neutralized with an aqueous potassium carbonate solution. After washing with water twice, the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 6.8g of compound Sub2-1-1. (yield: 45%, MS: [ M+H ]] + ＝283)
The compounds Sub2-1-1 (15 g,52.9 mmol) and bis (pinacolato) diboron (14.8 g,58.2 mmol) are added to 300ml of 1, 4-diboron
In an alkane, and the mixture was stirred under reflux. Then, potassium acetate (7.8 g,79.4 mmol) was added thereto, the mixture was sufficiently stirred, and bis (dibenzylideneacetone) palladium (0) ( 0.9g,1.6 mmol) and tricyclohexylphosphine (0.9 g,3.2 mmol). After the reaction for 6 hours, the reaction mixture was cooled to room temperature, and the organic layer was separated using chloroform and water, and then distilled. It was dissolved again in chloroform, washed twice with water, and then the organic layer was separated. Anhydrous magnesium sulfate was added thereto, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 13.1g of compound Sub2-1-2. (yield: 75%, MS: [ M+H)] + ＝331)/>
Compound Sub2-1-2 (15 g,45.4 mmol) and compound Trz20 (22.6 g,47.6 mmol) were added to 300ml THF and the mixture was stirred and refluxed. Then, potassium carbonate (18.8 g,136.1 mmol) was dissolved in 56ml of water and added to the mixture, and the mixture was stirred well, followed by addition of bis (tri-t-butylphosphine) palladium (0) (0.2 g,0.5 mmol). After 4 hours of reaction, the reaction mixture was cooled to room temperature, and the organic layer and the aqueous layer were separated, and then the organic layer was distilled. It was dissolved again in chloroform, washed twice with water, then the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 17.8g of compound 1-21_p1. (yield: 61%, MS: [ M+H) ] + ＝643)。
Compound 1-21_P1 (15 g,23.3 mmol) and (phenyl-d 5) boronic acid (3.1 g,24.5 mmol) were added to 300ml THF and the mixture stirred and refluxed. Then, potassium carbonate (9.7 g,70 mmol) was dissolved in 29ml of water and added to the mixture, and the mixture was stirred well, followed by addition of bis (tri-t-butylphosphine) palladium (0) (0.1 g,0.2 mmol). After 4 hours of reaction, the reaction mixture was cooled to room temperature, and the organic layer was then cooledAnd the aqueous layer were separated, and then the organic layer was distilled. It was dissolved again in chloroform, washed twice with water, then the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 11.9g of compounds 1 to 21. (yield: 74%, MS: [ M+H)] + ＝690)。
Synthesis examples 1 to 22
Compound Sub2-1-2 (15 g,45.4 mmol) and compound Trz21 (21.1 g,47.6 mmol) were added to 300ml THF and the mixture was stirred and refluxed. Then, potassium carbonate (18.8 g,136.1 mmol) was dissolved in 56ml of water and added to the mixture, and the mixture was stirred well, followed by addition of bis (tri-t-butylphosphine) palladium (0) (0.2 g,0.5 mmol). After 4 hours of reaction, the reaction mixture was cooled to room temperature, and the organic layer and the aqueous layer were separated, and then the organic layer was distilled. It was dissolved again in chloroform, washed twice with water, then the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 18.6g of compound 1-22_p1. (yield: 67%, MS: [ M+H) ] + ＝612)。
Compound 1-22_P1 (15 g,24.5 mmol) and (phenyl-d 5) boronic acid (3.3 g,25.7 mmol) were added to 300ml THF and the mixture stirred and refluxed. Then, potassium carbonate (10.2 g,73.5 mmol) was dissolved in 30ml of water and added to the mixture, and the mixture was stirred well, followed by addition of bis (tri-t-butylphosphine) palladium (0) (0.1 g,0.2 mmol). After 2 hours of reaction, the reaction mixture was cooled to room temperature, and the organic layer and the aqueous layer were separated, and then the organic layer was distilled. Dissolving in chloroform again, washing with waterThe organic layer was then separated twice, anhydrous magnesium sulfate was added thereto, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 10g of compounds 1 to 22. (yield: 62%, MS: [ M+H)] + ＝659)。
Synthesis examples 1 to 23
Trifluoromethanesulfonic anhydride (60.1 g,213.1 mmol) and deuterium oxide (21.4 g,1065.6 mmol) were added at 0℃and stirred for 5 hours to prepare a solution. 1-bromo-6-chlorodibenzo [ b, d ]]Furan (15 g,53.3 mmol) was added to 120ml 1,2, 4-trichlorobenzene and the mixture was stirred. Then, the prepared mixed solution of trifluoromethanesulfonic anhydride and deuterium oxide is slowly dropped to 1-bromo-6-chlorodibenzo [ b, d ] ]In a mixed solution of furan and 1,2, 4-trichlorobenzene, and the mixture was stirred while being heated to 140 ℃, and then the temperature was maintained. After 10 hours of reaction, the reaction mixture was cooled to room temperature, and the organic layer and the aqueous layer were separated. Then, the organic layer was neutralized with an aqueous potassium carbonate solution. After washing with water twice, the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 6.5g of compound Sub2-2-1. (yield: 43%, MS: [ M+H)] + ＝285)
The compounds Sub2-2-1 (15 g,52.5 mmol) and bis (pinacolato) diboron (14.7 g,57.8 mmol) are added to 300ml of 1, 4-di
In an alkane, and the mixture was stirred under reflux. Then, potassium acetate (7.7 g,78.8 mmol) was added thereto, and the mixture was stirred well, followed by addition of bis (dibenzylideneacetone) palladium (0) (0.9 g,1.6 mmol) and tricyclohexylphosphine (0.9 g,3.2 mmol). After reacting for 5 hours, the reaction mixture was cooled to room temperature, and the organic layer was separated using chloroform and water, and then distilled. Dissolving in chloroform againThe organic layer was then separated. Anhydrous magnesium sulfate was added thereto, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 13.1g of compound Sub2-2-2. (yield: 75%, MS: [ M+H) ] + ＝333)/>
Compound Sub2-2-2 (15 g,60.9 mmol) and compound Trz22 (36.1 g,63.9 mmol) were added to 300ml THF and the mixture was stirred and refluxed. Then, potassium carbonate (25.2 g,182.6 mmol) was dissolved in 76ml of water and added to the mixture, and the mixture was stirred well, followed by addition of bis (tri-t-butylphosphine) palladium (0) (0.3 g,0.6 mmol). After 3 hours of reaction, the reaction mixture was cooled to room temperature, and the organic layer and the aqueous layer were separated, and then the organic layer was distilled. It was dissolved again in chloroform, washed twice with water, then the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 28.9g of compound 1-23_p1. (yield: 69%, MS: [ M+H)] + ＝690)。
Compound 1-23_P1 (15 g,21.7 mmol) and phenylboronic acid (2.8 g,22.8 mmol) were added to 300ml THF and the mixture was stirred and refluxed. Then, potassium carbonate (9 g,65.2 mmol) was dissolved in 27ml of water and added to the mixture, and the mixture was stirred well, followed by addition of bis (tri-t-butylphosphine) palladium (0) (0.1 g,0.2 mmol). After 5 hours of reaction, the reaction mixture was cooled to room temperature, and the organic layer and the aqueous layer were separated, and then the organic layer was distilled. Dissolving in chloroform again, washing twice with water, separating organic layer, adding anhydrous magnesium sulfate, stirring, filtering, and steaming under reduced pressure And (3) distilling. The concentrated compound was purified by silica gel column chromatography to prepare 9.5g of compounds 1 to 23. (yield: 60%, MS: [ M+H)] + ＝732)。
Synthesis examples 1 to 24
Synthesis examples 1 to 25
(3-chlorodibenzo [ b, d)]Furan-1-yl) boronic acid (15 g,60.9 mmol) and compound Trz23 (25.2 g,63.9 mmol) were added to 300ml THF and the mixture was stirred and refluxed. Then, potassium carbonate (25.2 g,182.6 mmol) was dissolved in 76ml of water and added to the mixture, and the mixture was stirred well, followed by addition of bis (tri-t-butylphosphine) palladium (0) (0.3 g,0.6 mmol). After 3 hours of reaction, the reaction mixture was cooled to room temperature, and the organic layer and the aqueous layer were separated, and then the organic layer was distilled. It was dissolved again in chloroform, washed twice with water, then the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 20.7g of compound 1-25_p1. (yield: 63%, MS: [ M+H) ] + ＝540)。
Compounds 1-25_P1 (15 g,27.8 mmol) and dibenzo [ b, d]Furan-1-ylboronic acid (6.2 g,29.2 mmol) is added to 300ml THF and the mixture is stirred and refluxed. Then, potassium carbonate (11.5 g,83.3 mmol) was dissolved in 35ml of water and added to the mixture, and the mixture was stirred well, followed by addition of bis (tri-t-butylphosphine) palladium (0) (0.1 g,0.3 mmol). After 5 hours of reaction, the reaction mixture was cooled to room temperature, and the organic layer and the aqueous layer were separated, and then the organic layer was distilled. It was dissolved again in chloroform, washed twice with water, then the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 11.4g of compound 1-25_p2. (yield: 61%, MS: [ M+H)] + ＝672)。
Compound 1-25_P2 (10 g,14.9 mmol), ptO 2 (1 g,4.5 mmol) and D 2 O (74 ml) was added to the shaker tube, and the tube was then sealed and heated at 250℃and 600psi for 12 hours. When the reaction was completed, chloroform was added, and the reaction solution was transferred to a separating funnel and extracted. The extract was subjected to MgSO 4 Dried and concentrated, and then the sample was purified by silica gel column chromatography to prepare 3.7g of compounds 1 to 25. (yield: 36%, MS: [ M+H) ] + ＝695)
Synthesis examples 1 to 26
(7-chlorodibenzo [ b, d)]Furan-1-yl) boronic acid (15 g,60.9 mmol) and compound Trz19 (20.3 g,63.9 mmol) were added to 300ml THF and the mixture was stirred and refluxed. Then, potassium carbonate (25.2 g,182.6 mmol) was dissolved in 76ml of water and added to the mixture, and the mixture was stirred well, then bis (tri-t-butylphosphine) palladium (0) (0.3 g,0.6 mmol). After 4 hours of reaction, the reaction mixture was cooled to room temperature, and the organic layer and the aqueous layer were separated, and then the organic layer was distilled. It was dissolved again in chloroform, washed twice with water, then the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 17.6g of compound 1-26_p1. (yield: 60%, MS: [ M+H)] + ＝484)。
Compound 1-26_P1 (15 g,31 mmol) and naphthalen-2-ylboronic acid (5.6 g,32.5 mmol) are added to 300ml THF and the mixture is stirred and refluxed. Then, potassium carbonate (12.9 g,93 mmol) was dissolved in 39ml of water and added to the mixture, and the mixture was stirred well, followed by addition of bis (tri-t-butylphosphine) palladium (0) (0.2 g,0.3 mmol). After 2 hours of reaction, the reaction mixture was cooled to room temperature, and the organic layer and the aqueous layer were separated, and then the organic layer was distilled. It was dissolved again in chloroform, washed twice with water, then the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 13g of compounds 1 to 26. (yield: 73%, MS: [ M+H) ] + ＝576)。
Synthesis examples 1 to 27
(7-chlorodibenzo [ b, d)]Furan-1-yl) boronic acid (15 g,60.9 mmol) and compound Trz24 (22.9 g,63.9 mmol) were added to 300ml THF and the mixture was stirred and refluxed. Then, potassium carbonate (25.2 g,182.6 mmol) was dissolved in 76ml of water and added to the mixture, and the mixture was stirred well, followed by addition of bis (tri-t-butylphosphine) palladium (0) (0.3 g,0.6 mmol). After 5 hours of reaction, the reaction mixture was cooled to room temperature,and the organic layer and the aqueous layer were separated, and then the organic layer was distilled. It was dissolved again in chloroform, washed twice with water, then the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 20.4g of compound 1-27_p1. (yield: 64%, MS: [ M+H ]] + ＝524)。
Compound 1-27_P1 (15 g,28.6 mmol) and naphthalen-2-ylboronic acid (5.2 g,30.1 mmol) are added to 300ml THF and the mixture is stirred and refluxed. Then, potassium carbonate (11.9 g,85.9 mmol) was dissolved in 36ml of water and added to the mixture, and the mixture was stirred well, followed by addition of bis (tri-t-butylphosphine) palladium (0) (0.1 g,0.3 mmol). After 3 hours of reaction, the reaction mixture was cooled to room temperature, and the organic layer and the aqueous layer were separated, and then the organic layer was distilled. It was dissolved again in chloroform, washed twice with water, then the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 10.9g of compounds 1 to 27. (yield: 62%, MS: [ M+H) ] + ＝616)。
Synthesis examples 1 to 28
(7-chlorodibenzo [ b, d)]Furan-1-yl) boronic acid (15 g,60.9 mmol) and compound Trz25 (22.9 g,63.9 mmol) were added to 300ml THF and the mixture was stirred and refluxed. Then, potassium carbonate (25.2 g,182.6 mmol) was dissolved in 76ml of water and added to the mixture, and the mixture was stirred well, followed by addition of bis (tri-t-butylphosphine) palladium (0) (0.3 g,0.6 mmol). After 2 hours of reaction, the reaction mixture was cooled to room temperature, and the organic layer and the aqueous layer were separated, and then the organic layer was distilled. It is subjected toAgain dissolved in chloroform, washed twice with water, then the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 22.6g of compound 1-28_p1. (yield: 71%, MS: [ M+H)] + ＝524)。
Compound 1-28_P1 (15 g,28.6 mmol) and phenanthrene-3-ylboronic acid (6.7 g,30.1 mmol) are added to 300ml THF and the mixture is stirred and refluxed. Then, potassium carbonate (11.9 g,85.9 mmol) was dissolved in 36ml of water and added to the mixture, and the mixture was stirred well, followed by addition of bis (tri-t-butylphosphine) palladium (0) (0.1 g,0.3 mmol). After 3 hours of reaction, the reaction mixture was cooled to room temperature, and the organic layer and the aqueous layer were separated, and then the organic layer was distilled. It was dissolved again in chloroform, washed twice with water, then the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 12.9g of compounds 1 to 28. (yield: 68%, MS: [ M+H) ] + ＝666)。
Synthesis examples 1 to 29
(7-chlorodibenzo [ b, d)]Furan-1-yl) boronic acid (15 g,60.9 mmol) and compound Trz26 (25.2 g,63.9 mmol) were added to 300ml THF and the mixture was stirred and refluxed. Then, potassium carbonate (25.2 g,182.6 mmol) was dissolved in 76ml of water and added to the mixture, and the mixture was stirred well, followed by addition of bis (tri-t-butylphosphine) palladium (0) (0.3 g,0.6 mmol). After 2 hours of reaction, the reaction mixture was cooled to room temperature, and the organic layer and the aqueous layer were separated, and then the organic layer was distilled. It was redissolved in chloroform, washed twice with water and then the organic layer was washed with waterTo this, anhydrous magnesium sulfate was added, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 21.1g of compound 1-29_p1. (yield: 62%, MS: [ M+H)] + ＝560)。
Compound 1-29_P1 (15 g,26.8 mmol) and dibenzo [ b, d]Thiophene-4-ylboronic acid (6.4 g,28.1 mmol) was added to 300ml THF and the mixture was stirred and refluxed. Then, potassium carbonate (11.1 g,80.3 mmol) was dissolved in 33ml of water and added to the mixture, and the mixture was stirred well, followed by addition of bis (tri-t-butylphosphine) palladium (0) (0.1 g,0.3 mmol). After 3 hours of reaction, the reaction mixture was cooled to room temperature, and the organic layer and the aqueous layer were separated, and then the organic layer was distilled. It was dissolved again in chloroform, washed twice with water, then the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 12.3g of compounds 1 to 29. (yield: 65%, MS: [ M+H) ] + ＝708)。
Synthesis examples 1 to 30
(7-chlorodibenzo [ b, d)]Furan-1-yl) boronic acid (15 g,60.9 mmol) and compound Trz27 (38.6 g,63.9 mmol) were added to 300ml THF and the mixture was stirred and refluxed. Then, potassium carbonate (25.2 g,182.6 mmol) was dissolved in 76ml of water and added to the mixture, and the mixture was stirred well, followed by addition of bis (tri-t-butylphosphine) palladium (0) (0.3 g,0.6 mmol). After 5 hours of reaction, the reaction mixture was cooled to room temperature, and the organic layer and the aqueous layer were separated, and then the organic layer was distilled. Dissolving in chloroform again, washing twice with water, separating the organic layer, adding anhydrous magnesium sulfate thereto, stirring,then filtered and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 29.1g of compound 1-30_p1. (yield: 66%, MS: [ M+H)] + ＝726)。
Compound 1-30_P1 (15 g,20.7 mmol) and naphthalen-2-ylboronic acid (3.7 g,21.7 mmol) are added to 300ml THF and the mixture is stirred and refluxed. Then, potassium carbonate (8.6 g,62 mmol) was dissolved in 26ml of water and added to the mixture, and the mixture was stirred well, followed by addition of bis (tri-t-butylphosphine) palladium (0) (0.1 g,0.2 mmol). After 3 hours of reaction, the reaction mixture was cooled to room temperature, and the organic layer and the aqueous layer were separated, and then the organic layer was distilled. It was dissolved again in chloroform, washed twice with water, then the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 10.6g of compounds 1 to 30. (yield: 63%, MS: [ M+H) ] + ＝818)。
Synthesis examples 1 to 31
Trifluoromethanesulfonic anhydride (30.1 g,106.6 mmol) and deuterium oxide (10.7 g,532.8 mmol) were added at 0℃and stirred for 5 hours to prepare a solution. 1-bromo-7-chlorodibenzo [ b, d ]]Furan (15 g,53.3 mmol) was added to 120ml 1,2, 4-trichlorobenzene and the mixture was stirred. Then, the prepared mixed solution of trifluoromethanesulfonic anhydride and deuterium oxide is slowly dropped to 1-bromo-7-chlorodibenzo [ b, d ]]In a mixed solution of furan and 1,2, 4-trichlorobenzene, and the mixture was stirred while being heated to 140 ℃ and then maintained at that temperature. After 3 hours of reaction, the reaction mixture was cooled to room temperature, and the organic layer and the aqueous layer were separated. Then, the organic layer was neutralized with an aqueous potassium carbonate solution. After washing twice with water, the organic layer was separatedAnhydrous magnesium sulfate was added thereto, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 6g of compound Sub3-1-1. (yield: 40%, MS: [ M+H)] + ＝283)
The compounds Sub3-1-1 (15 g,52.9 mmol) and bis (pinacolato) diboron (14.8 g,58.2 mmol) are added to 300ml of 1, 4-diboron
In an alkane, and the mixture was stirred under reflux. Then, potassium acetate (7.8 g,79.4 mmol) was added thereto, and the mixture was stirred well, followed by addition of bis (dibenzylideneacetone) palladium (0) (0.9 g,1.6 mmol) and tricyclohexylphosphine (0.9 g,3.2 mmol). After 4 hours of reaction, the reaction mixture was cooled to room temperature, and the organic layer was separated using chloroform and water, and then distilled. It was dissolved again in chloroform, washed twice with water, and then the organic layer was separated. Anhydrous magnesium sulfate was added thereto, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 11.4g of compound Sub3-1-2. (yield: 65%, MS: [ M+H) ] + ＝331)
Compound Sub3-1-2 (15 g,45.4 mmol) and compound Trz28 (28.6 g,47.6 mmol) were added to 300ml THF and the mixture was stirred and refluxed. Then, potassium carbonate (18.8 g,136.1 mmol) was dissolved in 56ml of water and added to the mixture, and the mixture was stirred well, followed by addition of bis (tri-t-butylphosphine) palladium (0) (0.2 g,0.5 mmol). After 2 hours of reaction, the reaction mixture was cooled to room temperature, and the organic layer and the aqueous layer were separated, and then the organic layer was distilled. It was dissolved again in chloroform, washed twice with water, then the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 20.3g of compound 1-31_p1.(yield: 62%, MS: [ M+H)] + ＝723)。
Compound 1-31_P1 (15 g,20.7 mmol) and phenanthrene-3-ylboronic acid (4.8 g,21.8 mmol) are added to 300ml THF and the mixture is stirred and refluxed. Then, potassium carbonate (8.6 g,62.2 mmol) was dissolved in 26ml of water and added to the mixture, and the mixture was stirred well, followed by addition of bis (tri-t-butylphosphine) palladium (0) (0.1 g,0.2 mmol). After 2 hours of reaction, the reaction mixture was cooled to room temperature, and the organic layer and the aqueous layer were separated, and then the organic layer was distilled. It was dissolved again in chloroform, washed twice with water, then the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 11.5g of compounds 1 to 31. (yield: 64%, MS: [ M+H ] ] + ＝866)。
Synthesis examples 1 to 32
Trifluoromethanesulfonic anhydride (60.1 g,213.1 mmol) and deuterium oxide (21.4 g,1065.6 mmol) were added at 0℃and stirred for 5 hours to prepare a solution. 1-bromo-7-chlorodibenzo [ b, d ]]Furan (15 g,53.3 mmol) was added to 120ml 1,2, 4-trichlorobenzene and the mixture was stirred. Then, the prepared mixed solution of trifluoromethanesulfonic anhydride and deuterium oxide is slowly dropped to 1-bromo-7-chlorodibenzo [ b, d ]]In a mixed solution of furan and 1,2, 4-trichlorobenzene, and the mixture was stirred while being heated to 140 ℃ and then maintained at that temperature. After 10 hours of reaction, the reaction mixture was cooled to room temperature, and the organic layer and the aqueous layer were separated. Then, the organic layer was neutralized with an aqueous potassium carbonate solution. After washing with water twice, the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, then filtered, and the filtrate was distilled under reduced pressure. Passing the concentrated compound through silica gelPurification by column chromatography gave 6.7g of compound Sub3-2-1. (yield: 44%, MS: [ M+H)] + ＝285)
The compounds Sub3-2-1 (15 g,52.5 mmol) and bis (pinacolato) diboron (14.7 g,57.8 mmol) are added to 300ml of 1, 4-di
In an alkane, and the mixture was stirred under reflux. Then, potassium acetate (7.7 g,78.8 mmol) was added thereto, and the mixture was stirred well, followed by addition of bis (dibenzylideneacetone) palladium (0) (0.9 g,1.6 mmol) and tricyclohexylphosphine (0.9 g,3.2 mmol). After the reaction for 6 hours, the reaction mixture was cooled to room temperature, and the organic layer was separated using chloroform and water, and then distilled. It was dissolved again in chloroform, washed twice with water, and then the organic layer was separated. Anhydrous magnesium sulfate was added thereto, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 11.7g of compound Sub3-2-2. (yield: 67%, MS: [ M+H) ] + ＝333)
Compound Sub3-2-2 (15 g,45.1 mmol) and compound Trz29 (18.7 g,47.4 mmol) were added to 300ml THF and the mixture was stirred and refluxed. Then, potassium carbonate (18.7 g,135.3 mmol) was dissolved in 56ml of water and added to the mixture, and the mixture was stirred well, followed by addition of bis (tri-t-butylphosphine) palladium (0) (0.2 g,0.5 mmol). After 2 hours of reaction, the reaction mixture was cooled to room temperature, and the organic layer and the aqueous layer were separated, and then the organic layer was distilled. It was dissolved again in chloroform, washed twice with water, then the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 18g of compound 1-32_p1. (yield: 71%, MS: [ M+H)] + ＝564)。
Compound 1-32_P1 (15 g,26.6 mmol) and (phenyl-d 5) boronic acid (3.5 g,27.9 mmol) were added to 300ml THF and the mixture was stirred and refluxed. Then, potassium carbonate (11 g,79.8 mmol) was dissolved in 33ml of water and added to the mixture, and the mixture was sufficiently stirred, followed by addition of bis (tri-t-butylphosphine) palladium (0) (0.1 g,0.3 mmol). After 3 hours of reaction, the reaction mixture was cooled to room temperature, and the organic layer and the aqueous layer were separated, and then the organic layer was distilled. It was dissolved again in chloroform, washed twice with water, then the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 11.4g of compounds 1 to 32. (yield: 70%, MS: [ M+H ] ] + ＝611)。
Synthesis examples 1 to 33
Compound Sub3-2-2 (15 g,45.1 mmol) and compound Trz30 (24.8 g,47.4 mmol) were added to 300ml THF and the mixture was stirred and refluxed. Then, potassium carbonate (18.7 g,135.3 mmol) was dissolved in 56ml of water and added to the mixture, and the mixture was stirred well, followed by addition of bis (tri-t-butylphosphine) palladium (0) (0.2 g,0.5 mmol). After 2 hours of reaction, the reaction mixture was cooled to room temperature, and the organic layer and the aqueous layer were separated, and then the organic layer was distilled. It was dissolved again in chloroform, washed twice with water, then the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 18.4g of compound 1-33_p1. (yield: 63%, MS: [ M+H)] + ＝650)。
Compound 1-33_P1 (15 g,23.1 mmol) and phenylboronic acid (3 g,24.2 mmol) were added to 300ml THF and the mixture was stirred and refluxed. Then, potassium carbonate (9.6 g,69.2 mmol) was dissolved in 29ml of water and added to the mixture, and the mixture was stirred well, followed by addition of bis (tri-t-butylphosphine) palladium (0) (0.1 g,0.2 mmol). After 2 hours of reaction, the reaction mixture was cooled to room temperature, and the organic layer and the aqueous layer were separated, and then the organic layer was distilled. It was dissolved again in chloroform, washed twice with water, then the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 11.5g of compounds 1 to 33. (yield: 72%, MS: [ M+H) ] + ＝692)。
Synthesis examples 1 to 34
Synthesis examples 1 to 35
(7-chlorodibenzo [ b, d)]Furan-1-yl) boronic acid (15 g,60.9 mmol) and compound Trz29 (25.2 g,63.9 mmol) were added to 300ml THF and the mixture was stirred and refluxed. Then, potassium carbonate (25.2 g,182.6 mmol) was dissolved in 76ml of water and added to the mixture, and the mixture was sufficiently stirred, thenBis (tri-t-butylphosphine) palladium (0) (0.3 g,0.6 mmol) was added. After 2 hours of reaction, the reaction mixture was cooled to room temperature, and the organic layer and the aqueous layer were separated, and then the organic layer was distilled. It was dissolved again in chloroform, washed twice with water, then the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 23.8g of compound 1-35_p1. (yield: 70%, MS: [ M+H ] ] + ＝560)。
Compound 1-35_P1 (15 g,26.8 mmol) and phenylboronic acid (3.4 g,28.1 mmol) were added to 300ml THF and the mixture was stirred and refluxed. Then, potassium carbonate (11.1 g,80.3 mmol) was dissolved in 33ml of water and added to the mixture, and the mixture was stirred well, followed by addition of bis (tri-t-butylphosphine) palladium (0) (0.1 g,0.3 mmol). After 5 hours of reaction, the reaction mixture was cooled to room temperature, and the organic layer and the aqueous layer were separated, and then the organic layer was distilled. It was dissolved again in chloroform, washed twice with water, then the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 11.3g of compound 1-35_p2. (yield: 70%, MS: [ M+H ]] + ＝602)。
Compound 1-35_P2 (10 g,16.6 mmol), ptO 2 (1.1 g,5 mmol) and D 2 O (83 ml) was added to the shaker tube, and the tube was then sealed and heated at 250℃and 600psi for 12 hours. When the reaction was completed, chloroform was added, and the reaction solution was transferred to a separating funnel and extracted. The extract was subjected to MgSO 4 Dried and concentrated, and then the sample was purified by silica gel column chromatography to prepare 3.7g of compounds 1 to 35. (production) The rate is as follows: 36, MS: [ M+H ]] + ＝626)
Synthesis examples 1 to 36
Synthesis examples 1 to 37
(8-chlorodibenzo [ b, d)]Furan-1-yl) boronic acid (15 g,60.9 mmol) and compound Trz31 (26.8 g,63.9 mmol) were added to 300ml THF and the mixture was stirred and refluxed. Then, potassium carbonate (25.2 g,182.6 mmol) was dissolved in 76ml of water and added to the mixture, and the mixture was stirred well, followed by addition of bis (tri-t-butylphosphine) palladium (0) (0.3 g,0.6 mmol). After 5 hours of reaction, the reaction mixture was cooled to room temperature, and the organic layer and the aqueous layer were separated, and then the organic layer was distilled. It was dissolved again in chloroform, washed twice with water, then the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 26.7g of compound 1-37_p1. (yield: 75%, MS: [ M+H) ] + ＝586)。
Compound 1-37_P1 (15 g,25.6 mmol) and naphthalene2-Ylboronic acid (4.6 g,26.9 mmol) was added to 300ml THF and the mixture was stirred and refluxed. Then, potassium carbonate (10.6 g,76.8 mmol) was dissolved in 32ml of water and added to the mixture, and the mixture was stirred well, followed by addition of bis (tri-t-butylphosphine) palladium (0) (0.1 g,0.3 mmol). After 3 hours of reaction, the reaction mixture was cooled to room temperature, and the organic layer and the aqueous layer were separated, and then the organic layer was distilled. It was dissolved again in chloroform, washed twice with water, then the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 12.7g of compounds 1 to 37. (yield: 73%, MS: [ M+H)] + ＝678)。
Synthesis examples 1 to 38
(8-chlorodibenzo [ b, d)]Furan-1-yl) boronic acid (15 g,60.9 mmol) and compound Trz5 (17.1 g,63.9 mmol) were added to 300ml THF and the mixture was stirred and refluxed. Then, potassium carbonate (25.2 g,182.6 mmol) was dissolved in 76ml of water and added to the mixture, and the mixture was stirred well, followed by addition of bis (tri-t-butylphosphine) palladium (0) (0.3 g,0.6 mmol). After 2 hours of reaction, the reaction mixture was cooled to room temperature, and the organic layer and the aqueous layer were separated, and then the organic layer was distilled. It was dissolved again in chloroform, washed twice with water, then the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 16.3g of compound 1-38_p1. (yield: 62%, MS: [ M+H) ] + ＝434)。
Compound 1-38_P1 (15 g,34.6 mmol) and triphenylen-2-ylboronic acid (9.9 g,36.3 mmol) were added to 300ml of THF and the mixture was admixedThe mixture was stirred and refluxed. Then, potassium carbonate (14.3 g,103.7 mmol) was dissolved in 43ml of water and added to the mixture, and the mixture was stirred well, followed by addition of bis (tri-t-butylphosphine) palladium (0) (0.2 g,0.3 mmol). After 4 hours of reaction, the reaction mixture was cooled to room temperature, and the organic layer and the aqueous layer were separated, and then the organic layer was distilled. It was dissolved again in chloroform, washed twice with water, then the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 14.7g of compounds 1 to 38. (yield: 68%, MS: [ M+H)] + ＝626)。
Synthesis examples 1 to 39
(8-chlorodibenzo [ b, d)]Furan-1-yl) boronic acid (15 g,60.9 mmol) and compound Trz32 (32.9 g,63.9 mmol) were added to 300ml THF and the mixture was stirred and refluxed. Then, potassium carbonate (25.2 g,182.6 mmol) was dissolved in 76ml of water and added to the mixture, and the mixture was stirred well, followed by addition of bis (tri-t-butylphosphine) palladium (0) (0.3 g,0.6 mmol). After 2 hours of reaction, the reaction mixture was cooled to room temperature, and the organic layer and the aqueous layer were separated, and then the organic layer was distilled. It was dissolved again in chloroform, washed twice with water, then the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 27.8g of compound 1-39_p1. (yield: 72%, MS: [ M+H) ] + ＝636)。
Compound 1-39_P1 (15 g,23.6 mmol) and dibenzo [ b, d]Furan-4-ylboronic acid (5.2 g,24.8 mmol) was added to 300ml THF and the mixture was stirred and refluxed. Then, potassium carbonate (9.8)g,70.7 mmol) was dissolved in 29ml water and added to the mixture, and the mixture was stirred well, then bis (tri-t-butylphosphine) palladium (0) (0.1 g,0.2 mmol) was added. After 5 hours of reaction, the reaction mixture was cooled to room temperature, and the organic layer and the aqueous layer were separated, and then the organic layer was distilled. It was dissolved again in chloroform, washed twice with water, then the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 11.6g of compounds 1 to 39. (yield: 64%, MS: [ M+H ]] + ＝769)。
Synthesis examples 1 to 40
Trifluoromethanesulfonic anhydride (60.1 g,213.1 mmol) and deuterium oxide (21.4 g,1065.6 mmol) were added at 0℃and stirred for 5 hours to prepare a solution. 1-bromo-8-chlorodibenzo [ b, d ]]Furan (15 g,53.3 mmol) was added to 120ml 1,2, 4-trichlorobenzene and the mixture was stirred. Then, the prepared mixed solution of the trifluoromethanesulfonic anhydride and the deuterium oxide is slowly dropped to 1-bromo-8-chlorodibenzo [ b, d ] ]In a mixed solution of furan and 1,2, 4-trichlorobenzene, and the mixture was stirred while being heated to 140 ℃ and then maintained at that temperature. After 10 hours of reaction, the reaction mixture was cooled to room temperature, and the organic layer and the aqueous layer were separated. Then, the organic layer was neutralized with an aqueous potassium carbonate solution. After washing with water twice, the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 6.4g of compound Sub4-1-1. (yield: 42%, MS: [ M+H)] + ＝285)
The compounds Sub4-1-1 (15 g,52.5 mmol) and bis (pinacolato) diboron (14.7 g,57.8 mmol) are added to 300ml of 1, 4-di
In an alkane, and the mixture was stirred under reflux. Then, into itPotassium acetate (7.7 g,78.8 mmol) was added and the mixture was stirred well, followed by bis (dibenzylideneacetone) palladium (0) (0.9 g,1.6 mmol) and tricyclohexylphosphine (0.9 g,3.2 mmol). After the reaction for 6 hours, the reaction mixture was cooled to room temperature, and the organic layer was separated using chloroform and water, and then distilled. It was dissolved again in chloroform, washed twice with water, and then the organic layer was separated. Anhydrous magnesium sulfate was added thereto, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 12g of compound Sub4-1-2. (yield: 69%, MS: [ M+H) ] + ＝333)/>
Compound Sub4-1-2 (15 g,45.1 mmol) and compound Trz33 (17.8 g,47.4 mmol) were added to 300ml THF and the mixture was stirred and refluxed. Then, potassium carbonate (18.7 g,135.3 mmol) was dissolved in 56ml of water and added to the mixture, and the mixture was stirred well, followed by addition of bis (tri-t-butylphosphine) palladium (0) (0.2 g,0.5 mmol). After 5 hours of reaction, the reaction mixture was cooled to room temperature, and the organic layer and the aqueous layer were separated, and then the organic layer was distilled. It was dissolved again in chloroform, washed twice with water, then the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 16g of compound 1-40_p1. (yield: 65%, MS: [ M+H)] + ＝546)。
Compounds 1-40_P1 (15 g,27.5 mmol) and dibenzo [ b, d]Furan-4-ylboronic acid (6.1 g,28.8 mmol) is added to 300ml THF and the mixture is stirred and refluxed. Then, potassium carbonate (11.4 g,82.4 mmol) was dissolved in 34ml of water and added to the mixture, and the mixture was stirred well and then addedBis (tri-t-butylphosphine) palladium (0) (0.1 g,0.3 mmol). After 2 hours of reaction, the reaction mixture was cooled to room temperature, and the organic layer and the aqueous layer were separated, and then the organic layer was distilled. It was dissolved again in chloroform, washed twice with water, then the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 11.5g of compounds 1 to 40. (yield: 62%, MS: [ M+H) ] + ＝678)。
Synthesis examples 1 to 41
Compound Sub4-1-2 (15 g,45.1 mmol) and compound Trz34 (20.3 g,47.4 mmol) were added to 300ml THF and the mixture was stirred and refluxed. Then, potassium carbonate (18.7 g,135.3 mmol) was dissolved in 56ml of water and added to the mixture, and the mixture was stirred well, followed by addition of bis (tri-t-butylphosphine) palladium (0) (0.2 g,0.5 mmol). After 4 hours of reaction, the reaction mixture was cooled to room temperature, and the organic layer and the aqueous layer were separated, and then the organic layer was distilled. It was dissolved again in chloroform, washed twice with water, then the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 19.4g of compound 1-41_p1. (yield: 72%, MS: [ M+H)] + ＝599)。
Compound 1-41_P1 (15 g,25 mmol) and phenylboronic acid (3.2 g,26.3 mmol) were added to 300ml THF and the mixture was stirred and refluxed. Then, potassium carbonate (10.4 g,75.1 mmol) was dissolved in 31ml of water and added to the mixture, and the mixture was stirred well, followed by addition of bis (tri-t-butylphosphine) palladium (0) (0.1 g,0.3 mmol). After 2 hours of reaction, the reaction mixture was cooled To room temperature, and the organic layer and the aqueous layer were separated, and then the organic layer was distilled. It was dissolved again in chloroform, washed twice with water, then the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 9.8g of compounds 1 to 41. (yield: 61%, MS: [ M+H)] + ＝641)。
Synthesis examples 1 to 42
Compound Sub4-1-2 (15 g,45.1 mmol) and compound Trz35 (21.3 g,47.4 mmol) were added to 300ml THF and the mixture was stirred and refluxed. Then, potassium carbonate (18.7 g,135.3 mmol) was dissolved in 56ml of water and added to the mixture, and the mixture was stirred well, followed by addition of bis (tri-t-butylphosphine) palladium (0) (0.2 g,0.5 mmol). After 4 hours of reaction, the reaction mixture was cooled to room temperature, and the organic layer and the aqueous layer were separated, and then the organic layer was distilled. It was dissolved again in chloroform, washed twice with water, then the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 17g of compound 1-42_p1. (yield: 61%, MS: [ M+H) ] + ＝619)。
Compound 1-42_P1 (15 g,24.2 mmol) and (phenyl-d 5) boronic acid (3.2 g,25.4 mmol) were added to 300ml THF and the mixture stirred and refluxed. Then, potassium carbonate (10 g,72.7 mmol) was dissolved in 30ml of water and added to the mixture, and the mixture was stirred well, followed by addition of bis (tri-t-butylphosphine) palladium (0) (0.1 g,0.2 mmol). After 3 hours of reaction, the reaction mixture was cooled to room temperature, and the organic layer and the aqueous layer were separated, and then the organic layer was distilled. Re-dissolving it inIn chloroform, the organic layer was separated after washing twice with water, anhydrous magnesium sulfate was added thereto, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 11.1g of compounds 1 to 42. (yield: 69%, MS: [ M+H)] + ＝666)。
Synthesis examples 1 to 43
Synthesis examples 1 to 44
Trifluoromethanesulfonic anhydride (24 g,85 mmol) and deuterium oxide (8.5 g,424.9 mmol) were added at 0℃and stirred for 5 hours to prepare a solution. 1-bromodibenzo [ b, d ]]Furan (15 g,60.7 mmol) was added to 120ml 1,2, 4-trichlorobenzene and the mixture was stirred. Then, the prepared mixed solution of trifluoromethanesulfonic anhydride and deuterium oxide was slowly dropped to 1-bromodibenzo [ b, d ]]In a mixed solution of furan and 1,2, 4-trichlorobenzene, and the mixture was stirred while being heated to 140 ℃ and then maintained at that temperature. After 5 hours of reaction, the reaction mixture was cooled to room temperature, and the organic layer and the aqueous layer were separated. Then, the organic layer was neutralized with an aqueous potassium carbonate solution. After washing with water twice, the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 5.7g of a compoundCompound Sub5-1-1. (yield: 38%, MS: [ M+H)] + ＝248)
The compounds Sub5-1-1 (15 g,60.5 mmol) and bis (pinacolato) diboron (16.9 g,66.5 mmol) are added to 300ml of 1, 4-diboron
In an alkane, and the mixture was stirred under reflux. Then, potassium acetate (8.9 g,90.7 mmol) was added thereto, and the mixture was stirred well, followed by addition of bis (dibenzylideneacetone) palladium (0) (1 g,1.8 mmol) and tricyclohexylphosphine (1 g,3.6 mmol). After the reaction for 6 hours, the reaction mixture was cooled to room temperature, and the organic layer was separated using chloroform and water, and then distilled. It was dissolved again in chloroform, washed twice with water, and then the organic layer was separated. Anhydrous magnesium sulfate was added thereto, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 13.4g of compound Sub5-1-2. (yield: 75%, MS: [ M+H) ] + ＝296)
Compound Sub5-1-2 (15 g,50.8 mmol) and compound Trz36 (25.8 g,53.4 mmol) were added to 300ml THF and the mixture was stirred and refluxed. Then, potassium carbonate (21.1 g,152.5 mmol) was dissolved in 63ml of water and added to the mixture, and the mixture was stirred well, followed by addition of bis (tri-t-butylphosphine) palladium (0) (0.3 g,0.5 mmol). After 5 hours of reaction, the reaction mixture was cooled to room temperature, and the organic layer and the aqueous layer were separated, and then the organic layer was distilled. It was dissolved again in chloroform, washed twice with water, then the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 18.9g of compounds 1 to 44. (yield: 72%, MS: [ M+H)] + ＝518)。
Synthesis examples 1 to 45
Trifluoromethanesulfonic anhydride (48 g,170 mmol) and deuterium oxide (17 g,849.9 mmol) were added at 0℃and stirred for 5 hours to prepare a solution. 1-bromodibenzo [ b, d ]]Furan (15 g,60.7 mmol) was added to 120ml 1,2, 4-trichlorobenzene and the mixture was stirred. Then, the prepared mixed solution of trifluoromethanesulfonic anhydride and deuterium oxide was slowly dropped to 1-bromodibenzo [ b, d ] ]In a mixed solution of furan and 1,2, 4-trichlorobenzene, and the mixture was stirred while being heated to 140 ℃ and then maintained at that temperature. After 8 hours of reaction, the reaction mixture was cooled to room temperature, and the organic layer and the aqueous layer were separated. Then, the organic layer was neutralized with an aqueous potassium carbonate solution. After washing with water twice, the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 6g of compound Sub5-2-1. (yield: 40%, MS: [ M+H)] + ＝249)
The compounds Sub5-2-1 (15 g,60.2 mmol) and bis (pinacolato) diboron (16.8 g,66.2 mmol) are added to 300ml of 1, 4-diboron
In an alkane, and the mixture was stirred under reflux. Then, potassium acetate (8.9 g,90.3 mmol) was added thereto, and the mixture was stirred well, followed by addition of bis (dibenzylideneacetone) palladium (0) (1 g,1.8 mmol) and tricyclohexylphosphine (1 g,3.6 mmol). After 4 hours of reaction, the reaction mixture was cooled to room temperature, and the organic layer was separated using chloroform and water, and then distilled. It was dissolved again in chloroform, washed twice with water, and then the organic layer was separated. Anhydrous magnesium sulfate was added thereto, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 12.5g of compound Sub5-2-2. (yield: 70%, MS: [ M+H ] ] + ＝297)
Compound Sub5-2-2 (15 g,50.6 mmol) and compound Trz37 (23.9 g,53.2 mmol) were added to 300ml THF and the mixture was stirred and refluxed. Then, potassium carbonate (21 g,151.9 mmol) was dissolved in 63ml of water and added to the mixture, and the mixture was sufficiently stirred, followed by addition of bis (tri-t-butylphosphine) palladium (0) (0.3 g,0.5 mmol). After 2 hours of reaction, the reaction mixture was cooled to room temperature, and the organic layer and the aqueous layer were separated, and then the organic layer was distilled. It was dissolved again in chloroform, washed twice with water, then the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 19.5g of compounds 1 to 45. (yield: 66%, MS: [ M+H)] + ＝583)。
Synthesis examples 1 to 46
Compound Sub5-2-2 (15 g,50.6 mmol) and compound Trz38 (28 g,53.2 mmol) were added to 300ml THF and the mixture was stirred and refluxed. Then, potassium carbonate (21 g,151.9 mmol) was dissolved in 63ml of water and added to the mixture, and the mixture was sufficiently stirred, followed by addition of bis (tri-t-butylphosphine) palladium (0) (0.3 g,0.5 mmol). After 5 hours of reaction, the reaction mixture was cooled to room temperature, and the organic layer and the aqueous layer were separated, and then the organic layer was distilled. It was dissolved again in chloroform, washed twice with water, then the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 21.4g of compounds 1 to 46. (yield: 64%, MS: [ M+H ] ] + ＝660)。
Synthesis examples 1 to 47
Compound Sub5-2-2 (15 g,50.6 mmol) and compound Trz39 (21.9 g,53.2 mmol) were added to 300ml THF and the mixture was stirred and refluxed. Then, potassium carbonate (21 g,151.9 mmol) was dissolved in 63ml of water and added to the mixture, and the mixture was sufficiently stirred, followed by addition of bis (tri-t-butylphosphine) palladium (0) (0.3 g,0.5 mmol). After 5 hours of reaction, the reaction mixture was cooled to room temperature, and the organic layer and the aqueous layer were separated, and then the organic layer was distilled. It was dissolved again in chloroform, washed twice with water, then the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 19.1g of compounds 1 to 47. (yield: 69%, MS: [ M+H)] + ＝546)。
Synthesis examples 1 to 48
Compound Sub5-2-2 (15 g,50.6 mmol) and compound Trz40 (31.7 g,53.2 mmol) were added to 300ml THF and the mixture was stirred and refluxed. Then, potassium carbonate (21 g,151.9 mmol) was dissolved in 63ml of water and added to the mixture, and the mixture was sufficiently stirred, followed by addition of bis (tri-t-butylphosphine) palladium (0) (0.3 g,0.5 mmol). After 2 hours of reaction, the reaction mixture was cooled to room temperature, and the organic layer and the aqueous layer were separated, and then the organic layer was distilled. It was dissolved again in chloroform, washed twice with water, then the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 23.9g of compounds 1 to 48. (yield: 69%, MS: [ M+H) ] + ＝685)。
Synthesis examples 1 to 49
Compound Sub5-2-2 (15 g,50.6 mmol) and compound Trz41 (25.4 g,53.2 mmol) were added to 300ml THF and the mixture was stirred and refluxed. Then, potassium carbonate (21 g,151.9 mmol) was dissolved in 63ml of water and added to the mixture, and the mixture was sufficiently stirred, followed by addition of bis (tri-t-butylphosphine) palladium (0) (0.3 g,0.5 mmol). After 4 hours of reaction, the reaction mixture was cooled to room temperature, and the organic layer and the aqueous layer were separated, and then the organic layer was distilled. It was dissolved again in chloroform, washed twice with water, then the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 21.5g of compounds 1 to 49. (yield: 75%, MS: [ M+H)] + ＝568)。
Synthesis examples 1 to 50
Trifluoromethanesulfonic anhydride (71.9 g,255 mmol) and deuterium oxide (25.5 g,1274.8 mmol) were added at 0℃and stirred for 5 hours to prepare a solution. 1-bromodibenzo [ b, d ]]Furan (15 g,60.7 mmol) was added to 120ml 1,2, 4-trichlorobenzene and the mixture was stirred. Then, the prepared mixed solution of trifluoromethanesulfonic anhydride and deuterium oxide was slowly dropped to 1-bromodibenzo [ b, d ] ]In a mixed solution of furan and 1,2, 4-trichlorobenzene, and the mixture was stirred while being heated to 140 ℃ and then maintained at that temperature. After 14 hours of reaction, the reaction mixture was cooled to room temperature, and the organic layer and the aqueous layer were separated. Then, the organic layer was neutralized with an aqueous potassium carbonate solution. After washing with water twice, the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 6.3g of compound Sub5-3-1. (yield: 42%, MS: [ M+H)] + ＝250)
The compounds Sub5-3-1 (15 g,60 mmol) and bis (pinacolato) diboron (16.8 g,66 mmol) are added to 300ml of 1, 4-di
In an alkane, and the mixture was stirred under reflux. Then, potassium acetate (8.8 g,90 mmol) was added thereto, and the mixture was stirred well, followed by bis (dibenzylideneacetone) palladium (0) (1 g,1.8 mmol) and tricyclohexylphosphine (1 g,3.6 mmol). After the reaction for 6 hours, the reaction mixture was cooled to room temperature, and the organic layer was separated using chloroform and water, and then distilled. It was dissolved again in chloroform, washed twice with water, and then the organic layer was separated. Anhydrous magnesium sulfate was added thereto, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 11.4g of compound Sub5-3-2. (yield: 64%, MS: [ M+H ] ] + ＝298)/>
Compound Sub5-3-2 (15 g,50.5 mmol) and compound Trz42 (25.2 g,53 mmol) were added to 300ml THF and the mixture was stirred and refluxed. Then, potassium carbonate (20.9 g,151.4 mmol) was dissolved in 63ml of water and added to the mixture, and the mixture was stirred well, followed by addition of bis (tri-t-butylphosphine) palladium (0) (0.3 g,0.5 mmol). After 2 hours of reaction, the reaction mixture was cooled to room temperature, and the organic layer and the aqueous layer were separated, and then the organic layer was distilled. It was dissolved again in chloroform, washed twice with water, then the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 20.3g of compounds 1 to 50. (yield: 66%, MS: [ M+H)] + ＝610)。
Synthesis examples 1 to 51
Compound Sub5-3-2 (15 g,50.5 mmol) and compound Trz43 (23.5 g,53 mmol) were added to300ml of THF and the mixture was stirred and refluxed. Then, potassium carbonate (20.9 g,151.4 mmol) was dissolved in 63ml of water and added to the mixture, and the mixture was stirred well, followed by addition of bis (tri-t-butylphosphine) palladium (0) (0.3 g,0.5 mmol). After 3 hours of reaction, the reaction mixture was cooled to room temperature, and the organic layer and the aqueous layer were separated, and then the organic layer was distilled. It was dissolved again in chloroform, washed twice with water, then the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 18.6g of compounds 1 to 51. (yield: 69%, MS: [ M+H) ] + ＝534)。
Synthesis examples 1 to 52
Compound Sub5-3-2 (15 g,50.5 mmol) and compound Trz44 (22.8 g,53 mmol) were added to 300ml THF and the mixture was stirred and refluxed. Then, potassium carbonate (20.9 g,151.4 mmol) was dissolved in 63ml of water and added to the mixture, and the mixture was stirred well, followed by addition of bis (tri-t-butylphosphine) palladium (0) (0.3 g,0.5 mmol). After 4 hours of reaction, the reaction mixture was cooled to room temperature, and the organic layer and the aqueous layer were separated, and then the organic layer was distilled. It was dissolved again in chloroform, washed twice with water, then the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 21.1g of compounds 1 to 52. (yield: 74%, MS: [ M+H)] + ＝565)。
Synthesis examples 1 to 53
Trifluoromethanesulfonic anhydride (95.9 g,340 mmol) and deuterium oxide (34 g,1699.8 mmol) were added at 0℃and stirred for 5 hours to prepare a solution. 1-BromideDibenzo [ b, d]Furan (15 g,60.7 mmol) was added to 120ml 1,2, 4-trichlorobenzene and the mixture was stirred. Then, the prepared mixed solution of trifluoromethanesulfonic anhydride and deuterium oxide was slowly dropped to 1-bromodibenzo [ b, d ] ]In a mixed solution of furan and 1,2, 4-trichlorobenzene, and the mixture was stirred while being heated to 140 ℃ and then maintained at that temperature. After 20 hours of reaction, the reaction mixture was cooled to room temperature, and the organic layer and the aqueous layer were separated. Then, the organic layer was neutralized with an aqueous potassium carbonate solution. After washing with water twice, the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 5.6g of compound Sub5-4-1. (yield: 37%, MS: [ M+H)] + ＝251)
The compounds Sub5-4-1 (15 g,59.7 mmol) and bis (pinacolato) diboron (16.7 g,65.7 mmol) are added to 300ml of 1, 4-diboron
In an alkane, and the mixture was stirred under reflux. Then, potassium acetate (8.8 g,89.6 mmol) was added thereto, and the mixture was stirred well, followed by addition of bis (dibenzylideneacetone) palladium (0) (1 g,1.8 mmol) and tricyclohexylphosphine (1 g,3.6 mmol). After reacting for 5 hours, the reaction mixture was cooled to room temperature, and the organic layer was separated using chloroform and water, and then distilled. It was dissolved again in chloroform, washed twice with water, and then the organic layer was separated. Anhydrous magnesium sulfate was added thereto, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 12.5g of compound Sub5-4-2. (yield: 70%, MS: [ M+H ] ] + ＝299)
Compound Sub5-4-2 (15 g,50.3 mmol) and compound Trz45 (28.1 g,52.8 mmol) were added to 300ml THF and the mixture was stirred and refluxed. Then, potassium carbonate (20.9 g,150.9 mmol) was dissolved in63ml of water, and added to the mixture, and the mixture was stirred well, then bis (tri-t-butylphosphine) palladium (0) (0.3 g,0.5 mmol) was added. After 4 hours of reaction, the reaction mixture was cooled to room temperature, and the organic layer and the aqueous layer were separated, and then the organic layer was distilled. It was dissolved again in chloroform, washed twice with water, then the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 23.8g of compounds 1 to 53. (yield: 71%, MS: [ M+H)] + ＝668)。
Synthesis examples 1 to 54
Trifluoromethanesulfonic anhydride (119.9 g,424.9 mmol) and deuterium oxide (42.6 g,2124.7 mmol) were added at 0℃and stirred for 5 hours to prepare a solution. 1-bromodibenzo [ b, d ]]Furan (15 g,60.7 mmol) was added to 120ml 1,2, 4-trichlorobenzene and the mixture was stirred. Then, the prepared mixed solution of trifluoromethanesulfonic anhydride and deuterium oxide was slowly dropped to 1-bromodibenzo [ b, d ] ]In a mixed solution of furan and 1,2, 4-trichlorobenzene, and the mixture was stirred while being heated to 140 ℃ and then maintained at that temperature. After 24 hours of reaction, the reaction mixture was cooled to room temperature, and the organic layer and the aqueous layer were separated. Then, the organic layer was neutralized with an aqueous potassium carbonate solution. After washing with water twice, the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 5.9g of compound Sub5-5-1. (yield: 39%, MS: [ M+H)] + ＝252)
The compounds Sub5-5-1 (15 g,59.5 mmol) and bis (pinacolato) diboron (16.6 g,65.4 mmol) are added to 300ml of 1, 4-di
In an alkane, and the mixture was stirred under reflux. Then, potassium acetate (8.8 g,89.2 mmol) was added theretoThe mixture was stirred well, then bis (dibenzylideneacetone) palladium (0) (1 g,1.8 mmol) and tricyclohexylphosphine (1 g,3.6 mmol) were added. After 4 hours of reaction, the reaction mixture was cooled to room temperature, and the organic layer was separated using chloroform and water, and then distilled. It was dissolved again in chloroform, washed twice with water, and then the organic layer was separated. Anhydrous magnesium sulfate was added thereto, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 11.2g of compound Sub5-5-2. (yield: 63%, MS: [ M+H) ] + ＝300)
Compound Sub5-5-2 (15 g,50.1 mmol) and compound Trz46 (27.6 g,52.6 mmol) were added to 300ml THF and the mixture was stirred and refluxed. Then, potassium carbonate (20.8 g,150.4 mmol) was dissolved in 62ml of water and added to the mixture, and the mixture was stirred well, followed by addition of bis (tri-t-butylphosphine) palladium (0) (0.3 g,0.5 mmol). After 5 hours of reaction, the reaction mixture was cooled to room temperature, and the organic layer and the aqueous layer were separated, and then the organic layer was distilled. It was dissolved again in chloroform, washed twice with water, then the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 21.2g of compounds 1 to 54. (yield: 73%, MS: [ M+H)] + ＝581)。
Synthesis examples 1 to 55
Compound Sub5-5-2 (15 g,50.1 mmol) and compound Trz47 (27.6 g,52.6 mmol) were added to 300ml THF and the mixture was stirred and refluxed. Then, potassium carbonate (20.8 g,150.4 mmol) was dissolved in 62ml of water and added to the mixture, and the mixture was stirred well, then double [ ] was addedTri-tert-butylphosphine) palladium (0) (0.3 g,0.5 mmol). After 4 hours of reaction, the reaction mixture was cooled to room temperature, and the organic layer and the aqueous layer were separated, and then the organic layer was distilled. It was dissolved again in chloroform, washed twice with water, then the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 24.9g of compounds 1 to 55. (yield: 75%, MS: [ M+H) ] + ＝662)。
Synthesis examples 1 to 56
Compound Sub5-5-2 (15 g,50.1 mmol) and compound Trz22 (29.7 g,52.6 mmol) were added to 300ml THF and the mixture was stirred and refluxed. Then, potassium carbonate (20.8 g,150.4 mmol) was dissolved in 62ml of water and added to the mixture, and the mixture was stirred well, followed by addition of bis (tri-t-butylphosphine) palladium (0) (0.3 g,0.5 mmol). After 4 hours of reaction, the reaction mixture was cooled to room temperature, and the organic layer and the aqueous layer were separated, and then the organic layer was distilled. It was dissolved again in chloroform, washed twice with water, then the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 23.4g of compounds 1 to 56. (yield: 71%, MS: [ M+H)] + ＝657)。
Synthesis examples 1 to 57
Compound Sub5-5-2 (15 g,50.1 mmol) and compound Trz48 (27.3 g,52.6 mmol) were added to 300ml THF and the mixture was stirred and refluxed. Then, potassium carbonate (20.8 g,150.4 mmol) was dissolved in 62ml of water and added to the mixture, and the mixture was stirred well, followed by addition of bis (tri-t-butylphosphine) palladium (0) (0.3 g,0.5 mmol). After 4 hours of reaction, the reaction mixture was cooled to room temperature, and the organic layer and the aqueous layer were separated, and then the organic layer was distilled. It was dissolved again in chloroform, washed twice with water, then the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 19g of compounds 1 to 57. (yield: 62%, MS: [ M+H)] + ＝612)。
Synthesis examples 1 to 58
Compound Sub5-5-2 (15 g,50.1 mmol) and compound Trz49 (27.1 g,52.6 mmol) were added to 300ml THF and the mixture was stirred and refluxed. Then, potassium carbonate (20.8 g,150.4 mmol) was dissolved in 62ml of water and added to the mixture, and the mixture was stirred well, followed by addition of bis (tri-t-butylphosphine) palladium (0) (0.3 g,0.5 mmol). After 5 hours of reaction, the reaction mixture was cooled to room temperature, and the organic layer and the aqueous layer were separated, and then the organic layer was distilled. It was dissolved again in chloroform, washed twice with water, then the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 19.5g of compounds 1 to 58. (yield: 64%, MS: [ M+H ] ] + ＝607)。
Synthesis examples 1 to 59
Trifluoromethanesulfonic anhydride (167.8 g,594.9 mmol) and deuterium oxide (59.6 g,2974.6 mmol) were added at 0℃and stirred for 5 hours to prepare a solution. 1-bromodibenzo [ b, d ]]Furan (15 g,60.7 mmol) was added to 120ml 1,2, 4-trichlorobenzene and the mixture was stirred. Then, the prepared mixed solution of trifluoromethanesulfonic anhydride and deuterium oxide was slowly dropped to 1-bromodibenzo [ b, d ]]Furan and 1,2, 4-trichlorobenzeneThe solution was mixed and the mixture was stirred while being heated to 140 ℃ and then maintained at that temperature. After 36 hours of reaction, the reaction mixture was cooled to room temperature, and the organic layer and the aqueous layer were separated. Then, the organic layer was neutralized with an aqueous potassium carbonate solution. After washing with water twice, the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 6.1g of compound Sub5-6-1. (yield: 40%, MS: [ M+H)] + ＝254)
The compounds Sub5-6-1 (15 g,59 mmol) and bis (pinacolato) diboron (16.5 g,64.9 mmol) are added to 300ml of 1, 4-diboron
In an alkane, and the mixture was stirred under reflux. Then, potassium acetate (8.7 g,88.5 mmol) was added thereto, and the mixture was stirred well, followed by bis (dibenzylideneacetone) palladium (0) (1 g,1.8 mmol) and tricyclohexylphosphine (1 g,3.5 mmol). After 4 hours of reaction, the reaction mixture was cooled to room temperature, and the organic layer was separated using chloroform and water, and then distilled. It was dissolved again in chloroform, washed twice with water, and then the organic layer was separated. Anhydrous magnesium sulfate was added thereto, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 11.6g of compound Sub5-6-2. (yield: 65%, MS: [ M+H) ] + ＝302)
Compound Sub5-6-2 (15 g,50 mmol) and compound Trz50 (24.2 g,52.5 mmol) were added to 300ml THF and the mixture was stirred and refluxed. Then, potassium carbonate (20.7 g,149.9 mmol) was dissolved in 62ml of water and added to the mixture, and the mixture was stirred well, followed by addition of bis (tri-t-butylphosphine) palladium (0) (0.3 g,0.5 mmol). After 3 hours of reaction, the reaction mixture was cooled to room temperature, and the organic layer and the aqueous layer were separated, thenThe organic layer was distilled. It was dissolved again in chloroform, washed twice with water, then the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 22.5g of compounds 1 to 59. (yield: 75%, MS: [ M+H)] + ＝601)。
Synthesis examples 1 to 60
Compound Sub5-6-2 (15 g,50 mmol) and compound Trz51 (24.1 g,52.5 mmol) were added to 300ml THF and the mixture was stirred and refluxed. Then, potassium carbonate (20.7 g,149.9 mmol) was dissolved in 62ml of water and added to the mixture, and the mixture was stirred well, followed by addition of bis (tri-t-butylphosphine) palladium (0) (0.3 g,0.5 mmol). After 5 hours of reaction, the reaction mixture was cooled to room temperature, and the organic layer and the aqueous layer were separated, and then the organic layer was distilled. It was dissolved again in chloroform, washed twice with water, then the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 22.1g of compounds 1 to 60. (yield: 74%, MS: [ M+H) ] + ＝599)。
Synthesis examples 1 to 61
Compound Sub5-6-2 (15 g,50 mmol) and compound Trz52 (25.3 g,52.5 mmol) were added to 300ml THF and the mixture was stirred and refluxed. Then, potassium carbonate (20.7 g,149.9 mmol) was dissolved in 62ml of water and added to the mixture, and the mixture was stirred well, followed by addition of bis (tri-t-butylphosphine) palladium (0) (0.3 g,0.5 mmol). After 5 hours of reaction, the reaction mixture was cooled to room temperature, and the organic layer and the aqueous layer were separated, and then the organic layer was distilled. Re-dissolving it in chlorineIn the simulation, the organic layer was separated after washing twice with water, anhydrous magnesium sulfate was added thereto, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 21.6g of compounds 1 to 61. (yield: 75%, MS: [ M+H)] + ＝577)。
Synthesis examples 1 to 62
Compound Sub5-6-2 (15 g,50 mmol) and compound Trz53 (32 g,52.5 mmol) were added to 300ml THF and the mixture was stirred and refluxed. Then, potassium carbonate (20.7 g,149.9 mmol) was dissolved in 62ml of water and added to the mixture, and the mixture was stirred well, followed by addition of bis (tri-t-butylphosphine) palladium (0) (0.3 g,0.5 mmol). After 3 hours of reaction, the reaction mixture was cooled to room temperature, and the organic layer and the aqueous layer were separated, and then the organic layer was distilled. It was dissolved again in chloroform, washed twice with water, then the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 26g of compounds 1 to 62. (yield: 74%, MS: [ M+H) ] + ＝704)。
Synthesis examples 1 to 63
Compound Sub5-6-2 (15 g,50 mmol) and compound Trz54 (27.3 g,52.5 mmol) were added to 300ml THF and the mixture was stirred and refluxed. Then, potassium carbonate (20.7 g,149.9 mmol) was dissolved in 62ml of water and added to the mixture, and the mixture was stirred well, followed by addition of bis (tri-t-butylphosphine) palladium (0) (0.3 g,0.5 mmol). After 5 hours of reaction, the reaction mixture was cooled to room temperature, and the organic layer and the aqueous layer were separated, and then the organic layer was distilled. It was redissolved in chloroform, washed twice with water and then the organic layer was washed with waterTo this, anhydrous magnesium sulfate was added, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 18.4g of compounds 1 to 63. (yield: 60%, MS: [ M+H)] + ＝615)。
Synthesis examples 1 to 64
Dibenzo [ b, d]Furan-1-ylboronic acid (15 g,70.8 mmol) and compound Trz55 (45.7 g,74.3 mmol) were added to 300ml THF and the mixture was stirred and refluxed. Then, potassium carbonate (29.3 g,212.3 mmol) was dissolved in 88ml of water and added to the mixture, and the mixture was stirred well, followed by addition of bis (tri-t-butylphosphine) palladium (0) (0.4 g,0.7 mmol). After 5 hours of reaction, the reaction mixture was cooled to room temperature, and the organic layer and the aqueous layer were separated, and then the organic layer was distilled. It was dissolved again in chloroform, washed twice with water, then the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 32.2g of compound 1-64_p1. (yield: 65%, MS: [ M+H) ] + ＝702)。
Compound 1-64_P1 (10 g,14.2 mmol), ptO 2 (1 g,4.3 mmol) and D 2 O (71 ml) was added to the shaker tube, and the tube was then sealed and heated at 250℃and 600psi for 12 hours. When the reaction was completed, chloroform was added, and the reaction solution was transferred to a separating funnel and extracted. The extract was subjected to MgSO 4 Dried and concentrated, and then the sample was purified by silica gel column chromatography to prepare 4g of compounds 1 to 64. (yield: 39%, MS: [ M+H)] + ＝727)
Synthesis examples 1 to 65
Dibenzo [ b, d]Furan-1-ylboronic acid (15 g,70.8 mmol) and compound Trz56 (33 g,74.3 mmol) were added to 300ml THF and the mixture was stirred and refluxed. Then, potassium carbonate (29.3 g,212.3 mmol) was dissolved in 88ml of water and added to the mixture, and the mixture was stirred well, followed by addition of bis (tri-t-butylphosphine) palladium (0) (0.4 g,0.7 mmol). After 5 hours of reaction, the reaction mixture was cooled to room temperature, and the organic layer and the aqueous layer were separated, and then the organic layer was distilled. It was dissolved again in chloroform, washed twice with water, then the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 29.7g of compound 1-65_p1. (yield: 73%, MS: [ M+H) ] + ＝576)。
Compound 1-65_P1 (10 g,17.4 mmol), ptO 2 (1.2 g,5.2 mmol) and D 2 O (87 ml) was added to the shaker tube, and the tube was then sealed and heated at 250℃and 600psi for 12 hours. When the reaction was completed, chloroform was added, and the reaction solution was transferred to a separating funnel and extracted. The extract was subjected to MgSO 4 Dried and concentrated, and then the sample was purified by silica gel column chromatography to prepare 5.1g of compounds 1 to 65. (yield: 49%, MS: [ M+H)] + ＝599)
Synthesis examples 1 to 66
Dibenzo [ b, d]Furan-1-ylboronic acid (15 g,70.8 mmol) and compound Trz46 (33 g,74.3 mmol) were added to 300ml THF and the mixture was stirred and refluxed. Then, potassium carbonate (29.3 g,212.3 mmol) was dissolved in 88ml of water and added to the mixtureThe mixture was stirred well, and bis (tri-t-butylphosphine) palladium (0) (0.4 g,0.7 mmol) was then added. After 3 hours of reaction, the reaction mixture was cooled to room temperature, and the organic layer and the aqueous layer were separated, and then the organic layer was distilled. It was dissolved again in chloroform, washed twice with water, then the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 24.8g of compound 1-66_p1. (yield: 61%, MS: [ M+H) ] + ＝576)。
Compound 1-66_P1 (10 g,17.4 mmol), ptO 2 (1.2 g,5.2 mmol) and D 2 O (87 ml) was added to the shaker tube, and the tube was then sealed and heated at 250℃and 600psi for 12 hours. When the reaction was completed, chloroform was added, and the reaction solution was transferred to a separating funnel and extracted. The extract was subjected to MgSO 4 Dried and concentrated, and then the sample was purified by silica gel column chromatography to prepare 5g of compounds 1 to 66. (yield: 48%, MS: [ M+H)] + ＝598)
Synthesis examples 1 to 67
Dibenzo [ b, d]Furan-1-ylboronic acid (15 g,70.8 mmol) and compound Trz57 (33 g,74.3 mmol) were added to 300ml THF and the mixture was stirred and refluxed. Then, potassium carbonate (29.3 g,212.3 mmol) was dissolved in 88ml of water and added to the mixture, and the mixture was stirred well, followed by addition of bis (tri-t-butylphosphine) palladium (0) (0.4 g,0.7 mmol). After 5 hours of reaction, the reaction mixture was cooled to room temperature, and the organic layer and the aqueous layer were separated, and then the organic layer was distilled. Dissolving in chloroform again, washing twice with water, separating organic layer, adding anhydrous magnesium sulfate, stirring, filtering, and filteringThe solution was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 26.5g of compound 1-67_p1. (yield: 65%, MS: [ M+H) ] + ＝576)。
Compound 1-67_P1 (10 g,17.4 mmol), ptO 2 (1.2 g,5.2 mmol) and D 2 O (87 ml) was added to the shaker tube, and the tube was then sealed and heated at 250℃and 600psi for 12 hours. When the reaction was completed, chloroform was added, and the reaction solution was transferred to a separating funnel and extracted. The extract was subjected to MgSO 4 Dried and concentrated, and then the sample was purified by silica gel column chromatography to prepare 4.4g of compounds 1 to 67. (yield: 42%, MS: [ M+H)] + ＝598)
Synthesis examples 1 to 68
Dibenzo [ b, d]Furan-1-ylboronic acid (15 g,70.8 mmol) and compound Trz58 (33 g,74.3 mmol) were added to 300ml THF and the mixture was stirred and refluxed. Then, potassium carbonate (29.3 g,212.3 mmol) was dissolved in 88ml of water and added to the mixture, and the mixture was stirred well, followed by addition of bis (tri-t-butylphosphine) palladium (0) (0.4 g,0.7 mmol). After 4 hours of reaction, the reaction mixture was cooled to room temperature, and the organic layer and the aqueous layer were separated, and then the organic layer was distilled. It was dissolved again in chloroform, washed twice with water, then the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 26.5g of compound 1-68_p1. (yield: 65%, MS: [ M+H) ] + ＝576)。
Compound 1-68_P1 (10 g,17.4 mmol), ptO 2 (1.2 g,5.2 mmol) and D 2 O (87 ml) was added to the shaker tube, and the tube was then sealed and heated at 250℃and 600psi for 12 hours. When the reaction was completed, chloroform was added, and the reaction solution was transferred to a separating funnel and extracted. The extract was subjected to MgSO 4 Dried and concentrated, and then the sample was purified by silica gel column chromatography to prepare 3.6g of compounds 1 to 68. (yield: 35%, MS: [ M+H)] + ＝598)
Synthesis example 2-1
9H-carbazole (10 g,59.8 mmol), 1-bromo-4-chlorobenzene (12 g,62.8 mmol) and sodium tert-butoxide (7.5 g,77.7 mmol) were added to 200ml of xylene under nitrogen, and the mixture was stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.3 g,0.6 mmol) was added thereto. When the reaction was completed after 3 hours, the reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was completely dissolved again in chloroform, washed twice with water, then the organic layer was separated, treated with anhydrous magnesium sulfate, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 10.3g of compound sub A-1. (yield: 62%, MS: [ M+H ] +=278)
Compound sub A-1 (10 g,36 mmol), compound amine 1 (15 g,37.8 mmol) and sodium tert-butoxide (4.5 g,46.8 mmol) were added to 200ml of xylene under nitrogen and the mixture was stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.2 g,0.4 mmol) was added thereto. When the reaction was completed after 3 hours, the reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was completely dissolved again in chloroform, washed twice with water, and then the organic layer was separatedThe mixture was separated, treated with anhydrous magnesium sulfate, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 14.2g of compound 2-1. (yield: 62%, MS: [ M+H)] + ＝639)
Synthesis example 2-2
Compound sub A-1 (10 g,36 mmol), compound amine 2 (15.9 g,37.8 mmol) and sodium tert-butoxide (4.5 g,46.8 mmol) were added to 200ml of xylene under nitrogen and the mixture was stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.2 g,0.4 mmol) was added thereto. When the reaction was completed after 3 hours, the reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was completely dissolved again in chloroform, washed twice with water, then the organic layer was separated, treated with anhydrous magnesium sulfate, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 17.4g of compound 2-2. (yield: 73%, MS: [ M+H) ] + ＝663)
Synthesis examples 2 to 3
Compound sub A-1 (10 g,36 mmol), compound amine 3 (15.5 g,37.8 mmol) and sodium tert-butoxide (4.5 g,46.8 mmol) were added to 200ml of xylene under nitrogen and the mixture was stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.2 g,0.4 mmol) was added thereto. When the reaction was completed after 3 hours, the reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was completely dissolved again in chloroform, washed twice with water, then the organic layer was separated, treated with anhydrous magnesium sulfate, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 14.3g of compound 2-3. (yield: 61%, MS: [ M+H)] + ＝651)
Synthesis examples 2 to 4
Compound sub A-1 (10 g,36 mmol), compound amine 4 (15.6 g,37.8 mmol) and sodium tert-butoxide (4.5 g,46.8 mmol) were added to 200ml of xylene under nitrogen and the mixture was stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.2 g,0.4 mmol) was added thereto. When the reaction was completed after 3 hours, the reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was completely dissolved again in chloroform, washed twice with water, then the organic layer was separated, treated with anhydrous magnesium sulfate, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 14.3g of compound 2-4. (yield: 61%, MS: [ M+H) ] + ＝653)
Synthesis examples 2 to 5
Compound sub A-1 (10 g,36 mmol), compound amine 5 (15.5 g,37.8 mmol) and sodium tert-butoxide (4.5 g,46.8 mmol) were added to 200ml of xylene under nitrogen and the mixture was stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.2 g,0.4 mmol) was added thereto. When the reaction was completed after 3 hours, the reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was completely dissolved again in chloroform, washed twice with water, then the organic layer was separated, treated with anhydrous magnesium sulfate, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 15g of compound 2-5. (yield: 64%, MS: [ M+H ]] + ＝652)
Synthesis examples 2 to 6
Compound sub A-1 (10 g,36 mmol), compound amine 6 (13.7 g,37.8 mmol) and sodium tert-butoxide (4.5 g,46.8 mmol) were added to 200ml of xylene under nitrogen and the mixture was stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.2 g,0.4 mmol) was added thereto. When the reaction was completed after 2 hours, the reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was completely dissolved again in chloroform, washed twice with water, then the organic layer was separated, treated with anhydrous magnesium sulfate, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 15.8g of compounds 2 to 6. (yield: 73%, MS: [ M+H) ] + ＝603)
Synthesis examples 2 to 7
9H-carbazole (10 g,59.8 mmol), 2-bromo-5-chloro-1, 1' -biphenyl (16.8 g,62.8 mmol) and sodium tert-butoxide (7.5 g,77.7 mmol) were added to 200ml of xylene under nitrogen, and the mixture was stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.3 g,0.6 mmol) was added thereto. When the reaction was completed after 3 hours, the reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was completely dissolved again in chloroform, washed twice with water, then the organic layer was separated, treated with anhydrous magnesium sulfate, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 14.8g of compound sub A-2. (yield: 70%, MS: [ M+H ] +=354)
Compound sub A-2 (10 g,28.3 mmol), compound amine 7 (14.5 g,29.7 mmol) and sodium tert-butoxide (3.5 g,36.7 mmol) were added to 200ml of xylene under nitrogen atmosphere, andthe mixture was stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.1 g,0.3 mmol) was added thereto. When the reaction was completed after 2 hours, the reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was completely dissolved again in chloroform, washed twice with water, then the organic layer was separated, treated with anhydrous magnesium sulfate, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 15.7g of compounds 2 to 7. (yield: 69%, MS: [ M+H) ] + ＝805)
Synthesis examples 2 to 8
Compound sub A-2 (10 g,28.3 mmol), compound amine 8 (14 g,29.7 mmol) and sodium tert-butoxide (3.5 g,36.7 mmol) were added to 200ml of xylene under nitrogen and the mixture was stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.1 g,0.3 mmol) was added thereto. When the reaction was completed after 3 hours, the reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was completely dissolved again in chloroform, washed twice with water, then the organic layer was separated, treated with anhydrous magnesium sulfate, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 13.6g of compounds 2 to 8. (yield: 61%, MS: [ M+H)] + ＝789)
Synthesis examples 2 to 9
9H-carbazole (10 g,59.8 mmol), 5-bromo-2-chloro-1, 1' -biphenyl (16.8 g,62.8 mmol) and sodium tert-butoxide (7.5 g,77.7 mmol) were added to 200ml of xylene under nitrogen, and the mixture was stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.3 g,0.6 mmol) was added thereto. When the reaction was completed after 3 hours, the reaction mixture was cooled to room temperature and was divided under reduced pressureRemoving the solvent. Then, the compound was completely dissolved again in chloroform, washed twice with water, then the organic layer was separated, treated with anhydrous magnesium sulfate, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 15.6g of compound sub A-3. (yield: 74%, MS: [ M+H) ] + ＝354)
Compound sub A-3 (10 g,28.3 mmol), compound amine 9 (14 g,29.7 mmol) and sodium tert-butoxide (3.5 g,36.7 mmol) were added to 200ml of xylene under nitrogen and the mixture was stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.1 g,0.3 mmol) was added thereto. When the reaction was completed after 2 hours, the reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was completely dissolved again in chloroform, washed twice with water, then the organic layer was separated, treated with anhydrous magnesium sulfate, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 13.4g of compounds 2 to 9. (yield: 60%, MS: [ M+H)] + ＝789)
Synthesis examples 2 to 10
Compound sub A-2 (10 g,28.3 mmol), compound amine 10 (13.2 g,29.7 mmol) and sodium tert-butoxide (3.5 g,36.7 mmol) were added to 200ml of xylene under nitrogen and the mixture was stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.1 g,0.3 mmol) was added thereto. When the reaction was completed after 2 hours, the reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was completely dissolved again in chloroform, washed twice with water, then the organic layer was separated, treated with anhydrous magnesium sulfate, then filtered, and the filtrate was distilled under reduced pressure. Purifying the concentrated compound by silica gel column chromatography To prepare 15.9g of compound 2-10. (yield: 74%, MS: [ M+H)] + ＝763)
Synthesis examples 2 to 11
9H-carbazole (10 g,59.8 mmol), 1-bromo-4-chloronaphthalene (15.2 g,62.8 mmol) and sodium tert-butoxide (7.5 g,77.7 mmol) were added to 200ml of xylene under nitrogen, and the mixture was stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.3 g,0.6 mmol) was added thereto. When the reaction was completed after 2 hours, the reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was completely dissolved again in chloroform, washed twice with water, then the organic layer was separated, treated with anhydrous magnesium sulfate, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 12.7g of compound sub A-4. (yield: 65%, MS: [ M+H)] + ＝328)
Compound sub A-4 (10 g,30.5 mmol), compound amine 11 (12.8 g,32 mmol) and sodium tert-butoxide (3.8 g,39.7 mmol) were added to 200ml of xylene under nitrogen and the mixture was stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.2 g,0.3 mmol) was added thereto. When the reaction was completed after 2 hours, the reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was completely dissolved again in chloroform, washed twice with water, then the organic layer was separated, treated with anhydrous magnesium sulfate, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 13.9g of compounds 2 to 11. (yield: 66%, MS: [ M+H) ] + ＝691)
Synthesis examples 2 to 12
9H-carbazole (10 g,59.8 mmol), 4-bromo-4 '-chloro-1, 1' -biphenyl (16.8 g,62.8 mmol) and sodium tert-butoxide (7.5 g,77.7 mmol) were added to 200ml of xylene under nitrogen, and the mixture was stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.3 g,0.6 mmol) was added thereto. When the reaction was completed after 3 hours, the reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was completely dissolved again in chloroform, washed twice with water, then the organic layer was separated, treated with anhydrous magnesium sulfate, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 15.4g of compound sub A-5. (yield: 73%, MS: [ M+H)] + ＝354)
Compound sub A-5 (10 g,28.3 mmol), compound amine 12 (9.5 g,29.7 mmol) and sodium tert-butoxide (3.5 g,36.7 mmol) were added to 200ml of xylene under nitrogen and the mixture was stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.1 g,0.3 mmol) was added thereto. When the reaction was completed after 2 hours, the reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was completely dissolved again in chloroform, washed twice with water, then the organic layer was separated, treated with anhydrous magnesium sulfate, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 11.2g of compounds 2 to 12. (yield: 62%, MS: [ M+H) ] + ＝639)
Synthesis examples 2 to 13
Compound sub A-5 (10 g,28.3 mmol), compound amine 13 (10.4 g,29.7 mmol) and tert-butanol were reacted under nitrogenSodium (3.5 g,36.7 mmol) was added to 200ml of xylene and the mixture was stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.1 g,0.3 mmol) was added thereto. When the reaction was completed after 2 hours, the reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was completely dissolved again in chloroform, washed twice with water, then the organic layer was separated, treated with anhydrous magnesium sulfate, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 13.5g of compound 2-13. (yield: 72%, MS: [ M+H)] + ＝664)
Synthesis examples 2 to 14
Compound sub A-5 (10 g,28.3 mmol), compound amine 14 (10.7 g,29.7 mmol) and sodium tert-butoxide (3.5 g,36.7 mmol) were added to 200ml of xylene under nitrogen and the mixture was stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.1 g,0.3 mmol) was added thereto. When the reaction was completed after 3 hours, the reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was completely dissolved again in chloroform, washed twice with water, then the organic layer was separated, treated with anhydrous magnesium sulfate, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 12.5g of compounds 2 to 14. (yield: 65%, MS: [ M+H) ] + ＝679)
Synthesis examples 2 to 15
Compound sub A-5 (10 g,28.3 mmol), compound amine 15 (14.9 g,29.7 mmol) and sodium tert-butoxide (3.5 g,36.7 mmol) were added to 200ml of xylene under nitrogen and the mixture was stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.1 g,0.3 mmol) was added thereto. When the reaction was completed after 2 hoursThe reaction mixture was cooled to room temperature and the solvent was removed under reduced pressure. Then, the compound was completely dissolved again in chloroform, washed twice with water, then the organic layer was separated, treated with anhydrous magnesium sulfate, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 14.6g of compounds 2 to 15. (yield: 63%, MS: [ M+H)] + ＝821)
Synthesis examples 2 to 16
Compound sub A-5 (10 g,28.3 mmol), compound amine 16 (13.3 g,29.7 mmol) and sodium tert-butoxide (3.5 g,36.7 mmol) were added to 200ml of xylene under nitrogen and the mixture was stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.1 g,0.3 mmol) was added thereto. When the reaction was completed after 2 hours, the reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was completely dissolved again in chloroform, washed twice with water, then the organic layer was separated, treated with anhydrous magnesium sulfate, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 15.6g of compounds 2 to 16. (yield: 72%, MS: [ M+H) ] + ＝765)
Synthesis examples 2 to 17
9H-carbazole (10 g,59.8 mmol), 4-bromo-4 '-chloro-1, 1':3', 1' -terphenyl (21.6 g,62.8 mmol) and sodium tert-butoxide (7.5 g,77.7 mmol) were added to 200ml of xylene under nitrogen and the mixture was stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.3 g,0.6 mmol) was added thereto. When the reaction was completed after 3 hours, the reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was completely dissolved again in chloroform, washed twice with water, and then the organic layer was separatedThe mixture was separated, treated with anhydrous magnesium sulfate, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 15.4g of compound sub A-6. (yield: 60%, MS: [ M+H)] + ＝430)
Compound sub A-6 (10 g,23.3 mmol), compound amine 12 (7.8 g,24.4 mmol) and sodium tert-butoxide (2.9 g,30.2 mmol) were added to 200ml of xylene under nitrogen and the mixture was stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.1 g,0.2 mmol) was added thereto. When the reaction was completed after 2 hours, the reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was completely dissolved again in chloroform, washed twice with water, then the organic layer was separated, treated with anhydrous magnesium sulfate, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 11.5g of compounds 2 to 17. (yield: 69%, MS: [ M+H) ] + ＝715)
Synthesis examples 2 to 18
9H-carbazole (10 g,59.8 mmol), 1-bromo-4- (4-chlorophenyl) naphthalene (19.9 g,62.8 mmol) and sodium tert-butoxide (7.5 g,77.7 mmol) were added to 200ml of xylene under nitrogen, and the mixture was stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.3 g,0.6 mmol) was added thereto. When the reaction was completed after 2 hours, the reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was completely dissolved again in chloroform, washed twice with water, then the organic layer was separated, treated with anhydrous magnesium sulfate, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 15.7g of compound sub A-7. (yield: 65%, MS: [ M+H)] + ＝404)
Compound sub A-7 (10 g,24.8 mmol), compound amine 17 (11.6 g,26 mmol) and sodium tert-butoxide (3.1 g,32.2 mmol) were added to 200ml of xylene under nitrogen and the mixture was stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.1 g,0.2 mmol) was added thereto. When the reaction was completed after 2 hours, the reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was completely dissolved again in chloroform, washed twice with water, then the organic layer was separated, treated with anhydrous magnesium sulfate, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 13.1g of compounds 2 to 18. (yield: 65%, MS: [ M+H) ] + ＝815)
Synthesis examples 2 to 19
9H-carbazole (10 g,59.8 mmol), 1-bromo-4- (5-chloro- [1,1' -biphenyl) was reacted under nitrogen atmosphere]2-yl) naphthalene (24.7 g,62.8 mmol) and sodium tert-butoxide (7.5 g,77.7 mmol) were added to 200ml of xylene and the mixture was stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.3 g,0.6 mmol) was added thereto. When the reaction was completed after 2 hours, the reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was completely dissolved again in chloroform, washed twice with water, then the organic layer was separated, treated with anhydrous magnesium sulfate, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 18.6g of compound sub A-8. (yield: 65%, MS: [ M+H)] + ＝480)
At nitrogenCompound sub A-8 (10 g,20.8 mmol), compound amine 18 (9.8 g,21.9 mmol) and sodium tert-butoxide (2.6 g,27.1 mmol) were added to 200ml of xylene under a gaseous atmosphere, and the mixture was stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.1 g,0.2 mmol) was added thereto. When the reaction was completed after 2 hours, the reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was completely dissolved again in chloroform, washed twice with water, then the organic layer was separated, treated with anhydrous magnesium sulfate, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 13.5g of compounds 2 to 19. (yield: 73%, MS: [ M+H) ] + ＝891)
Synthesis examples 2 to 20
9H-carbazole (10 g,59.8 mmol), 4 '-bromo-4-chloro-1, 1':2', 1' -terphenyl (21.6 g,62.8 mmol) and sodium tert-butoxide (7.5 g,77.7 mmol) were added to 200ml of xylene under nitrogen and the mixture was stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.3 g,0.6 mmol) was added thereto. When the reaction was completed after 2 hours, the reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was completely dissolved again in chloroform, washed twice with water, then the organic layer was separated, treated with anhydrous magnesium sulfate, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 15.7g of compound sub A-9. (yield: 61%, MS: [ M+H)] + ＝430)
Compound sub A-9 (10 g,23.3 mmol), compound amine 19 (9.8 g,24.4 mmol) and sodium tert-butoxide (2.9 g,30.2 mmol) were added to 200ml of xylene under nitrogen and the mixture was stirred and refluxed. Then, bis (tri-t-butyl) was added theretoPalladium (0) (0.1 g,0.2 mmol). When the reaction was completed after 2 hours, the reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was completely dissolved again in chloroform, washed twice with water, then the organic layer was separated, treated with anhydrous magnesium sulfate, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 11.6g of compounds 2 to 20. (yield: 63%, MS: [ M+H) ] + ＝793)
Synthesis examples 2 to 21
9H-carbazole (10 g,59.8 mmol), 1- (4-bromophenyl) -4-chloronaphthalene (19.9 g,62.8 mmol) and sodium tert-butoxide (7.5 g,77.7 mmol) were added to 200ml of xylene under nitrogen, and the mixture was stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.3 g,0.6 mmol) was added thereto. When the reaction was completed after 3 hours, the reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was completely dissolved again in chloroform, washed twice with water, then the organic layer was separated, treated with anhydrous magnesium sulfate, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 17.4g of compound sub A-10. (yield: 72%, MS: [ M+H)] + ＝404)
Compound sub A-10 (10 g,24.8 mmol), compound amine 20 (8.4 g,26 mmol) and sodium tert-butoxide (3.1 g,32.2 mmol) were added to 200ml of xylene under nitrogen and the mixture was stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.1 g,0.2 mmol) was added thereto. When the reaction was completed after 2 hours, the reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was completely dissolved again in chloroform, washed twice with water, and then the organic layer was taken up The mixture was separated, treated with anhydrous magnesium sulfate, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 12.6g of compound 2-21. (yield: 74%, MS: [ M+H)] + ＝689)
Synthesis examples 2 to 22
9H-carbazole (10 g,59.8 mmol), 2-bromo-4 '-chloro-1, 1' -biphenyl (16.8 g,62.8 mmol) and sodium tert-butoxide (7.5 g,77.7 mmol) were added to 200ml of xylene under nitrogen, and the mixture was stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.3 g,0.6 mmol) was added thereto. When the reaction was completed after 2 hours, the reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was completely dissolved again in chloroform, washed twice with water, then the organic layer was separated, treated with anhydrous magnesium sulfate, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 15.6g of compound sub A-11. (yield: 74%, MS: [ M+H)] + ＝354)
Compound sub A-11 (10 g,28.3 mmol), compound amine 21 (12.5 g,29.7 mmol) and sodium tert-butoxide (3.5 g,36.7 mmol) were added to 200ml of xylene under nitrogen and the mixture was stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.1 g,0.3 mmol) was added thereto. When the reaction was completed after 2 hours, the reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was completely dissolved again in chloroform, washed twice with water, then the organic layer was separated, treated with anhydrous magnesium sulfate, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 12.9g of compound 2-22. (yield: 62%, MS: [ M+H) ] + ＝739)
Synthesis examples 2 to 23
Compound sub A-11 (10 g,28.3 mmol), compound amine 22 (13.3 g,29.7 mmol) and sodium tert-butoxide (3.5 g,36.7 mmol) were added to 200ml of xylene under nitrogen and the mixture was stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.1 g,0.3 mmol) was added thereto. When the reaction was completed after 3 hours, the reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was completely dissolved again in chloroform, washed twice with water, then the organic layer was separated, treated with anhydrous magnesium sulfate, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 13.6g of compound 2-23. (yield: 63%, MS: [ M+H)] + ＝765)
Synthesis examples 2 to 24
Compound sub A-11 (10 g,28.3 mmol), compound amine 23 (13.3 g,29.7 mmol) and sodium tert-butoxide (3.5 g,36.7 mmol) were added to 200ml of xylene under nitrogen and the mixture was stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.1 g,0.3 mmol) was added thereto. When the reaction was completed after 2 hours, the reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was completely dissolved again in chloroform, washed twice with water, then the organic layer was separated, treated with anhydrous magnesium sulfate, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 13.4g of compounds 2 to 24. (yield: 62%, MS: [ M+H) ] + ＝765)
Synthesis examples 2 to 25
Compound sub A-11 (10 g,28.3 mmol), compound amine 24 (14 g,29.7 mmol) and sodium tert-butoxide (3.5 g,36.7 mmol) were added to 200ml of xylene under nitrogen and the mixture was stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.1 g,0.3 mmol) was added thereto. When the reaction was completed after 2 hours, the reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was completely dissolved again in chloroform, washed twice with water, then the organic layer was separated, treated with anhydrous magnesium sulfate, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 15.6g of compounds 2 to 25. (yield: 70%, MS: [ M+H ]] + ＝789)
Synthesis examples 2 to 26
Compound sub A-11 (10 g,28.3 mmol), compound amine 25 (13.3 g,29.7 mmol) and sodium tert-butoxide (3.5 g,36.7 mmol) were added to 200ml of xylene under nitrogen and the mixture was stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.1 g,0.3 mmol) was added thereto. When the reaction was completed after 2 hours, the reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was completely dissolved again in chloroform, washed twice with water, then the organic layer was separated, treated with anhydrous magnesium sulfate, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 14.5g of compounds 2 to 26. (yield: 67%, MS: [ M+H) ] + ＝765)
Synthesis examples 2 to 27
Compound sub A-11 (10 g,28.3 mmol), compound amine 26 (14 g,29.7 mmol) and tert-butanol were reacted under nitrogenSodium (3.5 g,36.7 mmol) was added to 200ml of xylene and the mixture was stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.1 g,0.3 mmol) was added thereto. When the reaction was completed after 3 hours, the reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was completely dissolved again in chloroform, washed twice with water, then the organic layer was separated, treated with anhydrous magnesium sulfate, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 16.5g of compounds 2 to 27. (yield: 74%, MS: [ M+H)] + ＝789)
Synthesis examples 2 to 28
Compound sub A-11 (10 g,28.3 mmol), compound amine 27 (11 g,29.7 mmol) and sodium tert-butoxide (3.5 g,36.7 mmol) were added to 200ml of xylene under nitrogen and the mixture was stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.1 g,0.3 mmol) was added thereto. When the reaction was completed after 3 hours, the reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was completely dissolved again in chloroform, washed twice with water, then the organic layer was separated, treated with anhydrous magnesium sulfate, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 11.7g of compounds 2 to 28. (yield: 60%, MS: [ M+H) ] + ＝689)
Synthesis examples 2 to 29
Compound sub A-11 (10 g,28.3 mmol), compound amine 28 (14.9 g,29.7 mmol) and sodium tert-butoxide (3.5 g,36.7 mmol) were added to 200ml of xylene under nitrogen and the mixture was stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.1 g,0.3 mmol) was added thereto. When the reaction was completed after 3 hoursThe reaction mixture was cooled to room temperature and the solvent was removed under reduced pressure. Then, the compound was completely dissolved again in chloroform, washed twice with water, then the organic layer was separated, treated with anhydrous magnesium sulfate, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 14.1g of compounds 2 to 29. (yield: 61%, MS: [ M+H)] + ＝821)
Synthesis examples 2 to 30
Compound sub A-11 (10 g,28.3 mmol), compound amine 29 (13.3 g,29.7 mmol) and sodium tert-butoxide (3.5 g,36.7 mmol) were added to 200ml of xylene under nitrogen and the mixture was stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.1 g,0.3 mmol) was added thereto. When the reaction was completed after 2 hours, the reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was completely dissolved again in chloroform, washed twice with water, then the organic layer was separated, treated with anhydrous magnesium sulfate, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 15.3g of compound 2-30. (yield: 71%, MS: [ M+H) ] + ＝765)
Synthesis examples 2 to 31
Compound sub A-11 (10 g,28.3 mmol), compound amine 30 (11.4 g,29.7 mmol) and sodium tert-butoxide (3.5 g,36.7 mmol) were added to 200ml of xylene under nitrogen and the mixture was stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.1 g,0.3 mmol) was added thereto. When the reaction was completed after 3 hours, the reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was completely dissolved again in chloroform, washed twice with water, and then the organic layer was separated, and dried over anhydrous sulfurThe magnesium acid is treated, then filtered, and the filtrate is distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 13.1g of compounds 2 to 31. (yield: 66%, MS: [ M+H)] + ＝703)
Synthesis examples 2 to 32
Compound sub A-11 (10 g,28.3 mmol), compound amine 31 (12.5 g,29.7 mmol) and sodium tert-butoxide (3.5 g,36.7 mmol) were added to 200ml of xylene under nitrogen and the mixture was stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.1 g,0.3 mmol) was added thereto. When the reaction was completed after 3 hours, the reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was completely dissolved again in chloroform, washed twice with water, then the organic layer was separated, treated with anhydrous magnesium sulfate, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 14.2g of compound 2-32. (yield: 68%, MS: [ M+H) ] + ＝739)
Synthesis examples 2 to 33
9H-carbazole (10 g,59.8 mmol), 2-bromo-4 '-chloro-1, 1':2', 1' -terphenyl (21.6 g,62.8 mmol) and sodium tert-butoxide (7.5 g,77.7 mmol) were added to 200ml of xylene under nitrogen and the mixture was stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.3 g,0.6 mmol) was added thereto. When the reaction was completed after 2 hours, the reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was completely dissolved again in chloroform, washed twice with water, then the organic layer was separated, treated with anhydrous magnesium sulfate, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 16.9g of compound sub A-12. (yield: 66%)，MS:[M+H] + ＝430)
Compound sub A-12 (10 g,23.3 mmol), compound amine 32 (9.1 g,24.4 mmol) and sodium tert-butoxide (2.9 g,30.2 mmol) were added to 200ml of xylene under nitrogen and the mixture was stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.1 g,0.2 mmol) was added thereto. When the reaction was completed after 2 hours, the reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was completely dissolved again in chloroform, washed twice with water, then the organic layer was separated, treated with anhydrous magnesium sulfate, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 12.6g of compound 2-33. (yield: 71%, MS: [ M+H) ] + ＝765)
Synthesis examples 2 to 34
9H-carbazole (10 g,59.8 mmol), 2 '-bromo-4-chloro-1, 1':3', 1' -terphenyl (21.6 g,62.8 mmol) and sodium tert-butoxide (7.5 g,77.7 mmol) were added to 200ml of xylene under nitrogen and the mixture was stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.3 g,0.6 mmol) was added thereto. When the reaction was completed after 3 hours, the reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was completely dissolved again in chloroform, washed twice with water, then the organic layer was separated, treated with anhydrous magnesium sulfate, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 16.4g of compound sub A-13. (yield: 64%, MS: [ M+H ]] + ＝430)
Compound sub A-13 (10 g,23.3 mmol), compound amine 12 (7.8 g,24.4 mmol) and sodium tert-butoxide (2.9 g,30.2 mmol) were added to 200ml of xylene under nitrogen and the mixture was stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.1 g,0.2 mmol) was added thereto. When the reaction was completed after 3 hours, the reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was completely dissolved again in chloroform, washed twice with water, then the organic layer was separated, treated with anhydrous magnesium sulfate, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 11.8g of compounds 2 to 34. (yield: 71%, MS: [ M+H) ] + ＝715)
Synthesis examples 2 to 35
Compound sub A-12 (10 g,23.3 mmol), compound amine 33 (9.1 g,24.4 mmol) and sodium tert-butoxide (2.9 g,30.2 mmol) were added to 200ml of xylene under nitrogen and the mixture was stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.1 g,0.2 mmol) was added thereto. When the reaction was completed after 2 hours, the reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was completely dissolved again in chloroform, washed twice with water, then the organic layer was separated, treated with anhydrous magnesium sulfate, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 12.3g of compounds 2 to 35. (yield: 69%, MS: [ M+H)] + ＝765)
Synthesis examples 2 to 36
9H-carbazole (10 g,59.8 mmol), 3' -bromo 4 "-chloro-1, 1':2',1" -terphenyl (21.6 g,62.8 mmol) and sodium tert-butoxide (7.5 g, 7) were reacted under nitrogen7.7 mmol) was added to 200ml of xylene and the mixture was stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.3 g,0.6 mmol) was added thereto. When the reaction was completed after 2 hours, the reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was completely dissolved again in chloroform, washed twice with water, then the organic layer was separated, treated with anhydrous magnesium sulfate, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 15.7g of compound sub A-14. (yield: 61%, MS: [ M+H) ] + ＝430)
Compound sub A-14 (10 g,23.3 mmol), compound amine 34 (10.3 g,24.4 mmol) and sodium tert-butoxide (2.9 g,30.2 mmol) were added to 200ml of xylene under nitrogen and the mixture was stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.1 g,0.2 mmol) was added thereto. When the reaction was completed after 2 hours, the reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was completely dissolved again in chloroform, washed twice with water, then the organic layer was separated, treated with anhydrous magnesium sulfate, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 13.6g of compounds 2 to 36. (yield: 72%, MS: [ M+H)] + ＝815)
Synthesis examples 2 to 37
9H-carbazole (10 g,59.8 mmol), 3-bromo-4 '-chloro-1, 1' -biphenyl (16.8 g,62.8 mmol) and sodium tert-butoxide (7.5 g,77.7 mmol) were added to 200ml of xylene under nitrogen, and the mixture was stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.3 g,0.6 mmol) was added thereto. When the reaction was completed after 3 hours, the reaction mixture was cooled to room temperature and was depressurizedThe solvent was removed. Then, the compound was completely dissolved again in chloroform, washed twice with water, then the organic layer was separated, treated with anhydrous magnesium sulfate, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 13.3g of compound sub A-15. (yield: 63%, MS: [ M+H) ] + ＝354)
Compound sub A-15 (10 g,2.8 mmol), compound amine 35 (1.1 g,3 mmol) and sodium tert-butoxide (0.4 g,3.7 mmol) were added to 200ml of xylene under nitrogen and the mixture was stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0 g,0 mmol) was added thereto. When the reaction was completed after 3 hours, the reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was completely dissolved again in chloroform, washed twice with water, then the organic layer was separated, treated with anhydrous magnesium sulfate, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 1.3g of compounds 2 to 37. (yield: 68%, MS: [ M+H)] + ＝689)
Synthesis examples 2 to 38
Compound sub A-15 (10 g,2.8 mmol), compound amine 36 (1 g,3 mmol) and sodium tert-butoxide (0.4 g,3.7 mmol) were added to 200ml of xylene under nitrogen and the mixture was stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0 g,0 mmol) was added thereto. When the reaction was completed after 3 hours, the reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was completely dissolved again in chloroform, washed twice with water, then the organic layer was separated, treated with anhydrous magnesium sulfate, then filtered, and the filtrate was distilled under reduced pressure. Purifying the concentrated compound by silica gel column chromatography to obtain 1.3g of Compound 2-38 are prepared. (yield: 69%, MS: [ M+H)] + ＝653)
Synthesis examples 2 to 39
Compound sub A-15 (10 g,2.8 mmol), compound amine 37 (1.4 g,3 mmol) and sodium tert-butoxide (0.4 g,3.7 mmol) were added to 200ml of xylene under nitrogen and the mixture was stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0 g,0 mmol) was added thereto. When the reaction was completed after 3 hours, the reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was completely dissolved again in chloroform, washed twice with water, then the organic layer was separated, treated with anhydrous magnesium sulfate, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 1.4g of compound 2-39. (yield: 60%, MS: [ M+H)] + ＝805)
Synthesis examples 2 to 40
9H-carbazole (10 g,59.8 mmol), 5 '-bromo-4-chloro-1, 1':3', 1' -terphenyl (21.6 g,62.8 mmol) and sodium tert-butoxide (7.5 g,77.7 mmol) were added to 200ml of xylene under nitrogen and the mixture was stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.3 g,0.6 mmol) was added thereto. When the reaction was completed after 2 hours, the reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was completely dissolved again in chloroform, washed twice with water, then the organic layer was separated, treated with anhydrous magnesium sulfate, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 18g of compound sub A-16. (yield: 70%, MS: [ M+H ] ] + ＝430)
Compound sub A-16 (10 g,23.3 mmol), compound amine 38 (9 g,24.4 mmol) and sodium tert-butoxide (2.9 g,30.2 mmol) were added to 200ml of xylene under nitrogen and the mixture was stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.1 g,0.2 mmol) was added thereto. When the reaction was completed after 3 hours, the reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was completely dissolved again in chloroform, washed twice with water, then the organic layer was separated, treated with anhydrous magnesium sulfate, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 12.6g of compounds 2 to 40. (yield: 71%, MS: [ M+H)] + ＝763)
Synthesis examples 2 to 41
9H-carbazole (10 g,59.8 mmol), 5 '-bromo-4-chloro-1, 1':2', 1' -terphenyl (21.6 g,62.8 mmol) and sodium tert-butoxide (7.5 g,77.7 mmol) were added to 200ml of xylene under nitrogen and the mixture was stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.3 g,0.6 mmol) was added thereto. When the reaction was completed after 2 hours, the reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was completely dissolved again in chloroform, washed twice with water, then the organic layer was separated, treated with anhydrous magnesium sulfate, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 15.4g of compound sub A-17. (yield: 60%, MS: [ M+H) ] + ＝430)
Compound sub A-17 (10 g,23.3 mmol), compound amine 39 (9.1 g,24.4 mmol) were reacted under nitrogen atmosphereAnd sodium tert-butoxide (2.9 g,30.2 mmol) were added to 200ml of xylene and the mixture was stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.1 g,0.2 mmol) was added thereto. When the reaction was completed after 3 hours, the reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was completely dissolved again in chloroform, washed twice with water, then the organic layer was separated, treated with anhydrous magnesium sulfate, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 11.7g of compound 2-41. (yield: 66%, MS: [ M+H)] + ＝766)
Synthesis examples 2 to 42
9H-carbazole (10 g,59.8 mmol), 3-bromo-4 '-chloro-1, 1':2', 1' -terphenyl (21.6 g,62.8 mmol) and sodium tert-butoxide (7.5 g,77.7 mmol) were added to 200ml of xylene under nitrogen and the mixture was stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.3 g,0.6 mmol) was added thereto. When the reaction was completed after 2 hours, the reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was completely dissolved again in chloroform, washed twice with water, then the organic layer was separated, treated with anhydrous magnesium sulfate, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 19g of compound sub A-18. (yield: 74%, MS: [ M+H) ] + ＝430)
Compound sub A-18 (10 g,23.3 mmol), compound amine 40 (7.8 g,24.4 mmol) and sodium tert-butoxide (2.9 g,30.2 mmol) were added to 200ml of xylene under nitrogen and the mixture was stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.1 g,0.2 mmol) was added thereto. When the reaction was completed after 2 hours, the reaction was mixedThe compound was cooled to room temperature and the solvent was removed under reduced pressure. Then, the compound was completely dissolved again in chloroform, washed twice with water, then the organic layer was separated, treated with anhydrous magnesium sulfate, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 12.1g of compound 2-42. (yield: 73%, MS: [ M+H)] + ＝715)
Synthesis examples 2 to 43
9H-carbazole (10 g,59.8 mmol), 3-bromo-4 '-chloro-1, 1':3', 1' -terphenyl (21.6 g,62.8 mmol) and sodium tert-butoxide (7.5 g,77.7 mmol) were added to 200ml of xylene under nitrogen and the mixture was stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.3 g,0.6 mmol) was added thereto. When the reaction was completed after 3 hours, the reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was completely dissolved again in chloroform, washed twice with water, then the organic layer was separated, treated with anhydrous magnesium sulfate, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 16.7g of compound sub A-19. (yield: 65%, MS: [ M+H) ] + ＝430)。
Compound sub A-19 (10 g,23.3 mmol), compound amine 41 (9.1 g,24.4 mmol) and sodium tert-butoxide (2.9 g,30.2 mmol) were added to 200ml of xylene under nitrogen and the mixture was stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.1 g,0.2 mmol) was added thereto. When the reaction was completed after 2 hours, the reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was completely dissolved again in chloroform, washed twice with water, then the organic layer was separated, treated with anhydrous magnesium sulfate, then filtered, and the filtrate was taken outThe solution was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 12.6g of compounds 2 to 43. (yield: 71%, MS: [ M+H)] + ＝765)
Synthesis examples 2 to 44
9H-carbazole (10 g,59.8 mmol), 3-bromo-3 '-chloro-1, 1' -biphenyl (16.8 g,62.8 mmol) and sodium tert-butoxide (7.5 g,77.7 mmol) were added to 200ml of xylene under nitrogen, and the mixture was stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.3 g,0.6 mmol) was added thereto. When the reaction was completed after 2 hours, the reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was completely dissolved again in chloroform, washed twice with water, then the organic layer was separated, treated with anhydrous magnesium sulfate, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 14.1g of compound sub A-20. (yield: 67%, MS: [ M+H) ] + ＝354)
Compound sub A-20 (10 g,28.3 mmol), compound amine 42 (11.1 g,29.7 mmol) and sodium tert-butoxide (3.5 g,36.7 mmol) were added to 200ml of xylene under nitrogen and the mixture was stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.1 g,0.3 mmol) was added thereto. When the reaction was completed after 2 hours, the reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was completely dissolved again in chloroform, washed twice with water, then the organic layer was separated, treated with anhydrous magnesium sulfate, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 12.1g of compounds 2 to 44. (yield: 62%, MS: [ M+H)] + ＝689)
Synthesis examples 2 to 45
9H-carbazole (10 g,59.8 mmol), 2-bromo-3 '-chloro-1, 1' -biphenyl (16.8 g,62.8 mmol) and sodium tert-butoxide (7.5 g,77.7 mmol) were added to 200ml of xylene under nitrogen, and the mixture was stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.3 g,0.6 mmol) was added thereto. When the reaction was completed after 3 hours, the reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was completely dissolved again in chloroform, washed twice with water, then the organic layer was separated, treated with anhydrous magnesium sulfate, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 13.3g of compound sub A-21. (yield: 63%, MS: [ M+H) ] + ＝354)
Compound sub A-21 (10 g,28.3 mmol), compound amine 43 (11.7 g,29.7 mmol) and sodium tert-butoxide (3.5 g,36.7 mmol) were added to 200ml of xylene under nitrogen and the mixture was stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.1 g,0.3 mmol) was added thereto. When the reaction was completed after 2 hours, the reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was completely dissolved again in chloroform, washed twice with water, then the organic layer was separated, treated with anhydrous magnesium sulfate, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 14.7g of compounds 2 to 45. (yield: 73%, MS: [ M+H)] + ＝713)
Synthesis examples 2 to 46
Under nitrogen atmosphere9H-carbazole (10 g,59.8 mmol), 6 '-bromo-3-chloro-1, 1':3', 1' -terphenyl (21.6 g,62.8 mmol) and sodium tert-butoxide (7.5 g,77.7 mmol) were added to 200ml of xylene and the mixture was stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.3 g,0.6 mmol) was added thereto. When the reaction was completed after 2 hours, the reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was completely dissolved again in chloroform, washed twice with water, then the organic layer was separated, treated with anhydrous magnesium sulfate, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 16.4g of compound sub A-22. (yield: 64%, MS: [ M+H ] ] + ＝430)
Compound sub A-22 (10 g,23.3 mmol), compound amine 44 (7.8 g,24.4 mmol) and sodium tert-butoxide (2.9 g,30.2 mmol) were added to 200ml of xylene under nitrogen and the mixture was stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.1 g,0.2 mmol) was added thereto. When the reaction was completed after 2 hours, the reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was completely dissolved again in chloroform, washed twice with water, then the organic layer was separated, treated with anhydrous magnesium sulfate, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 10.1g of compounds 2 to 46. (yield: 61%, MS: [ M+H)] + ＝715)
Synthesis examples 2 to 47
Compound sub A-20 (10 g,28.3 mmol), compound amine 45 (13.3 g,29.7 mmol) and sodium tert-butoxide (3.5 g,36.7 mmol) were added to 200ml of xylene under nitrogen and the mixture was stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium was added thereto(0) (0.1 g,0.3 mmol). When the reaction was completed after 3 hours, the reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was completely dissolved again in chloroform, washed twice with water, then the organic layer was separated, treated with anhydrous magnesium sulfate, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 13.8g of compounds 2 to 47. (yield: 64%, MS: [ M+H ] ] + ＝765)
Synthesis examples 2 to 48
9H-carbazole (10 g,59.8 mmol), 1-bromo-2-chlorobenzene (12 g,62.8 mmol) and sodium tert-butoxide (7.5 g,77.7 mmol) were added to 200ml of xylene under nitrogen, and the mixture was stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.3 g,0.6 mmol) was added thereto. When the reaction was completed after 2 hours, the reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was completely dissolved again in chloroform, washed twice with water, then the organic layer was separated, treated with anhydrous magnesium sulfate, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 11.9g of compound sub A-23. (yield: 72%, MS: [ M+H)] + ＝278)
Compound sub A-23 (10 g,36 mmol), compound amine 46 (13.1 g,37.8 mmol) and sodium tert-butoxide (4.5 g,46.8 mmol) were added to 200ml of xylene under nitrogen and the mixture was stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.2 g,0.4 mmol) was added thereto. When the reaction was completed after 2 hours, the reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was completely dissolved again in chloroform, washed twice with water, and then the organic layer was separated, and dried over anhydrous sulfur The magnesium acid is treated, then filtered, and the filtrate is distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 13.9g of compounds 2 to 48. (yield: 66%, MS: [ M+H)] + ＝587)
Synthesis examples 2 to 49
9H-carbazole (10 g,59.8 mmol), 1-bromo-3-chlorobenzene (12 g,62.8 mmol) and sodium tert-butoxide (7.5 g,77.7 mmol) were added to 200ml of xylene under nitrogen, and the mixture was stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.3 g,0.6 mmol) was added thereto. When the reaction was completed after 3 hours, the reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was completely dissolved again in chloroform, washed twice with water, then the organic layer was separated, treated with anhydrous magnesium sulfate, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 9.9g of compound sub A-24. (yield: 60%, MS: [ M+H)] + ＝278)
Compound sub A-24 (10 g,36 mmol), compound amine 47 (16.8 g,37.8 mmol) and sodium tert-butoxide (4.5 g,46.8 mmol) were added to 200ml of xylene under nitrogen and the mixture was stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.2 g,0.4 mmol) was added thereto. When the reaction was completed after 3 hours, the reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was completely dissolved again in chloroform, washed twice with water, then the organic layer was separated, treated with anhydrous magnesium sulfate, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 18g of compounds 2 to 49. (yield: 73%, MS: [ M+H) ] + ＝687)
Synthesis examples 2 to 50
Compound sub A-24 (10 g,36 mmol), compound amine 48 (16.9 g,37.8 mmol) and sodium tert-butoxide (4.5 g,46.8 mmol) were added to 200ml of xylene under nitrogen and the mixture was stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.2 g,0.4 mmol) was added thereto. When the reaction was completed after 3 hours, the reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was completely dissolved again in chloroform, washed twice with water, then the organic layer was separated, treated with anhydrous magnesium sulfate, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 17g of compounds 2 to 50. (yield: 69%, MS: [ M+H)] + ＝687)
Synthesis examples 2 to 51
9H-carbazole (10 g,59.8 mmol), 2-bromo-4-chloro-1, 1' -biphenyl (16.8 g,62.8 mmol) and sodium tert-butoxide (7.5 g,77.7 mmol) were added to 200ml of xylene under nitrogen, and the mixture was stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.3 g,0.6 mmol) was added thereto. When the reaction was completed after 3 hours, the reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was completely dissolved again in chloroform, washed twice with water, then the organic layer was separated, treated with anhydrous magnesium sulfate, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 15.8g of compound sub A-25. (yield: 75%, MS: [ M+H) ] + ＝354)
At nitrogenCompound sub A-25 (10 g,28.3 mmol), compound amine 49 (9.5 g,29.7 mmol) and sodium tert-butoxide (3.5 g,36.7 mmol) were added to 200ml of xylene under a gaseous atmosphere and the mixture was stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.1 g,0.3 mmol) was added thereto. When the reaction was completed after 3 hours, the reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was completely dissolved again in chloroform, washed twice with water, then the organic layer was separated, treated with anhydrous magnesium sulfate, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 13.5g of compound 2-51. (yield: 75%, MS: [ M+H)] + ＝637)
Synthesis examples 2 to 52
9H-carbazole (10 g,59.8 mmol), 4-bromo-2-chloro-1, 1' -biphenyl (16.8 g,62.8 mmol) and sodium tert-butoxide (7.5 g,77.7 mmol) were added to 200ml of xylene under nitrogen, and the mixture was stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.3 g,0.6 mmol) was added thereto. When the reaction was completed after 3 hours, the reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was completely dissolved again in chloroform, washed twice with water, then the organic layer was separated, treated with anhydrous magnesium sulfate, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 15g of compound sub A-26. (yield: 71%, MS: [ M+H) ] + ＝354)
Compound sub A-26 (10 g,28.3 mmol), compound amine 50 (14 g,29.7 mmol) and sodium tert-butoxide (3.5 g,36.7 mmol) were added to 200ml of xylene under nitrogen and the mixture was stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) was added thereto.1g,0.3 mmol). When the reaction was completed after 2 hours, the reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was completely dissolved again in chloroform, washed twice with water, then the organic layer was separated, treated with anhydrous magnesium sulfate, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 14.9g of compound 2-52. (yield: 67%, MS: [ M+H)] + ＝789)
Synthesis examples 2 to 53
9H-carbazole (10 g,59.8 mmol), 3-bromo-5-chloro-1, 1' -biphenyl (16.8 g,62.8 mmol) and sodium tert-butoxide (7.5 g,77.7 mmol) were added to 200ml of xylene under nitrogen, and the mixture was stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.3 g,0.6 mmol) was added thereto. When the reaction was completed after 3 hours, the reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was completely dissolved again in chloroform, washed twice with water, then the organic layer was separated, treated with anhydrous magnesium sulfate, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 15.6g of compound sub A-27. (yield: 74%, MS: [ M+H) ] + ＝354)
Compound sub A-27 (10 g,2.8 mmol), compound amine 43 (1.2 g,3 mmol) and sodium tert-butoxide (0.4 g,3.7 mmol) were added to 200ml of xylene under nitrogen and the mixture was stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0 g,0 mmol) was added thereto. When the reaction was completed after 2 hours, the reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was completely dissolved again in chloroform, washed twice with water, and then the organic layer was separated, and washed with anhydrous sulfuric acidMagnesium treatment, then filtration, and distillation of the filtrate under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 1.2g of compound 2-53. (yield: 60%, MS: [ M+H)] + ＝713)
Synthesis examples 2 to 54
Compound sub A-27 (10 g,2.8 mmol), compound amine 51 (0.9 g,3 mmol) and sodium tert-butoxide (0.4 g,3.7 mmol) were added to 200ml of xylene under nitrogen and the mixture was stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0 g,0 mmol) was added thereto. When the reaction was completed after 3 hours, the reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was completely dissolved again in chloroform, washed twice with water, then the organic layer was separated, treated with anhydrous magnesium sulfate, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 1g of the compound 2-54. (yield: 60%, MS: [ M+H) ] + ＝613)
Synthesis examples 2 to 55
Compound sub A-20 (10 g,28.3 mmol), compound amine 52 (12.5 g,29.7 mmol) and sodium tert-butoxide (3.5 g,36.7 mmol) were added to 200ml of xylene under nitrogen and the mixture was stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.1 g,0.3 mmol) was added thereto. When the reaction was completed after 2 hours, the reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was completely dissolved again in chloroform, washed twice with water, then the organic layer was separated, treated with anhydrous magnesium sulfate, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 14.8g of compound 2-55. (yield: 71%, MS: [ M+H)] + ＝739)
Synthesis examples 2 to 56
9H-carbazole (10 g,59.8 mmol), 3-bromo-5 '-chloro-1, 1':2', 1' -terphenyl (21.6 g,62.8 mmol) and sodium tert-butoxide (7.5 g,77.7 mmol) were added to 200ml of xylene under nitrogen and the mixture was stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.3 g,0.6 mmol) was added thereto. When the reaction was completed after 3 hours, the reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was completely dissolved again in chloroform, washed twice with water, then the organic layer was separated, treated with anhydrous magnesium sulfate, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 15.4g of compound sub A-28. (yield: 60%, MS: [ M+H) ] + ＝430)
Compound sub A-28 (10 g,23.3 mmol), compound amine 53 (9.1 g,24.4 mmol) and sodium tert-butoxide (2.9 g,30.2 mmol) were added to 200ml of xylene under nitrogen and the mixture was stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.1 g,0.2 mmol) was added thereto. When the reaction was completed after 3 hours, the reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was completely dissolved again in chloroform, washed twice with water, then the organic layer was separated, treated with anhydrous magnesium sulfate, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 12.6g of compounds 2 to 56. (yield: 71%, MS: [ M+H)] + ＝765)
Synthesis examples 2 to 57
9H-carbazole (10 g,59.8 mmol), 3-bromo-5 '-chloro-1, 1':3', 1' -terphenyl (21.6 g,62.8 mmol) and sodium tert-butoxide (7.5 g,77.7 mmol) were added to 200ml of xylene under nitrogen and the mixture was stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.3 g,0.6 mmol) was added thereto. When the reaction was completed after 3 hours, the reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was completely dissolved again in chloroform, washed twice with water, then the organic layer was separated, treated with anhydrous magnesium sulfate, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 15.7g of compound sub A-29. (yield: 61%, MS: [ M+H) ] + ＝430)
Compound sub A-29 (10 g,23.3 mmol), compound amine 39 (9.1 g,24.4 mmol) and sodium tert-butoxide (2.9 g,30.2 mmol) were added to 200ml of xylene under nitrogen and the mixture was stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.1 g,0.2 mmol) was added thereto. When the reaction was completed after 2 hours, the reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was completely dissolved again in chloroform, washed twice with water, then the organic layer was separated, treated with anhydrous magnesium sulfate, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 13g of compounds 2 to 57. (yield: 73%, MS: [ M+H)] + ＝765)
Synthesis examples 2 to 58
9H-carbazole (10 g,59.8 mmol), 2-bromo-2 '-chloro-1, 1' -biphenyl (16.8 g,62.8 mmol) and sodium tert-butoxide (7.5 g,77.7 mmol) were added to 200ml of xylene under nitrogen,and the mixture was stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.3 g,0.6 mmol) was added thereto. When the reaction was completed after 2 hours, the reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was completely dissolved again in chloroform, washed twice with water, then the organic layer was separated, treated with anhydrous magnesium sulfate, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 15g of compound sub A-30. (yield: 71%, MS: [ M+H) ] + ＝354)
Compound sub A-30 (10 g,28.3 mmol), compound amine 54 (12.5 g,29.7 mmol) and sodium tert-butoxide (3.5 g,36.7 mmol) were added to 200ml of xylene under nitrogen and the mixture was stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.1 g,0.3 mmol) was added thereto. When the reaction was completed after 2 hours, the reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was completely dissolved again in chloroform, washed twice with water, then the organic layer was separated, treated with anhydrous magnesium sulfate, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 12.7g of compounds 2 to 58. (yield: 61%, MS: [ M+H)] + ＝739)
Synthesis examples 2 to 59
Compound sub A-30 (10 g,28.3 mmol), compound amine 55 (11.8 g,29.7 mmol) and sodium tert-butoxide (3.5 g,36.7 mmol) were added to 200ml of xylene under nitrogen and the mixture was stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.1 g,0.3 mmol) was added thereto. When the reaction was completed after 3 hours, the reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound is again Completely dissolved in chloroform, washed twice with water, then the organic layer was separated, treated with anhydrous magnesium sulfate, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 13.9g of compound 2-59. (yield: 69%, MS: [ M+H)] + ＝715)
Synthesis examples 2 to 60
9H-carbazole (10 g,59.8 mmol), 3 '-bromo-2-chloro-1, 1' -biphenyl (16.8 g,62.8 mmol) and sodium tert-butoxide (7.5 g,77.7 mmol) were added to 200ml of xylene under nitrogen, and the mixture was stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.3 g,0.6 mmol) was added thereto. When the reaction was completed after 3 hours, the reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was completely dissolved again in chloroform, washed twice with water, then the organic layer was separated, treated with anhydrous magnesium sulfate, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 13.1g of compound sub A-31. (yield: 62%, MS: [ M+H)] + ＝354)
Compound sub A-31 (10 g,28.3 mmol), compound amine 56 (12.5 g,29.7 mmol) and sodium tert-butoxide (3.5 g,36.7 mmol) were added to 200ml of xylene under nitrogen and the mixture was stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.1 g,0.3 mmol) was added thereto. When the reaction was completed after 3 hours, the reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was completely dissolved again in chloroform, washed twice with water, then the organic layer was separated, treated with anhydrous magnesium sulfate, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 14.8g of a compound 2-60 parts of a material. (yield: 71%, MS: [ M+H)] + ＝739)
Synthesis examples 2 to 61
9H-carbazole (10 g,59.8 mmol), 3-bromo-6 '-chloro-1, 1':2', 1' -terphenyl (21.6 g,62.8 mmol) and sodium tert-butoxide (7.5 g,77.7 mmol) were added to 200ml of xylene under nitrogen and the mixture was stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.3 g,0.6 mmol) was added thereto. When the reaction was completed after 3 hours, the reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was completely dissolved again in chloroform, washed twice with water, then the organic layer was separated, treated with anhydrous magnesium sulfate, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 17.5g of compound sub A-32. (yield: 68%, MS: [ M+H)] + ＝430)
Compound sub A-32 (10 g,23.3 mmol), compound amine 57 (9.7 g,24.4 mmol) and sodium tert-butoxide (2.9 g,30.2 mmol) were added to 200ml of xylene under nitrogen and the mixture was stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.1 g,0.2 mmol) was added thereto. When the reaction was completed after 2 hours, the reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was completely dissolved again in chloroform, washed twice with water, then the organic layer was separated, treated with anhydrous magnesium sulfate, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 13.4g of compound 2-61. (yield: 73%, MS: [ M+H) ] + ＝791)
Synthesis examples 2 to 62
9H-carbazole (10 g,59.8 mmol), 4 "-bromo-3 ' -chloro-1, 1':2',1" -terphenyl (21.6 g,62.8 mmol) and sodium tert-butoxide (7.5 g,77.7 mmol) were added to 200ml of xylene under nitrogen and the mixture was stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.3 g,0.6 mmol) was added thereto. When the reaction was completed after 3 hours, the reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was completely dissolved again in chloroform, washed twice with water, then the organic layer was separated, treated with anhydrous magnesium sulfate, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 16.9g of compound sub A-33. (yield: 66%, MS: [ M+H)] + ＝430)
Compound sub A-33 (10 g,23.3 mmol) and compound amine 40 (7.8 g,24.4 mmol), sodium tert-butoxide (2.9 g,30.2 mmol) were added to 200ml of xylene under nitrogen and the mixture was stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.1 g,0.2 mmol) was added thereto. When the reaction was completed after 2 hours, the reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was completely dissolved again in chloroform, washed twice with water, then the organic layer was separated, treated with anhydrous magnesium sulfate, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 10.1g of compound 2-62. (yield: 61%, MS: [ M+H) ] + ＝715)
Synthesis examples 2 to 63
Compound sub A-31 (10 g,28.3 mmol), compound amine 58 (14 g,29.7 m) was reacted under nitrogen atmospheremol) and sodium tert-butoxide (3.5 g,36.7 mmol) were added to 200ml of xylene and the mixture was stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.1 g,0.3 mmol) was added thereto. When the reaction was completed after 2 hours, the reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was completely dissolved again in chloroform, washed twice with water, then the organic layer was separated, treated with anhydrous magnesium sulfate, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 14.5g of compound 2-63. (yield: 65%, MS: [ M+H)] + ＝789)
Synthesis examples 2 to 64
11H-benzo [ a ] under nitrogen atmosphere]Carbazole (10 g,46 mmol), 1-bromo-4-chlorobenzene (9.3 g,48.3 mmol) and sodium tert-butoxide (5.7 g,59.8 mmol) were added to 200ml of xylene and the mixture was stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.2 g,0.5 mmol) was added thereto. When the reaction was completed after 3 hours, the reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was completely dissolved again in chloroform, washed twice with water, then the organic layer was separated, treated with anhydrous magnesium sulfate, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 9.5g of compound subsB-1. (yield: 63%, MS: [ M+H) ] + ＝328)
Compound sub B-1 (10 g,30.5 mmol), compound amine 59 (10.3 g,32 mmol) and sodium tert-butoxide (3.8 g,39.7 mmol) were added to 200ml of xylene under nitrogen and the mixture was stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.2 g,0.3 mmol) was added thereto. When the reaction was completed after 3 hours, the reaction mixture was cooled to a roomWarm and remove solvent under reduced pressure. Then, the compound was completely dissolved again in chloroform, washed twice with water, then the organic layer was separated, treated with anhydrous magnesium sulfate, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 13.1g of compounds 2 to 64. (yield: 70%, MS: [ M+H ]] + ＝613)
Synthesis examples 2 to 65
Compound sub B-1 (10 g,30.5 mmol), compound amine 60 (11.9 g,32 mmol) and sodium tert-butoxide (3.8 g,39.7 mmol) were added to 200ml of xylene under nitrogen and the mixture was stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.2 g,0.3 mmol) was added thereto. When the reaction was completed after 2 hours, the reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was completely dissolved again in chloroform, washed twice with water, then the organic layer was separated, treated with anhydrous magnesium sulfate, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 12.5g of compound 2-65. (yield: 62%, MS: [ M+H) ] + ＝663)
Synthesis examples 2 to 66
Compound sub B-1 (10 g,30.5 mmol), compound amine 61 (23.3 g,32 mmol) and sodium tert-butoxide (3.8 g,39.7 mmol) were added to 200ml of xylene under nitrogen and the mixture was stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.2 g,0.3 mmol) was added thereto. When the reaction was completed after 2 hours, the reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was completely dissolved again in chloroform, washed twice with water, then the organic layer was separated, treated with anhydrous magnesium sulfate, then filtered, and the filtrate was taken outThe solution was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 14.2g of the compound 2-66. (yield: 65%, MS: [ M+H)] + ＝719)
Synthesis examples 2 to 67
Compound sub B-1 (10 g,30.5 mmol), compound amine 62 (13.6 g,32 mmol) and sodium tert-butoxide (3.8 g,39.7 mmol) were added to 200ml of xylene under nitrogen and the mixture was stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.2 g,0.3 mmol) was added thereto. When the reaction was completed after 2 hours, the reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was completely dissolved again in chloroform, washed twice with water, then the organic layer was separated, treated with anhydrous magnesium sulfate, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 16.4g of compounds 2 to 67. (yield: 75%, MS: [ M+H) ] + ＝716)
Synthesis examples 2 to 68
11H-benzo [ a ] under nitrogen atmosphere]Carbazole (10 g,46 mmol), 5-bromo-2-chloro-1, 1' -biphenyl (12.9 g,48.3 mmol) and sodium tert-butoxide (5.7 g,59.8 mmol) were added to 200ml of xylene and the mixture was stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.2 g,0.5 mmol) was added thereto. When the reaction was completed after 3 hours, the reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was completely dissolved again in chloroform, washed twice with water, then the organic layer was separated, treated with anhydrous magnesium sulfate, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 13.9g of compound subsB-2. (yield: 75%, MS: [ M+H)] + ＝404)
Compound sub B-2 (10 g,24.8 mmol), compound amine 63 (9.7 g,26 mmol) and sodium tert-butoxide (3.1 g,32.2 mmol) were added to 200ml of xylene under nitrogen and the mixture was stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.1 g,0.2 mmol) was added thereto. When the reaction was completed after 2 hours, the reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was completely dissolved again in chloroform, washed twice with water, then the organic layer was separated, treated with anhydrous magnesium sulfate, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 13.2g of compound 2-68. (yield: 72%, MS: [ M+H) ] + ＝739)
Synthesis examples 2 to 69
11H-benzo [ a ] under nitrogen atmosphere]Carbazole (10 g,46 mmol), 2-bromo-5-chloro-1, 1' -biphenyl (12.9 g,48.3 mmol) and sodium tert-butoxide (5.7 g,59.8 mmol) were added to 200ml of xylene and the mixture was stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.2 g,0.5 mmol) was added thereto. When the reaction was completed after 2 hours, the reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was completely dissolved again in chloroform, washed twice with water, then the organic layer was separated, treated with anhydrous magnesium sulfate, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 12.4g of compound subsB-3. (yield: 67%, MS: [ M+H)] + ＝404)
Under nitrogen atmosphereCompound sub B-3 (10 g,24.8 mmol), compound amine 49 (8.3 g,26 mmol) and sodium tert-butoxide (3.1 g,32.2 mmol) were added to 200ml of xylene and the mixture was stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.1 g,0.2 mmol) was added thereto. When the reaction was completed after 3 hours, the reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was completely dissolved again in chloroform, washed twice with water, then the organic layer was separated, treated with anhydrous magnesium sulfate, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 11.6g of compounds 2 to 69. (yield: 68%, MS: [ M+H) ] + ＝687)
Synthesis examples 2 to 70
11H-benzo [ a ] under nitrogen atmosphere]Carbazole (10 g,46 mmol), and 4-bromo-4 '-chloro-1, 1' -biphenyl (12.9 g,48.3 mmol), sodium tert-butoxide (5.7 g,59.8 mmol) were added to 200ml of xylene, and the mixture was stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.2 g,0.5 mmol) was added thereto. When the reaction was completed after 2 hours, the reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was completely dissolved again in chloroform, washed twice with water, then the organic layer was separated, treated with anhydrous magnesium sulfate, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 12.1g of compound subsB-4. (yield: 65%, MS: [ M+H)] + ＝404)
Compound sub B-4 (10 g,24.8 mmol), compound amine 64 (7.7 g,26 mmol) and sodium tert-butoxide (3.1 g,32.2 mmol) were added to 200ml of xylene under nitrogen and the mixture was stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.1 g0.2 mmol). When the reaction was completed after 2 hours, the reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was completely dissolved again in chloroform, washed twice with water, then the organic layer was separated, treated with anhydrous magnesium sulfate, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 11.6g of compound 2-70. (yield: 71%, MS: [ M+H) ] + ＝663)
Synthesis examples 2 to 71
Compound sub B-4 (10 g,24.8 mmol), compound amine 65 (7.7 g,26 mmol) and sodium tert-butoxide (3.1 g,32.2 mmol) were added to 200ml of xylene under nitrogen and the mixture was stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.1 g,0.2 mmol) was added thereto. When the reaction was completed after 2 hours, the reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was completely dissolved again in chloroform, washed twice with water, then the organic layer was separated, treated with anhydrous magnesium sulfate, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 11.6g of compounds 2 to 71. (yield: 71%, MS: [ M+H)] + ＝663)
Synthesis examples 2 to 72
11H-benzo [ a ] under nitrogen atmosphere]Carbazole (10 g,46 mmol), 1-bromo-4- (4-chlorophenyl) naphthalene (15.3 g,48.3 mmol) and sodium tert-butoxide (5.7 g,59.8 mmol) were added to 200ml of xylene and the mixture was stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.2 g,0.5 mmol) was added thereto. When the reaction was completed after 3 hours, the reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was completely dissolved again in chloroform, and water was used The organic layer was then separated, treated with anhydrous magnesium sulfate, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 15.2g of compound subsB-5. (yield: 73%, MS: [ M+H)] + ＝454)
Compound sub B-5 (10 g,22 mmol), compound amine 66 (9.1 g,23.1 mmol) and sodium tert-butoxide (2.8 g,28.6 mmol) were added to 200ml of xylene under nitrogen and the mixture was stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.1 g,0.2 mmol) was added thereto. When the reaction was completed after 3 hours, the reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was completely dissolved again in chloroform, washed twice with water, then the organic layer was separated, treated with anhydrous magnesium sulfate, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 12.2g of compound 2-72. (yield: 68%, MS: [ M+H)] + ＝813)
Synthesis examples 2 to 73
11H-benzo [ a ] under nitrogen atmosphere]Carbazole (10 g,46 mmol), 4' -bromo-4-chloro-1, 1':2',1 "-terphenyl (16.6 g,48.3 mmol) and sodium tert-butoxide (5.7 g,59.8 mmol) were added to 200ml xylene and the mixture was stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.2 g,0.5 mmol) was added thereto. When the reaction was completed after 2 hours, the reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was completely dissolved again in chloroform, washed twice with water, then the organic layer was separated, treated with anhydrous magnesium sulfate, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 15g of compound subsB-6. (yield) ：68％，MS:[M+H] + ＝480)
Compound sub B-6 (10 g,20.8 mmol), compound amine 67 (8.7 g,21.9 mmol) and sodium tert-butoxide (2.6 g,27.1 mmol) were added to 200ml of xylene under nitrogen and the mixture was stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.1 g,0.2 mmol) was added thereto. When the reaction was completed after 2 hours, the reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was completely dissolved again in chloroform, washed twice with water, then the organic layer was separated, treated with anhydrous magnesium sulfate, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 12.4g of compound 2-73. (yield: 71%, MS: [ M+H)] + ＝839)
Synthesis examples 2 to 74
11H-benzo [ a ] under nitrogen atmosphere]Carbazole (10 g,46 mmol), 2-bromo-4 '-chloro-1, 1' -biphenyl (12.9 g,48.3 mmol) and sodium tert-butoxide (5.7 g,59.8 mmol) were added to 200ml of xylene and the mixture was stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.2 g,0.5 mmol) was added thereto. When the reaction was completed after 3 hours, the reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was completely dissolved again in chloroform, washed twice with water, then the organic layer was separated, treated with anhydrous magnesium sulfate, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 13.2g of compound subsB-7. (yield: 71%, MS: [ M+H) ] + ＝404)
Compound sub B-7 (10 g,24.8 mmol), compound amine 25 (11.6 g,26 mmol) and sodium tert-butoxide (3.1 g,32.2 mmol) were added to 200ml of xylene under nitrogen and the mixture was stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.1 g,0.2 mmol) was added thereto. When the reaction was completed after 3 hours, the reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was completely dissolved again in chloroform, washed twice with water, then the organic layer was separated, treated with anhydrous magnesium sulfate, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 13.3g of compound 2-74. (yield: 66%, MS: [ M+H)] + ＝815)
Synthesis examples 2 to 75
Compound sub B-7 (10 g,24.8 mmol), compound amine 42 (9.7 g,26 mmol) and sodium tert-butoxide (3.1 g,32.2 mmol) were added to 200ml of xylene under nitrogen and the mixture was stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.1 g,0.2 mmol) was added thereto. When the reaction was completed after 2 hours, the reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was completely dissolved again in chloroform, washed twice with water, then the organic layer was separated, treated with anhydrous magnesium sulfate, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 12.2g of compound 2-75. (yield: 67%, MS: [ M+H) ] + ＝739)
Synthesis examples 2 to 76
11H-benzo [ a ] under nitrogen atmosphere]Carbazole (10 g,46 mmol), 3' -bromo-4 "-chloro-1, 1':2',1" -terphenyl (16.6 g,48.3 mmol) and sodium tert-butoxide (5.7 g)59.8 mmol) was added to 200ml of xylene and the mixture was stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.2 g,0.5 mmol) was added thereto. When the reaction was completed after 3 hours, the reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was completely dissolved again in chloroform, washed twice with water, then the organic layer was separated, treated with anhydrous magnesium sulfate, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 14.3g of compound subsB-8. (yield: 65%, MS: [ M+H)] + ＝480)
Compound sub B-8 (10 g,20.8 mmol), compound amine 68 (7.6 g,21.9 mmol) and sodium tert-butoxide (2.6 g,27.1 mmol) were added to 200ml of xylene under nitrogen and the mixture was stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.1 g,0.2 mmol) was added thereto. When the reaction was completed after 2 hours, the reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was completely dissolved again in chloroform, washed twice with water, then the organic layer was separated, treated with anhydrous magnesium sulfate, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 12g of compounds 2 to 76. (yield: 73%, MS: [ M+H) ] + ＝789)
Synthesis examples 2 to 77
11H-benzo [ a ] under nitrogen atmosphere]Carbazole (10 g,46 mmol), 2-bromo-4 ' -chloro-1, 1':3',1 "-terphenyl (16.6 g,48.3 mmol) and sodium tert-butoxide (5.7 g,59.8 mmol) were added to 200ml xylene and the mixture was stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.2 g,0.5 mmol) was added thereto. When the reaction was completed after 2 hours, the reaction mixture was cooled toThe solvent was removed at room temperature under reduced pressure. Then, the compound was completely dissolved again in chloroform, washed twice with water, then the organic layer was separated, treated with anhydrous magnesium sulfate, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 15.7g of compound subsB-9. (yield: 71%, MS: [ M+H)] + ＝480)
Compound sub B-9 (10 g,20.8 mmol), compound amine 69 (7 g,21.9 mmol) and sodium tert-butoxide (2.6 g,27.1 mmol) were added to 200ml of xylene under nitrogen and the mixture was stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.1 g,0.2 mmol) was added thereto. When the reaction was completed after 2 hours, the reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was completely dissolved again in chloroform, washed twice with water, then the organic layer was separated, treated with anhydrous magnesium sulfate, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 9.6g of compound 2-77. (yield: 60%, MS: [ M+H) ] + ＝765)
Synthesis examples 2 to 78
11H-benzo [ a ] under nitrogen atmosphere]Carbazole (10 g,46 mmol), 2-bromo-4 ' -chloro-1, 1':2',1 "-terphenyl (16.6 g,48.3 mmol) and sodium tert-butoxide (5.7 g,59.8 mmol) were added to 200ml of xylene and the mixture was stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.2 g,0.5 mmol) was added thereto. When the reaction was completed after 3 hours, the reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was completely dissolved again in chloroform, washed twice with water, then the organic layer was separated, treated with anhydrous magnesium sulfate, then filtered, and the filtrate was subjected to reduced pressureAnd (5) distilling. The concentrated compound was purified by silica gel column chromatography to prepare 14.6g of compound subsB-10. (yield: 66%, MS: [ M+H)] + ＝480)
Compound sub B-10 (10 g,20.8 mmol), compound amine 70 (7.3 g,21.9 mmol) and sodium tert-butoxide (2.6 g,27.1 mmol) were added to 200ml of xylene under nitrogen and the mixture was stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.1 g,0.2 mmol) was added thereto. When the reaction was completed after 2 hours, the reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was completely dissolved again in chloroform, washed twice with water, then the organic layer was separated, treated with anhydrous magnesium sulfate, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 11.8g of compounds 2 to 78. (yield: 73%, MS: [ M+H) ] + ＝779)
Synthesis examples 2 to 79
11H-benzo [ a ] under nitrogen atmosphere]Carbazole (10 g,46 mmol), 3-bromo-5-chloro-1, 1' -biphenyl (12.9 g,48.3 mmol) and sodium tert-butoxide (5.7 g,59.8 mmol) were added to 200ml of xylene and the mixture was stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.2 g,0.5 mmol) was added thereto. When the reaction was completed after 2 hours, the reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was completely dissolved again in chloroform, washed twice with water, then the organic layer was separated, treated with anhydrous magnesium sulfate, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 13.5g of compound subsB-11. (yield: 73%, MS: [ M+H)] + ＝404)
Compound sub B-11 (10 g,24.8 mmol), compound amine 71 (9.7 g,26 mmol) and sodium tert-butoxide (3.1 g,32.2 mmol) were added to 200ml of xylene under nitrogen and the mixture was stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.1 g,0.2 mmol) was added thereto. When the reaction was completed after 3 hours, the reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was completely dissolved again in chloroform, washed twice with water, then the organic layer was separated, treated with anhydrous magnesium sulfate, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 13.3g of compound 2-79. (yield: 73%, MS: [ M+H) ] + ＝739)
Synthesis examples 2 to 80
11H-benzo [ a ] under nitrogen atmosphere]Carbazole (10 g,46 mmol), 3-bromo-4 '-chloro-1, 1' -biphenyl (12.9 g,48.3 mmol) and sodium tert-butoxide (5.7 g,59.8 mmol) were added to 200ml of xylene and the mixture was stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.2 g,0.5 mmol) was added thereto. When the reaction was completed after 2 hours, the reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was completely dissolved again in chloroform, washed twice with water, then the organic layer was separated, treated with anhydrous magnesium sulfate, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 13.4g of compound subsB-12. (yield: 72%, MS: [ M+H)] + ＝404)
Compound sub B-12 (10 g,24.8 mmol), compound amine under nitrogen atmosphere31 (11 g,26 mmol) and sodium tert-butoxide (3.1 g,32.2 mmol) were added to 200ml of xylene and the mixture was stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.1 g,0.2 mmol) was added thereto. When the reaction was completed after 3 hours, the reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was completely dissolved again in chloroform, washed twice with water, then the organic layer was separated, treated with anhydrous magnesium sulfate, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 12.1g of compound 2-80. (yield: 62%, MS: [ M+H) ] + ＝789)
Synthesis examples 2 to 81
11H-benzo [ a ] under nitrogen atmosphere]Carbazole (10 g,46 mmol), 5' -bromo-4-chloro-1, 1':3',1 "-terphenyl (16.6 g,48.3 mmol) and sodium tert-butoxide (5.7 g,59.8 mmol) were added to 200ml xylene and the mixture was stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.2 g,0.5 mmol) was added thereto. When the reaction was completed after 3 hours, the reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was completely dissolved again in chloroform, washed twice with water, then the organic layer was separated, treated with anhydrous magnesium sulfate, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 15.2g of compound subsubB-13. (yield: 69%, MS: [ M+H)] + ＝480)
Compound sub B-13 (10 g,20.8 mmol), compound amine 20 (7 g,21.9 mmol) and sodium tert-butoxide (2.6 g,27.1 mmol) were added to 200ml of xylene under nitrogen and the mixture was stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.1 g,0.2 mmol) was added thereto. When the reaction is carried out after 3 hoursUpon completion, the reaction mixture was cooled to room temperature and the solvent was removed under reduced pressure. Then, the compound was completely dissolved again in chloroform, washed twice with water, then the organic layer was separated, treated with anhydrous magnesium sulfate, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 11.1g of compound 2-81. (yield: 70%, MS: [ M+H ] ] + ＝765)
Synthesis examples 2 to 82
11H-benzo [ a ] under nitrogen atmosphere]Carbazole (10 g,46 mmol), 3-bromo-4 ' -chloro-1, 1':2',1 "-terphenyl (16.6 g,48.3 mmol) and sodium tert-butoxide (5.7 g,59.8 mmol) were added to 200ml of xylene and the mixture was stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.2 g,0.5 mmol) was added thereto. When the reaction was completed after 3 hours, the reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was completely dissolved again in chloroform, washed twice with water, then the organic layer was separated, treated with anhydrous magnesium sulfate, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 13.7g of compound subsubB-14. (yield: 62%, MS: [ M+H)] + ＝480)
Compound sub B-14 (10 g,20.8 mmol), compound amine 72 (7.6 g,21.9 mmol) and sodium tert-butoxide (2.6 g,27.1 mmol) were added to 200ml of xylene under nitrogen and the mixture was stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.1 g,0.2 mmol) was added thereto. When the reaction was completed after 3 hours, the reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was completely dissolved again in chloroform, washed twice with water, and then the organic layer was separated, and washed with anhydrous magnesium sulfate And then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 11.5g of compound 2-82. (yield: 70%, MS: [ M+H ]] + ＝789)
Synthesis examples 2 to 83
11H-benzo [ a ] under nitrogen atmosphere]Carbazole (10 g,46 mmol), 3-bromo-4 ' -chloro-1, 1':3',1 "-terphenyl (16.6 g,48.3 mmol) and sodium tert-butoxide (5.7 g,59.8 mmol) were added to 200ml of xylene and the mixture was stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.2 g,0.5 mmol) was added thereto. When the reaction was completed after 2 hours, the reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was completely dissolved again in chloroform, washed twice with water, then the organic layer was separated, treated with anhydrous magnesium sulfate, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 16.5g of compound subsubB-15. (yield: 75%, MS: [ M+H)] + ＝480)
Compound sub B-15 (10 g,20.8 mmol), compound amine 73 (8.7 g,21.9 mmol) and sodium tert-butoxide (2.6 g,27.1 mmol) were added to 200ml of xylene under nitrogen and the mixture was stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.1 g,0.2 mmol) was added thereto. When the reaction was completed after 2 hours, the reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was completely dissolved again in chloroform, washed twice with water, then the organic layer was separated, treated with anhydrous magnesium sulfate, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 12.1g of compound 2-83. (yield: 69%, MS: [ M+H) ] + ＝839)
Synthesis examples 2 to 84
11H-benzo [ a ] under nitrogen atmosphere]Carbazole (10 g,46 mmol), 3-bromo-3 '-chloro-1, 1' -biphenyl (12.9 g,48.3 mmol) and sodium tert-butoxide (5.7 g,59.8 mmol) were added to 200ml of xylene and the mixture was stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.2 g,0.5 mmol) was added thereto. When the reaction was completed after 2 hours, the reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was completely dissolved again in chloroform, washed twice with water, then the organic layer was separated, treated with anhydrous magnesium sulfate, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 12.1g of compound subsubB-16. (yield: 65%, MS: [ M+H)] + ＝404)
Compound sub B-16 (10 g,24.8 mmol), compound amine 74 (9.7 g,26 mmol) and sodium tert-butoxide (3.1 g,32.2 mmol) were added to 200ml of xylene under nitrogen and the mixture was stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.1 g,0.2 mmol) was added thereto. When the reaction was completed after 3 hours, the reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was completely dissolved again in chloroform, washed twice with water, then the organic layer was separated, treated with anhydrous magnesium sulfate, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 12.2g of compounds 2 to 84. (yield: 67%, MS: [ M+H) ] + ＝739)
Synthesis examples 2 to 85
11H-benzo [ a ] under nitrogen atmosphere]Carbazole (10 g,46 mmol), 4 "-bromo-3 ' -chloro-1, 1':2',1" -terphenyl (16.6 g,48.3 mmol) and sodium tert-butoxide (5.7 g,59.8 mmol) were added to 200ml xylene and the mixture was stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.2 g,0.5 mmol) was added thereto. When the reaction was completed after 2 hours, the reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was completely dissolved again in chloroform, washed twice with water, then the organic layer was separated, treated with anhydrous magnesium sulfate, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 14.6g of compound subsB-17. (yield: 66%, MS: [ M+H)] + ＝480)
Compound sub B-17 (10 g,20.8 mmol), compound amine 75 (7 g,21.9 mmol) and sodium tert-butoxide (2.6 g,27.1 mmol) were added to 200ml of xylene under nitrogen and the mixture was stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.1 g,0.2 mmol) was added thereto. When the reaction was completed after 2 hours, the reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was completely dissolved again in chloroform, washed twice with water, then the organic layer was separated, treated with anhydrous magnesium sulfate, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 11.2g of compound 2-85. (yield: 66%, MS: [ M+H) ] + ＝815)
Synthesis examples 2 to 86
5H-benzo [ b ] under nitrogen]Carbazole (10 g,46 mmol), 1-bromo-4-chlorobenzene (9.3 g,48.3 mmol) and sodium tert-butoxide (5.7 g,59.8 mmol) were added to 200ml of xylene and the mixture was taken upStirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.2 g,0.5 mmol) was added thereto. When the reaction was completed after 2 hours, the reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was completely dissolved again in chloroform, washed twice with water, then the organic layer was separated, treated with anhydrous magnesium sulfate, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 11.1g of the compound sub-c-1. (yield: 74%, MS: [ M+H)] + ＝328)
Compound sub-1 (10 g,30.5 mmol), compound amine 75 (9.5 g,32 mmol) and sodium tert-butoxide (3.8 g,39.7 mmol) were added to 200ml of xylene under nitrogen and the mixture was stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.2 g,0.3 mmol) was added thereto. When the reaction was completed after 2 hours, the reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was completely dissolved again in chloroform, washed twice with water, then the organic layer was separated, treated with anhydrous magnesium sulfate, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 10.9g of compounds 2 to 86. (yield: 61%, MS: [ M+H) ] + ＝587)
Synthesis examples 2 to 87
Compound sub-1 (10 g,30.5 mmol), compound amine 55 (12.7 g,32 mmol) and sodium tert-butoxide (3.8 g,39.7 mmol) were added to 200ml of xylene under nitrogen and the mixture was stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.2 g,0.3 mmol) was added thereto. When the reaction was completed after 2 hours, the reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was completely dissolved again in chloroformIn (c), the organic layer was separated, treated with anhydrous magnesium sulfate, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 14.9g of compounds 2 to 87. (yield: 71%, MS: [ M+H)] + ＝689)
Synthesis examples 2 to 88
Compound sub-1 (10 g,30.5 mmol), compound amine 76 (12.2 g,32 mmol) and sodium tert-butoxide (3.8 g,39.7 mmol) were added to 200ml of xylene under nitrogen and the mixture was stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.2 g,0.3 mmol) was added thereto. When the reaction was completed after 3 hours, the reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was completely dissolved again in chloroform, washed twice with water, then the organic layer was separated, treated with anhydrous magnesium sulfate, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 21.6g of compounds 2 to 88. (yield: 73%, MS: [ M+H) ] + ＝973)
Synthesis examples 2 to 89
Compound sub-1 (10 g,30.5 mmol), compound amine 77 (13.1 g,32 mmol) and sodium tert-butoxide (3.8 g,39.7 mmol) were added to 200ml of xylene under nitrogen and the mixture was stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.2 g,0.3 mmol) was added thereto. When the reaction was completed after 3 hours, the reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was completely dissolved again in chloroform, washed twice with water, then the organic layer was separated, treated with anhydrous magnesium sulfate, then filtered, and the filtrate was distilled under reduced pressure. Purification of the concentrated compound by silica gel column chromatography to prepare14.1g of Compound 2-89. (yield: 66%, MS: [ M+H)] + ＝702)
Synthesis examples 2 to 90
5H-benzo [ b ] under nitrogen]Carbazole (10 g,46 mmol), 2-bromo-5-chloro-1, 1' -biphenyl (12.9 g,48.3 mmol) and sodium tert-butoxide (5.7 g,59.8 mmol) were added to 200ml of xylene and the mixture was stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.2 g,0.5 mmol) was added thereto. When the reaction was completed after 2 hours, the reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was completely dissolved again in chloroform, washed twice with water, then the organic layer was separated, treated with anhydrous magnesium sulfate, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 11.3g of the compound sub-2. (yield: 61%, MS: [ M+H) ] + ＝404)
Compound sub-2 (10 g,24.8 mmol), compound amine 78 (10 g,26 mmol) and sodium tert-butoxide (3.1 g,32.2 mmol) were added to 200ml of xylene under nitrogen and the mixture was stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.1 g,0.2 mmol) was added thereto. When the reaction was completed after 3 hours, the reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was completely dissolved again in chloroform, washed twice with water, then the organic layer was separated, treated with anhydrous magnesium sulfate, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 11.1g of compound 2-90. (yield: 60%, MS: [ M+H)] + ＝751)
Synthesis examples 2 to 91
Compound sub-2 (10 g,24.8 mmol), compound amine 12 (8.4 g,26 mmol) and sodium tert-butoxide (3.1 g,32.2 mmol) were added to 200ml of xylene under nitrogen and the mixture was stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.1 g,0.2 mmol) was added thereto. When the reaction was completed after 3 hours, the reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was completely dissolved again in chloroform, washed twice with water, then the organic layer was separated, treated with anhydrous magnesium sulfate, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 12.1g of compound 2-91. (yield: 71%, MS: [ M+H) ] + ＝689)
Synthesis examples 2 to 92
5H-benzo [ b ] under nitrogen]Carbazole (10 g,46 mmol), 2-bromo-5-chloro-1, 1' -biphenyl (12.9 g,48.3 mmol) and sodium tert-butoxide (5.7 g,59.8 mmol) were added to 200ml of xylene and the mixture was stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.2 g,0.5 mmol) was added thereto. When the reaction was completed after 2 hours, the reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was completely dissolved again in chloroform, washed twice with water, then the organic layer was separated, treated with anhydrous magnesium sulfate, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 11.3g of the compound sub-c-3. (yield: 61%, MS: [ M+H)] + ＝404)
Compound sub-C-3 (10 g,24.8 mmol), compound amine 52 (6.4 g,26 mmol) and sodium tert-butoxide were combined under nitrogen(3.1 g,32.2 mmol) was added to 200ml of xylene and the mixture was stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.1 g,0.2 mmol) was added thereto. When the reaction was completed after 2 hours, the reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was completely dissolved again in chloroform, washed twice with water, then the organic layer was separated, treated with anhydrous magnesium sulfate, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 10.3g of compound 2-92. (yield: 68%, MS: [ M+H) ] + ＝613)
Synthesis examples 2 to 93
5H-benzo [ b ] under nitrogen]Carbazole (10 g,46 mmol), 4-bromo-4 '-chloro-1, 1' -biphenyl (12.9 g,48.3 mmol) and sodium tert-butoxide (5.7 g,59.8 mmol) were added to 200ml of xylene and the mixture was stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.2 g,0.5 mmol) was added thereto. When the reaction was completed after 2 hours, the reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was completely dissolved again in chloroform, washed twice with water, then the organic layer was separated, treated with anhydrous magnesium sulfate, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 12.2g of the compound sub-4. (yield: 66%, MS: [ M+H)] + ＝404)
Compound sub-4 (10 g,24.8 mmol), compound amine 79 (6.4 g,26 mmol) and sodium tert-butoxide (3.1 g,32.2 mmol) were added to 200ml of xylene under nitrogen and the mixture was stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.1 g,0.2 mmol) was added thereto. When the reaction was completed after 2 hours, the reaction mixture was cooled to room temperature,and the solvent was removed under reduced pressure. Then, the compound was completely dissolved again in chloroform, washed twice with water, then the organic layer was separated, treated with anhydrous magnesium sulfate, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 9.5g of compound 2-93. (yield: 63%, MS: [ M+H) ] + ＝613)
Synthesis examples 2 to 94
Compound sub-4 (10 g,24.8 mmol), compound amine 80 (8.7 g,26 mmol) and sodium tert-butoxide (3.1 g,32.2 mmol) were added to 200ml of xylene under nitrogen and the mixture was stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.1 g,0.2 mmol) was added thereto. When the reaction was completed after 3 hours, the reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was completely dissolved again in chloroform, washed twice with water, then the organic layer was separated, treated with anhydrous magnesium sulfate, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 11g of the compound 2-94. (yield: 63%, MS: [ M+H)] + ＝703)
Synthesis examples 2 to 95
5H-benzo [ b ] under nitrogen]Carbazole (10 g,46 mmol), 4' -bromo-4-chloro-1, 1':2',1 "-terphenyl (16.6 g,48.3 mmol) and sodium tert-butoxide (5.7 g,59.8 mmol) were added to 200ml xylene and the mixture was stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.2 g,0.5 mmol) was added thereto. When the reaction was completed after 2 hours, the reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was completely dissolved again in chloroform, washed twice with water, and then the organic layer was separated, treated with anhydrous magnesium sulfate, then Post-filtration and distillation of the filtrate under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 13.7g of the compound sub-c-5. (yield: 62%, MS: [ M+H)] + ＝480)
Compound sub-5 (10 g,20.8 mmol), compound amine 40 (7 g,21.9 mmol) and sodium tert-butoxide (2.6 g,27.1 mmol) were added to 200ml of xylene under nitrogen and the mixture was stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.1 g,0.2 mmol) was added thereto. When the reaction was completed after 2 hours, the reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was completely dissolved again in chloroform, washed twice with water, then the organic layer was separated, treated with anhydrous magnesium sulfate, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 10g of compounds 2 to 95. (yield: 64%, MS: [ M+H ]] + ＝751)
Synthesis examples 2 to 96
5H-benzo [ b ] under nitrogen]Carbazole (10 g,46 mmol), 1-bromo-4- (4-chlorophenyl) naphthalene (15.3 g,48.3 mmol) and sodium tert-butoxide (5.7 g,59.8 mmol) were added to 200ml of xylene and the mixture was stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.2 g,0.5 mmol) was added thereto. When the reaction was completed after 2 hours, the reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was completely dissolved again in chloroform, washed twice with water, then the organic layer was separated, treated with anhydrous magnesium sulfate, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 15.4g of the compound sub-6. (yield: 74%, MS: [ M+H) ] + ＝454)
Compound sub-6 (10 g,22 mmol), compound amine 81 (8.6 g,23.1 mmol) and sodium tert-butoxide (2.8 g,28.6 mmol) were added to 200ml of xylene under nitrogen and the mixture was stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.1 g,0.2 mmol) was added thereto. When the reaction was completed after 3 hours, the reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was completely dissolved again in chloroform, washed twice with water, then the organic layer was separated, treated with anhydrous magnesium sulfate, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 11.8g of compound 2-96. (yield: 68%, MS: [ M+H)] + ＝789)
Synthesis examples 2 to 97
5H-benzo [ b ] under nitrogen]Carbazole (10 g,46 mmol), 1-bromo-3-chlorobenzene (9.3 g,48.3 mmol) and sodium tert-butoxide (5.7 g,59.8 mmol) were added to 200ml of xylene and the mixture was stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.2 g,0.5 mmol) was added thereto. When the reaction was completed after 3 hours, the reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was completely dissolved again in chloroform, washed twice with water, then the organic layer was separated, treated with anhydrous magnesium sulfate, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 9g of the compound sub-c-7. (yield: 60%, MS: [ M+H) ] + ＝328)
The compound sub-7 (10 g,30.5 mmol), was combined under nitrogen atmosphereAmine 82 (11.9 g,32 mmol) and sodium t-butoxide (3.8 g,39.7 mmol) were added to 200ml xylene and the mixture was stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.2 g,0.3 mmol) was added thereto. When the reaction was completed after 3 hours, the reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was completely dissolved again in chloroform, washed twice with water, then the organic layer was separated, treated with anhydrous magnesium sulfate, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 14.3g of compound 2-97. (yield: 71%, MS: [ M+H)] + ＝663)
Synthesis examples 2 to 98
5H-benzo [ b ] under nitrogen]Carbazole (10 g,46 mmol), 3-bromo-4 '-chloro-1, 1' -biphenyl (12.9 g,48.3 mmol) and sodium tert-butoxide (5.7 g,59.8 mmol) were added to 200ml of xylene and the mixture was stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.2 g,0.5 mmol) was added thereto. When the reaction was completed after 2 hours, the reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was completely dissolved again in chloroform, washed twice with water, then the organic layer was separated, treated with anhydrous magnesium sulfate, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 11.7g of the compound sub-c-8. (yield: 63%, MS: [ M+H) ] + ＝405)
Compound sub-8 (10 g,24.8 mmol), compound amine 40 (8.4 g,26 mmol) and sodium tert-butoxide (3.1 g,32.2 mmol) were added to 200ml of xylene under nitrogen and the mixture was stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.1 g,0.2 mmol) was added thereto. When the reaction was completed after 3 hoursThe reaction mixture was cooled to room temperature and the solvent was removed under reduced pressure. Then, the compound was completely dissolved again in chloroform, washed twice with water, then the organic layer was separated, treated with anhydrous magnesium sulfate, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 11.2g of compound 2-98. (yield: 66%, MS: [ M+H)] + ＝689)
Synthesis examples 2 to 99
Compound sub-8 (10 g,24.8 mmol), compound amine 36 (8.7 g,26 mmol) and sodium tert-butoxide (3.1 g,32.2 mmol) were added to 200ml of xylene under nitrogen and the mixture was stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.1 g,0.2 mmol) was added thereto. When the reaction was completed after 3 hours, the reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was completely dissolved again in chloroform, washed twice with water, then the organic layer was separated, treated with anhydrous magnesium sulfate, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 10.4g of compound 2-99. (yield: 60%, MS: [ M+H) ] + ＝703)
Synthesis examples 2 to 100
5H-benzo [ b ] under nitrogen]Carbazole (10 g,46 mmol), 5' -bromo-4-chloro-1, 1':2',1 "-terphenyl (16.6 g,48.3 mmol) and sodium tert-butoxide (5.7 g,59.8 mmol) were added to 200ml xylene and the mixture was stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.2 g,0.5 mmol) was added thereto. When the reaction was completed after 3 hours, the reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was completely dissolved again in chloroform, washed twice with water, and then the organic matter was washed with waterThe layers were separated, treated with anhydrous magnesium sulfate, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 14.6g of the compound sub-c-9. (yield: 66%, MS: [ M+H)] + ＝480)
Compound sub-9 (10 g,20.8 mmol), compound amine 12 (7 g,21.9 mmol) and sodium tert-butoxide (2.6 g,27.1 mmol) were added to 200ml of xylene under nitrogen and the mixture was stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.1 g,0.2 mmol) was added thereto. When the reaction was completed after 2 hours, the reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was completely dissolved again in chloroform, washed twice with water, then the organic layer was separated, treated with anhydrous magnesium sulfate, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 11.3g of compound 2-100. (yield: 71%, MS: [ M+H) ] + ＝765)
Synthesis examples 2 to 101
5H-benzo [ b ] under nitrogen]Carbazole (10 g,46 mmol), 2-bromo-4 '-chloro-1, 1' -biphenyl (12.9 g,48.3 mmol) and sodium tert-butoxide (5.7 g,59.8 mmol) were added to 200ml of xylene and the mixture was stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.2 g,0.5 mmol) was added thereto. When the reaction was completed after 2 hours, the reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was completely dissolved again in chloroform, washed twice with water, then the organic layer was separated, treated with anhydrous magnesium sulfate, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 11.9g of the compound sub-10. (yield: 64%, MS: [ M+H ]] + ＝404)
Compound sub-10 (10 g,24.8 mmol), compound amine 35 (9.7 g,26 mmol) and sodium tert-butoxide (3.1 g,32.2 mmol) were added to 200ml of xylene under nitrogen and the mixture was stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.1 g,0.2 mmol) was added thereto. When the reaction was completed after 2 hours, the reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was completely dissolved again in chloroform, washed twice with water, then the organic layer was separated, treated with anhydrous magnesium sulfate, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 12.1g of compound 2-101. (yield: 66%, MS: [ M+H) ] + ＝739)
Synthesis examples 2 to 102
5H-benzo [ b ] under nitrogen]Carbazole (10 g,46 mmol), 2-bromo-4 ' -chloro-1, 1':3',1 "-terphenyl (16.6 g,48.3 mmol) and sodium tert-butoxide (5.7 g,59.8 mmol) were added to 200ml xylene and the mixture was stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.2 g,0.5 mmol) was added thereto. When the reaction was completed after 3 hours, the reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was completely dissolved again in chloroform, washed twice with water, then the organic layer was separated, treated with anhydrous magnesium sulfate, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 13.9g of the compound sub-c-11. (yield: 63%, MS: [ M+H)] + ＝480)
Compound sub-11 (10 g,20.8 mmol), compound amine 55 (8.6 g,21.9 mmol) and sodium tert-butoxide (2.6 g,27.1 mmol) were added to 200ml of xylene under nitrogen and the mixture was stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.1 g,0.2 mmol) was added thereto. When the reaction was completed after 2 hours, the reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was completely dissolved again in chloroform, washed twice with water, then the organic layer was separated, treated with anhydrous magnesium sulfate, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 11.2g of compounds 2 to 102. (yield: 64%, MS: [ M+H ] ] + ＝841)
Synthesis examples 2 to 103
5H-benzo [ b ] under nitrogen]Carbazole (10 g,46 mmol), 2-bromo-4 ' -chloro-1, 1':2',1 "-terphenyl (16.6 g,48.3 mmol) and sodium tert-butoxide (5.7 g,59.8 mmol) were added to 200ml of xylene and the mixture was stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.2 g,0.5 mmol) was added thereto. When the reaction was completed after 3 hours, the reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was completely dissolved again in chloroform, washed twice with water, then the organic layer was separated, treated with anhydrous magnesium sulfate, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 15.2g of the compound sub-12. (yield: 69%, MS: [ M+H)] + ＝480)
Compound sub-12 (10 g,20.8 mmol), compound amine 83 (6.5 g,21.9 mmol) and sodium tert-butoxide (2.6 g,27.1 mmol) were added to 200ml of xylene under nitrogen and the mixture was stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.1 g,0.2 mmol) was added thereto. When the reaction was completed after 2 hours, the reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was completely dissolved again in chloroform, washed twice with water, then the organic layer was separated, treated with anhydrous magnesium sulfate, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 11.4g of compounds 2 to 103. (yield: 74%, MS: [ M+H) ] + ＝739)
Synthesis examples 2 to 104
5H-benzo [ b ] under nitrogen]Carbazole (10 g,46 mmol), 2' -bromo-4-chloro-1, 1':4',1 "-terphenyl (16.6 g,48.3 mmol) and sodium tert-butoxide (5.7 g,59.8 mmol) were added to 200ml xylene and the mixture was stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.2 g,0.5 mmol) was added thereto. When the reaction was completed after 2 hours, the reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was completely dissolved again in chloroform, washed twice with water, then the organic layer was separated, treated with anhydrous magnesium sulfate, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 14.6g of the compound sub-13. (yield: 66%, MS: [ M+H)] + ＝480)
Compound sub-13 (10 g,20.8 mmol), compound amine 13 (7.6 g,21.9 mmol) and sodium tert-butoxide (2.6 g,27.1 mmol) were added to 200ml of xylene under nitrogen and the mixture was stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.1 g,0.2 mmol) was added thereto. When the reaction was completed after 3 hours, the reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound is again Completely dissolved in chloroform, washed twice with water, then the organic layer was separated, treated with anhydrous magnesium sulfate, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 10.9g of compounds 2 to 104. (yield: 66%, MS: [ M+H)] + ＝793)
Synthesis examples 2 to 105
5H-benzo [ b ] under nitrogen]Carbazole (10 g,46 mmol), 3' -bromo-2-chloro-1, 1 "-biphenyl (12.9 g,48.3 mmol) and sodium tert-butoxide (5.7 g,59.8 mmol) were added to 200ml of xylene and the mixture was stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.2 g,0.5 mmol) was added thereto. When the reaction was completed after 3 hours, the reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was completely dissolved again in chloroform, washed twice with water, then the organic layer was separated, treated with anhydrous magnesium sulfate, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 13.9g of the compound sub-14. (yield: 75%, MS: [ M+H)] + ＝405)
Compound sub-14 (10 g,24.8 mmol), compound amine 74 (9.7 g,26 mmol) and sodium tert-butoxide (3.1 g,32.2 mmol) were added to 200ml of xylene under nitrogen and the mixture was stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.1 g,0.2 mmol) was added thereto. When the reaction was completed after 2 hours, the reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was completely dissolved again in chloroform, washed twice with water, then the organic layer was separated, treated with anhydrous magnesium sulfate, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 13.2g of a compound 2-105. (yield: 72%, MS: [ M+H)] + ＝739)
Synthesis examples 2 to 106
5H-benzo [ b ] under nitrogen]Carbazole (10 g,46 mmol), 2' -bromo-2-chloro-1, 1':3',1 "-terphenyl (16.6 g,48.3 mmol) and sodium tert-butoxide (5.7 g,59.8 mmol) were added to 200ml xylene and the mixture was stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.2 g,0.5 mmol) was added thereto. When the reaction was completed after 2 hours, the reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was completely dissolved again in chloroform, washed twice with water, then the organic layer was separated, treated with anhydrous magnesium sulfate, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 14.1g of the compound sub-c-15. (yield: 64%, MS: [ M+H ]] + ＝480)
Compound sub-15 (10 g,20.8 mmol), compound amine 63 (8.1 g,21.9 mmol) and sodium tert-butoxide (2.6 g,27.1 mmol) were added to 200ml of xylene under nitrogen and the mixture was stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.1 g,0.2 mmol) was added thereto. When the reaction was completed after 3 hours, the reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was completely dissolved again in chloroform, washed twice with water, then the organic layer was separated, treated with anhydrous magnesium sulfate, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 11g of compounds 2 to 106. (yield: 65%, MS: [ M+H) ] + ＝815)
Synthesis examples 2 to 107
7H-benzo [ c ] under nitrogen]Carbazole (10 g,46 mmol), 1-bromo-4-chlorobenzene (9.3 g,48.3 mmol) and sodium tert-butoxide (5.7 g,59.8 mmol) were added to 200ml of xylene and the mixture was stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.2 g,0.5 mmol) was added thereto. When the reaction was completed after 2 hours, the reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was completely dissolved again in chloroform, washed twice with water, then the organic layer was separated, treated with anhydrous magnesium sulfate, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 10.8g of compound subD-1. (yield: 72%, MS: [ M+H)] + ＝328)
Compound sub D-1 (10 g,30.5 mmol), compound amine 63 (11.9 g,32 mmol) and sodium tert-butoxide (3.8 g,39.7 mmol) were added to 200ml of xylene under nitrogen and the mixture was stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.2 g,0.3 mmol) was added thereto. When the reaction was completed after 2 hours, the reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was completely dissolved again in chloroform, washed twice with water, then the organic layer was separated, treated with anhydrous magnesium sulfate, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 14.5g of compounds 2 to 107. (yield: 72%, MS: [ M+H) ] + ＝663)
Synthesis examples 2 to 108
Compound SubD-1 (10 g,30.5 mmol), compound amine 84 (12.9 g,32 mmol) and tert-butanol were reacted under nitrogenSodium (3.8 g,39.7 mmol) was added to 200ml of xylene and the mixture was stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.2 g,0.3 mmol) was added thereto. When the reaction was completed after 2 hours, the reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was completely dissolved again in chloroform, washed twice with water, then the organic layer was separated, treated with anhydrous magnesium sulfate, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 15.4g of compound 2-108. (yield: 73%, MS: [ M+H)] + ＝693)
Synthesis examples 2 to 109
7H-benzo [ c ] under nitrogen]Carbazole (10 g,46 mmol), 1- (4-bromophenyl) -4-chloronaphthalene (15.3 g,48.3 mmol) and sodium tert-butoxide (5.7 g,59.8 mmol) were added to 200ml of xylene and the mixture was stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.2 g,0.5 mmol) was added thereto. When the reaction was completed after 2 hours, the reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was completely dissolved again in chloroform, washed twice with water, then the organic layer was separated, treated with anhydrous magnesium sulfate, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 14.8g of compound subD-2. (yield: 71%, MS: [ M+H) ] + ＝454)
Compound sub-D-2 (10 g,22 mmol), compound amine 85 (8.6 g,23.1 mmol) and sodium tert-butoxide (2.8 g,28.6 mmol) were added to 200ml of xylene under nitrogen and the mixture was stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.1 g,0.2 mmol) was added thereto. When the reaction was completed after 3 hours, the reaction mixture was cooled to room temperatureAnd the solvent was removed under reduced pressure. Then, the compound was completely dissolved again in chloroform, washed twice with water, then the organic layer was separated, treated with anhydrous magnesium sulfate, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 10.8g of compound 2-109. (yield: 62%, MS: [ M+H)] + ＝789)
Synthesis examples 2 to 110
7H-benzo [ c ] under nitrogen]Carbazole (10 g,46 mmol), 1-bromo-4-chloronaphthalene (11.7 g,48.3 mmol) and sodium tert-butoxide (5.7 g,59.8 mmol) were added to 200ml of xylene and the mixture was stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.2 g,0.5 mmol) was added thereto. When the reaction was completed after 3 hours, the reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was completely dissolved again in chloroform, washed twice with water, then the organic layer was separated, treated with anhydrous magnesium sulfate, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 12.3g of compound subD-3. (yield: 71%, MS: [ M+H) ] + ＝378)
Compound sub D-3 (10 g,26.5 mmol), compound amine 86 (12.4 g,27.8 mmol) and sodium tert-butoxide (3.3 g,34.4 mmol) were added to 200ml of xylene under nitrogen and the mixture was stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.1 g,0.3 mmol) was added thereto. When the reaction was completed after 3 hours, the reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was completely dissolved again in chloroform, washed twice with water, then the organic layer was separated, treated with anhydrous magnesium sulfate, then filtered, and the filtrate was distilled under reduced pressure. Concentrating the mixtureThe material was purified by silica gel column chromatography to prepare 14.6g of the compound 2-110. (yield: 70%, MS: [ M+H ]] + ＝789)
Synthesis examples 2 to 111
7H-benzo [ c ] under nitrogen]Carbazole (10 g,46 mmol), 4-bromo-4 '-chloro-1, 1' -biphenyl (12.9 g,48.3 mmol) and sodium tert-butoxide (5.7 g,59.8 mmol) were added to 200ml of xylene and the mixture was stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.2 g,0.5 mmol) was added thereto. When the reaction was completed after 2 hours, the reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was completely dissolved again in chloroform, washed twice with water, then the organic layer was separated, treated with anhydrous magnesium sulfate, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 13.7g of compound subD-4. (yield: 74%, MS: [ M+H) ] + ＝404)
Compound sub-D-4 (10 g,24.8 mmol), compound amine 87 (7.7 g,26 mmol) and sodium tert-butoxide (3.1 g,32.2 mmol) were added to 200ml of xylene under nitrogen and the mixture was stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.1 g,0.2 mmol) was added thereto. When the reaction was completed after 3 hours, the reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was completely dissolved again in chloroform, washed twice with water, then the organic layer was separated, treated with anhydrous magnesium sulfate, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 11.8g of compounds 2 to 111. (yield: 72%, MS: [ M+H)] + ＝663)
Synthesis examples 2 to 112
Compound sub-D-4 (10 g,24.8 mmol), compound amine 44 (8.4 g,26 mmol) and sodium tert-butoxide (3.1 g,32.2 mmol) were added to 200ml of xylene under nitrogen and the mixture was stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.1 g,0.2 mmol) was added thereto. When the reaction was completed after 3 hours, the reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was completely dissolved again in chloroform, washed twice with water, then the organic layer was separated, treated with anhydrous magnesium sulfate, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 12.8g of compounds 2 to 112. (yield: 75%, MS: [ M+H) ] + ＝689)
Synthesis examples 2 to 113
Compound sub-D-4 (10 g,24.8 mmol), compound amine 88 (6.7 g,26 mmol) and sodium tert-butoxide (3.1 g,32.2 mmol) were added to 200ml of xylene under nitrogen and the mixture was stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.1 g,0.2 mmol) was added thereto. When the reaction was completed after 3 hours, the reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was completely dissolved again in chloroform, washed twice with water, then the organic layer was separated, treated with anhydrous magnesium sulfate, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 10.1g of compound 2-113. (yield: 65%, MS: [ M+H)] + ＝627)
Synthesis examples 2 to 114
Under nitrogen atmosphereCompound sub D-4 (10 g,24.8 mmol), compound amine 89 (8.7 g,26 mmol) and sodium tert-butoxide (3.1 g,32.2 mmol) were added to 200ml of xylene and the mixture was stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.1 g,0.2 mmol) was added thereto. When the reaction was completed after 3 hours, the reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was completely dissolved again in chloroform, washed twice with water, then the organic layer was separated, treated with anhydrous magnesium sulfate, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 11.3g of compounds 2 to 114. (yield: 65%, MS: [ M+H) ] + ＝702)
Synthesis examples 2 to 115
7H-benzo [ c ] under nitrogen]Carbazole (10 g,46 mmol), 4-bromo-4 ' -chloro-1, 1':2',1 "-terphenyl (16.6 g,48.3 mmol) and sodium tert-butoxide (5.7 g,59.8 mmol) were added to 200ml of xylene and the mixture was stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.2 g,0.5 mmol) was added thereto. When the reaction was completed after 3 hours, the reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was completely dissolved again in chloroform, washed twice with water, then the organic layer was separated, treated with anhydrous magnesium sulfate, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 15.7g of compound subD-5. (yield: 71%, MS: [ M+H)] + ＝480)
Compound sub-D-5 (10 g,20.8 mmol), compound amine 90 (7 g,21.9 mmol) and sodium tert-butoxide (2.6 g,27.1 mmol) were added to 200ml of xylene under nitrogen and the mixture was stirred and refluxed. Then, bis (tri-t-butylphosphine) was added theretoPalladium (0) (0.1 g,0.2 mmol). When the reaction was completed after 2 hours, the reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was completely dissolved again in chloroform, washed twice with water, then the organic layer was separated, treated with anhydrous magnesium sulfate, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 11.1g of compound 2-115. (yield: 70%, MS: [ M+H ] ] + ＝765)
Synthesis examples 2 to 116
7H-benzo [ c ] under nitrogen]Carbazole (10 g,46 mmol), 4' -bromo-4-chloro-1, 1':3',1 "-terphenyl (16.6 g,48.3 mmol) and sodium tert-butoxide (5.7 g,59.8 mmol) were added to 200ml xylene and the mixture was stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.2 g,0.5 mmol) was added thereto. When the reaction was completed after 2 hours, the reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was completely dissolved again in chloroform, washed twice with water, then the organic layer was separated, treated with anhydrous magnesium sulfate, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 16.1g of compound subD-6. (yield: 73%, MS: [ M+H)] + ＝480)
Compound sub-D-6 (10 g,20.8 mmol), compound amine 91 (8.1 g,21.9 mmol) and sodium tert-butoxide (2.6 g,27.1 mmol) were added to 200ml of xylene under nitrogen and the mixture was stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.1 g,0.2 mmol) was added thereto. When the reaction was completed after 2 hours, the reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was completely dissolved again in chloroform, washed twice with water, The organic layer was then separated, treated with anhydrous magnesium sulfate, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 10.9g of compound 2-116. (yield: 64%, MS: [ M+H ]] + ＝815)
Synthesis examples 2 to 117
7H-benzo [ c ] under nitrogen]Carbazole (10 g,46 mmol), 2-bromo-4 '-chloro-1, 1' -biphenyl (12.9 g,48.3 mmol) and sodium tert-butoxide (5.7 g,59.8 mmol) were added to 200ml of xylene and the mixture was stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.2 g,0.5 mmol) was added thereto. When the reaction was completed after 2 hours, the reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was completely dissolved again in chloroform, washed twice with water, then the organic layer was separated, treated with anhydrous magnesium sulfate, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 13.4g of compound subD-7. (yield: 72%, MS: [ M+H)] + ＝404)
Compound sub-D-7 (10 g,24.8 mmol), compound amine 1 (10.3 g,26 mmol) and sodium tert-butoxide (3.1 g,32.2 mmol) were added to 200ml of xylene under nitrogen and the mixture was stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.1 g,0.2 mmol) was added thereto. When the reaction was completed after 3 hours, the reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was completely dissolved again in chloroform, washed twice with water, then the organic layer was separated, treated with anhydrous magnesium sulfate, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 13.6g of compound 2-117. (yield: 72%, MS: [ M+H) ] + ＝765)
Synthesis examples 2 to 118
Compound sub-D-7 (10 g,24.8 mmol), compound amine 92 (9.1 g,26 mmol) and sodium tert-butoxide (3.1 g,32.2 mmol) were added to 200ml of xylene under nitrogen and the mixture was stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.1 g,0.2 mmol) was added thereto. When the reaction was completed after 2 hours, the reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was completely dissolved again in chloroform, washed twice with water, then the organic layer was separated, treated with anhydrous magnesium sulfate, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 12.1g of compound 2-118. (yield: 68%, MS: [ M+H)] + ＝719)
Synthesis examples 2 to 119
7H-benzo [ c ] under nitrogen]Carbazole (10 g,46 mmol), 2-bromo-4 ' -chloro-1, 1':2',1 "-terphenyl (16.6 g,48.3 mmol) and sodium tert-butoxide (5.7 g,59.8 mmol) were added to 200ml of xylene and the mixture was stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.2 g,0.5 mmol) was added thereto. When the reaction was completed after 2 hours, the reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was completely dissolved again in chloroform, washed twice with water, then the organic layer was separated, treated with anhydrous magnesium sulfate, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 16.3g of compound subD-8. (yield: 74%, MS: [ M+H) ] + ＝480)
Compound sub-D-8 (10 g,20.8 mmol), compound amine 93 (7 g,21.9 mmol) and sodium tert-butoxide (2.6 g,27.1 mmol) were added to 200ml of xylene under nitrogen and the mixture was stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.1 g,0.2 mmol) was added thereto. When the reaction was completed after 3 hours, the reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was completely dissolved again in chloroform, washed twice with water, then the organic layer was separated, treated with anhydrous magnesium sulfate, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 10.5g of compound 2-119. (yield: 66%, MS: [ M+H)] + ＝765)
Synthesis examples 2 to 120
7H-benzo [ c ] under nitrogen]Carbazole (10 g,46 mmol), 3' -bromo-4 "-chloro-1, 1':2',1" -terphenyl (16.6 g,48.3 mmol) and sodium tert-butoxide (5.7 g,59.8 mmol) were added to 200ml xylene and the mixture was stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.2 g,0.5 mmol) was added thereto. When the reaction was completed after 3 hours, the reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was completely dissolved again in chloroform, washed twice with water, then the organic layer was separated, treated with anhydrous magnesium sulfate, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 15.4g of compound subD-9. (yield: 70%, MS: [ M+H ] ] + ＝480)
Compound sub D-9 (10 g,20.8 mmol), compound amine 34 (9.2 g,21.9 mmol) and sodium tert-butoxide (2.6 g,27.1 mm) were combined under nitrogenol) was added to 200ml of xylene and the mixture was stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.1 g,0.2 mmol) was added thereto. When the reaction was completed after 3 hours, the reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was completely dissolved again in chloroform, washed twice with water, then the organic layer was separated, treated with anhydrous magnesium sulfate, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 11.9g of compound 2-120. (yield: 66%, MS: [ M+H)] + ＝865)
Synthesis examples 2 to 121
7H-benzo [ c ] under nitrogen]Carbazole (10 g,46 mmol), 2' -bromo-4-chloro-1, 1':3',1 "-terphenyl (16.6 g,48.3 mmol) and sodium tert-butoxide (5.7 g,59.8 mmol) were added to 200ml xylene and the mixture was stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.2 g,0.5 mmol) was added thereto. When the reaction was completed after 3 hours, the reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was completely dissolved again in chloroform, washed twice with water, then the organic layer was separated, treated with anhydrous magnesium sulfate, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 15.4g of compound subD-10. (yield: 70%, MS: [ M+H ] ] + ＝480)
Compound sub-D-10 (10 g,20.8 mmol), compound amine 91 (8.1 g,21.9 mmol) and sodium tert-butoxide (2.6 g,27.1 mmol) were added to 200ml of xylene under nitrogen and the mixture was stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.1 g,0.2 mmol) was added thereto. When the reaction was completed after 2 hours, the reaction mixture was cooled to a roomWarm and remove solvent under reduced pressure. Then, the compound was completely dissolved again in chloroform, washed twice with water, then the organic layer was separated, treated with anhydrous magnesium sulfate, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 11.9g of compounds 2 to 121. (yield: 70%, MS: [ M+H ]] + ＝815)
Synthesis examples 2 to 122
7H-benzo [ c ] under nitrogen]Carbazole (10 g,46 mmol), 6' -bromo-4-chloro-1, 1':3',1 "-terphenyl (16.6 g,48.3 mmol) and sodium tert-butoxide (5.7 g,59.8 mmol) were added to 200ml xylene and the mixture was stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.2 g,0.5 mmol) was added thereto. When the reaction was completed after 2 hours, the reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was completely dissolved again in chloroform, washed twice with water, then the organic layer was separated, treated with anhydrous magnesium sulfate, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 15.4g of compound subD-11. (yield: 70%, MS: [ M+H ] ] + ＝480)
Compound sub-D-11 (10 g,20.8 mmol), compound amine 91 (8.1 g,21.9 mmol) and sodium tert-butoxide (2.6 g,27.1 mmol) were added to 200ml of xylene under nitrogen and the mixture was stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.1 g,0.2 mmol) was added thereto. When the reaction was completed after 2 hours, the reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was completely dissolved again in chloroform, washed twice with water, then the organic layer was separated, treated with anhydrous magnesium sulfate, then filtered, and the filtrate was concentrated under reduced pressureAnd (5) distilling. The concentrated compound was purified by silica gel column chromatography to prepare 12.6g of compound 2-122. (yield: 74%, MS: [ M+H)] + ＝815)
Synthesis examples 2 to 123
7H-benzo [ c ] under nitrogen]Carbazole (10 g,46 mmol), 1-bromo-3-chlorobenzene (9.3 g,48.3 mmol) and sodium tert-butoxide (5.7 g,59.8 mmol) were added to 200ml of xylene and the mixture was stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.2 g,0.5 mmol) was added thereto. When the reaction was completed after 3 hours, the reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was completely dissolved again in chloroform, washed twice with water, then the organic layer was separated, treated with anhydrous magnesium sulfate, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 10.7g of compound subD-12. (yield: 71%, MS: [ M+H) ] + ＝328)
Compound sub-D-12 (10 g,30.5 mmol), compound amine 91 (11.9 g,32 mmol) and sodium tert-butoxide (3.8 g,39.7 mmol) were added to 200ml of xylene under nitrogen and the mixture was stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.2 g,0.3 mmol) was added thereto. When the reaction was completed after 2 hours, the reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was completely dissolved again in chloroform, washed twice with water, then the organic layer was separated, treated with anhydrous magnesium sulfate, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 13.5g of compound 2-123. (yield: 67%, MS: [ M+H)] + ＝663)
Synthesis examples 2 to 124
7H-benzo [ c ] under nitrogen]Carbazole (10 g,46 mmol), 2-bromo-3 '-chloro-1, 1' -biphenyl (12.9 g,48.3 mmol) and sodium tert-butoxide (5.7 g,59.8 mmol) were added to 200ml of xylene and the mixture was stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.2 g,0.5 mmol) was added thereto. When the reaction was completed after 2 hours, the reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was completely dissolved again in chloroform, washed twice with water, then the organic layer was separated, treated with anhydrous magnesium sulfate, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 12.6g of compound subD-13. (yield: 68%, MS: [ M+H) ] + ＝404)
Compound sub D-13 (10 g,24.8 mmol), compound amine 43 (10.3 g,26 mmol) and sodium tert-butoxide (3.1 g,32.2 mmol) were added to 200ml of xylene under nitrogen and the mixture was stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.1 g,0.2 mmol) was added thereto. When the reaction was completed after 2 hours, the reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was completely dissolved again in chloroform, washed twice with water, then the organic layer was separated, treated with anhydrous magnesium sulfate, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 13.2g of compound 2-124. (yield: 70%, MS: [ M+H ]] + ＝763)
Synthesis examples 2 to 125
The mixture was combined under nitrogen atmosphereSubD-13 (10 g,24.8 mmol), compound amine 44 (8.4 g,26 mmol) and sodium tert-butoxide (3.1 g,32.2 mmol) were added to 200ml of xylene and the mixture was stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.1 g,0.2 mmol) was added thereto. When the reaction was completed after 2 hours, the reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was completely dissolved again in chloroform, washed twice with water, then the organic layer was separated, treated with anhydrous magnesium sulfate, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 11.4g of compounds 2 to 125. (yield: 67%, MS: [ M+H) ] + ＝689)
Synthesis examples 2 to 126
7H-benzo [ c ] under nitrogen]Carbazole (10 g,46 mmol), 6' -bromo-3-chloro-1, 1':3',1 "-terphenyl (16.6 g,48.3 mmol) and sodium tert-butoxide (5.7 g,59.8 mmol) were added to 200ml xylene and the mixture was stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.2 g,0.5 mmol) was added thereto. When the reaction was completed after 3 hours, the reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was completely dissolved again in chloroform, washed twice with water, then the organic layer was separated, treated with anhydrous magnesium sulfate, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 14.3g of compound subD-14. (yield: 65%, MS: [ M+H)] + ＝480)
Compound sub-D-14 (10 g,20.8 mmol), compound amine 44 (7 g,21.9 mmol) and sodium tert-butoxide (2.6 g,27.1 mmol) were added to 200ml of xylene under nitrogen and the mixture was stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) was added thereto(0.1 g,0.2 mmol). When the reaction was completed after 3 hours, the reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was completely dissolved again in chloroform, washed twice with water, then the organic layer was separated, treated with anhydrous magnesium sulfate, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 10.2g of compound 2-126. (yield: 64%, MS: [ M+H ] ] + ＝765)
Synthesis examples 2 to 127
7H-benzo [ c ] under nitrogen]Carbazole (10 g,46 mmol), 2' -bromo-3 "-chloro-1, 1':4',1" -terphenyl (16.6 g,48.3 mmol) and sodium tert-butoxide (5.7 g,59.8 mmol) were added to 200ml xylene and the mixture was stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.2 g,0.5 mmol) was added thereto. When the reaction was completed after 3 hours, the reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was completely dissolved again in chloroform, washed twice with water, then the organic layer was separated, treated with anhydrous magnesium sulfate, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 15.9g of compound subD-15. (yield: 72%, MS: [ M+H)] + ＝480)
Compound sub-D-15 (10 g,20.8 mmol), compound amine 92 (10.3 g,21.9 mmol) and sodium tert-butoxide (2.6 g,27.1 mmol) were added to 200ml of xylene under nitrogen and the mixture was stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.1 g,0.2 mmol) was added thereto. When the reaction was completed after 2 hours, the reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was completely dissolved again in chloroform, washed twice with water, The organic layer was then separated, treated with anhydrous magnesium sulfate, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 13.1g of compound 2-127. (yield: 69%, MS: [ M+H)] + ＝915)
Synthesis examples 2 to 128
7H-benzo [ c ] under nitrogen]Carbazole (10 g,46 mmol), 2-bromo-2 '-chloro-1, 1' -biphenyl (12.9 g,48.3 mmol) and sodium tert-butoxide (5.7 g,59.8 mmol) were added to 200ml of xylene and the mixture was stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.2 g,0.5 mmol) was added thereto. When the reaction was completed after 3 hours, the reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was completely dissolved again in chloroform, washed twice with water, then the organic layer was separated, treated with anhydrous magnesium sulfate, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 11.7g of compound subD-16. (yield: 63%, MS: [ M+H)] + ＝404)
Compound sub-D-16 (10 g,24.8 mmol), compound amine 1 (10.3 g,26 mmol) and sodium tert-butoxide (3.1 g,32.2 mmol) were added to 200ml of xylene under nitrogen and the mixture was stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.1 g,0.2 mmol) was added thereto. When the reaction was completed after 3 hours, the reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was completely dissolved again in chloroform, washed twice with water, then the organic layer was separated, treated with anhydrous magnesium sulfate, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 14g of the compound 2-128. (yield: 74%, MS: [ M+H) ] + ＝765)
Synthesis examples 2 to 129
7H-benzo [ c ] under nitrogen]Carbazole (10 g,46 mmol), 3 '-bromo-2-chloro-1, 1' -biphenyl (12.9 g,48.3 mmol) and sodium tert-butoxide (5.7 g,59.8 mmol) were added to 200ml xylene and the mixture was stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.2 g,0.5 mmol) was added thereto. When the reaction was completed after 2 hours, the reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was completely dissolved again in chloroform, washed twice with water, then the organic layer was separated, treated with anhydrous magnesium sulfate, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 13g of compound subD-17. (yield: 70%, MS: [ M+H ]] + ＝404)
Compound sub-D-17 (10 g,24.8 mmol), compound amine 93 (11.6 g,26 mmol) and sodium tert-butoxide (3.1 g,32.2 mmol) were added to 200ml of xylene under nitrogen and the mixture was stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.1 g,0.2 mmol) was added thereto. When the reaction was completed after 3 hours, the reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was completely dissolved again in chloroform, washed twice with water, then the organic layer was separated, treated with anhydrous magnesium sulfate, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 13.9g of compounds 2 to 129. (yield: 69%, MS: [ M+H) ] + ＝815)
Synthesis examples 2 to 130
7H-benzo [ c ] under nitrogen]Carbazole (10 g,46 mmol), 4 '-bromo-2-chloro-1, 1' -biphenyl (12.9 g,48.3 mmol) and sodium tert-butoxide (5.7 g,59.8 mmol) were added to 200ml xylene and the mixture was stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.2 g,0.5 mmol) was added thereto. When the reaction was completed after 3 hours, the reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was completely dissolved again in chloroform, washed twice with water, then the organic layer was separated, treated with anhydrous magnesium sulfate, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 12.2g of compound subD-18. (yield: 66%, MS: [ M+H)] + ＝404)
Compound sub-D-18 (10 g,24.8 mmol), compound amine 94 (10.3 g,26 mmol) and sodium tert-butoxide (3.1 g,32.2 mmol) were added to 200ml of xylene under nitrogen and the mixture was stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.1 g,0.2 mmol) was added thereto. When the reaction was completed after 2 hours, the reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was completely dissolved again in chloroform, washed twice with water, then the organic layer was separated, treated with anhydrous magnesium sulfate, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 11.5g of compounds 2 to 130. (yield: 61%, MS: [ M+H) ] + ＝765)
Example 1:
coated with a coating having a thickness of
The glass substrate of the ITO (indium tin oxide) film of (c) is put into distilled water containing a cleaning agent dissolved therein and washed by ultrasonic waves. In this case, the cleaning agent used is commercially availableThe product from Fisher co. And distilled water are distilled water filtered twice by using a filter commercially available from Millipore co. The ITO was washed for 30 minutes, and then ultrasonic washing was repeated twice by using distilled water for 10 minutes. After washing with distilled water is completed, the substrate is ultrasonically washed with isopropanol, acetone and methanol solvents and dried, after which it is transferred to a plasma washer. Then, the substrate was cleaned with oxygen plasma for 5 minutes, and then transferred to a vacuum evaporator.
On the ITO transparent electrode thus prepared, the following compound HI-1 was formed into
As the hole injection layer, but the following compound a-1 was p-doped at a concentration of 1.5 wt%. Vacuum depositing the following compound HT-1 on the hole injection layer to form a film having a thickness +.>
Is provided. Then, the following compounds EB-1 to +.>
To form an electron blocking layer. Then, the previously prepared compound 1-1, compound 2-1 and the following compound Dp-7 were vacuum deposited on the EB-1 deposited film at a weight ratio of 49:49:2 to form a film thickness of 
Is provided. Vacuum deposition of the following compounds HB-1 to +.>
To form a hole blocking layer. Then, the following compound ET-1 and the following compound LiQ were vacuum deposited on the hole blocking layer at a weight ratio of 2:1 to form a film thickness +.>
Electron injection and transport layers of (a) are provided. Sequentially depositing lithium fluoride (LiF) and aluminum to a thickness of +.>
And->
Thereby forming a cathode. />
In the above process, the deposition rate of the organic material is maintained at
To->
The deposition rates of lithium fluoride and aluminum of the cathode are kept at +.>
And->
And the vacuum degree during deposition is maintained at 2×10 -7 To 5X 10 -6 And a support, thereby manufacturing an organic light emitting device.
Examples 2 to 340
An organic light emitting device was fabricated in the same manner as in example 1, except that in the organic light emitting device of example 1, the compound represented by chemical formula 1 and the compound represented by chemical formula 2 shown in the following table 1 were co-deposited and used as the first and second hosts in a weight ratio of 1:1 instead of the compound 1-1 and the compound 2-1.
Comparative examples 1 to 60
An organic light emitting device was fabricated in the same manner as in example 1, except that in the organic light emitting device of example 1, the following comparative compounds a-1 to a-12 were used instead of the compound 1-1 as a first host, and the compound represented by chemical formula 2 shown in table 2 below was used instead of the compound 2-1 as a second host, wherein the two host compounds were co-deposited and used at a weight ratio of 1:1. The specific structures of the compounds A-1 to A-12 are as follows.
Comparative examples 61 to 156
An organic light emitting device was fabricated in the same manner as in example 1, except that in the organic light emitting device of example 1, the compound represented by chemical formula 1 shown in the following table 3 was used instead of the compound 1-1 as a first host, and the following comparative compounds B-1 to B-12 were used instead of the compound 2-1 as a second host, wherein the two host compounds were co-deposited and used at a weight ratio of 1:1. The specific structures of the compounds B-1 to B-12 are as follows.
Experimental example
Voltage and efficiency were measured by applying current to the organic light emitting devices manufactured in examples 1 to 340 and comparative examples 1 to 156 (based on 15 mA/cm) 2 ) And the results are shown in tables 1 to 3 below. Lifetime (T95) is measured based on 7000 nits, and T95 means the time required for the luminance to decrease to 95% of the initial luminance.
TABLE 1
TABLE 2
TABLE 3
The results of the above tables 1 to 3 were obtained when current was applied to the organic light emitting devices manufactured in examples 1 to 340 and comparative examples 1 to 156. The red organic light emitting devices of examples and comparative examples use materials widely used in the prior art, and are configured to use the compound EB-1 as an electron blocking layer and Dp-7 as a dopant of the red light emitting layer. As shown in table 2, when example compounds a-1 to a-12 of the comparative example and the compound represented by chemical formula 2 of the present disclosure were co-deposited and used as a red light emitting layer, the results generally showed that the driving voltage was increased and the efficiency and lifetime were reduced as compared to the combination of the present disclosure. As shown in table 3, even when the compounds B-1 to B-12 of the comparative example and the compound represented by chemical formula 1 of the present disclosure were co-deposited and used as a red light emitting layer, the results showed an increase in driving voltage and a decrease in efficiency and lifetime.
In view of these results, it can be inferred that the reason why the driving voltage is improved and the efficiency and lifetime are increased is because the combination of the compound of formula 1 as the first host and the compound of formula 2 as the second host of the present disclosure promotes energy transfer to the red dopant in the red light emitting layer.
Accordingly, it can be determined that since the combination of the compound represented by chemical formula 1 and the compound represented by chemical formula 2 of the present disclosure has a more stable balance in the light emitting layer than the combination of the compounds of the comparative example, electrons and holes are combined to form excitons, thereby greatly increasing efficiency and lifetime. From these facts, it is determined that when the compound represented by chemical formula 1 and the compound represented by chemical formula 2 of the present disclosure are co-deposited and used as a host of a red light emitting layer, the driving voltage, light emitting efficiency, and lifetime characteristics of the organic light emitting device can be improved.
Reference numerals
1: substrate 2: anode
3: light emitting layer 4: cathode electrode
5: hole injection layer 6: hole transport layer
7: electron blocking layer 8: hole blocking layer
9: electron injection and transport layers
Claims (9)
1. An organic light emitting device comprising:
An anode;
a cathode; and
a light emitting layer between the anode and the cathode,
wherein the light emitting layer comprises a compound represented by the following chemical formula 1 and a compound represented by the following chemical formula 2:
[ chemical formula 1]
In the chemical formula 1, the chemical formula is shown in the drawing,
Ar 1 and Ar is a group 2 Each independently is a substituted or unsubstituted C 6-60 An aryl group; or substituted or unsubstituted C comprising any one or more selected from N, O and S 2-60 A heteroaryl group, which is a group,
L 1 is a single bond or any one selected from the group consisting of:
in the above group of the present invention,
d is deuterium, and the D is deuterium,
n1 to n3 and n5 are each independently integers from 0 to 4,
n4, n6 and n7 are each independently integers from 0 to 6,
L 2 and L 3 Each independently is a single bond; or C which is substituted or unsubstituted 6-60 An arylene group,
each R is 1 Independently hydrogen; deuterium; substituted or unsubstituted C 6-60 An aryl group; or substituted or unsubstituted C comprising any one or more selected from N, O and S 2-60 Heteroaryl, provided that at least one R 1 Deuterium, deuterium-substituted phenyl, substituted or unsubstituted C 10-60 Aryl, or substituted or unsubstituted C comprising any one or more selected from N, O and S 2-60 Heteroaryl group
a is an integer of 1 to 7,
Wherein the compound represented by chemical formula 1 may not include deuterium or may include at least one deuterium,
[ chemical formula 2]
In the chemical formula 2, the chemical formula is shown in the drawing,
a is a benzene ring or naphthalene ring condensed with an adjacent ring,
Ar 3 and Ar is a group 4 Each independently is a substituted or unsubstituted C 6-60 An aryl group; or substituted or unsubstituted C comprising any one or more selected from N, O and S 2-60 A heteroaryl group, which is a group,
L 4 is C substituted or unsubstituted 6-60 Arylene group
L 5 And L 6 Each independently is a single bond, substituted or unsubstituted C 6-60 Arylene, or substituted or unsubstituted C comprising any one or more selected from N, O and S 2-60 Heteroarylene group.
2. The organic light-emitting device of claim 1, wherein:
Ar 1 and Ar is a group 2 Each independently is phenyl, biphenyl, terphenyl, naphthyl, phenanthryl, dibenzofuranyl, dibenzothienyl, or triphenylsilylphenyl, and
the Ar is as follows 1 And Ar is a group 2 Each independently unsubstituted or substituted with deuterium.
3. The organic light-emitting device of claim 1, wherein:
L 2 and L 3 Each independently is a single bond, phenylene, biphenyldiyl, or naphthalenediyl, and
the hydrogens in the phenylene, biphenyldiyl, and naphthalenediyl groups are each independently unsubstituted or substituted with deuterium.
4. The organic light-emitting device of claim 1, wherein:
each R is 1 Independently is hydrogen, deuterium, phenyl, biphenyl, terphenyl, naphthyl, phenanthryl, triphenylene, fluoranthenyl, naphthylphenyl, phenylnaphthyl, indanyl, dibenzofuranyl, dibenzothienyl, benzonaphthofuranyl, or benzonaphthothienyl, provided that at least one R 1 Deuterium, deuterium-substituted phenyl, biphenyl, terphenyl, naphthyl, phenanthryl, triphenylene, fluoranthenyl, naphthylphenyl, phenylnaphthyl, dibenzofuranyl, dibenzothienyl, benzonaphthofuranyl, or benzonaphthothienyl, and
the hydrogens in the biphenyl, terphenyl, naphthyl, phenanthryl, triphenylene, fluoranthenyl, naphthylphenyl, phenylnaphthyl, dibenzofuranyl, dibenzothienyl, benzonaphthofuranyl, and benzonaphthobenzothienyl are each independently unsubstituted or substituted with deuterium.
5. The organic light-emitting device of claim 1, wherein:
the compound represented by chemical formula 1 is any one selected from the group consisting of:
6. the organic light-emitting device of claim 1, wherein:
Ar 3 and Ar is a group 4 Each independently is phenyl, biphenyl, terphenyl, tetrabiphenyl, triphenylmethylphenyl, triphenylsilylphenyl, naphthyl, phenanthryl, triphenylene, fluoranthenyl, 
Radical, benzo [ c ]]Phenanthryl, carbazole, phenylcarbazole, dimethylfluorenyl, dibenzofuranyl, or dibenzothiophenyl.
7. The organic light-emitting device of claim 1, wherein:
L 4 is phenylene, biphenyldiyl, terphenyldiyl, tetrabenzenediyl, naphthalenediyl, phenylnaphthalenediyl or phenylnaphthalenediyl substituted by one phenyl group.
8. The organic light-emitting device of claim 1, wherein:
L 5 and L 6 Each independently is a single bond, phenylene, biphenyldiyl, naphthalenediyl, phenylnaphthalenediyl, or carbazolediyl.
9. The organic light-emitting device of claim 1, wherein:
the compound represented by chemical formula 2 is any one selected from the group consisting of:
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| KR20210096451 | 2021-07-22 | ||
| KR10-2021-0096451 | 2021-07-22 | ||
| PCT/IB2022/056793 WO2023002447A1 (en) | 2021-07-22 | 2022-07-22 | Organic light-emitting device |
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|---|---|
| CN116406530A true CN116406530A (en) | 2023-07-07 |
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| KR (1) | KR20230015293A (en) |
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Family Cites Families (1)
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| KR100430549B1 (en) | 1999-01-27 | 2004-05-10 | 주식회사 엘지화학 | New organomattalic complex molecule for the fabrication of organic light emitting diodes |
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