CN117546629A - Organic light emitting device - Google Patents
Organic light emitting device Download PDFInfo
- Publication number
- CN117546629A CN117546629A CN202280039225.0A CN202280039225A CN117546629A CN 117546629 A CN117546629 A CN 117546629A CN 202280039225 A CN202280039225 A CN 202280039225A CN 117546629 A CN117546629 A CN 117546629A
- Authority
- CN
- China
- Prior art keywords
- mmol
- added
- mixture
- stirred
- organic layer
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 150000001875 compounds Chemical class 0.000 claims description 815
- -1 benzocarbazolyl Chemical group 0.000 claims description 87
- 229910052805 deuterium Inorganic materials 0.000 claims description 71
- YZCKVEUIGOORGS-OUBTZVSYSA-N Deuterium Chemical group [2H] YZCKVEUIGOORGS-OUBTZVSYSA-N 0.000 claims description 68
- 239000000126 substance Substances 0.000 claims description 61
- 125000003118 aryl group Chemical group 0.000 claims description 52
- 125000001424 substituent group Chemical group 0.000 claims description 47
- 125000001072 heteroaryl group Chemical group 0.000 claims description 30
- 125000001624 naphthyl group Chemical group 0.000 claims description 26
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 26
- 229910052760 oxygen Inorganic materials 0.000 claims description 24
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 claims description 20
- 229910052717 sulfur Inorganic materials 0.000 claims description 20
- 125000000732 arylene group Chemical group 0.000 claims description 11
- 125000005842 heteroatom Chemical group 0.000 claims description 11
- 235000010290 biphenyl Nutrition 0.000 claims description 10
- 239000004305 biphenyl Substances 0.000 claims description 10
- 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 9
- 125000005561 phenanthryl group Chemical group 0.000 claims description 9
- 229910052739 hydrogen Inorganic materials 0.000 claims description 8
- 239000001257 hydrogen Substances 0.000 claims description 8
- 125000000843 phenylene group Chemical class C1(=C(C=CC=C1)*)* 0.000 claims description 8
- 125000004957 naphthylene group Chemical class 0.000 claims description 6
- 125000000609 carbazolyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3NC12)* 0.000 claims description 5
- 125000005509 dibenzothiophenyl group Chemical group 0.000 claims description 4
- 125000004988 dibenzothienyl group Chemical group C1(=CC=CC=2SC3=C(C21)C=CC=C3)* 0.000 claims description 3
- 125000005549 heteroarylene group Chemical group 0.000 claims description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 3
- SLGBZMMZGDRARJ-UHFFFAOYSA-N Triphenylene Natural products C1=CC=C2C3=CC=CC=C3C3=CC=CC=C3C2=C1 SLGBZMMZGDRARJ-UHFFFAOYSA-N 0.000 claims description 2
- 125000005878 benzonaphthofuranyl group Chemical group 0.000 claims description 2
- 125000003914 fluoranthenyl group Chemical group C1(=CC=C2C=CC=C3C4=CC=CC=C4C1=C23)* 0.000 claims description 2
- 150000002431 hydrogen Chemical group 0.000 claims description 2
- 125000005580 triphenylene group Chemical group 0.000 claims description 2
- 239000012044 organic layer Substances 0.000 description 549
- 239000000203 mixture Substances 0.000 description 538
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 454
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 384
- 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 354
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 290
- 239000010410 layer Substances 0.000 description 282
- 238000006243 chemical reaction Methods 0.000 description 243
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 217
- 239000000706 filtrate Substances 0.000 description 216
- 239000011541 reaction mixture Substances 0.000 description 216
- 230000015572 biosynthetic process Effects 0.000 description 178
- 238000003786 synthesis reaction Methods 0.000 description 178
- 238000002360 preparation method Methods 0.000 description 171
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 147
- 239000000741 silica gel Substances 0.000 description 147
- 229910002027 silica gel Inorganic materials 0.000 description 147
- 229910000027 potassium carbonate Inorganic materials 0.000 description 145
- PBKONEOXTCPAFI-UHFFFAOYSA-N 1,2,4-trichlorobenzene Chemical compound ClC1=CC=C(Cl)C(Cl)=C1 PBKONEOXTCPAFI-UHFFFAOYSA-N 0.000 description 93
- 238000010898 silica gel chromatography Methods 0.000 description 80
- MFRIHAYPQRLWNB-UHFFFAOYSA-N sodium tert-butoxide Chemical compound [Na+].CC(C)(C)[O-] MFRIHAYPQRLWNB-UHFFFAOYSA-N 0.000 description 68
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 64
- XLYOFNOQVPJJNP-ZSJDYOACSA-N Heavy water Chemical compound [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 64
- 150000001412 amines Chemical group 0.000 description 63
- YLQBMQCUIZJEEH-UHFFFAOYSA-N Furan Chemical compound C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 60
- 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 60
- 239000000463 material Substances 0.000 description 37
- 239000002904 solvent Substances 0.000 description 35
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 34
- 239000008096 xylene Substances 0.000 description 34
- 229910052757 nitrogen Inorganic materials 0.000 description 33
- 238000002347 injection Methods 0.000 description 32
- 239000007924 injection Substances 0.000 description 32
- HXITXNWTGFUOAU-UHFFFAOYSA-N phenylboronic acid Chemical compound OB(O)C1=CC=CC=C1 HXITXNWTGFUOAU-UHFFFAOYSA-N 0.000 description 32
- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical compound [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 description 32
- 239000011259 mixed solution Substances 0.000 description 31
- 239000000243 solution Substances 0.000 description 31
- 230000000903 blocking effect Effects 0.000 description 23
- ZADPBFCGQRWHPN-UHFFFAOYSA-N boronic acid Chemical compound OBO ZADPBFCGQRWHPN-UHFFFAOYSA-N 0.000 description 22
- JOFBTOVNZIUWPX-UHFFFAOYSA-N dibenzofuran-1-ylboronic acid Chemical compound O1C2=CC=CC=C2C2=C1C=CC=C2B(O)O JOFBTOVNZIUWPX-UHFFFAOYSA-N 0.000 description 21
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 20
- 229910052799 carbon Inorganic materials 0.000 description 20
- 230000032258 transport Effects 0.000 description 20
- 125000000217 alkyl group Chemical group 0.000 description 19
- 239000011368 organic material Substances 0.000 description 18
- 238000005406 washing Methods 0.000 description 18
- 238000010992 reflux Methods 0.000 description 17
- 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 16
- 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 16
- 235000011056 potassium acetate Nutrition 0.000 description 16
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 description 16
- WLPUWLXVBWGYMZ-UHFFFAOYSA-N tricyclohexylphosphine Chemical compound C1CCCCC1P(C1CCCCC1)C1CCCCC1 WLPUWLXVBWGYMZ-UHFFFAOYSA-N 0.000 description 16
- 150000001335 aliphatic alkanes Chemical class 0.000 description 15
- 230000000052 comparative effect Effects 0.000 description 14
- 239000000284 extract Substances 0.000 description 11
- 230000005525 hole transport Effects 0.000 description 11
- 238000006467 substitution reaction Methods 0.000 description 11
- 239000000758 substrate Substances 0.000 description 11
- KPTRDYONBVUWPD-UHFFFAOYSA-N naphthalen-2-ylboronic acid Chemical compound C1=CC=CC2=CC(B(O)O)=CC=C21 KPTRDYONBVUWPD-UHFFFAOYSA-N 0.000 description 9
- 238000000151 deposition Methods 0.000 description 8
- TXCDCPKCNAJMEE-UHFFFAOYSA-N dibenzofuran Chemical group C1=CC=C2C3=CC=CC=C3OC2=C1 TXCDCPKCNAJMEE-UHFFFAOYSA-N 0.000 description 8
- 238000000034 method Methods 0.000 description 8
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 7
- 125000003342 alkenyl group Chemical group 0.000 description 7
- 150000004982 aromatic amines Chemical class 0.000 description 7
- 125000000753 cycloalkyl group Chemical group 0.000 description 7
- 239000002019 doping agent Substances 0.000 description 7
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Chemical compound [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- 238000006069 Suzuki reaction reaction Methods 0.000 description 6
- ABRVLXLNVJHDRQ-UHFFFAOYSA-N [2-pyridin-3-yl-6-(trifluoromethyl)pyridin-4-yl]methanamine Chemical compound FC(C1=CC(=CC(=N1)C=1C=NC=CC=1)CN)(F)F ABRVLXLNVJHDRQ-UHFFFAOYSA-N 0.000 description 6
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- 239000010405 anode material Substances 0.000 description 5
- 239000012153 distilled water Substances 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- PZEJRNFDLHIJQZ-UHFFFAOYSA-N (8-chloro-1-methylsulfanylnaphthalen-2-yl)boronic acid Chemical compound CSC1=C(B(O)O)C=CC2=CC=CC(Cl)=C12 PZEJRNFDLHIJQZ-UHFFFAOYSA-N 0.000 description 4
- GBESIUPWXGQOFP-UHFFFAOYSA-N 2-bromo-1-chloro-3-fluorobenzene Chemical compound FC1=CC=CC(Cl)=C1Br GBESIUPWXGQOFP-UHFFFAOYSA-N 0.000 description 4
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 4
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 4
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 description 4
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 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
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 4
- 229910052794 bromium Inorganic materials 0.000 description 4
- 239000010406 cathode material Substances 0.000 description 4
- 239000000460 chlorine Substances 0.000 description 4
- 229910052801 chlorine Inorganic materials 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 125000004185 ester group Chemical group 0.000 description 4
- 239000010408 film Substances 0.000 description 4
- 229910052736 halogen Inorganic materials 0.000 description 4
- 150000002367 halogens Chemical class 0.000 description 4
- 238000001840 matrix-assisted laser desorption--ionisation time-of-flight mass spectrometry Methods 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 125000004306 triazinyl group Chemical group 0.000 description 4
- 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 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- WTKZEGDFNFYCGP-UHFFFAOYSA-N Pyrazole Chemical class C=1C=NNC=1 WTKZEGDFNFYCGP-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
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 229920001940 conductive polymer Polymers 0.000 description 3
- 230000008021 deposition Effects 0.000 description 3
- 150000001975 deuterium Chemical class 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 229910052733 gallium Inorganic materials 0.000 description 3
- 125000000623 heterocyclic group Chemical group 0.000 description 3
- 238000004770 highest occupied molecular orbital Methods 0.000 description 3
- 125000005462 imide group Chemical group 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- 229910052763 palladium Inorganic materials 0.000 description 3
- 238000000746 purification Methods 0.000 description 3
- 239000007858 starting material Substances 0.000 description 3
- 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 2
- QDFKKJYEIFBEFC-UHFFFAOYSA-N 1-bromo-3-fluorobenzene Chemical compound FC1=CC=CC(Br)=C1 QDFKKJYEIFBEFC-UHFFFAOYSA-N 0.000 description 2
- WXKGFVXGRJHAML-UHFFFAOYSA-N 1-bromo-7-chlorodibenzofuran Chemical compound C1=CC2=C(C(=C1)Br)C1=CC=C(Cl)C=C1O2 WXKGFVXGRJHAML-UHFFFAOYSA-N 0.000 description 2
- KJCVRFUGPWSIIH-UHFFFAOYSA-N 1-naphthol Chemical compound C1=CC=C2C(O)=CC=CC2=C1 KJCVRFUGPWSIIH-UHFFFAOYSA-N 0.000 description 2
- VZSRBBMJRBPUNF-UHFFFAOYSA-N 2-(2,3-dihydro-1H-inden-2-ylamino)-N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]pyrimidine-5-carboxamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C(=O)NCCC(N1CC2=C(CC1)NN=N2)=O VZSRBBMJRBPUNF-UHFFFAOYSA-N 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
- QENGPZGAWFQWCZ-UHFFFAOYSA-N 3-Methylthiophene Chemical compound CC=1C=CSC=1 QENGPZGAWFQWCZ-UHFFFAOYSA-N 0.000 description 2
- DDTHMESPCBONDT-UHFFFAOYSA-N 4-(4-oxocyclohexa-2,5-dien-1-ylidene)cyclohexa-2,5-dien-1-one Chemical compound C1=CC(=O)C=CC1=C1C=CC(=O)C=C1 DDTHMESPCBONDT-UHFFFAOYSA-N 0.000 description 2
- 239000005725 8-Hydroxyquinoline Substances 0.000 description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- 125000003545 alkoxy group Chemical group 0.000 description 2
- 125000003282 alkyl amino group Chemical group 0.000 description 2
- 125000003277 amino group Chemical group 0.000 description 2
- 238000004458 analytical method Methods 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
- HAQFCILFQVZOJC-UHFFFAOYSA-N anthracene-9,10-dione;methane Chemical compound C.C.C1=CC=C2C(=O)C3=CC=CC=C3C(=O)C2=C1 HAQFCILFQVZOJC-UHFFFAOYSA-N 0.000 description 2
- RJGDLRCDCYRQOQ-UHFFFAOYSA-N anthrone Chemical compound C1=CC=C2C(=O)C3=CC=CC=C3CC2=C1 RJGDLRCDCYRQOQ-UHFFFAOYSA-N 0.000 description 2
- 125000005264 aryl amine group Chemical group 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- QARVLSVVCXYDNA-UHFFFAOYSA-N bromobenzene Chemical compound BrC1=CC=CC=C1 QARVLSVVCXYDNA-UHFFFAOYSA-N 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000004440 column chromatography Methods 0.000 description 2
- 230000008878 coupling Effects 0.000 description 2
- 238000010168 coupling process Methods 0.000 description 2
- 238000005859 coupling reaction Methods 0.000 description 2
- 239000003599 detergent Substances 0.000 description 2
- LDPCTBXVSGTSNJ-UHFFFAOYSA-N fluoranthen-3-ylboronic acid Chemical compound C12=CC=CC=C2C2=CC=CC3=C2C1=CC=C3B(O)O LDPCTBXVSGTSNJ-UHFFFAOYSA-N 0.000 description 2
- YLQWCDOCJODRMT-UHFFFAOYSA-N fluoren-9-one Chemical compound C1=CC=C2C(=O)C3=CC=CC=C3C2=C1 YLQWCDOCJODRMT-UHFFFAOYSA-N 0.000 description 2
- 125000003983 fluorenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3CC12)* 0.000 description 2
- 125000005843 halogen group Chemical group 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 125000005241 heteroarylamino group Chemical group 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 229910052738 indium Inorganic materials 0.000 description 2
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 2
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 125000002950 monocyclic group Chemical group 0.000 description 2
- BCBSVZISIWCHFM-UHFFFAOYSA-N naphtho[1,2-b][1]benzofuran Chemical group C1=CC2=CC=CC=C2C2=C1C1=CC=CC=C1O2 BCBSVZISIWCHFM-UHFFFAOYSA-N 0.000 description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 2
- QWVGKYWNOKOFNN-UHFFFAOYSA-N o-cresol Chemical compound CC1=CC=CC=C1O QWVGKYWNOKOFNN-UHFFFAOYSA-N 0.000 description 2
- 239000003960 organic solvent Substances 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
- 239000001301 oxygen Substances 0.000 description 2
- 229960003540 oxyquinoline Drugs 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
- 125000003367 polycyclic group Chemical group 0.000 description 2
- 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
- 230000006798 recombination Effects 0.000 description 2
- 238000005215 recombination Methods 0.000 description 2
- 230000004044 response Effects 0.000 description 2
- 125000003808 silyl group Chemical group [H][Si]([H])([H])[*] 0.000 description 2
- 150000000000 tetracarboxylic acids Chemical class 0.000 description 2
- 239000010409 thin film Substances 0.000 description 2
- IBBLKSWSCDAPIF-UHFFFAOYSA-N thiopyran Chemical compound S1C=CC=C=C1 IBBLKSWSCDAPIF-UHFFFAOYSA-N 0.000 description 2
- 150000003918 triazines Chemical class 0.000 description 2
- 150000003852 triazoles Chemical class 0.000 description 2
- 238000001771 vacuum deposition Methods 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
- FYFCLFLLJKQYIY-UHFFFAOYSA-N (1-hydroxynaphthalen-2-yl)boronic acid Chemical compound C1=CC=CC2=C(O)C(B(O)O)=CC=C21 FYFCLFLLJKQYIY-UHFFFAOYSA-N 0.000 description 1
- YPAYNUIDEFVJEK-UHFFFAOYSA-N (1-methylsulfanylnaphthalen-2-yl)boronic acid Chemical compound CSC1=C(C=CC2=CC=CC=C12)B(O)O YPAYNUIDEFVJEK-UHFFFAOYSA-N 0.000 description 1
- VJLYHTOSFSGXGH-CQSZACIVSA-N (2R)-1-[3-[4-(aminomethyl)-6-(trifluoromethyl)pyridin-2-yl]oxybenzoyl]pyrrolidine-2-carboxylic acid Chemical compound NCC1=CC(=NC(=C1)C(F)(F)F)OC=1C=C(C(=O)N2[C@H](CCC2)C(=O)O)C=CC=1 VJLYHTOSFSGXGH-CQSZACIVSA-N 0.000 description 1
- DQIAQYMRFJUTNP-UHFFFAOYSA-N (3-chloro-1-methylsulfanylnaphthalen-2-yl)boronic acid Chemical compound CSC1=C(B(O)O)C(Cl)=CC2=CC=CC=C12 DQIAQYMRFJUTNP-UHFFFAOYSA-N 0.000 description 1
- ZXAQFYZQHPGMMN-BZSJEYESSA-N (3R)-3-[4-(aminomethyl)-6-(trifluoromethyl)pyridin-2-yl]oxy-N-phenylcyclohexane-1-carboxamide Chemical compound C1C[C@H](CC(C1)C(=O)NC2=CC=CC=C2)OC3=CC(=CC(=N3)C(F)(F)F)CN ZXAQFYZQHPGMMN-BZSJEYESSA-N 0.000 description 1
- QFKVEBXSHWDJEW-UHFFFAOYSA-N (4-chloro-1-hydroxynaphthalen-2-yl)boronic acid Chemical compound OB(C(C=C(C1=CC=CC=C11)Cl)=C1O)O QFKVEBXSHWDJEW-UHFFFAOYSA-N 0.000 description 1
- GTHBURJHJKJRJN-UHFFFAOYSA-N (4-chloro-1-methylsulfanylnaphthalen-2-yl)boronic acid Chemical compound CSC(C1=CC=CC=C11)=C(B(O)O)C=C1Cl GTHBURJHJKJRJN-UHFFFAOYSA-N 0.000 description 1
- BQHVXFQXTOIMQM-UHFFFAOYSA-N (4-naphthalen-1-ylphenyl)boronic acid Chemical compound C1=CC(B(O)O)=CC=C1C1=CC=CC2=CC=CC=C12 BQHVXFQXTOIMQM-UHFFFAOYSA-N 0.000 description 1
- RLDVHTFHIOIVOV-UHFFFAOYSA-N (5-chloro-1-methylsulfanylnaphthalen-2-yl)boronic acid Chemical compound CSC(C1=CC=C2)=C(B(O)O)C=CC1=C2Cl RLDVHTFHIOIVOV-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
- 125000001140 1,4-phenylene group Chemical group [H]C1=C([H])C([*:2])=C([H])C([H])=C1[*:1] 0.000 description 1
- XAOMFUPJQYNDEG-LBPRGKRZSA-N 1-[(3S)-3-[4-(aminomethyl)-6-(trifluoromethyl)pyridin-2-yl]oxypiperidin-1-yl]-2-methylpropan-1-one Chemical compound NCC1=CC(=NC(=C1)C(F)(F)F)O[C@@H]1CN(CCC1)C(C(C)C)=O XAOMFUPJQYNDEG-LBPRGKRZSA-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
- IPWBFGUBXWMIPR-UHFFFAOYSA-N 1-bromo-2-fluorobenzene Chemical compound FC1=CC=CC=C1Br IPWBFGUBXWMIPR-UHFFFAOYSA-N 0.000 description 1
- DRNWNTAANHEQMK-UHFFFAOYSA-N 1-bromo-3-chloro-2-fluorobenzene Chemical compound FC1=C(Cl)C=CC=C1Br DRNWNTAANHEQMK-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
- FPNVMCMDWZNTEU-UHFFFAOYSA-N 1-bromo-4-chloro-2-fluorobenzene Chemical compound FC1=CC(Cl)=CC=C1Br FPNVMCMDWZNTEU-UHFFFAOYSA-N 0.000 description 1
- NHDODQWIKUYWMW-UHFFFAOYSA-N 1-bromo-4-chlorobenzene Chemical compound ClC1=CC=C(Br)C=C1 NHDODQWIKUYWMW-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
- 125000006023 1-pentenyl group Chemical group 0.000 description 1
- 125000006017 1-propenyl group Chemical group 0.000 description 1
- ZVFJWYZMQAEBMO-UHFFFAOYSA-N 1h-benzo[h]quinolin-10-one Chemical compound C1=CNC2=C3C(=O)C=CC=C3C=CC2=C1 ZVFJWYZMQAEBMO-UHFFFAOYSA-N 0.000 description 1
- DKAARCAIXKXVOU-UHFFFAOYSA-N 2-(2-aminophenyl)ethene-1,1,2-triamine Chemical compound C(=C(C=1C(=CC=CC=1)N)N)(N)N DKAARCAIXKXVOU-UHFFFAOYSA-N 0.000 description 1
- APDYPEOKIUKUQV-UHFFFAOYSA-N 2-[1-(2-oxo-2-piperidin-1-ylethyl)indol-4-yl]oxy-6-(trifluoromethyl)pyridine-4-carbonitrile Chemical compound O=C(CN1C=CC2=C(C=CC=C12)OC=1C=C(C#N)C=C(N=1)C(F)(F)F)N1CCCCC1 APDYPEOKIUKUQV-UHFFFAOYSA-N 0.000 description 1
- YFFUYGSLQXVHMB-UHFFFAOYSA-N 2-bromo-4-chloro-1-fluorobenzene Chemical compound FC1=CC=C(Cl)C=C1Br YFFUYGSLQXVHMB-UHFFFAOYSA-N 0.000 description 1
- 125000004974 2-butenyl group Chemical group C(C=CC)* 0.000 description 1
- 125000006176 2-ethylbutyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(C([H])([H])*)C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000003229 2-methylhexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000005916 2-methylpentyl group Chemical group 0.000 description 1
- 125000006024 2-pentenyl group Chemical group 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- DMEVMYSQZPJFOK-UHFFFAOYSA-N 3,4,5,6,9,10-hexazatetracyclo[12.4.0.02,7.08,13]octadeca-1(18),2(7),3,5,8(13),9,11,14,16-nonaene Chemical compound N1=NN=C2C3=CC=CC=C3C3=CC=NN=C3C2=N1 DMEVMYSQZPJFOK-UHFFFAOYSA-N 0.000 description 1
- YLZOPXRUQYQQID-UHFFFAOYSA-N 3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]propan-1-one Chemical compound N1N=NC=2CN(CCC=21)CCC(=O)N1CCN(CC1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F YLZOPXRUQYQQID-UHFFFAOYSA-N 0.000 description 1
- MROVZCRMXJZHCN-UHFFFAOYSA-N 3-[4-(aminomethyl)-6-(trifluoromethyl)pyridin-2-yl]oxy-N-(2-hydroxyethyl)benzamide Chemical compound NCC1=CC(=NC(=C1)C(F)(F)F)OC=1C=C(C(=O)NCCO)C=CC=1 MROVZCRMXJZHCN-UHFFFAOYSA-N 0.000 description 1
- SHBHYINHXNTBRP-UHFFFAOYSA-N 3-[4-(aminomethyl)-6-(trifluoromethyl)pyridin-2-yl]oxy-N-(2-methylsulfonylethyl)benzamide Chemical compound NCC1=CC(=NC(=C1)C(F)(F)F)OC=1C=C(C(=O)NCCS(=O)(=O)C)C=CC=1 SHBHYINHXNTBRP-UHFFFAOYSA-N 0.000 description 1
- SONNQRNOTIAJDS-GFCCVEGCSA-N 3-[4-(aminomethyl)-6-(trifluoromethyl)pyridin-2-yl]oxy-N-[(2R)-2,3-dihydroxypropyl]benzamide Chemical compound NCC1=CC(=NC(=C1)C(F)(F)F)OC=1C=C(C(=O)NC[C@H](CO)O)C=CC=1 SONNQRNOTIAJDS-GFCCVEGCSA-N 0.000 description 1
- GDSLUYKCPYECNN-UHFFFAOYSA-N 3-[4-(aminomethyl)-6-(trifluoromethyl)pyridin-2-yl]oxy-N-[(4-fluorophenyl)methyl]benzamide Chemical compound NCC1=CC(=NC(=C1)C(F)(F)F)OC=1C=C(C(=O)NCC2=CC=C(C=C2)F)C=CC=1 GDSLUYKCPYECNN-UHFFFAOYSA-N 0.000 description 1
- FJPUKTJEFOXMJX-UHFFFAOYSA-N 3-[4-(aminomethyl)-6-(trifluoromethyl)pyridin-2-yl]oxy-N-[1-(hydroxymethyl)cyclopropyl]benzamide Chemical compound NCC1=CC(=NC(=C1)C(F)(F)F)OC=1C=C(C(=O)NC2(CC2)CO)C=CC=1 FJPUKTJEFOXMJX-UHFFFAOYSA-N 0.000 description 1
- ZUNFPBNHELLPPP-UHFFFAOYSA-N 3-[4-(aminomethyl)-6-(trifluoromethyl)pyridin-2-yl]oxy-N-[2-(dimethylamino)ethyl]benzamide Chemical compound NCC1=CC(=NC(=C1)C(F)(F)F)OC=1C=C(C(=O)NCCN(C)C)C=CC=1 ZUNFPBNHELLPPP-UHFFFAOYSA-N 0.000 description 1
- AJZDHLHTTJRNQJ-UHFFFAOYSA-N 3-[4-(aminomethyl)-6-(trifluoromethyl)pyridin-2-yl]oxy-N-[2-(tetrazol-1-yl)ethyl]benzamide Chemical compound N1(N=NN=C1)CCNC(C1=CC(=CC=C1)OC1=NC(=CC(=C1)CN)C(F)(F)F)=O AJZDHLHTTJRNQJ-UHFFFAOYSA-N 0.000 description 1
- MZSAMHOCTRNOIZ-UHFFFAOYSA-N 3-[4-(aminomethyl)-6-(trifluoromethyl)pyridin-2-yl]oxy-N-phenylaniline Chemical compound NCC1=CC(=NC(=C1)C(F)(F)F)OC=1C=C(NC2=CC=CC=C2)C=CC=1 MZSAMHOCTRNOIZ-UHFFFAOYSA-N 0.000 description 1
- HAEQAUJYNHQVHV-UHFFFAOYSA-N 3-[4-(aminomethyl)-6-(trifluoromethyl)pyridin-2-yl]oxy-N-phenylbenzamide Chemical compound NCC1=CC(=NC(=C1)C(F)(F)F)OC=1C=C(C(=O)NC2=CC=CC=C2)C=CC=1 HAEQAUJYNHQVHV-UHFFFAOYSA-N 0.000 description 1
- VVPGEFWZAXBZHR-UHFFFAOYSA-N 3-[4-(aminomethyl)-6-(trifluoromethyl)pyridin-2-yl]sulfanyl-N-phenylbenzamide Chemical compound NCC1=CC(=NC(=C1)C(F)(F)F)SC=1C=C(C(=O)NC2=CC=CC=C2)C=CC=1 VVPGEFWZAXBZHR-UHFFFAOYSA-N 0.000 description 1
- 125000004975 3-butenyl group Chemical group C(CC=C)* 0.000 description 1
- 125000006027 3-methyl-1-butenyl group Chemical group 0.000 description 1
- 125000003469 3-methylhexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 1
- QEIVWSRXBYOTAZ-UHFFFAOYSA-N 4-[4-(aminomethyl)-6-(trifluoromethyl)pyridin-2-yl]oxy-N-phenylpiperidine-1-carboxamide Chemical compound NCC1=CC(=NC(=C1)C(F)(F)F)OC1CCN(CC1)C(=O)NC1=CC=CC=C1 QEIVWSRXBYOTAZ-UHFFFAOYSA-N 0.000 description 1
- HOWFLZVASJDZRZ-UHFFFAOYSA-N 4-[[4-(aminomethyl)-6-(trifluoromethyl)pyridin-2-yl]oxymethyl]-N-phenylpiperidine-1-carboxamide Chemical compound NCC1=CC(=NC(=C1)C(F)(F)F)OCC1CCN(CC1)C(=O)NC1=CC=CC=C1 HOWFLZVASJDZRZ-UHFFFAOYSA-N 0.000 description 1
- 125000004920 4-methyl-2-pentyl group Chemical group CC(CC(C)*)C 0.000 description 1
- FOFSNCRMWLKAIM-UHFFFAOYSA-N 5-[4-(aminomethyl)-6-(trifluoromethyl)pyridin-2-yl]oxy-3,4-dihydro-1H-quinolin-2-one Chemical compound NCC1=CC(=NC(=C1)C(F)(F)F)OC1=C2CCC(NC2=CC=C1)=O FOFSNCRMWLKAIM-UHFFFAOYSA-N 0.000 description 1
- ZFYXJIYPIORSQE-UHFFFAOYSA-N 5-[4-(aminomethyl)-6-(trifluoromethyl)pyridin-2-yl]oxy-N-(2-methylsulfonylethyl)pyridine-3-carboxamide Chemical compound NCC1=CC(=NC(=C1)C(F)(F)F)OC=1C=NC=C(C(=O)NCCS(=O)(=O)C)C=1 ZFYXJIYPIORSQE-UHFFFAOYSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- NRLQBVLOUUPAMI-UHFFFAOYSA-N 8-[3-[4-(aminomethyl)-6-(trifluoromethyl)pyridin-2-yl]oxybenzoyl]-1-oxa-3,8-diazaspiro[4.5]decan-2-one Chemical compound NCC1=CC(=NC(=C1)C(F)(F)F)OC=1C=C(C(=O)N2CCC3(CNC(O3)=O)CC2)C=CC=1 NRLQBVLOUUPAMI-UHFFFAOYSA-N 0.000 description 1
- YEUHHUCOSQOCIX-UHFFFAOYSA-N Benzo[b]naphtho[2,1-d]thiophene Chemical group C1=CC2=CC=CC=C2C2=C1C1=CC=CC=C1S2 YEUHHUCOSQOCIX-UHFFFAOYSA-N 0.000 description 1
- ROFVEXUMMXZLPA-UHFFFAOYSA-N Bipyridyl Chemical group N1=CC=CC=C1C1=CC=CC=N1 ROFVEXUMMXZLPA-UHFFFAOYSA-N 0.000 description 1
- BNDMNTXHMHALHM-UHFFFAOYSA-N C1=2C=3C=C(Cl)C=CC=3OC1=CC=CC=2B(O)O Chemical compound C1=2C=3C=C(Cl)C=CC=3OC1=CC=CC=2B(O)O BNDMNTXHMHALHM-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- MHZGKXUYDGKKIU-UHFFFAOYSA-N Decylamine Chemical compound CCCCCCCCCCN MHZGKXUYDGKKIU-UHFFFAOYSA-N 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- 229910052688 Gadolinium Inorganic materials 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 241001082241 Lythrum hyssopifolia Species 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 229920001609 Poly(3,4-ethylenedioxythiophene) Polymers 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- NRCMAYZCPIVABH-UHFFFAOYSA-N Quinacridone Chemical compound N1C2=CC=CC=C2C(=O)C2=C1C=C1C(=O)C3=CC=CC=C3NC1=C2 NRCMAYZCPIVABH-UHFFFAOYSA-N 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 229910006404 SnO 2 Inorganic materials 0.000 description 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 1
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Natural products C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 239000007983 Tris buffer Substances 0.000 description 1
- RWQJLIWMOBYOTI-AWEZNQCLSA-N [(3S)-3-[4-(aminomethyl)-6-(trifluoromethyl)pyridin-2-yl]oxypiperidin-1-yl]-pyridin-3-ylmethanone Chemical compound NCC1=CC(=NC(=C1)C(F)(F)F)O[C@@H]1CN(CCC1)C(=O)C=1C=NC=CC=1 RWQJLIWMOBYOTI-AWEZNQCLSA-N 0.000 description 1
- ZEEBGORNQSEQBE-UHFFFAOYSA-N [2-(3-phenylphenoxy)-6-(trifluoromethyl)pyridin-4-yl]methanamine Chemical compound C1(=CC(=CC=C1)OC1=NC(=CC(=C1)CN)C(F)(F)F)C1=CC=CC=C1 ZEEBGORNQSEQBE-UHFFFAOYSA-N 0.000 description 1
- GXFIJNNOECYQOJ-UHFFFAOYSA-N [2-[1-(1-methylpyrazol-4-yl)indol-4-yl]oxy-6-(trifluoromethyl)pyridin-4-yl]methanamine Chemical compound CN1N=CC(=C1)N1C=CC2=C(C=CC=C12)OC1=NC(=CC(=C1)CN)C(F)(F)F GXFIJNNOECYQOJ-UHFFFAOYSA-N 0.000 description 1
- SAHIZENKTPRYSN-UHFFFAOYSA-N [2-[3-(phenoxymethyl)phenoxy]-6-(trifluoromethyl)pyridin-4-yl]methanamine Chemical compound O(C1=CC=CC=C1)CC=1C=C(OC2=NC(=CC(=C2)CN)C(F)(F)F)C=CC=1 SAHIZENKTPRYSN-UHFFFAOYSA-N 0.000 description 1
- YQYBUJYBXOVWQW-UHFFFAOYSA-N [3-[4-(aminomethyl)-6-(trifluoromethyl)pyridin-2-yl]oxyphenyl]-(3,4-dihydro-1H-isoquinolin-2-yl)methanone Chemical compound NCC1=CC(=NC(=C1)C(F)(F)F)OC=1C=C(C=CC=1)C(=O)N1CC2=CC=CC=C2CC1 YQYBUJYBXOVWQW-UHFFFAOYSA-N 0.000 description 1
- YKKPYMXANSSQCA-UHFFFAOYSA-N [3-[4-(aminomethyl)-6-(trifluoromethyl)pyridin-2-yl]oxyphenyl]-(3-pyrazol-1-ylazetidin-1-yl)methanone Chemical compound N1(N=CC=C1)C1CN(C1)C(=O)C1=CC(=CC=C1)OC1=NC(=CC(=C1)CN)C(F)(F)F YKKPYMXANSSQCA-UHFFFAOYSA-N 0.000 description 1
- BYWBCSRCPLBDFU-CYBMUJFWSA-N [3-[4-(aminomethyl)-6-(trifluoromethyl)pyridin-2-yl]oxyphenyl]-[(3R)-3-aminopyrrolidin-1-yl]methanone Chemical compound NCC1=CC(=NC(=C1)C(F)(F)F)OC=1C=C(C=CC=1)C(=O)N1C[C@@H](CC1)N BYWBCSRCPLBDFU-CYBMUJFWSA-N 0.000 description 1
- LJHFUFVRZNYVMK-CYBMUJFWSA-N [3-[4-(aminomethyl)-6-(trifluoromethyl)pyridin-2-yl]oxyphenyl]-[(3R)-3-hydroxypyrrolidin-1-yl]methanone Chemical compound NCC1=CC(=NC(=C1)C(F)(F)F)OC=1C=C(C=CC=1)C(=O)N1C[C@@H](CC1)O LJHFUFVRZNYVMK-CYBMUJFWSA-N 0.000 description 1
- KDSYNTPPPISIJB-UHFFFAOYSA-N [3-[[4-(aminomethyl)-6-(trifluoromethyl)pyridin-2-yl]oxymethyl]phenyl]-(3-fluoro-4-hydroxypyrrolidin-1-yl)methanone Chemical compound NCc1cc(OCc2cccc(c2)C(=O)N2CC(O)C(F)C2)nc(c1)C(F)(F)F KDSYNTPPPISIJB-UHFFFAOYSA-N 0.000 description 1
- IQUWAPNUQVLWGG-GFCCVEGCSA-N [5-[4-(aminomethyl)-6-(trifluoromethyl)pyridin-2-yl]oxypyridin-3-yl]-[(3R)-3-aminopyrrolidin-1-yl]methanone Chemical compound NCC1=CC(=NC(=C1)C(F)(F)F)OC=1C=C(C=NC=1)C(=O)N1C[C@@H](CC1)N IQUWAPNUQVLWGG-GFCCVEGCSA-N 0.000 description 1
- 125000000641 acridinyl group Chemical group C1(=CC=CC2=NC3=CC=CC=C3C=C12)* 0.000 description 1
- 125000005073 adamantyl group Chemical group C12(CC3CC(CC(C1)C3)C2)* 0.000 description 1
- 125000004390 alkyl sulfonyl group Chemical group 0.000 description 1
- 125000004414 alkyl thio group Chemical group 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- 125000005577 anthracene group Chemical group 0.000 description 1
- PYKYMHQGRFAEBM-UHFFFAOYSA-N anthraquinone Natural products CCC(=O)c1c(O)c2C(=O)C3C(C=CC=C3O)C(=O)c2cc1CC(=O)OC PYKYMHQGRFAEBM-UHFFFAOYSA-N 0.000 description 1
- 150000004056 anthraquinones Chemical class 0.000 description 1
- 125000005428 anthryl group Chemical group [H]C1=C([H])C([H])=C2C([H])=C3C(*)=C([H])C([H])=C([H])C3=C([H])C2=C1[H] 0.000 description 1
- 150000003974 aralkylamines Chemical group 0.000 description 1
- 125000005104 aryl silyl group Chemical group 0.000 description 1
- 125000004391 aryl sulfonyl group Chemical group 0.000 description 1
- 125000005110 aryl thio group Chemical group 0.000 description 1
- 125000003609 aryl vinyl group Chemical group 0.000 description 1
- 125000004104 aryloxy group Chemical group 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 125000003943 azolyl group Chemical group 0.000 description 1
- 125000003785 benzimidazolyl group Chemical group N1=C(NC2=C1C=CC=C2)* 0.000 description 1
- 125000000499 benzofuranyl group Chemical group O1C(=CC2=C1C=CC=C2)* 0.000 description 1
- 125000001164 benzothiazolyl group Chemical group S1C(=NC2=C1C=CC=C2)* 0.000 description 1
- 125000004196 benzothienyl group Chemical group S1C(=CC2=C1C=CC=C2)* 0.000 description 1
- 229910052790 beryllium Inorganic materials 0.000 description 1
- ATBAMAFKBVZNFJ-UHFFFAOYSA-N beryllium atom Chemical compound [Be] ATBAMAFKBVZNFJ-UHFFFAOYSA-N 0.000 description 1
- 229950011260 betanaphthol Drugs 0.000 description 1
- 125000006267 biphenyl group Chemical group 0.000 description 1
- 229920001400 block copolymer Polymers 0.000 description 1
- 150000001638 boron Chemical class 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- XOYLJNJLGBYDTH-UHFFFAOYSA-M chlorogallium Chemical compound [Ga]Cl XOYLJNJLGBYDTH-UHFFFAOYSA-M 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 150000004696 coordination complex Chemical class 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- IURRXCRWRKQLGC-UHFFFAOYSA-N copper;quinolin-8-ol Chemical compound [Cu].C1=CN=C2C(O)=CC=CC2=C1.C1=CN=C2C(O)=CC=CC2=C1 IURRXCRWRKQLGC-UHFFFAOYSA-N 0.000 description 1
- 125000006165 cyclic alkyl group Chemical group 0.000 description 1
- 125000001995 cyclobutyl group Chemical group [H]C1([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 125000000582 cycloheptyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 125000004210 cyclohexylmethyl group Chemical group [H]C([H])(*)C1([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C1([H])[H] 0.000 description 1
- 125000000640 cyclooctyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C([H])([H])C1([H])[H] 0.000 description 1
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 125000004851 cyclopentylmethyl group Chemical group C1(CCCC1)C* 0.000 description 1
- 125000001559 cyclopropyl group Chemical group [H]C1([H])C([H])([H])C1([H])* 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 125000002720 diazolyl group Chemical group 0.000 description 1
- 238000003618 dip coating Methods 0.000 description 1
- JRBPAEWTRLWTQC-UHFFFAOYSA-N dodecylamine Chemical compound CCCCCCCCCCCCN JRBPAEWTRLWTQC-UHFFFAOYSA-N 0.000 description 1
- 238000005566 electron beam evaporation Methods 0.000 description 1
- 125000006575 electron-withdrawing group Chemical group 0.000 description 1
- ZVHRTJHLSYKEAK-UHFFFAOYSA-N ethyl 2-[5-[4-(aminomethyl)-6-(trifluoromethyl)pyridin-2-yl]oxy-2-oxo-3,4-dihydroquinolin-1-yl]acetate Chemical compound CCOC(=O)CN1C(=O)CCC2=C1C=CC=C2OC1=NC(=CC(CN)=C1)C(F)(F)F ZVHRTJHLSYKEAK-UHFFFAOYSA-N 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 150000002219 fluoranthenes Chemical class 0.000 description 1
- GVEPBJHOBDJJJI-UHFFFAOYSA-N fluoranthrene Natural products C1=CC(C2=CC=CC=C22)=C3C2=CC=CC3=C1 GVEPBJHOBDJJJI-UHFFFAOYSA-N 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 125000002541 furyl group Chemical group 0.000 description 1
- UIWYJDYFSGRHKR-UHFFFAOYSA-N gadolinium atom Chemical compound [Gd] UIWYJDYFSGRHKR-UHFFFAOYSA-N 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 230000005283 ground state Effects 0.000 description 1
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 150000002430 hydrocarbons Chemical group 0.000 description 1
- 125000002883 imidazolyl group Chemical group 0.000 description 1
- 125000001041 indolyl group Chemical group 0.000 description 1
- 238000007641 inkjet printing Methods 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000004491 isohexyl group Chemical group C(CCC(C)C)* 0.000 description 1
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000000555 isopropenyl group Chemical group [H]\C([H])=C(\*)C([H])([H])[H] 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 125000002183 isoquinolinyl group Chemical group C1(=NC=CC2=CC=CC=C12)* 0.000 description 1
- 239000011133 lead Substances 0.000 description 1
- 125000005647 linker group Chemical group 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- SKEDXQSRJSUMRP-UHFFFAOYSA-N lithium;quinolin-8-ol Chemical compound [Li].C1=CN=C2C(O)=CC=CC2=C1 SKEDXQSRJSUMRP-UHFFFAOYSA-N 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- 235000019341 magnesium sulphate Nutrition 0.000 description 1
- AMTZBMRZYODPHS-UHFFFAOYSA-N manganese;quinolin-8-ol Chemical compound [Mn].C1=CN=C2C(O)=CC=CC2=C1.C1=CN=C2C(O)=CC=CC2=C1 AMTZBMRZYODPHS-UHFFFAOYSA-N 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000003136 n-heptyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 1
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- HUMMCEUVDBVXTQ-UHFFFAOYSA-N naphthalen-1-ylboronic acid Chemical compound C1=CC=C2C(B(O)O)=CC=CC2=C1 HUMMCEUVDBVXTQ-UHFFFAOYSA-N 0.000 description 1
- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 125000002560 nitrile group Chemical group 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000001181 organosilyl group Chemical group [SiH3]* 0.000 description 1
- 150000004893 oxazines Chemical class 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 125000003538 pentan-3-yl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- MWIZGXJYCNZVDW-UHFFFAOYSA-N phenanthren-2-ylboronic acid Chemical compound C1=CC=C2C3=CC=C(B(O)O)C=C3C=CC2=C1 MWIZGXJYCNZVDW-UHFFFAOYSA-N 0.000 description 1
- JCDAUYWOHOLVMH-UHFFFAOYSA-N phenanthren-9-ylboronic acid Chemical compound C1=CC=C2C(B(O)O)=CC3=CC=CC=C3C2=C1 JCDAUYWOHOLVMH-UHFFFAOYSA-N 0.000 description 1
- YNPNZTXNASCQKK-UHFFFAOYSA-N phenanthrene Chemical group C1=CC=C2C3=CC=CC=C3C=CC2=C1 YNPNZTXNASCQKK-UHFFFAOYSA-N 0.000 description 1
- 150000005041 phenanthrolines Chemical class 0.000 description 1
- 125000004625 phenanthrolinyl group Chemical group N1=C(C=CC2=CC=C3C=CC=NC3=C12)* 0.000 description 1
- 125000001484 phenothiazinyl group Chemical group C1(=CC=CC=2SC3=CC=CC=C3NC12)* 0.000 description 1
- XPPWLXNXHSNMKC-UHFFFAOYSA-N phenylboron Chemical group [B]C1=CC=CC=C1 XPPWLXNXHSNMKC-UHFFFAOYSA-N 0.000 description 1
- 125000004592 phthalazinyl group Chemical group C1(=NN=CC2=CC=CC=C12)* 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920000128 polypyrrole Polymers 0.000 description 1
- 229920000123 polythiophene Polymers 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000003373 pyrazinyl group Chemical group 0.000 description 1
- 125000005581 pyrene group Chemical group 0.000 description 1
- 125000001725 pyrenyl group Chemical group 0.000 description 1
- 125000002098 pyridazinyl group Chemical group 0.000 description 1
- 125000004076 pyridyl group Chemical group 0.000 description 1
- 125000000714 pyrimidinyl group Chemical group 0.000 description 1
- 125000000168 pyrrolyl group Chemical group 0.000 description 1
- 125000002294 quinazolinyl group Chemical group N1=C(N=CC2=CC=CC=C12)* 0.000 description 1
- DLJHXMRDIWMMGO-UHFFFAOYSA-N quinolin-8-ol;zinc Chemical compound [Zn].C1=CN=C2C(O)=CC=CC2=C1.C1=CN=C2C(O)=CC=CC2=C1 DLJHXMRDIWMMGO-UHFFFAOYSA-N 0.000 description 1
- 125000002943 quinolinyl group Chemical group N1=C(C=CC2=CC=CC=C12)* 0.000 description 1
- 125000001567 quinoxalinyl group Chemical group N1=C(C=NC2=CC=CC=C12)* 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000007650 screen-printing Methods 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 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
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 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
- 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
- HONNWTDYWUAZJF-UHFFFAOYSA-N tert-butyl 4-[2-[4-[4-(aminomethyl)-6-(trifluoromethyl)pyridin-2-yl]oxyindol-1-yl]acetyl]piperazine-1-carboxylate Chemical compound NCC1=CC(=NC(=C1)C(F)(F)F)OC1=C2C=CN(C2=CC=C1)CC(=O)N1CCN(CC1)C(=O)OC(C)(C)C HONNWTDYWUAZJF-UHFFFAOYSA-N 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
- 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
- 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
- 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
- ITMCEJHCFYSIIV-UHFFFAOYSA-N triflic acid Chemical compound OS(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-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
- 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
- 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
Classifications
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/60—Organic compounds having low molecular weight
- H10K85/649—Aromatic compounds comprising a hetero atom
- H10K85/654—Aromatic compounds comprising a hetero atom comprising only nitrogen as heteroatom
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- 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
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/40—Organosilicon compounds, e.g. TIPS pentacene
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/60—Organic compounds having low molecular weight
- 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
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- 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
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/60—Organic compounds having low molecular weight
- H10K85/649—Aromatic compounds comprising a hetero atom
- H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
- H10K85/6576—Polycyclic condensed heteroaromatic hydrocarbons comprising only sulfur in the heteroaromatic polycondensed ring system, e.g. benzothiophene
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/549—Organic PV cells
Landscapes
- Physics & Mathematics (AREA)
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Optics & Photonics (AREA)
- Electroluminescent Light Sources (AREA)
Abstract
The present disclosure provides an organic light emitting device.
Description
Technical Field
Cross Reference to Related Applications
The present application claims the benefits of korean patent application No. 10-2021-0093019 filed at the korean intellectual property office on day 7, month 15 of 2021 and korean patent application No. 10-2022-0086895 filed at the korean intellectual property office on day 7, month 14 of 2022, the contents of which are incorporated herein by reference in their entireties.
The present disclosure relates to organic light emitting devices.
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 wide viewing angle, excellent contrast, 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, excitons are formed when the injected holes and electrons meet each other, and light is emitted when the excitons fall to a ground state again.
There is a continuing need to develop new materials for organic materials used in organic light emitting devices as described above.
[ Prior Art literature ]
[ patent literature ]
(patent document 0001) Korean unexamined patent publication No. 10-2000-0051826
Disclosure of Invention
Technical problem
An object of the present disclosure is to provide an organic light emitting device.
Technical proposal
According to the present disclosure, there is provided an organic light emitting device including:
an anode;
a cathode disposed opposite the anode; and
a light-emitting layer interposed between the anode and the cathode,
wherein the light emitting layer includes a first compound represented by the following chemical formula 1 and a second compound represented by the following chemical formula 2.
[ chemical formula 1]
Wherein, in the chemical formula 1,
L、L 1 and L 2 Each independently is a single bond; or C which is substituted or unsubstituted 6-60 An arylene group,
Ar 1 and Ar is a group 2 Each independently is a substituted or unsubstituted C 6-60 An aryl group,
r is deuterium; substituted or unsubstituted C 6-60 An aryl group; or substituted or unsubstituted C comprising at least one heteroatom of N, O and S 2-60 Heteroaryl, provided that carbazolyl and benzocarbazolyl are excluded from R,
a is an integer of 0 to 7,
[ chemical formula 2]
Wherein, in the chemical formula 2,
x is O or S, and the X is O or S,
R 1 To R 10 Each independently is hydrogen, deuterium, or a substituent represented by the following chemical formula 3, provided that R 1 To R 10 One of them is a substituent represented by the following chemical formula 3,
[ chemical formula 3]
Wherein, in the chemical formula 3,
L’、L 3 and L 4 Each independently is a single bond; substituted or unsubstituted C 6-60 Arylene groups; or substituted or unsubstituted containing at least one heteroatom of N, O and SC 2-60 Heteroarylene group
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 at least one heteroatom of N, O and S 2-60 Heteroaryl groups.
Advantageous effects
The above-described organic light emitting device includes two types of host compounds in a light emitting layer, and thus can improve efficiency, driving voltage, and/or 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 symbolOr->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 groupThe method comprises the steps of carrying out a first treatment on the surface of the And a heterocyclic group comprising at least one of N, O and S atoms, or a substituent which is unsubstituted or linked via 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 linked. In one example, the term "substituted or unsubstituted" may be interpreted as "unsubstituted or substituted or selected from deuterium, halogen, nitrile, C 1-10 Alkyl, C 1-10 Alkoxy and C 6-20 One or more (e.g., 1 to 5) substituents in the aryl group.
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, specific examples of the alkyl group include methyl, ethyl, propyl, n-propyl, isopropyl, butyl, n-butyl, isobutyl, t-butyl, sec-butyl, 1-methyl-butyl, 1-ethylbutyl, pentyl, n-pentyl, isopentyl, neopentyl, t-pentyl, 1-ethyl-propyl, 1, -dimethylpropyl, hexyl, n-hexyl, 1-methylpentyl, 2-methylpentyl, 4-methyl-2-pentyl, 3-dimethylbutyl, 2-ethylbutyl, heptyl, n-heptyl, isohexyl, 1-methylhexyl, 2-methylhexyl, 3-methylhexyl, 4-methylhexyl, 5-methylhexyl, cyclopentylmethyl, cyclohexylmethyl, octyl, n-octyl, t-octyl, 1-methylheptyl, 2-ethylhexyl, 2, 4-trimethyl-1-pentyl, 2, 4-trimethyl-2-pentyl, 2-propylpentyl, n-nonyl, 2-dimethylheptyl and the like, but are not limited thereto.
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-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-tert-butylcyclohexyl, cycloheptyl, cyclooctyl, adamantyl 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 radical, a fluorenyl radical, 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 formedEtc. However, the structure is not limited thereto.
Within the present disclosureIn this case, the heteroaryl group is a heterocyclic group containing one or more heteroatoms in O, N, si and S as heteroatoms, and the carbon number thereof is not particularly limited, but is preferably 2 to 60. 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, an aromatic ring means a fused single ring or fused multiple rings in which the entire molecule has aromaticity while containing only carbon as a ring-forming atom. The carbon number of the aromatic ring is 6 to 60, or 6 to 30, or 6 to 20, but is not limited thereto. Further, the aromatic ring may include a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, a pyrene ring, and the like, but is not limited thereto.
In the present disclosure, the aryl groups in the aralkyl group, the aralkenyl group, the alkylaryl group, the arylamine group, and the arylsilyl group are the same as the examples of the foregoing aryl groups. In the present disclosure, the alkyl groups in the aralkyl group, alkylaryl group, and alkylamino group are the same as the examples of the aforementioned alkyl groups. In the present disclosure, the heteroaryl group in the heteroaryl amine group may apply to the description of the heteroaryl group previously described. In the present disclosure, alkenyl groups in aralkenyl groups are the same as the examples of alkenyl groups described previously. In the present disclosure, the foregoing description of aryl groups may be applied, except that arylene groups are divalent groups. In the present disclosure, the foregoing description of heteroaryl groups may be applied, except that the heteroarylene group is a divalent group. In the present disclosure, the foregoing 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 foregoing description of heteroaryl groups may be applied, except that the heterocycle is not a monovalent group but is 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.
Provided is an organic light emitting device including: an anode; a cathode disposed opposite the anode; and a light emitting layer interposed between the anode and the cathode, wherein the light emitting layer includes a first compound represented by chemical formula 1 and a second compound represented by chemical formula 2.
The organic light emitting device according to the present disclosure includes two types of compounds having a specific structure as host materials in the light emitting layer at the same time, and thus efficiency, driving voltage, and/or lifetime characteristics in the organic light emitting device may be improved.
Hereinafter, the present disclosure will be described in detail for each configuration.
Anode and cathode
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, e.g. zinc oxide, oxidation Indium, indium Tin Oxide (ITO), and Indium Zinc Oxide (IZO); combinations of metals and oxides, e.g. 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 include a hole injection layer between the anode and a hole transport layer described below, if necessary.
The hole injection layer is a layer that is located on the anode and injects holes from the anode, and contains a hole injection material. The hole injection material is preferably a compound of: it has an ability to transport holes, an effect of injecting holes into 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 has an excellent thin film forming ability. In particular, it is suitable 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 aryl amine-based organic materialBut not limited to, anthraquinone, polyaniline-based and polythiophene-based conductive polymers, etc.
Hole transport layer
An organic light emitting device according to the present disclosure may include a hole transport layer between an anode and a light emitting layer. The hole transporting layer is a layer that receives holes from the anode or a hole injecting layer formed on the anode and transports the holes to the light emitting layer, and includes a hole transporting material. The hole transport material is suitably a material having a large hole mobility, which can receive holes from the anode or the hole injection layer and transfer the holes to the light emitting layer. Specific examples thereof may 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, preferably disposed in contact with the light emitting layer, and serves to adjust hole mobility, prevent excessive movement of electrons, and increase the possibility of hole-electron coupling, thereby improving the efficiency of the organic light emitting device. The electron blocking layer contains an electron blocking material, and examples of such an electron blocking material may include a compound represented by chemical formula 1, an arylamine-based organic material, or the like, but are not limited thereto.
Light-emitting layer
The organic light emitting device according to the present disclosure may include a light emitting layer between an anode and a cathode, and the light emitting layer includes a first compound and a second compound as host materials. Specifically, the first compound may function as a P-type host material in which hole transporting ability is superior to electron transporting ability, and the second compound may function as an N-type host material in which electron transporting ability is superior to hole transporting ability, and thus the ratio of holes to electrons in the light emitting layer may be appropriately maintained. Accordingly, the excitons uniformly emit light in the entire light emitting layer, so that the light emitting efficiency and lifetime characteristics of the organic light emitting device can be improved at the same time.
Hereinafter, the first compound and the second compound will be described sequentially.
(first Compound)
The first compound is represented by chemical formula 1. Specifically, the first compound is a compound in which the carbon at the 1-position of dibenzofuran is substituted with a triazinyl group, and the compound is characterized in that it has only an aryl group as a substituent of the triazinyl group, and it does not have a carbazolyl group and a benzocarbazolyl group as substituents of the dibenzofuran. Such a compound has more excellent electron transporting ability than a compound in which a triazinyl group is substituted at other positions of dibenzofuran, a compound having a heteroaryl group as a triazinyl substituent, and a compound having a carbazolyl group and/or a benzocarbazolyl group as a substituent of dibenzofuran, so that the possibility of recombination of holes and electrons in the light emitting layer can be increased by effectively transferring electrons to the dopant material.
In chemical formula 1, L may be a single bond; or unsubstituted or deuterium-substituted C 6-20 Arylene groups.
More specifically, L may be a single bond; unsubstituted or deuterium-substituted phenylene; or unsubstituted or deuterium-substituted naphthylene.
For example, L may be a single bond or a divalent linking group represented by the following chemical formulas 4a to 4 m:
wherein, in chemical formulas 4a to 4m,
d means that the number of the molecules of deuterium,
b is an integer of 0 to 6
c is an integer from 0 to 4.
In other words, in chemical formulas 4a to 4m,
b is 0, 1, 2, 3, 4, 5, or 6; and
c is 0, 1, 2, 3, or 4.
In addition, L 1 And L 2 Each independently may be a single bond; or unsubstituted or deuterium-substituted C 6-20 Arylene groups.
More specifically, L 1 And L 2 Each independently may be a single bond;unsubstituted or deuterium-substituted phenylene; an unsubstituted or deuterium-substituted biphenyldiyl group; or unsubstituted or deuterium-substituted naphthylene.
In this case, L 1 And L 2 May be the same or different from each other.
In addition, ar 1 And Ar is a group 2 Can each independently be unsubstituted or selected from deuterium, C 1-10 Alkyl, C 6-20 Aryl, -Si (C) 1-10 Alkyl group 3 and-Si (C) 6-20 Aryl group 3 C substituted by one or more substituents 6-20 Aryl groups.
More specifically, ar 1 And Ar is a group 2 Each independently is phenyl, biphenyl, terphenyl, naphthyl, or phenanthryl,
wherein Ar is 1 And Ar is a group 2 May be unsubstituted or substituted by a member selected from deuterium, phenyl, naphthyl and-Si (phenyl) 3 Is substituted with one or more substituents.
For example, ar 1 And Ar is a group 2 May each independently be any one selected from the group consisting of:
in one embodiment, ar 1 And Ar is a group 2 May be identical to each other. Alternatively, ar 1 And Ar is a group 2 May be different.
In other embodiments, L 1 -Ar 1 And L 2 -Ar 2 May be identical to each other. Alternatively, L 1 -Ar 1 And L 2 -Ar 2 May be different.
In addition, R is deuterium, C 6-20 Aryl, or C containing O or S 2-20 A heteroaryl group, which is a group,
wherein C is 6-20 Aryl and C 2-20 Heteroaryl groups may be unsubstituted or taken up by one or more selected from deuterium, phenyl substituted by 1 to 5 deuterium, naphthyl and naphthyl substituted by 1 to 7 deuteriumSubstituted.
More specifically, R is deuterium; any aryl group selected from phenyl, biphenyl, terphenyl, naphthyl, phenanthryl, triphenylene, and fluoranthenyl; or any heteroaryl group selected from dibenzofuranyl, dibenzothienyl, benzonaphthofuranyl and benzonaphthothienyl,
Wherein aryl and heteroaryl are unsubstituted or substituted with one or more substituents selected from deuterium, phenyl substituted with 1 to 5 deuterium, naphthyl and naphthyl substituted with 1 to 7 deuterium.
For example, R may be deuterium, or any one selected from the group consisting of:
further, a means the number of substituents R, and is 0, 1, 2, 3, 4, 5, 6, or 7. At this time, when a is 2 or more, two or more R are the same or different from each other.
For example, when a is 1, R is deuterium, C 6-20 Aryl, or C containing O or S 2-20 A heteroaryl group, which is a group,
when a is 2 to 7, R is all deuterium; or one of R is C 6-20 Aryl, or C containing O or S 2-20 Heteroaryl, and the balance deuterium,
wherein C is 6-20 Aryl and C 2-20 Heteroaryl is unsubstituted or substituted with one or more substituents selected from deuterium, phenyl substituted with 1 to 5 deuterium, naphthyl and naphthyl substituted with 1 to 7 deuterium.
Meanwhile, the first compound may be represented by any one of the following chemical formulas 1-1 to 1-7:
wherein, in chemical formulas 1-1 to 1-7,
r' is deuterium, C 6-20 Aryl, or C containing O or S 2-20 A heteroaryl group, which is a group,
wherein C is 6-20 Aryl and C 2-20 Heteroaryl is unsubstituted or substituted with one or more substituents selected from deuterium, phenyl substituted with 1 to 5 deuterium, naphthyl and naphthyl substituted with 1 to 7 deuterium.
D means that the number of the molecules of deuterium,
d is an integer of 0 to 6
L、L 1 、L 2 、Ar 1 And Ar is a group 2 As defined in chemical formula 1 above.
In other words, d is 0, 1, 2, 3, 4, 5, or 6.
Furthermore, the first compound may not include deuterium, or may include at least one deuterium.
In one 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 Spectrometer, matrix-assisted laser desorption/Ionization Time-of-flight mass spectrometry) analysis.
Representative examples of the first compounds are as follows:
in this case, when the first compound is represented by the following chemical formula 1", each substituent is described as follows:
[ chemical formula 1"]
Wherein, in the chemical formula 1',
dn means the number of deuterium substitutions in the compound,
L”、L” 1 、L” 2 、Ar” 1 、Ar” 2 and R' means L, L which is not substituted by deuterium 1 、L 2 、Ar 1 、Ar 2 And R substituents.
Meanwhile, the first compound may be prepared by a preparation method as shown in the following reaction scheme 1:
reaction scheme 1
In reaction scheme 1, Y is halogen, preferably bromine, or chlorine, and other substituents are as defined above.
Specifically, the first compound may be prepared by a Suzuki coupling reaction of starting materials A1 and A2. Such a Suzuki coupling reaction is preferably performed in the presence of a palladium catalyst and a base, and the reactive groups for the Suzuki coupling reaction may be appropriately changed. The preparation of the first compound may be further embodied in the preparation examples described below.
(second Compound)
The second compound is represented by the above chemical formula 2. Specifically, the second compound has a structure in which an amino group is bonded to a benzo [ b ] naphtho [2,1-d ] furan/benzo [ b ] naphtho [2,1-d ] thiophene core structure, and thus holes can be efficiently transported to the dopant material, so that the possibility of recombination of holes and electrons in the light-emitting layer can be increased together with the first compound having an excellent electron transport ability.
Meanwhile, according to the bonding position of the substituent represented by chemical formula 3, the second compound may be represented by any one of the following chemical formulas 2-1 to 2-10:
wherein, in chemical formulas 2-1 to 2-10,
R 1 to R 10 Each independently of the other is hydrogen or deuterium,
l' is a single bond; or unsubstituted or deuterium-substituted C 6-20 An arylene group,
L 3 、L 4 、Ar 3 and Ar is a group 4 As defined in chemical formula 2.
In chemical formula 2, L' may be a single bond; or unsubstituted or deuterium-substituted C 6-20 Arylene groups.
More specifically, L' may be a single bond, or phenylene.
For example, L' may be a single bond, 1, 2-phenylene, 1, 3-phenylene, or 1, 4-phenylene.
In addition, L 3 And L 4 Each independently may be a single bond; or unsubstituted or deuterium-substituted C 6-20 Arylene groups.
More specifically, L 3 And L 4 May each independently be a single bond, phenylene, or naphthylene.
For example, L 3 And L 4 Can each independently be a single bond, or
In addition, for example, L 3 And L 4 Both of which are single bonds; or alternatively
L 3 And L 4 One of them may be a single bond, and the others may be
In addition, ar 3 And Ar is a group 4 Can each independently be unsubstituted or selected from deuterium, C 1-10 Alkyl and C 6-20 C substituted by 1 to 3 substituents in aryl 6-20 An aryl group; or unsubstituted or selected from deuterium, C 1-10 Alkyl and C 6-20 C comprising 1 hetero atom in N, O and S substituted by 1 to 3 substituents in aryl 2-20 Heteroaryl groups.
More specifically, ar 3 And Ar is a group 4 Each independently is unsubstituted or is selected from deuterium, C 1-10 C substituted by 1 to 3 substituents in alkyl and phenyl 6-20 An aryl group; or alternatively
Ar 3 And Ar is a group 4 One of which is unsubstituted or is selected from deuterium, C 1-10 C substituted by 1 to 3 substituents in alkyl and phenyl 6-20 Aryl, the remainder being unsubstituted or substituted by deuterium, C 1-10 C comprising 1 heteroatom in N, O and S substituted by 1 to 3 substituents in alkyl and phenyl 2-20 Heteroaryl; or alternatively
Ar 3 And Ar is a group 4 Each independently is unsubstituted or is selected from deuterium, C 1-10 C comprising one heteroatom of N, O and S substituted by 1 to 3 substituents in alkyl and phenyl 2-20 Heteroaryl groups.
In one embodiment, ar 3 And Ar is a group 4 May each independently be phenyl, biphenyl, terphenyl, naphthyl, phenanthryl, 9-dimethylfluorenyl, 9-phenylcarbazolyl, dibenzofuranyl, or dibenzothiophenyl.
More specifically, ar 3 And Ar is a group 4 Each independently is phenyl, biphenyl, terphenyl, naphthyl, phenanthryl, or 9, 9-dimethylfluorenyl; or alternatively
Ar 3 And Ar is a group 4 One of them is phenyl, biphenyl, terphenyl, naphthyl, phenanthryl, or 9, 9-dimethylfluorenyl, and the remainder are 9-phenylcarbazolyl, dibenzofuranyl, or dibenzothiophenyl; or alternatively
Ar 3 And Ar is a group 4 Can be each independently 9-phenylcarbazoleOne of a group, dibenzofuranyl, or dibenzothienyl.
For example, ar 3 And Ar is a group 4 Each independently is any one selected from the group consisting of:
in one embodiment, ar 3 And Ar is a group 4 May be identical to each other. Alternatively, ar 3 And Ar is a group 4 May be different.
In other embodiments, L 3 -Ar 3 And L 4 -Ar 4 May be identical to each other. Alternatively, L 3 -Ar 3 And L 4 -Ar 4 May be different.
Representative examples of the second compounds are as follows:
。
meanwhile, for example, when the substituent represented by chemical formula 3 is R 1 And L' is a single bond, the second compound can be prepared by the preparation method shown in the following reaction scheme 2.
Reaction scheme 2
In scheme 2, Y' is halogen, preferably bromine, or chlorine, and the other substituents are as defined above.
In particular, the second compound may be prepared by amine substitution of starting materials A3 and A4. The amine substitution reaction is preferably carried out in the presence of a palladium catalyst and a base.
Meanwhile, for example, when the substituent represented by chemical formula 3 is R 1 And L' is not a single bond, the second compound can be prepared by the preparation method shown in the following reaction scheme 3.
Reaction scheme 3
In scheme 3, Y' is halogen, preferably bromine, or chlorine, and the other substituents are as defined above.
In particular, the second compound may be prepared by a Suzuki coupling reaction of starting materials A3 and A5. The Suzuki coupling reaction is preferably carried out in the presence of a palladium catalyst and a base, and the reactive groups for the Suzuki coupling reaction may be appropriately changed.
The process for preparing the second compound may be further embodied in the preparation examples described below.
Further, the first compound and the second compound may be included in the light emitting layer in a weight ratio of 1:99 to 99:1. At this time, the first compound and the second compound are more preferably contained in a weight ratio of 30:70 to 70:30 from the viewpoint of maintaining the ratio of holes and electrons in the light-emitting layer appropriately. Preferably, the first compound and the second compound may be included in the light emitting layer in a weight ratio of 50:50.
Meanwhile, the light emitting layer may contain a dopant material in addition to the two types of host materials. The dopant material may include aromatic amine derivatives, styrene amine compounds, boron complexes, fluoranthene compounds, metal complexes, and the like. Specifically, the aromatic amine derivative is a substituted or unsubstituted fused aromatic ring derivative having an arylamino group, and examples thereof include pyrene, anthracene having an arylamino group, Bisindenopyrene, and the like. 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, the metal complex includes iridium complex, platinum complex, and the like, but is not limited thereto.
More specifically, the following compounds may be used as dopant materials, but are not limited thereto:
hole blocking layer
The organic light emitting device according to the present disclosure may include a hole blocking layer between the light emitting layer and an electron transport layer described below, if necessary. The hole blocking layer refers to a layer of: which is formed on the light emitting layer, preferably disposed in contact with the light emitting layer, and serves to adjust electron mobility, prevent excessive movement of holes, and increase the possibility of hole-electron coupling, thereby improving the efficiency of the organic light emitting device. The hole blocking layer contains a hole blocking material, and examples of such a hole blocking material may include compounds having electron withdrawing groups introduced therein, such as oxazine derivatives Organisms, including triazines; triazole derivatives;an diazole derivative; phenanthroline derivatives; phosphine oxide derivatives, but are not limited thereto.
Electron injection and transport layers
The electron injection and transport layer is a layer for simultaneously injecting electrons from the electrode and transporting the received electrons to the electron transport layer and the electron injection layer of the light emitting layer, and is formed on the light emitting layer or the hole blocking layer. The electron injecting and transporting material is suitably a material that 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 injecting and transporting material include: al complexes of 8-hydroxyquinoline; comprising Alq 3 Is a complex of (a) and (b); an organic radical compound; hydroxyflavone-metal complexes; triazine derivatives, and the like, but are not limited thereto. Alternatively, it may be combined with fluorenone, anthraquinone dimethane, diphenoquinone, thiopyran dioxide, a,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 are used together, but are not limited thereto.
The electron injection and transport layers may also be formed as separate layers, such as an electron injection layer and an electron transport layer. In such a case, an electron transport layer is formed on the light emitting layer or the hole blocking layer, and the above-described electron injection and transport material may be used as an electron transport material contained in the electron transport layer. Further, an electron injection layer is formed on the electron transport layer, and examples of the electron injection material contained in the electron injection layer include LiF, naCl, csF, li 2 O, baO 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.
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.
Organic light emitting device
Fig. 1 illustrates 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. In such a structure, the first compound and the second compound may be included in the light-emitting layer.
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.
In such a structure, the first compound and the second compound may be included in the light-emitting layer.
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 be manufactured by sequentially depositing cathode materials to anode materials on a substrate. 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.
In addition to such a method, the organic light emitting device may be manufactured by sequentially depositing a cathode material, an organic material layer, and an anode material on a substrate (international publication WO 2003/012890). However, the manufacturing method is not limited thereto.
The organic light emitting device according to the present disclosure may be a bottom emission type device, a top emission type device, or a double-side emission type device, and in particular, it may be a bottom emission type light emitting device requiring relatively high light emitting efficiency.
Synthesis example 1-1: preparation of Compound 1-1
Trz1 (15 g,28.8 mmol) and dibenzo [ b, d]Furan-1-ylboronic acid (6.4 g,30.3 mmol) is added to 300mL THF and the mixture is stirred and refluxed. Then, potassium carbonate (12 g,86.5 mmol) was dissolved in 36mL of water and added to the mixture, the mixture was stirred well, and bis (tri-t-butylphosphine) palladium (0) (0.1 g,0.3 mmol) was then added. After 3 hours of reaction, the reaction mixture was cooled to room temperature, then the organic layer and the aqueous layer were separated, and the organic layer was distilled. It was redissolved in chloroform and washed twice with water. The organic layer was then separated, anhydrous magnesium sulfate was added, stirred and then filtered. The filtrate was distilled under reduced pressure. The concentrated compound was purified by a silica gel column to obtain 12.2g of Compound 1-1 (yield: 65%, M)S:[M+H] + ＝652)。
Synthesis examples 1 to 2: preparation of Compounds 1-2
Trz2 (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,91.1 mmol) was dissolved in 38mL of water and added to the mixture, the mixture was stirred well, and bis (tri-t-butylphosphine) palladium (0) (0.2 g,0.3 mmol) was then added. After 5 hours of reaction, the reaction mixture was cooled to room temperature, then the organic layer and the aqueous layer were separated, and the organic layer was distilled. It was redissolved in chloroform and washed twice with water. The organic layer was then separated, anhydrous magnesium sulfate was added, stirred and then filtered. The filtrate was distilled under reduced pressure. The concentrated compound was purified by a silica gel column to obtain 14g of Compound 1-2 (yield: 74%, MS: [ M+H) ] + ＝626)。
Synthesis examples 1 to 3: preparation of Compounds 1-3
Trz3 (15 g,33.8 mmol) and dibenzo [ b, d]Furan-1-ylboronic acid (7.5 g,35.5 mmol) is added to 300mL THF and the mixture is stirred and refluxed. Then, potassium carbonate (14 g,101.4 mmol) was dissolved in 42mL of water and added to the mixture, the mixture was stirred well, and bis (tri-t-butylphosphine) palladium (0) (0.2 g,0.3 mmol) was then added. After 5 hours of reaction, the reaction mixture was cooled to room temperature, then the organic layer and the aqueous layer were separated, and the organic layer was distilled. It was redissolved in chloroform and washed twice with water. The organic layer was then separated, anhydrous magnesium sulfate was added, stirred and then filtered. The filtrate was distilled under reduced pressure. The concentrated compound was purified by a silica gel column to obtain 13.4g of Compound 1-3 (yield: 69%, MS: [ M+H)] + ＝576)。
Synthesis examples 1 to 4: preparation of Compounds 1-4
Trz4 (15 g,24.9 mmol) and dibenzo [ b, d]Furan-1-ylboronic acid (5.5 g,26.2 mmol) is added to 300mL THF and the mixture is stirred and refluxed. Then, potassium carbonate (10.3 g,74.7 mmol) was dissolved in 31mL of water and added to the mixture, the mixture was stirred well, and bis (tri-t-butylphosphine) palladium (0) (0.1 g,0.2 mmol) was then added. After 3 hours of reaction, the reaction mixture was cooled to room temperature, then the organic layer and the aqueous layer were separated, and the organic layer was distilled. It was redissolved in chloroform and washed twice with water. The organic layer was then separated, anhydrous magnesium sulfate was added, stirred and then filtered. The filtrate was distilled under reduced pressure. The concentrated compound was purified by a silica gel column to obtain 12.6g of Compound 1-4 (yield: 69%, MS: [ M+H) ] + ＝734)。
Synthesis examples 1 to 5: preparation of Compounds 1-5
Trz5 (15 g,30.2 mmol) and dibenzo [ b, d]Furan-1-ylboronic acid (6.7 g,31.8 mmol) is added to 300mL THF and the mixture is stirred and refluxed. Then, potassium carbonate (12.5 g,90.7 mmol) was dissolved in 38mL of water and added to the mixture, the mixture was stirred well, and bis (tri-t-butylphosphine) palladium (0) (0.2 g,0.3 mmol) was then added. After 4 hours of reaction, the reaction mixture was cooled to room temperature, then the organic layer and the aqueous layer were separated, and the organic layer was distilled. It was redissolved in chloroform and washed twice with water. The organic layer was then separated, anhydrous magnesium sulfate was added, stirred and then filtered. The filtrate was distilled under reduced pressure. The concentrated compound was purified by a silica gel column to obtain 12.5g of Compound 1-5 (yield: 66%, MS: [ M+H)] + ＝629)。
Synthesis examples 1 to 6: preparation of Compounds 1-7
Trz7 (15 g,33.8 mmol) and dibenzo [ b, d]Furan-1-ylboronic acid (7.5 g,35.5 mmol) is added to 300mL THF and the mixture is stirred and refluxed. Then, potassium carbonate (14 g,101.4 mmol) was dissolved in 42mL of water and added to the mixture, the mixture was stirred well, and bis (tri-t-butylphosphine) palladium (0) (0.2 g,0.3 mmol) was then added. After 5 hours of reaction, the reaction mixture was cooled to room temperature, then the organic layer and the aqueous layer were separated, and the organic layer was distilled. It was redissolved in chloroform and washed twice with water. The organic layer was then separated, anhydrous magnesium sulfate was added, stirred and then filtered. The filtrate was distilled under reduced pressure. The concentrated compound was purified by a silica gel column to obtain 13.6g of compound 1-7 (yield: 70%, MS: [ M+H ] ] + ＝576)。
Synthesis examples 1 to 7: preparation of Compounds 1-8
Trz8 (15 g,35.9 mmol) and dibenzo [ b, d]Furan-1-ylboronic acid (8 g,37.7 mmol) was added to 300mL THF and the mixture was stirred and refluxed. Then, potassium carbonate (14.9 g,107.7 mmol) was dissolved in 45mL of water and added to the mixture, the mixture was stirred well, and bis (tri-t-butylphosphine) palladium (0) (0.2 g,0.4 mmol) was then added. After 3 hours of reaction, the reaction mixture was cooled to room temperature, then the organic layer and the aqueous layer were separated, and the organic layer was distilled. It was redissolved in chloroform and washed twice with water. The organic layer was then separated, anhydrous magnesium sulfate was added, stirred and then filtered. The filtrate was distilled under reduced pressure. The concentrated compound was purified by a silica gel column to obtain 13.8g of compound 1-8 (yield: 70%, MS: [ M+H ]] + ＝550)。
Synthesis examples 1 to 8: preparation of Compounds 1-9
Trz9 (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,91.1 mmol) was dissolved in 38mL of water and added to the mixture, the mixture was stirred well, and bis (tri-t-butylphosphine) palladium (0) (0.2 g,0.3 mmol) was then added. After 4 hours of reaction, the reaction mixture was cooled to room temperature, then the organic layer and the aqueous layer were separated, and the organic layer was distilled. It was redissolved in chloroform and washed twice with water. The organic layer was then separated, anhydrous magnesium sulfate was added, stirred and then filtered. The filtrate was distilled under reduced pressure. The concentrated compound was purified by a silica gel column to obtain 13.7g of compound 1-9 (yield: 72%, MS: [ M+H ] ] + ＝626)。
Synthesis examples 1 to 9: preparation of Compounds 1-10
Trz10 (15 g,33.8 mmol) and dibenzo [ b, d]Furan-1-ylboronic acid (7.5 g,35.5 mmol) is added to 300mL THF and the mixture is stirred and refluxed. Then, potassium carbonate (14 g,101.4 mmol) was dissolved in 42mL of water and added to the mixture, the mixture was stirred well, and bis (tri-t-butylphosphine) palladium (0) (0.2 g,0.3 mmol) was then added. After 5 hours of reaction, the reaction mixture was cooled to room temperature, then the organic layer and the aqueous layer were separated, and the organic layer was distilled. It was redissolved in chloroform and washed twice with water. The organic layer was then separated, anhydrous magnesium sulfate was added, stirred and then filtered. The filtrate was distilled under reduced pressure. The concentrated compound was purified by a silica gel column to obtain 14.2g of compounds 1 to 10. (yield: 73%, MS: [ M+H)] + ＝576)
Synthesis examples 1 to 10: preparation of Compounds 1-11
Trz11 (15 g,33.8 mmol) and dibenzo [ b, d]Furan-1-ylboronic acid (7.5 g,35.5 mmol) is added to 300mL THF and the mixture is stirred and refluxed. Then, potassium carbonate (14 g,101.4 mmol) was dissolved in 42mL of water and added to the mixture, the mixture was stirred well, and bis (tri-t-butylphosphine) palladium (0) (0.2 g,0.3 mmol) was then added. After 4 hours of reaction, the reaction mixture was cooled to room temperature, then the organic layer and the aqueous layer were separated, and the organic layer was distilled. It was redissolved in chloroform and washed twice with water. The organic layer was then separated, anhydrous magnesium sulfate was added, stirred and then filtered. The filtrate was distilled under reduced pressure. The concentrated compound was purified by a silica gel column to obtain 13.4g of Compound 1-11 (yield: 69%, MS: [ M+H) ] + ＝576)。
Synthesis examples 1 to 11: preparation of Compounds 1-12
Trz12 (15 g,31.9 mmol) and dibenzo [ b, d]Furan-1-ylboronic acid (7.1 g,33.5 mmol) is added to 300mL THF and the mixture is stirred and refluxed. Then, potassium carbonate (13.2 g,95.8 mmol) was dissolved in 40mL of water and added to the mixture, the mixture was stirred well, and bis (tri-t-butylphosphine) palladium (0) (0.2 g,0.3 mmol) was then added. After 5 hours of reaction, the reaction mixture was cooled to room temperature, then the organic layer and the aqueous layer were separated, and the organic layer was distilled. It was redissolved in chloroform and washed twice with water. The organic layer was then separated, anhydrous magnesium sulfate was added, stirred and then filtered. The filtrate was distilled under reduced pressure. The concentrated compound was purified by a silica gel column to obtain 14.2g of Compound 1-12 (yield: 74%, MS: [ M+H)] + ＝602)。
Synthesis examples 1 to 12: preparation of Compounds 1-15
Trz15 (15 g,31.6 mmol) and dibenzo [ b, d]Furan-1-ylboronic acid (7 g,33.2 mmol) was added to 300mL THF and the mixture was stirred and refluxed. Then, potassium carbonate (13.1 g,94.7 mmol) was dissolved in 39mL of water and added to the mixture, the mixture was stirred well, and bis (tri-t-butylphosphine) palladium (0) (0.2 g,0.3 mmol) was then added. After 3 hours of reaction, the reaction mixture was cooled to room temperature, then the organic layer and the aqueous layer were separated, and the organic layer was distilled. It was redissolved in chloroform and washed twice with water. The organic layer was then separated, anhydrous magnesium sulfate was added, stirred and then filtered. The filtrate was distilled under reduced pressure. The concentrated compound was purified by a silica gel column to obtain 14.2g of compound 1-15 (yield: 74%, MS: [ M+H) ] + ＝607)。
Synthesis examples 1 to 13: preparation of Compounds 1-16
Trz16 (15 g,31.9 mmol) and dibenzo [ b, d]Furan-1-ylboronic acid (7.1 g,33.5 mmol) is added to 300mL THF and the mixture is stirred and refluxed. Then, potassium carbonate (13.2 g,95.8 mmol) was dissolved in 40mL of water and added to the mixture, the mixture was stirred well, and bis (tri-t-butylphosphine) palladium (0) (0.2 g,0.3 mmol) was then added. After 5 hours of reaction, the reaction mixture was cooled to room temperature, then the organic layer and the aqueous layer were separated, and the organic layer was distilled. It was redissolved in chloroform and washed twice with water. The organic layer was then separated, anhydrous magnesium sulfate was added, stirred and then filtered. The filtrate was distilled under reduced pressure. The concentrated compound was purified by a silica gel column to obtain 12.7g of Compound 1-16 (yield: 66%, MS: [ M+H)] + ＝602)。
Synthesis examples 1 to 14: preparation of Compounds 1-18
Trz18 (15 g,28.8 mmol) and dibenzo [ b, d]Furan-1-ylboronic acid (6.4 g,30.3 mmol) is added to 300mL THF and the mixture is stirred and refluxed. Then, potassium carbonate (12 g,86.5 mmol) was dissolved in 36mL of water and added to the mixture, the mixture was stirred well, and bis (tri-t-butylphosphine) palladium (0) (0.1 g,0.3 mmol) was then added. After 4 hours of reaction, the reaction mixture was cooled to room temperature, then the organic layer and the aqueous layer were separated, and the organic layer was distilled. It was redissolved in chloroform and washed twice with water. The organic layer was then separated, anhydrous magnesium sulfate was added, stirred and then filtered. The filtrate was distilled under reduced pressure. The concentrated compound was purified by a silica gel column to obtain 13.3g of Compound 1-18 (yield: 71%, MS: [ M+H) ] + ＝652)。
Synthesis examples 1 to 15: preparation of Compounds 1-19
Trz19 (15 g,28.8 mmol) and dibenzo [ b, d]Furan-1-ylboronic acid (6.4 g,30.3 mmol) is added to 300mL THF and the mixture is stirred and refluxed. Then, potassium carbonate (12 g,86.5 mmol) was dissolved in 36mL of water and added to the mixture, the mixture was stirred well, and bis (tri-t-butylphosphine) palladium (0) (0.1 g,0.3 mmol) was then added. After 5 hours of reaction, the reaction mixture was cooled to room temperature, then the organic layer and the aqueous layer were separated, and the organic layer was distilled. It was redissolved in chloroform and washed twice with water. The organic layer was then separated, anhydrous magnesium sulfate was added, stirred and then filtered. The filtrate was distilled under reduced pressure. The concentrated compound was purified by a silica gel column to obtain 13.7g of Compound 1-19 (yield: 73%, MS: [ M+H ]] + ＝652)。
Synthesis examples 1 to 16: preparation of Compounds 1-20
Trz20 (15 g,28.8 mmol) and dibenzo [ b, d]Furan-1-ylboronic acid (6.4 g,30.3 mmol) is added to 300mL THF and the mixture is stirred and refluxed. Then, potassium carbonate (12 g,86.5 mmol) was dissolved in 36mL of water and added to the mixture, the mixture was stirred well, and bis (tri-t-butylphosphine) palladium (0) (0.1 g,0.3 mmol) was then added. After 4 hours of reaction, the reaction mixture was cooled to room temperature, then the organic layer and the aqueous layer were separated, and the organic layer was distilled. It was redissolved in chloroform and washed twice with water. The organic layer was then separated, anhydrous magnesium sulfate was added, stirred and then filtered. The filtrate was distilled under reduced pressure. The concentrated compound was purified by a silica gel column to obtain 12.6g of Compound 1-20 (yield: 67%, MS: [ M+H) ] + ＝652)。
Synthesis examples 1 to 17: preparation of Compounds 1-22
Trz22 (15 g,27.5 mmol) and dibenzo [ b, d]Furan-1-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, the mixture was stirred well, and bis (tri-t-butylphosphine) palladium (0) (0.1 g,0.3 mmol) was then added. After 3 hours of reaction, the reaction mixture was cooled to room temperature, then the organic layer and the aqueous layer were separated, and the organic layer was distilled. It was redissolved in chloroform and washed twice with water. The organic layer was then separated, anhydrous magnesium sulfate was added, stirred and then filtered. The filtrate was distilled under reduced pressure. The concentrated compound was purified by a silica gel column to obtain 14g of compound 1-22 (yield: 75%, MS: [ M+H ]] + ＝678)。
Synthesis examples 1 to 18: preparation of Compounds 1-25
Trz25 (15 g,28.2 mmol) and dibenzo [ b, d]Furan-1-ylboronic acid (6.3 g,29.7 mmol) is added to 300mL THF and the mixture is stirred and refluxed. Then, potassium carbonate (11.7 g,84.7 mmol) was dissolved in 35mL of water and added to the mixture, the mixture was stirred well, and bis (tri-t-butylphosphine) palladium (0) (0.1 g,0.3 mmol) was then added. After 3 hours of reaction, the reaction mixture was cooled to room temperature, then the organic layer and the aqueous layer were separated, and the organic layer was distilled. It was redissolved in chloroform and washed twice with water. The organic layer was then separated, anhydrous magnesium sulfate was added, stirred and then filtered. The filtrate was distilled under reduced pressure. The concentrated compound was purified by a silica gel column to obtain 12.9g of Compound 1-25 (yield: 69%, MS: [ M+H) ] + ＝663)。
Synthesis examples 1 to 19: preparation of Compounds 1-27
Trz27 (15 g,34.6 mmol) and dibenzo [ b, d]Furan-1-ylboronic acid (7.7 g,36.3 mmol) was added to 300mL THF and the 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, the mixture was stirred well, and bis (tri-t-butylphosphine) palladium (0) (0.2 g,0.3 mmol) was then added. After 4 hours of reaction, the reaction mixture was cooled to room temperature, then the organic layer and the aqueous layer were separated, and the organic layer was distilled. It was redissolved in chloroform and washed twice with water. The organic layer was then separated, anhydrous magnesium sulfate was added, stirred and then filtered. The filtrate was distilled under reduced pressure. The concentrated compound was purified by a silica gel column to obtain 13.9g of Compound 1-27 (yield: 71%, MS: [ M+H ]] + ＝566)。
Synthesis examples 1 to 20: preparation of Compounds 1-28
Adding trifluoromethanesulfonic acid at 0deg.CAnhydride (24 g,85 mmol) and deuterium oxide (8.5 g,424.9 mmol) 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 sub1-1-1. (yield: 38%, MS: [ M+H)] + ＝248)
Sub1-1-1 (15 g,60.5 mmol) and bis (pinacolato) diboron (16.9 g,66.5 mmol) were added to 300mL of 1, 4-diboronIn 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 sub1-1-2. (yield: 75%, MS: [ M+H) ] + ＝296)
Sub1-1-2 (15 g,50.8 mmol) and Trz28 (26.4 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, the mixture was stirred well, and bis (tri-t-butylphosphine) palladium (0) (0.3 g,0.5 mmol) was then added. In reaction 3 hoursAfter that time, the reaction mixture was cooled to room temperature, then the organic layer and the aqueous layer were separated, and the organic layer was distilled. It was redissolved in chloroform and washed twice with water. The organic layer was then separated, anhydrous magnesium sulfate was added, stirred and then filtered. The filtrate was distilled under reduced pressure. The concentrated compound was purified by a silica gel column to obtain 21g of compounds 1-28 (yield: 66%, MS: [ M+H)] + ＝627)。
Synthesis examples 1 to 21: preparation of Compounds 1-30
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 sub1-2-1. (yield: 40%, MS: [ M+H) ] + ＝249)
Sub1-2-1 (15 g,60.2 mmol) and bis (pinacolato) diboron (16.8 g,66.2 mmol) were added to 300mL of 1, 4-diboronIn 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 cooledThe 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 sub1-2-2. (yield: 70%, MS: [ M+H ]] + ＝297)
Sub1-2-2 (15 g,50.6 mmol) and Trz30 (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, the mixture was stirred well, and bis (tri-t-butylphosphine) palladium (0) (0.3 g,0.5 mmol) was then added. After 4 hours of reaction, the reaction mixture was cooled to room temperature, then the organic layer and the aqueous layer were separated, and the organic layer was distilled. It was redissolved in chloroform and washed twice with water. The organic layer was then separated, anhydrous magnesium sulfate was added, stirred and then filtered. The filtrate was distilled under reduced pressure. The concentrated compound was purified by a silica gel column to obtain 23.4g of compound 1-30 (yield: 70%, MS: [ M+H ] ] + ＝660)。
Synthesis examples 1 to 22: preparation of Compounds 1-31
Sub1-2-2 (15 g,50.6 mmol) and Trz31 (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, the mixture was stirred well, and bis (tri-t-butylphosphine) palladium (0) (0.3 g,0.5 mmol) was then added. After 4 hours of reaction, the reaction mixture was cooled to room temperature, then the organic layer and the aqueous layer were separated, and the organic layer was distilled. It was redissolved in chloroform and washed twice with water. The organic layer was then separated, anhydrous magnesium sulfate was added, stirred and then filtered. The filtrate was distilled under reduced pressure. The concentrated compound was purified by a silica gel column to obtain 22.5g of Compound 1-31 (yield: 68%, M)S:[M+H] + ＝654)。
Synthesis examples 1 to 23: preparation of Compounds 1-33
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 sub1-3-1. (yield: 42%, MS: [ M+H)] + ＝250)
Sub1-3-1 (15 g,60 mmol) and bis (pinacolato) diboron (16.8 g,66 mmol) were added to 300mL of 1, 4-bisIn 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 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 11.4g of sub1-3-2. (yield: 64%, M) S:[M+H] + ＝298)
Sub1-3-2 (15 g,50.5 mmol) and Trz15 (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, the mixture was stirred well, and bis (tri-t-butylphosphine) palladium (0) (0.3 g,0.5 mmol) was then added. After 3 hours of reaction, the reaction mixture was cooled to room temperature, then the organic layer and the aqueous layer were separated, and the organic layer was distilled. It was redissolved in chloroform and washed twice with water. The organic layer was then separated, anhydrous magnesium sulfate was added, stirred and then filtered. The filtrate was distilled under reduced pressure. The concentrated compound was purified by a silica gel column to obtain 23.1g of Compound 1-33 (yield: 75%, MS: [ M+H ]] + ＝610)。
Synthesis examples 1 to 24: preparation of Compounds 1-35
Sub1-3-2 (15 g,50.5 mmol) and Trz34 (21.1 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, the mixture was stirred well, and bis (tri-t-butylphosphine) palladium (0) (0.3 g,0.5 mmol) was then added. After 5 hours of reaction, the reaction mixture was cooled to room temperature, then the organic layer and the aqueous layer were separated, and the organic layer was distilled. It was redissolved in chloroform and washed twice with water. The organic layer was then separated, anhydrous magnesium sulfate was added, stirred and then filtered. The filtrate was distilled under reduced pressure. The concentrated compound was purified by a silica gel column to obtain 17.8g of Compound 1-35 (yield: 66%, MS: [ M+H) ] + ＝534)。
Synthesis examples 1 to 25: preparation of Compounds 1-36
Adding trifluoro at 0deg.CMethanesulfonic anhydride (95.9 g,340 mmol) and deuterium oxide (34 g,1699.8 mmol) were 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 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 sub1-4-1. (yield: 37%, MS: [ M+H)] + ＝251)
Sub1-4-1 (15 g,59.7 mmol) and bis (pinacolato) diboron (16.7 g,65.7 mmol) were added to 300mL of 1, 4-bisIn 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 sub1-4-2. (yield: 70%, MS: [ M+H ] ] + ＝299)
Sub1-4-2 (15 g,50.3 mmol) and Trz35 (26.1 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 in 63mL of water and added to the mixture, the mixture was stirred well, and bis (tri-t-butylphosphine) palladium (0) (0.3 g,0.5 mmol) was then addedl). After 4 hours of reaction, the reaction mixture was cooled to room temperature, then the organic layer and the aqueous layer were separated, and the organic layer was distilled. It was redissolved in chloroform and washed twice with water. The organic layer was then separated, anhydrous magnesium sulfate was added, stirred and then filtered. The filtrate was distilled under reduced pressure. The concentrated compound was purified by a silica gel column to obtain 21.5g of Compound 1-36 (yield: 68%, MS: [ M+H)] + ＝631)。
Synthesis examples 1 to 26: preparation of Compounds 1-38
Sub1-4-2 (15 g,50.3 mmol) and Trz36 (24.1 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 in 63mL of water and added to the mixture, the mixture was stirred well, and bis (tri-t-butylphosphine) palladium (0) (0.3 g,0.5 mmol) was then added. After 3 hours of reaction, the reaction mixture was cooled to room temperature, then the organic layer and the aqueous layer were separated, and the organic layer was distilled. It was redissolved in chloroform and washed twice with water. The organic layer was then separated, anhydrous magnesium sulfate was added, stirred and then filtered. The filtrate was distilled under reduced pressure. The concentrated compound was purified by a silica gel column to obtain 20.2g of Compound 1-37 (yield: 68%, MS: [ M+H) ] + ＝592)。
Synthesis examples 1 to 27: preparation of Compounds 1-38
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 ]]Mixed solvent of furan and 1,2, 4-trichlorobenzeneIn solution, 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 sub1-5-1. (yield: 39%, MS: [ M+H)] + ＝252)
Sub1-5-1 (15 g,59.5 mmol) and bis (pinacolato) diboron (16.6 g,65.4 mmol) were added to 300mL of 1, 4-diboronIn an alkane, and the mixture was stirred under reflux. Then, potassium acetate (8.8 g,89.2 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 11.2g of sub1-5-2. (yield: 63%, MS: [ M+H) ] + ＝300)
Sub1-5-2 (15 g,50.1 mmol) and Trz37 (23.4 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, the mixture was stirred well, and bis (tri-t-butylphosphine) palladium (0) (0.3 g,0.5 mmol) was then added. After 4 hours of reaction, the reaction mixture was cooled to room temperature, then the organic layer and the aqueous layer were separated, and the organic layer was distilled. It was redissolved in chloroform and washed twice with water. The organic layer was then separated, anhydrous magnesium sulfate was added, stirred and then filtered. The filtrate was distilled under reduced pressure. Purification of the concentrated compound by silica gel column20.1g of compounds 1-38 are obtained. (yield: 69%, MS: [ M+H)] + ＝581)
Synthesis examples 1 to 28: preparation of Compounds 1-39
Sub1-5-2 (15 g,50.1 mmol) and Trz38 (23.6 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, the mixture was stirred well, and bis (tri-t-butylphosphine) palladium (0) (0.3 g,0.5 mmol) was then added. After 5 hours of reaction, the reaction mixture was cooled to room temperature, then the organic layer and the aqueous layer were separated, and the organic layer was distilled. It was redissolved in chloroform and washed twice with water. The organic layer was then separated, anhydrous magnesium sulfate was added, stirred and then filtered. The filtrate was distilled under reduced pressure. The concentrated compound was purified by a silica gel column to obtain 20.2g of compounds 1 to 39. (yield: 69%, MS: [ M+H) ] + ＝586)
Synthesis examples 1 to 29: preparation of Compounds 1-40
Sub1-5-2 (15 g,50.1 mmol) and Trz39 (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, the mixture was stirred well, and bis (tri-t-butylphosphine) palladium (0) (0.3 g,0.5 mmol) was then added. After 5 hours of reaction, the reaction mixture was cooled to room temperature, then the organic layer and the aqueous layer were separated, and the organic layer was distilled. It was redissolved in chloroform and washed twice with water. The organic layer was then separated, anhydrous magnesium sulfate was added, stirred and then filtered. The filtrate was distilled under reduced pressure. The concentrated compound was purified by a silica gel column to obtain 22.5g of compounds 1 to 40. (yield: 68%, MS: [ M+H)] + ＝662)
Synthesis examples 1 to 30: preparation of Compounds 1-41
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 ] ]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 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 sub1-6-1. (yield: 40%, MS: [ M+H)] + ＝254)
Sub1-6-1 (15 g,59 mmol) and bis (pinacolato) diboron (16.5 g,64.9 mmol) were added to 300mL of 1, 4-diboronIn 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 addition of 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 sub1-6-2. (yield: 65%, MS: [ M+H) ] + ＝302)
Sub1-6-2 (15 g,49.8 mmol) and Trz40 (22.3 g,52.3 mmol) were added to 300mL THF and the mixture was stirred and refluxed. Then, potassium carbonate (20.6 g,149.4 mmol) was dissolved in 62mL of water and added to the mixture, the mixture was stirred well, and bis (tri-t-butylphosphine) palladium (0) (0.3 g,0.5 mmol) was then added. After 5 hours of reaction, the reaction mixture was cooled to room temperature, then the organic layer and the aqueous layer were separated, and the organic layer was distilled. It was redissolved in chloroform and washed twice with water. The organic layer was then separated, anhydrous magnesium sulfate was added, stirred and then filtered. The filtrate was distilled under reduced pressure. The concentrated compound was purified by a silica gel column to obtain 20.3g of Compound 1-41 (yield: 72%, MS: [ M+H)] + ＝566)。
Synthesis examples 1 to 31: preparation of Compounds 1-42
Sub1-6-2 (15 g,49.8 mmol) and Trz41 (27.9 g,52.3 mmol) were added to 300mL THF and the mixture was stirred and refluxed. Then, potassium carbonate (20.6 g,149.4 mmol) was dissolved in 62mL of water and added to the mixture, the mixture was stirred well, and bis (tri-t-butylphosphine) palladium (0) (0.3 g,0.5 mmol) was then added. After 3 hours of reaction, the reaction mixture was cooled to room temperature, then the organic layer and the aqueous layer were separated, and the organic layer was distilled. It was redissolved in chloroform and washed twice with water. The organic layer was then separated, anhydrous magnesium sulfate was added, stirred and then filtered. The filtrate was distilled under reduced pressure. The concentrated compound was purified by a silica gel column to obtain 24.7g of Compound 1-42 (yield: 74%, MS: [ M+H ] ] + ＝672)。
Synthesis examples 1 to 32: preparation of Compounds 1-43
Sub1-6-2 (15 g,49.8 mmol) and Trz42 (22.9 g,52.3mmol) was added to 300mL THF and the mixture was stirred and refluxed. Then, potassium carbonate (20.6 g,149.4 mmol) was dissolved in 62mL of water and added to the mixture, the mixture was stirred well, and bis (tri-t-butylphosphine) palladium (0) (0.3 g,0.5 mmol) was then added. After 3 hours of reaction, the reaction mixture was cooled to room temperature, then the organic layer and the aqueous layer were separated, and the organic layer was distilled. It was redissolved in chloroform and washed twice with water. The organic layer was then separated, anhydrous magnesium sulfate was added, stirred and then filtered. The filtrate was distilled under reduced pressure. The concentrated compound was purified by a silica gel column to obtain 18.7g of Compound 1-43 (yield: 65%, MS: [ M+H)] + ＝577)。
Synthesis examples 1 to 33: preparation of Compounds 1-44
Trz37 (15 g,33.8 mmol) and dibenzo [ b, d]Furan-1-ylboronic acid (7.5 g,35.5 mmol) is added to 300mL THF and the mixture is stirred and refluxed. Then, potassium carbonate (14 g,101.4 mmol) was dissolved in 42mL of water and added to the mixture, the mixture was stirred well, and bis (tri-t-butylphosphine) palladium (0) (0.2 g,0.3 mmol) was then added. After 4 hours of reaction, the reaction mixture was cooled to room temperature, then the organic layer and the aqueous layer were separated, and the organic layer was distilled. It was redissolved in chloroform and washed twice with water. The organic layer was then separated, anhydrous magnesium sulfate was added, stirred and then filtered. The filtrate was distilled under reduced pressure. The concentrated compound was purified by a silica gel column to obtain 12.8g of Compound 1-44_P1 (yield: 66%, MS: [ M+H) ] + ＝576)。
Compound 1-44_P1 (10 g,17.4 mmol), ptO 2 (1.2 g,5.2 mmol) and D 2 O (87 ml) was added to the vibrating tube, which 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 purified by silica gel column chromatography to give a sample4.1g of compounds 1-44 were prepared. (yield: 40%, MS: [ M+H)] + ＝598)
Synthesis examples 1 to 34: preparation of Compounds 1-45
Compounds 1 to 8 (10 g,18.2 mmol), ptO 2 (1.2 g,5.5 mmol) and D 2 O (91 ml) was added to the vibrating tube, which 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 4.1g of compounds 1 to 45. (yield: 40%, MS: [ M+H)] + ＝570)
Synthesis examples 1 to 35: preparation of Compounds 1-46
Compounds 1 to 11 (10 g,17.4 mmol), ptO 2 (1.2 g,5.2 mmol) and D 2 O (87 ml) was added to the vibrating tube, which 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 4.5g of compounds 1 to 46. (yield: 43%, MS: [ M+H)] + ＝598)
Synthesis examples 1 to 36: preparation of Compounds 1-47
Trz43 (15 g,31.9 mmol) and dibenzo [ b, d]Furan-1-ylboronic acid (7.1 g,33.5 mmol) is added to 300mL THF and the mixture is stirred and refluxed. Then, potassium carbonate (13.2 g,95.8 mmol) was dissolved in 40mL of water, andto the mixture was added, the mixture was stirred well, and bis (tri-t-butylphosphine) palladium (0) (0.2 g,0.3 mmol) was then added. After 3 hours of reaction, the reaction mixture was cooled to room temperature, then the organic layer and the aqueous layer were separated, and the organic layer was distilled. It was redissolved in chloroform and washed twice with water. The organic layer was then separated, anhydrous magnesium sulfate was added, stirred and then filtered. The filtrate was distilled under reduced pressure. The concentrated compound was purified by a silica gel column to obtain 14.2g of Compound 1-47_P1 (yield: 74%, MS: [ M+H)] + ＝602)。
Compound 1-47_P1 (10 g,16.6 mmol), ptO 2 (1.1 g,5 mmol) and D 2 O (83 ml) was added to the vibrating tube, which 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 4.5g of compounds 1 to 47. (yield: 43%, MS: [ M+H)] + ＝626)
Synthesis examples 1 to 37: preparation of Compounds 1-49
(8-chlorodibenzo [ b, d)]Furan-1-yl) boronic acid (15 g,60.9 mmol) and Trz44 (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, the mixture was stirred well, and bis (tri-t-butylphosphine) palladium (0) (0.3 g,0.6 mmol) was then added. After 5 hours of reaction, the reaction mixture was cooled to room temperature, then the organic layer and the aqueous layer were separated, and the organic layer was distilled. It was redissolved in chloroform and washed twice with water. The organic layer was then separated, anhydrous magnesium sulfate was added, stirred and then filtered. The filtrate was distilled under reduced pressure. The concentrated compound was purified by a silica gel column to obtain 23.5g of Compound 1-49_P1 (yield: 69%, MS: [ M+H)] + ＝560)。
Will be combined1-49_P1 (15 g,26.8 mmol) and naphthalen-1-ylboronic acid (4.8 g,28.1 mmol) were added to 300mL THF and the mixture stirred and refluxed. Then, potassium carbonate (11.1 g,80.3 mmol) was dissolved in 33mL of water and added to the mixture, the mixture was stirred well, and bis (tri-t-butylphosphine) palladium (0) (0.1 g,0.3 mmol) was then added. After 5 hours of reaction, the reaction mixture was cooled to room temperature, then the organic layer and the aqueous layer were separated, and the organic layer was distilled. It was redissolved in chloroform and washed twice with water. The organic layer was then separated, anhydrous magnesium sulfate was added, stirred and then filtered. The filtrate was distilled under reduced pressure. The concentrated compound was purified by a silica gel column to obtain 12.7g of Compound 1-49 (yield: 73%, MS: [ M+H) ] + ＝652)。
Synthesis examples 1 to 38: preparation of Compounds 1-52
(8-chlorodibenzo [ b, d ] furan-1-yl) boronic acid (15 g,60.9 mmol) and Trz47 (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, the mixture was stirred well, and bis (tri-t-butylphosphine) palladium (0) (0.3 g,0.6 mmol) was then added. After 3 hours of reaction, the reaction mixture was cooled to room temperature, then the organic layer and the aqueous layer were separated, and the organic layer was distilled. It was redissolved in chloroform and washed twice with water. The organic layer was then separated, anhydrous magnesium sulfate was added, stirred and then filtered. The filtrate was distilled under reduced pressure. The concentrated compound was purified by a silica gel column to obtain 17.9g of compound 1-52_P1 (yield: 68%, MS: [ M+H ] +=434).
Compound 1-52_P1 (15 g,34.6 mmol) and triphenylen-2-ylboronic acid (9.9 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, the mixture was stirred well, and bis (tri-t-butylphosphine) palladium (0) (0.2 g,0.3 mmol) was then added. In reaction 5 After an hour, the reaction mixture was cooled to room temperature, then the organic layer and the aqueous layer were separated, and the organic layer was distilled. It was redissolved in chloroform and washed twice with water. The organic layer was then separated, anhydrous magnesium sulfate was added, stirred and then filtered. The filtrate was distilled under reduced pressure. The concentrated compound was purified by a silica gel column to obtain 14.3g of Compound 1-52 (yield: 66%, MS: [ M+H)] + ＝626)。
Synthesis examples 1 to 39: preparation of Compounds 1-53
(8-chlorodibenzo [ b, d)]Furan-1-yl) boronic acid (15 g,60.9 mmol) and Trz48 (34.4 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, the mixture was stirred well, and bis (tri-t-butylphosphine) palladium (0) (0.3 g,0.6 mmol) was then added. After 5 hours of reaction, the reaction mixture was cooled to room temperature, then the organic layer and the aqueous layer were separated, and the organic layer was distilled. It was redissolved in chloroform and washed twice with water. The organic layer was then separated, anhydrous magnesium sulfate was added, stirred and then filtered. The filtrate was distilled under reduced pressure. The concentrated compound was purified by a silica gel column to obtain 30.1g of Compound 1-53_P1 (yield: 75%, MS: [ M+H) ] + ＝660)。
Compound 1-53_P1 (15 g,22.7 mmol) and phenylboronic acid (2.9 g,23.9 mmol) were added to 300mL of THF and the mixture was stirred and refluxed. Then, potassium carbonate (9.4 g,68.2 mmol) was dissolved in 28mL of water and added to the mixture, the mixture was stirred well, and bis (tri-t-butylphosphine) palladium (0) (0.1 g,0.2 mmol) was then added. After 5 hours of reaction, the reaction mixture was cooled to room temperature, then the organic layer and the aqueous layer were separated, and the organic layer was distilled. It was redissolved in chloroform and washed twice with water. The organic layer was then separated, anhydrous magnesium sulfate was added, stirred and then filtered. The filtrate was distilled under reduced pressure. Concentrated combination by silica gel columnThe resultant was purified to obtain 10.7g of Compound 1-53 (yield: 67%, MS: [ M+H)] + ＝702)。
Synthesis examples 1 to 40: preparation of Compounds 1-54
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-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 4 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 sub2-1-1. (yield: 43%, MS: [ M+H)] + ＝283)
Sub2-1-1 (15 g,52.9 mmol) and bis (pinacolato) diboron (14.8 g,58.2 mmol) were added to 300mL 1, 4-diboronIn 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 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. By means of silica gel The concentrated compound was purified by column chromatography to prepare 11.5g of sub2-1-2. (yield: 66%, MS: [ M+H)] + ＝331)/>
Sub2-1-2 (15 g,45.4 mmol) and Trz49 (21.4 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, the mixture was stirred well, and bis (tri-t-butylphosphine) palladium (0) (0.2 g,0.5 mmol) was then added. After 5 hours of reaction, the reaction mixture was cooled to room temperature, then the organic layer and the aqueous layer were separated, and the organic layer was distilled. It was redissolved in chloroform and washed twice with water. The organic layer was then separated, anhydrous magnesium sulfate was added, stirred and then filtered. The filtrate was distilled under reduced pressure. The concentrated compound was purified by a silica gel column to obtain 18.2g of Compound 1-54_P1 (yield: 65%, MS: [ M+H)] + ＝617)。
Compound 1-54_P1 (15 g,24.3 mmol) and phenylboronic acid (3.1 g,25.5 mmol) were added to 300mL THF and the mixture was stirred and refluxed. Then, potassium carbonate (10.1 g,72.9 mmol) was dissolved in 30mL of water and added to the mixture, the mixture was stirred well, and bis (tri-t-butylphosphine) palladium (0) (0.1 g,0.2 mmol) was then added. After 4 hours of reaction, the reaction mixture was cooled to room temperature, then the organic layer and the aqueous layer were separated, and the organic layer was distilled. It was redissolved in chloroform and washed twice with water. The organic layer was then separated, anhydrous magnesium sulfate was added, stirred and then filtered. The filtrate was distilled under reduced pressure. The concentrated compound was purified by a silica gel column to obtain 11g of compound 1-54 (yield: 69%, MS: [ M+H) ] + ＝659)。
Synthesis examples 1 to 41: preparation of Compounds 1-56
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 addedTo 120mL of 1,2, 4-trichlorobenzene was added 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 sub2-3-1. (yield: 42%, MS: [ M+H)] + ＝285)
Sub2-3-1 (15 g,52.5 mmol) and bis (pinacolato) diboron (14.7 g,57.8 mmol) were added to 300mL 1, 4-bisIn 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 12g of sub2-3-2. (yield: 69%, MS: [ M+H) ] + ＝333)
Sub2-3-2 (15 g,45.1 mmol) and Trz50 (22.7 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, the mixture was stirred well, and bis (tri-t-butylphosphine) palladium (0) (0.2 g,0.5 mmol) was then added. After 3 hours of reaction, the reaction mixture was cooled to room temperature, then the organic layer and the aqueous layer were separated, and the organic layer was distilled. Re-dissolving itIn chloroform and washed twice with water. The organic layer was then separated, anhydrous magnesium sulfate was added, stirred and then filtered. The filtrate was distilled under reduced pressure. The concentrated compound was purified by a silica gel column to obtain 20.2g of Compound 1-56_P1 (yield: 69%, MS: [ M+H)] + ＝650)。
Compound 1-56_P1 (15 g,23.1 mmol) and phenylboronic acid (2.9 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, the mixture was stirred well, and bis (tri-t-butylphosphine) palladium (0) (0.1 g,0.2 mmol) was then added. After 4 hours of reaction, the reaction mixture was cooled to room temperature, then the organic layer and the aqueous layer were separated, and the organic layer was distilled. It was redissolved in chloroform and washed twice with water. The organic layer was then separated, anhydrous magnesium sulfate was added, stirred and then filtered. The filtrate was distilled under reduced pressure. The concentrated compound was purified by a silica gel column to obtain 10.5g of compound 1-56 (yield: 66%, MS: [ M+H) ] + ＝692)。
Synthesis examples 1 to 42: preparation of Compounds 1-57
Sub2-3-2 (15 g,45.1 mmol) and Trz51 (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, the mixture was stirred well, and bis (tri-t-butylphosphine) palladium (0) (0.2 g,0.5 mmol) was then added. After 5 hours of reaction, the reaction mixture was cooled to room temperature, then the organic layer and the aqueous layer were separated, and the organic layer was distilled. It was redissolved in chloroform and washed twice with water. The organic layer was then separated, anhydrous magnesium sulfate was added, stirred and then filtered. The filtrate was distilled under reduced pressure. The concentrated compound was purified by a silica gel column to obtain 20.2g of Compound 1-57_P1 (yield: 75%, MS: [ M+H)] + ＝599)。
Compound 1-57_P1 (15 g,25mmol) 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, the mixture was stirred well, and bis (tri-t-butylphosphine) palladium (0) (0.1 g,0.3 mmol) was then added. After 5 hours of reaction, the reaction mixture was cooled to room temperature, then the organic layer and the aqueous layer were separated, and the organic layer was distilled. It was redissolved in chloroform and washed twice with water. The organic layer was then separated, anhydrous magnesium sulfate was added, stirred and then filtered. The filtrate was distilled under reduced pressure. The concentrated compound was purified by a silica gel column to obtain 11.9g of Compound 1-57 (yield: 74%, MS: [ M+H ] ] + ＝641)。
Synthesis examples 1 to 43: preparation of Compounds 1-58
Compounds 1 to 52 (10 g,16 mmol), ptO 2 (1.1 g,4.8 mmol) and D 2 O (80 mL) was added to the vibrating tube, which 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 3.9g of compounds 1 to 55. (yield: 38%, MS: [ M+H)] + ＝649)
Synthesis examples 1 to 44: preparation of Compounds 1-59
(7-chlorodibenzo [ b, d)]Furan-1-yl) boronic acid (15 g,60.9 mmol) and Trz52 (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, the mixture was stirred well, and bis (tri-t-butylphosphine) palladium (0) (0.3 g,0.6 mmol) was then added. After 5 hours of reaction, the reaction was allowed to proceedThe mixture was cooled to room temperature, then the organic layer and the aqueous layer were separated, and the organic layer was distilled. It was redissolved in chloroform and washed twice with water. The organic layer was then separated, anhydrous magnesium sulfate was added, stirred and then filtered. The filtrate was distilled under reduced pressure. The concentrated compound was purified by a silica gel column to obtain 25.2g of Compound 1-59_P1 (yield: 74%, MS: [ M+H) ] + ＝560)。
Compound 1-59_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, the mixture was stirred well, and bis (tri-t-butylphosphine) palladium (0) (0.1 g,0.3 mmol) was then added. After 5 hours of reaction, the reaction mixture was cooled to room temperature, then the organic layer and the aqueous layer were separated, and the organic layer was distilled. It was redissolved in chloroform and washed twice with water. The organic layer was then separated, anhydrous magnesium sulfate was added, stirred and then filtered. The filtrate was distilled under reduced pressure. The concentrated compound was purified by a silica gel column to obtain 11.6g of Compound 1-59 (yield: 72%, MS: [ M+H ]] + ＝602)。
Synthesis examples 1 to 45: preparation of Compounds 1-60
(7-chlorodibenzo [ b, d)]Furan-1-yl) boronic acid (15 g,60.9 mmol) and Trz53 (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, the mixture was stirred well, and bis (tri-t-butylphosphine) palladium (0) (0.3 g,0.6 mmol) was then added. After 3 hours of reaction, the reaction mixture was cooled to room temperature, then the organic layer and the aqueous layer were separated, and the organic layer was distilled. It was redissolved in chloroform and washed twice with water. The organic layer was then separated, anhydrous magnesium sulfate was added, stirred and then filtered. The filtrate was distilled under reduced pressure. Purification of the concentrated compound by silica gel column 25.2g of Compound 1-60_P1 (yield: 74%, MS: [ M+H)] + ＝560)。
Compound 1-60_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, the mixture was stirred well, and bis (tri-t-butylphosphine) palladium (0) (0.1 g,0.3 mmol) was then added. After 4 hours of reaction, the reaction mixture was cooled to room temperature, then the organic layer and the aqueous layer were separated, and the organic layer was distilled. It was redissolved in chloroform and washed twice with water. The organic layer was then separated, anhydrous magnesium sulfate was added, stirred and then filtered. The filtrate was distilled under reduced pressure. The concentrated compound was purified by a silica gel column to obtain 12.1g of compound 1-60 (yield: 75%, MS: [ M+H)] + ＝602)。
Synthesis examples 1 to 46: preparation of Compounds 1-62
(7-chlorodibenzo [ b, d)]Furan-1-yl) boronic acid (15 g,60.9 mmol) and Trz54 (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, the mixture was stirred well, and bis (tri-t-butylphosphine) palladium (0) (0.3 g,0.6 mmol) was then added. After 3 hours of reaction, the reaction mixture was cooled to room temperature, then the organic layer and the aqueous layer were separated, and the organic layer was distilled. It was redissolved in chloroform and washed twice with water. The organic layer was then separated, anhydrous magnesium sulfate was added, stirred and then filtered. The filtrate was distilled under reduced pressure. The concentrated compound was purified by a silica gel column to obtain 21.8g of Compound 1-62_P1 (yield: 74%, MS: [ M+H) ] + ＝484)。
Compound 1-62_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 addedTo the mixture, the mixture was stirred well, and bis (tri-t-butylphosphine) palladium (0) (0.2 g,0.3 mmol) was then added. After 5 hours of reaction, the reaction mixture was cooled to room temperature, then the organic layer and the aqueous layer were separated, and the organic layer was distilled. It was redissolved in chloroform and washed twice with water. The organic layer was then separated, anhydrous magnesium sulfate was added, stirred and then filtered. The filtrate was distilled under reduced pressure. The concentrated compound was purified by a silica gel column to obtain 12.3g of compound 1-62 (yield: 69%, MS: [ M+H ]] + ＝576)。
Synthesis examples 1 to 47: preparation of Compounds 1-64
(7-chlorodibenzo [ b, d)]Furan-1-yl) boronic acid (15 g,60.9 mmol) and Trz56 (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, the mixture was stirred well, and bis (tri-t-butylphosphine) palladium (0) (0.3 g,0.6 mmol) was then added. After 3 hours of reaction, the reaction mixture was cooled to room temperature, then the organic layer and the aqueous layer were separated, and the organic layer was distilled. It was redissolved in chloroform and washed twice with water. The organic layer was then separated, anhydrous magnesium sulfate was added, stirred and then filtered. The filtrate was distilled under reduced pressure. The concentrated compound was purified by a silica gel column to obtain 23.9g of Compound 1-64_P1 (yield: 67%, MS: [ M+H) ] + ＝586)。
Compound 1-64_P1 (15 g,25.6 mmol) and phenanthrene-3-ylboronic acid (6 g,26.9 mmol) are added to 300mL THF and the mixture is stirred and refluxed. Then, potassium carbonate (10.6 g,76.8 mmol) was dissolved in 32mL of water and added to the mixture, the mixture was stirred well, and bis (tri-t-butylphosphine) palladium (0) (0.1 g,0.3 mmol) was then added. After 3 hours of reaction, the reaction mixture was cooled to room temperature, then the organic layer and the aqueous layer were separated, and the organic layer was distilled. It was redissolved in chloroform and washed twice with water. Then separating the organicThe layers were added anhydrous magnesium sulfate, stirred and then filtered. The filtrate was distilled under reduced pressure. The concentrated compound was purified by a silica gel column to obtain 12.3g of Compound 1-64 (yield: 66%, MS: [ M+H)] + ＝728)。
Synthesis examples 1 to 48: preparation of Compounds 1-65
(7-chlorodibenzo [ b, d)]Furan-1-yl) boronic acid (15 g,60.9 mmol) and Trz57 (25.8 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, the mixture was stirred well, and bis (tri-t-butylphosphine) palladium (0) (0.3 g,0.6 mmol) was then added. After 5 hours of reaction, the reaction mixture was cooled to room temperature, then the organic layer and the aqueous layer were separated, and the organic layer was distilled. It was redissolved in chloroform and washed twice with water. The organic layer was then separated, anhydrous magnesium sulfate was added, stirred and then filtered. The filtrate was distilled under reduced pressure. The concentrated compound was purified by a silica gel column to obtain 24.6g of Compound 1-65_P1 (yield: 71%, MS: [ M+H) ] + ＝569)。
Compound 1-65_P1 (15 g,26.4 mmol) and (phenyl-d 5) boronic acid (3.5 g,27.7 mmol) were added to 300mL THF and the mixture was stirred and refluxed. Then, potassium carbonate (10.9 g,79.1 mmol) was dissolved in 33mL of water and added to the mixture, the mixture was stirred well, and bis (tri-t-butylphosphine) palladium (0) (0.1 g,0.3 mmol) was then added. After 5 hours of reaction, the reaction mixture was cooled to room temperature, then the organic layer and the aqueous layer were separated, and the organic layer was distilled. It was redissolved in chloroform and washed twice with water. The organic layer was then separated, anhydrous magnesium sulfate was added, stirred and then filtered. The filtrate was distilled under reduced pressure. The concentrated compound was purified by a silica gel column to obtain 11.7g of compound 1-65 (yield: 72%, MS: [ M+H)] + ＝616)。
Synthesis examples 1 to 49: preparation of Compounds 1-66
(7-chlorodibenzo [ b, d)]Furan-1-yl) boronic acid (15 g,60.9 mmol) and Trz58 (20.6 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, the mixture was stirred well, and bis (tri-t-butylphosphine) palladium (0) (0.3 g,0.6 mmol) was then added. After 3 hours of reaction, the reaction mixture was cooled to room temperature, then the organic layer and the aqueous layer were separated, and the organic layer was distilled. It was redissolved in chloroform and washed twice with water. The organic layer was then separated, anhydrous magnesium sulfate was added, stirred and then filtered. The filtrate was distilled under reduced pressure. The concentrated compound was purified by a silica gel column to obtain 20.2g of Compound 1-66_P1 (yield: 68%, MS: [ M+H) ] + ＝489)。
Compound 1-66_P1 (15 g,30.7 mmol) and naphthalen-2-ylboronic acid (5.5 g,32.2 mmol) are added to 300mL THF and the mixture is stirred and refluxed. Then, potassium carbonate (12.7 g,92 mmol) was dissolved in 38mL of water and added to the mixture, the mixture was stirred well, and bis (tri-t-butylphosphine) palladium (0) (0.2 g,0.3 mmol) was then added. After 5 hours of reaction, the reaction mixture was cooled to room temperature, then the organic layer and the aqueous layer were separated, and the organic layer was distilled. It was redissolved in chloroform and washed twice with water. The organic layer was then separated, anhydrous magnesium sulfate was added, stirred and then filtered. The filtrate was distilled under reduced pressure. The concentrated compound was purified by a silica gel column to obtain 12.6g of Compound 1-66 (yield: 71%, MS: [ M+H ]] + ＝581)。
Synthesis examples 1 to 50: preparation of Compounds 1-67
Trifluoromethanesulfonic anhydride (30.1 g,106.6 mmol) and deuterium oxide (10.7 g,532.8 mmol) are added at 0deg.CAnd 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 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 sub3-1-1. (yield: 40%, MS: [ M+H)] + ＝283)
Sub3-1-1 (15 g,52.9 mmol) and bis (pinacolato) diboron (14.8 g,58.2 mmol) were added to 300mL 1, 4-diboronIn 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 sub3-1-2. (yield: 65%, MS: [ M+H) ] + ＝331)
Sub3-1-2 (15 g,45.4 mmol) and Trz59 (19 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, the mixture was stirred well, and bis (tri-t-butylphosphine) palladium (0) (0.2 g,0.5 mmol) was then added. After 4 hours of reaction, the reaction mixture was cooled toThe organic and aqueous layers were then separated at room temperature, and the organic layer was distilled. It was redissolved in chloroform and washed twice with water. The organic layer was then separated, anhydrous magnesium sulfate was added, stirred and then filtered. The filtrate was distilled under reduced pressure. The concentrated compound was purified by a silica gel column to obtain 17.3g of Compound 1-67_P1 (yield: 73%, MS: [ M+H)] + ＝522)。
Compound 1-67_P1 (15 g,28.7 mmol) and naphthalen-2-ylboronic acid (5.2 g,30.2 mmol) are added to 300mL THF and the mixture is stirred and refluxed. Then, potassium carbonate (11.9 g,86.2 mmol) was dissolved in 36mL of water and added to the mixture, the mixture was stirred well, and bis (tri-t-butylphosphine) palladium (0) (0.1 g,0.3 mmol) was then added. After 4 hours of reaction, the reaction mixture was cooled to room temperature, then the organic layer and the aqueous layer were separated, and the organic layer was distilled. It was redissolved in chloroform and washed twice with water. The organic layer was then separated, anhydrous magnesium sulfate was added, stirred and then filtered. The filtrate was distilled under reduced pressure. The concentrated compound was purified by a silica gel column to obtain 12.5g of Compound 1-67 (yield: 71%, MS: [ M+H) ] + ＝614)。
Synthesis examples 1 to 51: preparation of Compounds 1-68
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 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-7-chlorodibenzo [ b, d ] furan and 1,2, 4-trichlorobenzene, and the mixture was stirred while heating to 140 ℃ and then maintaining the 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 mixture was washed with water,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 6.7g of sub3-2-1. (yield: 44%, MS: [ M+H)] + ＝285)
Sub3-2-1 (15 g,52.5 mmol) and bis (pinacolato) diboron (14.7 g,57.8 mmol) were added to 300mL 1, 4-bisIn 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 sub3-2-2. (yield: 67%, MS: [ M+H) ] + ＝333)
Sub3-2-2 (15 g,45.1 mmol) and Trz60 (22.7 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, the mixture was stirred well, and bis (tri-t-butylphosphine) palladium (0) (0.2 g,0.5 mmol) was then added. After 5 hours of reaction, the reaction mixture was cooled to room temperature, then the organic layer and the aqueous layer were separated, and the organic layer was distilled. It was redissolved in chloroform and washed twice with water. The organic layer was then separated, anhydrous magnesium sulfate was added, stirred and then filtered. The filtrate was distilled under reduced pressure. The concentrated compound was purified by a silica gel column to obtain 19.9g of Compound 1-68_P1 (yield: 68%, MS: [ M+H)] + ＝650)。
Compound 1-68_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, the mixture was stirred well, and bis (tri-t-butylphosphine) palladium (0) (0.1 g,0.2 mmol) was then added. After 3 hours of reaction, the reaction mixture was cooled to room temperature, then the organic layer and the aqueous layer were separated, and the organic layer was distilled. It was redissolved in chloroform and washed twice with water. The organic layer was then separated, anhydrous magnesium sulfate was added, stirred and then filtered. The filtrate was distilled under reduced pressure. The concentrated compound was purified by a silica gel column to obtain 11.6g of compound 1-68 (yield: 73%, MS: [ M+H ] ] + ＝692)。
Synthesis examples 1 to 52: preparation of Compounds 1-69
Compounds 1 to 60 (10 g,16.6 mmol), ptO 2 (1.1 g,5 mmol) and D 2 O (83 ml) was added to the vibrating tube, which 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 69. (yield: 30%, MS: [ M+H)] + ＝626)
Synthesis examples 1 to 53: preparation of Compounds 1-70
Compounds 1 to 62 (10 g,17.4 mmol), ptO 2 (1.2 g,5.2 mmol) and D 2 O (87 ml) was added to the vibrating tube, which 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 3.9g of compounds 1 to 70. (yield: 38%, MS: [ M+H)] + ＝598)
Synthesis examples 1 to 54: preparation of Compounds 1-72
(7-chlorodibenzo [ b, d)]Furan-1-yl) boronic acid (15 g,60.9 mmol) and Trz61 (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, the mixture was stirred well, and bis (tri-t-butylphosphine) palladium (0) (0.3 g,0.6 mmol) was then added. After 3 hours of reaction, the reaction mixture was cooled to room temperature, then the organic layer and the aqueous layer were separated, and the organic layer was distilled. It was redissolved in chloroform and washed twice with water. The organic layer was then separated, anhydrous magnesium sulfate was added, stirred and then filtered. The filtrate was distilled under reduced pressure. The concentrated compound was purified by a silica gel column to obtain 24.5g of Compound 1-72_P1 (yield: 66%, MS: [ M+H) ] + ＝610)。
Compound 1-72_P1 (15 g,24.6 mmol) and phenylboronic acid (3.1 g,25.8 mmol) were added to 300mL THF and the mixture was stirred and refluxed. Then, potassium carbonate (10.2 g,73.8 mmol) was dissolved in 31mL of water and added to the mixture, the mixture was stirred well, and bis (tri-t-butylphosphine) palladium (0) (0.1 g,0.2 mmol) was then added. After 4 hours of reaction, the reaction mixture was cooled to room temperature, then the organic layer and the aqueous layer were separated, and the organic layer was distilled. It was redissolved in chloroform and washed twice with water. The organic layer was then separated, anhydrous magnesium sulfate was added, stirred and then filtered. The filtrate was distilled under reduced pressure. The concentrated compound was purified by a silica gel column to obtain 10.6g of Compound 1-72_P2 (yield: 66%, MS: [ M+H)] + ＝652)。
Compound 1-72_P2 (10 g,15.3 mmol), ptO 2 (1 g,4.6 mmol) and D 2 O (77 ml) was added to the vibrating tube, which 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. Subjecting the extract to MgSO 4 Dried and concentrated, and then the sample was purified by silica gel column chromatography to prepare 4.6g of compounds 1 to 72. (yield: 44%, MS: [ M+H) ] + ＝678)
Synthesis examples 1 to 55: preparation of Compounds 1-73
(6-chlorodibenzo [ b, d)]Furan-1-yl) boronic acid (15 g,60.9 mmol) and Trz45 (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, the mixture was stirred well, and bis (tri-t-butylphosphine) palladium (0) (0.3 g,0.6 mmol) was then added. After 4 hours of reaction, the reaction mixture was cooled to room temperature, then the organic layer and the aqueous layer were separated, and the organic layer was distilled. It was redissolved in chloroform and washed twice with water. The organic layer was then separated, anhydrous magnesium sulfate was added, stirred and then filtered. The filtrate was distilled under reduced pressure. The concentrated compound was purified by a silica gel column to obtain 23.4g of Compound 1-73_P1 (yield: 72%, MS: [ M+H)] + ＝534)。
Compounds 1-73_P1 (15 g,28.1 mmol) and [1,1' -biphenyl]4-Ylboronic acid (5.8 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, the mixture was stirred well, and bis (tri-t-butylphosphine) palladium (0) (0.1 g,0.3 mmol) was then added. After 4 hours of reaction, the reaction mixture was cooled to room temperature, then the organic layer and the aqueous layer were separated, and the organic layer was distilled. It was redissolved in chloroform and washed twice with water. The organic layer was then separated, anhydrous magnesium sulfate was added, stirred and then filtered. The filtrate was distilled under reduced pressure. The concentrated compound was purified by a silica gel column to obtain 13.4g of Compound 1-73 (yield: 73%, MS: [ M+H ] ] + ＝652)。
Synthesis examples 1 to 56: preparation of Compounds 1-74
(6-chlorodibenzo [ b, d)]Furan-1-yl) boronic acid (15 g,60.9 mmol) and Trz47 (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, the mixture was stirred well, and bis (tri-t-butylphosphine) palladium (0) (0.3 g,0.6 mmol) was then added. After 5 hours of reaction, the reaction mixture was cooled to room temperature, then the organic layer and the aqueous layer were separated, and the organic layer was distilled. It was redissolved in chloroform and washed twice with water. The organic layer was then separated, anhydrous magnesium sulfate was added, stirred and then filtered. The filtrate was distilled under reduced pressure. The concentrated compound was purified by a silica gel column to obtain 17.4g of Compound 1-74_P1 (yield: 66%, MS: [ M+H)] + ＝434)。
Compound 1-74_P1 (15 g,34.6 mmol) and phenanthrene-2-ylboronic acid (8.1 g,36.3 mmol) are added to 300mL of 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, the mixture was stirred well, and bis (tri-t-butylphosphine) palladium (0) (0.2 g,0.3 mmol) was then added. After 3 hours of reaction, the reaction mixture was cooled to room temperature, then the organic layer and the aqueous layer were separated, and the organic layer was distilled. It was redissolved in chloroform and washed twice with water. The organic layer was then separated, anhydrous magnesium sulfate was added, stirred and then filtered. The filtrate was distilled under reduced pressure. The concentrated compound was purified by a silica gel column to obtain 13.3g of Compound 1-74 (yield: 67%, MS: [ M+H) ] + ＝576)。
Synthesis examples 1 to 57: preparation of Compounds 1-76
(6-chlorodibenzo [ b, d)]Furan-1-yl) boronic acid (15 g,60.9 mmol) and Trz63 (29.7 g,63.9 mmol) were added to 300mL THF and the mixture was admixedThe 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, the mixture was stirred well, and bis (tri-t-butylphosphine) palladium (0) (0.3 g,0.6 mmol) was then added. After 5 hours of reaction, the reaction mixture was cooled to room temperature, then the organic layer and the aqueous layer were separated, and the organic layer was distilled. It was redissolved in chloroform and washed twice with water. The organic layer was then separated, anhydrous magnesium sulfate was added, stirred and then filtered. The filtrate was distilled under reduced pressure. The concentrated compound was purified by a silica gel column to obtain 23.9g of Compound 1-76_P1 (yield: 67%, MS: [ M+H)] + ＝586)。
Compound 1-76_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 refluxed. Then, potassium carbonate (10.6 g,76.8 mmol) was dissolved in 32mL of water and added to the mixture, the mixture was stirred well, and bis (tri-t-butylphosphine) palladium (0) (0.1 g,0.3 mmol) was then added. After 5 hours of reaction, the reaction mixture was cooled to room temperature, then the organic layer and the aqueous layer were separated, and the organic layer was distilled. It was redissolved in chloroform and washed twice with water. The organic layer was then separated, anhydrous magnesium sulfate was added, stirred and then filtered. The filtrate was distilled under reduced pressure. The concentrated compound was purified by a silica gel column to obtain 12.8g of Compound 1-76 (yield: 74%, MS: [ M+H) ] + ＝678)。
Synthesis examples 1 to 58: preparation of Compounds 1-77
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 heating the mixture to 140 DEG CThe temperature was then maintained while stirring. 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 sub4-1-1. (yield: 45%, MS: [ M+H ]] + ＝283)
Sub4-1-1 (15 g,52.9 mmol) and bis (pinacolato) diboron (14.8 g,58.2 mmol) were added to 300mL 1, 4-diboronIn 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. 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 sub4-1-2. (yield: 75%, MS: [ M+H) ] + ＝331)
Sub4-1-2 (15 g,45.4 mmol) and Trz64 (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, the mixture was stirred well, and bis (tri-t-butylphosphine) palladium (0) (0.2 g,0.5 mmol) was then added. After 5 hours of reaction, the reaction mixture was cooled to room temperature, then the organic layer and the aqueous layer were separated, and the organic layer was distilled. It was redissolved in chloroform and washed twice with water. The organic layer was then separated, anhydrous magnesium sulfate was added, stirred and then filtered. The filtrate was distilled under reduced pressure. The concentrated compound was purified by a silica gel column to obtain 20.4g of Compound 1-77_P1 (yield: 70%, MS:[M+H] + ＝643)。
Compound 1-77_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 was stirred and refluxed. Then, potassium carbonate (9.7 g,70 mmol) was dissolved in 29mL of water and added to the mixture, the mixture was stirred well, and bis (tri-t-butylphosphine) palladium (0) (0.1 g,0.2 mmol) was then added. After 4 hours of reaction, the reaction mixture was cooled to room temperature, then the organic layer and the aqueous layer were separated, and the organic layer was distilled. It was redissolved in chloroform and washed twice with water. The organic layer was then separated, anhydrous magnesium sulfate was added, stirred and then filtered. The filtrate was distilled under reduced pressure. The concentrated compound was purified by a silica gel column to obtain 11.7g of Compound 1-77 (yield: 73%, MS: [ M+H) ] + ＝690)。
Synthesis examples 1 to 59: preparation of Compounds 1-78
Sub4-1-2 (15 g,45.4 mmol) and Trz7 (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, the mixture was stirred well, and bis (tri-t-butylphosphine) palladium (0) (0.2 g,0.5 mmol) was then added. After 3 hours of reaction, the reaction mixture was cooled to room temperature, then the organic layer and the aqueous layer were separated, and the organic layer was distilled. It was redissolved in chloroform and washed twice with water. The organic layer was then separated, anhydrous magnesium sulfate was added, stirred and then filtered. The filtrate was distilled under reduced pressure. The concentrated compound was purified by a silica gel column to obtain 18g of Compound 1-78_P1 (yield: 65%, MS: [ M+H)] + ＝612)。
Compound 1-78_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 was stirred and refluxed. Then, potassium carbonate (10.2 g,73.5 mmol) was dissolved in 30mL of water and added to the mixture, the mixture was stirred well, and then bis (tri-t) was addedButylphosphine) palladium (0) (0.1 g,0.2 mmol). After 3 hours of reaction, the reaction mixture was cooled to room temperature, then the organic layer and the aqueous layer were separated, and the organic layer was distilled. It was redissolved in chloroform and washed twice with water. The organic layer was then separated, anhydrous magnesium sulfate was added, stirred and then filtered. The filtrate was distilled under reduced pressure. The concentrated compound was purified by a silica gel column to obtain 11.1g of Compound 1-78 (yield: 69%, MS: [ M+H) ] + ＝659)。
Synthesis examples 1 to 60: preparation of Compounds 1-81
Sub4-3-2 (15 g,45.1 mmol) and Trz66 (18.9 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, the mixture was stirred well, and bis (tri-t-butylphosphine) palladium (0) (0.2 g,0.5 mmol) was then added. After 3 hours of reaction, the reaction mixture was cooled to room temperature, then the organic layer and the aqueous layer were separated, and the organic layer was distilled. It was redissolved in chloroform and washed twice with water. The organic layer was then separated, anhydrous magnesium sulfate was added, stirred and then filtered. The filtrate was distilled under reduced pressure. The concentrated compound was purified by a silica gel column to obtain 19g of Compound 1-81_P1 (yield: 74%, MS: [ M+H)] + ＝569)。
Compound 1-81_P1 (15 g,26.4 mmol) and naphthalen-2-ylboronic acid (4.8 g,27.7 mmol) are added to 300mL THF and the mixture is stirred and refluxed. Then, potassium carbonate (10.9 g,79.1 mmol) was dissolved in 33mL of water and added to the mixture, the mixture was stirred well, and bis (tri-t-butylphosphine) palladium (0) (0.1 g,0.3 mmol) was then added. After 3 hours of reaction, the reaction mixture was cooled to room temperature, then the organic layer and the aqueous layer were separated, and the organic layer was distilled. It was redissolved in chloroform and washed twice with water. The organic layer was then separated, anhydrous magnesium sulfate was added, stirred and then filtered. The filtrate was distilled under reduced pressure. Through silica gel column pair The concentrated compound was purified to obtain 12.5g of Compound 1-81 (yield: 72%, MS: [ M+H)] + ＝661)。
Synthesis examples 1 to 61: preparation of Compounds 1-83
(4-chlorodibenzo [ b, d)]Furan-1-yl) boronic acid (15 g,60.9 mmol) and Trz54 (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, the mixture was stirred well, and bis (tri-t-butylphosphine) palladium (0) (0.3 g,0.6 mmol) was then added. After 5 hours of reaction, the reaction mixture was cooled to room temperature, then the organic layer and the aqueous layer were separated, and the organic layer was distilled. It was redissolved in chloroform and washed twice with water. The organic layer was then separated, anhydrous magnesium sulfate was added, stirred and then filtered. The filtrate was distilled under reduced pressure. The concentrated compound was purified by a silica gel column to obtain 19.1g of Compound 1-83_P1 (yield: 65%, MS: [ M+H)] + ＝484)。
Compound 1-83_P1 (15 g,31 mmol) and phenanthren-9-ylboronic acid (7.2 g,32.6 mmol) are added to 300mL THF and the mixture is stirred and refluxed. Then, potassium carbonate (12.9 g,93.1 mmol) was dissolved in 39mL of water and added to the mixture, the mixture was stirred well, and bis (tri-t-butylphosphine) palladium (0) (0.2 g,0.3 mmol) was then added. After 5 hours of reaction, the reaction mixture was cooled to room temperature, then the organic layer and the aqueous layer were separated, and the organic layer was distilled. It was redissolved in chloroform and washed twice with water. The organic layer was then separated, anhydrous magnesium sulfate was added, stirred and then filtered. The filtrate was distilled under reduced pressure. The concentrated compound was purified by a silica gel column to obtain 14.2g of compound 1-83 (yield: 73%, MS: [ M+H ] ] + ＝626)。
Synthesis examples 1 to 62: preparation of Compounds 1-84
Compound 1-83_P1 (15 g,31 mmol) and fluoranthen-3-ylboronic acid (8 g,32.6 mmol) are added to 300mL THF and the mixture is stirred and refluxed. Then, potassium carbonate (12.9 g,93.1 mmol) was dissolved in 39mL of water and added to the mixture, the mixture was stirred well, and bis (tri-t-butylphosphine) palladium (0) (0.2 g,0.3 mmol) was then added. After 5 hours of reaction, the reaction mixture was cooled to room temperature, then the organic layer and the aqueous layer were separated, and the organic layer was distilled. It was redissolved in chloroform and washed twice with water. The organic layer was then separated, anhydrous magnesium sulfate was added, stirred and then filtered. The filtrate was distilled under reduced pressure. The concentrated compound was purified by a silica gel column to obtain 13.3g of Compound 1-84 (yield: 66%, MS: [ M+H)] + ＝650)。
Synthesis examples 1 to 63: preparation of Compounds 1-88
(4-chlorodibenzo [ b, d)]Furan-1-yl) boronic acid (15 g,60.9 mmol) and Trz69 (28 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, the mixture was stirred well, and bis (tri-t-butylphosphine) palladium (0) (0.3 g,0.6 mmol) was then added. After 3 hours of reaction, the reaction mixture was cooled to room temperature, then the organic layer and the aqueous layer were separated, and the organic layer was distilled. It was redissolved in chloroform and washed twice with water. The organic layer was then separated, anhydrous magnesium sulfate was added, stirred and then filtered. The filtrate was distilled under reduced pressure. The concentrated compound was purified by a silica gel column to obtain 24.2g of Compound 1-88_P1 (yield: 71%, MS: [ M+H) ] + ＝560)。
Compound 1-88_P1 (15 g,26.8 mmol) and naphthalen-2-ylboronic acid (4.8 g,28.1 mmol) are added to 300mL THF and the mixture is stirred and refluxed. Then, potassium carbonate (11.1 g,80.3 mmol) was dissolved in 33mL of water, andto the mixture was added, the mixture was stirred well, and bis (tri-t-butylphosphine) palladium (0) (0.1 g,0.3 mmol) was then added. After 5 hours of reaction, the reaction mixture was cooled to room temperature, then the organic layer and the aqueous layer were separated, and the organic layer was distilled. It was redissolved in chloroform and washed twice with water. The organic layer was then separated, anhydrous magnesium sulfate was added, stirred and then filtered. The filtrate was distilled under reduced pressure. The concentrated compound was purified by a silica gel column to obtain 11.5g of compounds 1-88 (yield: 66%, MS: [ M+H ]] + ＝652)。
Synthesis examples 1 to 64: preparation of Compounds 1-90
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 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 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 sub5-1-1. (yield: 43%, MS: [ M+H)] + ＝283)
Sub5-1-1 (15 g,52.9 mmol) and bis (pinacolato) diboron (14.8 g,58.2 mmol) were added to 300mL 1, 4-diboronIn 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 sufficientlyAfter stirring, bis (dibenzylideneacetone) palladium (0) (0.9 g,1.6 mmol) and tricyclohexylphosphine (0.9 g,3.2 mmol) were added. 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 10.8g of sub5-1-2. (yield: 62%, MS: [ M+H) ] + ＝331)
Sub5-1-2 (15 g,45.4 mmol) and Trz71 (20.2 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, the mixture was stirred well, and bis (tri-t-butylphosphine) palladium (0) (0.2 g,0.5 mmol) was then added. After 4 hours of reaction, the reaction mixture was cooled to room temperature, then the organic layer and the aqueous layer were separated, and the organic layer was distilled. It was redissolved in chloroform and washed twice with water. The organic layer was then separated, anhydrous magnesium sulfate was added, stirred and then filtered. The filtrate was distilled under reduced pressure. The concentrated compound was purified by a silica gel column to obtain 19.9g of Compound 1-90_P1 (yield: 74%, MS: [ M+H)] + ＝594)。
Compound 1-90_P1 (15 g,25.3 mmol) and phenylboronic acid (3.2 g,26.6 mmol) are added to 300mL of THF and the mixture is stirred and refluxed. Then, potassium carbonate (10.5 g,75.9 mmol) was dissolved in 31mL of water and added to the mixture, the mixture was stirred well, and bis (tri-t-butylphosphine) palladium (0) (0.1 g,0.3 mmol) was then added. After 3 hours of reaction, the reaction mixture was cooled to room temperature, then the organic layer and the aqueous layer were separated, and the organic layer was distilled. It was redissolved in chloroform and washed twice with water. The organic layer was then separated, anhydrous magnesium sulfate was added, stirred and then filtered. The filtrate was distilled under reduced pressure. The concentrated compound was purified by a silica gel column to obtain 11.7g of compound 1-90 (yield: 73%, MS: [ M+H ] ] + ＝635)。
Synthesis examples 1 to 65: preparation of Compounds 1-92
Sub5-2-2 (15 g,45.1 mmol) and Trz72 (21.2 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, the mixture was stirred well, and bis (tri-t-butylphosphine) palladium (0) (0.2 g,0.5 mmol) was then added. After 3 hours of reaction, the reaction mixture was cooled to room temperature, then the organic layer and the aqueous layer were separated, and the organic layer was distilled. It was redissolved in chloroform and washed twice with water. The organic layer was then separated, anhydrous magnesium sulfate was added, stirred and then filtered. The filtrate was distilled under reduced pressure. The concentrated compound was purified by a silica gel column to obtain 18.4g of Compound 1-92_P1. (yield: 71%, MS: [ M+H)] + ＝574)
Compound 1-92_P1 (15 g,26.1 mmol) and naphthalen-2-ylboronic acid (4.7 g,27.4 mmol) are added to 300mL THF and the mixture is stirred and refluxed. Then, potassium carbonate (10.8 g,78.4 mmol) was dissolved in 32mL of water and added to the mixture, the mixture was stirred well, and bis (tri-t-butylphosphine) palladium (0) (0.1 g,0.3 mmol) was then added. After 5 hours of reaction, the reaction mixture was cooled to room temperature, then the organic layer and the aqueous layer were separated, and the organic layer was distilled. It was redissolved in chloroform and washed twice with water. The organic layer was then separated, anhydrous magnesium sulfate was added, stirred and then filtered. The filtrate was distilled under reduced pressure. The concentrated compound was purified by a silica gel column to obtain 11.6g of compounds 1 to 92. (yield: 67%, MS: [ M+H) ] + ＝666)
Synthesis examples 1 to 66: preparation of Compounds 1-93
Trifluoromethanesulfonic anhydride (90.2 g,319.7 mmol) and deuterium oxide (32 g,1598.4 mmol) are added at 0deg.C and stirred5 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 18 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 5.8g of sub5-3-1. (yield: 38%, MS: [ M+H)] + ＝287)
Sub5-3-1 (15 g,52.2 mmol) and bis (pinacolato) diboron (14.6 g,57.4 mmol) were added to 300mL 1, 4-diboronIn an alkane, and the mixture was stirred under reflux. Then, potassium acetate (7.7 g,78.2 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,3.1 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 12.9g of sub5-3-2. (yield: 74%, MS: [ M+H) ] + ＝335)
Sub5-3-2 (15 g,44.8 mmol) and Trz58 (15.7 g,47.1 mmol) were added to 300mL THF and the mixture was stirred and refluxed. Then, potassium carbonate (18.6 g,134.5 mmol) was dissolved in 56mL of water and added to the mixture, the mixture was stirred well, and bis (tri-t-butylphosphine) palladium (0) (0.2 g,0.4 mmol) was then added. After 4 hours of reaction, the reaction mixture was cooled to room temperatureThe organic and aqueous layers were then separated and the organic layer was distilled. It was redissolved in chloroform and washed twice with water. The organic layer was then separated, anhydrous magnesium sulfate was added, stirred and then filtered. The filtrate was distilled under reduced pressure. The concentrated compound was purified by a silica gel column to give 16.2g of compound 1-93_P1. (yield: 73%, MS: [ M+H)] + ＝495)
Compound 1-93_P1 (15 g,30.3 mmol) and fluoranthen-3-ylboronic acid (7.8 g,31.8 mmol) are added to 300mL THF and the mixture is stirred and refluxed. Then, potassium carbonate (12.6 g,90.9 mmol) was dissolved in 38mL of water and added to the mixture, the mixture was stirred well, and bis (tri-t-butylphosphine) palladium (0) (0.2 g,0.3 mmol) was then added. After 5 hours of reaction, the reaction mixture was cooled to room temperature, then the organic layer and the aqueous layer were separated, and the organic layer was distilled. It was redissolved in chloroform and washed twice with water. The organic layer was then separated, anhydrous magnesium sulfate was added, stirred and then filtered. The filtrate was distilled under reduced pressure. The concentrated compound was purified by a silica gel column to obtain 15g of compounds 1 to 93. (yield: 75%, MS: [ M+H) ] + ＝661)
Synthesis examples 1 to 67: preparation of Compounds 1-94
Compounds 1 to 83 (10 g,16 mmol), ptO 2 (1.1 g,4.8 mmol) and D 2 O (80 mL) was added to the vibrating tube, which 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 3.9g of compounds 1 to 94. (yield: 38%, MS: [ M+H)] + ＝650)
Synthesis examples 1 to 68: preparation of Compounds 1-95
(3-chlorodibenzo [ b, d)]Furan-1-yl) boronic acid (15 g,60.9 mmol) and Trz47 (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, the mixture was stirred well, and bis (tri-t-butylphosphine) palladium (0) (0.3 g,0.6 mmol) was then added. After 4 hours of reaction, the reaction mixture was cooled to room temperature, then the organic layer and the aqueous layer were separated, and the organic layer was distilled. It was redissolved in chloroform and washed twice with water. The organic layer was then separated, anhydrous magnesium sulfate was added, stirred and then filtered. The filtrate was distilled under reduced pressure. The concentrated compound was purified by a silica gel column to obtain 19g of compound 1-95_P1. (yield: 72%, MS: [ M+H) ] + ＝434)
Compound 1-95_P1 (15 g,34.6 mmol) and phenanthrene-3-ylboronic acid (8.1 g,36.3 mmol) are added to 300mL of 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, the mixture was stirred well, and bis (tri-t-butylphosphine) palladium (0) (0.2 g,0.3 mmol) was then added. After 5 hours of reaction, the reaction mixture was cooled to room temperature, then the organic layer and the aqueous layer were separated, and the organic layer was distilled. It was redissolved in chloroform and washed twice with water. The organic layer was then separated, anhydrous magnesium sulfate was added, stirred and then filtered. The filtrate was distilled under reduced pressure. The concentrated compound was purified by a silica gel column to obtain 14.1g of compounds 1 to 95. (yield: 71%, MS: [ M+H)] + ＝576)
Synthesis examples 1 to 69: preparation of Compounds 1-98
(3-chlorodibenzo [ b, d)]Furan-1-yl) boronic acid (15 g,60.9 mmol) and Trz73 (33.2 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 mixtureThe mixture was stirred well, and bis (tri-t-butylphosphine) palladium (0) (0.3 g,0.6 mmol) was then added. After 4 hours of reaction, the reaction mixture was cooled to room temperature, then the organic layer and the aqueous layer were separated, and the organic layer was distilled. It was redissolved in chloroform and washed twice with water. The organic layer was then separated, anhydrous magnesium sulfate was added, stirred and then filtered. The filtrate was distilled under reduced pressure. The concentrated compound was purified by a silica gel column to obtain 29.6g of compound 1-98_P1. (yield: 71%, MS: [ M+H) ] + ＝686)
Compound 1-98_P1 (15 g,21.9 mmol) and phenylboronic acid (2.8 g,23 mmol) were added to 300mL THF and the mixture was stirred and refluxed. Then, potassium carbonate (9.1 g,65.6 mmol) was dissolved in 27mL of water and added to the mixture, the mixture was stirred well, and bis (tri-t-butylphosphine) palladium (0) (0.1 g,0.2 mmol) was then added. After 3 hours of reaction, the reaction mixture was cooled to room temperature, then the organic layer and the aqueous layer were separated, and the organic layer was distilled. It was redissolved in chloroform and washed twice with water. The organic layer was then separated, anhydrous magnesium sulfate was added, stirred and then filtered. The filtrate was distilled under reduced pressure. The concentrated compound was purified by a silica gel column to obtain 11.3g of compounds 1 to 98. (yield: 68%, MS: [ M+H)] + ＝758)
Synthesis examples 1 to 70: preparation of Compounds 1-101
(3-chlorodibenzo [ b, d)]Furan-1-yl) boronic acid (15 g,60.9 mmol) and Trz76 (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, the mixture was stirred well, and bis (tri-t-butylphosphine) palladium (0) (0.3 g,0.6 mmol) was then added. After 5 hours of reaction, the reaction mixture was cooled to room temperature, then the organic layer and the aqueous layer were separated, and the organic layer was distilled. It was redissolved in chloroform and washed twice with water. Then the organic layer was separated and anhydrous was added Magnesium sulfate, stirred and then filtered. The filtrate was distilled under reduced pressure. The concentrated compound was purified by a silica gel column to obtain 25.5g of compound 1-101_P1. (yield: 66%, MS: [ M+H)] + ＝636)
Compound 1-101_P1 (15 g,23.6 mmol) and phenylboronic acid (3 g,24.8 mmol) were added to 300mL THF and the mixture was stirred and refluxed. Then, potassium carbonate (9.8 g,70.7 mmol) was dissolved in 29mL of water and added to the mixture, the mixture was stirred well, and bis (tri-t-butylphosphine) palladium (0) (0.1 g,0.2 mmol) was then added. After 4 hours of reaction, the reaction mixture was cooled to room temperature, then the organic layer and the aqueous layer were separated, and the organic layer was distilled. It was redissolved in chloroform and washed twice with water. The organic layer was then separated, anhydrous magnesium sulfate was added, stirred and then filtered. The filtrate was distilled under reduced pressure. The concentrated compound was purified by a silica gel column to obtain 10.7g of compounds 1 to 101. (yield: 67%, MS: [ M+H)] + ＝678)
Synthesis examples 1 to 71: preparation of Compounds 1-102
(3-chlorodibenzo [ b, d)]Furan-1-yl) boronic acid (15 g,60.9 mmol) and Trz77 (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, the mixture was stirred well, and bis (tri-t-butylphosphine) palladium (0) (0.3 g,0.6 mmol) was then added. After 5 hours of reaction, the reaction mixture was cooled to room temperature, then the organic layer and the aqueous layer were separated, and the organic layer was distilled. It was redissolved in chloroform and washed twice with water. The organic layer was then separated, anhydrous magnesium sulfate was added, stirred and then filtered. The filtrate was distilled under reduced pressure. The concentrated compound was purified by a silica gel column to obtain 26.3g of compound 1-102_P1. (yield: 68%, MS: [ M+H) ] + ＝636)
Compound 1-102_P1 (15 g,23.6 mmol) and phenylboronic acid (3 g,24.8 mmol) were addedTo 300mL THF and the mixture was stirred and refluxed. Then, potassium carbonate (9.8 g,70.7 mmol) was dissolved in 29mL of water and added to the mixture, the mixture was stirred well, and bis (tri-t-butylphosphine) palladium (0) (0.1 g,0.2 mmol) was then added. After 4 hours of reaction, the reaction mixture was cooled to room temperature, then the organic layer and the aqueous layer were separated, and the organic layer was distilled. It was redissolved in chloroform and washed twice with water. The organic layer was then separated, anhydrous magnesium sulfate was added, stirred and then filtered. The filtrate was distilled under reduced pressure. The concentrated compound was purified by a silica gel column to obtain 10.5g of compounds 1 to 102. (yield: 66%, MS: [ M+H)] + ＝678)
Synthesis examples 1 to 72: preparation of Compounds 1-104
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-3-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-3-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 4 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 sub6-1-1. (yield: 40%, MS: [ M+H)] + ＝283)
Sub6-1-1 (15 g,52.9 mmol) and bis (pinacolato) diboron (14.8 g,58.2 mmol) were added to 300mL 1, 4-diboronIn the alkyl group, the alkyl group is a hydroxyl group,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. 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 sub6-1-2. (yield: 56%, MS: [ M+H) ] + ＝331)/>
Sub6-1-2 (15 g,45.4 mmol) and Trz79 (27.3 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, the mixture was stirred well, and bis (tri-t-butylphosphine) palladium (0) (0.2 g,0.5 mmol) was then added. After 5 hours of reaction, the reaction mixture was cooled to room temperature, then the organic layer and the aqueous layer were separated, and the organic layer was distilled. It was redissolved in chloroform and washed twice with water. The organic layer was then separated, anhydrous magnesium sulfate was added, stirred and then filtered. The filtrate was distilled under reduced pressure. The concentrated compound was purified by a silica gel column to obtain 21.8g of compound 1-104_P1. (yield: 69%, MS: [ M+H)] + ＝698)
Compound 1-104_P1 (15 g,21.5 mmol) and phenylboronic acid (2.8 g,22.6 mmol) were added to 300mL of THF and the mixture was stirred and refluxed. Then, potassium carbonate (8.9 g,64.5 mmol) was dissolved in 27mL of water and added to the mixture, the mixture was stirred well, and bis (tri-t-butylphosphine) palladium (0) (0.1 g,0.2 mmol) was then added. After 3 hours of reaction, the reaction mixture was cooled to room temperature, then the organic layer and the aqueous layer were separated, and the organic layer was distilled. It was redissolved in chloroform and washed twice with water. The organic layer was then separated, anhydrous magnesium sulfate was added, stirred and then filtered. The filtrate was distilled under reduced pressure. The concentrated compound was purified by a silica gel column to obtain 11.6g of Compound 1- 104. (yield: 73%, MS: [ M+H)] + ＝739)
Synthesis examples 1 to 73: preparation of Compounds 1-106
Trifluoromethanesulfonic anhydride (75.2 g,266.4 mmol) and deuterium oxide (26.7 g,1332 mmol) were added at 0℃and stirred for 5 hours to prepare a solution. 1-bromo-3-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-3-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 12 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 sub6-3-1. (yield: 37%, MS: [ M+H)] + ＝286)
Sub6-3-1 (15 g,52.3 mmol) and bis (pinacolato) diboron (14.6 g,57.6 mmol) were added to 300mL 1, 4-diboronIn an alkane, and the mixture was stirred under reflux. Then, potassium acetate (7.7 g,78.5 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,3.1 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. Purification of the concentrated compound by silica gel column chromatography To prepare 12g of sub6-3-2. (yield: 69%, MS: [ M+H)] + ＝334)
Sub6-3-2 (15 g,45 mmol) and Trz81 (17.4 g,47.2 mmol) were added to 300mL THF and the mixture was stirred and refluxed. Then, potassium carbonate (18.6 g,134.9 mmol) was dissolved in 56mL of water and added to the mixture, the mixture was stirred well, and bis (tri-t-butylphosphine) palladium (0) (0.2 g,0.4 mmol) was then added. After 4 hours of reaction, the reaction mixture was cooled to room temperature, then the organic layer and the aqueous layer were separated, and the organic layer was distilled. It was redissolved in chloroform and washed twice with water. The organic layer was then separated, anhydrous magnesium sulfate was added, stirred and then filtered. The filtrate was distilled under reduced pressure. The concentrated compound was purified by a silica gel column to obtain 17.2g of compound 1-106_P1. (yield: 71%, MS: [ M+H)] + ＝539)
Compound 1-106_P1 (15 g,27.8 mmol) and naphthalen-2-ylboronic acid (5 g,29.2 mmol) are added to 300mL THF and the mixture is stirred and refluxed. Then, potassium carbonate (11.5 g,83.5 mmol) was dissolved in 35mL of water and added to the mixture, the mixture was stirred well, and bis (tri-t-butylphosphine) palladium (0) (0.1 g,0.3 mmol) was then added. After 5 hours of reaction, the reaction mixture was cooled to room temperature, then the organic layer and the aqueous layer were separated, and the organic layer was distilled. It was redissolved in chloroform and washed twice with water. The organic layer was then separated, anhydrous magnesium sulfate was added, stirred and then filtered. The filtrate was distilled under reduced pressure. The concentrated compound was purified by a silica gel column to obtain 12.3g of compounds 1 to 106. (yield: 70%, MS: [ M+H ] ] + ＝631)
Synthesis examples 1 to 74: preparation of Compounds 1-107
(3-chlorodibenzo [ b, d)]Furan-1-yl) boronic acid (15 g,60.9 mmol) and Trz52 (25.2 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 thoroughly stirred, and bis (tri-t-butylphosphine) palladium (0) (0.3 g,0.6 mmol) was then added. After 5 hours of reaction, the reaction mixture was cooled to room temperature, then the organic layer and the aqueous layer were separated, and the organic layer was distilled. It was redissolved in chloroform and washed twice with water. The organic layer was then separated, anhydrous magnesium sulfate was added, stirred and then filtered. The filtrate was distilled under reduced pressure. The concentrated compound was purified by a silica gel column to obtain 22.8g of compound 1-107_P1. (yield: 67%, MS: [ M+H)] + ＝560)
Compound 1-107_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, the mixture was stirred well, and bis (tri-t-butylphosphine) palladium (0) (0.1 g,0.3 mmol) was then added. After 5 hours of reaction, the reaction mixture was cooled to room temperature, then the organic layer and the aqueous layer were separated, and the organic layer was distilled. It was redissolved in chloroform and washed twice with water. The organic layer was then separated, anhydrous magnesium sulfate was added, stirred and then filtered. The filtrate was distilled under reduced pressure. The concentrated compound was purified by a silica gel column to obtain 10.9g of compound 1-107_P2. (yield: 68%, MS: [ M+H) ] + ＝602)
Compound 1-107_P2 (10 g,16.6 mmol), ptO 2 (1.1 g,5 mmol) and D 2 O (83 ml) was added to the vibrating tube, which 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 107. (yield: 39%, MS: [ M+H)] + ＝626)
Synthesis examples 1 to 75: preparation of Compounds 1-109
(3-chlorodibenzo [ b, d)]Furan-1-yl) boronAcid (15 g,60.9 mmol) and Trz82 (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, the mixture was stirred well, and bis (tri-t-butylphosphine) palladium (0) (0.3 g,0.6 mmol) was then added. After 5 hours of reaction, the reaction mixture was cooled to room temperature, then the organic layer and the aqueous layer were separated, and the organic layer was distilled. It was redissolved in chloroform and washed twice with water. The organic layer was then separated, anhydrous magnesium sulfate was added, stirred and then filtered. The filtrate was distilled under reduced pressure. The concentrated compound was purified by a silica gel column to obtain 25.3g of compound 1-109_P1. (yield: 71%, MS: [ M+H) ] + ＝586)
Compound 1-109_P1 (15 g,25.6 mmol) and phenylboronic acid (3.3 g,26.9 mmol) were 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, the mixture was stirred well, and bis (tri-t-butylphosphine) palladium (0) (0.1 g,0.3 mmol) was then added. After 4 hours of reaction, the reaction mixture was cooled to room temperature, then the organic layer and the aqueous layer were separated, and the organic layer was distilled. It was redissolved in chloroform and washed twice with water. The organic layer was then separated, anhydrous magnesium sulfate was added, stirred and then filtered. The filtrate was distilled under reduced pressure. The concentrated compound was purified by a silica gel column to obtain 12g of compound 1-109_P2. (yield: 75%, MS: [ M+H)] + ＝628)
Compound 1-109_P2 (10 g,15.9 mmol), ptO 2 (1.1 g,4.8 mmol) and D 2 O (80 mL) was added to the vibrating tube, which 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 109. (yield: 39%, MS: [ M+H) ] + ＝653)
Synthesis examples 1 to 76: preparation of Compounds 1-110
(2-chlorodibenzo [ b, d)]Furan-1-yl) boronic acid (15 g,60.9 mmol) and Trz83 (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, the mixture was stirred well, and bis (tri-t-butylphosphine) palladium (0) (0.3 g,0.6 mmol) was then added. After 5 hours of reaction, the reaction mixture was cooled to room temperature, then the organic layer and the aqueous layer were separated, and the organic layer was distilled. It was redissolved in chloroform and washed twice with water. The organic layer was then separated, anhydrous magnesium sulfate was added, stirred and then filtered. The filtrate was distilled under reduced pressure. The concentrated compound was purified by a silica gel column to obtain 24.8g of compound 1-110_P1. (yield: 67%, MS: [ M+H)] + ＝610)
Compound 1-110_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, the mixture was stirred well, and bis (tri-t-butylphosphine) palladium (0) (0.1 g,0.2 mmol) was then added. After 3 hours of reaction, the reaction mixture was cooled to room temperature, then the organic layer and the aqueous layer were separated, and the organic layer was distilled. It was redissolved in chloroform and washed twice with water. The organic layer was then separated, anhydrous magnesium sulfate was added, stirred and then filtered. The filtrate was distilled under reduced pressure. The concentrated compound was purified by a silica gel column to obtain 12.1g of compounds 1 to 110. (yield: 70%, MS: [ M+H ] ] + ＝702)
Synthesis examples 1 to 77: preparation of Compounds 1-111
(2-chlorodibenzo [ b, d)]Furan-1-yl) boronic acid (15 g,60.9 mmol) and Trz84 (23.5 g,63.9 mmol) were added to 300mL THF and the mixture was stirred and refluxed. ThenPotassium carbonate (25.2 g,182.6 mmol) was dissolved in 76mL of water and added to the mixture, the mixture was stirred well, and bis (tri-t-butylphosphine) palladium (0) (0.3 g,0.6 mmol) was then added. After 5 hours of reaction, the reaction mixture was cooled to room temperature, then the organic layer and the aqueous layer were separated, and the organic layer was distilled. It was redissolved in chloroform and washed twice with water. The organic layer was then separated, anhydrous magnesium sulfate was added, stirred and then filtered. The filtrate was distilled under reduced pressure. The concentrated compound was purified by a silica gel column to obtain 23.4g of compound 1-111_P1. (yield: 72%, MS: [ M+H)] + ＝534)
Compounds 1-111_P1 (15 g,28.1 mmol) and [1,1' -biphenyl]4-Ylboronic acid (5.8 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, the mixture was stirred well, and bis (tri-t-butylphosphine) palladium (0) (0.1 g,0.3 mmol) was then added. After 3 hours of reaction, the reaction mixture was cooled to room temperature, then the organic layer and the aqueous layer were separated, and the organic layer was distilled. It was redissolved in chloroform and washed twice with water. The organic layer was then separated, anhydrous magnesium sulfate was added, stirred and then filtered. The filtrate was distilled under reduced pressure. The concentrated compound was purified by a silica gel column to obtain 12.1g of compounds 1 to 111. (yield: 66%, MS: [ M+H) ] + ＝652)
Synthesis examples 1 to 78: preparation of Compounds 1-112
(2-chlorodibenzo [ b, d)]Furan-1-yl) boronic acid (15 g,60.9 mmol) and Trz85 (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, the mixture was stirred well, and bis (tri-t-butylphosphine) palladium (0) (0.3 g,0.6 mmol) was then added. After 3 hours of reaction, the reaction mixture was cooled to room temperature, then the organic layer and the aqueous layer were separated, and the organic layer was evaporatedAnd (3) distilling. It was redissolved in chloroform and washed twice with water. The organic layer was then separated, anhydrous magnesium sulfate was added, stirred and then filtered. The filtrate was distilled under reduced pressure. The concentrated compound was purified by a silica gel column to obtain 20.1g of compound 1-112_P1. (yield: 65%, MS: [ M+H)] + ＝510)
Compounds 1-112_P1 (15 g,29.4 mmol) and (4- (naphthalen-1-yl) phenyl) boronic acid (7.7 g,30.9 mmol) were added to 300mL THF and the mixture stirred and refluxed. Then, potassium carbonate (12.2 g,88.2 mmol) was dissolved in 37mL of water and added to the mixture, the mixture was stirred well, and bis (tri-t-butylphosphine) palladium (0) (0.2 g,0.3 mmol) was then added. After 4 hours of reaction, the reaction mixture was cooled to room temperature, then the organic layer and the aqueous layer were separated, and the organic layer was distilled. It was redissolved in chloroform and washed twice with water. The organic layer was then separated, anhydrous magnesium sulfate was added, stirred and then filtered. The filtrate was distilled under reduced pressure. The concentrated compound was purified by a silica gel column to obtain 12.9g of compounds 1 to 112. (yield: 65%, MS: [ M+H) ] + ＝678)
Synthesis examples 1 to 79: preparation of Compounds 1-115
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-2-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-2-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 washed with waterThe solution was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 6.1g of sub7-1-1. (yield: 40%, MS: [ M+H)] + ＝285)
Sub7-1-1 (15 g,52.5 mmol) and bis (pinacolato) diboron (14.7 g,57.8 mmol) were added to 300mL of 1, 4-bisIn 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. 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 10.5g of sub7-1-2. (yield: 60%, MS: [ M+H) ] + ＝333)
Sub7-1-2 (15 g,45.1 mmol) and Trz88 (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, the mixture was stirred well, and bis (tri-t-butylphosphine) palladium (0) (0.2 g,0.5 mmol) was then added. After 4 hours of reaction, the reaction mixture was cooled to room temperature, then the organic layer and the aqueous layer were separated, and the organic layer was distilled. It was redissolved in chloroform and washed twice with water. The organic layer was then separated, anhydrous magnesium sulfate was added, stirred and then filtered. The filtrate was distilled under reduced pressure. The concentrated compound was purified by a silica gel column to obtain 18.1g of Compound 1-115_P1 (yield: 65%, MS: [ M+H)] + ＝619)。
Compound 1-115_P1 (15 g,24.2 mmol) and phenylboronic acid (3.1 g,25.4 mmol) were added to 300mL THF and the mixture was 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 thoroughlyAfter stirring, bis (tri-t-butylphosphine) palladium (0) (0.1 g,0.2 mmol) was added. After 3 hours of reaction, the reaction mixture was cooled to room temperature, then the organic layer and the aqueous layer were separated, and the organic layer was distilled. It was redissolved in chloroform and washed twice with water. The organic layer was then separated, anhydrous magnesium sulfate was added, stirred and then filtered. The filtrate was distilled under reduced pressure. The concentrated compound was purified by a silica gel column to obtain 11g of compounds 1 to 115. (yield: 69%, MS: [ M+H) ] + ＝661)
Intermediate synthesis example 1: preparation of intermediate Compounds A-e
1-bromo-2-fluorobenzene (15 g,85.7 mmol) and (4-chloro-1-hydroxynaphthalen-2-yl) boronic acid (20 g,90 mmol) were added to 300mL THF and the mixture stirred and refluxed. Then, potassium carbonate (35.5 g,257.1 mmol) was dissolved in 107mL of water and added to the mixture, the mixture was stirred well, and bis (tri-t-butylphosphine) palladium (0) (0.4 g,0.9 mmol) was then added. After 3 hours of reaction, the reaction mixture was cooled to room temperature, then the organic layer and the aqueous layer were separated, and the organic layer was distilled. It was redissolved in chloroform and washed twice with water. The organic layer was then separated, anhydrous magnesium sulfate was added, stirred and then filtered. The filtrate was distilled under reduced pressure. The concentrated compound was purified by a silica gel column to obtain 17.7g of compound A-e_P1. (yield: 76%, MS: [ M+H)] + ＝273)
Compound A-e-P1 (15 g,55 mmol) and potassium carbonate (22.8 g,165 mmol) were added to 300mL of DMAc and the mixture was stirred and refluxed. After 4 hours of reaction, the reaction mixture was cooled to room temperature, and the organic solvent was removed under reduced pressure. It was redissolved in chloroform and washed twice with water. The organic layer was then separated, anhydrous magnesium sulfate was added, stirred and then filtered. The filtrate was distilled under reduced pressure. The concentrated compound was purified by a silica gel column to obtain 10.7g of compound A-e. (yield: 77%, MS: [ M+H) ] + ＝253)
Intermediate synthesis example 2: preparation of intermediate compound A-a
Compound a-a was prepared in the same manner as in intermediate synthesis example 1, except that (8-chloro-1-hydroxynaphthalen-2-yl) boric acid was used instead of (4-chloro-1-hydroxynaphthalen-2-yl) boric acid.
Intermediate synthesis example 3: preparation of intermediate Compounds A-b
Compounds A-b were prepared in the same manner as in intermediate Synthesis example 1 except that (7-chloro-1-hydroxynaphthalen-2-yl) boric acid was used in place of (4-chloro-1-hydroxynaphthalen-2-yl) boric acid.
Intermediate synthesis example 4: preparation of intermediate Compounds A-c
Compounds A to c were prepared in the same manner as in intermediate Synthesis example 1 except that (6-chloro-1-hydroxynaphthalen-2-yl) boric acid was used in place of (4-chloro-1-hydroxynaphthalen-2-yl) boric acid.
Intermediate synthesis example 5: preparation of intermediate Compounds A-d
Compounds A to d were prepared in the same manner as in intermediate Synthesis example 1 except that (5-chloro-1-hydroxynaphthalen-2-yl) boric acid was used in place of (4-chloro-1-hydroxynaphthalen-2-yl) boric acid.
Intermediate synthesis example 6: preparation of intermediate Compounds A-f
Compounds A to f were prepared in the same manner as in intermediate Synthesis example 1 except that (3-chloro-1-hydroxynaphthalen-2-yl) boric acid was used in place of (4-chloro-1-hydroxynaphthalen-2-yl) boric acid.
Intermediate synthesis example 7: preparation of intermediate Compounds A-g
2-bromo-1-chloro-3-fluorobenzene (15 g,71.6 mmol) and (1-hydroxynaphthalen-2-yl) boronic acid (14.1 g,75.2 mmol) were added to 300mL THF and the mixture stirred and refluxed. Then, potassium carbonate (29.7 g,214.9 mmol) was dissolved in 89mL of water and added to the mixture, the mixture was stirred well, and bis (tri-t-butylphosphine) palladium (0) (0.4 g,0.7 mmol) was then added. After 5 hours of reaction, the reaction mixture was cooled to room temperature, then the organic layer and the aqueous layer were separated, and the organic layer was distilled. It was redissolved in chloroform and washed twice with water. The organic layer was then separated, anhydrous magnesium sulfate was added, stirred and then filtered. The filtrate was distilled under reduced pressure. The concentrated compound was purified by a silica gel column to obtain 13.6g of compound A-g_P1. (yield: 70%, MS: [ M+H ]] + ＝273)
Compound A-g-P1 (15 g,55 mmol) and potassium carbonate (22.8 g,165 mmol) were added to 300mL of DMAc, and the mixture was stirred and refluxed. After 4 hours of reaction, the reaction mixture was cooled to room temperature, and the organic solvent was removed under reduced pressure. It was redissolved in chloroform and washed twice with water. The organic layer was then separated, anhydrous magnesium sulfate was added, stirred and then filtered. The filtrate was distilled under reduced pressure. The concentrated compound was purified by a silica gel column to obtain 10.3g of compound A-g. (yield: 74%, MS: [ M+H) ] + ＝253)
Intermediate synthesis example 8: preparation of intermediate Compounds A-h
Compound a-h was prepared in the same manner as in preparation example 7 except that 2-bromo-4-chloro-1-fluorobenzene was used instead of 2-bromo-1-chloro-3-fluorobenzene.
Intermediate synthesis example 9: preparation of intermediate compound A-ia
Compound a-i was prepared in the same manner as in preparation example 7, except that 1-bromo-4-chloro-2-fluorobenzene was used instead of 2-bromo-1-chloro-3-fluorobenzene.
Intermediate synthesis example 10: preparation of intermediate compound A-j
Compound a-j was prepared in the same manner as in preparation example 7 except that 1-bromo-3-chloro-2-fluorobenzene was used instead of 2-bromo-1-chloro-3-fluorobenzene.
Intermediate synthesis example 11: preparation of intermediate compound B-a
Bromobenzene (15 g,95.5 mmol) and (8-chloro-1- (methylthio) naphthalen-2-yl) boronic acid (25.3 g,100.3 mmol) were added to 300mL THF and the mixture was stirred and refluxed. Then, potassium carbonate (39.6 g,286.6 mmol) was dissolved in 119mL of water and added to the mixture, the mixture was stirred well, and bis (tri-t-butylphosphine) palladium (0) (0.5 g,1 mmol) was then added. After 2 hours of reaction, the reaction mixture was cooled to room temperature, then the organic layer and the aqueous layer were separated, and the organic layer was distilled. It was redissolved in chloroform and washed twice with water. The organic layer was then separated, anhydrous magnesium sulfate was added, stirred and then filtered. The filtrate was distilled under reduced pressure. By passing through The concentrated compound was purified by a silica gel column to obtain 16.3g of compound B-a-P1. (yield: 60%, MS: [ M+H)] + ＝285)
Compound B-a-P1 (15 g,52.7 mmol) and hydrogen peroxide (2.7 g,79 mmol) were added to 300mL of acetic acid, and the mixture was stirred and refluxed. After 3 hours of reaction, the reaction mixture was poured into water, and crystals were precipitated and filtered. The filtered solid was dissolved in chloroform, washed twice with water, the organic layer was separated, 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 10.3g of compound B-a_p2. (yield 65%, MS: [ M+H)] + ＝301)
Compound B-a-P2 (15 g,49.9 mmol) was added to 300mL H 2 SO 4 And stirring the mixture. After completion of the reaction after 2 hours, the reaction mixture was poured into water, crystals were precipitated and filtered. The filtered solid was dissolved in chloroform, washed twice with water, the organic layer was separated, 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 5.3g of compound B-a (yield: 40%, MS: [ M+H ] + ＝269)
Intermediate synthesis example 12: preparation of intermediate compound B-B
Compound B-B was prepared in the same manner as in intermediate Synthesis example 11, except that (7-chloro-1- (methylthio) naphthalen-2-yl) boric acid was used instead of (8-chloro-1- (methylthio) naphthalen-2-yl) boric acid.
Intermediate synthesis example 13: preparation of intermediate compounds B-c
Compound B-c was prepared in the same manner as in intermediate Synthesis example 11, except that (6-chloro-1- (methylthio) naphthalen-2-yl) boric acid was used instead of (8-chloro-1- (methylthio) naphthalen-2-yl) boric acid.
Intermediate synthesis example 14: preparation of intermediate compounds B-d
Compound B-d was prepared in the same manner as in intermediate Synthesis example 11, except that (5-chloro-1- (methylthio) naphthalen-2-yl) boronic acid was used instead of (8-chloro-1- (methylthio) naphthalen-2-yl) boronic acid.
Intermediate synthesis example 15: preparation of intermediate compounds B-e
Compound B-e was prepared in the same manner as in intermediate Synthesis example 11, except that (4-chloro-1- (methylthio) naphthalen-2-yl) boronic acid was used instead of (8-chloro-1- (methylthio) naphthalen-2-yl) boronic acid.
Intermediate synthesis example 16: preparation of intermediate compounds B-f
Compounds B-f were prepared in the same manner as in intermediate Synthesis example 11 except that (3-chloro-1- (methylthio) naphthalen-2-yl) boronic acid was used in place of (8-chloro-1- (methylthio) naphthalen-2-yl) boronic acid.
Intermediate synthesis example 17: preparation of intermediate compound B-h
1-bromo-3-chlorobenzene (15 g,78.3 mmol) and (1- (methylthio) naphthalen-2-yl) boronic acid (17.9 g,82.3 mmol) were added to 300mL THF and the mixture was stirred and refluxed. Then, potassium carbonate (32.5 g,235mmol) was dissolved in 97mL of water and added to the mixture, the mixture was stirred well, and bis (tri-t-butylphosphine) palladium (0) (0.4 g,0.8 mmol) was then added. After 2 hours of reaction, the reaction mixture was cooled to room temperature, then the organic layer and the aqueous layer were separated, and the organic layer was distilled. It was redissolved in chloroform and washed twice with water. The organic layer was then separated, anhydrous magnesium sulfate was added, stirred and then filtered. The filtrate was distilled under reduced pressure. The concentrated compound was purified by a silica gel column to obtain 13.6g of compound B-h_P1. (yield: 61%, MS: [ M+H)] + ＝285)
Compound B-h-P1 (15 g,52.7 mmol) and hydrogen peroxide (2.7 g,79 mmol) were added to 300mL of acetic acid and the mixture was stirred and refluxed. After 3 hours of reaction, the reaction mixture was poured into water, and crystals were precipitated and filtered. The filtered solid was dissolved in chloroform, washed twice with water, the organic layer was separated, 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 9g of compound B-h_p2. (yield 57%, MS: [ M+H) ] + ＝301)
Compound B-h_P2 (15 g,49.9 mmol) was added to 300mL H 2 SO 4 And stirring the mixture. After completion of the reaction after 2 hours, the reaction mixture was poured into water, crystals were precipitated and filtered. The filtered solid was dissolved in chloroform, washed twice with water, the organic layer was separated, 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 4.9g of compound B-h. (yield: 37%, MS: [ M+H)] + ＝269)
Intermediate synthesis example 18: preparation of intermediate compound B-g
Compound B-g was prepared in the same manner as in intermediate Synthesis example 17, except that 1-bromo-2-chlorobenzene was used instead of 1-bromo-3-fluorobenzene.
Intermediate synthesis example 19: preparation of intermediate compound B-i
Compound B-i was prepared in the same manner as in intermediate Synthesis example 17, except that 1-bromo-4-chlorobenzene was used instead of 1-bromo-3-fluorobenzene.
Intermediate synthesis example 20: preparation of intermediate compound B-j
Compound B-j was produced in the same manner as in intermediate Synthesis example 17, except that the isomers (Compound B-h and Compound B-j) produced in the final reaction were separated by column chromatography.
Synthesis example 2-1: preparation of Compound 2-1
Compound a-a (10 g,39.6 mmol), amine 1 (15.4 g,41.6 mmol) and sodium tert-butoxide (4.9 g,51.4 mmol) were added to 200mL of xylene under nitrogen and the mixture was stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.4 g,0.8 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, 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 16g of compound 2-1. (yield: 69%, MS: [ M+H)] + ＝588)
Synthesis example 2-2: preparation of Compound 2-2
Compound A-a (15 g,59.4 mmol) and amine 2 (29.4 g,62.3 mmol) were added to 300mL THF and the mixture was stirred and refluxed. Then, potassium carbonate (24.6 g,178.1 mmol) was dissolved in 74mL of water and added to the mixture, the mixture was stirred well, and bis (tri-t-butylphosphine) palladium (0) (0.3 g,0.6 mmol) was then added. After 3 hours of reaction, the reaction mixture was cooled to room temperature, then the organic layer and the aqueous layer were separated, and the organic layer was distilled. It was redissolved in chloroform and washed twice with water. The organic layer was then separated, anhydrous magnesium sulfate was added, stirred and then filtered. The filtrate was distilled under reduced pressure. The concentrated compound was purified by a silica gel column to obtain 23.7g of compound 2-2. (yield: 62%, MS: [ M+H) ] + ＝644)
Synthesis examples 2 to 3: preparation of Compounds 2-3
Compound A-a (15 g,59.4 mmol) and amine 3 (30.6 g,62.3 mmol) were added to 300mL THF and the mixture was stirred and refluxed. Then, potassium carbonate (24.6 g,178.1 mmol) was dissolved in 74mL of water and added to the mixture, the mixture was stirred well, and bis (tri-t-butylphosphine) palladium (0) (0.3 g,0.6 mmol) was then added. After 3 hours of reaction, the reaction mixture was cooled to room temperature, then the organic layer and the aqueous layer were separated, and the organic layer was distilled. It was redissolved in chloroform and washed twice with water. The organic layer was then separated, anhydrous magnesium sulfate was added, stirred and then filtered. The filtrate was distilled under reduced pressure. The concentrated compound was purified by a silica gel column to obtain 29.1g of compound 2-3. (yield: 74%, MS: [ M+H)] + ＝664)
Synthesis examples 2 to 4: preparation of Compounds 2-4
Compound a-b (10 g,39.6 mmol), amine 4 (17.5 g,41.6 mmol) and sodium tert-butoxide (4.9 g,51.4 mmol) were added to 200mL of xylene under nitrogen and the mixture was stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.4 g,0.8 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 filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 16.9g of compounds 2 to 4. (yield: 67%, MS: [ M+H) ] + ＝638)
Synthesis examples 2 to 5: preparation of Compounds 2-5
Compound a-b (10 g,39.6 mmol), amine 5 (17.6 g,41.6 mmol) and sodium tert-butoxide (4.9 g,51.4 mmol) were added to 200mL of xylene under nitrogen and the mixture was stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.4 g,0.8 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 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 2-5. (yield: 60%, MS: [ M+H)] + ＝641)
Synthesis examples 2 to 6: preparation of Compounds 2-6
Compound A-b (15 g,59.4 mmol) and amine 6 (25.9 g,62.3 mmol) were added to 300mL THF and the mixture was stirred and refluxed. Then, potassium carbonate (24.6 g,178.1 mmol) was dissolved in 74mL of water and added to the mixture, the mixture was stirred well, and bis (tri-t-butylphosphine) palladium (0) (0.3 g,0.6 mmol) was then added. After 3 hours of reaction, the reaction mixture was cooled to room temperature, then the organic layer and the aqueous layer were separated, and the organic layer was distilled. It was redissolved in chloroform and washed twice with water. The organic layer was then separated, anhydrous magnesium sulfate was added, stirred and then filtered. The filtrate was distilled under reduced pressure. The concentrated compound was purified by a silica gel column to obtain 26.1g of compound 2-6. (yield: 75%, MS: [ M+H) ] + ＝588)
Synthesis examples 2 to 7: preparation of Compounds 2-7
Compound a-b (10 g,39.6 mmol), amine 7 (15.2 g,41.6 mmol) and sodium tert-butoxide (4.9 g,51.4 mmol) were added to 200mL of xylene under nitrogen and the mixture was stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.4 g,0.8 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, 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 compounds 2 to 7. (yield: 66%, MS: [ M+H)] + ＝582)
Synthesis examples 2 to 8: preparation of Compounds 2-8
Compounds A-c (10 g,39.6 mmol), amine 8 (12.3 g,41.6 mmol) and sodium tert-butoxide (4.9 g,51.4 mmol) were added to 200mL of xylene under nitrogen and the mixture was stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.4 g,0.8 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, and 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 8. (yield: 62%, MS: [ M+H) ] + ＝512)
Synthesis examples 2 to 9: preparation of Compounds 2-9
Compounds A-c (15 g,59.4 mmol) and amine 9 (30.6 g,62.3 mmol) were added to 300mL THF and the mixture was stirred and refluxed. Then, potassium carbonate (24.6 g,178.1 mmol) was dissolved in 74mL of water and added to the mixture, the mixture was stirred well, and bis (tri-t-butylphosphine) palladium (0) (0.3 g,0.6 mmol) was then added. After 4 hours of reaction, the reaction mixture was cooled to room temperature, then the organic layer and the aqueous layer were separated, and the organic layer was distilled. It was redissolved in chloroform and washed twice with water. The organic layer was then separated, anhydrous magnesium sulfate was added, stirred and then filtered. The filtrate was distilled under reduced pressure. The concentrated compound was purified by a silica gel column to obtain 27.2g of compound 2-9. (yield: 69%, MS: [ M+H)] + ＝664)
Synthesis examples 2 to 10: preparation of Compounds 2-10
Compounds A-c (10 g,39.6 mmol), amine 10 (15 g,41.6 mmol) and sodium tert-butoxide (4.9 g,51.4 mmol) were added to 200mL of xylene under nitrogen and the mixture was stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.4 g,0.8 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 filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 13.7g of compounds 2 to 10. (yield: 60%, MS: [ M+H)] + ＝578)
Synthesis examples 2 to 11: preparation of Compounds 2-11
Compounds A-d (10 g,39.6 mmol), amine 11 (17.1 g,41.6 mmol) and sodium tert-butoxide (4.9 g,51.4 mmol) were added to 200mL of xylene under nitrogen and the mixture was stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.4 g,0.8 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 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: 56%, MS: [ M+H)] + ＝627)
Synthesis examples 2 to 12: preparation of Compounds 2-12
Compounds A-d (10 g,39.6 mmol), amine 12 (14.5 g,41.6 mmol) and sodium tert-butoxide (4.9 g,51.4 mmol) were added to 200mL of xylene under nitrogen and the mixture was stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.4 g,0.8 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 then 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 12. (yield: 61%, MS: [ M+H)] + ＝566)
Synthesis examples 2 to 13: preparation of Compounds 2-13
Compounds A-d (15 g,59.4 mmol) and amine 13 (27.5 g,62.3 mmol) were added to 300mL THF and the mixture was stirred and refluxed. Then, potassium carbonate (24.6 g,178.1 mmol) was dissolved in 74mL of water and added to the mixture, the mixture was stirred well, and bis (tri-t-butylphosphine) palladium (0) (0.3 g,0.6 mmol) was then added. After 4 hours of reaction, the reaction mixture was cooled to room temperature, then the organic layer and the aqueous layer were separated, and the organic layer was distilled. It was redissolved in chloroform and washed twice with water. The organic layer was then separated, anhydrous magnesium sulfate was added, stirred and then filtered. The filtrate was distilled under reduced pressure. The concentrated compound was purified by a silica gel column to obtain 22.6g of compound 2-13. (yield: 62%, MS: [ M+H)] + ＝614)
Synthesis examples 2 to 14: preparation of Compounds 2-14
Compounds A-e (10 g,39.6 mmol), amine 14 (13.4 g,41.6 mmol) and sodium tert-butoxide (4.9 g,51.4 mmol) were added to 200mL of xylene under nitrogen and the mixture was stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.4 g,0.8 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 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 2- 14. (yield: 74%, MS: [ M+H)] + ＝538)
Synthesis examples 2 to 15: preparation of Compounds 2-15
Compounds A-e (15 g,59.4 mmol) and amine 15 (30.6 g,62.3 mmol) were added to 300mL THF and the mixture was stirred and refluxed. Then, potassium carbonate (24.6 g,178.1 mmol) was dissolved in 74mL of water and added to the mixture, the mixture was stirred well, and bis (tri-t-butylphosphine) palladium (0) (0.3 g,0.6 mmol) was then added. After 5 hours of reaction, the reaction mixture was cooled to room temperature, then the organic layer and the aqueous layer were separated, and the organic layer was distilled. It was redissolved in chloroform and washed twice with water. The organic layer was then separated, anhydrous magnesium sulfate was added, stirred and then filtered. The filtrate was distilled under reduced pressure. The concentrated compound was purified by a silica gel column to obtain 24.4g of compound 2-15. (yield: 62%, MS: [ M+H)] + ＝664)
Synthesis examples 2 to 16: preparation of Compounds 2-16
Compound a-e (15 g,59.4 mmol) and amine 16 (32.5 g,62.3 mmol) were added to 300mL THF and the mixture was stirred and refluxed. Then, potassium carbonate (24.6 g,178.1 mmol) was dissolved in 74mL of water and added to the mixture, 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, then the organic layer and the aqueous layer were separated, and the organic layer was distilled. It was redissolved in chloroform and washed twice with water. The organic layer was then separated, anhydrous magnesium sulfate was added, stirred and then filtered. The filtrate was distilled under reduced pressure. The concentrated compound was purified by a silica gel column to obtain 27.2g of compounds 2 to 16. (yield: 66%, MS: [ M+H) ] + ＝694)
Synthesis examples 2 to 17: preparation of Compounds 2-17
Compounds A-f (10 g,39.6 mmol), amine 17 (13.9 g,41.6 mmol) and sodium tert-butoxide (4.9 g,51.4 mmol) were added to 200mL of xylene under nitrogen and the mixture was stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.4 g,0.8 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 filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 13.7g of compounds 2 to 17. (yield: 63%, MS: [ M+H)] + ＝552)
Synthesis examples 2 to 18: preparation of Compounds 2-18
Compounds A-f (15 g,59.4 mmol) and amine 18 (32.3 g,62.3 mmol) were added to 300mL THF and the mixture was stirred and refluxed. Then, potassium carbonate (24.6 g,178.1 mmol) was dissolved in 74mL of water and added to the mixture, the mixture was stirred well, and bis (tri-t-butylphosphine) palladium (0) (0.3 g,0.6 mmol) was then added. After 4 hours of reaction, the reaction mixture was cooled to room temperature, then the organic layer and the aqueous layer were separated, and the organic layer was distilled. It was redissolved in chloroform and washed twice with water. The organic layer was then separated, anhydrous magnesium sulfate was added, stirred and then filtered. The filtrate was distilled under reduced pressure. The concentrated compound was purified by a silica gel column to obtain 26.2g of compound 2-18. (yield: 64%, MS: [ M+H ] ] + ＝690)
Synthesis examples 2 to 19: preparation of Compounds 2-19
Compounds A-f (15 g,59.4 mmol) and amine 19 (25.3 g,62.3 mmol) were added to 300mL THF and the mixture was stirred and refluxed. Then, potassium carbonate (24.6 g,178.1 mmol) was dissolved in 74mL of water and added to the mixture, 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, then the organic layer and the aqueous layer were separated, and the organic layer was distilled. It was redissolved in chloroform and washed twice with water. The organic layer was then separated, anhydrous magnesium sulfate was added, stirred and then filtered. The filtrate was distilled under reduced pressure. The concentrated compound was purified by a silica gel column to obtain 24g of compounds 2 to 19. (yield: 70%, MS: [ M+H ]] + ＝578)
Synthesis examples 2 to 20: preparation of Compounds 2-20
Compound a-g (10 g,39.6 mmol), amine 20 (17.5 g,41.6 mmol) and sodium tert-butoxide (4.9 g,51.4 mmol) were added to 200mL of xylene under nitrogen and the mixture was stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.4 g,0.8 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 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 2-20. (yield: 61%, MS: [ M+H) ] + ＝638)
Synthesis examples 2 to 21: preparation of Compounds 2-21
Compound A-g (15 g,59.4 mmol) and amine 21 (27.5 g,62.3 mmol) were added to 300mL THF and the mixture was stirred and refluxed. Then, potassium carbonate (24.6 g,178.1 mmol) was dissolved in 74mL of water and added to the mixture, the mixture was stirred well, and bis (tri-t-butylphosphine) palladium (0) (0.3 g,0.6 mmol) was then added. After 5 hours of reaction, the reaction mixture was cooled to room temperature, then the organic layer and the aqueous layer were separated, and the organic layer was distilled. It was redissolved in chloroform and washed twice with water. The organic layer was then separated, anhydrous magnesium sulfate was added, stirred and then filtered. The filtrate was distilled under reduced pressure. The concentrated compound was purified by a silica gel column to obtain 26.2g of compound 2-21. (yield: 72%, MS: [ M+H)] + ＝614)
Synthesis examples 2 to 22: preparation of Compounds 2-22
Compound A-g (10 g,39.6 mmol), amine 22 (13.9 g,41.6 mmol) and sodium tert-butoxide (4.9 g,51.4 mmol) were added to 200mL of xylene under nitrogen and the mixture was stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.4 g,0.8 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, 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 compounds 2 to 22. (yield: 57%, MS: [ M+H) ] + ＝552)
Synthesis examples 2 to 23: preparation of Compounds 2-23
Compounds A-h (10 g, 39) were reacted under nitrogen.6 mmol), amine 23 (15.4 g,41.6 mmol) and sodium tert-butoxide (4.9 g,51.4 mmol) were added to 200mL of xylene and the mixture was stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.4 g,0.8 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, 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 2-23. (yield: 58%, MS: [ M+H)] + ＝588)
Synthesis examples 2 to 24: preparation of Compounds 2-24
Compound a-h (15 g,59.4 mmol) and amine 24 (27.5 g,62.3 mmol) were added to 300mL THF and the mixture was stirred and refluxed. Then, potassium carbonate (24.6 g,178.1 mmol) was dissolved in 74mL of water and added to the mixture, the mixture was stirred well, and bis (tri-t-butylphosphine) palladium (0) (0.3 g,0.6 mmol) was then added. After 4 hours of reaction, the reaction mixture was cooled to room temperature, then the organic layer and the aqueous layer were separated, and the organic layer was distilled. It was redissolved in chloroform and washed twice with water. The organic layer was then separated, anhydrous magnesium sulfate was added, stirred and then filtered. The filtrate was distilled under reduced pressure. The concentrated compound was purified by a silica gel column to obtain 24g of compound 2-24. (yield: 66%, MS: [ M+H) ] + ＝614)
Synthesis examples 2 to 25: preparation of Compounds 2-25
Compound A-h (10 g,39.6 mmol), amine 25 (17.1 g,41.6 mmol) and sodium tert-butoxide (4.9 g,51.4 mmol) were added to 200mL of xylene under nitrogen and the mixture was admixedThe mixture was stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.4 g,0.8 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 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 25. (yield: 60%, MS: [ M+H)] + ＝627)
Synthesis examples 2 to 26: preparation of Compounds 2-26
Compound a-i (10 g,39.6 mmol), amine 1 (15.4 g,41.6 mmol) and sodium tert-butoxide (4.9 g,51.4 mmol) were added to 200mL of xylene under nitrogen and the mixture was stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.4 g,0.8 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, 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 compounds 2 to 26. (yield: 61%, MS: [ M+H) ] + ＝588)
Synthesis examples 2 to 27: preparation of Compounds 2-27
Compound A-i (15 g,59.4 mmol) and amine 26 (32.3 g,62.3 mmol) were added to 300mL THF and the mixture was stirred and refluxed. Then, potassium carbonate (24.6 g,178.1 mmol) was dissolved in 74mL of water and added to the mixture, the mixture was stirred well, and bis (tri-t-butylphosphine) palladium (0) (0.3 g,0.6 mmol) was then added. In the reaction for 5 hoursAfter that time, the reaction mixture was cooled to room temperature, then the organic layer and the aqueous layer were separated, and the organic layer was distilled. It was redissolved in chloroform and washed twice with water. The organic layer was then separated, anhydrous magnesium sulfate was added, stirred and then filtered. The filtrate was distilled under reduced pressure. The concentrated compound was purified by a silica gel column to obtain 27.4g of compound 2-27. (yield: 67%, MS: [ M+H)] + ＝690)
Synthesis examples 2 to 28: preparation of Compounds 2-28
Compound a-i (10 g,39.6 mmol), amine 27 (17.8 g,41.6 mmol) and sodium tert-butoxide (4.9 g,51.4 mmol) were added to 200mL of xylene under nitrogen and the mixture was stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.4 g,0.8 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 filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 17.1g of compounds 2 to 28. (yield: 67%, MS: [ M+H) ] + ＝644)
Synthesis examples 2 to 29: preparation of Compounds 2-29
Compound a-j (10 g,39.6 mmol), amine 28 (13.4 g,41.6 mmol) and sodium tert-butoxide (4.9 g,51.4 mmol) were added to 200mL of xylene under nitrogen and the mixture was stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.4 g,0.8 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 washed with waterThe organic layer was then separated twice, 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 29. (yield: 74%, MS: [ M+H)] + ＝538)
Synthesis examples 2 to 30: preparation of Compounds 2-30
Compound a-j (10 g,39.6 mmol), amine 29 (16.3 g,41.6 mmol) and sodium tert-butoxide (4.9 g,51.4 mmol) were added to 200mL of xylene under nitrogen and the mixture was stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.4 g,0.8 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, 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 30. (yield: 61%, MS: [ M+H) ] + ＝608)
Synthesis examples 2 to 31: preparation of Compounds 2-31
Compound A-j (15 g,59.4 mmol) and amine 30 (33.7 g,62.3 mmol) were added to 300mL THF and the mixture was stirred and refluxed. Then, potassium carbonate (24.6 g,178.1 mmol) was dissolved in 74mL of water and added to the mixture, the mixture was stirred well, and bis (tri-t-butylphosphine) palladium (0) (0.3 g,0.6 mmol) was then added. After 4 hours of reaction, the reaction mixture was cooled to room temperature, then the organic layer and the aqueous layer were separated, and the organic layer was distilled. It was redissolved in chloroform and washed twice with water. The organic layer was then separated, anhydrous magnesium sulfate was added, stirred and then filtered. Steaming the filtrate under reduced pressureAnd (3) distilling. The concentrated compound was purified by a silica gel column to obtain 27.5g of compound 2-31. (yield: 65%, MS: [ M+H)] + ＝714)
Synthesis examples 2 to 32: preparation of Compounds 2-32
Compound B-a (10 g,37.2 mmol), amine 31 (15.5 g,39.1 mmol) and sodium tert-butoxide (4.6 g,48.4 mmol) were added to 200mL of xylene under nitrogen and the mixture was stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.4 g,0.7 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 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 2-32. (yield: 62%, MS: [ M+H) ] + ＝630)
Synthesis examples 2 to 33: preparation of Compounds 2-33
Compound B-a (10 g,37.2 mmol), amine 32 (16.7 g,39.1 mmol) and sodium tert-butoxide (4.6 g,48.4 mmol) were added to 200mL of xylene under nitrogen and the mixture was stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.4 g,0.7 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 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 2-33. (yield: 55%, MS: [ M+H)] + ＝660)
Synthesis examples 2 to 34: preparation of Compounds 2-34
Compound B-a (15 g,55.8 mmol) and amine 33 (28.2 g,58.6 mmol) were added to 300mL THF and the mixture was stirred and refluxed. Then, potassium carbonate (23.1 g,167.4 mmol) was dissolved in 69mL of water and added to the mixture, the mixture was stirred well, and bis (tri-t-butylphosphine) palladium (0) (0.3 g,0.6 mmol) was then added. After 3 hours of reaction, the reaction mixture was cooled to room temperature, then the organic layer and the aqueous layer were separated, and the organic layer was distilled. It was redissolved in chloroform and washed twice with water. The organic layer was then separated, anhydrous magnesium sulfate was added, stirred and then filtered. The filtrate was distilled under reduced pressure. The concentrated compound was purified by a silica gel column to obtain 21.3g of compound 2-34. (yield: 57%, MS: [ M+H) ] + ＝670)
Synthesis examples 2 to 35: preparation of Compounds 2-35
Compound B-B (10 g,37.2 mmol), amine 34 (14.5 g,39.1 mmol) and sodium tert-butoxide (4.6 g,48.4 mmol) were added to 200mL of xylene under nitrogen and the mixture was stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.4 g,0.7 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 filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 13.2g of compounds 2 to 35. (yield: 59%, MS: [ M+H)] + ＝604)
Synthesis examples 2 to 36: preparation of Compounds 2-36
Compound B-B (15 g,55.8 mmol) and amine 21 (25.9 g,58.6 mmol) were added to 300mL THF and the mixture was stirred and refluxed. Then, potassium carbonate (23.1 g,167.4 mmol) was dissolved in 69mL of water and added to the mixture, the mixture was stirred well, and bis (tri-t-butylphosphine) palladium (0) (0.3 g,0.6 mmol) was then added. After 4 hours of reaction, the reaction mixture was cooled to room temperature, then the organic layer and the aqueous layer were separated, and the organic layer was distilled. It was redissolved in chloroform and washed twice with water. The organic layer was then separated, anhydrous magnesium sulfate was added, stirred and then filtered. The filtrate was distilled under reduced pressure. The concentrated compound was purified by a silica gel column to obtain 21.8g of compound 2-36. (yield: 62%, MS: [ M+H) ] + ＝630)
Synthesis examples 2 to 37: preparation of Compounds 2-37
Compound B-B (15 g,55.8 mmol) and amine 35 (27.6 g,58.6 mmol) were added to 300mL THF and the mixture was stirred and refluxed. Then, potassium carbonate (23.1 g,167.4 mmol) was dissolved in 69mL of water and added to the mixture, the mixture was stirred well, and bis (tri-t-butylphosphine) palladium (0) (0.3 g,0.6 mmol) was then added. After 4 hours of reaction, the reaction mixture was cooled to room temperature, then the organic layer and the aqueous layer were separated, and the organic layer was distilled. It was redissolved in chloroform and washed twice with water. The organic layer was then separated, anhydrous magnesium sulfate was added, stirred and then filtered. The filtrate was distilled under reduced pressure. The concentrated compound was purified by a silica gel column to obtain 22.8g of compound 2-37. (yield: 62%, MS: [ M+H)] + ＝660)
Synthesis examples 2 to 38: preparation of Compounds 2-38
Compounds B-c (10 g,37.2 mmol), amine 36 (16 g,39.1 mmol) and sodium tert-butoxide (4.6 g,48.4 mmol) were added to 200mL of xylene under nitrogen and the mixture was stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.4 g,0.7 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 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 2-38. (yield: 58%, MS: [ M+H) ] + ＝643)
Synthesis examples 2 to 39: preparation of Compounds 2-39
Compound B-c (10 g,37.2 mmol), amine 37 (14.5 g,39.1 mmol) and sodium tert-butoxide (4.6 g,48.4 mmol) were added to 200mL of xylene under nitrogen and the mixture was stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.4 g,0.7 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, 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 6.5g of compound 2-39. (yield: 57%, MS: [ M+H)] + ＝307)
Synthesis examples 2 to 40: preparation of Compounds 2-40
Compound B-c (15 g,55.8 mmol) and amine 38 (21).4g,58.6 mmol) was added to 300mL THF and the mixture was stirred and refluxed. Then, potassium carbonate (23.1 g,167.4 mmol) was dissolved in 69mL of water and added to the mixture, the mixture was stirred well, and bis (tri-t-butylphosphine) palladium (0) (0.3 g,0.6 mmol) was then added. After 5 hours of reaction, the reaction mixture was cooled to room temperature, then the organic layer and the aqueous layer were separated, and the organic layer was distilled. It was redissolved in chloroform and washed twice with water. The organic layer was then separated, anhydrous magnesium sulfate was added, stirred and then filtered. The filtrate was distilled under reduced pressure. The concentrated compound was purified by a silica gel column to obtain 19.1g of compound 2-40. (yield: 62%, MS: [ M+H) ] + ＝554)
Synthesis examples 2 to 41: preparation of Compounds 2-41
Compound B-c (10 g,37.2 mmol), amine 39 (13.1 g,39.1 mmol) and sodium tert-butoxide (4.6 g,48.4 mmol) were added to 200mL of xylene under nitrogen and the mixture was stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.4 g,0.7 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, 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 2-41. (yield: 59%, MS: [ M+H)] + ＝568)
Synthesis examples 2 to 42: preparation of Compounds 2-42
Compound B-d (10 g,37.2 mmol), amine 40 (13.5 g,39.1 mmol) and sodium tert-butoxide (4.6 g,48.4 mmol) were added to 200mL of xylene under nitrogen and the mixture was stirredStirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.4 g,0.7 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, 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 compounds 2 to 42. (yield: 65%, MS: [ M+H) ] + ＝578)
Synthesis examples 2 to 43: preparation of Compounds 2-43
Compound B-d (15 g,55.8 mmol) and amine 41 (30.6 g,58.6 mmol) were added to 300mL THF and the mixture was stirred and refluxed. Then, potassium carbonate (23.1 g,167.4 mmol) was dissolved in 69mL of water and added to the mixture, the mixture was stirred well, and bis (tri-t-butylphosphine) palladium (0) (0.3 g,0.6 mmol) was then added. After 4 hours of reaction, the reaction mixture was cooled to room temperature, then the organic layer and the aqueous layer were separated, and the organic layer was distilled. It was redissolved in chloroform and washed twice with water. The organic layer was then separated, anhydrous magnesium sulfate was added, stirred and then filtered. The filtrate was distilled under reduced pressure. The concentrated compound was purified by a silica gel column to obtain 24.9g of Compound 2-43 (yield: 63%, MS: [ M+H ]] + ＝710)
Synthesis examples 2 to 44: preparation of Compounds 2-44
Compound B-d (15 g,55.8 mmol) and amine 42 (28.2 g,58.6 mmol) were added to 300mL THF and the mixture was stirred and refluxed. Then, potassium carbonate (23.1 g,167.4 mmol) was dissolved in 69mL of water and added to the mixture, the mixture was stirred well, and bis (tri-t-butylphosphine) palladium (0) was then added(0.3 g,0.6 mmol). After 4 hours of reaction, the reaction mixture was cooled to room temperature, then the organic layer and the aqueous layer were separated, and the organic layer was distilled. It was redissolved in chloroform and washed twice with water. The organic layer was then separated, anhydrous magnesium sulfate was added, stirred and then filtered. The filtrate was distilled under reduced pressure. The concentrated compound was purified by a silica gel column to obtain 23.2g of compound 2-44. (yield: 62%, MS: [ M+H) ] + ＝670)
Synthesis examples 2 to 45: preparation of Compounds 2-45
Compound B-e (10 g,37.2 mmol), amine 43 (14.5 g,39.1 mmol) and sodium tert-butoxide (4.6 g,48.4 mmol) were added to 200mL of xylene under nitrogen and the mixture was stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.4 g,0.7 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, 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 45. (yield: 55%, MS: [ M+H)] + ＝604)
Synthesis examples 2 to 46: preparation of Compounds 2-46
Compound B-e (15 g,55.8 mmol) and amine 44 (25.9 g,58.6 mmol) were added to 300mL THF and the mixture was stirred and refluxed. Then, potassium carbonate (23.1 g,167.4 mmol) was dissolved in 69mL of water and added to the mixture, the mixture was stirred well, and bis (tri-t-butylphosphine) palladium (0) (0.3 g,0.6 mmol) was then added. After reacting for 5 hours, the reaction mixture was cooled to room temperature, and then the organic layer and the aqueous layer were separated The organic layer was separated and distilled. It was redissolved in chloroform and washed twice with water. The organic layer was then separated, anhydrous magnesium sulfate was added, stirred and then filtered. The filtrate was distilled under reduced pressure. The concentrated compound was purified by a silica gel column to obtain 19.3g of compound 2-46. (yield: 55%, MS: [ M+H)] + ＝630)
Synthesis examples 2 to 47: preparation of Compounds 2-47
Compound B-e (15 g,55.8 mmol) and amine 45 (31.1 g,58.6 mmol) were added to 300mL THF and the mixture was stirred and refluxed. Then, potassium carbonate (23.1 g,167.4 mmol) was dissolved in 69mL of water and added to the mixture, the mixture was stirred well, and bis (tri-t-butylphosphine) palladium (0) (0.3 g,0.6 mmol) was then added. After 4 hours of reaction, the reaction mixture was cooled to room temperature, then the organic layer and the aqueous layer were separated, and the organic layer was distilled. It was redissolved in chloroform and washed twice with water. The organic layer was then separated, anhydrous magnesium sulfate was added, stirred and then filtered. The filtrate was distilled under reduced pressure. The concentrated compound was purified by a silica gel column to obtain 25.3g of compound 2-47. (yield: 63%, MS: [ M+H)] + ＝720)
Synthesis examples 2 to 48: preparation of Compounds 2-48
Compound B-e (15 g,55.8 mmol) and amine 46 (26.6 g,58.6 mmol) were added to 300mL THF and the mixture was stirred and refluxed. Then, potassium carbonate (23.1 g,167.4 mmol) was dissolved in 69mL of water and added to the mixture, 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, then the organic layer and the aqueous layer were separated, and the organic layer was distilled. Dissolving in chloroform again, and using waterWashing twice. The organic layer was then separated, anhydrous magnesium sulfate was added, stirred and then filtered. The filtrate was distilled under reduced pressure. The concentrated compound was purified by a silica gel column to obtain 22.6g of compound 2-48. (yield: 63%, MS: [ M+H)] + ＝643)
Synthesis examples 2 to 49: preparation of Compounds 2-49
Compounds B-f (10 g,37.2 mmol), amine 47 (13.5 g,39.1 mmol) and sodium tert-butoxide (4.6 g,48.4 mmol) were added to 200mL of xylene under nitrogen and the mixture was stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.4 g,0.7 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, 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 compounds 2 to 49. (yield: 64%, MS: [ M+H ] ] + ＝578)
Synthesis examples 2 to 50: preparation of Compounds 2-50
Compounds B-f (15 g,55.8 mmol) and amine 48 (28.8 g,58.6 mmol) were added to 300mL THF and the mixture was stirred and refluxed. Then, potassium carbonate (23.1 g,167.4 mmol) was dissolved in 69mL of water and added to the mixture, 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, then the organic layer and the aqueous layer were separated, and the organic layer was distilled. It was redissolved in chloroform and washed twice with water. The organic layer was then separated, anhydrous magnesium sulfate was added, stirred and then filtered. Distilling the filtrate under reduced pressure. The concentrated compound was purified by a silica gel column to obtain 23.1g of compound 2-50. (yield: 61%, MS: [ M+H)] + ＝680)
Synthesis examples 2 to 51: preparation of Compounds 2-51
Compounds B-f (10 g,37.2 mmol), amine 49 (16.1 g,39.1 mmol) and sodium tert-butoxide (4.6 g,48.4 mmol) were added to 200mL of xylene under nitrogen and the mixture was stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.4 g,0.7 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 filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 15.1g of compound 2-51. (yield: 63%, MS: [ M+H) ] + ＝644)
Synthesis examples 2 to 52: preparation of Compounds 2-52
Compound B-g (10 g,37.2 mmol), amine 50 (14.5 g,39.1 mmol) and sodium tert-butoxide (4.6 g,48.4 mmol) were added to 200mL of xylene under nitrogen and the mixture was stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.4 g,0.7 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 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 2-52. (yield: 61%, MS: [ M+H)] + ＝604)
Synthesis examples 2 to 53: preparation of Compounds 2-53
Compound B-g (15 g,55.8 mmol) and amine 51 (27.3 g,58.6 mmol) were added to 300mL THF and the mixture was stirred and refluxed. Then, potassium carbonate (23.1 g,167.4 mmol) was dissolved in 69mL of water and added to the mixture, the mixture was stirred well, and bis (tri-t-butylphosphine) palladium (0) (0.3 g,0.6 mmol) was then added. After 3 hours of reaction, the reaction mixture was cooled to room temperature, then the organic layer and the aqueous layer were separated, and the organic layer was distilled. It was redissolved in chloroform and washed twice with water. The organic layer was then separated, anhydrous magnesium sulfate was added, stirred and then filtered. The filtrate was distilled under reduced pressure. The concentrated compound was purified by a silica gel column to obtain 21.9g of compound 2-53. (yield: 60%, MS: [ M+H) ] + ＝654)
Synthesis examples 2 to 54: preparation of Compounds 2-54
Compound B-g (15 g,55.8 mmol) and amine 52 (31.1 g,58.6 mmol) were added to 300mL THF and the mixture was stirred and refluxed. Then, potassium carbonate (23.1 g,167.4 mmol) was dissolved in 69mL of water and added to the mixture, the mixture was stirred well, and bis (tri-t-butylphosphine) palladium (0) (0.3 g,0.6 mmol) was then added. After 3 hours of reaction, the reaction mixture was cooled to room temperature, then the organic layer and the aqueous layer were separated, and the organic layer was distilled. It was redissolved in chloroform and washed twice with water. The organic layer was then separated, anhydrous magnesium sulfate was added, stirred and then filtered. The filtrate was distilled under reduced pressure. The concentrated compound was purified by a silica gel column to obtain 26.1g of compound 2-54. (yield: 65%, MS: [ M+H)] + ＝720)
Synthesis examples 2 to 55: preparation of Compounds 2-55
Compound B-h (10 g,37.2 mmol), amine 53 (14.5 g,39.1 mmol) and sodium tert-butoxide (4.6 g,48.4 mmol) were added to 200mL of xylene under nitrogen and the mixture was stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.4 g,0.7 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, 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 55. (yield: 58%, MS: [ M+H) ] + ＝604)
Synthesis examples 2 to 56: preparation of Compounds 2-56
Compound B-h (15 g,55.8 mmol) and amine 54 (28.4 g,58.6 mmol) were added to 300mL THF and the mixture was stirred and refluxed. Then, potassium carbonate (23.1 g,167.4 mmol) was dissolved in 69mL of water and added to the mixture, the mixture was stirred well, and bis (tri-t-butylphosphine) palladium (0) (0.3 g,0.6 mmol) was then added. After 4 hours of reaction, the reaction mixture was cooled to room temperature, then the organic layer and the aqueous layer were separated, and the organic layer was distilled. It was redissolved in chloroform and washed twice with water. The organic layer was then separated, anhydrous magnesium sulfate was added, stirred and then filtered. The filtrate was distilled under reduced pressure. The concentrated compound was purified by a silica gel column to obtain 23.7g of compound 2-56. (yield: 63%, MS: [ M+H)] + ＝674)
Synthesis examples 2 to 57: preparation of Compounds 2-57
Compound B-h (10 g,37.2 mmol), amine 55 (16.1 g,39.1 mmol) and sodium tert-butoxide (4.6 g,48.4 mmol) were added to 200mL of xylene under nitrogen and the mixture was stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.4 g,0.7 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 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 57. (yield: 61%, MS: [ M+H) ] + ＝644)
Synthesis examples 2 to 58: preparation of Compounds 2-58
Compound B-i (10 g,37.2 mmol), amine 56 (14.5 g,39.1 mmol) and sodium tert-butoxide (4.6 g,48.4 mmol) were added to 200mL of xylene under a nitrogen atmosphere and the mixture was stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.4 g,0.7 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, 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 58. (yield: 55%, MS: [ M+H)] + ＝604)
Synthesis examples 2 to 59: preparation of Compounds 2-59
Compound B-i (10 g,37.2 mmol), amine 57 (16 g,39.1 mmol) and sodium tert-butoxide (4.6 g,48.4 mmol) were added to 200mL of xylene and the mixture was stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.4 g,0.7 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 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 2-59. (yield: 57%, MS: [ M+H) ] + ＝643)
Synthesis examples 2 to 60: preparation of Compounds 2-60
Compound B-i (15 g,55.8 mmol) and amine 58 (26.7 g,58.6 mmol) were added to 300mL THF and the mixture was stirred and refluxed. Then, potassium carbonate (23.1 g,167.4 mmol) was dissolved in 69mL of water and added to the mixture, the mixture was stirred well, and bis (tri-t-butylphosphine) palladium (0) (0.3 g,0.6 mmol) was then added. After 5 hours of reaction, the reaction mixture was cooled to room temperature, then the organic layer and the aqueous layer were separated, and the organic layer was distilled. It was redissolved in chloroform and washed twice with water. The organic layer was then separated, anhydrous magnesium sulfate was added, stirred and then filtered. The filtrate was distilled under reduced pressure. The concentrated compound was purified by a silica gel column to obtain 19.7g of compound 2-60. (yield: 55%, MS: [ M+H)] + ＝644)
Synthesis examples 2 to 61: preparation of Compounds 2-61
Compound B-j (10 g,37.2 mmol), amine 31 (15.5 g,39.1 mmol) and sodium tert-butoxide (4.6 g,48.4 mmol) were added to 200mL of xylene under nitrogen and the mixture was stirredStirring and refluxing. Then, bis (tri-t-butylphosphine) palladium (0) (0.4 g,0.7 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, 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 compounds 2 to 61. (yield: 60%, MS: [ M+H) ] + ＝630)
Synthesis examples 2 to 62: preparation of Compounds 2-62
Compound B-j (15 g,55.8 mmol) and amine 59 (28.8 g,58.6 mmol) were added to 300mL THF and the mixture was stirred and refluxed. Then, potassium carbonate (23.1 g,167.4 mmol) was dissolved in 69mL of water and added to the mixture, the mixture was stirred well, and bis (tri-t-butylphosphine) palladium (0) (0.3 g,0.6 mmol) was then added. After 4 hours of reaction, the reaction mixture was cooled to room temperature, then the organic layer and the aqueous layer were separated, and the organic layer was distilled. It was redissolved in chloroform and washed twice with water. The organic layer was then separated, anhydrous magnesium sulfate was added, stirred and then filtered. The filtrate was distilled under reduced pressure. The concentrated compound was purified by a silica gel column to obtain 21.6g of compound 2-62. (yield: 57%, MS: [ M+H)] + ＝680)
Synthesis examples 2 to 63: preparation of Compounds 2-63
Compound B-j (15 g,55.8 mmol) and amine 60 (26.6 g,58.6 mmol) were added to 300mL THF and the mixture was stirred and refluxed. Then, potassium carbonate (23.1 g,167.4 mmol) was dissolved in 69mL of water and added to the mixture, the mixture was stirred well, and bis (tri-t-butylphosphine) palladium (0) was then added(0.3 g,0.6 mmol). After 4 hours of reaction, the reaction mixture was cooled to room temperature, then the organic layer and the aqueous layer were separated, and the organic layer was distilled. It was redissolved in chloroform and washed twice with water. The organic layer was then separated, anhydrous magnesium sulfate was added, stirred and then filtered. The filtrate was distilled under reduced pressure. The concentrated compound was purified by a silica gel column to obtain 21.9g of compound 2-63. (yield: 61%, MS: [ M+H) ] + ＝643)
Experimental example 1: determination of deuterium substitution rate
Regarding the compounds represented by chemical formula 1″ among the compounds prepared in synthesis examples 1-1 to 1-79, the number of deuterium substitutions in the compound was obtained by MALDI-TOF MS (matrix assisted laser desorption/ionization time of flight mass spectrometry) analysis, and then the deuterium substitution rate was calculated as a percentage of the number of deuterium substitutions relative to the total number of hydrogen that may be present in the chemical formula. The results are shown in table 1 below.
TABLE 1
Example 1
Coated with a coating having a thickness ofThe glass substrate of the thin film of ITO (indium tin oxide) is put into distilled water containing a detergent dissolved therein, and washed by ultrasonic waves. In this case, the detergent used is a product commercially available from Fischer co, and the distilled water is 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 preparedThe following compound HI-1 was formed intoAs 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 thicknessIs provided.
Then, the following compounds EB-1 to EB-1 were vacuum deposited on the hole transport layerTo form an electron blocking layer.
Then, the compound 1-1 produced in Synthesis example 1-1, the compound 2-1 produced in Synthesis example 2-1, and the 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 ofIs provided.
Vacuum deposition of the following Compounds HB-1 toTo 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 ofElectron injection and transport layers of (a) are provided.
Sequentially depositing lithium fluoride (LiF) and aluminum on electron injection and transport layers to have respectivelyAndthereby forming a cathode. />
In the above process, the deposition rate of the organic material is maintained atSecond to->Per second, the deposition rates of lithium fluoride and aluminum of the cathode are kept at +. >Second and->Per second, and maintaining the vacuum level during deposition at 2 x 10 -7 To 5 x 10 -6 And a support, thereby manufacturing an organic light emitting device.
Examples 2 to 390
An organic light emitting device was manufactured in the same manner as in example 1, except that in the organic light emitting device of example 1, the compound of chemical formula 1 shown in the following tables 2 to 11 was used instead of the compound 1-1 as a first host, and the compound of chemical formula 2 shown in the following tables 1 to 11 was used instead of the compound 2-1 as a second host.
Comparative examples 1 to 60
An organic light emitting device was manufactured in the same manner as in example 1, except that in the organic light emitting device of example 1, comparative compounds a-1 to a-12 shown in the following tables 12 and 13 were used instead of the compound 1-1 as a first host, and compounds of chemical formula 2 shown in the following tables 12 and 13 were used instead of the compound 2-1 as a second host, wherein the structures of the comparative compounds a-1 to a-12 were as follows.
Comparative examples 61 to 156
An organic light emitting device was manufactured in the same manner as in example 1, except that in the organic light emitting device of example 1, the compounds of chemical formula 1 shown in the following tables 14 to 15 were used instead of the compound 1-1 as a first host, and the comparative compounds B-1 to B-12 shown in the following tables 14 to 16 were used instead of the compound 2-1 as a second host. Among them, the structures of comparative compounds B-1 to B-12 are as follows.
Experimental example 2: evaluation of device characteristics
Voltage, efficiency and lifetime (15 mA/cm) were measured by applying current to the organic light emitting devices manufactured in examples 1 to 390 and comparative examples 1 to 156 2 ) The results are shown in tables 2 to 16 below. The lifetime T95 is measured on the basis of 7000 nits, and T95 means the time required for the lifetime to decrease to 95% of the initial lifetime.
TABLE 2
TABLE 3
TABLE 4
TABLE 5
TABLE 6
TABLE 7
TABLE 8
TABLE 9
TABLE 10
TABLE 11
TABLE 12
TABLE 13
TABLE 14
TABLE 15
TABLE 16
As shown in tables 2 to 16 above, the organic light emitting device of the example in which the first compound represented by chemical formula 1 and the second compound represented by chemical formula 2 were simultaneously used as host materials of the light emitting layer exhibited excellent driving voltage, light emitting efficiency and lifetime characteristics as compared with the organic light emitting device of the comparative example using compounds having different structures from one of the compounds represented by chemical formula 1 and chemical formula 2,
in particular, the device according to the embodiment is improved in terms of driving voltage, efficiency and lifetime characteristics as compared to all of the comparative example devices using the comparative compounds a-1 to a-12 as the first host and using the compound represented by chemical formula 2 as the second host and the comparative example devices using the compound represented by chemical formula 1 as the first host and using the comparative compounds B-1 to B-12 as the second host. Therefore, it was determined that when the combination of the first compound represented by chemical formula 1 and the second compound represented by chemical formula 2 is used as a co-host, energy transfer to the red dopant is effectively achieved in the red light emitting layer. This is ultimately believed to be because the co-host combination of the examples maintains a more stable balance in the light emitting layer than the co-host combination of the device of the comparative example.
Accordingly, it was determined that when the first compound and the second compound are simultaneously used as a host material of the organic light emitting device, the driving voltage, the light emitting efficiency, and the lifetime characteristics of the organic light emitting device can be improved. In general, when considering that the light emission efficiency and lifetime characteristics of the organic light emitting device have a trade-off relationship with each other, it can be seen that the organic light emitting device employing the combination of the compounds of the present disclosure exhibits significantly improved device characteristics compared to the device of the comparative example.
< 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 (13)
1. An organic light emitting device comprising:
an anode;
a cathode disposed opposite the anode; and
a light emitting layer between the anode and the cathode,
wherein the light emitting layer comprises a first compound represented by the following chemical formula 1 and a second compound represented by the following chemical formula 2,
[ chemical formula 1]
Wherein, in the chemical formula 1,
L、L 1 and L 2 Each independently is a single bond; or C which is substituted or unsubstituted 6-60 An arylene group,
Ar 1 and Ar is a group 2 Each independently is a substituted or unsubstituted C 6-60 An aryl group,
r is deuterium; substituted or unsubstituted C 6-60 An aryl group; or substituted or unsubstituted C comprising at least one heteroatom of N, O and S 2-60 Heteroaryl, provided that carbazolyl and benzocarbazolyl are excluded from R,
a is an integer of 0 to 7,
[ chemical formula 2]
Wherein, in the chemical formula 2,
x is O or S, and the X is O or S,
R 1 to R 10 Each independently is hydrogen, deuterium, or a substituent represented by the following chemical formula 3, provided that R 1 To R 10 One of them is a substituent represented by the following chemical formula 3,
[ chemical formula 3]
Wherein, in the chemical formula 3,
L’、L 3 and L 4 Each independently is a single bond; substituted or unsubstituted C 6-60 Arylene groups; or substituted or unsubstituted C comprising at least one heteroatom of N, O and S 2-60 Heteroarylene group
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 at least one heteroatom of N, O and S 2-60 Heteroaryl groups.
2. The organic light-emitting device of claim 1, wherein:
l is a single bond; unsubstituted or deuterium-substituted phenylene; or unsubstituted or deuterium-substituted naphthylene.
3. The organic light-emitting device of claim 1, wherein:
L 1 And L 2 Each independently is a single bond; unsubstituted or deuterium-substituted phenylene; an unsubstituted or deuterium-substituted biphenyldiyl group; or unsubstituted or deuterium-substituted naphthylene.
4. The organic light-emitting device of claim 1, wherein:
Ar 1 and Ar is a group 2 Each independently is phenyl, biphenyl, terphenyl, naphthyl, or phenanthryl,
wherein Ar is 1 And Ar is a group 2 Unsubstituted or substituted by a member selected from deuterium, phenyl, naphthyl and-Si (phenyl) 3 Is substituted with one or more substituents.
5. The organic light-emitting device of claim 1, wherein:
r is deuterium; any aryl group selected from phenyl, biphenyl, terphenyl, naphthyl, phenanthryl, triphenylene, and fluoranthenyl; or any heteroaryl group selected from dibenzofuranyl, dibenzothienyl, benzonaphthofuranyl and benzonaphthothienyl,
wherein the aryl and heteroaryl groups are unsubstituted or substituted with one or more substituents selected from deuterium, phenyl substituted with 1 to 5 deuterium, naphthyl, and naphthyl substituted with 1 to 7 deuterium.
6. The organic light-emitting device of claim 1, wherein:
when a is 1, R is deuterium, C 6-20 Aryl, or C containing O or S 2-20 A heteroaryl group, which is a group,
when a is 2 to 7, R is all deuterium; or one of R is C 6-20 Aryl, or C containing O or S 2-20 Heteroaryl, and the balance deuterium,
wherein said C 6-20 Aryl and said C 2-20 Heteroaryl is unsubstituted or substituted with one or more substituents selected from deuterium, phenyl substituted with 1 to 5 deuterium, naphthyl and naphthyl substituted with 1 to 7 deuterium.
7. The organic light-emitting device of claim 1, wherein:
the first compound is represented by any one of the following chemical formulas 1-1 to 1-7:
wherein, in chemical formulas 1-1 to 1-7,
r' is deuterium, C 6-20 Aryl, or C containing O or S 2-20 A heteroaryl group, which is a group,
wherein said C 6-20 Aryl and said C 2-20 Heteroaryl is unsubstituted or substituted with one or more substituents selected from deuterium, phenyl substituted with 1 to 5 deuterium, naphthyl and naphthyl substituted with 1 to 7 deuterium,
d means that the number of the molecules of deuterium,
d is an integer of 0 to 6
L、L 1 、L 2 、Ar 1 And Ar is a group 2 As defined in claim 1.
8. The organic light-emitting device of claim 1, wherein:
the first compound is any one selected from the following compounds:
9. the organic light-emitting device of claim 1, wherein:
the second compound is represented by any one of the following chemical formulas 2-1 to 2-10:
Wherein, in chemical formulas 2-1 to 2-10,
R 1 to R 10 Each independently of the other is hydrogen or deuterium,
l' is a single bond; or unsubstituted or deuterium-substituted C 6-20 Arylene group
L 3 、L 4 、Ar 3 And Ar is a group 4 As defined in claim 1.
10. The organic light-emitting device of claim 1, wherein:
l' is a single bond, or phenylene.
11. The organic light-emitting device of claim 1, wherein:
L 3 and L 4 Each independently is a single bond, phenylene, or naphthylene.
12. The organic light-emitting device of claim 1, wherein:
Ar 3 and Ar is a group 4 Each independently is phenyl, biphenyl, terphenyl, naphthyl, phenanthryl, 9-dimethylfluorenyl, 9-phenylcarbazolyl, dibenzofuranyl, or dibenzothiophenyl.
13. The organic light-emitting device of claim 1, wherein:
the second compound is any one selected from the following compounds:
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR10-2021-0093019 | 2021-07-15 | ||
| KR20210093019 | 2021-07-15 | ||
| PCT/KR2022/010298 WO2023287228A1 (en) | 2021-07-15 | 2022-07-14 | Organic light emitting device |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN117546629A true CN117546629A (en) | 2024-02-09 |
Family
ID=85110539
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202280039225.0A Pending CN117546629A (en) | 2021-07-15 | 2022-07-14 | Organic light emitting device |
Country Status (2)
| Country | Link |
|---|---|
| KR (1) | KR20230012435A (en) |
| CN (1) | CN117546629A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116134030A (en) * | 2020-08-24 | 2023-05-16 | 株式会社Lg化学 | Novel compound and organic light emitting device comprising the same |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100430549B1 (en) | 1999-01-27 | 2004-05-10 | 주식회사 엘지화학 | New organomattalic complex molecule for the fabrication of organic light emitting diodes |
-
2022
- 2022-07-14 CN CN202280039225.0A patent/CN117546629A/en active Pending
- 2022-07-14 KR KR1020220086895A patent/KR20230012435A/en not_active Application Discontinuation
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116134030A (en) * | 2020-08-24 | 2023-05-16 | 株式会社Lg化学 | Novel compound and organic light emitting device comprising the same |
Also Published As
| Publication number | Publication date |
|---|---|
| KR20230012435A (en) | 2023-01-26 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP7293565B2 (en) | organic light emitting device | |
| TWI806011B (en) | Organic light emitting device | |
| JP7500914B2 (en) | Novel compound and organic light-emitting device using the same | |
| KR102576737B1 (en) | Novel compound and organic light emitting device comprising the same | |
| CN115066761A (en) | Organic light emitting device | |
| CN114097103B (en) | Organic light emitting device | |
| CN116508410A (en) | Organic light emitting device | |
| KR20230170637A (en) | Organic light emitting device | |
| CN117546629A (en) | Organic light emitting device | |
| KR102669564B1 (en) | Organic light emitting device | |
| US20240341175A1 (en) | Organic light emitting device | |
| TWI805307B (en) | Organic light emitting device | |
| CN116671279A (en) | Organic light emitting device | |
| CN116710459A (en) | Novel compound and organic light emitting device comprising the same | |
| JP2024500617A (en) | organic light emitting device | |
| CN116323621A (en) | Novel compound and organic light emitting device comprising the same | |
| CN116157407A (en) | Novel compound and organic light emitting device including the same | |
| CN114144901B (en) | Organic light emitting device | |
| CN115605464B (en) | Novel compound and organic light emitting device comprising the same | |
| KR102671015B1 (en) | Organic light emitting device | |
| JP7508742B2 (en) | Organic light-emitting device | |
| CN114144902B (en) | Organic light emitting device | |
| US20240172559A1 (en) | Organic light emitting device | |
| EP4243100A1 (en) | Organic light-emitting device | |
| CN116671280A (en) | Organic light emitting device |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |