CN108017662A - Boric acid or borate or the method that polycyclc aromatic compound or Ppolynuclear aromatic polymer compounds are manufactured using them - Google Patents
Boric acid or borate or the method that polycyclc aromatic compound or Ppolynuclear aromatic polymer compounds are manufactured using them Download PDFInfo
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- CN108017662A CN108017662A CN201711020839.1A CN201711020839A CN108017662A CN 108017662 A CN108017662 A CN 108017662A CN 201711020839 A CN201711020839 A CN 201711020839A CN 108017662 A CN108017662 A CN 108017662A
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- 150000001875 compounds Chemical class 0.000 title claims abstract description 192
- 125000003118 aryl group Chemical group 0.000 title claims abstract description 109
- 229920000642 polymer Polymers 0.000 title claims abstract description 63
- 150000001491 aromatic compounds Chemical class 0.000 title claims abstract description 57
- 238000000034 method Methods 0.000 title claims abstract description 39
- 239000004327 boric acid Substances 0.000 title abstract description 39
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 title abstract description 37
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 title abstract description 33
- 125000001072 heteroaryl group Chemical group 0.000 claims abstract description 72
- 238000004519 manufacturing process Methods 0.000 claims abstract description 49
- 239000002253 acid Substances 0.000 claims abstract description 11
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 72
- 125000000217 alkyl group Chemical group 0.000 claims description 70
- 229910052799 carbon Inorganic materials 0.000 claims description 69
- 229910052739 hydrogen Inorganic materials 0.000 claims description 55
- 239000001257 hydrogen Substances 0.000 claims description 55
- 229910052736 halogen Inorganic materials 0.000 claims description 53
- 150000002367 halogens Chemical class 0.000 claims description 52
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 51
- -1 compounds Compound Chemical class 0.000 claims description 33
- 125000003545 alkoxy group Chemical group 0.000 claims description 24
- 229910021529 ammonia Inorganic materials 0.000 claims description 15
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 15
- IVDFJHOHABJVEH-UHFFFAOYSA-N pinacol Chemical compound CC(C)(O)C(C)(C)O IVDFJHOHABJVEH-UHFFFAOYSA-N 0.000 claims description 14
- 125000004104 aryloxy group Chemical group 0.000 claims description 13
- 238000005886 esterification reaction Methods 0.000 claims description 13
- 238000006467 substitution reaction Methods 0.000 claims description 13
- YZCKVEUIGOORGS-OUBTZVSYSA-N Deuterium Chemical group [2H] YZCKVEUIGOORGS-OUBTZVSYSA-N 0.000 claims description 12
- 229910052805 deuterium Inorganic materials 0.000 claims description 12
- 230000032050 esterification Effects 0.000 claims description 12
- 125000005241 heteroarylamino group Chemical group 0.000 claims description 12
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 12
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 10
- 125000005647 linker group Chemical group 0.000 claims description 9
- 239000000126 substance Substances 0.000 claims description 8
- 125000000547 substituted alkyl group Chemical group 0.000 claims description 5
- 150000002431 hydrogen Chemical class 0.000 claims description 4
- 125000003107 substituted aryl group Chemical group 0.000 claims description 4
- 125000001769 aryl amino group Chemical group 0.000 claims description 2
- 125000005842 heteroatom Chemical group 0.000 claims 1
- 150000001642 boronic acid derivatives Chemical class 0.000 abstract description 7
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 174
- 239000010410 layer Substances 0.000 description 75
- 238000006243 chemical reaction Methods 0.000 description 45
- 239000000463 material Substances 0.000 description 39
- 239000002585 base Substances 0.000 description 35
- 239000007787 solid Substances 0.000 description 33
- 239000002904 solvent Substances 0.000 description 32
- 0 CC(C)*C1[C@](C*(*)CC2*C*=**=NC=CCC2)CCCCCC(C)(C)C1*CC*=C Chemical compound CC(C)*C1[C@](C*(*)CC2*C*=**=NC=CCC2)CCCCCC(C)(C)C1*CC*=C 0.000 description 29
- 238000003756 stirring Methods 0.000 description 29
- 125000001424 substituent group Chemical group 0.000 description 29
- 239000003480 eluent Substances 0.000 description 27
- 239000000243 solution Substances 0.000 description 26
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 25
- 229910052757 nitrogen Inorganic materials 0.000 description 25
- 239000012044 organic layer Substances 0.000 description 25
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 24
- 230000015572 biosynthetic process Effects 0.000 description 24
- 238000003786 synthesis reaction Methods 0.000 description 24
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 22
- 239000012299 nitrogen atmosphere Substances 0.000 description 22
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 20
- 238000005292 vacuum distillation Methods 0.000 description 20
- 239000007788 liquid Substances 0.000 description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 19
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 18
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 17
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 17
- 238000000926 separation method Methods 0.000 description 16
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 15
- 239000000741 silica gel Substances 0.000 description 15
- 229910002027 silica gel Inorganic materials 0.000 description 15
- 229960001866 silicon dioxide Drugs 0.000 description 15
- 238000010792 warming Methods 0.000 description 15
- ILAHWRKJUDSMFH-UHFFFAOYSA-N boron tribromide Chemical compound BrB(Br)Br ILAHWRKJUDSMFH-UHFFFAOYSA-N 0.000 description 14
- 229910052744 lithium Inorganic materials 0.000 description 14
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 14
- 238000005160 1H NMR spectroscopy Methods 0.000 description 12
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 12
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 12
- 238000005481 NMR spectroscopy Methods 0.000 description 12
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 12
- 239000000758 substrate Substances 0.000 description 12
- 238000005401 electroluminescence Methods 0.000 description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 10
- 230000005540 biological transmission Effects 0.000 description 10
- 230000001413 cellular effect Effects 0.000 description 10
- 238000010276 construction Methods 0.000 description 10
- 230000005284 excitation Effects 0.000 description 10
- MZRVEZGGRBJDDB-UHFFFAOYSA-N n-Butyllithium Substances [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 10
- 239000004065 semiconductor Substances 0.000 description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 9
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 9
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 8
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical group C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 8
- 239000003153 chemical reaction reagent Substances 0.000 description 8
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 8
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical group C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 8
- 239000000284 extract Substances 0.000 description 8
- 230000005669 field effect Effects 0.000 description 8
- 239000010408 film Substances 0.000 description 8
- 238000010438 heat treatment Methods 0.000 description 8
- 238000002347 injection Methods 0.000 description 8
- 239000007924 injection Substances 0.000 description 8
- DLEDOFVPSDKWEF-UHFFFAOYSA-N lithium butane Chemical compound [Li+].CCC[CH2-] DLEDOFVPSDKWEF-UHFFFAOYSA-N 0.000 description 8
- IUYHWZFSGMZEOG-UHFFFAOYSA-M magnesium;propane;chloride Chemical compound [Mg+2].[Cl-].C[CH-]C IUYHWZFSGMZEOG-UHFFFAOYSA-M 0.000 description 8
- 239000000203 mixture Substances 0.000 description 8
- 238000010992 reflux Methods 0.000 description 8
- 230000027756 respiratory electron transport chain Effects 0.000 description 8
- 238000010898 silica gel chromatography Methods 0.000 description 8
- 239000010409 thin film Substances 0.000 description 8
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 7
- 238000004821 distillation Methods 0.000 description 7
- 230000004927 fusion Effects 0.000 description 7
- 239000012046 mixed solvent Substances 0.000 description 7
- 239000002841 Lewis acid Substances 0.000 description 6
- 230000008859 change Effects 0.000 description 6
- 150000002148 esters Chemical group 0.000 description 6
- 238000001704 evaporation Methods 0.000 description 6
- 229910000027 potassium carbonate Inorganic materials 0.000 description 6
- 239000002243 precursor Substances 0.000 description 6
- 239000011541 reaction mixture Substances 0.000 description 6
- 238000001226 reprecipitation Methods 0.000 description 6
- 230000004044 response Effects 0.000 description 6
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical group [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 5
- JGFZNNIVVJXRND-UHFFFAOYSA-N N,N-Diisopropylethylamine (DIPEA) Chemical compound CCN(C(C)C)C(C)C JGFZNNIVVJXRND-UHFFFAOYSA-N 0.000 description 5
- 229910052796 boron Inorganic materials 0.000 description 5
- 238000005660 chlorination reaction Methods 0.000 description 5
- 230000008020 evaporation Effects 0.000 description 5
- 238000001914 filtration Methods 0.000 description 5
- 150000007517 lewis acids Chemical class 0.000 description 5
- WGOPGODQLGJZGL-UHFFFAOYSA-N lithium;butane Chemical compound [Li+].CC[CH-]C WGOPGODQLGJZGL-UHFFFAOYSA-N 0.000 description 5
- 238000004768 lowest unoccupied molecular orbital Methods 0.000 description 5
- 239000007848 Bronsted acid Substances 0.000 description 4
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 150000001335 aliphatic alkanes Chemical class 0.000 description 4
- 235000010290 biphenyl Nutrition 0.000 description 4
- 150000002118 epoxides Chemical class 0.000 description 4
- 239000012212 insulator Substances 0.000 description 4
- UBJFKNSINUCEAL-UHFFFAOYSA-N lithium;2-methylpropane Chemical compound [Li+].C[C-](C)C UBJFKNSINUCEAL-UHFFFAOYSA-N 0.000 description 4
- QPJVMBTYPHYUOC-UHFFFAOYSA-N methyl benzoate Chemical compound COC(=O)C1=CC=CC=C1 QPJVMBTYPHYUOC-UHFFFAOYSA-N 0.000 description 4
- 239000011368 organic material Substances 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- MFRIHAYPQRLWNB-UHFFFAOYSA-N sodium tert-butoxide Chemical compound [Na+].CC(C)(C)[O-] MFRIHAYPQRLWNB-UHFFFAOYSA-N 0.000 description 4
- FCEHBMOGCRZNNI-UHFFFAOYSA-N 1-benzothiophene Chemical group C1=CC=C2SC=CC2=C1 FCEHBMOGCRZNNI-UHFFFAOYSA-N 0.000 description 3
- HRZTZLCMURHWFY-UHFFFAOYSA-N 2-bromo-1,3-difluorobenzene Chemical class FC1=CC=CC(F)=C1Br HRZTZLCMURHWFY-UHFFFAOYSA-N 0.000 description 3
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 3
- 239000005864 Sulphur Substances 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 125000000641 acridinyl group Chemical group C1(=CC=CC2=NC3=CC=CC=C3C=C12)* 0.000 description 3
- 239000003513 alkali Substances 0.000 description 3
- RDOXTESZEPMUJZ-UHFFFAOYSA-N anisole Chemical class COC1=CC=CC=C1 RDOXTESZEPMUJZ-UHFFFAOYSA-N 0.000 description 3
- 239000012298 atmosphere Substances 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 239000000460 chlorine Substances 0.000 description 3
- 229910052801 chlorine Inorganic materials 0.000 description 3
- 238000004440 column chromatography Methods 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000006471 dimerization reaction Methods 0.000 description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 3
- 239000000706 filtrate Substances 0.000 description 3
- YCOZIPAWZNQLMR-UHFFFAOYSA-N heptane - octane Natural products CCCCCCCCCCCCCCC YCOZIPAWZNQLMR-UHFFFAOYSA-N 0.000 description 3
- 230000008676 import Effects 0.000 description 3
- 125000001041 indolyl group Chemical group 0.000 description 3
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- SKTCDJAMAYNROS-UHFFFAOYSA-N methoxycyclopentane Chemical compound COC1CCCC1 SKTCDJAMAYNROS-UHFFFAOYSA-N 0.000 description 3
- 229910052763 palladium Inorganic materials 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 239000001632 sodium acetate Substances 0.000 description 3
- 235000017281 sodium acetate Nutrition 0.000 description 3
- VNDYJBBGRKZCSX-UHFFFAOYSA-L zinc bromide Chemical compound Br[Zn]Br VNDYJBBGRKZCSX-UHFFFAOYSA-L 0.000 description 3
- YJTKZCDBKVTVBY-UHFFFAOYSA-N 1,3-Diphenylbenzene Chemical group C1=CC=CC=C1C1=CC=CC(C=2C=CC=CC=2)=C1 YJTKZCDBKVTVBY-UHFFFAOYSA-N 0.000 description 2
- IANQTJSKSUMEQM-UHFFFAOYSA-N 1-benzofuran Chemical group C1=CC=C2OC=CC2=C1 IANQTJSKSUMEQM-UHFFFAOYSA-N 0.000 description 2
- BMIBJCFFZPYJHF-UHFFFAOYSA-N 2-methoxy-5-methyl-3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)pyridine Chemical compound COC1=NC=C(C)C=C1B1OC(C)(C)C(C)(C)O1 BMIBJCFFZPYJHF-UHFFFAOYSA-N 0.000 description 2
- UJOBWOGCFQCDNV-UHFFFAOYSA-N 9H-carbazole Chemical compound C1=CC=C2C3=CC=CC=C3NC2=C1 UJOBWOGCFQCDNV-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- KLZUFWVZNOTSEM-UHFFFAOYSA-K Aluminium flouride Chemical compound F[Al](F)F KLZUFWVZNOTSEM-UHFFFAOYSA-K 0.000 description 2
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- 229940126062 Compound A Drugs 0.000 description 2
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 2
- NLDMNSXOCDLTTB-UHFFFAOYSA-N Heterophylliin A Natural products O1C2COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC2C(OC(=O)C=2C=C(O)C(O)=C(O)C=2)C(O)C1OC(=O)C1=CC(O)=C(O)C(O)=C1 NLDMNSXOCDLTTB-UHFFFAOYSA-N 0.000 description 2
- CPELXLSAUQHCOX-UHFFFAOYSA-N Hydrogen bromide Chemical compound Br CPELXLSAUQHCOX-UHFFFAOYSA-N 0.000 description 2
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 2
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 description 2
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- 229920002472 Starch Polymers 0.000 description 2
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 description 2
- 150000001412 amines Chemical class 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
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 229910000085 borane Inorganic materials 0.000 description 2
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 description 2
- 125000000609 carbazolyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3NC12)* 0.000 description 2
- 239000012043 crude product Substances 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- NNBZCPXTIHJBJL-UHFFFAOYSA-N decalin Chemical compound C1CCCC2CCCCC21 NNBZCPXTIHJBJL-UHFFFAOYSA-N 0.000 description 2
- 230000003111 delayed effect Effects 0.000 description 2
- TXCDCPKCNAJMEE-UHFFFAOYSA-N dibenzofuran Chemical group C1=CC=C2C3=CC=CC=C3OC2=C1 TXCDCPKCNAJMEE-UHFFFAOYSA-N 0.000 description 2
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 2
- DMBHHRLKUKUOEG-UHFFFAOYSA-N diphenylamine Chemical compound C=1C=CC=CC=1NC1=CC=CC=C1 DMBHHRLKUKUOEG-UHFFFAOYSA-N 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 230000005684 electric field Effects 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 238000010931 ester hydrolysis Methods 0.000 description 2
- AIGRXSNSLVJMEA-FQEVSTJZSA-N ethoxy-(4-nitrophenoxy)-phenyl-sulfanylidene-$l^{5}-phosphane Chemical compound O([P@@](=S)(OCC)C=1C=CC=CC=1)C1=CC=C([N+]([O-])=O)C=C1 AIGRXSNSLVJMEA-FQEVSTJZSA-N 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 239000000499 gel Substances 0.000 description 2
- NDJKXXJCMXVBJW-UHFFFAOYSA-N heptadecane Chemical compound CCCCCCCCCCCCCCCCC NDJKXXJCMXVBJW-UHFFFAOYSA-N 0.000 description 2
- DCAYPVUWAIABOU-UHFFFAOYSA-N hexadecane Chemical compound CCCCCCCCCCCCCCCC DCAYPVUWAIABOU-UHFFFAOYSA-N 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- CBFCDTFDPHXCNY-UHFFFAOYSA-N icosane Chemical compound CCCCCCCCCCCCCCCCCCCC CBFCDTFDPHXCNY-UHFFFAOYSA-N 0.000 description 2
- PSCMQHVBLHHWTO-UHFFFAOYSA-K indium(iii) chloride Chemical compound Cl[In](Cl)Cl PSCMQHVBLHHWTO-UHFFFAOYSA-K 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 125000003253 isopropoxy group Chemical group [H]C([H])([H])C([H])(O*)C([H])([H])[H] 0.000 description 2
- ZCSHNCUQKCANBX-UHFFFAOYSA-N lithium diisopropylamide Chemical compound [Li+].CC(C)[N-]C(C)C ZCSHNCUQKCANBX-UHFFFAOYSA-N 0.000 description 2
- 230000004807 localization Effects 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 229940095102 methyl benzoate Drugs 0.000 description 2
- GYVGXEWAOAAJEU-UHFFFAOYSA-N n,n,4-trimethylaniline Chemical class CN(C)C1=CC=C(C)C=C1 GYVGXEWAOAAJEU-UHFFFAOYSA-N 0.000 description 2
- 150000002790 naphthalenes Chemical class 0.000 description 2
- RZJRJXONCZWCBN-UHFFFAOYSA-N octadecane Chemical compound CCCCCCCCCCCCCCCCCC RZJRJXONCZWCBN-UHFFFAOYSA-N 0.000 description 2
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 2
- 150000002894 organic compounds Chemical class 0.000 description 2
- WCPAKWJPBJAGKN-UHFFFAOYSA-N oxadiazole Chemical group C1=CON=N1 WCPAKWJPBJAGKN-UHFFFAOYSA-N 0.000 description 2
- 230000033116 oxidation-reduction process Effects 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
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- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 1
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- 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
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- KWYHDKDOAIKMQN-UHFFFAOYSA-N N,N,N',N'-tetramethylethylenediamine Chemical compound CN(C)CCN(C)C KWYHDKDOAIKMQN-UHFFFAOYSA-N 0.000 description 1
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- PQLAYKMGZDUDLQ-UHFFFAOYSA-K aluminium bromide Chemical compound Br[Al](Br)Br PQLAYKMGZDUDLQ-UHFFFAOYSA-K 0.000 description 1
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- 230000004888 barrier function Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 125000003785 benzimidazolyl group Chemical group N1=C(NC2=C1C=CC=C2)* 0.000 description 1
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- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical group C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
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- HDBYLQMYLREYAD-UHFFFAOYSA-N c(cc1)cc(Oc2ccc3)c1S1c2c3Oc2c1cccc2 Chemical compound c(cc1)cc(Oc2ccc3)c1S1c2c3Oc2c1cccc2 HDBYLQMYLREYAD-UHFFFAOYSA-N 0.000 description 1
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- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
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- 238000004140 cleaning Methods 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 229940125904 compound 1 Drugs 0.000 description 1
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- SBTSVTLGWRLWOD-UHFFFAOYSA-L copper(ii) triflate Chemical compound [Cu+2].[O-]S(=O)(=O)C(F)(F)F.[O-]S(=O)(=O)C(F)(F)F SBTSVTLGWRLWOD-UHFFFAOYSA-L 0.000 description 1
- 150000001907 coumarones Chemical class 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 230000006837 decompression Effects 0.000 description 1
- 125000002704 decyl 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])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- IYYZUPMFVPLQIF-UHFFFAOYSA-N dibenzothiophene Chemical group C1=CC=C2C3=CC=CC=C3SC2=C1 IYYZUPMFVPLQIF-UHFFFAOYSA-N 0.000 description 1
- 150000002012 dioxanes Chemical class 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 125000003438 dodecyl 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])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
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- 238000005516 engineering process Methods 0.000 description 1
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- 238000002474 experimental method Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
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- 238000003682 fluorination reaction Methods 0.000 description 1
- UQSQSQZYBQSBJZ-UHFFFAOYSA-N fluorosulfonic acid Chemical compound OS(F)(=O)=O UQSQSQZYBQSBJZ-UHFFFAOYSA-N 0.000 description 1
- 150000002240 furans Chemical class 0.000 description 1
- JKFAIQOWCVVSKC-UHFFFAOYSA-N furazan Chemical compound C=1C=NON=1 JKFAIQOWCVVSKC-UHFFFAOYSA-N 0.000 description 1
- UPWPDUACHOATKO-UHFFFAOYSA-K gallium trichloride Chemical compound Cl[Ga](Cl)Cl UPWPDUACHOATKO-UHFFFAOYSA-K 0.000 description 1
- SRVXDMYFQIODQI-UHFFFAOYSA-K gallium(iii) bromide Chemical compound Br[Ga](Br)Br SRVXDMYFQIODQI-UHFFFAOYSA-K 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000009499 grossing Methods 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- UQWQCMSYGMAGKF-UHFFFAOYSA-N hexane;lithium Chemical compound [Li].CCCCCC UQWQCMSYGMAGKF-UHFFFAOYSA-N 0.000 description 1
- 238000004770 highest occupied molecular orbital Methods 0.000 description 1
- 229910000042 hydrogen bromide Inorganic materials 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 1
- 229910000040 hydrogen fluoride Inorganic materials 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 125000002883 imidazolyl group Chemical group 0.000 description 1
- 150000002466 imines Chemical class 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 125000003406 indolizinyl group Chemical group C=1(C=CN2C=CC=CC12)* 0.000 description 1
- 238000003402 intramolecular cyclocondensation reaction Methods 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 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
- 125000000904 isoindolyl group Chemical group C=1(NC=C2C=CC=CC12)* 0.000 description 1
- 238000002955 isolation Methods 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
- AWJUIBRHMBBTKR-UHFFFAOYSA-N isoquinoline Chemical group C1=NC=CC2=CC=CC=C21 AWJUIBRHMBBTKR-UHFFFAOYSA-N 0.000 description 1
- ZLTPDFXIESTBQG-UHFFFAOYSA-N isothiazole Chemical compound C=1C=NSC=1 ZLTPDFXIESTBQG-UHFFFAOYSA-N 0.000 description 1
- 125000000842 isoxazolyl group Chemical group 0.000 description 1
- 238000004895 liquid chromatography mass spectrometry Methods 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- YNESATAKKCNGOF-UHFFFAOYSA-N lithium bis(trimethylsilyl)amide Chemical compound [Li+].C[Si](C)(C)[N-][Si](C)(C)C YNESATAKKCNGOF-UHFFFAOYSA-N 0.000 description 1
- BNHFWQQYLUPDOG-UHFFFAOYSA-N lithium;1,2,2,3-tetramethylpiperidine Chemical compound [Li].CC1CCCN(C)C1(C)C BNHFWQQYLUPDOG-UHFFFAOYSA-N 0.000 description 1
- DBTNVRCCIDISMV-UHFFFAOYSA-L lithium;magnesium;propane;dichloride Chemical compound [Li+].[Mg+2].[Cl-].[Cl-].C[CH-]C DBTNVRCCIDISMV-UHFFFAOYSA-L 0.000 description 1
- MCVFFRWZNYZUIJ-UHFFFAOYSA-M lithium;trifluoromethanesulfonate Chemical compound [Li+].[O-]S(=O)(=O)C(F)(F)F MCVFFRWZNYZUIJ-UHFFFAOYSA-M 0.000 description 1
- 238000004020 luminiscence type Methods 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
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- OTCKOJUMXQWKQG-UHFFFAOYSA-L magnesium bromide Chemical compound [Mg+2].[Br-].[Br-] OTCKOJUMXQWKQG-UHFFFAOYSA-L 0.000 description 1
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- IWCVDCOJSPWGRW-UHFFFAOYSA-M magnesium;benzene;chloride Chemical compound [Mg+2].[Cl-].C1=CC=[C-]C=C1 IWCVDCOJSPWGRW-UHFFFAOYSA-M 0.000 description 1
- NXPHGHWWQRMDIA-UHFFFAOYSA-M magnesium;carbanide;bromide Chemical compound [CH3-].[Mg+2].[Br-] NXPHGHWWQRMDIA-UHFFFAOYSA-M 0.000 description 1
- LVKCSZQWLOVUGB-UHFFFAOYSA-M magnesium;propane;bromide Chemical compound [Mg+2].[Br-].C[CH-]C LVKCSZQWLOVUGB-UHFFFAOYSA-M 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000001465 metallisation Methods 0.000 description 1
- 229940098779 methanesulfonic acid Drugs 0.000 description 1
- UZKWTJUDCOPSNM-UHFFFAOYSA-N methoxybenzene Substances CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 description 1
- KRDDXSIKPQVLDP-UHFFFAOYSA-N methylarsenic Chemical compound [As]C KRDDXSIKPQVLDP-UHFFFAOYSA-N 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 125000002950 monocyclic group Chemical group 0.000 description 1
- VAMFXQBUQXONLZ-UHFFFAOYSA-N n-alpha-eicosene Natural products CCCCCCCCCCCCCCCCCCC=C VAMFXQBUQXONLZ-UHFFFAOYSA-N 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
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 125000004957 naphthylene group Chemical group 0.000 description 1
- 150000005054 naphthyridines Chemical group 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
- 238000010534 nucleophilic substitution reaction Methods 0.000 description 1
- 125000005447 octyloxy 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])C([H])([H])O* 0.000 description 1
- 150000002900 organolithium compounds Chemical class 0.000 description 1
- 125000001979 organolithium group Chemical group 0.000 description 1
- 230000003534 oscillatory effect Effects 0.000 description 1
- 125000002971 oxazolyl group Chemical group 0.000 description 1
- 125000005582 pentacene group Chemical group 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 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
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 description 1
- ANRQGKOBLBYXFM-UHFFFAOYSA-M phenylmagnesium bromide Chemical compound Br[Mg]C1=CC=CC=C1 ANRQGKOBLBYXFM-UHFFFAOYSA-M 0.000 description 1
- 150000003003 phosphines Chemical class 0.000 description 1
- 125000004437 phosphorous atom Chemical group 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 1
- LFSXCDWNBUNEEM-UHFFFAOYSA-N phthalazine Chemical group C1=NN=CC2=CC=CC=C21 LFSXCDWNBUNEEM-UHFFFAOYSA-N 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 125000004193 piperazinyl group Chemical group 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- CPNGPNLZQNNVQM-UHFFFAOYSA-N pteridine Chemical group N1=CN=CC2=NC=CN=C21 CPNGPNLZQNNVQM-UHFFFAOYSA-N 0.000 description 1
- 125000003226 pyrazolyl group Chemical group 0.000 description 1
- 125000005581 pyrene group Chemical group 0.000 description 1
- PBMFSQRYOILNGV-UHFFFAOYSA-N pyridazine Chemical group C1=CC=NN=C1 PBMFSQRYOILNGV-UHFFFAOYSA-N 0.000 description 1
- 125000000714 pyrimidinyl group Chemical group 0.000 description 1
- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical compound O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 description 1
- 125000002294 quinazolinyl group Chemical group N1=C(N=CC2=CC=CC=C12)* 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
- 125000006413 ring segment Chemical group 0.000 description 1
- 150000003839 salts Chemical class 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
- 239000010703 silicon Substances 0.000 description 1
- QRUBYZBWAOOHSV-UHFFFAOYSA-M silver trifluoromethanesulfonate Chemical compound [Ag+].[O-]S(=O)(=O)C(F)(F)F QRUBYZBWAOOHSV-UHFFFAOYSA-M 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 238000010025 steaming Methods 0.000 description 1
- 239000002887 superconductor Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- UEUXEKPTXMALOB-UHFFFAOYSA-J tetrasodium;2-[2-[bis(carboxylatomethyl)amino]ethyl-(carboxylatomethyl)amino]acetate Chemical compound [Na+].[Na+].[Na+].[Na+].[O-]C(=O)CN(CC([O-])=O)CCN(CC([O-])=O)CC([O-])=O UEUXEKPTXMALOB-UHFFFAOYSA-J 0.000 description 1
- 125000003831 tetrazolyl group Chemical group 0.000 description 1
- VLLMWSRANPNYQX-UHFFFAOYSA-N thiadiazole Chemical compound C1=CSN=N1.C1=CSN=N1 VLLMWSRANPNYQX-UHFFFAOYSA-N 0.000 description 1
- GVIJJXMXTUZIOD-UHFFFAOYSA-N thianthrene Chemical group C1=CC=C2SC3=CC=CC=C3SC2=C1 GVIJJXMXTUZIOD-UHFFFAOYSA-N 0.000 description 1
- WHLUQAYNVOGZST-UHFFFAOYSA-N tifenamil Chemical group C=1C=CC=CC=1C(C(=O)SCCN(CC)CC)C1=CC=CC=C1 WHLUQAYNVOGZST-UHFFFAOYSA-N 0.000 description 1
- LTSUHJWLSNQKIP-UHFFFAOYSA-J tin(iv) bromide Chemical compound Br[Sn](Br)(Br)Br LTSUHJWLSNQKIP-UHFFFAOYSA-J 0.000 description 1
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 1
- UBZYKBZMAMTNKW-UHFFFAOYSA-J titanium tetrabromide Chemical compound Br[Ti](Br)(Br)Br UBZYKBZMAMTNKW-UHFFFAOYSA-J 0.000 description 1
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 1
- 125000001425 triazolyl group Chemical group 0.000 description 1
- FEONEKOZSGPOFN-UHFFFAOYSA-K tribromoiron Chemical compound Br[Fe](Br)Br FEONEKOZSGPOFN-UHFFFAOYSA-K 0.000 description 1
- FAQYAMRNWDIXMY-UHFFFAOYSA-N trichloroborane Chemical compound ClB(Cl)Cl FAQYAMRNWDIXMY-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
- 125000001889 triflyl group Chemical group FC(F)(F)S(*)(=O)=O 0.000 description 1
- FTVLMFQEYACZNP-UHFFFAOYSA-N trimethylsilyl trifluoromethanesulfonate Chemical compound C[Si](C)(C)OS(=O)(=O)C(F)(F)F FTVLMFQEYACZNP-UHFFFAOYSA-N 0.000 description 1
- ODHXBMXNKOYIBV-UHFFFAOYSA-N triphenylamine Chemical compound C1=CC=CC=C1N(C=1C=CC=CC=1)C1=CC=CC=C1 ODHXBMXNKOYIBV-UHFFFAOYSA-N 0.000 description 1
- 125000006617 triphenylamine group Chemical group 0.000 description 1
- SLGBZMMZGDRARJ-UHFFFAOYSA-N triphenylene Chemical group C1=CC=C2C3=CC=CC=C3C3=CC=CC=C3C2=C1 SLGBZMMZGDRARJ-UHFFFAOYSA-N 0.000 description 1
- 229910000404 tripotassium phosphate Inorganic materials 0.000 description 1
- 235000019798 tripotassium phosphate Nutrition 0.000 description 1
- RSJKGSCJYJTIGS-UHFFFAOYSA-N undecane Chemical compound CCCCCCCCCCC RSJKGSCJYJTIGS-UHFFFAOYSA-N 0.000 description 1
- PCMOZDDGXKIOLL-UHFFFAOYSA-K yttrium chloride Chemical compound [Cl-].[Cl-].[Cl-].[Y+3] PCMOZDDGXKIOLL-UHFFFAOYSA-K 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 1
- DUNKXUFBGCUVQW-UHFFFAOYSA-J zirconium tetrachloride Chemical compound Cl[Zr](Cl)(Cl)Cl DUNKXUFBGCUVQW-UHFFFAOYSA-J 0.000 description 1
- LSWWNKUULMMMIL-UHFFFAOYSA-J zirconium(iv) bromide Chemical compound Br[Zr](Br)(Br)Br LSWWNKUULMMMIL-UHFFFAOYSA-J 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic Table
- C07F5/02—Boron compounds
- C07F5/022—Boron compounds without C-boron linkages
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic Table
- C07F5/02—Boron compounds
- C07F5/025—Boronic and borinic acid compounds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic Table
- C07F5/02—Boron compounds
-
- 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
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Electroluminescent Light Sources (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Heterocyclic Carbon Compounds Containing A Hetero Ring Having Nitrogen And Oxygen As The Only Ring Hetero Atoms (AREA)
Abstract
The method that polycyclc aromatic compound or Ppolynuclear aromatic polymer compounds are manufactured the present invention relates to boric acid or borate or using them.The effective boronic acid compounds of manufacture for polycyclc aromatic compound and the method using boronic acid compounds manufacture polycyclc aromatic compound are provided.Acid is acted on the compound shown in the following general formula (1), manufacture polycyclc aromatic compound.In formula, A rings, B ring and C rings are aromatic ring or hetero-aromatic ring independently of one another, Y1For optional esterified B (OH)2, X1And X2For O, ＞ N Ar (Ar is aryl etc.), S or Se.
Description
Technical field
The present invention relates to can manufacture in organic electroluminescence device, organic field effect tube and organic thin film solar
Used in battery and display device and lighting device polycyclc aromatic compound or Ppolynuclear aromatic polymer compounds (with
Be also referred to as polycyclc aromatic compound etc. down) boric acid and borate.
Background technology
All the time, using the display device of electroluminescent luminescent device due to can be carried out with power saving, slimming
Various researchs, and then, by the organic electroluminescence device that organic material is formed due to easy lightweight, maximization and carry out
Actively research.Exploitation especially with regard to the organic material of the characteristics of luminescence of the blueness with one of optics three primary colors etc. and
Possess the exploitation of the organic material of the charge transport abilities such as hole, electronics (having as semiconductor, the possibility of superconductor), nothing
By being high-molecular compound or low molecular compound, positive research has all been carried out so far.
Organic EL element has following structure, i.e. the structure includes：A pair of electrodes for being made of anode and cathode and
Configure a layer between a pair of electrodes and comprising organic compound or multiple layers.In layer comprising organic compound, have
Luminescent layer, be used for transmission or inject hole, the electric charge transmission/implanted layer of electric charge such as electronics etc., develops and is suitable for these layers
Various organic materials.
As luminescent layer material, such as develop (No. 2004/061047 public affairs of International Publication No. such as benzfluorene based compound
Report).In addition, as hole mobile material, such as develop (the Japanese Unexamined Patent Publication 2001-172232 public affairs such as triphen amine compound
Report).In addition, as electron transport material, such as develop anthracene based compound etc. (Japanese Unexamined Patent Publication 2005-170911 publications).
In addition, in recent years, as the material used in organic EL element, organic thin film solar cell, also report by
The material (No. 2012/118164 publication of International Publication No.) that triphenylamine derivative improvement forms.The material is that have following feature
Material：With practical N, N '-diphenyl-N, N '-bis- (3- aminomethyl phenyls) -1,1 '-biphenyl -4,4 '-diamines (TPD) are made
To refer to, by the way that the aromatic ring for forming triphenylamine is connected to each other, so as to improve its flatness.In the document, it have rated
Such as the charge transmission of NO connections based compound (compound 1 of page 63), but be chemical combination without related NO connections are recorded
The manufacture method of material beyond thing, if in addition, the element of connection is different, the electronic state of compound entirety is different, therefore
The characteristic obtained by the material beyond NO connection based compounds is also unknown.The example of this compound also can elsewhere
See (No. 2011/107186 publication of International Publication No.).For example, the big conjugated structure of the energy (T1) with triplet exciton
Compound can send shorter wavelengths of phosphorescence, therefore be beneficial with material as blue luminescent layer.In addition, as clamping
Electron transport material, the hole mobile material of luminescent layer, also pursue the compound with new conjugated structure big T1.
The material of main part of organic EL element is typically by the existing virtue such as multiple benzene, carbazole with singly-bound, phosphorus atoms, silicon atom
The molecule that fragrant race's ring is formed by connecting.This is because by the way that the less aromatic ring of multiple conjugated systems is connected, so as to ensure to lead
Big HOMO-LUMO energy gaps (the band gap Eg of film) needed for body material.And then for using phosphor material, thermally activated sluggishness
The material of main part of the organic EL element of fluorescent material, high triplet excitation energy (ET) it is also necessary, by molecule
Donor or Receptor aromatic ring, substituent are connected, so that SOMO1 the and SOMO2 localizations of triplet excitation state (T1),
Reduce the exchange interaction of two interorbitals, thus, it is possible to improve triplet excitation energy (ET).But the virtue that conjugated system is small
The oxidation-reduction stability of fragrant race's ring is insufficient, using the molecule of existing aromatic ring is connected with as the element of material of main part
Service life it is insufficient.On the other hand, it is excellent with the usual oxidation-reduction stability of polycyclc aromatic compound for expanding pi-conjugated system
It is different, but HOMO-LUMO energy gaps (the band gap Eg of film), triplet excitation energy (ET) low, it is taken as that being not suitable for main body material
Material.
Prior art literature
Patent document
Patent document 1：No. 2004/061047 publication of International Publication No.
Patent document 2：Japanese Unexamined Patent Publication 2001-172232 publications
Patent document 3：Japanese Unexamined Patent Publication 2005-170911 publications
Patent document 4：No. 2012/118164 publication of International Publication No.
Patent document 5：No. 2011/107186 publication of International Publication No.
Patent document 6：No. 2015/102118 publication of International Publication No.
The content of the invention
Problems to be solved by the invention
In No. 2015/102118 publication of International Publication No., as the method for manufacturing above-mentioned polycyclc aromatic compound, record
：Make the organo-lithium compound and Boron tribromide that are generated by the methods of halogen-lithium exchange reactions, ortho-metalated reaction anti-
Should, the method for directly carrying out intramolecular cyclization in the reaction system is imported after boron atom.However, there are the following problems：(1) for
Sometimes the reaction produced in the process because adding the Boron tribromide of same high response in the organolithium intermediate to high response
The reasons such as superheat state that is hot and producing part, yield reduces sometimes particularly when improving reaction scale；(2) cyclization precursor
Boron compound also tends to unstable, it is therefore desirable to without isolation, purifying is carried out continuously the molecule inner ring as next step reaction
Change reaction, accumulate the accessory substance of the successive reaction in final product sometimes as impurity；(3) as a result, the choosing of obtained product
Selecting property is low, and more purification procedures are needed for high purity, and the yield of object is also reduced.In addition, in existing method,
After the importing for carrying out lithiumation and borane reagent at low temperature, generally require directly to carry out cyclization at high temperature, it is necessary to same
The reaction of low temperature and high temperature is carried out continuously in reactor, therefore, limitation also is produced to device, operation sometimes.Industrial utilizationization
During compound, it is preferably able to stably largely manufacture, moreover, the material of usually organic EL element especially requires high-purity, therefore
Easy, the high efficiency of the purification procedures of terminal stage also become important.
The solution used to solve the problem
The inventors of the present invention have made intensive studies to solve the above-mentioned problems, are closed it turns out that Ppolynuclear aromatic is cyclized
The boric acid or borate of the precursor of thing etc. make lewis acid, particularly Bronsted acid, road as aluminium chloride as raw material
Lewis acid reacts, so as to manufacture the polycyclc aromatic compound etc..
Compound shown in a kind of 1. the following general formula (1) of item is (wherein, not including following X1And X2It is the situation of-O-)；One
Polymer compounds of the kind with structure shown in multiple the following general formula (1) are (wherein, not including following X1And X2It is the feelings of-O-
Condition)；It is a kind of to be used to manufacture the compound shown in the following general formula (1) of polycyclc aromatic compound；It is or, a kind of polycyclic for manufacturing
The polymer compounds with structure shown in multiple the following general formula (1) of aromatic series polymer compounds.
(in above-mentioned formula (1),
A rings, B ring and C rings are aromatic ring or hetero-aromatic ring independently of one another, and at least one hydrogen in these rings is optionally substituted,
Y1For optional esterified-B (OH)2,
X1And X2It is-O-, ＞ N-Ar ,-S- or-Se- independently of one another, herein, the Ar of foregoing N-Ar is optionally substituted
Aryl, optionally substituted heteroaryl or optionally substituted alkyl, the Ar of foregoing N-Ar optionally pass through linking group or singly-bound
And be bonded with foregoing A rings, B rings and/or C rings, moreover,
At least one hydrogen in compound or structure shown in formula (1) is optionally substituted by deuterium.)
2. compound or polymer compounds according to item 1 of item, wherein, A rings, B ring and C rings are independently of one another virtue
Ring or hetero-aromatic ring, aryl that at least one hydrogen in these rings is optionally substituted or unsubstituted, substituted or unsubstituted heteroaryl,
Substituted or unsubstituted ammonia diaryl base, substituted or unsubstituted two heteroaryl amino, substituted or unsubstituted aryl heteroaryl
Amino, substituted or unsubstituted alkyl, substituted or unsubstituted alkoxy, substituted or unsubstituted aryloxy group or halogen take
Generation,
Y1For optional esterified-B (OH)2,
X1And X2Be-O-, ＞ N-Ar ,-S- or-Se- independently of one another, herein, the Ar of foregoing N-Ar for optionally by alkyl or
The aryl of halogen substitution, optionally by heteroaryl that alkyl or halogen substitute or the alkyl optionally substituted by alkyl or halogen, it is preceding
The Ar of N-Ar is stated optionally by-O- ,-S-, ＞ C (R)2Or singly-bound and be bonded with foregoing A rings, B rings and/or C rings, it is also, foregoing
＞ C (R)2R be hydrogen or alkyl independently of one another, at least one hydrogen in the alkyl is optionally optionally substituted by halogen,
At least one hydrogen in compound or structure shown in formula (1) is optionally substituted by deuterium, moreover,
Foregoing polymer compounds are 2 dimmer compounds or 3 dimmer compounds.
Compound shown in a kind of 3. the following general formula (2) of item is (wherein, not including following X1And X2It is the situation of-O-)；
A kind of or, compound for manufacturing shown in the following general formula (2) of polycyclc aromatic compound.
(in above-mentioned formula (2),
R1、R2、R3、R4、R5、R6、R7、R8、R9、R10And R11Independently of one another for hydrogen, aryl, heteroaryl, ammonia diaryl base,
Two heteroaryl aminos, aryl heteroaryl amino, alkyl, alkoxy, aryloxy group or halogen, at least one hydrogen optionally quilt in them
Aryl, heteroaryl, alkyl or halogen substitution, also, R1~R11Among adjacent group optionally bond together and with a rings, b rings or
C rings form aromatic ring or hetero-aromatic ring together, at least one hydrogen in the ring formed optionally by aryl, heteroaryl, ammonia diaryl base,
Two heteroaryl aminos, aryl heteroaryl amino, alkyl, alkoxy, aryloxy group or halogen substitution, at least one hydrogen in them are appointed
Choosing is substituted by aryl, heteroaryl, alkyl or halogen,
Y1For optional esterified-B (OH)2,
X1And X2It is-O-, ＞ N-Ar ,-S- or-Se- independently of one another, herein, the Ar of foregoing N-Ar is carbon number 6~12
The alkyl of aryl, the heteroaryl of carbon number 2~15 or carbon number 1~6, at least one hydrogen in them is optionally optionally substituted by halogen, foregoing
The Ar of N-Ar optionally passes through-O- ,-S-, ＞ C (R)2Or singly-bound and be bonded with foregoing a rings, b rings and/or c rings, also, foregoing ＞ C
(R)2R be independently of one another carbon number 1~6 alkyl, at least one hydrogen in the alkyl is optionally optionally substituted by halogen, moreover,
At least one hydrogen in compound shown in formula (2) is optionally substituted by deuterium.)
4. compound according to item 3 of item, wherein, R1、R2、R3、R4、R5、R6、R7、R8、R9、R10And R11Independently of one another
Ground is hydrogen, the aryl of carbon number 6~30, the heteroaryl of carbon number 2~30, (wherein, aryl is the virtue of carbon number 6~12 to ammonia diaryl base
Base) or halogen, at least one hydrogen in them is optionally optionally substituted by halogen, also, R1~R11Among adjacent group optionally each other
It is bonded and the aromatic ring of carbon number 9~16 or the hetero-aromatic ring of carbon number 6~15 is formed together with a rings, b rings or c rings, in the ring formed
At least one hydrogen is optionally substituted by the aryl of carbon number 6~10 or halogen, and at least one hydrogen in the aryl of the carbon number 6~10 is optional
It is optionally substituted by halogen,
Y1To make-B (OH)2Group obtained from esterification,
X1And X2Be-O-, ＞ N-Ar or-S- independently of one another, herein, the Ar of foregoing N-Ar be carbon number 6~10 aryl or
The alkyl of carbon number 1~4, at least one hydrogen in them are optionally optionally substituted by halogen, moreover,
At least one hydrogen in compound shown in formula (2) is optionally substituted by deuterium.
Compound shown in a kind of 5. following formula (1-1-98) of item；It is or, a kind of for manufacturing polycyclc aromatic compound
Compound shown in following formula (1-1-98).
Bpin in formula is to make-B (OH)2Group obtained from pinacol esterification, tBu is the tert-butyl group.
Item 6. is a kind of to be used to manufacture polycyclc aromatic compound, following formula (1-3-139), formula (1-3-252), formula (1-
3-386) or the compound shown in formula (1-3-439).
Bpin in formula is to make-B (OH)2Group obtained from pinacol esterification, Me is methyl.
7. a kind of are used to manufacturing shown in polycyclc aromatic compound, following formula (1-2-340) or formula (1-2-343)
Compound.
Bpin in formula is to make-B (OH)2Group obtained from pinacol esterification, Me is methyl, and tBu is the tert-butyl group.
A kind of 8. manufacture methods of item, wherein, acid is acted on compound or tool shown in the following general formula (1) described in item 1
There are the polymer compounds of structure shown in multiple the following general formula (1), manufacture polycyclc aromatic compound or Ppolynuclear aromatic poly
Body compound.
(in structure above,
A rings, B ring and C rings are aromatic ring or hetero-aromatic ring independently of one another, and at least one hydrogen in these rings is optionally substituted,
Y1For optional esterified-B (OH)2,
X1And X2It is-O-, ＞ N-Ar ,-S- or-Se- independently of one another, herein, the Ar of foregoing N-Ar is optionally substituted
Aryl, optionally substituted heteroaryl or optionally substituted alkyl, the Ar of foregoing N-Ar optionally pass through linking group or singly-bound
And be bonded with foregoing A rings, B rings and/or C rings, moreover,
At least one hydrogen in structure above is optionally substituted by deuterium.)
The effect of invention
The stability of boric acid or borate shown in above-mentioned general formula (1) etc. is high, therefore in the reaction with acid
Avoid the problem that being derived from high response, avoid yield during popularization from reducing.In addition, the high boric acid of stability or borate hold
It is easily separated and purify, therefore product can be obtained with high selectivity, as a result it is easier using high-purity and obtains in high yield as having
The polycyclc aromatic compound of machine EL element material.And then the changing temperature only in same reactor, can be with simple
Heating react and manufactured.
In addition, obtained by above-mentioned boric acid or borate, with the miscellaneous element such as boron, phosphorus, oxygen, nitrogen, sulphur by aromatic rings connection and
Into polycyclc aromatic compound there is big HOMO-LUMO energy gaps (the band gap Eg of film) and high triplet excitation energy
(ET).It is thought that because the armaticity of 6 yuan of rings comprising miscellaneous element is low, therefore, with the HOMO- of conjugated system expansion
LUMO energy gaps are reduced and are suppressed, SOMO1 the and SOMO2 locals of triplet excitation state (T1) are made because of the electronic perturbation of miscellaneous element
Change.In addition, this polycyclc aromatic compound makes two rails because of the localization of the SOMO1 and SOMO2 of triplet excitation state (T1)
Exchange interaction between road diminishes, therefore triplet excitation state (T1) and the energy difference of singlet state excitation state (S1) are small, display
Go out thermally activated delayed fluorescence, therefore be also useful as the fluorescent material of organic EL element.In addition, with high triplet
Excitation energy (ET) material as phosphorescence organic EL element, using thermally activated delayed fluorescence organic EL element electronics pass
Defeated layer, hole transmission layer are also useful.And then these polycyclc aromatic compounds can be made by the importing of substituent
The energy of HOMO and LUMO arbitrarily changes, therefore can optimize ionization potential, electron affinity according to periphery material.
Brief description of the drawings
Fig. 1 is the schematic cross-section for the organic EL element for showing present embodiment.
Description of reference numerals
100 organic electroluminescence devices
101 substrates
102 anodes
103 hole injection layers
104 hole transmission layers
105 luminescent layers
106 electron transfer layers
107 electron injecting layers
108 cathodes
Embodiment
1. the summary of the present invention
If the roughly explanation present invention, one embodiment of the present invention is related to compound and tool shown in the following general formula (1)
There are the polymer compounds of structure shown in multiple the following general formula (1).It should be noted that on polymer compounds, according to more
Quantity, the form of dimerization and compound structure is different, therefore following polymer compounds are an example, central polymer compounds
It is the compound for being formed the bonding of structure shown in 2 formulas (1) with singly-bound, the polymer compounds on right side are to share the side of ring A
The compound that formula forms the bonding of structure shown in 2 formulas (1).In addition, the symbol in formula is identical with defined in above-mentioned item 1.
For these compounds, due to Y1For optional esterified-B (OH)2, therefore boric acid is also referred to as in the present specification
Or borate.The usage of these compounds is not particularly limited, not including X1And X2It is the situation of-O-.
In addition, the other manner of the present invention is related to shown in the following general formula (1) for manufacturing polycyclc aromatic compound
Compound or the polymer with structure shown in multiple the following general formula (1) for manufacturing Ppolynuclear aromatic polymer compounds
Compound.Wherein, for manufacturing polycyclc aromatic compound, these compounds of Ppolynuclear aromatic polymer compounds can be with X1
And X2It is-O-.These compounds are also due to Y1For optional esterified-B (OH)2And be referred to as in the present specification boric acid or
Borate.It should be noted that on polymer compounds, according to the quantity of multimerization, form, compound structure is different, because
This following structure is an example.In addition, the symbol in formula is identical with defined in above-mentioned item 1.
It is to manufacture Ppolynuclear aromatic using the compound for being used to manufacture shown in the general formula (1) of polycyclc aromatic compound below
The summary of the process of compound.In addition, the symbol in formula is identical with defined in above-mentioned item 7.
In addition, following tie to use for manufacturing having for Ppolynuclear aromatic polymer compounds shown in multiple general formulas (1)
The summary of the process of the polymer compounds manufacture Ppolynuclear aromatic polymer compounds of structure.It should be noted that on poly
Body compound, Ppolynuclear aromatic polymer compounds, according to the quantity of multimerization, form, compound structure is different, therefore under
It is an example to state structure.In addition, the symbol in formula is identical with defined in above-mentioned item 7.
2. the boric acid and borate of the present invention
The present application is the compound or more with structure shown in multiple the following general formula (1) shown in the following general formula (1)
Dimmer compound.The present application is preferably compound shown in the following general formula (2) or with shown in multiple the following general formula (2)
The polymer compounds of structure.It should be noted that the Y in following formula (1)1、X1And X2It is identical with defined in above-mentioned item 1, it is following
Y in formula (2)1、X1、X2And R1~R11It is identical with defined in above-mentioned item 3.
A rings, B ring and C rings in general formula (1) are aromatic ring or hetero-aromatic ring independently of one another, at least one hydrogen in these rings
Optionally it is substituted with a substituent.The substituent be preferably substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, substitution or
Unsubstituted ammonia diaryl base, substituted or unsubstituted two heteroaryl amino, substituted or unsubstituted aryl heteroaryl amino (tool
Have the amino of aryl and heteroaryl), it is substituted or unsubstituted alkyl, substituted or unsubstituted alkoxy, substituted or unsubstituted
Aryloxy group or halogen.There is substituent during substituent as these groups, aryl, heteroaryl, alkyl or halogen can be included
Element.
In addition, A rings, B ring and C rings are preferably 5 yuan of rings or 6 yuan optionally condensed by other rings independently of one another
Ring.The example that the structure of general formula (2) is A rings, B ring and C rings are phenyl ring (6 yuan of rings).Wherein, as described later, R1~R11Among phase
Adjacent group optionally bonds together and aromatic ring or hetero-aromatic ring is formed together with a rings, b rings or c rings, therefore the phenyl ring can also become
Fusion has the structure of other rings.
A rings (or B rings, C rings) in general formula (1) correspond to a rings and its substituent R in general formula (2)1~R3(or b rings and
Its substituent R4~R7, c rings and its substituent R8~R11).In the sense that, by a~c tables of each ring small letter of general formula (2)
Show.
In general formula (2), the substituent R of a rings, b rings and c rings1~R11Among adjacent group optionally bond together and and a
Ring, b rings or c rings form aromatic ring or hetero-aromatic ring together, and at least one hydrogen in the ring formed is optionally by aryl, heteroaryl, two
Arylamino, two heteroaryl aminos, aryl heteroaryl amino, alkyl, alkoxy, aryloxy group or halogen substitution, in them extremely
Few hydrogen is optionally substituted by aryl, heteroaryl, alkyl or halogen.Therefore, the compound shown in general formula (2) is according to a rings, b rings
With the mutual speciation of the substituent in c rings as shown in following formula (2-1) and formula (2-2) composition compound ring structure
Change.A ' rings, B ' rings and C ' rings in various correspond respectively to A rings, B ring and C rings in general formula (1).Need what is illustrated
It is the Y in following formula1、X1、X2And R1~R11It is identical with defined in above-mentioned item 3.
Above-mentioned formula (2-1) and A ' rings, B ' rings and C ' in formula (2-2) are if ring is illustrated by general formula (2), then it represents that substituent
R1~R11Among adjacent the group aromatic ring or hetero-aromatic ring that bond together and formed respectively together with a rings, b rings and c rings (can also
Say it is that other ring structures condense the condensed ring formed in a rings, b rings or c rings).Though it should be noted that be not shown in formula,
Become the compound for turning to A ' rings, B ' rings and C ' rings there are a rings, b rings and c rings.In addition, can by above-mentioned formula (2-1) and formula (2-2)
Know, for example, the R of b rings8With the R of c rings7, b rings R11With the R of a rings1, c rings R4With the R of a rings3Etc. being not belonging to " adjacent group
Each other ", they are not bonded.That is, " adjacent group " refers to adjacent group on same ring.
Compound shown in above-mentioned formula (2-1), formula (2-2) corresponds to for example aftermentioned formula enumerated as particular compound
Compound shown in (1-3-323)~(1-3-391).That is, for example, having makes phenyl ring, indole ring, pyrrole ring, benzofuran ring
Or benzothiophene ring etc. condenses the chemical combination of the A ' rings (or B ' rings or C ' rings) formed in the phenyl ring as a rings (or b rings or c rings)
Thing, the condensed ring A ' formed (or condensed ring B ' or condensed ring C ') is respectively naphthalene nucleus, carbazole ring, indole ring, dibenzofurans ring or two
Benzothiophene ring etc..
Y in general formula (1)1For optional esterified-B (OH)2.Preferable Y1To make-B (OH)2Base obtained from esterification
Group.The explanation is for the Y in general formula (2)1For it is also identical.
As making-B (OH)2(- the B (OR) of group obtained from esterification2), it is not particularly limited, can includes by with hydroxyl
Group obtained from such as alkyl, aryl and acid reaction of base.As-B (OR)2R, optionally substituted carbon can be included
The alkyl (branched alkyl of carbon number 3~4) of number 1~4, R optionally bonds together and forms ring, also, the ring formed can wrap
Containing aromatic rings such as benzene.Specifically, the group of following structure can be included.
X in general formula (1)1And X2It is-O-, ＞ N-Ar ,-S- or-Se- independently of one another, the Ar of foregoing N-Ar is optionally quilt
Substituted aryl, optionally substituted heteroaryl or optionally substituted alkyl, the Ar of foregoing N-Ar optionally pass through linking group
Or singly-bound and be bonded with foregoing A rings, B rings and/or C rings, as linking group, preferably-O- ,-S- or ＞ C (R)2.Need to illustrate
, foregoing " ＞ C (R)2" R be hydrogen or alkyl independently of one another, at least one hydrogen in the alkyl is optionally optionally substituted by halogen.
The specification is for the X in general formula (2)1And X2Also it is identical.
Herein, in general formula (1) " Ar of N-Ar by linking group or singly-bound and with foregoing A rings, B rings and/or C ring keys
The restriction of conjunction " is corresponding to " Ar of N-Ar passes through-O- ,-S-, ＞ C (R) in general formula (2)2Or singly-bound and with foregoing a rings, b rings and/
Or c rings bonding " restriction.
The restriction can use following formula (2-3-1) shown in, there is X1、X2Entered by group to the ring in condensed ring B ' and condensed ring C '
The compound of structure shows.That is, for example, having makes the phenyl ring as b rings (or c rings) in general formula (2) with by X1(or X2)
The compound for the B ' rings (or C ' rings) that the mode that group enters is condensed and formed with other rings.Condensed ring B ' (or condensed ring C ') example formed
As Wei phenoxazine ring, phenthazine ring or acridine ring.
In addition, above-mentioned restriction can also use following formula (2-3-2), shown in formula (2-3-3), there is X1And/or X2Entered by group
Showed to the compound of the ring structure in condensed ring A '.That is, for example, having incites somebody to action the phenyl ring as a rings in general formula (2)
X1(and/or X2) mode that enters of group and the fusion of other rings and the compound of A ' rings that is formed.The condensed ring A ' formed is, for example, Fen Evil
Piperazine ring, phenthazine ring or acridine ring.
It should be noted that the Y in following formula1、X1、X2And R1~R11It is identical with defined in above-mentioned item 3.
On general formula (1) as A rings, " aromatic ring " of B ring and C rings, such as the aromatic ring of carbon number 6~30 can be included, it is excellent
Select the aromatic ring of the aromatic ring of carbon number 6~16, more preferably carbon number 6~12, the aromatic ring of particularly preferred carbon number 6~10.It should be noted that
It is somebody's turn to do " aromatic ring " and corresponds to " the R limited in general formula (2)1~R11Among adjacent group bond together and with a rings, b rings or c rings one
Act the aromatic ring formed ", in addition, a rings (or b rings, c rings) are formed via the phenyl ring of carbon number 6, therefore it is condensed with 5 yuan of rings and
Into condensed ring total carbon number 9 be lower limit carbon number.
As specific " aromatic ring ", the phenyl ring for belonging to monocyclic system can be included；Belong to the cyclohexyl biphenyl of second cycle line；Belong to fusion
The naphthalene nucleus of second cycle line；Belong to the terphenyl ring (meta-terphenyl, ortho-terphenyl, para-terpheny) of three ring systems；Belong to fused tricyclic system
Acenaphthylene ring, fluorenes ring, non-that alkene ring, phenanthrene ring；Belong to the benzo phenanthrene ring, pyrene ring, aphthacene ring of fused tetracyclic system；Belong to fusion five
The ring of ring system, pentacene ring etc..
On general formula (1) as A rings, " hetero-aromatic ring " of B ring and C rings, such as the heteroaryl of carbon number 2~30 can be included
The hetero-aromatic ring of the hetero-aromatic ring of ring, preferably carbon number 2~25, more preferably carbon number 2~20, the hetero-aromatic ring of further preferred carbon number 2~15,
The hetero-aromatic ring of particularly preferred carbon number 2~10.In addition, as " hetero-aromatic ring ", such as can include as ring atom except carbon
Outside also containing 1~5 heteroatomic heterocycle in oxygen, sulphur and nitrogen etc..Correspond to it should be noted that being somebody's turn to do " hetero-aromatic ring "
" the R limited in general formula (2)1~R11Among the adjacent group heteroaryl that bonds together and formed together with a rings, b rings or c rings
Ring ", in addition, a rings (or b rings, c rings) are formed via the phenyl ring of carbon number 6, therefore makes its condensed ring formed with the fusion of 5 yuan of rings
Total carbon number 6 is the carbon number of lower limit.
As specific " hetero-aromatic ring ", such as pyrrole ring, oxazole ring, isoxazole rings, thiazole ring, isothiazole can be included
Ring, imidazole ring, oxadiazole rings, Thiadiazole, triazole ring, tetrazole ring, pyrazole ring, pyridine ring, pyrimidine ring, pyridazine ring, pyridine ring,
Triazine ring, indole ring, iso-indoles ring, 1H- indazoles ring, benzimidazole ring, benzoxazole ring, benzothiazole ring, 1H- benzotriazole
Ring, quinoline ring, isoquinolin ring, cinnolines ring, quinazoline ring, quinoxaline ring, phthalazines ring, naphthyridines ring, purine ring, pteridine ring, carbazole
Ring, acridine ring, Fen Evil thiophene ring, phenoxazines ring, phenthazine ring, azophenlyene ring, indolizine ring, furan nucleus, benzofuran ring, different benzo
Furan nucleus, dibenzofurans ring, thiphene ring, benzothiophene ring, dibenzothiophenes ring, furazan Huan, oxadiazole rings, thianthrene ring etc..
At least one hydrogen in above-mentioned " aromatic ring " or " hetero-aromatic ring " is optionally by as the 1st substituent, substitution or unsubstituted
" aryl ", substituted or unsubstituted " heteroaryl ", substituted or unsubstituted " ammonia diaryl base ", substituted or unsubstituted " two
Heteroaryl amino ", substituted or unsubstituted " aryl heteroaryl amino ", substituted or unsubstituted " alkyl ", substitution or unsubstituted
" alkoxy ", substituted or unsubstituted " aryloxy group " or halogen substitution, on " aryl " as the 1st substituent,
The aryl of " heteroaryl ", " ammonia diaryl base ", the heteroaryl of " two heteroaryl aminos ", the aryl of " aryl heteroaryl amino " and miscellaneous
The aryl of aryl or " aryloxy group ", can include the univalent perssad of above-mentioned " aromatic ring " or " hetero-aromatic ring ".
In addition, on " alkyl " as the 1st substituent, can be straight chain and side chain any one, such as carbon can be included
The straight chained alkyl of number 1~24 or the branched alkyl of carbon number 3~24.It is preferred that alkyl (the branched alkane of carbon number 3~18 of carbon number 1~18
Base), the more preferably alkyl (branched alkyl of carbon number 3~12) of carbon number 1~12, the alkyl (carbon number 3 of further preferred carbon number 1~6
~6 branched alkyl), the alkyl (branched alkyl of carbon number 3~4) of particularly preferred carbon number 1~4.
As specific alkyl, can include methyl, ethyl, n-propyl, isopropyl, normal-butyl, isobutyl group, sec-butyl,
The tert-butyl group, n-pentyl, isopentyl, neopentyl, tertiary pentyl, n-hexyl, 1- methyl amyls, 4- methyl -2- amyl groups, 3,3- dimethyl
Butyl, 2- ethyl-butyls, n-heptyl, 1- methylhexyls, n-octyl, t-octyl, 1- methylheptyls, 2- ethylhexyls, 2- propyl group
Amyl group, n-nonyl, 2,2- dimethyl heptyl, 2,6- dimethyl -4- heptyl, 3,5,5- trimethyls, positive decyl, n-undecane
Base, 1- methyldecyls, dodecyl, n-tridecane base, 1- hexyls heptyl, n-tetradecane base, n-pentadecane base, hexadecane
Base, n-heptadecane base, n-octadecane base, n-eicosane base etc..
In addition, on " alkoxy " as the 1st substituent, for example, can include carbon number 1~24 straight chain or carbon number 3~
The alkoxy of 24 side chain.It is preferred that the alkoxy (alkoxy of the side chain of carbon number 3~18) of carbon number 1~18, more preferably carbon number 1~
12 alkoxy (alkoxy of the side chain of carbon number 3~12), the alkoxy (side chain of carbon number 3~6 of further preferred carbon number 1~6
Alkoxy), the alkoxy (alkoxy of the side chain of carbon number 3~4) of particularly preferred carbon number 1~4.
As specific alkoxy, methoxyl group, ethyoxyl, propoxyl group, isopropoxy, butoxy, isobutyl oxygen can be included
Base, sec-butoxy, tert-butoxy, amoxy, hexyloxy, epoxide in heptan, octyloxy etc..
In addition, on " halogen " as the 1st substituent, fluorine, chlorine, bromine or iodine can be included.
On as the 1st substituent, substituted or unsubstituted " aryl ", substituted or unsubstituted " heteroaryl ", substitution
Or unsubstituted " ammonia diaryl base ", substituted or unsubstituted " two heteroaryl aminos ", substituted or unsubstituted " aryl heteroaryl
Amino ", substituted or unsubstituted " alkyl ", substituted or unsubstituted " alkoxy " or substituted or unsubstituted " aryloxy group ",
Substitution or unsubstituted such as described, at least one hydrogen in them is optionally substituted by the 2nd substituent.Taken as the 2nd
Dai Ji, such as aryl, heteroaryl, alkyl or halogen can be included, their specific example is referred to above-mentioned " aromatic ring " or " miscellaneous
The univalent perssad of aromatic ring " or " alkyl ", the explanation of " halogen " as the 1st substituent.In addition, the virtue as the 2nd substituent
In base, heteroaryl, at least one hydrogen in them is (specific by alkyl such as the aryl such as phenyl (specific example is as described above), methyl
Example is as described above) substitute the group formed to be also included in the aryl as the 2nd substituent, within heteroaryl.As one
Example, in the case that the 2nd substituent is carbazyl, what at least one hydrogen of 9 was substituted by alkyl such as the aryl such as phenyl, methyl
Carbazyl is also included within the heteroaryl as the 2nd substituent.
R as general formula (2)1~R11In aryl, heteroaryl, the aryl of ammonia diaryl base, two heteroaryl aminos it is miscellaneous
The aryl or halogen of aryl, the aryl of aryl heteroaryl amino and heteroaryl, aryloxy group, can include explanation in general formula (1)
The univalent perssad of " aromatic ring " or " hetero-aromatic ring ".In addition, as R1~R11In alkyl, alkoxy or halogen, be referred to above-mentioned
The explanation as " alkyl " of the 1st substituent, " alkoxy " or " halogen " in the explanation of general formula (1).And then as these bases
Aryl, heteroaryl, alkyl or the halogen of substituent in group are similarly.In addition, on R1~R11Among adjacent group each other
Bonding and in the case of forming aromatic ring or hetero-aromatic ring together with a rings, b rings or c rings, heteroaryl as the substituent on these rings
Base, ammonia diaryl base, two heteroaryl aminos, aryl heteroaryl amino, alkyl, alkoxy, aryloxy group or halogen and as into one
Aryl, heteroaryl, alkyl or the halogen of the substituent of step, similarly.
The X of general formula (1)1And X2In the Ar of N-Ar be the aryl, heteroaryl or the alkane that are optionally substituted by above-mentioned 2nd substituent
Base, at least one hydrogen in aryl, heteroaryl or alkyl are optionally substituted by such as alkyl, halogen.As the aryl, heteroaryl,
Alkyl and halogen, can include above-mentioned group.The aryl (such as phenyl, naphthyl etc.) of particularly preferred carbon number 6~10, carbon number 2~
15 heteroaryl (such as carbazyl etc.), the alkyl (such as methyl, ethyl etc.) of carbon number 1~4.The explanation is in general formula (2)
X1And X2For it is also identical.
" the ＞ C (R) as linking group in general formula (1)2" R be hydrogen or alkyl independently of one another, in the alkyl
At least one hydrogen is optionally optionally substituted by halogen, and as the alkyl, halogen, can include above-mentioned group.As alkyl, particularly preferred carbon
The alkyl (such as methyl, ethyl etc.) of number 1~4.The explanation is for " the ＞ C (R) as linking group in general formula (2)2" and
Speech is also identical.
In addition, the present application be with the polymer compounds of cellular construction shown in multiple general formulas (1), be preferably with
The polymer compounds of cellular construction shown in multiple general formulas (2).Polymer compounds are preferably 2~6 aggressiveness, and more preferably 2~3
Aggressiveness, particularly preferably 2 aggressiveness.As long as polymer compounds are the form with multiple said units structures in a compound
, for example, can be that multiple said units structures are connected by singly-bound, the alkylidene of carbon number 1~3, phenylene, naphthylene etc.
The form (such as corresponding to such compound shown in aftermentioned formula (1-1-223), formula (1-1-226)) that group bonding forms, this
Outside, can also be to share any ring (A rings, B rings or C rings, a rings, the b contained by said units structure in multiple cellular constructions
Ring or c rings) the form that is bonded of mode, alternatively, it is also possible to be any ring (A rings, B rings or the C contained by said units structure
Ring, a rings, b rings or c rings) it is bonded the form formed to fusion each other.
As this polymer compounds, such as following formula (2-4), formula (2-4-1), formula (2-4-2), formula can be included
Polymer compounds shown in (2-5-1)~formula (2-5-4) or formula (2-6).Specifically, such as corresponding to aftermentioned formula (1-1-
224), formula (1-1-225), formula (1-1-227), such compound shown in formula (1-1-228).It is more shown in following formula (2-4)
It is more to have in a compound in a manner of the shared phenyl ring as a rings if dimmer compound is illustrated by general formula (2)
The polymer compounds of cellular construction shown in a general formula (2).More specifically, the polymer chemical combination shown in following formula (2-4-1)
If thing is illustrated by general formula (2), for there are two general formulas in a manner of the shared phenyl ring as a rings in a compound
(2) polymer compounds of cellular construction shown in, following formula (2-4-2) if shown in polymer compounds by general formula (2) for
It is bright, then in a compound in a manner of the shared phenyl ring as a rings with the more of cellular construction shown in three general formulas (2)
Dimmer compound.In addition, following formula (2-5-1)~formula (2-5-4) if shown in polymer compounds illustrated by general formula (2),
It is then that there is cellular construction shown in multiple general formulas (2) in a manner of the shared phenyl ring as b rings (or c rings) in a compound
Polymer compounds.In addition, following formula (2-6) if shown in polymer compounds illustrated by general formula (2), at one
Phenyl ring in compound using such as some cellular construction as b rings (or a rings, c rings) is used as b rings with some cellular construction
The mode of the phenyl ring fusion of (or a rings, c rings) has the polymer compounds of cellular construction shown in multiple general formulas (2).Need to illustrate
, the Y in following formula1、X1、X2And R1~R11It is identical with defined in above-mentioned item 3.
Polymer compounds can also be with formula (2-4), formula (2-4-1) or formula (2-4-2) show multimerization form with
The polymer chemical combination that the multimerization form families showed with any one in formula (2-5-1)~formula (2-5-4) or formula (2-6) forms
Thing, or more with being showed with formula (2-6) with the multimerization form that any one in formula (2-5-1)~formula (2-5-4) shows
The polymer compounds that dimerization form families forms, or showed with formula (2-4), formula (2-4-1) or formula (2-4-2) more
Dimerization form and the multimerization form showed with any one in formula (2-5-1)~formula (2-5-4) and the poly with formula (2-6) performance
Change the polymer compounds that form families forms.
In addition, general formula (1) or the compound shown in (2) or the poly with structure shown in multiple general formulas (1) or (2)
Optionally its all or part of be deuterium for hydrogen in the chemical constitution of body compound.
As the boric acid of the present invention and the more specifically example of borate, following compound can be included.In various,
Bpin is to make-B (OH)2Group obtained from pinacol esterification, Me is methyl,tBu is the tert-butyl group,iPr is isopropyl.
In above-mentioned illustration, compound, formula (1-2-1) shown in any one in preferred formula (1-1-1)~formula (1-1-209)~
Compound shown in any one in compound and formula (1-3-1)~formula (1-3-466) shown in any one in formula (1-2-306).
3. the manufacture method of the boric acid such as general formula (1) or borate
Compound (boric acid or borate) shown in general formula (1) or (2) can substantially manufacture as follows：By using bonding base
Group (X1And X2) A rings (a rings) are bonded with B rings (b rings) and C rings (c rings) and manufacture intermediate (the 1st reaction), it is then introduced into Y1Base
Group, so that borate can be manufactured first, by being hydrolyzed, so as to manufacture its boric acid.In 1st reaction, such as if
Etherification reaction, then can utilize the popular response of nucleophilic substitution, ullmann reaction etc, if ammoxidation, then may be used
To utilize the popular response of Buchwald-Hartwig reaction etc.It should be noted that each scheme described below
(scheme) symbol in structural formula in is as defined above.
2nd reaction is to import to be used as to the intermediate obtained by the above-mentioned 1st reaction as shown in following proposal (1) or (2)
Y1Bpin as borate reaction.
Scheme (1)
Scheme (2)
In such scheme (1) and (2), first, ortho position is carried out by using n-BuLi, s-butyl lithium or tert-butyl lithium etc.
Metallization, so that lithiumation occurs for hydrogen atom.Herein, show and n-BuLi, s-butyl lithium or tert-butyl lithium etc. is used alone
Method, but in order to improve reactivity, N, N, N can also be added ', N '-tetramethylethylenediamine etc..Then, to obtained lithium
Change and 2- isopropoxies -4,4 are added in body, 5,5- tetramethyls -1,3, acid esterification reactant as 2- dioxaborolans, from
And the pinacol ester of boric acid can be manufactured.Herein, 2- isopropoxies -4,4,5,5- tetramethyls -1,3,2- dioxas penta are shown
The method of borine, in addition it is also possible to use trimethoxy borine, three isopropoxy borines etc..In addition, using International Publication No.
Method described in No. 2013/016185 publication, 4,4,5,5- tetramethyls -1,3,2- dioxaborolans etc. can similarly make
With.
In addition, as shown in following proposal (3) or (4), will the method for (1) or (2) manufacture through the above scheme borate
Hydrolysis, so as to manufacture boric acid.
Scheme (3)
Scheme (4)
And then appropriate alcohol is acted on (1)~(4) obtain through the above scheme borate or boric acid, so as to
Different borates is manufactured via ester exchange or resterification.
It should be noted that such scheme (1) and (2) show the manufacturer of general formula (1) or the borate shown in (2)
Method, can be by using with multiple A rings (a on the polymer compounds with structure shown in multiple general formulas (1) or (2)
Ring), the intermediate of B rings (b rings) and C rings (c rings) manufactures.Use following proposal (5)~(7) explanation in detail.At this time, by that will make
The amount of the reagents such as butyl lithium be set to 2 times amount, 3 times amount etc., the targets such as 2 dimmer compounds, 3 dimmer compounds can be obtained
Thing.
Scheme (5)
Scheme (6)
Scheme (7)
The manufacture method of the polymer compounds of borate is shown in such scheme (5)~(7), its boric acid body can root
Manufactured according to such scheme (4) by hydrolyzing, in addition, different ester bodies can also come via the ester exchange using alcohol, resterification
Manufacture.
By proper choice of above-mentioned synthetic method, also raw material used in appropriate selection, can synthesize and have in desired position
The boric acid or borate of substituted base.
In such scheme (1)~(7), lithium is imported to desired position by ortho-metalated, has passed through such as following proposal
(8) or (9) import the halogens such as bromine atoms in the position for wanting importing lithium like that and carry out halogen-metal exchange, also can be to the phase
The position of prestige imports lithium.It is then possible to borate is manufactured by obtained lithiumation body.
Scheme (8)
Scheme (9)
In such scheme (8) and (9), first, halogen-lithium is carried out using n-BuLi, s-butyl lithium or tert-butyl lithium etc.
Exchange reaction, so that lithiumation occurs for halogen atom.Herein, show and n-BuLi, s-butyl lithium or the tert-butyl group is used alone
The method of lithium etc., but in order to improve reactivity, N, N, N can also be added ', N '-tetramethylethylenediamine etc..Then to obtained
Addition 2- isopropoxies -4,4 in lithiumation body, 5,5- tetramethyls -1,3, acid esterification reactant as 2- dioxaborolans,
So as to manufacture the pinacol ester of boric acid.Herein, show using 2- isopropoxies -4,4,5,5- tetramethyls -1,3,2- bis-
The method of oxa- pentaborane, further, it is also possible to use trimethoxy borine, three isopropoxy borines etc..In addition, application is international public
The method described in No. 2013/016185 publication, 4,4,5,5- tetramethyls -1,3 are opened, 2- dioxaborolans etc. similarly may be used
To use.
It should be noted that such scheme (8) and (9) show the manufacturer of general formula (1) or the borate shown in (2)
Method, by the way that boric acid by so obtained boric acid ester hydrolysis, can be manufactured (with reference to such scheme (3) or (4)).In addition, make suitably
Alcohol act on these borates, boric acid, so as to manufacture different borates via ester exchange or resterification.And then
, can also be by using with multiple A rings (a on the polymer compounds with structure shown in multiple general formulas (1) or (2)
Ring), the intermediate of B rings (b rings) and C rings (c rings) manufactures (with reference to such scheme (5)~(7)).
In addition, as shown in following proposal (10) or (11), bromination body and double (pinacols are made by using palladium catalyst and alkali
Close) two boron or 4,4,5,5- tetramethyls -1,3,2- dioxaborolans etc. carry out coupling reaction, can similarly synthesize boric acid
Ester.
Scheme (10)
Scheme (11)
It should be noted that such scheme (10) and (11) show the manufacturer of general formula (1) or the borate shown in (2)
Method, by the way that boric acid by so obtained boric acid ester hydrolysis, can be manufactured (with reference to such scheme (3) or (4)).In addition, make suitably
Alcohol act on these borates, boric acid, so as to manufacture different borates via ester exchange or resterification.And then
, can also be by using with multiple A rings (a on the polymer compounds with structure shown in multiple general formulas (1) or (2)
Ring), the intermediate of B rings (b rings) and C rings (c rings) manufactures (with reference to such scheme (5)~(7)).
As the metalating reagent used in the halogen-metal exchange reaction in the scheme so far illustrated, first can be included
The lithium alkylides such as base lithium, n-BuLi, s-butyl lithium, tert-butyl lithium, isopropylmagnesium chloride, isopropyl magnesium bromide, phenyl-magnesium-chloride,
Phenyl-magnesium-bromide and the chlorination lithium complex of isopropylmagnesium chloride that is known as TurboGrignard reagents etc..
In addition, as the metalating reagent used in the ortho position metal exchange reaction in the scheme so far illustrated, except upper
State outside reagent, can also include lithium diisopropylamide, tetramethyl piperidine lithium, hexamethyldisilazide lithium, hexamethyl two
The organo-alkali compounds such as silicon substrate amido potassium, lithium chloride tetramethyl-piperidyl magnesium chlorination lithium complex, three n-butyl magnesium acid lithiums.
And then in the case of as metalating reagent using lithium alkylide, as the additive for promoting reaction, N can be included,
N, N ', N '-tetramethylethylenediamine, 1,4- diazabicyclos [2.2.2] octane, N, N- dimethylpropylene ureas etc..
In addition, also include the boric acid or boron that at least a portion hydrogen atom instead of by deuterium in the boric acid or borate of the present invention
Acid esters, the boric acid or borate that instead of by halogens such as fluorine and/or chlorine, this compound etc. can be sent out by using desired locations
Deuterate, fluorination or the raw material of chlorination are given birth to and have synthesized as described above.
4. boric acid by general formula (1) etc. manufactures the manufacture method of polycyclc aromatic compound
Then, for using the boric acid shown in general formula (1) etc. or borate manufacture polycyclc aromatic compound and more cyclophanes
The method of fragrant race's polymer compounds illustrates.It should be noted that the symbol in structural formula in each scheme described below
It is number as defined above.
In following proposal (12) or (13), by make boric acid shown in general formula (1) etc. or borate with as aluminium chloride
Lewis acid reacts, so as to manufacture polycyclc aromatic compound.
Scheme (12)
Scheme (13)
Alternatively, it is also possible to use Bronsted acid as p-methyl benzenesulfonic acid.Carried out especially with lewis acid anti-
In the case of answering, in order to improve selectivity, yield, the alkali such as diisopropyl ethyl amine can also be added.
In addition, the method shown in by following proposal (14)~(16), using with knot shown in multiple general formulas (1) or (2)
The polymer compounds of structure, can also manufacture Ppolynuclear aromatic polymer compounds.At this time, the knot with polymer compounds is passed through
The amount of the reagents such as used aluminium chloride is accordingly set to 2 times of amounts, 3 times of amounts etc. by structure, can obtain 2 dimmer compounds, 3 poly-
The object of body compound etc..
Scheme (14)
Scheme (15)
Scheme (16)
As the lewis acid used in such scheme (12)~(16), AlCl can be included3、AlBr3、AlF3、BF3·
OEt2、BCl3、BBr3、GaCl3、GaBr3、InCl3、InBr3、In(OTf)3、SnCl4、SnBr4、AgOTf、ScCl3、Sc(OTf)3、
ZnCl2、ZnBr2、Zn(OTf)2、MgCl2、MgBr2、Mg(OTf)2、LiOTf、NaOTf、KOTf、Me3SiOTf、Cu(OTf)2、
CuCl2、YCl3、Y(OTf)3、TiCl4、TiBr4、ZrCl4、ZrBr4、FeCl3、FeBr3、CoCl3、CoBr3Deng.In addition, by these
Lewis acid is carried on the material that solid forms and can similarly use.
As the Bronsted acid used in such scheme (12)~(16), can include p-methyl benzenesulfonic acid, methanesulfonic acid,
Trifluoromethanesulfonic acid, fluosulfonic acid, carboxylic acid, trifluoroacetic acid, (trifluoro methylsulfonyl) imines, three (trifyl) methane, hydrogen chloride,
Hydrogen bromide, hydrogen fluoride etc..In addition, as solid Bronsted acid, Amberlist (trade names can be included：DOW Chemical),
Nafion (trade names：Du Pont), zeolite, Taycacure (trade names：Tayca Corporation) etc..
As the amine that can be added in such scheme (12)~(16), diisopropyl ethyl amine, triethylamine, three can be included
Butylamine, 1,4- diazabicyclos [2.2.2] octane, N, N- dimethyl-paratoluidines, N, accelerine, pyridine, 2,6- bis-
The pyridine of methyl arsenic, 2,6- di-t-butyl amine etc..
In addition, as the solvent used in such scheme (12)~(16), can include o-dichlorohenzene, chlorobenzene, toluene,
Benzene, dichloromethane, chloroform, dichloroethylene, benzotrifluoride, decahydronaphthalene, hexamethylene, hexane, heptane, 1,2,4- trimethylbenzenes, two
Toluene, diphenyl ether, methyl phenyl ethers anisole, cyclopentyl-methyl ether, tetrahydrofuran, dioxanes, methyl t-butyl ether etc..
5. organic assembly
The polycyclc aromatic compound and Ppolynuclear aromatic polymer compounds manufactured in the present invention may be used as machine
Part material.As organic assembly, such as organic electroluminescence device, organic field effect tube or organic film can be included
Solar cell etc..
5-1. organic electroluminescence device
The polycyclc aromatic compound and Ppolynuclear aromatic polymer compounds manufactured in the present invention, which may be used as composition, to be had
The material of each layer of organic electroluminescence devices.Hereinafter, the organic EL element of present embodiment is described in detail based on attached drawing.Fig. 1 is
The schematic cross-section of the organic EL element of present embodiment is shown.
The organic electroluminescence device 100 shown in Fig. 1 has substrate 101, the anode 102 being arranged on substrate 101, sets
The hole injection layer 103 that is placed on anode 102, the hole transmission layer 104 being arranged on hole injection layer 103, be arranged at hole
Luminescent layer 105 in transport layer 104, the electron transfer layer 106 being arranged on luminescent layer 105, be arranged on electron transfer layer 106
Electron injecting layer 107 and the cathode 108 that is arranged on electron injecting layer 107.
It should be noted that organic electroluminescence device 100 can also overturn production order, using for example with substrate
101st, the cathode 108 that is arranged on substrate 101, the electron injecting layer 107 being arranged on cathode 108, be arranged at electron injecting layer
Electron transfer layer 106 on 107, the luminescent layer 105 being arranged on electron transfer layer 106, the hole being arranged on luminescent layer 105
Transport layer 104, the hole injection layer 103 being arranged on hole transmission layer 104, the anode 102 being arranged on hole injection layer 103
Composition.
Above layers be not all of it is all indispensable, by minimum Component units be set to by anode 102 and luminescent layer 105 with it is cloudy
The composition that pole 108 is formed, hole injection layer 103, hole transmission layer 104, electron transfer layer 106, electron injecting layer 107 are optional
The layer of setting.In addition, above layers can be formed by simple layer respectively, can also be formed by multiple layers.
Each layer for forming organic electroluminescence device can be formed：Evaporation will be passed through for forming the material of each layer
The methods of method, resistance heating evaporation, electron beam evaporation plating, sputtering, molecular stacks method, print process, spin-coating method or casting, rubbing method
Film is made, so as to be formed.The thickness of each layer to being thusly-formed is not particularly limited, and can suitably be set according to the property of material
It is fixed, it is usually the scope of 2nm~5000nm.Thickness can usually use the measure such as crystal oscillatory type film thickness measuring device.Use steaming
In the case that plating method carries out filming, its evaporation condition is according to the species of material, the target crystal structure of film and associative structure etc.
It is and different.Evaporation condition is generally preferably in+50~+400 DEG C of boat heating-up temperature, vacuum 10-6~10-3Pa, evaporation rate 0.01~
50nm/ seconds, substrate temperature -150~+300 DEG C, the scope of thickness 2nm~5 μm suitably set.
In the case of applying DC voltage to so obtained organic electroluminescence device, anode is set to+, cathode set
For-polarity and application, can be from transparent or semitransparent electrode side (anode or the moon when applying voltage 2~40V or so
Pole and both) observe shine.In addition, the organic electroluminescence device can also be sent out when being applied with pulse current, alternating current
Light.It should be noted that the waveform of the exchange applied can be any.
5-2. organic field effect tube
The polycyclc aromatic compound and Ppolynuclear aromatic polymer compounds manufactured in the present invention, which may be used as composition, to be had
The material of field effect transistors.Organic field effect tube is to control electric current using the electric field produced by control source
Transistor, is additionally provided with gate electrode in addition to source electrode and drain electrode.Electric field is produced when applying voltage to gate electrode, can be any
Ground blocks the flowing of the electronics (or hole) flowed between source electrode and drain electrode, so as to control electric current.Field-effect transistor
The easily miniaturization compared with simple transistor (bipolar transistor), is commonly used for forming the element of integrated circuit etc..
On the structure of organic field effect tube, as long as in general, make source electrode and drain electrode with using being made in the present invention
The organic semiconductor active layer that the polycyclc aromatic compound and Ppolynuclear aromatic polymer compounds made are formed is placed in contact with,
And then the insulating layer (dielectric layer) that is contacted with organic semiconductor active layer is clipped to set gate electrode.As its element knot
Structure, can include for example following structure.
(1) substrate/gate electrode/insulator layer/source electrode drain electrode/organic semiconductor active layer
(2) substrate/gate electrode/insulator layer/organic semiconductor active layer/source electrode drain electrode
(3) substrate/organic semiconductor active layer/source electrode drain electrode/insulator layer/gate electrode
(4) substrate/source electrode drain electrode/organic semiconductor active layer/insulator layer/gate electrode
The organic field effect tube so formed may be used as the liquid crystal display of driven with active matrix mode, Organic Electricity
Pixel driver switching device of electroluminescent display etc..
5-3. organic thin film solar cell
The polycyclc aromatic compound and Ppolynuclear aromatic polymer compounds manufactured in the present invention, which may be used as composition, to be had
The material of machine thin-film solar cells.Organic thin film solar cell has is laminated with the sun such as ITO on the transparent substrates such as glass
Pole, hole transmission layer, photoelectric conversion layer, electron transfer layer, the structure of cathode.Photoelectric conversion layer in anode-side there is p-type partly to lead
Body layer, has n-type semiconductor layer in cathode side.The polycyclc aromatic compound and Ppolynuclear aromatic polymer manufactured in the present invention
Compound may be used as the material of hole transmission layer, p-type semiconductor layer, n-type semiconductor layer, electron transfer layer according to its physical property.
The polycyclc aromatic compound and Ppolynuclear aromatic polymer compounds manufactured in the present invention can be in organic thin film solar electricity
Played function in pond as hole mobile material, electron transport material.Organic thin film solar cell may be used also in addition to that mentioned above
Suitably to possess hole blocking layer, electronic barrier layer, electron injecting layer, hole injection layer, smoothing layer etc..The organic film sun
Can be in battery, the known materials that suitably can select to use in organic thin film solar cell are applied in combination.
Embodiment
Hereinafter, the present invention is further illustrated using embodiment, but the present invention is not limited to them.First, on boric acid
Or the synthesis example of borate, described below.
Synthesis example (1)：The synthesis of compound (1-1-98)
Having the flask of intermediate 1 (15g) and toluene (300ml) to be warming up to 70 DEG C in a nitrogen atmosphere addition makes intermediate
1 is completely dissolved.After flask is cooled to -20 DEG C, add tetramethylethylenediamine (20.8g), 1.00M s-butyl lithium hexamethylene
With n-hexane mixed solution (89ml).Be warming up to 0 DEG C, when stirring 3 is small after, add 2- isopropoxies -4,4,5,5- tetramethyl -1,
3,2- dioxaborolans (33.3g), when reflux 1 is small.Add water and toluene and carry out liquid separation, vacuum distillation removes organic layer
Solvent.By obtained solid Solmix A-11 (trade names：Japan Alcohol Trading Co., Ltd.) cleaning
Afterwards, toluene is dissolved in, when placement 1 is small at 0 DEG C.The precipitation of precipitation is separated by filtration, filtrate is passed through silicagel column (eluent：First
The mixed solvent (Capacity Ratio) of benzene/heptane=1/5).After distillation removes solvent, the mixing with ethyl acetate and Solmix A-11 is molten
Agent carries out reprecipitation, so as to obtain the compound (9.5g) shown in formula (1-1-98) in the form of white solid.
The structure of obtained compound is confirmed using NMR measure.
1H-NMR (400MHz, CDCl3)：δ=7.18~7.16 (m, 8H), 7.05~7.02 (m, 4H), 6.95~6.92
(m, 12H), 6.86~6.84 (m, 2H), 6.44 (s, 2H), 1.27 (s, 36H), 0.54 (s, 12H)
Synthesis example (2)：The synthesis of compound (1-3-139)
Addition there are into the bromo- 2,6- difluorobenzenes (85.4g) of 1-, phenol (100g), potassium carbonate (244.7g) and N- methyl -2- pyrroles
The flask of pyrrolidone (NMP, 300ml) is warming up to 180 DEG C, when stirring 22 is small in a nitrogen atmosphere.After reaction, at 150 DEG C
Under be separated by filtration potassium carbonate, vacuum distillation removes the solvent of filtrate.Obtained solid is set to be dissolved in toluene, it is short logical by silica gel
Column (eluent：Toluene).After vacuum distillation removes solvent, by obtained solid washed with heptane, so that with white solid
Form obtains intermediate 2 (126.6g).
Have to addition in the flask of intermediate 2 (103g) and tetrahydrofuran (500ml) and add at room temperature in a nitrogen atmosphere
Enter the tetrahydrofuran solution (351ml) of the isopropylmagnesium chloride chlorination lithium complex of 1.29M.Stir 1 it is small when after, add 2- it is different
Propoxyl group -4,4,5,5- tetramethyls -1,3,2- dioxaborolans (65.7g), be stirred at room temperature 2 it is small when.Add 3% dilute salt
Sour (1L) and toluene (500ml) simultaneously carry out liquid separation, extract organic layer.After vacuum distillation removes solvent, make obtained solid molten
Solution passes through silicagel column (eluent in toluene：Toluene).Distillation removes solvent, so as to obtain formula (1-3- in the form of white solid
139) compound (109g) shown in.
The structure of obtained compound is confirmed using NMR measure.
1H-NMR (400MHz, CDCl3)：δ=7.31~7.25 (m, 6H), 7.05~6.98 (m, 5H), 6.71 (d, 2H),
1.08 (s, 12H)
Synthesis example (3)：The synthesis of compound (1-3-252)
To add intermediate 3 (40g) that the method that has and recorded by No. 2015/102118 publication of International Publication No. synthesizes and
After the flask of tetrahydrofuran (200ml) is cooled to -20 DEG C in a nitrogen atmosphere, the hexane solution of the n-BuLi of 1.6M is added
(60ml), when stirring 2 is small at 0 DEG C.After being cooled to -20 DEG C again, addition 2- isopropoxies -4,4,5,5- tetramethyls -1,3,
2- dioxaborolans (22.2g), be stirred at room temperature when being cooled to room temperature 1 it is small when.Add toluene and dilute hydrochloric acid and carry out
Liquid separation, vacuum distillation remove the solvent of organic layer.By the mixed solvent reprecipitation of obtained solid toluene and heptane, so that
The compound (33.3g) shown in formula (1-3-252) is obtained in the form of white solid.
The structure of obtained compound is confirmed using NMR measure.
1H-NMR (400MHz, CDCl3)：δ=8.13 (d, 2H), 7.69 (d, 2H), 7.57 (d, 2H), 7.40~7.39 (m,
4H), 7.36~7.33 (m, 4H) 7.29~7.26 (m, 2H) 7.09~7.07 (m, 6H) 1.11 (s, 12H)
Synthesis example (4)：The synthesis of compound (1-3-386)
Addition is had to the flask of 4- methoxysalicylic acids methyl esters (50.0g), pyridine (dehydration) (350ml) in a nitrogen atmosphere
Cooled down in ice bath.Then, trifluoromethanesulfanhydride anhydride (154.9g) is added drop-wise in the solution.Ice bath is removed after completion of dropwise addition,
When stirring 2 is small at room temperature, water is added to stop reaction.After adding toluene and liquid separation, with the short through post chromatography (eluent of silica gel：Toluene)
Purifying, so as to obtain 4- methoxyl groups -2- ((trifluoromethyl) sulphonyl) epoxide) methyl benzoate (86.0g).
In a nitrogen atmosphere to 4- methoxyl groups -2- ((trifluoromethyl) sulphonyl) epoxide) methyl benzoate (23.0g), (4-
(diphenyl amino) phenyl) boric acid (25.4g), tripotassium phosphate (31.1g), toluene (184ml), ethanol (27.6ml) and water
Pd (PPh are added in the suspension solution of (27.6ml)3)4(2.5g), is stirred when progress 3 is small at a reflux temperature.Reaction solution is cooled down
To room temperature, add water and toluene and carry out liquid separation, vacuum distillation removes the solvent of organic layer.By obtained solid silicagel column
Chromatography (eluent：Heptane/toluene Mixed Solvent) purifying.Obtain 4 '-(diphenyl amino) -5- methoxyl group-[1,1 '-biphenyl] -
2- carboxylate methyl esters (29.7g).At this time, with reference to published by Co., Ltd.'s chemistry with people《Guidance (1)-material of Experiment of Organic Chemistry
Facture and isolate and purify method-》Method described in page 94, the ratio for the toluene being slowly increased in eluent, makes object
Dissolution.
4 '-(diphenyl amino) -5- methoxyl groups-[1,1 '-biphenyl] -2- carboxylate methyl esters will be dissolved with a nitrogen atmosphere
THF (111.4ml) solution of (11.4g) cools down in a water bath, be added dropwise into the solution methyl-magnesium-bromide THF solution (1.0M,
295ml).After completion of dropwise addition, water-bath is removed, reflux temperature is warming up to, when stirring 4 is small.Then, cooled down in ice bath, add chlorine
Changing aqueous ammonium stops reaction, and after adding ethyl acetate and liquid separation, vacuum distillation removes solvent.By obtained solid silicon
Rubber column gel column chromatography (eluent：Toluene) purifying, obtain 2- (5 '-(diphenyl amino) -5- methoxyl groups-[1,1 '-biphenyl] -2- bases) third
Alkane -2- alcohol (8.3g).
Addition there is into 2- (5 '-(diphenyl amino) -5- methoxyl groups-[1,1 '-biphenyl] -2- bases) third in a nitrogen atmosphere
Alkane -2- alcohol (27.0g), TAYCACURE-15 (trade names：Tayca Corporation) (13.5g) and toluene (162ml) burning
Bottle at a reflux temperature stirring 2 it is small when.Reaction solution is cooled to room temperature, is passed to the short through post (eluent of silica gel：Toluene), from
And remove TAYCACURE-15.Then, vacuum distillation removes solvent, so that 6- methoxyl group -9 are obtained, 9 '-dimethyl-N, N- bis-
Phenyl -9H- fluorenes -2- amine (25.8g).
Addition there is into 6- methoxyl groups -9,9 '-dimethyl-N, N- diphenyl -9H- fluorenes -2- amine in a nitrogen atmosphere
The flask of (25.0g), pyridine hydrochloride (36.9g) and NMP (22.5ml) stir at a reflux temperature 6 it is small when.Reaction solution is cold
But to room temperature, water and ethyl acetate is added and carries out liquid separation.After vacuum distillation removes solvent, with silica gel column chromatography (eluent：First
Benzene) purifying, so that 7- (diphenyl amino) -9 is obtained, 9 '-dimethyl -9H- fluorenes -3- alcohol (22.0g).
Addition there are into 7- (diphenyl amino) -9,9 '-dimethyl -9H- fluorenes -3- alcohol (14.1g), 2- in a nitrogen atmosphere
The flask of bromo- 1,3- difluorobenzenes (3.6g), potassium carbonate (12.9g) and NMP (30ml) carry out at a reflux temperature 5 it is small when heating stir
Mix.After reaction stops, reaction solution is cooled to room temperature, adds water, the sediment separated out by filtering collection.Will be obtained heavy
Starch washes with water, after then being cleaned with methanol, with silica gel column chromatography (eluent：Heptane/toluene Mixed Solvent) purifying, obtain
6,6 '-((the bromo- 1,3- phenylenes of 2-) double (epoxides)) is double (9,9- dimethyl-N, N- diphenyl -9H- fluorenes -2- amine) (12.6g).
At this time, the ratio for the toluene being slowly increased in eluent, makes object dissolution.
There are intermediate 4 (25g) and the flask of tetrahydrofuran (250ml) to be warming up to 70 DEG C in a nitrogen atmosphere addition, make
Intermediate 4 is completely dissolved.Flask is impregnated in ice bath, after being cooled to 5 DEG C, adds the isopropylmagnesium chloride lithium chloride of 1.28M
The tetrahydrofuran solution (65ml) of complex compound.Be warming up to room temperature, when stirring 3 is small after, add 2- isopropoxies -4,4,5,5- tetramethyls
Base -1,3,2- dioxaborolans (15.4g), be stirred at room temperature 1 it is small when.Add 3% dilute hydrochloric acid (100ml) and toluene
(100ml) and liquid separation is carried out, vacuum distillation removes the solvent of organic layer.Obtained solid is re-dissolved in toluene, passes through silicon
Rubber column gel column (eluent：Toluene).After distillation removes solvent, make thick purified reprecipitation using tetrahydrofuran and Solmix A-11, from
And the compound (19.6g) shown in formula (1-3-386) is obtained in the form of white solid.
The structure of obtained compound is confirmed using NMR measure.
1H-NMR (400MHz, CDCl3)：δ=7.49 (d, 2H), 7.30~7.22 (m, 13H), 7.17 (d, 2H), 7.13~
7.11 (m, 8H), 7.03~6.99 (m, 6H), 6.93 (dd, 2H), 6.67 (d, 2H), 1.39 (s, 12H), 1.14 (s, 12H)
Synthesis example (5)：The synthesis of compound (1-3-439)
Addition there are into the bromo- 2,6- difluorobenzenes (62.5g) of 1-, 3- chlorophenols (100g), potassium carbonate (179.2g) and NMP
The flask of (300ml) is warming up to 180 DEG C, when stirring 15 is small in a nitrogen atmosphere.After reaction, potassium carbonate is separated by filtration, is subtracted
Pressure distillation removes the solvent of filtrate.Toluene and water are added into obtained solid, extracts organic layer.By organic layer with anhydrous sulphur
After sour sodium drying, pass through the short through post (eluent of silica gel：Toluene).After vacuum distillation removes solvent, obtained solid is used into heptan
Alkane cleans, so as to obtain intermediate 5 (105.3g) in the form of light pink solid.
Have to addition in the flask of intermediate 5 (30g) and tetrahydrofuran (500ml) and add at room temperature in a nitrogen atmosphere
The tetrahydrofuran solution (68ml) of the isopropylmagnesium chloride chlorination lithium complex of 1.29M.Stir 2 it is small when after, add 2- isopropyls
Epoxide -4,4,5,5- tetramethyls -1,3,2- dioxaborolans (24.5g), be stirred at room temperature 2 it is small when.After reaction, to
3% dilute hydrochloric acid (200ml) and toluene (200ml) are added in reaction mixture and carries out liquid separation, extracts organic layer.Vacuum distillation is gone
After solvent, obtained solid is dissolved in toluene, pass through silicagel column (eluent：Toluene).Distillation removes solvent, so that with
The form of white solid obtains the compound (29.6g) shown in formula (1-3-439).
The structure of obtained compound is confirmed using LC-MS measure.It should be noted that the solvent used during measure is
Methanol, therefore measurement result has obtained the quality for the addition body that methanol addition is formed in boric acid ester compound.
MS (ACPI) m/z=488 (M+MeOH)
Synthesis example (6)：The synthesis of compound (1-2-340)
There are 7- (diphenyl amino) -9,9 '-dimethyl -9H- fluorenes -3- alcohol (100g), 1- bromo- addition in a nitrogen atmosphere
The flask of the chloro- 3- fluorobenzene (58.3g) of 2-, potassium carbonate (91.5g) and NMP (500ml) carry out at a reflux temperature 4 it is small when heating stir
Mix.After reaction stops, reaction solution is cooled to room temperature, adds water, the sediment separated out by filtering collection.Will be obtained heavy
Starch washes with water, after then being cleaned with methanol, with silica gel column chromatography (eluent：Toluene) purifying, obtain midbody compound
6- (the bromo- 2- chlorophenoxies of 3-) -9,9- dimethyl-N, N- diphenyl -9H- fluorenes -2- amine) (150g).
Heating addition in a nitrogen atmosphere has 6- (the bromo- 2- chlorophenoxies of 3-) -9,9- dimethyl-N, N- diphenyl -9H-
Fluorenes -2- amine) (40g), diphenylamine (12.5g), double (di-t-butyl (4- dimethylaminophenyls) phosphines) as palladium catalyst
The flask of palladium chloride (1.5g), sodium tert-butoxide (17.0g) and dimethylbenzene (200ml), when stirring 2 is small at 85 DEG C.Will reaction
After liquid is cooled to room temperature, adds water and toluene and carry out liquid separation, vacuum distillation removes the solvent of organic layer.By obtained solid
With Solmix A-11 (trade names：Japan Alcohol Trading Co., Ltd.s) clean several times, then use silica gel column chromatography
(eluent：Toluene/heptane=1/2 (Capacity Ratio)) purifying, obtain the compound (35.6g) represented with intermediate 6.
There are intermediate 6 (18.9g) and the flask of toluene (150ml) to be warming up to 70 DEG C in a nitrogen atmosphere addition, make it
It is completely dissolved.After flask is cooled to 0 DEG C, the hexane solution (14.4ml) of the n-BuLi of 2.6M is added.65 DEG C are warming up to,
Carry out 3 it is small when stir.Then, flask is cooled to -10 DEG C, adds 2- isopropoxies -4,4,5,5- tetramethyls -1,3,2- dioxies
Miscellaneous pentaborane (13.4g), be stirred at room temperature 2 it is small when.Add water and toluene and carry out liquid separation, organic layer is passed through into NH2 silica gel
Short column (eluent：Toluene).After vacuum distillation removes solvent, the compound (22.0g) shown in formula (1-2-340) is obtained.
The structure of obtained compound is confirmed using NMR measure.
1H-NMR (400MHz, CDCl3)：δ=7.49 (d, 1H), 7.30~7.08 (m, 19H), 7.04~6.99 (m, 6H),
6.94 (dd, 1H), 6.77 (d, 1H), 6.73 (d, 1H), 1.39 (s, 6H), 0.93 (s, 12H)
Synthesis example (7)：The synthesis of compound (1-2-343)
Heating addition in a nitrogen atmosphere has 6- (the bromo- 2- chlorophenoxies of 3-) -9,9- dimethyl-N, N- diphenyl -9H-
Fluorenes -2- amine) (60g), double (4- tert-butyl-phenyls) amine (29.8g), double (di-t-butyl (4- dimethylaminos as palladium catalyst
Base phenyl) phosphine) palladium chloride (2.2g), sodium tert-butoxide (25.4g) and dimethylbenzene (300ml) flask, stirred at 85 DEG C 2 small
When.After reaction solution is cooled to room temperature, adds water and toluene and carry out liquid separation, vacuum distillation removes the solvent of organic layer.By institute
Obtained solid Solmix A-11 (trade names：Japan Alcohol Trading Co., Ltd.s) clean several times, Ran Houyong
Silica gel column chromatography (eluent：Toluene) purifying, obtain intermediate 7 (66.2g).
There are intermediate 7 (2.5g) and the flask of dimethylbenzene (20ml) to be warming up to 70 DEG C in a nitrogen atmosphere addition, make it
It is completely dissolved.After flask is cooled to 0 DEG C, the hexane solution (3.1ml) of the n-BuLi of 2.6M is added.65 DEG C are warming up to,
Carry out 3 it is small when stir.Then, flask is cooled to -10 DEG C, adds 2- isopropoxies -4,4,5,5- tetramethyls -1,3,2- dioxies
Miscellaneous pentaborane (3.0g), be stirred at room temperature 2 it is small when.Add water and toluene and carry out liquid separation, make organic layer short by NH2 silica gel
Through post (eluent：Toluene).After vacuum distillation removes solvent, the compound (2.7g) shown in formula (1-2-343) is obtained.
The structure of obtained compound is confirmed using NMR measure.
1H-NMR (400MHz, CDCl3)：δ=7.49 (d, 1H), 7.29~7.10 (m, 15H), 7.01 (d, 8H), 6.93
(dd, 1H), 6.75 (d, 1H), 6.69 (d, 1H), 1.39 (s, 6H), 1.28 (s, 18H), 0.96 (s, 12H)
The compound of appropriate change raw material, so as to synthesize other boron of the present invention by the method according to above-mentioned synthesis example
Acid or borate.
Then, the example by boric acid or borate manufacture polycyclc aromatic compound is illustrated.
[embodiment 1]
＜ uses the synthesis ＞ of the polycyclc aromatic compound A of compound (1-1-98)
Addition there are into compound (1-1-98) (8.7g), aluminium chloride (12.5g), N, N- diisopropyl ethyl amines (DIPEA)
When the flask of (6.0g) and chlorobenzene (44ml) is in a nitrogen atmosphere, stirring 1 is small at 120 DEG C.The reaction that will be cooled to room temperature mixes
Close liquid to be injected into frozen water (200ml), add toluene, extract organic layer.Vacuum distillation removes the solvent of organic layer, so as to get
Solid is dissolved in chloroform, passes through the short through post (eluent of silica gel：Toluene).Thick purified obtained from vacuum distillation is removed solvent
With cyclopentyl-methyl ether and Solmix A-11 reprecipitations, so as to obtain polycyclc aromatic compound A in the form of yellow solid
(6.2g, yield 70%).
The structure of obtained compound is confirmed using NMR measure.
1H-NMR (400MHz, CDCl3)：δ=8.95 (d, 2H), 7.45 (dd, 6H), 7.13 (d, 4H), 7.08-7.04 (m,
4H), 6.95-6.88 (m, 6H), 6.75 (d, 2H), 5.56 (s, 2H), 1.46 (s, 18H), 1.33 (s, 18H)
[embodiment 2]
＜ uses the synthesis ＞ of the polycyclc aromatic compound B of compound (1-3-139)
Addition there is into the flask of compound (1-3-139) (22.8g), aluminium chloride (23.5g) and chlorobenzene (230ml) in nitrogen
When stirring 2 is small at 130 DEG C under atmosphere.The reaction mixture that will be cooled to room temperature is injected into 0 DEG C of frozen water (1L), adds first
Benzene (500ml) simultaneously extracts organic layer.Solid Solmix A-11 obtained from the solvent of removal organic layer being evaporated under reduced pressure
(500ml) is cleaned, so as to obtain polycyclc aromatic compound B (14.2g, yield 60%) in the form of light yellow solid.
The structure of obtained compound is confirmed using NMR measure.
1H-NMR (400MHz, CDCl3)：δ=8.69 (dd, 2H), 7.79 (t, 1H), 7.70 (ddd, 2H), 7.54 (dt,
2H), 7.38 (ddd, 2H), 7.22 (d, 2H)
[embodiment 3]
＜ uses the synthesis ＞ of the polycyclc aromatic compound C of compound (1-3-252)
Addition there is into the flask of compound (1-3-252) (124g), aluminium chloride (131.3g) and toluene (620ml) in nitrogen
When stirring 1 is small at 90 DEG C under atmosphere.The reaction mixture that will be cooled to room temperature is injected into 5 DEG C of aqueous sodium acetate solution, is carried
Take organic layer.Crude product o-dichlorohenzene and ethyl acetate reprecipitation obtained from vacuum distillation is removed solvent, so that with Huang
The form of color solid obtains polycyclc aromatic compound C (91g, yield 63%).
The structure of obtained compound is confirmed using NMR measure.
1H-NMR (400MHz, CDCl3)：δ=8.73 (d, 2H), 8.17 (d, 2H), 8.01 (d, 2H), 7.74 (m, 4H),
7.60 (d, 2H), 7.58 (s, 2H), 7.53 (d, 2H), 7.40-7.48 (m, 4H), 7.32 (t, 2H)
[embodiment 4]
＜ uses the synthesis ＞ of the polycyclc aromatic compound D of compound (1-3-386)
Addition there are into compound (1-3-386) (32g), aluminium chloride (44.7g), N, N- dimethyl-p-toluidines (4.53g)
When stirring 10 is small at 85 DEG C in a nitrogen atmosphere with the flask of toluene (170ml).It will be cooled to the reaction mixture note of room temperature
Enter into the tetrasodium ethylenediamine tetraacetate aqueous solution (200ml) of 0 DEG C of 0.2M, add toluene and extract organic layer.Decompression is steamed
Solid obtained from evaporating the solvent except organic layer is dissolved in chloroform, passes through silicagel column (eluent：Chloroform/heptane=1/10 is mixed
Bonding solvent (Capacity Ratio)).Thick purified obtained from vacuum distillation is removed solvent is cleaned with the mixed solvent of toluene and acetone
Afterwards, recrystallized using cyclopentyl-methyl ether, so as to obtain polycyclc aromatic compound D in the form of yellow solid
(24.9g, yield 77%).
The structure of obtained polycyclc aromatic compound D is confirmed using NMR measure.
1H-NMR (400MHz, CDCl3)：δ=8.64 (s, 2H), 7.75 (m, 3H), 7.69 (d, 2H), 7.30 (t, 8H),
7.25 (s, 2H), 7.20 (m, 10H), 7.08 (m, 6H), 1.58 (s, 12H)
[embodiment 5]
＜ uses the synthesis ＞ of the polycyclc aromatic compound E of compound (1-3-439)
Addition there is into the flask of compound (1-3-439) (29.5g), aluminium chloride (25.8g) and chlorobenzene (290ml) in nitrogen
When stirring 2 is small at 110 DEG C under atmosphere.After reaction, the reaction mixture that will be cooled to room temperature is injected into 0 DEG C of frozen water
In (1L), add toluene (500ml) and extract organic layer.Solid obtained from the solvent of removal organic layer being evaporated under reduced pressure is used
Solmix A-11 (500ml) are cleaned, so as to obtain polycyclc aromatic compound E (12.3g, yield in the form of light yellow solid
41%).
The structure of obtained compound is confirmed using NMR measure.
1H-NMR (400MHz, CDCl3)：δ=8.51 (dd, 2H), 7.81 (t, 1H), 7.56 (d, 2H), 7.36 (dd, 2H),
7.38 (m, 2H)
[embodiment 6]
＜ uses the synthesis ＞ of the polycyclc aromatic compound F of compound (1-2-340)
Have to addition and aluminium chloride (19.2g) is added in the flask of compound (1-2-340) (21.5g) and toluene (215ml)
And N, N- diisopropyl ethyl amine (DIPEA) (3.7g), when reflux 3 is small.Then, it will be cooled to the reaction mixture injection of room temperature
Into frozen water (250ml), add toluene and extract organic layer.Solid obtained from the solvent of removal organic layer being evaporated under reduced pressure is used
NH2 silica gel carries out short column purifying (eluent：Toluene/heptane=1/4 (Capacity Ratio)) after, carry out reprecipitation several times with methanol.Will
Obtained crude product carries out short column with silica gel and purifies (eluent：Toluene/heptane=1/2 (Capacity Ratio)), with yellow solid
Form obtains polycyclc aromatic compound F (15.5g, yield 71%).
The structure of obtained compound is confirmed using NMR measure.
1H-NMR (400MHz, CDCl3)：δ=8.94 (dd, 1H), 8.70 (s, 1H), 7.74~7.69 (m, 4H), 7.62
(t, 1H), 7.53~7.47 (m, 2H), 7.38 (dd, 2H), 7.33~7.28 (m, 5H), 7.24 (d, 1H), 7.18 (dd, 4H),
7.09~7.05 (m, 4H), 6.80 (d, 1H), 6.30 (d, 1H), 1.58 (s, 6H)
[comparative example 1]
＜ uses the synthesis ＞ of the bromide of precursor and the polycyclc aromatic compound D of Boron tribromide
The intermediate 4 (11.0g) and dimethylbenzene (60.5ml) for having the bromide as precursor using adding in a nitrogen atmosphere
Flask be cooled to -40 DEG C, the lithium hexane solution (5.1ml) of 2.6M is added dropwise.After completion of dropwise addition, stir at such a temperature
0.5 it is small when after, 60 DEG C are warming up to, when stirring 3 is small.Then, reaction solution is depressurized, distillation removes low-boiling component, Ran Houleng
But to -40 DEG C, Boron tribromide (4.3g) is added.Be warming up to room temperature, when stirring 0.5 is small after, be cooled to 0 DEG C, add N, N- bis- is different
Ethylamine (3.8g), heating stirring when progress 8 is small at 125 DEG C.Reaction solution is cooled to room temperature, it is water-soluble to add sodium acetate
After liquid stops reaction, add toluene and carry out liquid separation.By the short through post purifying of organic layer silica gel, silica gel column chromatography is then used
(eluent：The mixed solvent (Capacity Ratio) of heptane/toluene=4/1) purifying, further with activated carbon column chromatography (eluent：Toluene)
Purifying, obtains polycyclc aromatic compound D (1.2g, yield 12%).
[comparative example 2]
＜ uses the synthesis ＞ of the chloride of precursor and the polycyclc aromatic compound F of Boron tribromide
The intermediate 6 (5.0g) for having chloride as precursor and dimethylbenzene (100ml) will be added in a nitrogen atmosphere
Flask is cooled to -40 DEG C, and the s-butyl lithium hexane solution (9.3ml) of 2.6M is added dropwise.After completion of dropwise addition, stir at such a temperature
0.5 it is small when after, 60 DEG C are warming up to, when stirring 3 is small.Then, reaction solution is depressurized, distillation removes low-boiling component, Ran Houleng
But to -40 DEG C, Boron tribromide (7.1g) is added.Be warming up to room temperature, when stirring 0.5 is small after, be cooled to 0 DEG C, add N, N- bis- is different
Ethylamine (2.6g), heating stirring when progress 8 is small at 125 DEG C.Reaction solution is cooled to room temperature, it is water-soluble to add sodium acetate
After liquid stops reaction, add toluene and carry out liquid separation.By the short through post purifying of organic layer silica gel, silica gel column chromatography is then used
(eluent：The mixed solvent (Capacity Ratio) of heptane/toluene=4/1) purifying, further with activated carbon column chromatography (eluent：Toluene)
Purifying, obtains polycyclc aromatic compound F (0.8g, yield 16%).
The result of above-described embodiment 1~6 and comparative example 1~2 is shown in table 1 in the lump.
Table 1
Industrial applicability
The boric acid or borate of the present invention can also avoid being derived from since stability is high in the reaction with acid
The problem of high response, can avoid yield during popularization from reducing.In addition, the high boric acid of stability or borate easily carry out
Separation and purify, therefore product can be obtained with high selectivity, as a result, easily being obtained using high-purity and high yield as having
The polycyclc aromatic compound of machine EL element material.
Claims (8)
1. the compound shown in a kind of the following general formula (1), wherein, not including following X1And X2It is the situation of-O-；
One kind has the polymer compounds of structure shown in multiple the following general formula (1), wherein, not including following X1And X2It is-O-
Situation；
It is a kind of to be used to manufacture the compound shown in the following general formula (1) of polycyclc aromatic compound；Or,
A kind of polymer with structure shown in multiple the following general formula (1) for being used to manufacture Ppolynuclear aromatic polymer compounds
Compound,
In above-mentioned formula (1),
A rings, B ring and C rings are aromatic ring or hetero-aromatic ring independently of one another, and at least one hydrogen in these rings is optionally substituted,
Y1For optional esterified-B (OH)2,
X1And X2It is-O-, ＞ N-Ar ,-S- or-Se- independently of one another, herein, the Ar of the N-Ar is optionally substituted virtue
Base, optionally substituted heteroaryl or optionally substituted alkyl, the Ar of the N-Ar optionally by linking group or singly-bound and
It is bonded with the A rings, B rings and/or C rings, moreover,
At least one hydrogen in compound or structure shown in formula (1) is optionally substituted by deuterium.
2. compound according to claim 1 or polymer compounds, wherein,
A rings, B ring and C rings are aromatic ring or hetero-aromatic ring independently of one another, and at least one hydrogen in these rings is optionally substituted or does not take
The aryl in generation, substituted or unsubstituted heteroaryl, substituted or unsubstituted ammonia diaryl base, substituted or unsubstituted two heteroaryl
Amino, substituted or unsubstituted aryl heteroaryl amino, substituted or unsubstituted alkyl, substituted or unsubstituted alkoxy, take
Generation or the substitution of unsubstituted aryloxy group or halogen,
Y1For optional esterified-B (OH)2,
X1And X2It is-O-, ＞ N-Ar ,-S- or-Se- independently of one another, herein, the Ar of the N-Ar is optionally by alkyl or halogen
Substituted aryl, optionally by heteroaryl that alkyl or halogen substitute or the alkyl optionally substituted by alkyl or halogen, the N-
The Ar of Ar optionally passes through-O- ,-S-, ＞ C (R)2Or singly-bound and be bonded with the A rings, B rings and/or C rings, also, ＞ C
(R)2R be hydrogen or alkyl independently of one another, at least one hydrogen in the alkyl is optionally optionally substituted by halogen,
At least one hydrogen in compound or structure shown in formula (1) is optionally substituted by deuterium, moreover,
The polymer compounds are 2 dimmer compounds or 3 dimmer compounds.
3. the compound shown in a kind of the following general formula (2), wherein, not including following X1And X2It is the situation of-O-；Or,
It is a kind of to be used to manufacture the compound shown in the following general formula (2) of polycyclc aromatic compound,
In above-mentioned formula (2),
R1、R2、R3、R4、R5、R6、R7、R8、R9、R10And R11It is independently of one another hydrogen, aryl, heteroaryl, ammonia diaryl base, di (hetero)
Arylamino, aryl heteroaryl amino, alkyl, alkoxy, aryloxy group or halogen, at least one hydrogen in them are optionally fragrant
Base, heteroaryl, alkyl or halogen substitution, also, R1~R11Among adjacent group optionally bond together and with a rings, b rings or c
Ring forms aromatic ring or hetero-aromatic ring together, at least one hydrogen in the ring formed optionally by aryl, heteroaryl, ammonia diaryl base,
Two heteroaryl aminos, aryl heteroaryl amino, alkyl, alkoxy, aryloxy group or halogen substitution, at least one hydrogen in them are appointed
Choosing is substituted by aryl, heteroaryl, alkyl or halogen,
Y1For optional esterified-B (OH)2,
X1And X2Be-O-, ＞ N-Ar ,-S- or-Se- independently of one another, herein, the Ar of the N-Ar be the aryl of carbon number 6~12,
The heteroaryl of carbon number 2~15 or the alkyl of carbon number 1~6, at least one hydrogen in them are optionally optionally substituted by halogen, the N-Ar's
Ar optionally passes through-O- ,-S-, ＞ C (R)2Or singly-bound and be bonded with a rings, b rings and/or c rings, also, ＞ C (R)2R
It is independently of one another the alkyl of carbon number 1~6, at least one hydrogen in the alkyl is optionally optionally substituted by halogen, moreover,
At least one hydrogen in compound shown in formula (2) is optionally substituted by deuterium.
4. compound according to claim 3, wherein,
R1、R2、R3、R4、R5、R6、R7、R8、R9、R10And R11It is hydrogen, the aryl of carbon number 6~30, carbon number 2~30 independently of one another
Heteroaryl, ammonia diaryl base or halogen, at least one hydrogen in them are optionally optionally substituted by halogen, wherein, in ammonia diaryl base
Aryl is the aryl of carbon number 6~12, also, R1~R11Among adjacent group optionally bond together and with a rings, b rings or c rings one
The hetero-aromatic ring of the aromatic ring or carbon number 6~15 that form carbon number 9~16 is acted, at least one hydrogen in the ring formed is optionally by carbon number 6
~10 aryl or halogen substitutes, and at least one hydrogen in the aryl of the carbon number 6~10 is optionally optionally substituted by halogen,
Y1To make-B (OH)2Group obtained from esterification,
X1And X2It is-O-, ＞ N-Ar or-S- independently of one another, herein, the Ar of the N-Ar is the aryl or carbon number of carbon number 6~10
1~4 alkyl, at least one hydrogen in them are optionally optionally substituted by halogen, moreover,
At least one hydrogen in compound shown in formula (2) is optionally substituted by deuterium.
A kind of 5. compound shown in following formula (1-1-98)；Or,
It is a kind of to be used to manufacture the compound shown in the following formula (1-1-98) of polycyclc aromatic compound,
Bpin in formula is to make-B (OH)2Group obtained from pinacol esterification, tBu is the tert-butyl group.
6. a kind of be used to manufacture polycyclc aromatic compound, following formula (1-3-139), formula (1-3-252), formula (1-3-386)
Or the compound shown in formula (1-3-439),
Bpin in formula is to make-B (OH)2Group obtained from pinacol esterification, Me is methyl.
7. a kind of be used to manufacturing polycyclc aromatic compound, following formula (1-2-340) or the chemical combination shown in formula (1-2-343)
Thing,
Bpin in formula is to make-B (OH)2Group obtained from pinacol esterification, Me is methyl, and tBu is the tert-butyl group.
8. a kind of manufacture method, wherein, acid is acted on compound or tool shown in the following general formula (1) described in claim 1
There are the polymer compounds of structure shown in multiple the following general formula (1), manufacture polycyclc aromatic compound or Ppolynuclear aromatic poly
Body compound,
In structure above,
A rings, B ring and C rings are aromatic ring or hetero-aromatic ring independently of one another, and at least one hydrogen in these rings is optionally substituted,
Y1For optional esterified-B (OH)2,
X1And X2It is independently of one another-O-, ＞ N-Ar ,-S- or-Se-, herein, the Ar of N-Ar is optional described in the Ar of the N-Ar
Substituted aryl, optionally substituted heteroaryl or optionally substituted alkyl, the Ar of the N-Ar optionally pass through linker
Group or singly-bound and be bonded with the A rings, B rings and/or C rings, moreover,
At least one hydrogen in structure above is optionally substituted by deuterium.
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| KR20210053945A (en) * | 2018-08-31 | 2021-05-12 | 가꼬우 호징 관세이 가쿠잉 | Organic electroluminescent device using light emitting material of polycyclic aromatic compound |
| KR20200094262A (en) | 2019-01-29 | 2020-08-07 | 삼성디스플레이 주식회사 | Organic electroluminescence device and polycyclic compound for organic electroluminescence device |
| KR20200107028A (en) | 2019-03-05 | 2020-09-16 | 삼성디스플레이 주식회사 | Organic electroluminescence device and polycyclic compound for organic electroluminescence device |
| KR20210014834A (en) | 2019-07-30 | 2021-02-10 | 삼성디스플레이 주식회사 | Organometallic compound and organic light emitting device comprising the same |
| KR20210018574A (en) | 2019-08-05 | 2021-02-18 | 삼성디스플레이 주식회사 | Organometallic compound and organic light emitting device comprising the same |
| KR20210065258A (en) | 2019-11-26 | 2021-06-04 | 삼성디스플레이 주식회사 | Compound and light emitting device comprising same |
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