CN108912157A - A method of being simple and efficient synthesis boron azepine aromatic hydrocarbons - Google Patents
A method of being simple and efficient synthesis boron azepine aromatic hydrocarbons Download PDFInfo
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- CN108912157A CN108912157A CN201811165383.2A CN201811165383A CN108912157A CN 108912157 A CN108912157 A CN 108912157A CN 201811165383 A CN201811165383 A CN 201811165383A CN 108912157 A CN108912157 A CN 108912157A
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- aromatic hydrocarbons
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- -1 boron azepine aromatic hydrocarbons Chemical class 0.000 title claims abstract description 45
- 238000000034 method Methods 0.000 title claims abstract description 28
- 230000015572 biosynthetic process Effects 0.000 title claims description 42
- 238000003786 synthesis reaction Methods 0.000 title claims description 42
- 150000001875 compounds Chemical class 0.000 claims abstract description 42
- 229910052794 bromium Inorganic materials 0.000 claims abstract description 6
- 229910052801 chlorine Inorganic materials 0.000 claims abstract description 6
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 6
- 229910052740 iodine Inorganic materials 0.000 claims abstract description 6
- 238000006243 chemical reaction Methods 0.000 claims description 80
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 51
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical class CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 36
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 33
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 31
- 239000000706 filtrate Substances 0.000 claims description 29
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 26
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 claims description 24
- 238000007789 sealing Methods 0.000 claims description 24
- 239000002904 solvent Substances 0.000 claims description 24
- 239000003208 petroleum Substances 0.000 claims description 23
- 238000001514 detection method Methods 0.000 claims description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 21
- 238000007445 Chromatographic isolation Methods 0.000 claims description 20
- 238000011097 chromatography purification Methods 0.000 claims description 20
- 239000003480 eluent Substances 0.000 claims description 19
- 239000007789 gas Substances 0.000 claims description 19
- ILAHWRKJUDSMFH-UHFFFAOYSA-N boron tribromide Chemical compound BrB(Br)Br ILAHWRKJUDSMFH-UHFFFAOYSA-N 0.000 claims description 16
- 229910052757 nitrogen Inorganic materials 0.000 claims description 16
- 239000007787 solid Substances 0.000 claims description 16
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 13
- 239000012044 organic layer Substances 0.000 claims description 13
- 239000000243 solution Substances 0.000 claims description 12
- 239000012141 concentrate Substances 0.000 claims description 10
- MFRIHAYPQRLWNB-UHFFFAOYSA-N sodium tert-butoxide Chemical compound [Na+].CC(C)(C)[O-] MFRIHAYPQRLWNB-UHFFFAOYSA-N 0.000 claims description 10
- 239000013078 crystal Substances 0.000 claims description 9
- KTWOOEGAPBSYNW-UHFFFAOYSA-N ferrocene Chemical compound [Fe+2].C=1C=C[CH-]C=1.C=1C=C[CH-]C=1 KTWOOEGAPBSYNW-UHFFFAOYSA-N 0.000 claims description 9
- 238000010438 heat treatment Methods 0.000 claims description 8
- 239000012074 organic phase Substances 0.000 claims description 8
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 claims description 8
- 238000010992 reflux Methods 0.000 claims description 8
- 239000012266 salt solution Substances 0.000 claims description 8
- 229920006395 saturated elastomer Chemical class 0.000 claims description 8
- 238000005303 weighing Methods 0.000 claims description 8
- CYPYTURSJDMMMP-WVCUSYJESA-N (1e,4e)-1,5-diphenylpenta-1,4-dien-3-one;palladium Chemical compound [Pd].[Pd].C=1C=CC=CC=1\C=C\C(=O)\C=C\C1=CC=CC=C1.C=1C=CC=CC=1\C=C\C(=O)\C=C\C1=CC=CC=C1.C=1C=CC=CC=1\C=C\C(=O)\C=C\C1=CC=CC=C1 CYPYTURSJDMMMP-WVCUSYJESA-N 0.000 claims description 7
- OIRHKGBNGGSCGS-UHFFFAOYSA-N 1-bromo-2-iodobenzene Chemical group BrC1=CC=CC=C1I OIRHKGBNGGSCGS-UHFFFAOYSA-N 0.000 claims description 7
- AOPBDRUWRLBSDB-UHFFFAOYSA-N 2-bromoaniline Chemical compound NC1=CC=CC=C1Br AOPBDRUWRLBSDB-UHFFFAOYSA-N 0.000 claims description 7
- 239000000463 material Substances 0.000 claims description 6
- 150000004818 1,2-dichlorobenzenes Chemical class 0.000 claims description 5
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 5
- 238000000605 extraction Methods 0.000 claims description 4
- 238000011017 operating method Methods 0.000 claims description 4
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Natural products P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 claims description 3
- 238000005859 coupling reaction Methods 0.000 claims description 3
- QNMBSXGYAQZCTN-UHFFFAOYSA-N thiophen-3-ylboronic acid Chemical compound OB(O)C=1C=CSC=1 QNMBSXGYAQZCTN-UHFFFAOYSA-N 0.000 claims description 3
- 239000007864 aqueous solution Substances 0.000 claims description 2
- 230000008878 coupling Effects 0.000 claims description 2
- 238000010168 coupling process Methods 0.000 claims description 2
- 238000005401 electroluminescence Methods 0.000 claims description 2
- 239000013067 intermediate product Substances 0.000 claims description 2
- 229910000073 phosphorus hydride Inorganic materials 0.000 claims description 2
- 238000002360 preparation method Methods 0.000 claims description 2
- 238000003756 stirring Methods 0.000 claims description 2
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 claims 1
- 235000010290 biphenyl Nutrition 0.000 claims 1
- 239000004305 biphenyl Substances 0.000 claims 1
- 125000006267 biphenyl group Chemical group 0.000 claims 1
- 238000001816 cooling Methods 0.000 claims 1
- 238000010828 elution Methods 0.000 claims 1
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 claims 1
- 230000001681 protective effect Effects 0.000 claims 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 abstract description 10
- FCEHBMOGCRZNNI-UHFFFAOYSA-N 1-benzothiophene Chemical compound C1=CC=C2SC=CC2=C1 FCEHBMOGCRZNNI-UHFFFAOYSA-N 0.000 abstract description 8
- SIKJAQJRHWYJAI-UHFFFAOYSA-N Indole Chemical compound C1=CC=C2NC=CC2=C1 SIKJAQJRHWYJAI-UHFFFAOYSA-N 0.000 abstract description 8
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 abstract description 8
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 abstract description 8
- 125000003118 aryl group Chemical group 0.000 abstract description 8
- 238000010189 synthetic method Methods 0.000 abstract description 7
- 150000002240 furans Chemical class 0.000 abstract description 5
- 150000003233 pyrroles Chemical class 0.000 abstract description 5
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 abstract description 4
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 abstract description 4
- RFRXIWQYSOIBDI-UHFFFAOYSA-N benzarone Chemical compound CCC=1OC2=CC=CC=C2C=1C(=O)C1=CC=C(O)C=C1 RFRXIWQYSOIBDI-UHFFFAOYSA-N 0.000 abstract description 3
- 125000000217 alkyl group Chemical group 0.000 abstract description 2
- 125000005843 halogen group Chemical group 0.000 abstract description 2
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 21
- HIXDQWDOVZUNNA-UHFFFAOYSA-N 2-(3,4-dimethoxyphenyl)-5-hydroxy-7-methoxychromen-4-one Chemical compound C=1C(OC)=CC(O)=C(C(C=2)=O)C=1OC=2C1=CC=C(OC)C(OC)=C1 HIXDQWDOVZUNNA-UHFFFAOYSA-N 0.000 description 20
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 18
- ABRVLXLNVJHDRQ-UHFFFAOYSA-N [2-pyridin-3-yl-6-(trifluoromethyl)pyridin-4-yl]methanamine Chemical compound FC(C1=CC(=CC(=N1)C=1C=NC=CC=1)CN)(F)F ABRVLXLNVJHDRQ-UHFFFAOYSA-N 0.000 description 15
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 11
- 238000005160 1H NMR spectroscopy Methods 0.000 description 9
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 9
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 7
- 229910052796 boron Inorganic materials 0.000 description 7
- 235000002597 Solanum melongena Nutrition 0.000 description 6
- 244000061458 Solanum melongena Species 0.000 description 6
- 229930192474 thiophene Natural products 0.000 description 6
- GPAYUJZHTULNBE-UHFFFAOYSA-N diphenylphosphine Chemical compound C=1C=CC=CC=1PC1=CC=CC=C1 GPAYUJZHTULNBE-UHFFFAOYSA-N 0.000 description 5
- 239000010410 layer Substances 0.000 description 5
- 238000005406 washing Methods 0.000 description 5
- ZEEBGORNQSEQBE-UHFFFAOYSA-N [2-(3-phenylphenoxy)-6-(trifluoromethyl)pyridin-4-yl]methanamine Chemical compound C1(=CC(=CC=C1)OC1=NC(=CC(=C1)CN)C(F)(F)F)C1=CC=CC=C1 ZEEBGORNQSEQBE-UHFFFAOYSA-N 0.000 description 4
- TZHYBRCGYCPGBQ-UHFFFAOYSA-N [B].[N] Chemical group [B].[N] TZHYBRCGYCPGBQ-UHFFFAOYSA-N 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 4
- 238000011160 research Methods 0.000 description 4
- SYXYWTXQFUUWLP-UHFFFAOYSA-N sodium;butan-1-olate Chemical compound [Na+].CCCC[O-] SYXYWTXQFUUWLP-UHFFFAOYSA-N 0.000 description 4
- 238000010025 steaming Methods 0.000 description 4
- 150000001491 aromatic compounds Chemical class 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 238000004440 column chromatography Methods 0.000 description 3
- 229940125898 compound 5 Drugs 0.000 description 3
- 230000005622 photoelectricity Effects 0.000 description 3
- 230000000704 physical effect Effects 0.000 description 3
- 125000005575 polycyclic aromatic hydrocarbon group Chemical group 0.000 description 3
- FYGHSUNMUKGBRK-UHFFFAOYSA-N 1,2,3-trimethylbenzene Chemical compound CC1=CC=CC(C)=C1C FYGHSUNMUKGBRK-UHFFFAOYSA-N 0.000 description 2
- WDBQJSCPCGTAFG-QHCPKHFHSA-N 4,4-difluoro-N-[(1S)-3-[4-(3-methyl-5-propan-2-yl-1,2,4-triazol-4-yl)piperidin-1-yl]-1-pyridin-3-ylpropyl]cyclohexane-1-carboxamide Chemical compound FC1(CCC(CC1)C(=O)N[C@@H](CCN1CCC(CC1)N1C(=NN=C1C)C(C)C)C=1C=NC=CC=1)F WDBQJSCPCGTAFG-QHCPKHFHSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 239000005864 Sulphur Substances 0.000 description 2
- LJOOWESTVASNOG-UFJKPHDISA-N [(1s,3r,4ar,7s,8s,8as)-3-hydroxy-8-[2-[(4r)-4-hydroxy-6-oxooxan-2-yl]ethyl]-7-methyl-1,2,3,4,4a,7,8,8a-octahydronaphthalen-1-yl] (2s)-2-methylbutanoate Chemical compound C([C@H]1[C@@H](C)C=C[C@H]2C[C@@H](O)C[C@@H]([C@H]12)OC(=O)[C@@H](C)CC)CC1C[C@@H](O)CC(=O)O1 LJOOWESTVASNOG-UFJKPHDISA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- IOJUPLGTWVMSFF-UHFFFAOYSA-N benzothiazole Chemical compound C1=CC=C2SC=NC2=C1 IOJUPLGTWVMSFF-UHFFFAOYSA-N 0.000 description 2
- 125000000707 boryl group Chemical group B* 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 229940125904 compound 1 Drugs 0.000 description 2
- 229940127204 compound 29 Drugs 0.000 description 2
- 239000012043 crude product Substances 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 238000007689 inspection Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- UKVIEHSSVKSQBA-UHFFFAOYSA-N methane;palladium Chemical compound C.[Pd] UKVIEHSSVKSQBA-UHFFFAOYSA-N 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- RPGWZZNNEUHDAQ-UHFFFAOYSA-N phenylphosphine Chemical compound PC1=CC=CC=C1 RPGWZZNNEUHDAQ-UHFFFAOYSA-N 0.000 description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 235000002639 sodium chloride Nutrition 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- OTEKOJQFKOIXMU-UHFFFAOYSA-N 1,4-bis(trichloromethyl)benzene Chemical compound ClC(Cl)(Cl)C1=CC=C(C(Cl)(Cl)Cl)C=C1 OTEKOJQFKOIXMU-UHFFFAOYSA-N 0.000 description 1
- 238000006443 Buchwald-Hartwig cross coupling reaction Methods 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 241000237903 Hirudo Species 0.000 description 1
- 239000005909 Kieselgur Substances 0.000 description 1
- 239000002879 Lewis base Substances 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- CYMHIEKFNUNIBB-UHFFFAOYSA-N N1C=CC=CC=C1.[B] Chemical compound N1C=CC=CC=C1.[B] CYMHIEKFNUNIBB-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- JHBHAUSZOCYCRN-UHFFFAOYSA-N benzo[c][1,2]benzazaborinine Chemical compound C1=CC=CC=2C3=CC=CC=C3N=BC1=2 JHBHAUSZOCYCRN-UHFFFAOYSA-N 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- 238000006795 borylation reaction Methods 0.000 description 1
- CREMABGTGYGIQB-UHFFFAOYSA-N carbon carbon Chemical compound C.C CREMABGTGYGIQB-UHFFFAOYSA-N 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000007810 chemical reaction solvent Substances 0.000 description 1
- 230000021615 conjugation Effects 0.000 description 1
- 229920006037 cross link polymer Polymers 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000006477 desulfuration reaction Methods 0.000 description 1
- 230000023556 desulfurization Effects 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000005669 field effect Effects 0.000 description 1
- 125000001072 heteroaryl group Chemical group 0.000 description 1
- UOYPNWSDSPYOSN-UHFFFAOYSA-N hexahelicene Chemical compound C1=CC=CC2=C(C=3C(=CC=C4C=CC=5C(C=34)=CC=CC=5)C=C3)C3=CC=C21 UOYPNWSDSPYOSN-UHFFFAOYSA-N 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 150000007527 lewis bases Chemical class 0.000 description 1
- 238000004020 luminiscence type Methods 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- AUHZEENZYGFFBQ-UHFFFAOYSA-N mesitylene Substances CC1=CC(C)=CC(C)=C1 AUHZEENZYGFFBQ-UHFFFAOYSA-N 0.000 description 1
- 125000001827 mesitylenyl group Chemical group [H]C1=C(C(*)=C(C([H])=C1C([H])([H])[H])C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- UFWIBTONFRDIAS-UHFFFAOYSA-N naphthalene-acid Natural products C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- SLIUAWYAILUBJU-UHFFFAOYSA-N pentacene Chemical compound C1=CC=CC2=CC3=CC4=CC5=CC=CC=C5C=C4C=C3C=C21 SLIUAWYAILUBJU-UHFFFAOYSA-N 0.000 description 1
- 125000003367 polycyclic group Chemical group 0.000 description 1
- 230000003334 potential effect Effects 0.000 description 1
- 238000007363 ring formation reaction Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000009897 systematic effect Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
Classifications
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- 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
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K50/00—Organic light-emitting devices
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- H—ELECTRICITY
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- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/60—Organic compounds having low molecular weight
- H10K85/649—Aromatic compounds comprising a hetero atom
- H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1018—Heterocyclic compounds
- C09K2211/1025—Heterocyclic compounds characterised by ligands
- C09K2211/1029—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1018—Heterocyclic compounds
- C09K2211/1025—Heterocyclic compounds characterised by ligands
- C09K2211/1029—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom
- C09K2211/104—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom with other heteroatoms
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1018—Heterocyclic compounds
- C09K2211/1025—Heterocyclic compounds characterised by ligands
- C09K2211/1088—Heterocyclic compounds characterised by ligands containing oxygen as the only heteroatom
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1018—Heterocyclic compounds
- C09K2211/1025—Heterocyclic compounds characterised by ligands
- C09K2211/1092—Heterocyclic compounds characterised by ligands containing sulfur as the only heteroatom
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- Chemical & Material Sciences (AREA)
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- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Physics & Mathematics (AREA)
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Abstract
The present invention provides the synthetic method of the simple and effective of a kind of boron azepine aromatic hydrocarbons, the compound formula that this method finally synthesizes is as follows：Ar1, Ar2Be respectively it is independent, can be substituted or non-substituted single aromatic ring system, be also possible to substituted or non-substituted multiple aromatic ring systems.Such as Ar1, Ar2It can be phenyl ring, thiphene ring, furan nucleus, pyrroles, pyridine, benzothiophene, benzofuran, benzopyrrole, benzo pyridine etc..R1, R2It is independent substituted or non-substituted group respectively.Such as R1, R2It can be single halogen atom F, Cl, Br, I etc.；It is also possible to various alkyl；It is also possible to various aromatic rings or the aromatic heterocycles such as various aryl such as phenyl ring, thiphene ring, furan nucleus, pyrroles, pyridine, benzothiophene, benzofuran, benzopyrrole, benzo pyridine.
Description
Technical field
The present invention relates to boron azepine aromatic hydrocarbons fields, and in particular to a method of it is simple and efficient synthesis boron azepine aromatic hydrocarbons.This
The synthetic method of class boron azepine aromatic hydrocarbons is related to Buchwald-Hartwig coupling reaction, C-C coupling, lewis base guiding
Electrophilic boron cyclization etc..
Background technique
Organic conjugate material is since it is in organic photoelectric equipment, field effect transistor, Organic Light Emitting Diode, organic photoelectric
The potential properties such as material and sensor etc. have low cost, wide field, light-weight, flexibility is good, cause ours
It pays high attention to.Nowadays boron azepine chemistry is increasingly becoming the important branch in organic semiconductor luminescent material, in conjugated molecule
Sulphur is introduced in skeleton, nitrogen and oxygen can assign conjugated molecule different photoelectric properties, carbon carbon especially substituted with carbon-to-nitrogen double bon
Double bond can generate the different analogs of benzene, therefore the conjugation aromatic hydrocarbons of BN doping causes our great interest.
1958, Dewar group synthesized the naphthalene compound of boron nitrogen substitution for the first time, and nineteen sixty Dewar andWhite is for the first time
The 1- azepine boron derivative of monocycle is synthesized, 1962, the method for Dewar et al. desulfurization was obtained from the benzothiazole that boron nitrogen replaces
More polysubstituted 1,2- azepine boron is arrived, White in 1963 et al. has synthesized 1-H-2- phenyl -1,2- azepine boron, opened boron
Gate (M.J.S.Dewar, V.P.Kubba, R.Pettit, the 624.New heteroaromatic of nitrogen chemical
compounds.Part I.9-Aza-10-boraphenanthrene,J.Chem.Soc.1958,3073–3076)。
Due to the limitation of boron azepine aromatic hydrocarbons synthetic method, people more than a 40 year left side quiet to the research of such compound
The right side, after 2000, researcher has invented comparatively easy synthetic method.Some scientists study discoveries
Boron azepine aromatic hydrocarbons can effectively adjust the photoelectricity physical property of aroma system, and the conjugated polycyclic aromatic hydrocarbons of boron N doping causes again
The research interest of people.
The Ashe group of University of Michigan in 2000 is in terms of synthesizing monocycle 1,2- azepine boron compound with mild method
It made breakthrough progress.2011, Japanese Nakamura group synthesized the virtue of boron nitrogen substitution using the method for Dewar
Fragrant hydrocarbon and developed a series of intramolecular boryls method (T.Hatakeyama, S.Hashimoto, S.Seki,
M.Nakamura,Synthesis of BN-fused polycyclic aromatics via
tandemintramolecular electrophilic areneborylation,J.Am.Chem.Soc.2011,133,
18614–18617).2012, Nakamura et al. synthesized double benzene [6] helicenes of racemic boron nitrogen with same method
(T.Hatakeyama,S.Hashimoto,T.Oba,M.Nakamura,Azaboradibenzo[6]helicene:carrier
inversion inducedby helical homochirality,J.Am.Chem.Soc.2012,134,19600–
19603).2014, Nakamura group was using the poly-ring aromatic compounds of the boron N doping of synthesis and its derivative as phosphorescence
The material of main part layer of light emitting diode, this kind of device have the better service life.Yamaguchi group recent report is based on three alkane
Base replaces to synthesize the 1,2- azepine boron of big π system.Kawashima is small to be combined into using 1,4- boron nitrogen molecular as center unit
Pentacene, heptacene compound.Hatakeyama, Nakamura et al. report a series of electrophilic boryl by intramoleculars
Change to synthesize the polycyclic aromatic hydrocarbons (PAH) of double boron azo-cycle bondings.
The Feng Xinliang of recent Shanghai Communications University and seminar is lift a sail respectively at 2013,2015, deliver within 2016
A series of poly-ring aromatic compounds (the Ladder-type BN-embedded Heteroacenes of boron N doping bithiophenes
with Blue Emission.Wang,X.；Zhang,F.；Liu,J.；Feng,X.L.Org.Lett.2013,15,5714-
5717/Cross-linked polymer-derived B/N co-doped carbon materials with
selective capture of CO2.Zhao,WX；Zhuang,XD；Zhang,F.；Mai,YY；Feng,
X.L.J.Mater.Chem.A,2015,3,23352-23359./Synthesis of Stable Nanographenes with
OBO-Doped Zigzag Edges Based on Tandem Demethylation-Electrophilic
Borylation.Xiao-Ye Wang,Akimitsu Narita,Wen Zhang,Xinliang Feng,Klaus Mü
2016,138,9021-9024.), and systematic research their photoelectricity physical property llen.J.Am.Chem.Soc.,.
In the past few years, it is greatly improved to the chemical research of boron azepine aromatic hydrocarbons, is synthesized with different methods
The aromatic compound of the boron N doping of diversified forms.However these synthetic route relative productivities of boron azepine aromatic hydrocarbons are lower, arrive
So far, yield relatively high synthetic route and method are had not seen.
Summary of the invention
Object of the present invention is to solve the problems, such as that boron azepine aromatic hydrocarbons synthetic method yield is lower, one kind is provided and is simple and efficient synthesis
The method for synthesizing boron azepine aromatic hydrocarbons, while the potential using value of such compound is provided to be luminous organic material, organic
The fields such as solar battery contribute.
The purpose of the present invention is achieved through the following technical solutions：
A kind of boron azepine aromatic hydrocarbons, structural formula are：
Ar1, Ar2Be respectively it is independent, can be substituted or non-substituted single aromatic ring system, be also possible to replace or it is non-
The multiple aromatic ring systems replaced.Such as Ar1, Ar2It can be phenyl ring, thiphene ring, furan nucleus, pyrroles, pyridine, benzothiophene, benzene
And furans, benzopyrrole, benzo pyridine etc..R1, R2It is independent substituted or non-substituted group respectively.Such as R1, R2It can be list
A halogen atom F, Cl, Br, I etc.；It is also possible to various alkyl；It is also possible to various aryl such as phenyl ring, thiphene ring, furans
Various aromatic rings or the aromatic heterocycles such as ring, pyrroles, pyridine, benzothiophene, benzofuran, benzopyrrole, benzo pyridine.
A method of it being simple and efficient synthesis boron azepine aromatic hydrocarbons, synthetic route and operating procedure are as follows：
1) synthesis of compound SLY-1：Weigh tris(dibenzylideneacetone) dipalladium 0.025-0.03eq, 1,1'- it is bis- (Hexichol Base phosphine) system in twoport reaction flask, substituted gas three times, in nitrogen by ferrocene 0.05-0.6eq and sodium tert-butoxide 1.5-2.0eq
Under the conditions of gas shielded, adjacent bromo-iodobenzene 1.0eq, o-bromoaniline 1.2-1.3eq and toluene 50-100ml is added and carries out back flow reaction,
The detection reaction of TLC method is until fully reacting；Stop reaction after stirring 24-36h, is restored to room temperature to system, uses saturated sodium-chloride
Aqueous solution and methylene chloride extraction, organic layer merge, and dry with anhydrous magnesium sulfate, and dry system is filtered, is collected
To filtrate and be spin-dried for solvent, using petroleum ether as eluant, eluent, the concentrate being spin-dried for quickly carries out column chromatographic isolation and purification, final
To white crystal, i.e. target compound SLY-1；
2) synthesis of compound SLY-2：1.0eq compound SLY-1 is weighed, system is substituted into gas three times under a nitrogen atmosphere
It is placed in glove box, then weighs tetrakis triphenylphosphine palladium 0.17-0.20eq and 3 thienylboronic acid 1.2-3.0eq, this step foundation
The reaction condition of coupling reaction is operated with the equivalents ratio of above range, and the system that is sealed removes glove box, then will reaction
Solvent 10-30ml is injected into reaction system, and system is then carried out back flow reaction under the conditions of 110 DEG C, and TLC detection reaction is straight
To fully reacting；Stop reaction after 12-16h, be restored to room temperature to system, is extracted with methylene chloride and saturated sodium-chloride water solution
It takes, and dry with anhydrous magnesium sulfate, dry system is filtered, the filtrate collected simultaneously is spin-dried for solvent, is with petroleum ether
The concentrate being spin-dried for quickly is carried out column chromatographic isolation and purification by washing and dehydrating integrated machine, finally obtains the solid of white, i.e. intermediate product SLY-
2；
3) synthesis of compound SLY-3：1.0eq compound SLY-2, Boron tribromide 2.0-2.5eq are weighed in glove box
With triethylamine 3.0-5.0eq in tube sealing, 1,2- dichloro-benzenes 5-10ml is solvent, and weighing finishes, and sealing tube sealing moves the system
Glove box out is heated to reflux under the conditions of 180 DEG C, and TLC detection reaction is until fully reacting；12-16h stops heating, to system
It is cooled to room temperature, is extracted with ethyl acetate and saturated salt solution, merges organic phase, and dry with anhydrous magnesium sulfate, then will dry
System is filtered, and the filtrate collected simultaneously is spin-dried for filtrate, carries out column chromatographic isolation and purification by eluant, eluent of petroleum ether, finally
Obtain the solid of white, i.e. target compound SLY-3.
Ar in the target compound SLY-31, Ar2Identical boron azepine aromatic hydrocarbons is one in following 1-28 structural formula
Kind, but it is not limited to following compound：
Wherein, X=F, Cl, Br or I.
Ar in the target compound SLY-31, Ar2Different boron azepine aromatic hydrocarbons is one in following 29-48 structural formula
Kind, but it is not limited to following compound：
Wherein, X=F, Cl, Br or I.
Invention also provides following a kind of synthesis sides being simple and efficient for containing two two thiphene ring boron azepine aromatic hydrocarbons
Method, including following synthesis step and reaction condition：
1) synthesis of compound 1-1：Weigh tris(dibenzylideneacetone) dipalladium, 1,1'- bis- (Diphenylphosphine) ferrocene, uncle
Sodium butoxide substitutes gas three times in twoport reaction flask, by system, and under the conditions of nitrogen protection, adjacent bromo-iodobenzene, o-bromoaniline is added
And toluene carries out back flow reaction, the detection reaction of TLC method is until fully reacting.Stop reaction after 2-3 days, is restored to room to system
Temperature is extracted with saturated sodium-chloride water solution and methylene chloride, and organic layer merges, and dry with anhydrous magnesium sulfate, by dry system
It is filtered, the filtrate collected simultaneously is spin-dried for solvent, and using petroleum ether as eluant, eluent, the concentrate being spin-dried for quickly carries out column chromatography
It isolates and purifies, finally obtains white crystal, i.e. compound 1-1.
2) synthesis of compound 1-2：Weigh Compound 1-1 substitutes gas in a dry eggplant type bottle under a nitrogen atmosphere
Three times, then system is placed in glove box, weighs tetrakis triphenylphosphine palladium and 2- tributylstamlyl thiophene in glove box
Pheno is sealed system and removes glove box, then the toluene solvant of the anhydrous and oxygen-free of steaming is injected into reaction system, and then system exists
Back flow reaction is carried out under the conditions of 110 DEG C, TLC detection reaction is until fully reacting.Stop reaction after one day, is cooled to room to system
Temperature is extracted with methylene chloride and saturated sodium-chloride water solution, and organic layer merges, and dry with anhydrous magnesium sulfate, by dry system
It is filtered, the filtrate collected simultaneously is spin-dried for solvent, quickly carries out column chromatographic isolation and purification by eluant, eluent of petroleum ether, finally
Obtain the solid of white, i.e. intermediate 1-2.
3) synthesis of compound 1：Compound 1-2 is weighed in glove box, Boron tribromide, triethylamine is in tube sealing, and 1,2-
Dichloro-benzenes is solvent, and weighing finishes, which is removed glove box by sealing tube sealing, is heated to reflux under the conditions of 180 DEG C, TLC inspection
Reaction is surveyed until fully reacting.Stop heating overnight, be cooled to room temperature to system, is extracted with ethyl acetate and saturated salt solution,
Merging organic phase, and dry with anhydrous magnesium sulfate, then dry system is filtered, the filtrate collected simultaneously is spin-dried for filtrate,
Column chromatographic isolation and purification is carried out by eluant, eluent of petroleum ether, finally obtains the solid of white, i.e. boron azepine aromatic hydrocarbons 1.
The present invention also provides a kind of synthetic methods being simple and efficient for containing two three thiphene ring boron azepine aromatic hydrocarbons, including
Following synthesis step and reaction condition：
1) synthesis of compound 1-1：Weigh tris(dibenzylideneacetone) dipalladium, 1,1'- bis- (Diphenylphosphine) ferrocene, uncle
Sodium butoxide substitutes gas three times in twoport reaction flask, by system, and under the conditions of nitrogen protection, adjacent bromo-iodobenzene, o-bromoaniline is added
And toluene carries out back flow reaction, the detection reaction of TLC method is until fully reacting.Stop reaction after 2-3 days, is restored to room to system
Temperature is extracted with saturated sodium-chloride water solution and methylene chloride, and organic layer merges, and dry with anhydrous magnesium sulfate, by dry system
It is filtered, the filtrate collected simultaneously is spin-dried for solvent, and using petroleum ether as eluant, eluent, the concentrate being spin-dried for quickly is carried out column layer
Analysis isolates and purifies, and finally obtains white crystal, i.e. compound 1-1.
2) synthesis of compound 5-1：Weigh Compound 1-1 and potassium carbonate are in a dry eggplant type bottle, in condition of nitrogen gas
It is lower that system is substituted into gas three times, system is placed in glove box, tetrakis triphenylphosphine palladium and 3- thiophene are weighed in glove box
Boric acid is sealed system and removes glove box, then by Isosorbide-5-Nitrae-dioxane of appropriate amount：Water=4:1 mixed solution is injected into instead
It answers in system, system is then subjected to back flow reaction under the conditions of 110 DEG C, TLC detection reaction is until fully reacting.Stop after overnight
It only reacts, is restored to room temperature to system, extracted with methylene chloride and saturated sodium-chloride water solution, and is dry with anhydrous magnesium sulfate,
Dry system is filtered, the filtrate collected simultaneously is spin-dried for solvent, using petroleum ether as washing and dehydrating integrated machine, the concentrate being spin-dried for is fast
Speed carries out column chromatographic isolation and purification, finally obtains the solid of white, i.e. intermediate 5-1.
3) synthesis of compound 5：Compound 5-1 is weighed in glove box, Boron tribromide, triethylamine is in tube sealing, and 1,2-
Dichloro-benzenes is solvent, and weighing finishes, which is removed glove box by sealing tube sealing, is heated to reflux under the conditions of 180 DEG C, TLC inspection
Reaction is surveyed until fully reacting.Stop heating after overnight, be cooled to room temperature to system, is extracted with ethyl acetate and saturated salt solution
It takes, merges organic phase, and dry with anhydrous magnesium sulfate, then dry system is filtered, the filtrate collected simultaneously is spin-dried for filtering
Liquid carries out column chromatographic isolation and purification by eluant, eluent of petroleum ether, finally obtains white solid, i.e. boron azepine aromatic hydrocarbons 5.
The present invention also provides the synthesis sides of a kind of boron azepine aromatic hydrocarbons containing a pyrroles and a thiophene being simple and efficient
Method, including following synthesis step and reaction condition：
1) synthesis of compound 1-1：Weigh tris(dibenzylideneacetone) dipalladium, 1,1'- bis- (diphenylphosphine) ferrocene, uncle
Sodium butoxide substitutes gas three times in twoport reaction flask, by system, and under the conditions of nitrogen protection, adjacent bromo-iodobenzene, o-bromoaniline is added
And toluene carries out back flow reaction, the detection reaction of TLC method is until fully reacting.Stop reaction after 2-3 days, is restored to room to system
Temperature is extracted with saturated sodium-chloride water solution and methylene chloride, and organic layer merges, and dry with anhydrous magnesium sulfate, by dry system
It is filtered, the filtrate collected simultaneously is spin-dried for solvent, and using petroleum ether as eluant, eluent, the concentrate being spin-dried for quickly is carried out column layer
Analysis isolates and purifies, and finally obtains white crystal, i.e. compound 1-1.
2) synthesis of compound 29-1：Weigh compound 1-1,1,1'- bis- (diphenylphosphine) ferrocene, 10% palladium carbon, uncle
Sodium butoxide substitutes gas three times in a twoport reaction flask, by system, under the conditions of nitrogen protection ground, injects compound pyrroles and molten
Agent mesitylene.Then system is placed at 180 DEG C, in nitrogen environment, carries out back flow reaction, TLC detection reaction is until anti-
It should be complete.Stop reaction after after one day, be restored to room temperature to system, ethyl acetate and water are added into obtained mixture, makes
Catalyst is removed with suction filtered through kieselguhr mixture.Filtrate is divided into two layers, water and salt water washing organic layer are successively used, with anhydrous sulphur
Sour magnesium is dry, filters and is concentrated under resulting filter vacuum.With petroleum ether：Ethyl acetate (20：It 1) is eluant, eluent, it is dense by what is be spin-dried for
Contracting object quickly carries out column chromatographic isolation and purification, finally obtains yellow oil, i.e. intermediate 29-1.
3) synthesis of compound 29-2：Weigh Compound 29-1 substitutes under a nitrogen atmosphere in a dry eggplant type bottle
System three times, is then placed in glove box by gas, weighs tetrakis triphenylphosphine palladium and 2- tributylstamlyl in glove box
Thiophene is sealed system and removes glove box, then the toluene solvant of the anhydrous and oxygen-free of steaming is injected into reaction system, then system
Back flow reaction is carried out under the conditions of 110 DEG C, TLC detection reaction is until fully reacting.Stop reaction after one day, is cooled to system
Room temperature is extracted with methylene chloride and saturated sodium-chloride water solution, and organic layer merges, and dry with anhydrous magnesium sulfate, by hirudo leech
System is filtered, and the filtrate collected simultaneously is spin-dried for solvent, quickly carries out column chromatographic isolation and purification by eluant, eluent of petroleum ether, most
The solid of white, i.e. intermediate 29-2 are obtained eventually.
4) synthesis of compound 29：Compound 29-2 is weighed in glove box, Boron tribromide, triethylamine is in tube sealing, and 1,
2- dichloro-benzenes is solvent, and weighing finishes, which is removed glove box by sealing tube sealing, is heated to reflux under the conditions of 180 DEG C, TLC
Detection reaction is until fully reacting.Stop heating overnight, be cooled to room temperature to system, is extracted with ethyl acetate and saturated salt solution
It takes, merges organic phase, and dry with anhydrous magnesium sulfate, then dry system is filtered, the filtrate collected simultaneously is spin-dried for filtering
Liquid carries out column chromatographic isolation and purification by eluant, eluent of petroleum ether, finally obtains the solid of white, i.e. boron azepine aromatic hydrocarbons 29.
The scope of use for a kind of boron azepine aromatic hydrocarbons that the present invention synthesizes is extremely wide, can be used for organic photoelectrical material, solar-electricity
Pond, electroluminescence device, sensor preparation.
The beneficial effects of the invention are as follows：
The present invention makes operating procedure simple and easy using the synthetic method of improvement, and can successfully be efficiently obtained mesh
Compound is marked, the lower disadvantage of the relative complex yield of traditional route is successfully overcome.
Detailed description of the invention
Fig. 1 is in present example structure containing there are two in the boron azepine aromatic hydrocarbons 1 of two thiphene rings and structure there are two containing
The UV absorption spectrogram of the boron azepine aromatic hydrocarbons 5 of three thiphene rings in methylene chloride.
Fig. 2 is in present example structure containing there are two in the boron azepine aromatic hydrocarbons 1 of two thiphene rings and structure there are two containing
The fluorescent emission spectrogram of the boron azepine aromatic hydrocarbons 5 of three thiphene rings in methylene chloride.
Fig. 3 is the single crystal diffraction for containing the boron azepine aromatic hydrocarbons 5 there are two three thiphene rings in application example of the present invention in structure
Structure.
Specific embodiment
Present invention will be further explained below with reference to the attached drawings and examples, but the scope of protection of present invention not office
It is limited to the range of embodiment statement.
A kind of method for being simple and efficient synthesis boron azepine aromatic hydrocarbons and being simple and efficient of the present invention, including following operating procedure and synthesis
Route：
It illustrates to above-mentioned part of compounds, particular content is as follows：
Embodiment 1：
1) synthesis of compound 1-1：It weighs tris(dibenzylideneacetone) dipalladium (916mg, 0.025eq), 1,1'- bis- (two
Phenylphosphine) ferrocene (1.11g, 0.05eq), sodium tert-butoxide (5.8g, 1.5eq) substitutes gas three in twoport reaction flask, by system
It is secondary, under the conditions of nitrogen protection, adjacent bromo-iodobenzene (11.3g, 1.0eq), o-bromoaniline (8.25g, 1.2eq) and toluene is added
(100ml) carries out back flow reaction.It after reacting 36h, is detected and is reacted with TLC method, after completion of the reaction, extracted with water and methylene chloride,
Organic layer merges, and dry with anhydrous magnesium sulfate, filters, is spin-dried for solvent, quickly progress column chromatographic isolation and purification crude product, final
To white crystal, i.e. compound 1-1 (9.8g, yield=75%).
1H NMR(400MHz,CDCl3):δ 7.58 (d, J=7.9Hz, 2H, Ar), 7.29 (d, J=7.8Hz, 2H, Ar),
7.21 (t, J=7.7Hz, 2H, Ar), 6.84 (t, J=7.5Hz, 2H, Ar), 6.44 (br, 1H, NH)
2) synthesis of compound 1-2：Weigh Compound 1-1 (1.05g, 1.0eq) is in a dry eggplant type bottle, in nitrogen
Under the conditions of substitute gas three times, then system is placed in glove box, glove box weigh tetrakis triphenylphosphine palladium (374mg,
0.1eq) and 2- tributylstamlyl thiophene (3.02g, 2.5eq), system is sealed and removes glove box, then by the anhydrous nothing of steaming
The toluene solvant (20ml) of oxygen is injected into reaction system, and then system carries out back flow reaction, TLC detection under the conditions of 110 DEG C
Reaction is until fully reacting.Stop reaction afterwards for 24 hours, room temperature is cooled to system, with methylene chloride and saturated sodium-chloride water solution
Extraction merges organic layer, and dry with anhydrous magnesium sulfate, dry system is filtered, the filtrate collected simultaneously is spin-dried for molten
Agent quickly carries out column chromatographic isolation and purification by eluant, eluent of petroleum ether, finally obtains the solid of white, i.e. intermediate 1-2
(0.75g, yield=70%).
1HNMR(400MHz,CDCl3) δ 7.42 (d, J=8.0Hz, 2H, Ar), 7.29 (d, J=4.0Hz, 2H, Ar),
7.20-7.26 (m, 4H, Ar), 7.11 (d, J=4.0Hz, 2H, Ar), 7.02 (dd, J1=4.0Hz, J2=8.0Hz, 2H, Ar),
6.96-7.00(m,2H,Ar),6.24(br,1H,NH).
3) synthesis of compound 1：Compound 1-2 (360mg, 1.0eq) is weighed in glove box, Boron tribromide (200ul,
2.0eq), triethylamine (449ul, 3.0eq) is in tube sealing, solubilizer 1, and 2- dichloro-benzenes (6ml), weighing finishes, and sealing tube sealing will
The system removes glove box, is heated to reflux under the conditions of 180 DEG C, and TLC detection reaction is until fully reacting.12h stops heating, to
System is cooled to room temperature, is extracted with ethyl acetate and saturated salt solution, merges organic phase, and dry with anhydrous magnesium sulfate, then will
Dry system is filtered, and the filtrate collected simultaneously is spin-dried for filtrate, carries out column chromatographic isolation and purification by eluant, eluent of petroleum ether,
Finally obtain the solid of white, i.e. boron azepine aromatic hydrocarbons 1 (320mg, yield=87%).
1HNMR(400MHz,CDCl3)δ8.33(dd,J1=8.3Hz, J2=1.3Hz, 2H, Ar), 8.05-8.09 (m, 4H,
), Ar 7.55 (d, J=5.0Hz, 2H, Ar), 7.31-7.40 (m, 4H, Ar)
Embodiment 2：
1) synthesis of compound 1-1：It weighs tris(dibenzylideneacetone) dipalladium (916mg, 0.025eq), 1,1'- bis- (two
Phenylphosphine) ferrocene (1.11g, 0.05eq), sodium tert-butoxide (5.8g, 1.5eq) substitutes gas three in twoport reaction flask, by system
It is secondary, under the conditions of nitrogen protection, adjacent bromo-iodobenzene (11.3g, 1.0eq), o-bromoaniline (8.25g, 1.2eq) and toluene is added
(100ml) carries out back flow reaction.It after reacting 36h, is detected and is reacted with TLC method, after completion of the reaction, extracted with water and methylene chloride,
Organic layer merges, and dry with anhydrous magnesium sulfate, filters, is spin-dried for solvent, quickly progress column chromatographic isolation and purification crude product, final
To white crystal, i.e. compound 1-1 (9.8g, yield=75%).
1H NMR(400MHz,CDCl3):δ 7.58 (d, J=7.9Hz, 2H, Ar), 7.29 (d, J=7.8Hz, 2H, Ar),
7.21 (t, J=7.7Hz, 2H, Ar), 6.84 (t, J=7.5Hz, 2H, Ar), 6.44 (br, 1H, NH)
2) synthesis of compound 5-1：Weigh Compound 1-1 (271mg, 1.0eq) and potassium carbonate (1.22g, 10eq) are in one
In dry eggplant type bottle, system is substituted into gas three times under a nitrogen atmosphere, system is placed in glove box, is claimed in glove box
Tetrakis triphenylphosphine palladium (163mg, 0.17eq) and 3 thienylboronic acid (265mg, 2.5eq) are taken, system is sealed and removes glove box,
Again by Isosorbide-5-Nitrae-dioxane of appropriate amount：Water=4:1 mixed solution (7.5ml) is injected into reaction system, then by system
Back flow reaction is carried out under the conditions of 110 DEG C, TLC detection reaction is until fully reacting.Stop reaction afterwards for 24 hours, is restored to system
Room temperature is extracted with methylene chloride and saturated sodium-chloride water solution, and dry with anhydrous magnesium sulfate, and dry system is filtered,
It collects obtained filtrate and is spin-dried for solvent, using petroleum ether as washing and dehydrating integrated machine, it is pure that the concentrate being spin-dried for quickly is carried out to column chromatography for separation
Change, finally obtains the solid of white, i.e. compound 5-1 (266mg, yield=96%).
1HNMR(400MHz,CDCl3):δ 7.40 (d, J=0.9Hz, 1HAr), 7.38 (d, J=0.8Hz, 1H, Ar),
7.32(dd,J1=4.9, J2=3.0Hz, 2H), 7.30 (d, J=1.5Hz, 1H), 7.28 (d, J=1.5Hz, 1H), 7.22-
7.26(m,,2H,Ar),7.17(dd,J1=2.9Hz, J2=1.3Hz, 2H, Ar), 7.06 (dd, J1=4.9Hz, J2=1.3Hz,
2H,Ar),6.96(td,J1=7.4Hz, J2=1.1Hz, 2H), 5.98 (br, 1H, NH)
3) synthesis of compound 5：Compound 5-1 (165mg, 1.0eq) is weighed in glove box, Boron tribromide (92ul,
2.0eq), triethylamine (206ul, 3.0eq) is in tube sealing, solubilizer 1, and 2- dichloro-benzenes (5ml), weighing finishes, and sealing tube sealing will
The system removes glove box, is heated to reflux under the conditions of 180 DEG C, and TLC detection reaction is until fully reacting.12h stops heating, to
System is cooled to room temperature, is extracted with ethyl acetate and saturated salt solution, merges organic phase, and dry with anhydrous magnesium sulfate, then will
Dry system is filtered, and the filtrate collected simultaneously is spin-dried for filtrate, carries out column chromatographic isolation and purification by eluant, eluent of petroleum ether,
Finally obtain the solid of white, i.e. boron azepine aromatic hydrocarbons 5 (150mg, yield=89%).
1H NMR(400MHz,CDCl3):δ8.39-8.44(m,2H,Ar),8.21-8.26(m,2H,Ar),7.99-8.04
(m,4H,Ar),7.35-7.42(m,4H,Ar).
Fig. 1 is the UV absorption spectrogram that above example 1 and 5 is tested in five kinds of different solvents, and Fig. 2 is above example 1 and 5
The fluorescent emission spectrogram tested in five kinds of different solvents.
Embodiment 3：
1) synthesis of compound 29-1：It weighs compound 1-1 (295mg, 1.0eq), 1,1'- bis- (diphenylphosphine) ferrocene
(11.1mg, 0.02eq), 10% palladium carbon (2.0mg, 0.02eq), sodium tert-butoxide (15.0mg, 0.025eq) is in a twoport reaction flask
In, system is substituted into gas three times, under the conditions of nitrogen protection ground, compound pyrroles (80.3mg, 1.33eq) is injected and solvent is equal
Trimethylbenzene (5ml).Then system is placed at 180 DEG C, in nitrogen environment, carries out back flow reaction, TLC detection reaction is until anti-
It should be complete.Stop reaction afterwards for 24 hours, be restored to room temperature to system, ethyl acetate and water are added into obtained mixture, uses silicon
Diatomaceous earth filters mixture and removes catalyst.Filtrate is divided into two layers, water and salt water washing organic layer is successively used, uses anhydrous magnesium sulfate
It is dry, it filters and is concentrated under resulting filter vacuum.With petroleum ether：Ethyl acetate (20：It 1) is eluant, eluent, the concentrate that will be spin-dried for
Column chromatographic isolation and purification is quickly carried out, yellow oil, i.e. intermediate 29-1 (260mg, yield=92%) are finally obtained.
1H NMR(400MHz,CDCl3):δ 7.52 (d, J=7.6Hz, 1H, Ar), 7.27-7.38 (m, 4H, Ar), 7.21
(t, J=7.6Hz, 1H, Ar), 7.04 (t, J=7.6Hz, 1H, Ar), 6.88 (m, 2H, Ar), 6.81 (t, J=7.6Hz, 1H,
Ar),6.37(m,2H,Ar),5.98(br,1H,NH).
2) synthesis of compound 29-2：Weigh Compound 29-1 (523mg, 1.0eq) is in a dry eggplant type bottle, in nitrogen
Substitute gas under the conditions of gas three times, then system be placed in glove box, glove box weigh tetrakis triphenylphosphine palladium (330mg,
0.17eq) and 2- tributylstamlyl thiophene (829mg, 1.33eq), system is sealed and removes glove box, then by the anhydrous of steaming
The toluene solvant (5ml) of anaerobic is injected into reaction system, and then system carries out back flow reaction, TLC detection under the conditions of 110 DEG C
Reaction is until fully reacting.Stop reaction afterwards for 24 hours, room temperature is cooled to system, with methylene chloride and saturated sodium-chloride water solution
Extraction merges organic layer, and dry with anhydrous magnesium sulfate, dry system is filtered, the filtrate collected simultaneously is spin-dried for molten
Agent quickly carries out column chromatographic isolation and purification by eluant, eluent of petroleum ether, finally obtains the solid of white, i.e. intermediate 29-2
(412mg, yield=78%).
1HNMR(400MHz,CDCl3):δ7.53(dd,J1=1.2Hz, J2=7.6Hz, 1H, Ar), 7.43 (d, J=
7.6Hz,1H,Ar),7.28-7.37(m,5H,Ar),7.08-7.14(m,3H,Ar),6.96-6.99(m,1H,Ar),6.85(t,
J=2.0Hz, 2H, Ar), 6.38 (t, J=2.0Hz, 2H, Ar), 5.98 (br, 1H, NH)
3) synthesis of compound 29：Compound 29-2 (377mg, 1.0eq) is weighed in glove box, Boron tribromide
(222ul, 2.0eq), triethylamine (509ul, 3.0eq) is in tube sealing, solubilizer 1, and 2- dichloro-benzenes (5ml), weighing finishes, sealing
The system is removed glove box by tube sealing, is heated to reflux under the conditions of 180 DEG C, and TLC detection reaction is until fully reacting.12h stops
Heating, is cooled to room temperature to system, is extracted with ethyl acetate and saturated salt solution, merges organic phase, and dry with anhydrous magnesium sulfate
It is dry, then dry system is filtered, the filtrate collected simultaneously is spin-dried for filtrate, carries out column chromatography point by eluant, eluent of petroleum ether
From purifying, the solid of white, i.e. boron azepine aromatic hydrocarbons 29 (332mg, yield=86%) are finally obtained.
1HNMR(400MHz,CDCl3):δ8.18(dd,J1=8.4Hz, J2=18.8Hz, 2H, Ar), 8.00 (dd, J1=
1.2Hz,J2=6.4Hz, 1H, Ar), 7.94 (d, J=4.8Hz, 1H, Ar), 7.89 (t, J=1.6Hz, 1H, Ar), 7.79-
7.82 (m, 1H, Ar), 7.51 (d, J=4.8Hz, 1H, Ar), 7.19-7.41 (m, 5H, Ar), 6.78 (t, J=3.6Hz, 1H,
Ar).
In order to further study the photoelectricity physical property of such boron azepine aromatic hydrocarbons, we have carried out such compound ultraviolet
It absorbs, fluorescent emission test, electrochemical properties are tested and single crystal diffraction structural characterization.
Application Example：
Potential application citing 1 based on the compounds of this invention：Organic Light Emitting Diode.
Compound 5 is the boron azepine aromatic hydrocarbons in use above embodiment, containing three thiphene rings in structure, in visible light
And have apparent color change under the irradiation of 365nm long wave, compound 5 shows bluish violet fluorescence under 365nm wavelength illumination,
Illustrate that compound 5 has certain characteristics of luminescence with reference to its fluorescent emission spectrogram (Fig. 2).Therefore it can be applied to make organic hair
Optical diode.
It should be noted that only explaining the present invention the foregoing is merely the preferred embodiment of the present invention, not thereby limiting
The invention patent range processed.It is only obviously changed to the technology of the present invention design is belonged to, equally protects model in the present invention
Within enclosing.
Claims (4)
1. a kind of method for being simple and efficient synthesis boron azepine aromatic hydrocarbons, it is characterised in that synthetic route and operating procedure are as follows：
1) synthesis of compound SLY-1：Weigh the bis- (diphenyl of tris(dibenzylideneacetone) dipalladium 0.025-0.03eq, 1,1'-
Phosphine) system in twoport reaction flask, substituted gas three times, in nitrogen by ferrocene 0.05-0.6eq and sodium tert-butoxide 1.5-2.0eq
Under protective condition, adjacent bromo-iodobenzene 1.0eq, o-bromoaniline 1.2-1.3eq and toluene 50-100ml is added and carries out back flow reaction,
The detection reaction of TLC method is until fully reacting；Stop reaction after stirring 24-36h, is restored to room temperature to system, uses saturated sodium-chloride
Aqueous solution and methylene chloride extraction, organic layer merge, and dry with anhydrous magnesium sulfate, and dry system is filtered, is collected
To filtrate and be spin-dried for solvent, using petroleum ether as eluant, eluent, the concentrate being spin-dried for quickly carries out column chromatographic isolation and purification, final
To white crystal, i.e. target compound SLY-1；
2) synthesis of compound SLY-2：1.0eq compound SLY-1 is weighed, system is substituted into gas under a nitrogen atmosphere and is placed three times
In in glove box, then tetrakis triphenylphosphine palladium 0.17-0.20eq and 3 thienylboronic acid 1.2-3.0eq are weighed, this step is according to coupling
The reaction condition of reaction is operated with the equivalents ratio of above range, and system is sealed and removes glove box, then by reaction dissolvent
10-30ml is injected into reaction system, system is then carried out back flow reaction under the conditions of 110 DEG C, TLC detection reaction is until anti-
It should be complete；Stop reaction after 12-16h, be restored to room temperature to system, is extracted with methylene chloride and saturated sodium-chloride water solution, and
It is dry with anhydrous magnesium sulfate, dry system is filtered, the filtrate collected simultaneously is spin-dried for solvent, is elution with petroleum ether
The concentrate being spin-dried for quickly is carried out column chromatographic isolation and purification by machine, finally obtains the solid of white, i.e. intermediate product SLY-2；
3) synthesis of compound SLY-3：1.0eq compound SLY-2, Boron tribromide 2.0-2.5eq and three are weighed in glove box
For ethamine 3.0-5.0eq in tube sealing, 1,2- dichloro-benzenes 5-10ml is solvent, and weighing finishes, which is removed hand by sealing tube sealing
Casing is heated to reflux under the conditions of 180 DEG C, and TLC detection reaction is until fully reacting；12-16h stops heating, cooling to system
It to room temperature, is extracted with ethyl acetate and saturated salt solution, merges organic phase, and dry with anhydrous magnesium sulfate, then will dry system
It is filtered, the filtrate collected simultaneously is spin-dried for filtrate, carries out column chromatographic isolation and purification by eluant, eluent of petroleum ether, finally obtains
The solid of white, i.e. target compound SLY-3.
2. a kind of method for being simple and efficient synthesis boron azepine aromatic hydrocarbons according to claim 1, which is characterized in that the target
Ar in compound SLY-31, Ar2One of identical following 1-28 structural formula of boron azepine aromatic hydrocarbons, but be not limited to change as follows
Close object：
Wherein, X=F, Cl, Br or I.
3. a kind of method for being simple and efficient synthesis boron azepine aromatic hydrocarbons according to claim 1, which is characterized in that the target
Ar in compound SLY-31, Ar2Different boron azepine aromatic hydrocarbons is one of following 29-48 structural formula, but is not limited to as follows
Compound：
Wherein, X=F, Cl, Br or I.
4. the purposes of a kind of boron azepine aromatic hydrocarbons of claim 1 the method synthesis, can be used for organic photoelectrical material, organic sun
It can battery, electroluminescence device and sensor preparation.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109709169A (en) * | 2018-12-30 | 2019-05-03 | 天津理工大学 | The method of electrochemical luminescence detection dopamine based on boron-nitrogen compound |
| CN111620899A (en) * | 2020-07-20 | 2020-09-04 | 九江学院 | Synthetic method of benzo-boron-nitrogen-naphthalene thiophene derivative |
| CN113603715A (en) * | 2021-08-23 | 2021-11-05 | 黑龙江省科学院石油化学研究院 | Preparation method of 10, 10-diphenylsilaacridine |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104396042A (en) * | 2012-06-28 | 2015-03-04 | 新日铁住金化学株式会社 | Organic electroluminescence element and material for the organic electroluminescence element |
| CN104641483A (en) * | 2012-09-11 | 2015-05-20 | 捷恩智株式会社 | Material for organic electroluminescent elements, organic electroluminescent element, display device, and lighting device |
| CN108503657A (en) * | 2017-12-20 | 2018-09-07 | 天津理工大学 | Boron N doping polycyclic aromatic hydrocarbon and its synthetic method containing five-ring heterocycles and application |
-
2018
- 2018-10-08 CN CN201811165383.2A patent/CN108912157A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104396042A (en) * | 2012-06-28 | 2015-03-04 | 新日铁住金化学株式会社 | Organic electroluminescence element and material for the organic electroluminescence element |
| CN104641483A (en) * | 2012-09-11 | 2015-05-20 | 捷恩智株式会社 | Material for organic electroluminescent elements, organic electroluminescent element, display device, and lighting device |
| CN107266481A (en) * | 2012-09-11 | 2017-10-20 | 捷恩智株式会社 | Organic electric-field light-emitting element material, organic electric-field light-emitting element, display device and lighting device |
| CN108503657A (en) * | 2017-12-20 | 2018-09-07 | 天津理工大学 | Boron N doping polycyclic aromatic hydrocarbon and its synthetic method containing five-ring heterocycles and application |
Non-Patent Citations (2)
| Title |
|---|
| MIGUEL PARAJA ET AL: "Pd-Catalyzed Autotandem Reactions withN-Tosylhydrazones.Synthesis of Condensed Carbo- and Heterocycles by Formation of a C=C Single Bond and a C=C Double Bond on the Same Carbon Atom", 《ORG. LETT.》 * |
| 麻生明著: "《金属参与的现代有机合成反应[M].》", 31 December 2001 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109709169A (en) * | 2018-12-30 | 2019-05-03 | 天津理工大学 | The method of electrochemical luminescence detection dopamine based on boron-nitrogen compound |
| CN111620899A (en) * | 2020-07-20 | 2020-09-04 | 九江学院 | Synthetic method of benzo-boron-nitrogen-naphthalene thiophene derivative |
| CN113603715A (en) * | 2021-08-23 | 2021-11-05 | 黑龙江省科学院石油化学研究院 | Preparation method of 10, 10-diphenylsilaacridine |
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