CN114149307B - 一类溴芘中间体及其衍生物、制备方法和应用 - Google Patents
一类溴芘中间体及其衍生物、制备方法和应用 Download PDFInfo
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- CN114149307B CN114149307B CN202111484670.1A CN202111484670A CN114149307B CN 114149307 B CN114149307 B CN 114149307B CN 202111484670 A CN202111484670 A CN 202111484670A CN 114149307 B CN114149307 B CN 114149307B
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- Prior art keywords
- pyrenyl
- bromopyrene
- organic functional
- methoxyphenyl
- tetrakis
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- 238000002360 preparation method Methods 0.000 title claims abstract description 34
- HYGLETVERPVXOS-UHFFFAOYSA-N 1-bromopyrene Chemical compound C1=C2C(Br)=CC=C(C=C3)C2=C2C3=CC=CC2=C1 HYGLETVERPVXOS-UHFFFAOYSA-N 0.000 title claims abstract description 26
- 239000000463 material Substances 0.000 claims abstract description 43
- 125000001725 pyrenyl group Chemical group 0.000 claims abstract description 33
- BBEAQIROQSPTKN-UHFFFAOYSA-N pyrene Chemical compound C1=CC=C2C=CC3=CC=CC4=CC=C1C2=C43 BBEAQIROQSPTKN-UHFFFAOYSA-N 0.000 claims abstract description 21
- 238000006243 chemical reaction Methods 0.000 claims abstract description 20
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims abstract description 18
- NKFFJDXMGAZKEQ-UHFFFAOYSA-N 2-Hydroxypyrene Chemical compound C1=CC=C2C=CC3=CC(O)=CC4=CC=C1C2=C43 NKFFJDXMGAZKEQ-UHFFFAOYSA-N 0.000 claims abstract description 11
- GVEPBJHOBDJJJI-UHFFFAOYSA-N fluoranthrene Natural products C1=CC(C2=CC=CC=C22)=C3C2=CC=CC3=C1 GVEPBJHOBDJJJI-UHFFFAOYSA-N 0.000 claims abstract description 11
- 125000001424 substituent group Chemical group 0.000 claims abstract description 11
- 238000000034 method Methods 0.000 claims abstract description 9
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 9
- QKYIPVJKWYKQLX-UHFFFAOYSA-N pyrene-2,7-diol Chemical compound C1=C(O)C=C2C=CC3=CC(O)=CC4=CC=C1C2=C43 QKYIPVJKWYKQLX-UHFFFAOYSA-N 0.000 claims abstract description 7
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000004327 boric acid Substances 0.000 claims abstract description 6
- 239000002994 raw material Substances 0.000 claims abstract description 5
- 238000006467 substitution reaction Methods 0.000 claims abstract description 5
- 238000005893 bromination reaction Methods 0.000 claims abstract description 3
- 230000003197 catalytic effect Effects 0.000 claims abstract description 3
- 238000005859 coupling reaction Methods 0.000 claims abstract description 3
- -1 4- (N, N-di (p-methoxyphenyl) amino) phenyl Chemical group 0.000 claims description 58
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 54
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 36
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 33
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 26
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 24
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 22
- 229910052757 nitrogen Inorganic materials 0.000 claims description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 19
- JNIGGVWHPOEIIR-UHFFFAOYSA-N OC(C(Br)=C(C=C1)C(C2=CC=C3C(Br)=C4O)=C3C1=C4Br)=C2Br Chemical compound OC(C(Br)=C(C=C1)C(C2=CC=C3C(Br)=C4O)=C3C1=C4Br)=C2Br JNIGGVWHPOEIIR-UHFFFAOYSA-N 0.000 claims description 14
- LWTGAJXJWBBNIX-UHFFFAOYSA-N OC(C(Br)=C(C=C1)C(C2=CC=C3C(Br)=C4)=C3C1=C4Br)=C2Br Chemical compound OC(C(Br)=C(C=C1)C(C2=CC=C3C(Br)=C4)=C3C1=C4Br)=C2Br LWTGAJXJWBBNIX-UHFFFAOYSA-N 0.000 claims description 13
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 13
- 235000011181 potassium carbonates Nutrition 0.000 claims description 13
- 238000002390 rotary evaporation Methods 0.000 claims description 13
- 238000003756 stirring Methods 0.000 claims description 13
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 12
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 12
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 12
- 150000007529 inorganic bases Chemical class 0.000 claims description 12
- 238000000926 separation method Methods 0.000 claims description 12
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 11
- 239000012298 atmosphere Substances 0.000 claims description 10
- 238000001816 cooling Methods 0.000 claims description 10
- 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 10
- 238000005406 washing Methods 0.000 claims description 9
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 claims description 8
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 claims description 8
- 239000003960 organic solvent Substances 0.000 claims description 8
- 229920006395 saturated elastomer Polymers 0.000 claims description 8
- 125000000175 2-thienyl group Chemical group S1C([*])=C([H])C([H])=C1[H] 0.000 claims description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 6
- 229910052786 argon Inorganic materials 0.000 claims description 6
- 239000003054 catalyst Substances 0.000 claims description 6
- 239000003795 chemical substances by application Substances 0.000 claims description 6
- 150000004820 halides Chemical class 0.000 claims description 6
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 6
- 150000003839 salts Chemical class 0.000 claims description 6
- 125000004172 4-methoxyphenyl group Chemical group [H]C1=C([H])C(OC([H])([H])[H])=C([H])C([H])=C1* 0.000 claims description 4
- PCLIMKBDDGJMGD-UHFFFAOYSA-N N-bromosuccinimide Chemical compound BrN1C(=O)CCC1=O PCLIMKBDDGJMGD-UHFFFAOYSA-N 0.000 claims description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 4
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 claims description 4
- AGEZXYOZHKGVCM-UHFFFAOYSA-N benzyl bromide Chemical compound BrCC1=CC=CC=C1 AGEZXYOZHKGVCM-UHFFFAOYSA-N 0.000 claims description 4
- QARVLSVVCXYDNA-UHFFFAOYSA-N bromobenzene Chemical compound BrC1=CC=CC=C1 QARVLSVVCXYDNA-UHFFFAOYSA-N 0.000 claims description 4
- JGJLWPGRMCADHB-UHFFFAOYSA-N hypobromite Inorganic materials Br[O-] JGJLWPGRMCADHB-UHFFFAOYSA-N 0.000 claims description 4
- HVTICUPFWKNHNG-UHFFFAOYSA-N iodoethane Chemical compound CCI HVTICUPFWKNHNG-UHFFFAOYSA-N 0.000 claims description 4
- INQOMBQAUSQDDS-UHFFFAOYSA-N iodomethane Chemical compound IC INQOMBQAUSQDDS-UHFFFAOYSA-N 0.000 claims description 4
- 239000011736 potassium bicarbonate Substances 0.000 claims description 4
- 235000015497 potassium bicarbonate Nutrition 0.000 claims description 4
- 229910000028 potassium bicarbonate Inorganic materials 0.000 claims description 4
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 claims description 4
- 230000001681 protective effect Effects 0.000 claims description 4
- 235000011121 sodium hydroxide Nutrition 0.000 claims description 4
- 239000002904 solvent Chemical class 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 3
- IBXMKLPFLZYRQZ-UHFFFAOYSA-N 1,5-diphenylpenta-1,4-dien-3-one;palladium Chemical compound [Pd].[Pd].C=1C=CC=CC=1C=CC(=O)C=CC1=CC=CC=C1 IBXMKLPFLZYRQZ-UHFFFAOYSA-N 0.000 claims description 2
- FWDBZJBJTDRIIY-UHFFFAOYSA-N CC(C)(C)[K] Chemical compound CC(C)(C)[K] FWDBZJBJTDRIIY-UHFFFAOYSA-N 0.000 claims description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 2
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 2
- OQESKQAHRXOSMS-UHFFFAOYSA-N benzyltrimethylammonium tribromide Chemical compound Br[Br-]Br.C[N+](C)(C)CC1=CC=CC=C1 OQESKQAHRXOSMS-UHFFFAOYSA-N 0.000 claims description 2
- YNHIGQDRGKUECZ-UHFFFAOYSA-L bis(triphenylphosphine)palladium(ii) dichloride Chemical compound [Cl-].[Cl-].[Pd+2].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 YNHIGQDRGKUECZ-UHFFFAOYSA-L 0.000 claims description 2
- 229960001701 chloroform Drugs 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims description 2
- 238000001914 filtration Methods 0.000 claims description 2
- YJVFFLUZDVXJQI-UHFFFAOYSA-L palladium(ii) acetate Chemical compound [Pd+2].CC([O-])=O.CC([O-])=O YJVFFLUZDVXJQI-UHFFFAOYSA-L 0.000 claims description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 2
- 235000017550 sodium carbonate Nutrition 0.000 claims description 2
- 125000004199 4-trifluoromethylphenyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)C(F)(F)F 0.000 claims 2
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims 1
- 239000000543 intermediate Substances 0.000 abstract description 26
- 230000015572 biosynthetic process Effects 0.000 abstract description 5
- 238000003786 synthesis reaction Methods 0.000 abstract description 5
- 125000002887 hydroxy group Chemical group [H]O* 0.000 abstract description 4
- 230000009286 beneficial effect Effects 0.000 abstract description 3
- 239000012847 fine chemical Substances 0.000 abstract description 2
- 230000032050 esterification Effects 0.000 abstract 1
- 238000005886 esterification reaction Methods 0.000 abstract 1
- 230000033444 hydroxylation Effects 0.000 abstract 1
- 238000005805 hydroxylation reaction Methods 0.000 abstract 1
- 238000009776 industrial production Methods 0.000 abstract 1
- INGILXCCWSKOGV-UHFFFAOYSA-N COC(C=C1)=CC=C1C(C1=CC=C(C(C(C=C2)=CC=C2OC)=C(C(C(C=C2)=CC=C2OC)=C2C=C3)O)C2=C1C3=C1C(C=C2)=CC=C2OC)=C1O Chemical compound COC(C=C1)=CC=C1C(C1=CC=C(C(C(C=C2)=CC=C2OC)=C(C(C(C=C2)=CC=C2OC)=C2C=C3)O)C2=C1C3=C1C(C=C2)=CC=C2OC)=C1O INGILXCCWSKOGV-UHFFFAOYSA-N 0.000 description 16
- DNGDWVFQIMHKPK-UHFFFAOYSA-N COC(C=C1)=CC=C1C1=CC(C(C=C2)=CC=C2OC)=C(C=C2)C3=C4C2=C(C(C=C2)=CC=C2OC)C(O)=C(C(C=C2)=CC=C2OC)C4=CC=C13 Chemical compound COC(C=C1)=CC=C1C1=CC(C(C=C2)=CC=C2OC)=C(C=C2)C3=C4C2=C(C(C=C2)=CC=C2OC)C(O)=C(C(C=C2)=CC=C2OC)C4=CC=C13 DNGDWVFQIMHKPK-UHFFFAOYSA-N 0.000 description 14
- 239000013078 crystal Substances 0.000 description 14
- 239000000047 product Substances 0.000 description 12
- UORZRCYQRHQGQE-UHFFFAOYSA-N COC(C=C1)=CC=C1C1=CC(C(C=C2)=CC=C2OC)=C(C=C2)C3=C4C2=C(C(C=C2)=CC=C2OC)C(OC)=C(C(C=C2)=CC=C2OC)C4=CC=C13 Chemical compound COC(C=C1)=CC=C1C1=CC(C(C=C2)=CC=C2OC)=C(C=C2)C3=C4C2=C(C(C=C2)=CC=C2OC)C(OC)=C(C(C=C2)=CC=C2OC)C4=CC=C13 UORZRCYQRHQGQE-UHFFFAOYSA-N 0.000 description 11
- 238000001953 recrystallisation Methods 0.000 description 9
- 239000011259 mixed solution Substances 0.000 description 8
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 7
- 125000004432 carbon atom Chemical group C* 0.000 description 7
- 238000010586 diagram Methods 0.000 description 6
- 239000000203 mixture Substances 0.000 description 5
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 4
- LPNYRYFBWFDTMA-UHFFFAOYSA-N potassium tert-butoxide Chemical compound [K+].CC(C)(C)[O-] LPNYRYFBWFDTMA-UHFFFAOYSA-N 0.000 description 4
- 125000006413 ring segment Chemical group 0.000 description 4
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 4
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 239000004065 semiconductor Substances 0.000 description 3
- VOAAEKKFGLPLLU-UHFFFAOYSA-N (4-methoxyphenyl)boronic acid Chemical compound COC1=CC=C(B(O)O)C=C1 VOAAEKKFGLPLLU-UHFFFAOYSA-N 0.000 description 2
- ZKBKRTZIYOKNRG-UHFFFAOYSA-N 1,3,6,8-tetrabromopyrene Chemical compound C1=C2C(Br)=CC(Br)=C(C=C3)C2=C2C3=C(Br)C=C(Br)C2=C1 ZKBKRTZIYOKNRG-UHFFFAOYSA-N 0.000 description 2
- HTFXWAOSQODIBI-UHFFFAOYSA-N 2-benzyl-1,3-dihydropyrrolo[3,4-c]pyridine Chemical compound C1C2=CC=NC=C2CN1CC1=CC=CC=C1 HTFXWAOSQODIBI-UHFFFAOYSA-N 0.000 description 2
- QETCSIRGOWNFJE-UHFFFAOYSA-N 2-methoxypyrene Chemical compound C1=CC=C2C=CC3=CC(OC)=CC4=CC=C1C2=C43 QETCSIRGOWNFJE-UHFFFAOYSA-N 0.000 description 2
- 150000004982 aromatic amines Chemical class 0.000 description 2
- 125000006615 aromatic heterocyclic group Chemical group 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 125000004104 aryloxy group Chemical group 0.000 description 2
- 229910052796 boron Inorganic materials 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 239000003245 coal Substances 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 238000002189 fluorescence spectrum Methods 0.000 description 2
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- 239000008204 material by function Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 125000005581 pyrene group Chemical group 0.000 description 2
- 239000012266 salt solution Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- ARYHTUPFQTUBBG-UHFFFAOYSA-N thiophen-2-ylboronic acid Chemical compound OB(O)C1=CC=CS1 ARYHTUPFQTUBBG-UHFFFAOYSA-N 0.000 description 2
- 238000002371 ultraviolet--visible spectrum Methods 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- NAWXUBYGYWOOIX-SFHVURJKSA-N (2s)-2-[[4-[2-(2,4-diaminoquinazolin-6-yl)ethyl]benzoyl]amino]-4-methylidenepentanedioic acid Chemical compound C1=CC2=NC(N)=NC(N)=C2C=C1CCC1=CC=C(C(=O)N[C@@H](CC(=C)C(O)=O)C(O)=O)C=C1 NAWXUBYGYWOOIX-SFHVURJKSA-N 0.000 description 1
- SXLHAMYMTUEALX-UHFFFAOYSA-N (4-methoxyphenoxy)boronic acid Chemical compound COC1=CC=C(OB(O)O)C=C1 SXLHAMYMTUEALX-UHFFFAOYSA-N 0.000 description 1
- HMUNWXXNJPVALC-UHFFFAOYSA-N 1-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)C(CN1CC2=C(CC1)NN=N2)=O HMUNWXXNJPVALC-UHFFFAOYSA-N 0.000 description 1
- IIEJGTQVBJHMDL-UHFFFAOYSA-N 2-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]-5-[2-oxo-2-[3-(sulfamoylamino)pyrrolidin-1-yl]ethyl]-1,3,4-oxadiazole Chemical compound C1CN(CC1NS(=O)(=O)N)C(=O)CC2=NN=C(O2)C3=CN=C(N=C3)NC4CC5=CC=CC=C5C4 IIEJGTQVBJHMDL-UHFFFAOYSA-N 0.000 description 1
- SXAMGRAIZSSWIH-UHFFFAOYSA-N 2-[3-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]-1,2,4-oxadiazol-5-yl]-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C1=NOC(=N1)CC(=O)N1CC2=C(CC1)NN=N2 SXAMGRAIZSSWIH-UHFFFAOYSA-N 0.000 description 1
- FARHYDJOXLCMRP-UHFFFAOYSA-N 2-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]-1-[2-oxo-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethyl]pyrazol-3-yl]oxyacetic acid Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C=1C(=NN(C=1)CC(N1CC2=C(CC1)NN=N2)=O)OCC(=O)O FARHYDJOXLCMRP-UHFFFAOYSA-N 0.000 description 1
- WZFUQSJFWNHZHM-UHFFFAOYSA-N 2-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)CC(=O)N1CC2=C(CC1)NN=N2 WZFUQSJFWNHZHM-UHFFFAOYSA-N 0.000 description 1
- ZRPAUEVGEGEPFQ-UHFFFAOYSA-N 2-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]pyrazol-1-yl]-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C=1C=NN(C=1)CC(=O)N1CC2=C(CC1)NN=N2 ZRPAUEVGEGEPFQ-UHFFFAOYSA-N 0.000 description 1
- YJLUBHOZZTYQIP-UHFFFAOYSA-N 2-[5-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]-1,3,4-oxadiazol-2-yl]-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C1=NN=C(O1)CC(=O)N1CC2=C(CC1)NN=N2 YJLUBHOZZTYQIP-UHFFFAOYSA-N 0.000 description 1
- KBEKICQYZXSFSA-UHFFFAOYSA-N 4,5,9,10-tetrabromo-2,7-ditert-butylpyrene Chemical compound C1=C(C(C)(C)C)C=C2C(Br)=C(Br)C3=CC(C(C)(C)C)=CC4=C(Br)C(Br)=C1C2=C43 KBEKICQYZXSFSA-UHFFFAOYSA-N 0.000 description 1
- CONKBQPVFMXDOV-QHCPKHFHSA-N 6-[(5S)-5-[[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]methyl]-2-oxo-1,3-oxazolidin-3-yl]-3H-1,3-benzoxazol-2-one Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)C[C@H]1CN(C(O1)=O)C1=CC2=C(NC(O2)=O)C=C1 CONKBQPVFMXDOV-QHCPKHFHSA-N 0.000 description 1
- HCIMXTXCDVBLOA-UHFFFAOYSA-N [4-(trifluoromethyl)phenoxy]boronic acid Chemical compound OB(O)OC1=CC=C(C(F)(F)F)C=C1 HCIMXTXCDVBLOA-UHFFFAOYSA-N 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- RDOXTESZEPMUJZ-UHFFFAOYSA-N anisole Chemical compound COC1=CC=CC=C1 RDOXTESZEPMUJZ-UHFFFAOYSA-N 0.000 description 1
- 238000012984 biological imaging Methods 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000000711 cancerogenic effect Effects 0.000 description 1
- 231100000357 carcinogen Toxicity 0.000 description 1
- 239000003183 carcinogenic agent Substances 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 238000004664 delocalization energy Methods 0.000 description 1
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Abstract
Description
技术领域
本发明属于精细化工和光电材料交叉领域,具体涉及一类溴芘中间体及其衍生物、制备方法和应用。
背景技术
芘是一种常见的稠环芳香烃化合物,其主要来源是石油/煤化工的副产品,具有较强的π-电子离域能和独特的蓝光性质,被广泛应用于有机光电器件、生物传感器、荧光探针等领域,现在已经成为一种设计和合成有机半导体材料的流行砌块。
中间体的设计与合成对开发新型功能材料至关重要。截止目前,已经有至少12种新型芘基中间体得以开发,如1,3,6,8-四溴芘、2,7-二叔丁基-4,5,9,10-四溴芘、2,7-芘硼酸、4,5,9,10-芘四醌等都得到了广泛的关注和应用,特别是自从1937年以较为简单的方法成功合成1,3,6,8-四溴芘后,基于此中间体,多达1900余种新型芘衍生物被开发,极大的丰富了有机半导体材料库,促进了有机半导体科学的发展。
另一方面,芘作为煤化工工业的副产品,是一类强致癌物质,如不充分利用,将对环境产生极大地破坏,因此,秉承“变废为宝,变废为宝”的思路,本发明旨在设计一种简便的合成方法,并通过优化合成路线,将化工副产品开发成新型化工原中间体,并提高合成路线的产率,加速推进这类中间体进入工业链,应用于有机半导体、生物成像等领域。新型芘基中间体的开发将便于开发新型的芘基衍生物,通过调控分子结构,制备高性能的芘基光电材料,促进芘基功能材料的发展。
发明内容
本发明的首要目的是提供一种溴芘中间体。
本发明的另一目的在于提供上述溴芘中间体的合成方法,该方法工艺设计合理、收率高、反应条件温和、原料价格低廉。
发明的再一目的在于基于芘基中间体制得的芘基发光材料。
发明的进一步目的在于提供上述芘基功能材料的应用。
本发明的目的通过下述技术方案实现:
一类溴芘中间体,所述溴芘中间体的分子结构式如(1)所示:
其中,R为H或者OH。
所述的溴芘中间体为2-羟基-1,3,6,8-四溴芘或2,7-二羟基-1,3,6,8-四溴芘;其分子结构式如1a或1b所示:
所述的溴芘中间体的制备方法,所述溴芘中间体是以2-羟基芘或2,7-二羟基芘为原料,在惰性气氛下加入溴化剂和有机溶剂,在50~130℃加热搅拌10~40h进行溴代反应,制得2-羟基-1,3,6,8-四溴芘或2,7-二羟基-1,3,6,8-四溴芘。
优选地,所述溴化剂为溴水、N-溴代琥珀酰亚胺或苄基三甲基溴化铵二溴中的一种以上;所述惰性气氛为氮气或者氩气;所述有机溶剂为硝基苯、二氯甲烷、三氯甲烷、乙腈中的一种以上;所述的2-羟基芘或2,7-二羟基芘:溴化剂的摩尔比为1:(1~10)。
一种芘基有机功能发光材料,所述芘基有机功能发光材料是在保护气氛下,将所述的溴芘中间体加入钯催化剂、芳香烃硼酸及其衍生物、无机碱和溶剂,在50~100℃通过钯催化偶联反应,分别在芘的多个位点进行功能化取代制备得到。
优选地,所述保护气氛为氮气或者氩气;所述钯催化剂为四(三苯基膦)钯、醋酸钯、四氟硼酸三(叔丁基膦)或三(二亚苄基丙酮)二钯、二氯双(三苯基膦)合钯中的一种及以上,所述无机碱为碳酸钾、碳酸钠、碳酸氢钠、碳酸氢钾、氢氧化钠中的一种及以上;所述溶剂为甲苯、乙醇、水、四氢呋喃、N,N-二甲基甲酰胺、乙腈、三乙胺中的一种及以上;所述芳香烃硼酸及其衍生物为4-甲氧基苯基硼酸、4-三氟甲基苯基硼酸、2-噻吩基硼酸、4-三甲氧基苯胺基硼酸酯;所述2-羟基-1,3,6,8-四溴芘或2,7-二羟基-1,3,6,8-四溴芘:芳香烃硼酸及其衍生物:钯催化剂:无机碱的摩尔比为1:(4~10):(0.05~0.2):(5~20)。
优选地,所述的芘基有机功能发光材料的分子结构通式如2a或2b所示:
其中,R1为具有5至30个碳原子的取代芳香烃、具有6至50个环原子的芳氧基、具有5至30个碳原子的芳香胺、具有含有6至20个碳原子的硼芳烃或具有5至40个环原子的芳族杂环基团。
更为优选地,所述的芘基有机功能发光材料的结构式为:
一种芘基有机功能发光材料,所述芘基有机功能发光材料是将上述的芘基有机功能发光材料、R2取代基团的卤化物和无机碱溶解在有机溶剂中,在60~80℃加热搅拌5~12h,反应结束后冷却至室温,用二氯甲烷萃取洗涤,饱和食盐水萃取,无水硫酸镁除水后过滤,旋蒸后进行色谱柱分离并重结晶制得;
所述的芘基有机功能发光材料的分子结构通式如3a或3b所示:
R2取代基团选自具有1至10个碳原子的取代烷烃、具有5至30个碳原子的取代芳香烃、具有6至50个环原子的芳氧基、具有5至30个碳原子的芳香胺、具有含有6至20个碳原子的硼芳烃或具有5至40个环原子的芳族杂环基中的一种及以上的任意组合。
优选地,所述R2取代基团的卤化物为碘甲烷、碘乙烷、苄基溴或溴苯;所述惰性气氛为氮气或氩气;所述无机碱为碳酸钾、叔丁基醇钾、碳酸钠、碳酸氢钠、碳酸氢钾、氢氧化钠中的一种以上;所述有机溶剂为乙腈、四氢呋喃、二氯甲烷、乙醇中的一种以上;所述的芘基有机功能发光材料:R2取代基团的卤化物:无机碱的摩尔比为1:(1~10):(5~20)。
所述的芘类发光材料在有机电子学或生物领域中的应用。
本发明2-羟基-1,3,6,8-四溴芘和2,7-二羟基-1,3,6,8-四溴芘的合成步骤如(I)和(II)所示:
与现有技术相比,本发明具有以下有益效果:
1.以本发明的溴芘中间体为前驱体制备的有机发光材料,通过在芘的2-和7-位引入羟基,使得1,3,6,8-位的取代基团能够与芘环形成较大的二面角,有效抑制分子间的相互作用,提升目标分子的发光效率,通过平衡分子内的电荷,提高其电荷传输性能,此外,羟基或者R2取代基团的引入能够有效的提高目标分子的亲水性,有利于将这类发光分子应用于生物领域;
2.本发明的合成方法具有实验操作简单、反应条件温和、中间体产率高等优点;
3.本发明的芘基有机发光材料能够有效地提高材料的固体发光效率,应用于有机光电领域;
4.本发明的溴芘中间体和芘基有机发光材料由于羟基或者R2取代基团的存在,能够增加溴芘中间体和芘基有机发光材料的亲水性能,提高材料的溶解度,便于直接应用于生物成像等领域。
附图说明
图1为实施例1的2-羟基-1,3,6,8-四溴芘的HRMS图。
图2为实施例2的2,7-二羟基-1,3,6,8-四溴芘的HRMS图。
图3为实施例3的1,3,6,8-四-(4-甲氧基苯基)-2-羟基芘的1H NMR图。
图4为实施例3的1,3,6,8-四-(4-甲氧基苯基)-2-羟基芘的13C NMR图。
图5为实施例3的1,3,6,8-四-(4-甲氧基苯基)-2-羟基芘的HRMS图。
图6为实施例3的1,3,6,8-四-(4-甲氧基苯基)-2-羟基芘的单晶结构图。
图7为实施例4的1,3,6,8-四-(4-甲氧基苯基)-2,7-二羟基芘1H NMR图。
图8为实施例4的1,3,6,8-四-(4-甲氧基苯基)-2,7-二羟基芘的13C NMR图。
图9为实施例4的1,3,6,8-四-(4-甲氧基苯基)-2,7-二羟基芘的HRMS图。
图10为实施例4的1,3,6,8-四-(4-甲氧基苯基)-2,7-二羟基芘的单晶结构图。
图11为实施例5的1,3,6,8-四-(4-三氟甲基苯基)-2-羟基芘的1HNMR图。
图12为实施例5的1,3,6,8-四-(4-三氟甲基苯基)-2-羟基芘的13C NMR图。
图13为实施例5的1,3,6,8-四-(4-三氟甲基苯基)-2-羟基芘的HRMS图。
图14为实施例5的1,3,6,8-四-(4-三氟甲基苯基)-2-羟基芘的单晶结构图。
图15为实施例6的1,3,6,8-四-(4-三氟甲基苯基)-2,7-二羟基芘的1H NMR图。
图16为实施例6的1,3,6,8-四-(4-三氟甲基苯基)-2,7-二羟基芘的13C NMR图。
图17为实施例6的1,3,6,8-四-(4-三氟甲基苯基)-2,7-二羟基芘的HRMS图。
图18为实施例6的1,3,6,8-四-(4-三氟甲基苯基)-2,7-二羟基芘的单晶结构图。
图19为实施例7的1,3,6,8-四-(2-噻吩基)-2-羟基芘的1H NMR图。
图20为实施例7的1,3,6,8-四-(2-噻吩基)-2-羟基芘的13C NMR图。
图21为实施例7的1,3,6,8-四-(2-噻吩基)-2-羟基芘的HRMS图。
图22为实施例7的1,3,6,8-四-(2-噻吩基)-2-羟基芘的单晶结构图。
图23为实施例8的1,3,6,8-四-(2-噻吩基)-2,7-羟基芘的1HNMR图。
图24为实施例8的1,3,6,8-四-(2-噻吩基)-2,7-羟基芘的13C NMR图。
图25为实施例8的1,3,6,8-四-(2-噻吩基)-2,7-羟基芘的HRMS图。
图26为实施例8的1,3,6,8-四-(2-噻吩基)-2,7-羟基芘的单晶结构图。
图27为实施例9的1,3,6,8-四-(4-三苯胺)-2,7-二羟基芘的1H NMR图。
图28为实施例9的1,3,6,8-四-(4-三苯胺)-2,7-二羟基芘的13C NMR图。
图29为实施例9的1,3,6,8-四-(4-三苯胺)-2,7-二羟基芘的HRMS图。
图30为实施例10的1,3,6,8-四-(4-甲氧基苯基)-2-甲氧基-芘的1H NMR图。
图31为实施例10的1,3,6,8-四-(4-甲氧基苯基)-2-甲氧基-芘的13C NMR图。
图32为实施例10的1,3,6,8-四-(4-甲氧基苯基)-2-甲氧基-芘的HRMS图。
图33为实施例10的1,3,6,8-四-(4-甲氧基苯基)-2-甲氧基-芘的单晶结构图。
图34为实施例3、4、5、6、10由溴芘中间体得到的1,3,6,8-四取代-2,7-二羟基-芘衍生物、1,3,6,8-四取代-2-羟基-芘衍生物和1,3,6,8-四取代-2-甲氧基-芘衍生物的UV-vis和荧光光谱图。
具体实施方式
下面结合具体实施例进一步说明本发明的内容,但不应理解为对本发明的限制。若未特别指明,实施例中所用的技术手段为本领域技术人员所熟知的常规手段。除非特别说明,本发明采用的试剂、方法和设备为本技术领域常规试剂、方法和设备。
实施例1 2-羟基-1,3,6,8-四溴芘的制备
1.根据文献报道的方法(Chem.Commun.,2005,2172~2174,Chem.Eur.J.2012,18,5022~5035),将芘逐步进行硼酸酯化和羟基化,得到2-羟基芘。
2.在氮气的保护下,将2-羟基芘(1eq.)和15~50mL硝基苯加入250ml的双颈瓶中,室温搅拌10分钟后加入溴水(4~10eq.),混合溶液在120℃条件下强力搅拌24h。室温冷却后,将混合物过滤,乙醇冲洗三次,得到浅棕色粉末,产率约为92%,其合成路线如式(1)所示。
图1为本实施例得到的2-羟基-1,3,6,8-四溴芘的高分辨质谱图,从图1可知,成功制备出溴芘中间体2-羟基-1,3,6,8-四溴芘。
实施例2 2,7-二羟基-1,3,6,8-四溴芘的制备
1.根据文献报道的方法(Chem.Commun.,2005,2172~2174,Chem.Eur.J.2012,18,5022~5035),将芘逐步进行硼酸酯化和羟基化,得到2,7-二羟基芘。
2.在氮气的保护下,将2,7-二羟基芘(1eq.)和15~50mL硝基苯加入250ml的双颈瓶中,室温搅拌10分钟后加入溴水(4~10eq.),混合溶液在120℃条件下强力搅拌24h。室温冷却后,将混合物过滤,乙醇冲洗三次,得到浅绿色粉末,产率约为95%,其合成路线如式(2)所示。
图2为本实施例得到的2,7-二羟基-1,3,6,8-四溴芘的高分辨质谱图,从图2可知,成功制备出溴芘中间体2,7-二羟基-1,3,6,8-四溴芘。
实施例3 1,3,6,8-四-(4-甲氧基苯基)-2-羟基芘的制备
在氮气的保护下,将实施例1的2-羟基-1,3,6,8-四溴芘(1eq.)和4-甲氧基苯基硼酸(4~8eq.)、碳酸钾(10~20eq.)加入100ml的双颈瓶中,溶解在体积比为5:1:1的甲苯、乙醇和水的混合溶液(8~20mL)中,加入四(三苯基膦)钯(0.05~0.2eq.),在90℃下强力搅拌24h,反应京结束后冷却至室温,用二氯甲烷萃取洗涤三次,饱和食盐水萃取一次,旋蒸后进行色谱柱分离,得到目标产物1,3,6,8-四-(4-甲氧基苯基)-2-羟基芘,产率约为70%,其合成路线如式(3)所示。
图3为本实施例得到的1,3,6,8-四-(4-甲氧基苯基)-2-羟基芘的1HNMR图。图4为本实施例得到的1,3,6,8-四-(4-甲氧基苯基)-2-羟基芘的13C NMR图,图5为本实施例得到的1,3,6,8-四-(4-甲氧基苯基)-2-羟基芘的HRMS图,图6为本实施例得到的1,3,6,8-四-(4-甲氧基苯基)-2-羟基芘的单晶结构图,从图3-6可知,成功制备出1,3,6,8-四-(4-甲氧基苯基)-2-羟基芘有机蓝光材料。
实施例4 1,3,6,8-四-(4-甲氧基苯基)-2,7-二羟基芘的制备
在氮气的保护下,将实施例2的2,7-二羟基-1,3,6,8-四溴芘(1eq.)和4-甲氧基苯基硼酸(4~8eq.)、碳酸钾(10~20eq.)加入100mL的双颈瓶中,加入四氢呋喃(8~20mL)和四(三苯基膦)钯(0.05~0.2eq.),在90℃下强力搅拌24h,反应结束后冷却至室温,用二氯甲烷萃取洗涤三次,饱和食盐水萃取一次,旋蒸后进行色谱柱分离和重结晶,得到目标产物1,3,6,8-四-(4-甲氧基苯基)-2,7-二羟基芘,产率约为47%,其合成路线如式(4)所示。
图7为本实施例得到的1,3,6,8-四-(4-甲氧基苯基)-2,7-二羟基芘的1H NMR图,图8本实施例得到的1,3,6,8-四-(4-甲氧基苯基)-2,7二羟基芘的13C NMR图,图9为本实施例得到的1,3,6,8-四-(4-甲氧基苯基)-2,7-二羟基芘的HRMS图,图10为本实施例得到的1,3,6,8-四-(4-甲氧基苯基)-2,7-二羟基芘的单晶结构图,从图7-10可知,成功制备出1,3,6,8-四-(4-甲氧基苯基)-2,7-二羟基芘,所制备的1,3,6,8-四-(4-甲氧基苯基)-2,7-二羟基芘是蓝光材料。
实施例5 1,3,6,8-四-(4-三氟甲基苯基)-2-羟基芘的制备
在氮气的保护下,将实施例1的2-羟基-1,3,6,8-四溴芘(1eq.)和4-三氟甲基苯基硼酸(4~8eq.)、碳酸钾(10~20eq.)加入100mL的双颈瓶中,溶解在体积比为4:1的四氢呋喃和水的混合溶液(8~20mL)中,加入Pd2(dba)3(0.05~0.2eq.)和(t-Bu)3PBF4(0.2~0.8eq.),在90℃下强力搅拌24h,反应结束后冷却至室温,用二氯甲烷萃取洗涤三次,饱和食盐水萃取一次,旋蒸进行色谱柱分离并重结晶,得到目标产物1,3,6,8-四-(4-三氟甲基苯基)-2-羟基芘,产率约为65%,其合成路线如式(5)所示。
图11为本实施例得到的1,3,6,8-四-(4-三氟甲基苯基)-2-羟基芘的1HNMR图,图12为本实施例得到的1,3,6,8-四-(4-三氟甲基苯基)-2-羟基芘的13C NMR图,图13为本实施例得到的1,3,6,8-四-(4-三氟甲基苯基)-2-羟基芘的HRMS图,图14为本实施例得到的1,3,6,8-四-(4-三氟甲基苯基)-2-羟基芘的单晶结构图,从图11-14可知,成功制备出1,3,6,8-四-(4-三氟甲基苯基)-2-羟基芘有机蓝光材料。
实施例6 1,3,6,8-四-(4-三氟甲基苯基)-2,7-二羟基芘的制备
在氮气的保护下,将实施例2的2,7-二羟基-1,3,6,8-四溴芘(1eq.)和4-三氟甲基苯基硼酸(4~8eq.)、碳酸钾(10~20eq.)加入100mL的双颈瓶中,溶解在体积比为4:1的四氢呋喃和水的混合溶液(8~20mL)中,加入Pd2(dba)3(0.05~0.2eq.)和(t-Bu)3PBF4(0.2~0.8eq.),在90℃下强力搅拌24h,反应结束后冷却至室温,用乙酸乙酯萃取洗涤三次,饱和食盐水萃取一次,旋蒸后进行色谱柱分离并重结晶,得到目标产物1,3,6,8-四-(4-三氟甲基苯基)-2,7-二羟基芘,产率约为38%,其合成路线如式(6)所示。
图15为本实施例得到的1,3,6,8-四-(4-三氟甲基苯基)-2,7-二羟基芘的1HNMR图,图16为本实施例得到的1,3,6,8-四-(4-三氟甲基苯基)-2,7-二羟基芘的13C NMR图,图17为本实施例得到的1,3,6,8-四-(4-三氟甲基苯基)-2,7-二羟基芘的HRMS图,图18为本实施例得到的1,3,6,8-四-(4-三氟甲基苯基)-2,7-二羟基芘的单晶结构图,从图15-18可知,成功制备出1,3,6,8-四-(4-三氟甲基苯基)-2,7-二羟基芘有机蓝光材料。
实施例7 1,3,6,8-四-(2-噻吩基)-2-羟基芘的制备
在氮气的保护下,将实施例1的2-羟基-1,3,6,8-四溴芘(1eq.)和2-噻吩基硼酸(4~8eq.)、碳酸钾(10~20eq.)加入100mL的双颈瓶中,溶解在体积比为4:1的四氢呋喃和水的混合溶液(8~20mL)中,加入Pd2(dba)3(0.05~0.2eq.)和(t-Bu)3PBF4(0.2~0.8eq.),在90℃下强力搅拌24h,反应结束后冷却至室温,用二氯甲烷萃取洗涤三次,饱和食盐水萃取一次,旋蒸后进行色谱柱分离并重结晶,得到目标产物1,3,6,8-四-(2-噻吩基)-2-羟基芘,产率约为72%,其合成路线如式(7)所示。
图19为本实施例得到的1,3,6,8-四-(2-噻吩基)-2-羟基芘的1H NMR图,图20为本实施例得到的1,3,6,8-四-(2-噻吩基)-2-羟基芘的13C NMR图,图21为本实施例得到的1,3,6,8-四-(2-噻吩基)-2-羟基芘的HRMS图,图22为本实施例得到的1,3,6,8-四-(2-噻吩基)-2-羟基芘的单晶结构图,从图19-22可知,成功制备出1,3,6,8-四-(2-噻吩基)-2-羟基芘。
实施例8 1,3,6,8-四-(2-噻吩基)-2,7-二羟基芘的制备
在氮气的保护下,将实施例2的2,7-二羟基-1,3,6,8-四溴芘(1eq.)和2-噻吩基硼酸(4~8eq.)、碳酸钾(10~20eq.)加入100ml的双颈瓶中,溶解在体积比为4:1的四氢呋喃和水的混合溶液(8~20mL)中,加入Pd2(dba)3(0.05~0.2eq.)和(t-Bu)3PBF4(0.2~0.8eq.),在90℃下强力搅拌24h,反应结束后冷却至室温,用二氯甲烷萃取洗涤三次,饱和食盐水萃取一次,旋蒸后进行色谱柱分离并重结晶,得到目标产物1,3,6,8-四-(2-噻吩基)-2,7-二羟基芘,产率约为40%,其合成路线如式(8)所示。
图23为本实施例得到的1,3,6,8-四-(2-噻吩基)-2,7-二羟基芘的1HNMR图,图24为本实施例得到的1,3,6,8-四-(2-噻吩基)-2,7-二羟基芘的13C NMR图,图25为本实施例得到的1,3,6,8-四-(2-噻吩基)-2,7-二羟基芘的HRMS图,图26为本实施例得到的1,3,6,8-四-(2-噻吩基)-2,7-二羟基芘的单晶结构图,从图23-26可知,成功制备出1,3,6,8-四-(2-噻吩基)-2,7-二羟基芘。
实施例9 1,3,6,8-四-(4-三甲氧基苯胺)-2,7-二羟基芘的制备
在氮气的保护下,将实施例2的2,7-二羟基-1,3,6,8-四溴芘(1eq.)和4-三甲氧基苯胺基硼酸酯(4~8eq.)、碳酸钾(10~20eq.)加入100mL的双颈瓶中,溶解在体积比为5:1:1的甲苯、乙醇和水的混合溶液(8~20mL)中,加入四(三苯基膦)钯(0.05~0.2eq.),在90℃下强力搅拌24h,反应结束后冷却至室温,用二氯甲烷萃取洗涤三次,饱和食盐水萃取一次,旋蒸后进行色谱柱分离,得到目标产物1,3,6,8-四-(4-三甲氧基苯胺)-2,7-二羟基芘,产率约为50%,其合成路线如式(9)所示。
图27为本实施例得到的1,3,6,8-四-(4-三甲氧基苯胺)-2,7-二羟基芘的1HNMR图,图28为本实施例得到的1,3,6,8-四-(4-三甲氧基苯胺)-2,7-二羟基芘的13C NMR图,图29为本实施例得到的1,3,6,8-四-(4-三甲氧基苯胺)-2,7-二羟基芘的HRMS图,从图27-29可知,成功制备出1,3,6,8-四-(4-三甲氧基苯胺)-2,7-二羟基芘。
实施例10 1,3,6,8-四-(4-甲氧基苯基)-2-甲氧基-芘的制备
在氮气的保护下,将实施例3的1,3,6,8-四-(4-甲氧基苯基)-2-羟基芘(1eq.)和碘甲烷(1~10eq.)、碳酸钾(10~20eq.)加入100mL的双颈瓶中,溶解在乙腈(5~20mL)中,加热回流,强力搅拌12h,反应结束后冷却至室温,用二氯甲烷萃取洗涤三次,饱和食盐水萃取一次,无水硫酸镁除水后过滤,旋蒸后进行色谱柱分离并重结晶,得到目标产物1,3,6,8-四-(4-甲氧基苯基)-2-甲氧基-芘,产率约为70%,其合成路线如式(10)所示。
图30为本实施例得到的1,3,6,8-四-(4-甲氧基苯基)-2-甲氧基-芘的1HNMR图,图31为本实施例得到的1,3,6,8-四-(4-甲氧基苯基)-2-甲氧基-芘的13C NMR图,图32为本实施例得到的1,3,6,8-四-(4-甲氧基苯基)-2-甲氧基-芘的HRMS图,图33为本实施例得到的1,3,6,8-四-(4-甲氧基苯基)-2-甲氧基-芘的单晶结构图,从图30-33可知,成功制备出1,3,6,8-四-(4-甲氧基苯基)-2-甲氧基-芘。
图34为实施例3、4、5、6、10由溴芘中间体得到的1,3,6,8-四取代-2,7-二羟基-芘衍生物、1,3,6,8-四取代-2-羟基-芘衍生物和1,3,6,8-四取代-2-甲氧基-芘衍生物的UV-vis和荧光光谱图。其中,3a为1,3,6,8-四-(4-甲氧基苯基)-2,7-二羟基芘,3b为1,3,6,8-四-(4-三氟甲基苯基)-2,7-二羟基芘,4a为1,3,6,8-四-(4-甲氧基苯基)-2-羟基芘,4b为1,3,6,8-四-(4-三氟甲基苯基)-2-羟基芘,5为1,3,6,8-四-(4-甲氧基苯基)-2-甲氧基-芘。从图34可知,3a,3b,4a,4b和5在四氢呋喃溶液中最大发射波长处于426-432nm,这四类发光材料均是蓝光材料。
实施例11 1,3,6,8-四-(4-甲氧基苯基)-2,7-二甲氧基-芘的制备
在氮气的保护下,将实施例4的1,3,6,8-四-(4-甲氧基苯基)-2,7-二羟基芘(1eq.)和碘甲烷(2~20eq.)、碳酸钾(10~20eq.)加入100mL的双颈瓶中,溶解在乙腈(5~20mL)中,加热回流,强力搅拌12h,反应结束后冷却至室温,用二氯甲烷萃取洗涤三次,饱和食盐水萃取一次,无水硫酸镁除水后过滤,旋蒸后进行色谱柱分离并重结晶,得到目标产物1,3,6,8-四-(4-甲氧基苯基)-2,7-甲氧基-芘,产率约为80%,其合成路线如式(11)所示。
实施例12 1,3,6,8-四-(4-甲氧基苯基)-2-乙氧基-芘的制备
在氮气的保护下,将实施例3的1,3,6,8-四-(4-甲氧基苯基)-2-羟基芘(1eq.)和碘乙烷(1~10eq.)、叔丁基醇钾(10~20eq.)加入100mL的双颈瓶中,溶解在四氢呋喃(5~20mL)中,加热回流,强力搅拌12h,反应结束后冷却至室温,用二氯甲烷萃取洗涤三次,饱和食盐水萃取一次,无水硫酸镁除水后过滤,旋蒸后进行色谱柱分离并重结晶,得到目标产物1,3,6,8-四-(4-甲氧基苯基)-2-乙氧基-芘,产率约为80%,其合成路线如式(12)所示。
实施例13 1,3,6,8-四-(4-甲氧基苯基)-2,7-二乙氧基-芘的制备
在氮气的保护下,将实施例4的1,3,6,8-四-(4-甲氧基苯基)-2,7-二羟基芘(1eq.)和碘乙烷(2~20eq.)、叔丁基醇钾(10~20eq.)加入100mL的双颈瓶中,溶解在乙腈(5~20mL)中,加热回流,强力搅拌12h,反应结束后冷却至室温,用二氯甲烷萃取洗涤三次,饱和食盐水萃取一次,无水硫酸镁除水后过滤,旋蒸后进行色谱柱分离并重结晶,得到目标产物1,3,6,8-四-(4-甲氧基苯基)-2,7-甲氧基-芘,产率约为75%,其合成路线如式(13)所示。
实施例14 1,3,6,8-四-(4-甲氧基苯基)-2-苄氧基-芘的制备
在氮气的保护下,将实施例3的1,3,6,8-四-(4-甲氧基苯基)-2-羟基芘(1eq.)和苄基溴(2~20eq.)、叔丁基醇钾(10~20eq.)加入100mL的双颈瓶中,溶解在乙腈(5~20mL)中,加热回流,强力搅拌12h,反应结束后冷却至室温,用二氯甲烷萃取洗涤三次,饱和食盐水萃取一次,无水硫酸镁除水后过滤,旋蒸后进行色谱柱分离并重结晶,得到目标产物1,3,6,8-四-(4-甲氧基苯基)-2-苄氧基-芘,产率约为63%,其合成路线如式(14)所示。
实施例15 1,3,6,8-四-(4-甲氧基苯基)-2,7-二苄氧基-芘的制备
在氮气的保护下,将实施例4的1,3,6,8-四-(4-甲氧基苯基)-2,7-二羟基芘(1eq.)和苄基溴(2~20eq.)、叔丁基醇钾(10~20eq.)加入100mL的双颈瓶中,溶解在乙腈(5~20mL)中,加热回流,强力搅拌12h,反应结束后冷却至室温,用二氯甲烷萃取洗涤三次,饱和食盐水萃取一次,无水硫酸镁除水后过滤,旋蒸后进行色谱柱分离并重结晶,得到目标产物1,3,6,8-四-(4-甲氧基苯基)-2,7-二苄氧基-芘,产率约为51%,其合成路线如式(15)所示。
上述实施例为本发明较佳的实施方式,但本发明的实施方式并不受上述实施例的限制,其他的任何未背离本发明的精神实质与原理下所作的改变、修饰、替代、组合和简化,均应为等效的置换方式,都包含在本发明的保护范围之内。
Claims (10)
2.根据权利要求1所述的溴芘中间体的制备方法,其特征在于,所述溴芘中间体是以2-羟基芘或2,7-二羟基芘为原料,在惰性气氛下加入溴化剂和有机溶剂,在50~130℃加热搅拌10~40h进行溴代反应,制得2-羟基-1,3,6,8-四溴芘或2,7-二羟基-1,3,6,8-四溴芘。
3.根据权利要求2所述的溴芘中间体的制备方法,其特征在于,所述溴化剂为溴水、N-溴代琥珀酰亚胺或苄基三甲基溴化铵二溴中的一种以上;所述惰性气氛为氮气或者氩气;所述有机溶剂为硝基苯、二氯甲烷、三氯甲烷、乙腈中的一种以上;所述的2-羟基芘或2,7-二羟基芘:溴化剂的摩尔比为1:(1~10)。
6.根据权利要求4或5所述的芘基有机功能发光材料的制备方法,其特征在于,所述芘基有机功能发光材料是在保护气氛下,将权利要求1所述的溴芘中间体加入钯催化剂、R1取代的硼酸、无机碱和溶剂,在50~100℃通过钯催化偶联反应,分别在芘的多个位点进行功能化取代制备得到。
7.根据权利要求6所述的芘基有机功能发光材料的制备方法,其特征在于,所述保护气氛为氮气或者氩气;所述钯催化剂为四(三苯基膦)钯、醋酸钯、四氟硼酸三(叔丁基膦)或三(二亚苄基丙酮)二钯、二氯双(三苯基膦)合钯中的一种及以上,所述无机碱为碳酸钾、碳酸钠、碳酸氢钠、碳酸氢钾、氢氧化钠中的一种及以上;所述溶剂为甲苯、乙醇、水、四氢呋喃、N,N-二甲基甲酰胺、乙腈、三乙胺中的一种及以上;R1选自4-甲氧基苯基、4-三氟甲基苯基、2-噻吩基、4-(N,N-二(对甲氧基苯基)氨基)苯基;所述2-羟基-1,3,6,8-四溴芘或2,7-二羟基-1,3,6,8-四溴芘:R1取代的硼酸:钯催化剂:无机碱的摩尔比为1:(4~10):(0.05~0.2):(5~20)。
9.根据权利要求8所述的芘基有机功能发光材料,其特征在于,所述R2取代基团的卤化物为碘甲烷、碘乙烷、苄基溴或溴苯;所述惰性气氛为氮气或氩气;所述无机碱为碳酸钾、叔丁基醇钾、碳酸钠、碳酸氢钠、碳酸氢钾、氢氧化钠中的一种以上;所述有机溶剂为乙腈、四氢呋喃、二氯甲烷、乙醇中的一种以上;所述的芘基有机功能发光材料:R2取代基团的卤化物:无机碱的摩尔比为1:(1~10):(5~20)。
10.权利要求4-5任一项或权利要求8-9任一项所述的芘类发光材料在有机电子学或生物领域中的应用。
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