CN116836180A - 一种氮、氧杂稠环芳烃及其合成方法和应用 - Google Patents
一种氮、氧杂稠环芳烃及其合成方法和应用 Download PDFInfo
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- CN116836180A CN116836180A CN202310563635.1A CN202310563635A CN116836180A CN 116836180 A CN116836180 A CN 116836180A CN 202310563635 A CN202310563635 A CN 202310563635A CN 116836180 A CN116836180 A CN 116836180A
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- Prior art keywords
- aromatic hydrocarbon
- nitrogen
- compound
- polycyclic aromatic
- silver
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 title claims abstract description 48
- 229910052757 nitrogen Inorganic materials 0.000 title claims abstract description 24
- 239000001301 oxygen Substances 0.000 title claims abstract description 9
- 229910052760 oxygen Inorganic materials 0.000 title claims abstract description 9
- 229930195733 hydrocarbon Natural products 0.000 title claims description 8
- 239000004215 Carbon black (E152) Substances 0.000 title claims description 7
- 238000010189 synthetic method Methods 0.000 title description 3
- 238000006243 chemical reaction Methods 0.000 claims abstract description 53
- 239000002904 solvent Substances 0.000 claims abstract description 39
- 150000008049 diazo compounds Chemical class 0.000 claims abstract description 20
- 239000003054 catalyst Substances 0.000 claims abstract description 19
- 125000005575 polycyclic aromatic hydrocarbon group Chemical group 0.000 claims abstract description 19
- 238000000034 method Methods 0.000 claims abstract description 18
- 230000002194 synthesizing effect Effects 0.000 claims abstract description 10
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims abstract description 9
- 239000000654 additive Substances 0.000 claims abstract description 7
- 230000000996 additive effect Effects 0.000 claims abstract description 7
- 239000012298 atmosphere Substances 0.000 claims abstract description 6
- BCHZICNRHXRCHY-UHFFFAOYSA-N 2h-oxazine Chemical compound N1OC=CC=C1 BCHZICNRHXRCHY-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229940125904 compound 1 Drugs 0.000 claims abstract description 5
- 229940125782 compound 2 Drugs 0.000 claims abstract description 5
- 150000001491 aromatic compounds Chemical class 0.000 claims abstract description 4
- 229940126214 compound 3 Drugs 0.000 claims abstract description 4
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 claims description 18
- -1 bis (hexafluoroantimonic acid) triacetonitrile (pentamethyl cyclopentadienyl) rhodium Chemical compound 0.000 claims description 15
- 239000010948 rhodium Substances 0.000 claims description 12
- 229910052703 rhodium Inorganic materials 0.000 claims description 11
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims description 11
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 9
- DOTMOQHOJINYBL-UHFFFAOYSA-N molecular nitrogen;molecular oxygen Chemical compound N#N.O=O DOTMOQHOJINYBL-UHFFFAOYSA-N 0.000 claims description 9
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 6
- QVLTVILSYOWFRM-UHFFFAOYSA-L CC1=C(C)C(C)([Rh](Cl)Cl)C(C)=C1C Chemical class CC1=C(C)C(C)([Rh](Cl)Cl)C(C)=C1C QVLTVILSYOWFRM-UHFFFAOYSA-L 0.000 claims description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 6
- GGCZERPQGJTIQP-UHFFFAOYSA-N sodium;9,10-dioxoanthracene-2-sulfonic acid Chemical compound [Na+].C1=CC=C2C(=O)C3=CC(S(=O)(=O)O)=CC=C3C(=O)C2=C1 GGCZERPQGJTIQP-UHFFFAOYSA-N 0.000 claims description 6
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 5
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 4
- 150000001555 benzenes Chemical group 0.000 claims description 4
- 239000007850 fluorescent dye Substances 0.000 claims description 4
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 4
- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical compound [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 claims description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 4
- FFFIRKXTFQCCKJ-UHFFFAOYSA-N 2,4,6-trimethylbenzoic acid Chemical compound CC1=CC(C)=C(C(O)=O)C(C)=C1 FFFIRKXTFQCCKJ-UHFFFAOYSA-N 0.000 claims description 2
- GFCVQYCZHGSRMA-UHFFFAOYSA-L C(C)(=O)[O-].CC1=C(C(=C(C1([Rh+2])C)C)C)C.C(C)(=O)[O-] Chemical compound C(C)(=O)[O-].CC1=C(C(=C(C1([Rh+2])C)C)C)C.C(C)(=O)[O-] GFCVQYCZHGSRMA-UHFFFAOYSA-L 0.000 claims description 2
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 claims description 2
- JIMXXGFJRDUSRO-UHFFFAOYSA-N adamantane-1-carboxylic acid Chemical compound C1C(C2)CC3CC2CC1(C(=O)O)C3 JIMXXGFJRDUSRO-UHFFFAOYSA-N 0.000 claims description 2
- IUGYQRQAERSCNH-UHFFFAOYSA-N pivalic acid Chemical compound CC(C)(C)C(O)=O IUGYQRQAERSCNH-UHFFFAOYSA-N 0.000 claims description 2
- 235000011056 potassium acetate Nutrition 0.000 claims description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- CQLFBEKRDQMJLZ-UHFFFAOYSA-M silver acetate Chemical compound [Ag+].CC([O-])=O CQLFBEKRDQMJLZ-UHFFFAOYSA-M 0.000 claims description 2
- 229940071536 silver acetate Drugs 0.000 claims description 2
- 229910000367 silver sulfate Inorganic materials 0.000 claims description 2
- YPNVIBVEFVRZPJ-UHFFFAOYSA-L silver sulfate Chemical compound [Ag+].[Ag+].[O-]S([O-])(=O)=O YPNVIBVEFVRZPJ-UHFFFAOYSA-L 0.000 claims description 2
- 229910001494 silver tetrafluoroborate Inorganic materials 0.000 claims description 2
- QRUBYZBWAOOHSV-UHFFFAOYSA-M silver trifluoromethanesulfonate Chemical compound [Ag+].[O-]S(=O)(=O)C(F)(F)F QRUBYZBWAOOHSV-UHFFFAOYSA-M 0.000 claims description 2
- KZJPVUDYAMEDRM-UHFFFAOYSA-M silver;2,2,2-trifluoroacetate Chemical compound [Ag+].[O-]C(=O)C(F)(F)F KZJPVUDYAMEDRM-UHFFFAOYSA-M 0.000 claims description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 2
- 239000004246 zinc acetate Substances 0.000 claims description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 12
- 238000003786 synthesis reaction Methods 0.000 abstract description 11
- 230000015572 biosynthetic process Effects 0.000 abstract description 9
- 238000001308 synthesis method Methods 0.000 abstract description 8
- 239000003814 drug Substances 0.000 abstract description 4
- 125000005842 heteroatom Chemical group 0.000 abstract description 4
- 239000000758 substrate Substances 0.000 abstract description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 3
- 229930014626 natural product Natural products 0.000 abstract description 3
- 125000004429 atom Chemical group 0.000 abstract 1
- 125000000524 functional group Chemical group 0.000 abstract 1
- 150000001875 compounds Chemical class 0.000 description 50
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 48
- 238000005481 NMR spectroscopy Methods 0.000 description 33
- 230000005311 nuclear magnetism Effects 0.000 description 28
- 210000004027 cell Anatomy 0.000 description 16
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 15
- 238000012512 characterization method Methods 0.000 description 15
- 239000003480 eluent Substances 0.000 description 15
- 239000003208 petroleum Substances 0.000 description 15
- 239000000741 silica gel Substances 0.000 description 15
- 229910002027 silica gel Inorganic materials 0.000 description 15
- 239000007787 solid Substances 0.000 description 15
- 239000000543 intermediate Substances 0.000 description 14
- 238000000926 separation method Methods 0.000 description 14
- SRCZQMGIVIYBBJ-UHFFFAOYSA-N ethoxyethane;ethyl acetate Chemical compound CCOCC.CCOC(C)=O SRCZQMGIVIYBBJ-UHFFFAOYSA-N 0.000 description 11
- 239000007788 liquid Substances 0.000 description 7
- 238000002844 melting Methods 0.000 description 7
- 230000008018 melting Effects 0.000 description 7
- 238000002189 fluorescence spectrum Methods 0.000 description 6
- WLWNRAWQDZRXMB-YLFCFFPRSA-N (2r,3r,4r,5s)-n,3,4,5-tetrahydroxy-1-(4-phenoxyphenyl)sulfonylpiperidine-2-carboxamide Chemical compound ONC(=O)[C@H]1[C@@H](O)[C@H](O)[C@@H](O)CN1S(=O)(=O)C(C=C1)=CC=C1OC1=CC=CC=C1 WLWNRAWQDZRXMB-YLFCFFPRSA-N 0.000 description 5
- 230000008878 coupling Effects 0.000 description 5
- 238000010168 coupling process Methods 0.000 description 5
- 238000005859 coupling reaction Methods 0.000 description 5
- JLYXXMFPNIAWKQ-GNIYUCBRSA-N gamma-hexachlorocyclohexane Chemical compound Cl[C@H]1[C@H](Cl)[C@@H](Cl)[C@@H](Cl)[C@H](Cl)[C@H]1Cl JLYXXMFPNIAWKQ-GNIYUCBRSA-N 0.000 description 5
- 229960002809 lindane Drugs 0.000 description 5
- 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 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 4
- 244000055346 Paulownia Species 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 230000003287 optical effect Effects 0.000 description 3
- JUJWROOIHBZHMG-UHFFFAOYSA-N pyridine Substances C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- RUVJFMSQTCEAAB-UHFFFAOYSA-M 2-[3-[5,6-dichloro-1,3-bis[[4-(chloromethyl)phenyl]methyl]benzimidazol-2-ylidene]prop-1-enyl]-3-methyl-1,3-benzoxazol-3-ium;chloride Chemical compound [Cl-].O1C2=CC=CC=C2[N+](C)=C1C=CC=C(N(C1=CC(Cl)=C(Cl)C=C11)CC=2C=CC(CCl)=CC=2)N1CC1=CC=C(CCl)C=C1 RUVJFMSQTCEAAB-UHFFFAOYSA-M 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 238000010499 C–H functionalization reaction Methods 0.000 description 2
- 238000000862 absorption spectrum Methods 0.000 description 2
- 238000009825 accumulation Methods 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 125000006615 aromatic heterocyclic group Chemical group 0.000 description 2
- 238000012984 biological imaging Methods 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 238000010276 construction Methods 0.000 description 2
- 150000001989 diazonium salts Chemical class 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000011534 incubation Methods 0.000 description 2
- QWXYZCJEXYQNEI-OSZHWHEXSA-N intermediate I Chemical compound COC(=O)[C@@]1(C=O)[C@H]2CC=[N+](C\C2=C\C)CCc2c1[nH]c1ccccc21 QWXYZCJEXYQNEI-OSZHWHEXSA-N 0.000 description 2
- AWJUIBRHMBBTKR-UHFFFAOYSA-N iso-quinoline Natural products C1=NC=CC2=CC=CC=C21 AWJUIBRHMBBTKR-UHFFFAOYSA-N 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- HZVOZRGWRWCICA-UHFFFAOYSA-N methanediyl Chemical compound [CH2] HZVOZRGWRWCICA-UHFFFAOYSA-N 0.000 description 2
- OJURWUUOVGOHJZ-UHFFFAOYSA-N methyl 2-[(2-acetyloxyphenyl)methyl-[2-[(2-acetyloxyphenyl)methyl-(2-methoxy-2-oxoethyl)amino]ethyl]amino]acetate Chemical compound C=1C=CC=C(OC(C)=O)C=1CN(CC(=O)OC)CCN(CC(=O)OC)CC1=CC=CC=C1OC(C)=O OJURWUUOVGOHJZ-UHFFFAOYSA-N 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000005693 optoelectronics Effects 0.000 description 2
- 150000004893 oxazines Chemical class 0.000 description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 150000003624 transition metals Chemical class 0.000 description 2
- HBENZIXOGRCSQN-VQWWACLZSA-N (1S,2S,6R,14R,15R,16R)-5-(cyclopropylmethyl)-16-[(2S)-2-hydroxy-3,3-dimethylpentan-2-yl]-15-methoxy-13-oxa-5-azahexacyclo[13.2.2.12,8.01,6.02,14.012,20]icosa-8(20),9,11-trien-11-ol Chemical compound N1([C@@H]2CC=3C4=C(C(=CC=3)O)O[C@H]3[C@@]5(OC)CC[C@@]2([C@@]43CC1)C[C@@H]5[C@](C)(O)C(C)(C)CC)CC1CC1 HBENZIXOGRCSQN-VQWWACLZSA-N 0.000 description 1
- PHDIJLFSKNMCMI-ITGJKDDRSA-N (3R,4S,5R,6R)-6-(hydroxymethyl)-4-(8-quinolin-6-yloxyoctoxy)oxane-2,3,5-triol Chemical compound OC[C@@H]1[C@H]([C@@H]([C@H](C(O1)O)O)OCCCCCCCCOC=1C=C2C=CC=NC2=CC=1)O PHDIJLFSKNMCMI-ITGJKDDRSA-N 0.000 description 1
- VAVHMEQFYYBAPR-ITWZMISCSA-N (e,3r,5s)-7-[4-(4-fluorophenyl)-1-phenyl-2-propan-2-ylpyrrol-3-yl]-3,5-dihydroxyhept-6-enoic acid Chemical compound CC(C)C1=C(\C=C\[C@@H](O)C[C@@H](O)CC(O)=O)C(C=2C=CC(F)=CC=2)=CN1C1=CC=CC=C1 VAVHMEQFYYBAPR-ITWZMISCSA-N 0.000 description 1
- FZTLLUYFWAOGGB-UHFFFAOYSA-N 1,4-dioxane dioxane Chemical compound C1COCCO1.C1COCCO1 FZTLLUYFWAOGGB-UHFFFAOYSA-N 0.000 description 1
- RAIKREKWRHXJRW-UHFFFAOYSA-N 2H-naphtho[1,2-h]quinolin-1-one Chemical class C1(CC=NC=2C3=C(C=CC1=2)C1=CC=CC=C1C=C3)=O RAIKREKWRHXJRW-UHFFFAOYSA-N 0.000 description 1
- HIHOEGPXVVKJPP-JTQLQIEISA-N 5-fluoro-2-[[(1s)-1-(5-fluoropyridin-2-yl)ethyl]amino]-6-[(5-methyl-1h-pyrazol-3-yl)amino]pyridine-3-carbonitrile Chemical compound N([C@@H](C)C=1N=CC(F)=CC=1)C(C(=CC=1F)C#N)=NC=1NC=1C=C(C)NN=1 HIHOEGPXVVKJPP-JTQLQIEISA-N 0.000 description 1
- DGJMHKMYSDYOFP-MRXNPFEDSA-N C=CC(N(CCC1)C[C@@H]1N1N=C(C2=CN(CC(C3=CC=CC=C3)(F)F)N=N2)C2=C(N)N=CN=C12)=O Chemical compound C=CC(N(CCC1)C[C@@H]1N1N=C(C2=CN(CC(C3=CC=CC=C3)(F)F)N=N2)C2=C(N)N=CN=C12)=O DGJMHKMYSDYOFP-MRXNPFEDSA-N 0.000 description 1
- ZDQWESQEGGJUCH-UHFFFAOYSA-N Diisopropyl adipate Chemical compound CC(C)OC(=O)CCCCC(=O)OC(C)C ZDQWESQEGGJUCH-UHFFFAOYSA-N 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- 108010043121 Green Fluorescent Proteins Proteins 0.000 description 1
- HGDWHTASNMRJMP-UHFFFAOYSA-N [1-(hydroxyamino)-1-oxo-5-(3-phenoxyphenyl)pentan-2-yl]phosphonic acid Chemical compound ONC(=O)C(P(O)(O)=O)CCCC1=CC=CC(OC=2C=CC=CC=2)=C1 HGDWHTASNMRJMP-UHFFFAOYSA-N 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000004071 biological effect Effects 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 230000030833 cell death Effects 0.000 description 1
- 238000006757 chemical reactions by type Methods 0.000 description 1
- 238000003501 co-culture Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 125000000664 diazo group Chemical group [N-]=[N+]=[*] 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 238000000295 emission spectrum Methods 0.000 description 1
- 150000002085 enols Chemical class 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 230000005669 field effect Effects 0.000 description 1
- 238000007306 functionalization reaction Methods 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000003384 imaging method Methods 0.000 description 1
- 150000002466 imines Chemical class 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000003780 insertion Methods 0.000 description 1
- 230000037431 insertion Effects 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 210000003470 mitochondria Anatomy 0.000 description 1
- 230000002438 mitochondrial effect Effects 0.000 description 1
- 229910052754 neon Inorganic materials 0.000 description 1
- GKAOGPIIYCISHV-UHFFFAOYSA-N neon atom Chemical compound [Ne] GKAOGPIIYCISHV-UHFFFAOYSA-N 0.000 description 1
- 230000000269 nucleophilic effect Effects 0.000 description 1
- 125000003367 polycyclic group Chemical group 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 239000000523 sample Substances 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 238000002371 ultraviolet--visible spectrum Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D498/00—Heterocyclic compounds containing in the condensed system at least one hetero ring having nitrogen and oxygen atoms as the only ring hetero atoms
- C07D498/02—Heterocyclic compounds containing in the condensed system at least one hetero ring having nitrogen and oxygen atoms as the only ring hetero atoms in which the condensed system contains two hetero rings
- C07D498/06—Peri-condensed systems
-
- 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
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
- G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
- G01N21/64—Fluorescence; Phosphorescence
- G01N21/6428—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes"
-
- 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
- C09K2211/1033—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom with oxygen
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/549—Organic PV cells
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Immunology (AREA)
- Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Engineering & Computer Science (AREA)
- Nuclear Medicine, Radiotherapy & Molecular Imaging (AREA)
- Life Sciences & Earth Sciences (AREA)
- Analytical Chemistry (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
- Pathology (AREA)
- Heterocyclic Carbon Compounds Containing A Hetero Ring Having Nitrogen And Oxygen As The Only Ring Hetero Atoms (AREA)
Abstract
本发明提出了一种氮、氧杂稠环芳烃及其合成方法和应用,用以解决现有稠杂环芳烃合成方法单一、底物合成复杂以及产物结构局限等技术问题。本发明的合成方法包括以下步骤:惰性氛围下将噁嗪类化合物1、重氮化合物2、催化剂、添加剂加入到溶剂当中,在惰性氛围中进行反应,反应结束后得到杂稠环芳烃化合物3。本发明为含多杂原子稠环芳烃的合成提供了一种简单有效的合成方法,并且该方法具有反应条件温和、操作简单、原子经济、步骤经济、官能团耐受性强以及收率良好等特点。所得产物有广阔的工业应用前景,同时为医药、天然产物合成以及发光材料等领域上提供了一种新思路和新方法。
Description
技术领域
本发明属于有机合成化学的技术领域,尤其涉及一种氮、氧杂稠环芳烃及其合成方法和应用。
背景技术
稠环芳烃是指由两个或多个芳烃组成的多环芳烃化合物,广泛应用于药物、染料等行业。稠环芳烃的晶体排列存在π-π相互作用,分子之间形成有序堆积,其在有机光电器件(包括有机场效应晶体管(Organic Field-Effect Transistor,OFET)、有机太阳能电池(Organic Solar Cell,OSC)和有机发光二极管(Organic Light-Emitting Diode,OLED)等)、有机半导体材料等领域都具有广阔的应用前景(Chem.Rev.,2007,107,926;Chem.Soc.Rev.,2010,39,1489;Chem.Soc.Rev.,2012,41,4245;Nature,2004,428,911)。与传统的无机光电材料相比,大尺寸的共轭分子具有分子级别的结构调整;溶解性好、易加工;质轻、柔性,可实现大面积器件制备等优势。因此,设计并合成新型有机稠环芳烃,并对其进行性质以及应用研究,一直以来都是化学、材料和生物等领域科学家的研究热点之一。特别地,以杂原子替代多环化合物中的部分碳原子,形成含杂原子共轭骨架分子,即杂稠环芳烃,可显著提高材料的稳定性及组装性能,从而显著改善有机光电材料的光电性能和多功能性(Angew.Chem.,Int.Ed.,2010,49,8209;Chem.Mater.,2015,28,3)。同时,对稠环芳烃进行多功能修饰,也是赋予有机光电分子可调控性和多样性的重要手段。
惰性C-H键直接官能团化反应由于高原子经济与步骤经济的优越性,现已无可争议的成为化学家们追求的理想合成手段,其一度被人们称为“化学的圣杯”。过去20年里,过渡金属催化C-H活化反应的确已经取得了非常显著的成效,实现了诸多传统化学所不能完成的转化。其中,铑催化导向C-H键活化1:2偶联构筑多环芳烃的合成得到了快速发展,制备了一大批在有机光电材料和药物领域具有重要应用前景的新型稠环芳烃骨架。而重氮化合物作为有机合成中的重要中间体,将其应用在过渡金属催化1:2偶联构建稠杂环芳烃的研究尚处于初级阶段。迄今为止,有关铑催化导向C-H活化1:2偶联构筑稠环芳烃分子仅有一例报道(Org.Lett.2017,19,2294),研究相对缓慢。上述方法以强配位的吡啶类化合物作为导向基,在铑催化剂的作用下实现了和重氮化合物的1:2偶联,构筑了一系列萘并喹啉酮骨架。
一方面,现有的合成手段所使用导向基团为强配位能力的吡啶,底物合成复杂,产物类型单一,所得骨架仅为氮杂的稠环芳烃。另一方面,苯并噁嗪型亚胺作为有机合成当中的关键中间体,合成简单、来源广泛。将其作为弱的导向基团应用在铑催化的卡宾1:2偶联的研究尚没有报道。根据已有文献报道,杂稠环芳烃,可显著提高材料的稳定性及组装性能,从而显著改善有机光电材料的光电性能和多功能性(Angew.Chem.,Int.Ed.,2010,49,8209;Chem.Mater.,2015,28,3),杂稠环芳烃在有机光电材料方面的应用具有广阔的前景;因此急需寻找一种合成杂稠环芳烃的新方法。
发明内容
针对现有稠杂环芳烃合成方法单一、底物合成复杂以及产物结构局限等技术问题,本发明提出一种氮、氧杂稠环芳烃及其合成方法和应用,本发明为含多杂原子稠环芳烃的合成提供了一种简单有效的合成方法,并且该方法具有反应条件温和、操作简单、原子经济、步骤经济、官能团耐受性强以及收率良好等特点。
为了达到上述目的,本发明的技术方案是这样实现的:
一种氮、氧杂稠环芳烃,结构式如下所示:
其中R为H、Me、OMe、F、Cl或Br其中任意一种;R1为Me、n-Pr或Ph其中任意一种;R2为n-Am或iPr;Ar为Me、OMe、F、Cl,Br、Ph或CF3任意一种取代的苯环。
上述氮、氧杂稠环芳烃的合成方法,包括以下步骤:惰性氛围下将噁嗪类化合物1、重氮化合物2、催化剂、添加剂加入到溶剂当中并进行反应,反应结束后得到杂稠环芳烃化合物3,反应方程式为:
其中R为H、Me、OMe、F、Cl或Br其中任意一种;R1为Me、n-Pr或Ph其中任意一种;R2为n-Am或iPr;Ar为Me、OMe、F、Cl,Br、Ph或CF3任意一种取代的苯环;式中Rh(Ⅲ)为催化剂。
所述反应结束后对反应结束的溶液进行分离提纯得到杂稠环芳烃化合物3。
所述反应的过程中反应温度为80-120℃,反应时间为到6-12h。
所述催化剂包括铑催化剂和银盐;铑催化剂和银盐的摩尔比为1:4;所述铑催化剂为二氯(五甲基环戊二烯基)合铑二聚体、五甲基环戊二烯基醋酸铑或二(六氟锑酸)三乙腈(五甲基环戊二烯基)铑其中任意一种或组合;银盐为六氟锑酸银、四氟硼酸银、双三氟甲烷磺酰亚胺银、三氟甲烷磺酸银、硫酸银、醋酸银、三氟醋酸银其中任意一种或组合。
所述催化剂由二氯(五甲基环戊二烯基)合铑二聚体和六氟锑酸银组成;二氯(五甲基环戊二烯基)合铑二聚体与六氟锑酸银的摩尔比为1:4。
所述添加剂为2,4,6-三甲基苯甲酸、特戊酸、醋酸、1-金刚烷甲酸、醋酸锌、碳酸钠、醋酸钾或碳酸钾其中任意一种或组合。
所述溶剂为二氯乙烷(DCE)、甲醇(MeOH)、乙腈(MeCN)、1,4-二氧六环(1,4-dioxane)或甲苯(toluene)其中任意一种或组合。
所述惰性氛围为氮气氛围,此外,还可以为氦气、氖气和氩气等气体氛围。
所述噁嗪类化合物1、重氮化合物2、催化剂、添加剂和溶剂的摩尔比为:1:(2-3):(0.02-0.04):(0.08-0.16)。
所述溶剂当中反应体系的浓度为0.05M-0.2M。
所述的氮、氧杂稠环芳烃作为荧光探针的应用,用于识别活细胞中外源HSO3 -。
对于该反应的反应模式,其反应原理如图31所示:首先底物1a和催化剂作用得到环金属中间体A,随后充氮化合物和中间体A作用得到中间体B,紧接着中间体B发生卡宾的迁移插入得到中间体C,然后发生金属的脱除得到中间体D,中间体D再次发生上述过程得到双烷基化中间体E,中间体E快速互变为烯醇式F,中间体F中的羟基对亚胺键进行进攻得到中间体G,中间体G的NH对另外一分子的羰基进行亲核加成-消除得到中间体I,随后中间体I经历酸化-开环-关环-脱水等连续的转化给出了目标氮、氧杂稠环芳烃3aa。
本发明的有益效果:本发明开创性地选取简单易得的噁嗪类化合物和重氮化合物作为反应物,在金属铑催化剂的作用下,以噁嗪类化合物当中的亚胺作为弱的反应型定位基,通过连续的[4+2]串联策略一步实现了新型氮、氧杂稠环芳烃骨架的构建,该方法操作简单,具有显著的原子经济、步骤经济,为杂稠环芳烃的合成提供了一种简单有效的方法,并且该方法反应条件温和,其反应温度仅为80-120℃;另外,所制备氮、氧杂稠环芳烃的收率良好,产率普遍在80%以上,最高达到98%。所得产物有广阔的工业应用前景,同时为医药、天然产物合成以及发光材料等领域了提供了一种新思路和新方法。
附图说明
为了更清楚地说明本发明实施例或现有技术中的技术方案,下面将对实施例或现有技术描述中所需要使用的附图作简单地介绍,显而易见地,下面描述中的附图仅仅是本发明的一些实施例,对于本领域普通技术人员来讲,在不付出创造性劳动的前提下,还可以根据这些附图获得其他的附图。
图1是化合物3aa的核磁1H谱图;图2是化合物3aa的核磁13C谱图。
图3是化合物3ba的核磁1H谱图;图4是化合物3ba的核磁13C谱图。
图5是化合物3ca的核磁1H谱图;图6是化合物3ca的核磁13C谱图。
图7是化合物3da的核磁1H谱图;图8是化合物3da的核磁13C谱图。
图9是化合物3ea的核磁1H谱图;图10是化合物3ea的核磁13C谱图。
图11是化合物3fa的核磁1H谱图;图12是化合物3fa的核磁13C谱图。
图13是化合物3ga的核磁1H谱图;图14是化合物3ga的核磁13C谱图。
图15是化合物3ha的核磁1H谱图;图16是化合物3ha的核磁13C谱图。
图17是化合物3ia的核磁1H谱图;图18是化合物3ia的核磁13C谱图。
图19是化合物3ja的核磁1H谱图;图20是化合物3ja的核磁13C谱图。
图21是化合物3ka的核磁1H谱图;图22是化合物3ka的核磁13C谱图。
图23是化合物3ab的核磁1H谱图;图24是化合物3ab的核磁13C谱图。
图25是化合物3ac的核磁1H谱图;图26是化合物3ac的核磁13C谱图。
图27是化合物3ad的核磁1H谱图;图28是化合物3ad的核磁13C谱图。
图29是化合物3ae的核磁1H谱图;图30是化合物3ae的核磁13C谱图。
图31是本发明反应机理图。
图32是五种化合物的紫外-可见吸收光谱。
图33是五种化合物的液态荧光发射光谱。
图34是五种化合物的固态荧光发射光谱。
图35是化合物3fa在泡桐根细胞中的荧光照片。
具体实施方式
下面将结合本发明实施例中的附图,对本发明实施例中的技术方案进行清楚、完整地描述,显然,所描述的实施例仅仅是本发明一部分实施例,而不是全部的实施例。基于本发明中的实施例,本领域普通技术人员在没有付出创造性劳动前提下所获得的所有其他实施例,都属于本发明保护的范围。
实施例1
在氮气条件下,将3-芳基苯并噁嗪化合物1a(0.20mmol),重氮化合物2a(0.44mmol),[Cp*RhCl2]2(4mol%),AgSbF6(16mol%),MesCOOH(0.4mmol)和溶剂DCE(2.0mL)加入到10mL密封管中,在80度的反应模块中反应10h,反应结束后减压除去溶剂,用硅胶柱分离得到目标产物5,12-二甲基异喹啉[2,1,8-mna]吩恶嗪-4,13-二羧酸二乙酯(3aa),所有洗脱剂为石油醚乙酸乙酯和二氯甲烷按30:1:1的比例配制而成。产物数据表征:黄褐色液体,78%的产率。产物的核磁图谱如图1和2所示,1H NMR(400MHz,CDCl3)δ7.23(d,J=8.6Hz,1H),7.11(t,J=8.0Hz,1H),7.03–6.97(m,1H),6.94(t,J=7.6Hz,1H),6.89(d,J=7.7Hz,1H),6.82(d,J=7.9Hz,1H),6.77(d,J=7.3Hz,1H),4.49–4.38(m,4H),2.33(s,6H),1.45–1.40(m,6H).13C NMR(101MHz,CDCl3)δ168.6,167.7,150.6,138.6,137.1,131.2,130.2,129.1,128.4,127.7,125.8,125.7,125.0,123.9,123.6,120.1,119.6,117.1,116.8,115.2,61.1,61.0,19.0,14.4,14.3,13.2.HRMS:[M+H]+calculated forC26H24NO5 +:430.1649,found:430.1635.
实施例2
在氮气条件下,将3-芳基苯并噁嗪化合物1b(0.20mmol),重氮化合物2a(0.44mmol),[Cp*RhCl2]2(4mol%),AgSbF6(16mol%),MesCOOH(0.4mmol)和溶剂DCE(2.0mL)加入到10mL密封管中,在80度的反应模块中反应10h,反应结束后减压除去溶剂,用硅胶柱分离得到目标产物7-溴-5,12-二甲基异喹啉[2,1,8-mna]吩恶嗪-4,13-二羧酸二乙酯(3ba),所有洗脱剂为石油醚乙酸乙酯和二氯甲烷按30:1:1的比例配制而成。产物数据表征:黄褐色固体,98%的产率,熔程:119-120℃。产物的核磁图谱如图3和4所示,1H NMR(400MHz,CDCl3)δ7.26(t,J=8.3Hz,2H),7.14(t,J=8.0Hz,1H),6.86(t,J=8.0Hz,1H),6.79(dd,J=7.5,4.6Hz,2H),4.49–4.39(m,4H),2.44(s,3H),2.33(s,3H),1.45–1.40(m,6H).13C NMR(101MHz,CDCl3)δ168.6,167.6,147.7,138.0,137.1,132.0,131.0,129.2,128.8,128.7,128.0,126.3,124.7,124.6,124.0,120.6,118.5,117.6,115.7,111.2,61.3,61.2,19.0,14.4,14.4,13.5.HRMS:[M+H]+calculated for C26H23BrNO5 +:508.0754,found:508.0717.
实施例3
在氮气条件下,将3-芳基苯并噁嗪化合物1c(0.20mmol),重氮化合物2a(0.44mmol),[Cp*RhCl2]2(4mol%),AgSbF6(16mol%),MesCOOH(0.4mmol)和溶剂DCE(2.0mL)加入到10mL密封管中,在80度的反应模块中反应10h,反应结束后减压除去溶剂,用硅胶柱分离得到目标产物8-氟-5,12-二甲基异喹啉[2,1,8-mna]吩恶嗪-4,13-二羧酸二乙酯(3ca),所有洗脱剂为石油醚乙酸乙酯和二氯甲烷按30:1:1的比例配制而成。产物数据表征:黄色固体,89%的产率,熔程:104-105℃。产物的核磁图谱如图5和6所示,1H NMR(400MHz,CDCl3)δ7.26(t,J=8.3Hz,2H),7.14(t,J=8.0Hz,1H),6.86(t,J=8.0Hz,1H),6.79(dd,J=7.5,4.6Hz,2H),4.49–4.39(m,4H),2.44(s,3H),2.33(s,3H),1.45–1.40(m,6H).13C NMR(101MHz,CDCl3)δ168.6,167.6,147.7,138.0,137.1,132.0,131.0,129.2,128.8,128.7,128.0,126.3,124.7,124.6,124.0,120.6,118.5,117.6,115.7,111.2,61.3,61.2,19.0,14.4,14.4,13.5.HRMS:[M+Na]+calculated for C26H22FNNaO5 +:470.1374,found:470.1371.
实施例4
在氮气条件下,将3-芳基苯并噁嗪化合物1d(0.20mmol),重氮化合物2a(0.44mmol),[Cp*RhCl2]2(4mol%),AgSbF6(16mol%),MesCOOH(0.4mmol)和溶剂DCE(2.0mL)加入到10mL密封管中,在80度的反应模块中反应10h,反应结束后减压除去溶剂,用硅胶柱分离得到目标产物8-氯-5,12-二甲基异喹啉[2,1,8-mna]吩恶嗪-4,13-二羧酸二乙酯(3da),所有洗脱剂为石油醚乙酸乙酯和二氯甲烷按30:1:1的比例配制而成。产物数据表征:黄褐色固体,82%的产率,熔程:127-128℃。产物的核磁图谱如图7和8所示,1H NMR(400MHz,CDCl3)δ7.21(d,J=8.6Hz,1H),7.15–7.06(m,1H),6.98–6.89(m,2H),6.74(t,J=7.6Hz,2H),4.46–4.36(m,4H),2.30(s,3H),2.29(s,3H),1.43-1.38(m,6H).13C NMR(101MHz,CDCl3)13C NMR(101MHz,CDCl3)δ168.6,167.7,151.2,138.0,136.8,131.1,130.9,129.2,128.9,128.6,128.0,125.9,124.9,124.0,123.9,120.4,119.9,117.7,117.3,115.6,61.4,61.2,19.0,14.5,14.4,13.3.HRMS:[M+H]+calculated for C26H23ClNO5 +:464.1259,found:464.1244.
实施例5
在氮气条件下,将3-芳基苯并噁嗪化合物1e(0.20mmol),重氮化合物2a(0.44mmol),[Cp*RhCl2]2(4mol%),AgSbF6(16mol%),MesCOOH(0.4mmol)和溶剂DCE(2.0mL)加入到10mL密封管中,在80度的反应模块中反应10h,反应结束后减压除去溶剂,用硅胶柱分离得到目标产物8-溴-5,12-二甲基异喹啉[2,1,8-mna]吩恶嗪-4,13-二羧酸二乙酯(3ea),所有洗脱剂为石油醚乙酸乙酯和二氯甲烷按30:1:1的比例配制而成。产物数据表征:黄色固体,89%的产率,熔程:144-145℃。产物的核磁图谱如图9和10所示,1H NMR(400MHz,CDCl3)δ7.20(d,J=8.6Hz,1H),7.13–7.00(m,3H),6.74(d,J=7.2Hz,1H),6.64(d,J=8.4Hz,1H),4.46–4.35(m,4H),2.28(s,3H),2.27(s,3H),1.40(td,J=7.1,5.2Hz,6H).13C NMR(101MHz,CDCl3)δ168.5,167.6,151.2,137.9,136.8,130.8,129.6,128.8,128.5,127.9,126.9,125.8,124.8,123.9,120.4,120.4,120.2,118.3,117.3,115.6,61.3,61.2,18.9,14.4,14.4,13.2.HRMS:[M+Na]+calculated for C26H22BrNNaO5 +=530.0574,found:530.0564.
实施例6
在氮气条件下,将3-芳基苯并噁嗪化合物1f(0.20mmol),重氮化合物2a(0.44mmol),[Cp*RhCl2]2(4mol%),AgSbF6(16mol%),MesCOOH(0.4mmol)和溶剂DCE(2.0mL)加入到10mL密封管中,在80度的反应模块中反应10h,反应结束后减压除去溶剂,用硅胶柱分离得到目标产物8-甲基-5,12-二甲基异喹啉[2,1,8-mna]吩恶嗪-4,13-二羧酸二乙酯(3fa),所有洗脱剂为石油醚乙酸乙酯和二氯甲烷按30:1:1的比例配制而成。产物数据表征:黄色固体,77%的产率,熔程:100-101℃。产物的核磁图谱如图11和12所示,1H NMR(400MHz,CDCl3)δ7.18(d,J=8.6Hz,1H),7.08(t,J=8.0Hz,1H),6.78–6.68(m,4H),4.48–4.34(m,4H),2.31(s,3H),2.31(s,3H),2.26(s,3H),1.40(td,J=7.1,3.7Hz,6H).13C NMR(101MHz,CDCl3)δ168.8,168.0,150.6,139.0,137.1,136.1,131.4,129.3,128.4,127.8,127.5,125.9,125.1,124.4,123.4,120.0,119.4,117.9,116.2,115.1,61.2,61.0,20.7,19.2,14.5,14.4,13.3.HRMS:[M+Na]+calculated for C27H25NNaO5 +=466.1625,found:466.1617.
实施例7
在氮气条件下,将3-芳基苯并噁嗪化合物1g(0.20mmol),重氮化合物2a(0.44mmol),[Cp*RhCl2]2(4mol%),AgSbF6(16mol%),MesCOOH(0.4mmol)和溶剂DCE(2.0mL)加入到10mL密封管中,在80度的反应模块中反应10h,反应结束后减压除去溶剂,用硅胶柱分离得到目标产物9-溴-5,12-二甲基异喹啉[2,1,8-mna]吩恶嗪-4,13-二羧酸二乙酯(3ga),所有洗脱剂为石油醚乙酸乙酯和二氯甲烷按30:1:1的比例配制而成。产物数据表征:黄色固体,91%的产率,熔程:132-133℃。产物的核磁图谱如图13和14所示,1H NMR(400MHz,CDCl3)δ7.21(d,J=8.6Hz,1H),7.13–7.08(m,2H),6.94(d,J=1.6Hz,1H),6.77–6.74(m,2H),4.45–4.37(m,4H),2.31(s,3H),2.30(s,3H),1.43–1.39(m,6H).13C NMR(101MHz,CDCl3)δ168.6,167.6,149.8,137.6,137.1,131.8,130.7,128.7,128.4,128.4,128.0,125.9,124.8,124.2,122.3,120.6,118.3,117.9,116.3,115.8,61.4,61.3,18.9,14.5,14.4,13.3.HRMS:[M+H]+calculated for C26H23BrNO5 +=508.0754,found:508.0747.
实施例8
在氮气条件下,将3-芳基苯并噁嗪化合物1h(0.20mmol),重氮化合物2a(0.44mmol),[Cp*RhCl2]2(4mol%),AgSbF6(16mol%),MesCOOH(0.4mmol)和溶剂DCE(2.0mL)加入到10mL密封管中,在80度的反应模块中反应10h,反应结束后减压除去溶剂,用硅胶柱分离得到目标产物9-甲氧基-5,12-二甲基异喹啉[2,1,8-mna]吩恶嗪-4,13-二羧酸二乙酯(3ha),所有洗脱剂为石油醚乙酸乙酯和二氯甲烷按30:1:1的比例配制而成。产物数据表征:黄色固体,53%的产率,熔程:162-163℃。产物的核磁图谱如图15和16所示,1H NMR(400MHz,CDCl3)δ7.20(d,J=8.3Hz,1H),7.14–7.04(m,1H),6.80(d,J=8.8Hz,1H),6.74(d,J=7.0Hz,1H),6.52(dd,J=8.8,2.6Hz,1H),6.39(d,J=2.7Hz,1H),4.46–4.36(m,4H),2.34(s,3H),2.31(s,3H),1.42–1.38(m,6H).13C NMR(101MHz,CDCl3)δ168.7,167.8,156.2,144.2,138.4,137.6,131.0,130.9,128.9,128.2,127.6,125.9,125.0,123.7,120.3,117.0,115.3,109.4,106.6,61.2,61.1,55.9,19.2,14.4,14.4,13.3.HRMS:[M+H]+calculated for C27H26NO6 +=460.1755,found:460.1753.
实施例9
在氮气条件下,将3-芳基苯并噁嗪化合物1i(0.20mmol),重氮化合物2a(0.44mmol),[Cp*RhCl2]2(4mol%),AgSbF6(16mol%),MesCOOH(0.4mmol)和溶剂DCE(2.0mL)加入到10mL密封管中,在80度的反应模块中反应10h,反应结束后减压除去溶剂,用硅胶柱分离得到目标产物2-氟-5,12-二甲基异喹啉[2,1,8-mna]吩恶嗪-4,13-二羧酸二乙酯(3ia),所有洗脱剂为石油醚乙酸乙酯和二氯甲烷按30:1:1的比例配制而成。产物数据表征:黄色固体,82%的产率,熔程:162-163℃。产物的核磁图谱如图17和18所示,1H NMR(400MHz,CDCl3)δ7.07–7.03(m,1H),7.00–6.96(m,1H),6.92(dd,J=7.9,1.5Hz,1H),6.88(dd,J=11.4,2.0Hz,1H),6.85(dd,J=8.0,1.2Hz,1H),6.61(dd,J=10.2,2.0Hz,1H),4.46–4.37(m,4H),2.37(s,3H),2.32(s,3H),1.43–1.39(m,6H).13C NMR(101MHz,CDCl3)δ168.2,167.1,162.6(d,J=243.1Hz),150.7,140.8,136.6,131.9(d,J=11.2Hz),131.3,129.6,129.5,127.3,126.2,123.9,122.8(d,J=5.4Hz),122.2,120.0,117.3,115.5,105.4(d,J=29.2Hz),103.8(d,J=24.6Hz),61.2,61.2,19.4,14.4,14.3,13.4.HRMS:[M+H]+calculated for C26H23FNO5 +=448.1555,found:448.1539.
实施例10
在氮气条件下,将3-芳基苯并噁嗪化合物1j(0.20mmol),重氮化合物2a(0.44mmol),[Cp*RhCl2]2(4mol%),AgSbF6(16mol%),MesCOOH(0.4mmol)和溶剂DCE(2.0mL)加入到10mL密封管中,在80度的反应模块中反应10h,反应结束后减压除去溶剂,用硅胶柱分离得到目标产物2-溴-5,12-二甲基异喹啉[2,1,8-mna]吩恶嗪-4,13-二羧酸二乙酯(3ja),所有洗脱剂为石油醚乙酸乙酯和二氯甲烷按30:1:1的比例配制而成。产物数据表征:黄色固体,87%的产率,熔程:142-143℃。产物的核磁图谱如图19和20所示,1H NMR(400MHz,CDCl3)δ7.39d,J=1.5Hz,1H),7.10–7.05(m,1H),7.03–7.01(m,1H),6.94(dd,J=7.8,1.5Hz,1H),6.89–6.84(m,2H),4.49–4.39(m,4H),2.38(s,3H),2.34(s,3H),1.45–1.42(m,6H).13C NMR(101MHz,CDCl3)δ168.1,167.2,150.7,140.5,137.4,131.3,131.0,129.7,129.4,127.0,126.3,124.2,123.6,122.8,122.1,120.0,118.4,117.4,115.4,77.2,61.4,61.3,19.4,14.4,14.4,13.4.HRMS:[M+H]+calculated for C26H23BrNO5 +=508.0754,found:508.0742.
实施例11
在氮气条件下,将3-芳基苯并噁嗪化合物1k(0.20mmol),重氮化合物2a(0.44mmol),[Cp*RhCl2]2(4mol%),AgSbF6(16mol%),MesCOOH(0.4mmol)和溶剂DCE(2.0mL)加入到10mL密封管中,在80度的反应模块中反应10h,反应结束后减压除去溶剂,用硅胶柱分离得到目标产物2-甲氧基-5,12-二甲基异喹啉[2,1,8-mna]吩恶嗪-4,13-二羧酸二乙酯(3ka),所有洗脱剂为石油醚乙酸乙酯和二氯甲烷按30:1:1的比例配制而成。产物数据表征:红色固体,77%的产率,熔程:172-173℃。产物的核磁图谱如图21和22所示,1H NMR(400MHz,CDCl3)δ7.52(s,1H),7.08(t,J=7.7Hz,1H),7.03–6.99(m,1H),6.95–6.93(m,2H),6.88–6.86(d,J=7.4Hz,1H),4.49(q,J=7.1Hz,1H),4.43(q,J=7.2Hz,1H),2.39(s,3H),2.36(s,3H),1.45–1.41(m,6H).13C NMR(101MHz,CDCl3)δ167.9,167.2,150.5,140.9,138.7,131.1,130.7,129.7(q,J=31.8Hz),129.5,127.3,126.3,126.2,124.7,124.3,124.2(q,J=272.7Hz),120.0,117.7(dd,J=9.2),117.7(d,J=4.7Hz),117.4,115.7,110.8(d,J=3.2Hz).61.5,61.3,19.5,14.3,14.3,13.3.HRMS:[M+H]+calculated forC27H23F3NO5 +=498.1523,found:498.1508.
实施例12
在氮气条件下,将3-芳基苯并噁嗪化合物1a(0.20mmol),重氮化合物2b(0.44mmol),[Cp*RhCl2]2(4mol%),AgSbF6(16mol%),MesCOOH(0.4mmol)和溶剂DCE(2.0mL)加入到10mL密封管中,在80度的反应模块中反应10h,反应结束后减压除去溶剂,用硅胶柱分离得到目标产物5,12-二甲基异喹啉[2,1,8-mna]吩恶嗪-4,13-二羧酸二戊酯(3ab),所有洗脱剂为石油醚乙酸乙酯和二氯甲烷按30:1:1的比例配制而成。产物数据表征:黄色液体,96%的产率。产物的核磁图谱如图23和24所示,1H NMR(400MHz,CDCl3)δ7.23–7.15(m,1H),7.09(t,J=7.9Hz,1H),7.03(t,J=7.4Hz,1H),6.99–6.95(m,1H),6.91(dd,J=7.7,1.6Hz,1H),6.84(d,J=7.7Hz,1H),6.79–6.67(m,1H),4.36(t,J=6.7Hz,3H),4.31(t,J=6.8Hz,3H),2.32(s,3H),2.31(s,3H),1.80–1.73(m,4H),1.43–1.36(m,8H),0.95–0.90(m,6H).13C NMR(101MHz,CDCl3)δ168.9,168.0,150.7,138.6,137.2,131.3,130.3,129.2,128.4,127.8,125.9,125.8,125.1,124.0,123.7,120.2,119.7,117.2,116.9,115.3,65.4,65.3,28.5,28.4,28.3,28.3,22.4,22.4,19.1,14.1,14.1,13.3.HRMS:[M+H]+calculated for C32H36NO5 +=514.2588,found:514.2577.
实施例13
在氮气条件下,将3-芳基苯并噁嗪化合物1a(0.20mmol),重氮化合物2c(0.44mmol),[Cp*RhCl2]2(4mol%),AgSbF6(16mol%),MesCOOH(0.4mmol)和溶剂DCE(2.0mL)加入到10mL密封管中,在80度的反应模块中反应10h,反应结束后减压除去溶剂,用硅胶柱分离得到目标产物5,12-二甲基异喹啉[2,1,8-mna]吩恶嗪-4,13-二羧酸二异丙酯(3ac),所有洗脱剂为石油醚乙酸乙酯和二氯甲烷按30:1:1的比例配制而成。产物数据表征:红色液体,80%的产率。产物的核磁图谱如图25和26所示,1H NMR(400MHz,CDCl3)δ7.24(d,J=23.1Hz,1H),7.16–7.07(m,1H),7.02–6.89(m,3H),6.84–6.80(m,1H),6.75–6.70(m,1H),5.39–5.28(m,2H),2.33(s,6H),1.44–1.36(m,12H).13C NMR(101MHz,CD Cl3)δ168.1,167.2,150.5,137.9,137.1,131.1,130.2,129.1,128.2,127.7,125.6,125.4,125.0,123.9,119.9,119.5,117.1,114.9,68.8,68.7,22.0,21.9,18.9,13.1.HRMS:[M+H]+calculated for C28H28NO5 +=458.1962,found:458.1943.
实施例14
在氮气条件下,将3-芳基苯并噁嗪化合物1a(0.20mmol),重氮化合物2d(0.44mmol),[Cp*RhCl2]2(4mol%),AgSbF6(16mol%),MesCOOH(0.4mmol)和溶剂DCE(2.0mL)加入到10mL密封管中,在80度的反应模块中反应10h,反应结束后减压除去溶剂,用硅胶柱分离得到目标产物5,12-二乙基异喹啉[2,1,8-mna]吩恶嗪-4,13-二羧酸二甲酯(3ad),所有洗脱剂为石油醚乙酸乙酯和二氯甲烷按30:1:1的比例配制而成。产物数据表征:黄色液体,60%的产率。产物的核磁图谱如图27和28所示,1H NMR(400MHz,CDCl3)δ7.17(t,J=8.5Hz,1H),7.13–7.08(m,1H),7.07–7.03(m,1H),7.01–6.95(m,1H),6.94–6.88(m,2H),6.70(d,J=7.1Hz,1H),3.94(s,3H),3.91(s,3H),2.81–2.74(m,2H),2.69(dd,J=8.7,6.8Hz,2H),1.71–1.52(m,4H),0.99(t,J=7.4Hz,3H),0.94(t,J=7.3Hz,3H).13C NMR(101MHz,CDCl3)δ169.3,168.5,150.7,142.8,137.4,132.2,131.6,130.9,129.0,128.5,127.8,125.7,124.9,124.1,123.1,120.8,119.3,118.2,117.3,115.6,52.2,52.2,32.4,30.2,23.9,22.8,14.5,13.9.HRMS:[M+H]+calculated for C28H28NO5 +=458.1962,found:458.1949.
实施例15
在氮气条件下,将3-芳基苯并噁嗪化合物1a(0.20mmol),重氮化合物2e(0.44mmol),[Cp*RhCl2]2(4mol%),AgSbF6(16mol%),MesCOOH(0.4mmol)和溶剂DCE(2.0mL)加入到10mL密封管中,在80度的反应模块中反应10h,反应结束后减压除去溶剂,用硅胶柱分离得到目标产物5,12-二丙基异喹啉[2,1,8-mna]吩恶嗪-4,13-二羧酸二甲酯(3ae),所有洗脱剂为石油醚乙酸乙酯和二氯甲烷按30:1:1的比例配制而成。产物数据表征:黄色液体,63%的产率。产物的核磁图谱如图29和30所示,1H NMR(400MHz,CDCl3)δ7.19(dd,J=8.6,0.7Hz,1H),7.13–7.09(m,1H),7.07–7.03(m,1H),7.00–6.96(m,1H),6.93(dd,J=7.8,1.5Hz,0H),6.90(dd,J=7.9,1.4Hz,1H),6.70(dd,J=7.2,0.7Hz,1H),3.94(s,3H),3.91(s,3H),2.82–2.79(m,2H),2.76–2.65(m,2H),1.65–1.51(m,4H),1.48–1.39(m,2H),1.37–1.32(m,2H),0.96(t,J=7.3Hz,3H),0.85(t,J=7.3Hz,3H).13C NMR(101MHz,CDCl3)δ169.3,168.5,150.7,143.1,137.4,132.2,131.6,131.2,129.1,128.5,127.7,125.7,124.8,124.1,123.0,120.7,119.3,118.1,117.2,115.5,52.2,52.1,32.7,31.5,30.1,27.9,23.0,22.4,14.1,13.8.HRMS:[M+H]+calculated for C30H32NO5 +=486.2275,found:486.2266.
对实施例所合成的3aa,3ja,3ia,3fa以及3ea等五种化合物进行了光谱性质研究,其结构如下式所示:测试了液体状态下的紫外-可见吸收光谱和荧光发射光谱以及固态下的荧光发射光谱,首先在二氯甲烷溶液中对其紫外-可见光谱进行了测定(图32),溶液浓度为10-5mmol/mL。五种化合物对250-600nm的光均具一定的吸收,最大吸收波长出现在410nm,摩尔吸光系数为4.0×105L·mol-1·cm-1-1.2×106L·mol-1·cm-1之间。此外,也在溶液状态下测试了上述五种化合物的荧光发射光谱,化合物3ea的最大发射波长出现在505nm,化合物3aa,3ia和3fa在同等条件下则是出现了一定程度的红移(图33),五种化合物均表现出比较好的荧光光学性质,并且谱图峰型对称,荧光性质稳定,可以作为荧光探针。也测试了上述五种化合物的固态荧光发射光谱(图34),不难看出,在固态下,五种化合物的发射光谱均发生了不同程度的红移,表明3aa,3ja,3ia,3fa以及3ea有较好的光稳定性,具有应用于生物系统的潜在价值。综上所述,所开发的氮、氧杂稠环芳烃及其衍生物由于其分子中存在较大的共轭体系,具有优良的非线性光学性能,良好的生物活性和热稳定性使其在生物成像、荧光探针以及光电功能材料领域具有较好的的应用价值,为新型非线性光学材料的开发和应用研究奠定了坚实的理论基础和实践基础。
随后,用化合物3fa追踪了活细胞中外源HSO3 -和六氯环己烷之间的相互作用。对于生物学应用,探针应尽量减少对活细胞正常功能的影响。在化合物3fa和泡桐根细胞共培养3天的过程中,细胞生长良好,没有发现细胞死亡或活性下降。因此,化合物3fa可以用于植物细胞系统的细胞成像。上述研究表明,化合物3fa对溶液体系中的HSO3 -具有突出的识别能力,并且在添加六氯环己烷的情况下具有足够的特异性可逆性。随后,我们试图证实在复杂的活细胞中对HSO3 -的识别性能以及对六氯环己烷的可逆性。如图35A所示,在正常泡桐根细胞中没有荧光背景。用10μM的3fa溶液处理并在室温下孵育2小时后,根细胞呈现出强烈的近红外荧光(图35B)。这表明3fa可以有效地进入根细胞并产生良好的生物成像。为了揭示其在细胞中的位置积累,用Mito Tracker Green对细胞进行染色,这是一种市售的线粒体指示剂。由于3fa的正电性,它也位于与Mito Tracker Green相同的位置(图35C)。绿色和红色通道的合并图像显示红色和绿色荧光信号之间有很好的重叠绿色。因此,这些结果证实了其对线粒体的准确定位能力。然而,在加入2.0当量的NaHSO3溶液(20μM)后,近红外荧光迅速消失,表明HSO3 -破坏了3fa的π-共轭体系(图35D)。在与100μM六氯环己烷孵育30分钟后,记录近红外荧光(图35E)。同样,在加入六氯环己烷并用紫外线(365nm)照射2分钟后,荧光可以充分且快速恢复(图35F)。
以上所述仅为本发明的较佳实施例而已,并不用以限制本发明,凡在本发明的精神和原则之内,所作的任何修改、等同替换、改进等,均应包含在本发明的保护范围之内。
Claims (10)
1.一种氮、氧杂稠环芳烃,其特征在于,结构式如下所示:
其中R为H、Me、OMe、F、Cl或Br其中任意一种;R1为Me、n-Pr或Ph其中任意一种;R2为n-Am或iPr;Ar为Me、OMe、F、Cl,Br、Ph或CF3任意一种取代的苯环。
2.权利要求1所述氮、氧杂稠环芳烃的合成方法,其特征在于,包括以下步骤:惰性氛围下将噁嗪类化合物1、重氮化合物2、催化剂、添加剂加入到溶剂当中并进行反应,反应结束后得到杂稠环芳烃化合物3,反应方程式为:
其中R为H、Me、OMe、F、Cl或Br其中任意一种;R1为Me、n-Pr或Ph其中任意一种;R2为n-Am或iPr;Ar为Me、OMe、F、Cl,Br、Ph或CF3任意一种取代的苯环。
3.根据权利要求2所述的氮、氧杂稠环芳烃的合成方法,其特征在于:所述反应的过程中反应温度为80-120℃,反应时间为到6-12h。
4.根据权利要求2或3所述的氮、氧杂稠环芳烃的合成方法,其特征在于:所述催化剂包括铑催化剂和银盐;铑催化剂和银盐的摩尔比为1:4;所述铑催化剂为二氯(五甲基环戊二烯基)合铑二聚体、五甲基环戊二烯基醋酸铑或二(六氟锑酸)三乙腈(五甲基环戊二烯基)铑其中任意一种或组合;银盐为六氟锑酸银、四氟硼酸银、双三氟甲烷磺酰亚胺银、三氟甲烷磺酸银、硫酸银、醋酸银、三氟醋酸银其中任意一种或组合。
5.根据权利要求4所述的氮、氧杂稠环芳烃的合成方法,其特征在于:所述催化剂由二氯(五甲基环戊二烯基)合铑二聚体和六氟锑酸银组成;二氯(五甲基环戊二烯基)合铑二聚体与六氟锑酸银的摩尔比为1:4。
6.根据权利要求5所述的氮、氧杂稠环芳烃的合成方法,其特征在于:所述添加剂为2,4,6-三甲基苯甲酸、特戊酸、醋酸、1-金刚烷甲酸、醋酸锌、碳酸钠、醋酸钾或碳酸钾其中任意一种或组合。
7.根据权利要求6所述的氮、氧杂稠环芳烃的合成方法,其特征在于:所述溶剂为二氯乙烷、甲醇、乙腈、1,4-二氧六环或甲苯其中任意一种或组合。
8.根据权利要求5-7任意一项所述的氮、氧杂稠环芳烃的合成方法,其特征在于:所述惰性氛围为氮气氛围。
9.根据权利要求8所述的氮、氧杂稠环芳烃的合成方法,其特征在于:所述噁嗪类化合物1、重氮化合物2、催化剂、添加剂和溶剂的摩尔比为:1:(2-3):(0.02-0.04):(0.08-0.16);所述溶剂当中反应体系的浓度为0.05M-0.2M。
10.权利要求1所述的氮、氧杂稠环芳烃作为荧光探针的应用。
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