CN106632063B - Compound I and compound II based on phenanthro- imidazoles and its preparation method and application - Google Patents
Compound I and compound II based on phenanthro- imidazoles and its preparation method and application Download PDFInfo
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- CN106632063B CN106632063B CN201510730596.5A CN201510730596A CN106632063B CN 106632063 B CN106632063 B CN 106632063B CN 201510730596 A CN201510730596 A CN 201510730596A CN 106632063 B CN106632063 B CN 106632063B
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- carboxylic acid
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- naphthalene
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- 150000001875 compounds Chemical class 0.000 title claims abstract description 45
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- HTSGKJQDMSTCGS-UHFFFAOYSA-N 1,4-bis(4-chlorophenyl)-2-(4-methylphenyl)sulfonylbutane-1,4-dione Chemical compound C1=CC(C)=CC=C1S(=O)(=O)C(C(=O)C=1C=CC(Cl)=CC=1)CC(=O)C1=CC=C(Cl)C=C1 HTSGKJQDMSTCGS-UHFFFAOYSA-N 0.000 title abstract 3
- 239000000523 sample Substances 0.000 claims abstract description 20
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Natural products CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 39
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 28
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 27
- UFWIBTONFRDIAS-UHFFFAOYSA-N naphthalene-acid Natural products C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 claims description 27
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 18
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 16
- 238000006243 chemical reaction Methods 0.000 claims description 15
- 229910052736 halogen Inorganic materials 0.000 claims description 14
- 150000002367 halogens Chemical class 0.000 claims description 14
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 14
- ALYNCZNDIQEVRV-UHFFFAOYSA-N 4-aminobenzoic acid Chemical compound NC1=CC=C(C(O)=O)C=C1 ALYNCZNDIQEVRV-UHFFFAOYSA-N 0.000 claims description 11
- USFZMSVCRYTOJT-UHFFFAOYSA-N Ammonium acetate Chemical compound N.CC(O)=O USFZMSVCRYTOJT-UHFFFAOYSA-N 0.000 claims description 11
- 239000005695 Ammonium acetate Substances 0.000 claims description 11
- 229910052739 hydrogen Inorganic materials 0.000 claims description 11
- 239000001257 hydrogen Substances 0.000 claims description 11
- 239000003960 organic solvent Substances 0.000 claims description 9
- JLZUZNKTTIRERF-UHFFFAOYSA-N tetraphenylethylene Chemical group C1=CC=CC=C1C(C=1C=CC=CC=1)=C(C=1C=CC=CC=1)C1=CC=CC=C1 JLZUZNKTTIRERF-UHFFFAOYSA-N 0.000 claims description 9
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 7
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 7
- MKYQPGPNVYRMHI-UHFFFAOYSA-N Triphenylethylene Chemical group C=1C=CC=CC=1C=C(C=1C=CC=CC=1)C1=CC=CC=C1 MKYQPGPNVYRMHI-UHFFFAOYSA-N 0.000 claims description 7
- 229960004050 aminobenzoic acid Drugs 0.000 claims description 7
- LMBFAGIMSUYTBN-MPZNNTNKSA-N teixobactin Chemical compound C([C@H](C(=O)N[C@@H]([C@@H](C)CC)C(=O)N[C@@H](CO)C(=O)N[C@H](CCC(N)=O)C(=O)N[C@H]([C@@H](C)CC)C(=O)N[C@@H]([C@@H](C)CC)C(=O)N[C@@H](CO)C(=O)N[C@H]1C(N[C@@H](C)C(=O)N[C@@H](C[C@@H]2NC(=N)NC2)C(=O)N[C@H](C(=O)O[C@H]1C)[C@@H](C)CC)=O)NC)C1=CC=CC=C1 LMBFAGIMSUYTBN-MPZNNTNKSA-N 0.000 claims description 7
- ZHNUHDYFZUAESO-UHFFFAOYSA-N Formamide Chemical compound NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 claims description 6
- 238000006467 substitution reaction Methods 0.000 claims description 6
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 5
- WGLQHUKCXBXUDV-UHFFFAOYSA-N 3-aminophthalic acid Chemical compound NC1=CC=CC(C(O)=O)=C1C(O)=O WGLQHUKCXBXUDV-UHFFFAOYSA-N 0.000 claims description 4
- MHABMANUFPZXEB-UHFFFAOYSA-N O-demethyl-aloesaponarin I Natural products O=C1C2=CC=CC(O)=C2C(=O)C2=C1C=C(O)C(C(O)=O)=C2C MHABMANUFPZXEB-UHFFFAOYSA-N 0.000 claims description 2
- 125000001624 naphthyl group Chemical group 0.000 claims 3
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 claims 2
- 125000000218 acetic acid group Chemical group C(C)(=O)* 0.000 claims 1
- 229940113088 dimethylacetamide Drugs 0.000 claims 1
- 150000001732 carboxylic acid derivatives Chemical group 0.000 abstract description 22
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 abstract description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 19
- 125000001424 substituent group Chemical group 0.000 abstract description 9
- 238000000034 method Methods 0.000 abstract description 7
- 230000036541 health Effects 0.000 abstract description 4
- 238000003384 imaging method Methods 0.000 abstract description 4
- KXDHJXZQYSOELW-UHFFFAOYSA-N Carbamic acid Chemical group NC(O)=O KXDHJXZQYSOELW-UHFFFAOYSA-N 0.000 abstract description 2
- 238000012544 monitoring process Methods 0.000 abstract description 2
- 238000006862 quantum yield reaction Methods 0.000 abstract description 2
- 239000000376 reactant Substances 0.000 abstract description 2
- 239000007787 solid Substances 0.000 abstract description 2
- 150000001735 carboxylic acids Chemical group 0.000 abstract 2
- -1 Pyrrole radicals Chemical class 0.000 description 41
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 30
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 description 16
- 125000003545 alkoxy group Chemical group 0.000 description 15
- 229960000583 acetic acid Drugs 0.000 description 14
- 125000003368 amide group Chemical group 0.000 description 13
- 210000004027 cell Anatomy 0.000 description 12
- KAESVJOAVNADME-UHFFFAOYSA-N 1H-pyrrole Natural products C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 description 11
- 125000002541 furyl group Chemical group 0.000 description 11
- 150000003214 pyranose derivatives Chemical class 0.000 description 11
- 125000004076 pyridyl group Chemical group 0.000 description 11
- 125000001544 thienyl group Chemical group 0.000 description 11
- 125000003944 tolyl group Chemical group 0.000 description 11
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 10
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 description 10
- 239000003205 fragrance Substances 0.000 description 10
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 9
- 125000000217 alkyl group Chemical group 0.000 description 9
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 9
- 239000002904 solvent Substances 0.000 description 9
- 230000015572 biosynthetic process Effects 0.000 description 8
- 229940043376 ammonium acetate Drugs 0.000 description 7
- 235000019257 ammonium acetate Nutrition 0.000 description 7
- YNPNZTXNASCQKK-UHFFFAOYSA-N phenanthrene Chemical group C1=CC=C2C3=CC=CC=C3C=CC2=C1 YNPNZTXNASCQKK-UHFFFAOYSA-N 0.000 description 7
- 125000005493 quinolyl group Chemical group 0.000 description 7
- 238000003786 synthesis reaction Methods 0.000 description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- 238000004043 dyeing Methods 0.000 description 6
- 238000001840 matrix-assisted laser desorption--ionisation time-of-flight mass spectrometry Methods 0.000 description 6
- 238000001953 recrystallisation Methods 0.000 description 6
- DRSHXJFUUPIBHX-UHFFFAOYSA-N COc1ccc(cc1)N1N=CC2C=NC(Nc3cc(OC)c(OC)c(OCCCN4CCN(C)CC4)c3)=NC12 Chemical compound COc1ccc(cc1)N1N=CC2C=NC(Nc3cc(OC)c(OC)c(OCCCN4CCN(C)CC4)c3)=NC12 DRSHXJFUUPIBHX-UHFFFAOYSA-N 0.000 description 5
- 150000001263 acyl chlorides Chemical group 0.000 description 5
- 125000003118 aryl group Chemical group 0.000 description 5
- 230000008859 change Effects 0.000 description 5
- 239000012362 glacial acetic acid Substances 0.000 description 5
- IAZDPXIOMUYVGZ-WFGJKAKNSA-N Dimethyl sulfoxide Chemical compound [2H]C([2H])([2H])S(=O)C([2H])([2H])[2H] IAZDPXIOMUYVGZ-WFGJKAKNSA-N 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 125000002843 carboxylic acid group Chemical group 0.000 description 4
- 238000004440 column chromatography Methods 0.000 description 4
- 238000001514 detection method Methods 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- 238000002189 fluorescence spectrum Methods 0.000 description 4
- 125000005843 halogen group Chemical group 0.000 description 4
- 150000002431 hydrogen Chemical class 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 238000011160 research Methods 0.000 description 4
- 238000000926 separation method Methods 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 238000005160 1H NMR spectroscopy Methods 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- 230000002776 aggregation Effects 0.000 description 3
- 238000004220 aggregation Methods 0.000 description 3
- 150000001299 aldehydes Chemical class 0.000 description 3
- 150000003934 aromatic aldehydes Chemical class 0.000 description 3
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 3
- 238000004587 chromatography analysis Methods 0.000 description 3
- OBISXEJSEGNNKL-UHFFFAOYSA-N dinitrogen-n-sulfide Chemical compound [N-]=[N+]=S OBISXEJSEGNNKL-UHFFFAOYSA-N 0.000 description 3
- 239000003814 drug Substances 0.000 description 3
- 235000019441 ethanol Nutrition 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- UJOBWOGCFQCDNV-UHFFFAOYSA-N 9H-carbazole Chemical compound C1=CC=C2C3=CC=CC=C3NC2=C1 UJOBWOGCFQCDNV-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 description 2
- 239000012930 cell culture fluid Substances 0.000 description 2
- 210000002421 cell wall Anatomy 0.000 description 2
- 210000000805 cytoplasm Anatomy 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 2
- 150000002460 imidazoles Chemical class 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 150000002475 indoles Chemical class 0.000 description 2
- 229910052740 iodine Inorganic materials 0.000 description 2
- AWJUIBRHMBBTKR-UHFFFAOYSA-N isoquinoline Chemical compound C1=NC=CC2=CC=CC=C21 AWJUIBRHMBBTKR-UHFFFAOYSA-N 0.000 description 2
- 238000004020 luminiscence type Methods 0.000 description 2
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000003068 molecular probe Substances 0.000 description 2
- 150000002790 naphthalenes Chemical class 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 description 2
- 239000002304 perfume Substances 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 210000001519 tissue Anatomy 0.000 description 2
- 230000000007 visual effect Effects 0.000 description 2
- SQAINHDHICKHLX-UHFFFAOYSA-N 1-naphthaldehyde Chemical compound C1=CC=C2C(C=O)=CC=CC2=C1 SQAINHDHICKHLX-UHFFFAOYSA-N 0.000 description 1
- PJKVFARRVXDXAD-UHFFFAOYSA-N 2-naphthaldehyde Chemical compound C1=CC=CC2=CC(C=O)=CC=C21 PJKVFARRVXDXAD-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- 241001597008 Nomeidae Species 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 150000001454 anthracenes Chemical class 0.000 description 1
- 229940045799 anthracyclines and related substance Drugs 0.000 description 1
- RWZYAGGXGHYGMB-UHFFFAOYSA-N anthranilic acid Chemical compound NC1=CC=CC=C1C(O)=O RWZYAGGXGHYGMB-UHFFFAOYSA-N 0.000 description 1
- 230000001093 anti-cancer Effects 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 230000001413 cellular effect Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- UKJLNMAFNRKWGR-UHFFFAOYSA-N cyclohexatrienamine Chemical group NC1=CC=C=C[CH]1 UKJLNMAFNRKWGR-UHFFFAOYSA-N 0.000 description 1
- 150000001991 dicarboxylic acids Chemical group 0.000 description 1
- 201000010099 disease Diseases 0.000 description 1
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 239000007850 fluorescent dye Substances 0.000 description 1
- 238000012632 fluorescent imaging Methods 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 150000002240 furans Chemical group 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 230000003760 hair shine Effects 0.000 description 1
- 230000026030 halogenation Effects 0.000 description 1
- 238000005658 halogenation reaction Methods 0.000 description 1
- 125000001072 heteroaryl group Chemical group 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 230000005291 magnetic effect Effects 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 210000005036 nerve Anatomy 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 description 1
- 230000007170 pathology Effects 0.000 description 1
- 150000007965 phenolic acids Chemical class 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 125000004309 pyranyl group Chemical class O1C(C=CC=C1)* 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 150000003233 pyrroles Chemical class 0.000 description 1
- 150000004053 quinones Chemical class 0.000 description 1
- 230000002285 radioactive effect Effects 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000010186 staining Methods 0.000 description 1
- 230000008685 targeting Effects 0.000 description 1
- 229930192474 thiophene Natural products 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D235/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, condensed with other rings
- C07D235/02—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, condensed with other rings condensed with carbocyclic rings or ring 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
-
- 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
- C09K2211/1003—Carbocyclic compounds
- C09K2211/1007—Non-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
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1003—Carbocyclic compounds
- C09K2211/1011—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
- 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
- C09K2211/1044—Heterocyclic compounds characterised by ligands containing two nitrogen atoms as heteroatoms
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Nitrogen Condensed Heterocyclic Rings (AREA)
- Plural Heterocyclic Compounds (AREA)
Abstract
The present invention relates to compound I and compound II and its preparation method and application to realize the adjusting to the luminescent color, efficiency of above compound by introducing different substituent structures at Ar；Effective containment compound loss of efficiency in the solid state realizes high fluorescence quantum yield under the conditions of its water system；By selecting different amino carboxylic acid structures as reactant, different carboxylic acid structures is introduced at N1 phenyl ring, and various carboxylic acid derivative structures are prepared by method appropriate, with molecule compatibility, the recognition capability etc. for improving above compound structure.Compound I and compound II is as a kind of novel probe structure, phenanthro- imidazolyl carboxylic acid and carboxylic acid derivates can freely pass in and out cell, and Selective recognition and imaging are carried out to specific structure, make it in biology, medical treatment, health and monitoring field, there is extremely wide application prospect.
Description
Technical field
The present invention relates to analysis and detection technique fields, more specifically to compound I and compound II and its preparation
Methods and applications.
Background technique
With the fast development of national economy and the continuous improvement of living standards of the people, the real-time prison of personal health
It surveys, the prevention and treatment of disease are increasingly becoming the livelihood issues that people focus more on.It is examined relative to traditional iii vitro chemical
The harmfulness of retardance and radioactive ray on-line checking, the online imaging technique of fluorescence with its efficiently, green, strong real-time advantage gradually
The visual field for gradually entering into people is widely used in cellular immunology, microbiology, molecular biology, science of heredity, nerve biology
The fields such as the scientific research of, pathology, oncology, Clinical laboratory medicine, medicine, botany etc. and the people's livelihood.
The key technology of fluorescent imaging technology is exactly selection of the fluorescent material as label probe (or coloring agent).Preferably
Probe molecule is by physically or chemically acting on, and specific adsorption is in specific cell and tissue, under low energy Optical irradation
Two dimension or three-dimensional imaging are realized, by the health condition for judging cell or tissue with fluorescence color, intensity and distribution situation.
Compared with common chemical staining, the sensitivity of fluorescent staining will be higher by 100-1000 times, and pass through functionalized modification appropriate
The on-line analysis to living body can be realized.
In general, fluorescence probe structure is made of the part 2-3, that is, the primitive that shines, link primitive (optional) and Recognition unit.Its
In, luminous primitive be mainly responsible for extraneous environmental stimulus (light, electric or magnetic effect) realize it is efficient shine, and then believed by the external world
The detection of number detection device becomes visual information；Recognition unit mainly plays identification to cell or intracorporal targeting target and makees
With to improve the stationkeeping ability of probe；The two is mainly chained up by link primitive, has luminous position and detected structure
There is stable corresponding relationship, guarantees the accuracy of detection process.In practical applications, it was prepared to simplify fluorescence probe structure
Journey and cost being reduced, the Recognition unit and luminescent core of fluorescence probe can also be served as by the same chemical structure in probe molecule,
But the luminescence mechanism and recognition reaction of this and compound have much relations, can neither interfere with each other, realize quick response again
With height differentiate, this by be fluorescence probe future development main flow direction.
Phenanthro- imidazoles is luminous efficiency with higher, excellent photo and thermal stability, opposite as a kind of advanced luminescent material
Balance carrier injection transmittability, present biggish application potential in field of light emitting materials；Meanwhile phenanthro- imidazoles
It is the precursor structure of a kind of anti-cancer type drug, illustrates it with certain molecular recognition and stationkeeping ability.Although above two excellent
The combination of gesture makes phenanthro- imidazoles meet the requirement that a kind of ideal fluorescence probe constructs primitive, but this kind of Gao Fang of phenanthro- imidazoles
The biocompatibility of fragrance condensed ring is poor, and identifies that stationkeeping ability is poor, can not also be applied as fluorescence probe, need to draw
Enter other groups its performance is adjusted.
Summary of the invention
The purpose of the present invention is to provide general structure be Formulas I and the compound of Formula II and its preparation method and application, i.e.,
Compound I and compound II and its preparation method and application, be specifically to provide a kind of carboxylic acid replaced based on phenanthro- imidazoles N1 and
Carboxylic acid derivates, solve phenanthro- glyoxaline compound in the prior art be not possible to realize asked as what fluorescence probe was applied
Topic.
The technical proposal for solving the technical problem of the invention is: a kind of compound of Formulas I has the following structure logical
Formula:
Wherein, Ar indicates aromatic group or its derivative structure, Ar be selected from phenyl, tolyl, naphthalene, furyl, thienyl,
Pyrrole radicals, pyridyl group, pyranose, quinolyl, indyl, carbazyl, anilino-, triphenylethylene, tetraphenylethylene and its phase
One of derivative structure answered；R is selected from hydroxyl, halogen, alkoxy, fragrance phenolic group, amido and aromatic amino and its accordingly
One of derivative；G1 and G2 respectively indicates any substituent group of any position on phenanthrene ring.
In the compound of formula I, G1 and G2 respectively indicate hydrogen.
The present invention also provides the preparation methods of the compound of above-mentioned Formulas I, include the following steps:
S1, by fragrant aldehyde derivativesPhenanthrenequione derivativeAmmonium acetate and aminobenzoic acidIt is heated to 80 DEG C -180 DEG C in organic solvent, reaction is cooled to room temperature after 1-24 hours, is filtered, is obtained
Wherein, Ar is selected from phenyl, tolyl, naphthalene, furyl, thienyl, pyrrole radicals, pyridyl group, pyranose, quinoline
One of base, indyl, carbazyl, anilino-, triphenylethylene, tetraphenylethylene and its corresponding derivative structure；G1 and
G2 respectively indicates any substituent group of any position on phenanthrene ring.
Further include step S2 after step S1:
S2, by what is be prepared in S1 stepIn hydroxyl carry out respectively it is corresponding replace it is anti-
Should obtain by R replace Formulas I compound, wherein R be selected from halogen, alkoxy, fragrance phenolic group, amido and aromatic amino and its
One of corresponding derivative.
In the preparation method of the compound of formula I, in step sl, it is preferably heated to 100 DEG C -120 DEG C；It is preferred that
Reaction is cooled to room temperature after 2-4 hours；The organic solvent is preferably selected from acetic acid, tetrahydrofuran, toluene, benzene, N, N- dimethyl
Any one or more in formamide, n,N-dimethylacetamide and N-Methyl pyrrolidone, most preferably acetic acid and acetic acid
With the mixed system of other solvents, i.e. acetic acid and tetrahydrofuran, toluene, benzene, n,N-Dimethylformamide, N, N- dimethylacetamide
The mixed system of any one or more in amine and N-Methyl pyrrolidone.
Further, it may also include step S3 between step S1 and step S2: S1 step obtainedFurther purification, recrystallization and column chromatography can be used, wherein the preferred tetrahydrofuran of recrystallization solvent,
Ethyl alcohol, toluene or n,N-Dimethylformamide, more preferable n,N-Dimethylformamide.
The present invention also provides the compounds of another Formula II, have the following structure general formula:
Wherein, Ar indicates aromatic group or its derivative structure, Ar be selected from phenyl, tolyl, naphthalene, furyl, thienyl,
Pyrrole radicals, pyridyl group, pyranose, quinolyl, indyl, carbazyl, anilino-, triphenylethylene, tetraphenylethylene and its phase
One of derivative structure answered；R and R1Respectively it is selected from hydroxyl, halogen, alkoxy, fragrance phenolic group, amido and fragrance
One of amido and its corresponding derivative；G1 and G2 respectively indicates any substituent group of any position on phenanthrene ring.
In the compound of Formula II of the invention, G1 and G2 respectively indicate hydrogen.
The present invention also provides the preparation methods of the compound of above-mentioned Formula II, include the following steps: Sa, derive aromatic aldehyde
ObjectPhenanthrenequione derivativeAmmonium acetate and amino phthalic acidIt heats in organic solvent
To 80 DEG C -180 DEG C, reaction is cooled to room temperature after 1-24 hours, is filtered, is obtained
Wherein, Ar is selected from phenyl, tolyl, naphthalene, furyl, thienyl, pyrrole radicals, pyridyl group, pyranose, quinoline
One of base, indyl, carbazyl, anilino-, triphenylethylene, tetraphenylethylene and its corresponding derivative structure；G1 and
G2 respectively indicates any substituent group of any position on phenanthrene ring.
Further include step Sb after step Sa in the preparation method of the compound of Formula II:
Sb, by what is be prepared in Sa stepIn two hydroxyls respectively carry out relatively
The substitution reaction answered obtains respectively by R and R1The compound of substituted Formula II, wherein R and R1Respectively it is selected from halogen, alcoxyl
One of base, fragrance phenolic group, amido and aromatic amino and its corresponding derivative.
In the preparation method of the compound of Formula II of the present invention, in step Sa, it is preferably heated to 100 DEG C -120 DEG C；It is excellent
Choosing reaction is cooled to room temperature after 2-4 hours；The organic solvent is preferably selected from acetic acid, tetrahydrofuran, toluene, benzene, N, N- diformazan
Any one or more in base formamide, n,N-dimethylacetamide and N-Methyl pyrrolidone, most preferably acetic acid and second
The sour mixed system with other solvents, i.e. acetic acid and tetrahydrofuran, toluene, benzene, n,N-Dimethylformamide, N, N- dimethyl second
The mixed system of any one or more in amide and N-Methyl pyrrolidone.
Further, it may also include step Sc between step Sa and step Sb: Sa step obtainedFurther purification, can be used recrystallization and column chromatography, wherein the preferred tetrahydro furan of recrystallization solvent
It mutters, ethyl alcohol, toluene or n,N-Dimethylformamide, more preferable n,N-Dimethylformamide.
The compound of above-mentioned Formulas I and Formula II is used to prepare the purposes of fluorescence probe respectively, is especially used to prepare biology
The purposes of fluorescence probe.
The compound and its preparation method and application for implementing Formulas I and Formula II of the invention, has the advantages that this hair
The compound of the bright Formulas I and Formula II substituent structure different by (C2 substituting group position) introducing at Ar, is realized to above-mentioned
The adjusting of the luminescent color, efficiency of compound；Emphasis is by introducing triphenylethylene or tetraphenylethylene primitive and its derivative
Structure, it is effective to contain compound loss of efficiency in the solid state, realize high fluorescence quantum yield under the conditions of its water system；Pass through
It selects different amino carboxylic acid structures as reactant, different carboxylic acid structures is introduced at N1 phenyl ring, and pass through side appropriate
Method prepares various carboxylic acid derivative structures, such as carboxylic acid halides, aromatic acid Arrcostab, aromatic acid aryl ester, aromatic acid alkylamide or aromatic acid aryl acyl
Amine etc., with molecule compatibility, the recognition capability etc. for improving above compound structure；Special attention will be given to is obtained by simple halogenation
The stable acyl chlorides structure of a kind of water system has been arrived, and has proved that intramolecular charge separation may be to stablize this class formation by crystal structure
Key factor；As a kind of novel probe structure, phenanthro- imidazolyl carboxylic acid and carboxylic acid derivates can for Formulas I and Formula II compound
Free disengaging cell, and Selective recognition and imaging are carried out to specific structure, make it in biology, medical treatment, health and monitoring neck
Domain has extremely wide application prospect.
Detailed description of the invention
Figure 1A is fluorescence spectrum relative intensity of fluorescence change curve of the TPE-PA under the different proportion of tetrahydrofuran and water
Figure；
Figure 1B is fluorescence spectrum relative intensity of fluorescence change curve of the TPE-PAC under the different proportion of tetrahydrofuran and water
Figure；
Fig. 2 is TPE-PAC pH value time history plot in water；
Fig. 3 A is photograph via bright field of the Hela cell of TPE-PAC dyeing under fluorescence microscope；
Fig. 3 B is fluorescence photo of the Hela cell of TPE-PAC dyeing under fluorescence microscope；
Fig. 4 is fluorescence spectrum change curve of the TPE-P2A under the different proportion of tetrahydrofuran and water；
Fig. 5 A is photograph via bright field of the Hela cell of TPE-P2A dyeing under fluorescence microscope；
Fig. 5 B is fluorescence photo of the Hela cell of TPE-P2A dyeing under fluorescence microscope.
Specific embodiment
With reference to the accompanying drawings and examples, the compound of the present invention I and compound II and its preparation method and application are made
It further illustrates:
One kind provided by the invention can be used as the Formulas I of novel fluorescence probe material and the compound of Formula II, i.e. compound I
With compound II, which is that phenanthro- imidazolyl carboxylic acid and carboxylic acid derivates structure, structure have following structure general formula:
For above structure with 9,10- phenanthro- imidazoles for nuclear structure, Ar indicates aromatic group or its derivative structure, is respectively selected from
Phenyl, tolyl, naphthalene, furyl, thienyl, pyrrole radicals, pyridyl group, pyranose, quinolyl, indyl, carbazyl, aniline
Base, triphenylethylene, tetraphenylethylene etc. and one of corresponding derivative structure.R and R1N1 in imidazoles is illustrated respectively in take
Substituent structure is linked for the carbonyl of any the position of substitution on phenyl ring, is respectively selected from hydroxyl, halogen, alkoxy or fragrant phenolic group
The carboxylic acid group derivative structure that group, amido and aromatic amino etc. are constructed.G1 and G2 indicates any substitution of any position on phenanthrene ring
Group.
Specific synthesis process:
(1)
It the reactions such as couples, replace and is condensed by various and obtain the derivant structure of aromatic aldehyde and phenanthrenequione.Aromatic aldehyde and phenanthrene
The derivative of quinone is existing compound, and synthesis process is the prior art, specific preparation process which is not described herein again.
(2)
Above-mentioned fragrant aldehyde derivatives, phenanthrenequione derivative, ammonium acetate and aminobenzoic acid (or amino phthalic acid) are used
" one kettle way " prepares important carboxylic acid structure in solvent appropriate and temperature.
Concrete operations: by fragrant aldehyde derivatives, phenanthrenequione derivative, ammonium acetate and aminobenzoic acid (or amino phthalic acid)
It is heated to proper temperature in organic solvent, is cooled to room temperature after reacting a period of time, carboxylic acid structure is obtained by filtration and (further mentions
It is pure to use recrystallization and column chromatography).Wherein, the preferred acetic acid of organic solvent, tetrahydrofuran, toluene, benzene, N, N- dimethyl formyl
Amine (DMF), n,N-dimethylacetamide (DMAC) and N-Methyl pyrrolidone (NMP) etc. or both, three mixed system, most
It is preferred that acetic acid and its mixed system with other solvents；Preferably 80 DEG C to 180 DEG C of temperature, wherein most preferably 100 DEG C to 120
℃；Reaction time preferably 1 hour to 24 hours, wherein most preferably 2 hours to 4 hours；Recrystallization solvent, preferably tetrahydrofuran,
Ethyl alcohol, toluene, DMF etc., most preferably DMF.
(3)
Above-mentioned carboxylic acid structure is used into corresponding method, respectively obtains substituted carboxylic acid halides, the aromatic acid alkane of phenanthro- imidazoles N1 phenyl ring
Base ester, aromatic acid aryl ester, aromatic acid alkylamide or aromatic acid aryl amide etc..It should be noted that its specific substitution reaction
The Cheng Junwei prior art, is no longer described in detail here.
Further, G1 and G2 respectively indicate hydrogen.
Further, Ar is any heteroaryl structure, substituent R and R1For hydroxyl, halogen, alkoxy or fragrance phenolic group,
When amido and aromatic amino and its derivative, preferred compound structure are as follows:
Wherein, one of X F, Cl, Br and I, R2-R5It is respectively hydrogen, alkyl, hydroxyl, alkoxy, nitro, cyanogen
Base, amino, sulfydryl, halogen atom etc. (further, wherein the carbon atom number of alkyl or alkoxy is 1~12), Ar ' and Ar "
Respectively it is selected from phenyl, tolyl, naphthalene, furyl, thienyl, pyrrole radicals, pyridyl group, pyranose, quinolyl, indoles
Base, carbazyl, anilino-, triphenylethylene, tetraphenylethylene etc. and one of corresponding derivative structure.
Further, Ar is restricted to phenyl ring or phenyl ring derivative, naphthalene nucleus or naphthalene derivative, anthracene nucleus or anthracycline derivatives
Substituent group, compound formula and preferred compound structure are as follows, and useIndicate N1 phenyl ring on by hydroxyl, halogen,
Carboxylic acid group derivative structure constructed by alkoxy or fragrance phenolic group, amido and aromatic amino etc.:
Wherein, A1-A9Respectively for hydrogen, alkyl, hydroxyl, alkoxy, nitro, cyano, amino, sulfydryl, halogen atom,
Phenyl, tolyl, naphthalene, furyl, thienyl, pyrrole radicals, pyridyl group, pyranose, quinolyl, indyl, carboxylic acid or carboxylic acid
(further, wherein the carbon of alkyl or alkoxy is former for one of derivative, carbazyl or anilino- and corresponding derivative structure
Subnumber is 1~12).
Further, Ar is restricted to triphenylethylene and triphenylethylene derivative, compound formula and preferredization
It is as follows to close object structure, and usesIt indicates on N1 phenyl ring by hydroxyl, halogen, alkoxy or fragrance phenolic group, amido and virtue
Carboxylic acid group derivative structure constructed by fragrant amido etc.:
Wherein, Ar " ' is selected from phenyl, tolyl, naphthalene, furyl, thienyl, pyrrole radicals, pyridyl group, pyranose, quinoline
The new virtue of either both any composition of base, indyl, carbazyl, anilino-, diazosulfide and corresponding derivative structure
One kind of perfume base group；B1-B15Respectively for hydrogen, alkyl, hydroxyl, alkoxy, nitro, cyano, amino, sulfydryl, halogen atom,
Phenyl, tolyl, naphthalene, furyl, thienyl, pyrrole radicals, pyridyl group, pyranose, quinolyl, indyl, carboxylic acid or carboxylic acid
One of derivative, carbazyl or anilino- or one of corresponding derivative etc. (further, wherein alkyl or alkoxy
Carbon atom number be 1~12).
Further, Ar is restricted to tetraphenylethylene and tetraphenylethylene derivative, compound formula and preferredization
It is as follows to close object structure, and usesIt indicates on N1 phenyl ring by hydroxyl, halogen, alkoxy or fragrance phenolic group, amido and virtue
Carboxylic acid group derivative structure constructed by fragrant amido etc.:
Wherein, Ar " ' is selected from phenyl, tolyl, naphthalene, furyl, thienyl, pyrrole radicals, pyridyl group, pyranose, quinoline
The new virtue of either both any composition of base, indyl, carbazyl, anilino-, diazosulfide and corresponding derivative structure
One kind of perfume base group；B1-B15Respectively for hydrogen, alkyl, hydroxyl, alkoxy, nitro, cyano, amino, sulfydryl, halogen atom,
Phenyl, tolyl, naphthalene, furyl, thienyl, pyrrole radicals, pyridyl group, pyranose, quinolyl, indyl, carboxylic acid or carboxylic acid
One of derivative, carbazyl or anilino- or one of corresponding derivative etc. (further, wherein alkyl or alkoxy
Carbon atom number be 1~12).
Further, Ar is furans, thiophene, pyrroles, pyridine, pyrans, quinoline (isoquinoline-containing), indoles, carbazole, aniline
Base, diazosulfide and its corresponding derivative structure, or one kind of both any new aromatic group formed, chemical combination
Object general formula and preferred compound structure are as follows, and useIt indicates on N1 phenyl ring by hydroxyl, halogen, alkoxy or fragrant phenol
Carboxylic acid group derivative structure constructed by group, amido and aromatic amino etc.:
In above-mentioned all structural formulas, wherein aryl and alkyl preferred structure can be selected from one of 29 kinds shown in following formula
Or hydrogen atom:
Embodiment 1: the synthesis of phenyl-phenanthro- imidazoles-N1- carboxylic acid and derivative
Appropriate benzaldehyde, phenanthrenequione, p-aminobenzoic acid and excessive ammonium acetate are reacted 3 hours for 120 DEG C in glacial acetic acid
After be cooled to room temperature, carboxylic acid derivates are obtained by filtration.The mixing for being dissolved in n,N-Dimethylformamide and thionyl chloride is molten
In agent, 80 DEG C of reactions, 4 hours back spins walk unreacted thionyl chloride.Excessive aniline is added to flow back 4 hours, chromatography post separation obtains
To target compound structure.1H NMR(DMSO,500MHz):δ:10.6(s,1H),8.96(d,1H),8.90(d,1H),8.70
(d,1H),8.21(d,2H),7.85(d,2H),7.79(t,1H),7.71(t,1H),7.60-7.56(m,5H),7.40-7.37
(m,7H),7.11(d,1H).MALDI-TOF(m/z):[M+]calcd.C34H23N3O,489.5659；found,490.59.
The synthesis of embodiment 2:1- naphthalene-phenanthro- imidazoles-N1- carboxylic acid and derivative
By appropriate 1- naphthaldehyde, phenanthrenequione, p-aminobenzoic acid and excessive ammonium acetate, 120 DEG C of reactions 3 are small in glacial acetic acid
When after be cooled to room temperature, carboxylic acid derivates are obtained by filtration.It is dissolved in the mixing of n,N-Dimethylformamide and thionyl chloride
In solvent, 80 DEG C of reactions, 4 hours back spins walk unreacted thionyl chloride.Excessive aniline is added to flow back 4 hours, chromatography post separation
Obtain target compound structure.1H NMR(500MHz,DMSO-d6)δ13.27(s,1H),9.02-8.97(m,1H),8.94(d,J
=8.3Hz, 1H), 8.67 (dd, J=7.9,1.4Hz, 1H), 8.02-7.93 (m, 4H), 7.91 (dd, J=8.2,1.4Hz,
1H), 7.83-7.65 (m, 5H), 7.61 (ddd, J=8.4,7.0,1.4Hz, 1H), 7.60-7.45 (m, 3H), 7.41 (ddd, J
=8.1,6.9,1.1Hz, 1H), 7.14 (dd, J=8.3,1.2Hz, 1H) .MALDI-TOF (m/z): [M+]
calcd.C38H25N3O,539.6246；found,540.77.
The synthesis of embodiment 3:2- naphthalene-phenanthro- imidazoles-N1- carboxylic acid and derivative
By appropriate 2- naphthaldehyde, phenanthrenequione, p-aminobenzoic acid and excessive ammonium acetate, 120 DEG C of reactions 3 are small in glacial acetic acid
When after be cooled to room temperature, carboxylic acid derivates are obtained by filtration.It is dissolved in the mixing of n,N-Dimethylformamide and thionyl chloride
In solvent, 80 DEG C of reactions, 4 hours back spins walk unreacted thionyl chloride.Excessive aniline is added to flow back 4 hours, chromatography post separation
Obtain target compound structure.1HNMR(500MHz,DMSO-d6) δ 10.36 (s, 1H), 8.98 (dd, J=28.1,8.4Hz,
2H), 8.67 (dd, J=8.0,1.4Hz, 1H), 8.04-7.90 (m, 5H), 7.83-7.69 (m, 7H), 7.66-7.49 (m, 4H),
7.43 (ddd, J=8.2,7.0,1.1Hz, 1H), 7.35 (t, J=7.9Hz, 2H), 7.18 (dd, J=8.4,1.2Hz, 1H),
7.11 (dd, J=8.0,6.7Hz, 1H) .MALDI-TOF (m/z): [M+] calcd.C38H25N3O,539.6246；found,
540.45.
Embodiment 4: the synthesis of tetraphenylethylene-phenanthro- imidazoles-N1- carboxylic acid and derivative
By appropriate tetraphenyl ethylene base formaldehyde, phenanthrenequione, p-aminobenzoic acid and excessive ammonium acetate in glacial acetic acid 120 DEG C it is anti-
It is cooled to room temperature, filters after answering 3 hours, column chromatographs to obtain carboxylic acid derivates TPE-PA.MALDI-TOF(m/z):[M+]
calcd.C48H32N2O2,668.7799；found,668.8732.Anal Calc.for C48H32N2O2:C,86.20；H,4.82；
N,4.19；O,4.78.Found:C,86.12；H,4.77；N,4.20；O,4.74.
TPE-PA is dissolved in the in the mixed solvent of n,N-Dimethylformamide (a small amount of) and thionyl chloride, 80 DEG C of reactions 4
Hour back spin walks unreacted thionyl chloride, with dry, the isolated chloride compounds of chromatographic column after water and methylene chloride extraction
Structure TPE-PAC.MALDI-TOF(m/z):[M+]calcd.C48H31ClN2O,687.2255；found,687.2345.Anal
Calc.for C48H31ClN2O:C,83.89；H,4.55；Cl,5.16；N,4.08；O,2.33Found:C,83.87；H,4.53；
N,4.09；O,2.32.
Aggregation-induced emission (AIE) property research of embodiment 5:TPE-PA and TPE-PAC
As shown in Figure 1A and 1B, fluorescence of the respectively TPE-PA and TPE-PAC under the different proportion of tetrahydrofuran and water
Spectrum relative intensity of fluorescence change curve, with the increase of water content, the fluorescence intensity of the two is obviously increased, and is had apparent poly-
Collect induced luminescence phenomenon, is a kind of potential fluorescent molecular probe.
Embodiment 6:TPE-PAC water system stability study
As shown in Fig. 2, for TPE-PAC, pH value changes over time curve in water.Under usual conditions, acyl chlorides in water can be fast
Speed is hydrolyzed to corresponding carboxylic acid and hydrogen chloride, and then loses high reactivity, but TPE-PAC is due to the particularity of imidazoles
Significant stability can be shown in water system condition.Under agitation, changed in 1500 minutes by pH value and estimate its point
Solution rate is only 25%, is acyl chlorides structure stable under a kind of water system.Moreover, the acyl chlorides structure can normally carry out extraction and column
Chromatography, shows the fluorescent molecular probe primitive under the conditions of it can be used as water system.
The experiment of embodiment 7:TPE-PAC cell dyeing
It after TPE-PAC is made into certain density DMSO solution, instills in cell culture fluid, selects Hela cell as grinding
Study carefully object, its polarity is observed using fluorescence microscope after cultivating a period of time, as shown in figs.3 a and 3b, discovery TPE-PAC can
Smoothly to penetrate cell wall, and what is oriented is enriched at cytoplasm, to show blue-fluorescence, illustrates such acyl chlorides structure
It can be used as fluorescence probe use under the conditions of water system.
Embodiment 8: tetraphenylethylene-phenanthro- imidazoles-N1- carboxylic acid derivates TPE-P2A synthesis
By appropriate tetraphenyl ethylene base formaldehyde, phenanthrenequione, p-aminophenyl diacid and excessive ammonium acetate in glacial acetic acid 120 DEG C it is anti-
It is cooled to room temperature, filters after answering 3 hours, column chromatographs to obtain carboxylic acid derivates TPE-P2A.MALDI-TOF(m/z):[M+]
calcd.C49H32N2O4,712.7894；found,712.7902.Anal Calc.for C49H32N2O4:C,82.57；H,4.53；
N,3.93；O,8.98.Found:C,82.48；H,4.45；N,3.9387；O,8.68.
Aggregation-induced emission (AIE) property research of embodiment 9:TPE-P2A
As shown in figure 4, be fluorescence spectrum change curve of the TPE-P2A under the different proportion of tetrahydrofuran and water, with
The fluorescence intensity of the increase of water content, the two obviously increases, and has apparent aggregation-induced emission phenomenon, can be used as a kind of glimmering
Optical molecule probe.
The experiment of embodiment 10:TPE-P2A cell dyeing
After TPE-P2A is made into certain concentration solution DMSO solution, instill cell culture fluid in, select Hela cell as
Research object observes its polarity using fluorescence microscope after cultivating a period of time, as shown in Figure 5 A and 5B, finds TPE-P2A
Cell wall can be smoothly penetrated, and what is oriented is enriched at cytoplasm, to show blue-fluorescence, illustrates such dicarboxylic acids
Structure has self-activation performance, can be used as fluorescence probe use.
It should be understood that for those of ordinary skills, it can be modified or changed according to the above description,
Within all these improvement or transformation should all belong to the protection domain of appended claims of the present invention.
Claims (8)
1. a kind of compound of Formulas I, has the following structure general formula:
Wherein, Ar is selected from naphthalene, triphenylethylene or tetraphenylethylene；R is selected fromOr one of halogen；G1 and
G2 respectively indicates hydrogen.
2. a kind of preparation method of the compound of Formulas I, which comprises the steps of:
S1, by fragrant aldehyde derivativesPhenanthrenequione derivativeAmmonium acetate and aminobenzoic acid?
80 DEG C -180 DEG C are heated in organic solvent, reaction is cooled to room temperature after 1-24 hours, is filtered, is obtained
Wherein, Ar is selected from naphthalene, triphenylethylene or tetraphenylethylene；G1 and G2 respectively indicate hydrogen.
3. the preparation method of compound according to claim 2, which is characterized in that further include step S2 after step S1:
S2, by what is be prepared in S1 stepIn hydroxyl carry out corresponding substitution reaction respectively and obtain
By the compound of the R Formulas I replaced, wherein R is selected fromOr one of halogen.
4. the preparation method of compound according to claim 2, which is characterized in that in step sl, be heated to 100 DEG C-
120℃；Reaction is cooled to room temperature after 2-4 hours；The organic solvent is selected from acetic acid, tetrahydrofuran, toluene, benzene, N, N- diformazan
Any one or more in base formamide, DMAC N,N' dimethyl acetamide and N-Methyl pyrrolidone.
5. a kind of compound of Formula II, has the following structure general formula:
Wherein, Ar indicates naphthalene, triphenylethylene or tetraphenylethylene；R and R1Respectively it is selected fromOr in halogen
One kind；G1 and G2 respectively indicate hydrogen.
6. a kind of preparation method of the compound of Formula II, which comprises the steps of:
Sa, by fragrant aldehyde derivativesPhenanthrenequione derivativeAmmonium acetate and amino phthalic acidIt is heated to 80 DEG C -180 DEG C in organic solvent, reaction is cooled to room temperature after 1-24 hours, is filtered, is obtained
Wherein, Ar is selected from naphthalene, triphenylethylene or tetraphenylethylene；G1 and G2 respectively indicate hydrogen.
7. the preparation method of compound according to claim 6, which is characterized in that further include step Sb after step Sa:
Sb, by what is be prepared in Sa stepIn two hydroxyls respectively carry out it is corresponding
Substitution reaction obtains respectively by R and R1The compound of substituted Formula II, wherein R and R1Respectively it is selected fromOr halogen
One of.
8. the purposes that compound described in claim 1 or 5 is used to prepare fluorescence probe.
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| N1取代基结构对菲并咪唑荧光色纯度的影响;王志明等;《高等学校化学学报》;20141231;第35卷(第3期);第505-510页 * |
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