CN108373478A - 一类牛磺酸取代的氟硼荧荧光化合物及其制备方法和用途 - Google Patents
一类牛磺酸取代的氟硼荧荧光化合物及其制备方法和用途 Download PDFInfo
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- CN108373478A CN108373478A CN201711325937.6A CN201711325937A CN108373478A CN 108373478 A CN108373478 A CN 108373478A CN 201711325937 A CN201711325937 A CN 201711325937A CN 108373478 A CN108373478 A CN 108373478A
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- Prior art keywords
- fluorine boron
- taurine
- glimmering
- substitution
- gleaming
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- XOAAWQZATWQOTB-UHFFFAOYSA-N taurine Chemical group NCCS(O)(=O)=O XOAAWQZATWQOTB-UHFFFAOYSA-N 0.000 title claims abstract description 88
- LIQLLTGUOSHGKY-UHFFFAOYSA-N [B].[F] Chemical compound [B].[F] LIQLLTGUOSHGKY-UHFFFAOYSA-N 0.000 title claims abstract description 76
- 238000006467 substitution reaction Methods 0.000 title claims abstract description 48
- 229960003080 taurine Drugs 0.000 title claims abstract description 44
- 150000001875 compounds Chemical class 0.000 title claims abstract description 34
- 230000003287 optical effect Effects 0.000 title claims abstract description 30
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims abstract description 23
- 239000002904 solvent Substances 0.000 claims abstract description 20
- 150000001412 amines Chemical class 0.000 claims abstract description 13
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000000654 additive Substances 0.000 claims abstract description 9
- 230000000996 additive effect Effects 0.000 claims abstract description 9
- 239000003054 catalyst Substances 0.000 claims abstract description 9
- CCIVGXIOQKPBKL-UHFFFAOYSA-N ethanesulfonic acid Chemical compound CCS(O)(=O)=O CCIVGXIOQKPBKL-UHFFFAOYSA-N 0.000 claims abstract description 9
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 38
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 26
- -1 sulfydryl Chemical group 0.000 claims description 26
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 19
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 18
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 18
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 18
- 125000003368 amide group Chemical group 0.000 claims description 16
- 125000001072 heteroaryl group Chemical group 0.000 claims description 16
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 claims description 16
- 238000006243 chemical reaction Methods 0.000 claims description 14
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 13
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 12
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 12
- 229910052763 palladium Inorganic materials 0.000 claims description 12
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 10
- 229910052799 carbon Inorganic materials 0.000 claims description 10
- 239000003208 petroleum Substances 0.000 claims description 10
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 9
- 239000000460 chlorine Substances 0.000 claims description 9
- 229910052801 chlorine Inorganic materials 0.000 claims description 9
- 239000011737 fluorine Substances 0.000 claims description 9
- 229910052731 fluorine Inorganic materials 0.000 claims description 9
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 8
- 125000003342 alkenyl group Chemical group 0.000 claims description 8
- 125000003545 alkoxy group Chemical group 0.000 claims description 8
- 125000000304 alkynyl group Chemical group 0.000 claims description 8
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 8
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 8
- 229910052794 bromium Inorganic materials 0.000 claims description 8
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 claims description 8
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 8
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 8
- 125000004185 ester group Chemical group 0.000 claims description 8
- 229910052739 hydrogen Inorganic materials 0.000 claims description 8
- 239000001257 hydrogen Substances 0.000 claims description 8
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims description 8
- 150000003949 imides Chemical class 0.000 claims description 8
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 8
- 229910052757 nitrogen Inorganic materials 0.000 claims description 8
- 125000003107 substituted aryl group Chemical group 0.000 claims description 8
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 claims description 7
- 125000000101 thioether group Chemical group 0.000 claims description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical group OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- 235000011054 acetic acid Nutrition 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 6
- UAOMVDZJSHZZME-UHFFFAOYSA-N diisopropylamine Chemical compound CC(C)NC(C)C UAOMVDZJSHZZME-UHFFFAOYSA-N 0.000 claims description 6
- 238000001914 filtration Methods 0.000 claims description 6
- 239000000126 substance Substances 0.000 claims description 6
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 5
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 5
- 125000003118 aryl group Chemical group 0.000 claims description 5
- 238000004440 column chromatography Methods 0.000 claims description 5
- 229910052802 copper Inorganic materials 0.000 claims description 5
- 239000010949 copper Substances 0.000 claims description 5
- 235000019441 ethanol Nutrition 0.000 claims description 5
- 239000007850 fluorescent dye Substances 0.000 claims description 5
- 238000002428 photodynamic therapy Methods 0.000 claims description 5
- 238000010898 silica gel chromatography Methods 0.000 claims description 5
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical class CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 claims description 4
- MSXVEPNJUHWQHW-UHFFFAOYSA-N 2-methylbutan-2-ol Chemical compound CCC(C)(C)O MSXVEPNJUHWQHW-UHFFFAOYSA-N 0.000 claims description 4
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 4
- 125000000339 4-pyridyl group Chemical group N1=C([H])C([H])=C([*])C([H])=C1[H] 0.000 claims description 4
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 4
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 claims description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 4
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 4
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 4
- 241000255964 Pieridae Species 0.000 claims description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 4
- PQLVXDKIJBQVDF-UHFFFAOYSA-N acetic acid;hydrate Chemical compound O.CC(O)=O PQLVXDKIJBQVDF-UHFFFAOYSA-N 0.000 claims description 4
- ZOAIGCHJWKDIPJ-UHFFFAOYSA-M caesium acetate Chemical compound [Cs+].CC([O-])=O ZOAIGCHJWKDIPJ-UHFFFAOYSA-M 0.000 claims description 4
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 claims description 4
- 230000006837 decompression Effects 0.000 claims description 4
- 235000019253 formic acid Nutrition 0.000 claims description 4
- 239000003504 photosensitizing agent Substances 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 Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 4
- 229910052703 rhodium Inorganic materials 0.000 claims description 4
- 239000010948 rhodium Substances 0.000 claims description 4
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims description 4
- 238000005660 chlorination reaction Methods 0.000 claims description 3
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 claims description 3
- IUGYQRQAERSCNH-UHFFFAOYSA-N pivalic acid Chemical compound CC(C)(C)C(O)=O IUGYQRQAERSCNH-UHFFFAOYSA-N 0.000 claims description 3
- 238000000746 purification Methods 0.000 claims description 3
- RWRDJVNMSZYMDV-UHFFFAOYSA-L radium chloride Chemical class [Cl-].[Cl-].[Ra+2] RWRDJVNMSZYMDV-UHFFFAOYSA-L 0.000 claims description 3
- 238000001291 vacuum drying Methods 0.000 claims description 3
- TXUICONDJPYNPY-UHFFFAOYSA-N (1,10,13-trimethyl-3-oxo-4,5,6,7,8,9,11,12,14,15,16,17-dodecahydrocyclopenta[a]phenanthren-17-yl) heptanoate Chemical compound C1CC2CC(=O)C=C(C)C2(C)C2C1C1CCC(OC(=O)CCCCCC)C1(C)CC2 TXUICONDJPYNPY-UHFFFAOYSA-N 0.000 claims description 2
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical class ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 claims description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 2
- MWVTWFVJZLCBMC-UHFFFAOYSA-N 4,4'-bipyridine Chemical compound C1=NC=CC(C=2C=CN=CC=2)=C1 MWVTWFVJZLCBMC-UHFFFAOYSA-N 0.000 claims description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 2
- OVEMSLBFEHSYSF-UHFFFAOYSA-N ClC(CBBB)Cl Chemical compound ClC(CBBB)Cl OVEMSLBFEHSYSF-UHFFFAOYSA-N 0.000 claims description 2
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 claims description 2
- 239000005751 Copper oxide Substances 0.000 claims description 2
- 229910021595 Copper(I) iodide Inorganic materials 0.000 claims description 2
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical class CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 2
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 2
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 claims description 2
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 claims description 2
- 229910021626 Tin(II) chloride Inorganic materials 0.000 claims description 2
- UMRSVAKGZBVPKD-UHFFFAOYSA-N acetic acid;copper Chemical compound [Cu].CC(O)=O UMRSVAKGZBVPKD-UHFFFAOYSA-N 0.000 claims description 2
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 claims description 2
- 239000000908 ammonium hydroxide Substances 0.000 claims description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 2
- ODWXUNBKCRECNW-UHFFFAOYSA-M bromocopper(1+) Chemical compound Br[Cu+] ODWXUNBKCRECNW-UHFFFAOYSA-M 0.000 claims description 2
- 229910052792 caesium Inorganic materials 0.000 claims description 2
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 claims description 2
- 229940011182 cobalt acetate Drugs 0.000 claims description 2
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 claims description 2
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 claims description 2
- 229910000431 copper oxide Inorganic materials 0.000 claims description 2
- LSXDOTMGLUJQCM-UHFFFAOYSA-M copper(i) iodide Chemical compound I[Cu] LSXDOTMGLUJQCM-UHFFFAOYSA-M 0.000 claims description 2
- GBRBMTNGQBKBQE-UHFFFAOYSA-L copper;diiodide Chemical compound I[Cu]I GBRBMTNGQBKBQE-UHFFFAOYSA-L 0.000 claims description 2
- 125000004802 cyanophenyl group Chemical group 0.000 claims description 2
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 claims description 2
- 229940043279 diisopropylamine Drugs 0.000 claims description 2
- 239000000539 dimer Substances 0.000 claims description 2
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical group Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 2
- AUHZEENZYGFFBQ-UHFFFAOYSA-N mesitylene Substances CC1=CC(C)=CC(C)=C1 AUHZEENZYGFFBQ-UHFFFAOYSA-N 0.000 claims description 2
- 125000001827 mesitylenyl group Chemical group [H]C1=C(C(*)=C(C([H])=C1C([H])([H])[H])C([H])([H])[H])C([H])([H])[H] 0.000 claims description 2
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 claims description 2
- NGWSAUQBWVWFCU-UHFFFAOYSA-N n-ethyl-2,3-dimethylbutan-2-amine Chemical compound CCNC(C)(C)C(C)C NGWSAUQBWVWFCU-UHFFFAOYSA-N 0.000 claims description 2
- XQOIBQBPAXOVGP-UHFFFAOYSA-N n-ethyl-2-methylpropan-2-amine Chemical compound CCNC(C)(C)C XQOIBQBPAXOVGP-UHFFFAOYSA-N 0.000 claims description 2
- MHJUNMARMFAUBI-UHFFFAOYSA-N n-phenyliminobenzamide Chemical compound C=1C=CC=CC=1C(=O)N=NC1=CC=CC=C1 MHJUNMARMFAUBI-UHFFFAOYSA-N 0.000 claims description 2
- 229940078494 nickel acetate Drugs 0.000 claims description 2
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 2
- 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 2
- 235000011056 potassium acetate Nutrition 0.000 claims description 2
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- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 2
- SONJTKJMTWTJCT-UHFFFAOYSA-K rhodium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Rh+3] SONJTKJMTWTJCT-UHFFFAOYSA-K 0.000 claims description 2
- YBCAZPLXEGKKFM-UHFFFAOYSA-K ruthenium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Ru+3] YBCAZPLXEGKKFM-UHFFFAOYSA-K 0.000 claims description 2
- 239000001632 sodium acetate Substances 0.000 claims description 2
- 235000017281 sodium acetate Nutrition 0.000 claims description 2
- FQENQNTWSFEDLI-UHFFFAOYSA-J sodium diphosphate Chemical compound [Na+].[Na+].[Na+].[Na+].[O-]P([O-])(=O)OP([O-])([O-])=O FQENQNTWSFEDLI-UHFFFAOYSA-J 0.000 claims description 2
- 239000001488 sodium phosphate Substances 0.000 claims description 2
- 229910000162 sodium phosphate Inorganic materials 0.000 claims description 2
- 235000011008 sodium phosphates Nutrition 0.000 claims description 2
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- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 2
- RYCLIXPGLDDLTM-UHFFFAOYSA-J tetrapotassium;phosphonato phosphate Chemical compound [K+].[K+].[K+].[K+].[O-]P([O-])(=O)OP([O-])([O-])=O RYCLIXPGLDDLTM-UHFFFAOYSA-J 0.000 claims description 2
- 235000019818 tetrasodium diphosphate Nutrition 0.000 claims description 2
- 239000001577 tetrasodium phosphonato phosphate Substances 0.000 claims description 2
- WLPUWLXVBWGYMZ-UHFFFAOYSA-N tricyclohexylphosphine Chemical compound C1CCCCC1P(C1CCCCC1)C1CCCCC1 WLPUWLXVBWGYMZ-UHFFFAOYSA-N 0.000 claims description 2
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 claims description 2
- VYXHVRARDIDEHS-UHFFFAOYSA-N 1,5-cyclooctadiene Chemical compound C1CC=CCCC=C1 VYXHVRARDIDEHS-UHFFFAOYSA-N 0.000 claims 2
- 239000004912 1,5-cyclooctadiene Substances 0.000 claims 2
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- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 claims 2
- 239000001211 (E)-4-phenylbut-3-en-2-one Substances 0.000 claims 1
- 239000005711 Benzoic acid Substances 0.000 claims 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims 1
- 235000010233 benzoic acid Nutrition 0.000 claims 1
- 229930008407 benzylideneacetone Natural products 0.000 claims 1
- WMKGGPCROCCUDY-PHEQNACWSA-N dibenzylideneacetone Chemical compound C=1C=CC=CC=1\C=C\C(=O)\C=C\C1=CC=CC=C1 WMKGGPCROCCUDY-PHEQNACWSA-N 0.000 claims 1
- 229910000073 phosphorus hydride Inorganic materials 0.000 claims 1
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- 229910052710 silicon Inorganic materials 0.000 claims 1
- 239000010703 silicon Substances 0.000 claims 1
- 229910000029 sodium carbonate Inorganic materials 0.000 claims 1
- 238000002560 therapeutic procedure Methods 0.000 claims 1
- BWHOZHOGCMHOBV-BQYQJAHWSA-N trans-benzylideneacetone Chemical compound CC(=O)\C=C\C1=CC=CC=C1 BWHOZHOGCMHOBV-BQYQJAHWSA-N 0.000 claims 1
- 229940005605 valeric acid Drugs 0.000 claims 1
- 239000000052 vinegar Substances 0.000 claims 1
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- 238000000034 method Methods 0.000 abstract description 8
- 230000004913 activation Effects 0.000 abstract description 4
- 229910052796 boron Inorganic materials 0.000 abstract description 3
- 238000006555 catalytic reaction Methods 0.000 abstract description 3
- 229910052751 metal Inorganic materials 0.000 abstract description 3
- 239000002184 metal Substances 0.000 abstract description 3
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 abstract 1
- 229910052740 iodine Inorganic materials 0.000 abstract 1
- 239000011630 iodine Substances 0.000 abstract 1
- HEDRZPFGACZZDS-MICDWDOJSA-N deuterated chloroform Substances [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 25
- 238000010521 absorption reaction Methods 0.000 description 17
- 239000000047 product Substances 0.000 description 11
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Abstract
本申请提供了一种牛磺酸取代的氟硼荧荧光化合物,还提供了其制备方法,该方法为:将8‑(4‑位取代的苯基)‑3,5‑二碘‑1,2,6,7‑四取代的氟硼荧、1,2‑二取代的牛磺酸在添加剂、催化剂和溶剂的条件下进行反应,得到8‑(4‑位取代的苯基)3‑碘‑5‑(2‑乙磺酸)胺)‑1,2,6,7‑四取代的氟硼荧和8‑(4‑位取代的苯基)3,5‑二((2‑乙磺酸)胺)‑1,2,6,7‑四取代的氟硼荧。该牛磺酸取代的氟硼荧荧光化合物是利用廉价金属催化的直接C‑X/N‑H活化方法,在明星荧光分子氟硼荧的3,5活化位点,引入具有生物活性的牛磺酸,从而形成新型荧光分子骨架。
Description
技术领域
本申请属于有机小分子功能性荧光染料技术,更具体地说,本申请涉及一类牛磺酸取代的氟硼荧荧光化合物及其制备方法和用途。
背景技术
牛磺酸(2-氨基乙磺酸)作为一种结构简单的含硫氨基酸,以游离形式大量存在于人和动物的所有脏器中,是人和动物的重要营养物质。又由于其是神经元内含量较丰富的自由氨基酸,具有调节细胞内钙稳态,清除氧自由基和稳定细胞膜等多种生物功能,具有抗惊厥、降血压、降血糖、调节神经传导、参与动物和人体内分泌活动等功效,因此它在国内外一些功能饮料和保健品中受到广泛欢迎[参见:(a)Huxtable,R.J.;Physiol Rev., 1992,72,101;(b)Bakker,A.J.;Berg,H.M.;J.Physiol.,2002,538, 185-194.]。但是,由于牛磺酸分子结构简单,在紫外光区到近红外光区都没有明显紫外吸收和荧光,在研究其在细胞内的药理机制时受到限制[参见:Zheng,X.X;Li C.;Liu,L.;Yang,H.T.;Hu,Y.F.;Ye,Y.;J.Bengbu Med. Coll.,2005,03,226-227.]。
氟硼荧衍生物作为一种具有生物活性的明星荧光分子,具有摩尔消光系数大、荧光光谱窄等特点,在生物显影、荧光探针、光动力学疗法上有广泛的应用[参见:(a)Aurore,L.;Kevin,B.;Chem.Rev.,2007,107, 4891-4932;(b)Gilles,U.;Raymond,Z.;Anthony,H.;Angew.Chem.Int.Ed., 2008,47,1184-1201;(c)Lu,H.;Mack,J.;Yang,Y.C;Shen,Z.;Chem.Soc. Rev.,2014,43,4778-4823]。2015年,西班牙科学家Ramón在氟硼荧的8位苯环上的对位连了一个羟基乙胺助溶基团,该化合物在光照条件下,能选择性杀死Hela宫颈癌细胞[参见:Gorbe,M.;Barba-Bon,A.; Torre,C.D.L.;Gil.S.;Costero,A.M.;Sancenón,F.;Murguía,J.R.;R.;Chem.Asian.J.,2015,10,2121-2125]。连有靶向基团的氟硼荧分子,生物相容性好,在定向识别细胞种类和细胞器方面也有着潜在应用。2015年Hsiao-hua Yu课题组在氟硼荧的2,6位分别连了一个3,4- 乙烯二氧噻吩衍生物,该化合物能选择性识别线粒体[参见:Chong,H.;Lin, H.A.;Shen,M.Y.;Liu,C.Y.;Zhao,H.;Yu;H.;Org.Lett.,2015,17, 3198–3201]。要想实现氟硼荧衍生物的功能多样性,科学家就必须在氟硼荧母核上嵌入不同的基团,但由于传统合成方法不仅步骤冗长,原子经济性低,而且还会产生环境不友好的有机金属试剂。因此利用过渡金属催化的直接C-H活化方法,在氟硼荧的不同位点引入功能化的分子,在近十年里得到了蓬勃发展[参见:(a)Luo,L.;Wu,D.;Li,W.;Zhang,S.;Ma,Y.h.; Su,Y.;You,J.S.;Org.Lett.,2014,16,6080-6083;(b)Verbelen,B.;Boodts, S.;Hofkens,J.;Boens,N.;Dehaen,W.;Angew.Chem.Int.Ed.,2015,54, 4612-4616;(c)Yu,Y.,Jiao,L.J.;Wang,J.,Wang,H.,Yu,C.J.;Hao E.H.; Boens,N.;Chem.Commun.,2017,53,581-584.]。因此,在氟硼荧上引入具有生物活性的靶向基团和功能分子,不仅步骤简单、成本低廉、环境友好,并且符合原子经济性原则,且形成的新型氟硼荧荧光分子,摩尔消光系数大,吸收光谱、发射光谱及荧光量子产率均可调节,在靶向识别细胞器和细胞种类上,具有更高的效率和可控制性。
因此,为了克服现有技术中所存在的上述不足,特提出本申请。
发明内容
本申请的目的之一在于,提供一种牛磺酸取代的氟硼荧荧光化合物。该牛磺酸取代的氟硼荧荧光化合物是利用廉价金属催化的直接C-X/N-H 活化方法,在明星荧光分子氟硼荧的3,5活化位点,引入具有生物活性的牛磺酸,从而形成新型荧光分子骨架。
为了实现上述目的,本申请采用如下技术方案:
一类牛磺酸取代的氟硼荧荧光化合物,其特征在于,其结构式如下所示:
R1、R2、R3、R4和R5为氢、氟、氯、溴、碘、烷基、烯基、炔基、烷氧基、苄基、巯基、硫醚基、芳基、取代芳基、杂芳基、取代杂芳基、胺基、酰胺基、酰亚胺基、氰基、醛基、羰基、羧基、磺酸基、酯基中的一种或一种以上,且R1、R2、R3、R4和R5中涉及的碳链为碳个数为1~40 的直链或支链。
一类牛磺酸取代的氟硼荧荧光化合物,其特征在于,其结构式如下所示:
R1、R2、R3、R4和R5为氢、氟、氯、溴、碘、烷基、烯基、炔基、烷氧基、苄基、巯基、硫醚基、芳基、取代芳基、杂芳基、取代杂芳基、胺基、酰胺基、酰亚胺基、氰基、醛基、羰基、羧基、磺酸基、酯基中的一种或一种以上,且R1、R2、R3、R4和R5中涉及的碳链为碳个数为1~40 的直链或支链。
本申请中化合物(1)的水溶性为10-3-10mg/mL;化合物(2)的水溶性为10-3-10mg/mL,增强了其生物相容性。
本申请的目的之二在于,提供一种牛磺酸取代的氟硼荧荧光化合物的制备方法。
为了实现上述目的,本申请采用如下技术方案:
一种牛磺酸取代的氟硼荧荧光化合物的制备方法,其特征在于,所述制备方法包括:
将8-(4-位取代的苯基)-3,5-二碘-1,2,6,7-四取代的氟硼荧、1,2-二取代的牛磺酸在添加剂、催化剂和溶剂的条件下进行反应,得到8-(4-位取代的苯基)3-碘-5-(2-乙磺酸)胺)-1,2,6,7-四取代的氟硼荧和8-(4-位取代的苯基)3,5-二((2-乙磺酸)胺)-1,2,6,7-四取代的氟硼荧。
优选地,所述的制备方法具体包括:
向反应器中加入8-(4-位取代的苯基)-3,5-二碘-1,2,6,7-四取代的氟硼荧、1,2-二取代的牛磺酸、添加剂、催化剂和溶剂,在氮气保护下,在 -40~120℃下反应0.1~480小时,冷至室温,加入二氯甲烷,过滤,减压移去溶剂,剩余物用硅胶柱层析分离纯化,真空干燥,得到8-(4-位取代的苯基)3-碘-5-(2-乙磺酸)胺)-1,2,6,7-四取代的氟硼荧和8-(4-位取代的苯基)3,5-二((2-乙磺酸)胺)-1,2,6,7-四取代的氟硼荧。
优选地,所述催化剂为三氯化铁、醋酸钴、氯化钴、醋酸镍、氯化镍、氧化铜、醋酸铜、一水醋酸铜、氯化铜、溴化铜、碘化铜、氯化亚铜、碘化亚铜、四(三苯基膦)钯、醋酸钯、氯化钯、氢氧化钯、二(乙腈)二氯化钯、二(苯腈)二氯化钯、二(三苯基膦)二氯化钯、双(二亚苄基丙酮)钯、三(二亚苄基丙酮)二钯、氯化烯丙基钯(II)二聚物、(1,5-环辛二烯)二氯化钯(II)、三氯化铑、醋酸铑、乙酰丙酮三苯基膦羰基铑、双环辛烯氯化铑二聚体、三苯基膦氯化铑、三氯化钌、三苯基膦氯化钌、二氯二羰基双(三苯基膦)钌、双(2-甲基烯丙基)(1,5-环辛二烯)钌(II)中的一种或一种以上组合;所述溶剂为甲醇、乙醇、异丙醇、正丁醇、叔戊醇、乙腈、四氢呋喃、甲酸、乙酸、1,2-二氯乙烷、二氯乙烷、三氯甲烷、乙醚、1,4- 二氧六环、二甲基亚砜、苯、氯苯、邻二氯苯、甲苯、二甲苯、均三甲苯、环己烷、石油醚、N,N-二甲基甲酰胺、N,N-二甲基乙酰胺、乙腈中的一种或一种以上组合;所述添加剂为吡啶,2,2’-联吡啶,4,4’-联吡啶,1, 2-二(4-吡啶基)乙烷,三苯基膦,三环己基膦,三环己基膦四氟硼酸盐、碳酸钠、醋酸钠、碳酸钾、焦磷酸钾、磷酸钠、醋酸钾、焦磷酸钠、碳酸氢钠、氨水、三乙胺、二乙胺、二异丙基胺、环己二胺、六(亚甲基)四胺、四甲基二乙胺、二甲基二乙胺、甲酸、乙酸、苯甲酸、特戊酸、醋酸铯、特戊酸铯中的一种或一种以上组合。
优选地,8-(4-位取代的苯基)-3,5-二碘-1,2,6,7-四取代的氟硼荧的反应浓度为0.001~10mol/L;8-(4-位取代的苯基)-3,5-二碘-1,2,6,7-四取代的氟硼荧、1,2-二取代的牛磺酸、添加剂、催化剂的摩尔比为1:(0.01~50): (0.01~10):(0.001~100)。。
优选地,硅胶柱层析分离纯化时所用的溶剂为石油醚、乙酸乙酯、二氯甲烷、丙酮中的一种或几种。
优选地,所述的8-(4-位取代的苯基)-3,5-二碘-1,2,6,7-四取代的氟硼荧,其结构通式如下:
其中R1、R2和R5分别为氢、氟、氯、溴、碘、烷基、烯基、炔基、烷氧基、苄基、巯基、硫醚基、芳基、取代芳基、杂芳基、取代杂芳基、胺基、酰胺基、酰亚胺基、氰基、醛基、羰基、羧基、磺酸基、酯基中的一种或一种以上,上述基团中涉及的碳链为碳个数为1~40的直链或支链;
所述的1,2-二取代的牛磺酸的结构通式如下:
其中R3和R4分别为氢、氟、氯、溴、碘、烷基、烯基、炔基、烷氧基、苄基、巯基、硫醚基、芳基、取代芳基、杂芳基、取代杂芳基、胺基、酰胺基、酰亚胺基、氰基、醛基、羰基、羧基、磺酸基、酯基中的一种或一种以上,上述基团中涉及的碳链为碳个数为1~40的直链或支链。
用核磁共振氢谱(1H NMR)、碳谱(13C NMR)以及高分辨质谱证实了本申请中牛磺酸取代的氟硼荧的荧光化合物的结构。检测所用仪器为: Bruker AV II-400MHz型核磁共振仪,其中TMS为内标,氘代CDCl3为溶剂;Waters-Q-TOF-Premier(ESI)型高分辨质谱仪。
本申请中牛磺酸取代的氟硼荧荧光化合物具有高的摩尔消光系数。
本申请中牛磺酸取代的氟硼荧荧光化合物具有高强度的吸收光谱。
本申请中牛磺酸取代的氟硼荧荧光化合物具有在近红外光区的荧光光谱。
本申请中牛磺酸取代的氟硼荧荧光化合物具有高的荧光量子产率。
本申请的目的之三在于,提供一类牛磺酸取代的氟硼荧荧光化合物的用途。
一类牛磺酸取代的氟硼荧荧光化合物作为近红外荧光染料和/或动力学疗法中的光敏剂的用途。
一类牛磺酸取代的氟硼荧荧光化合物作为近红外荧光染料和/或动力学疗法中的光敏剂的用途。
与现有技术相比,本申请较传统方法更简洁、高效、环境友好,具体包括:
1.本申请采用廉价金属催化的C–X/N–H直接偶联,实现了氟硼荧3, 5位的氨化反应,解决了牛磺酸自身不能发光的难题,利用简洁、高效、环境友好的方法,将牛磺酸连接到明星荧光分子上,合成得到了一类牛磺酸取代的氟硼荧荧光化合物,与原料相比,新得到的产物不仅具有更好的水溶性,单边产物在光照条件下可以产生单线态氧,在PDT上有潜在的应用,双边产物发射光谱发生红移,为其生物相容性及靶向识别功能提供了有效依据;
2.原料A和B化学性质稳定,易于合成,有利于降低工艺难度;
3.本技术普适性好,将神经元内丰富存在的牛磺酸引入荧光基团,增加了产物所带官能团的多样性,有利于对生物荧光分子的修饰和性质调整;
4.通过一步法实现C–H/N–H直接偶联,体现了步骤经济性、原子经济性和环境友好性。
5、综上所述,本发明的制备技术更加有利于工业化生产。
附图说明
图1为B物质的紫外-可见-近红外吸收光谱
图2为B物质的荧光发射光谱
图3为TB-a的紫外-可见-近红外吸收光谱
图4为TB-a的荧光发射光谱
图5为TB-b的紫外-可见-近红外吸收光谱
图6为TB-b荧光发射光谱
图7为DPBF的特征吸收峰随照射时间的变化
具体实施方式
下面结合实施例详述本申请,但本申请并不局限于这些实施例。
如无特别说明,本申请的实施例中的原料均通过商业途径购买。
实施例1
TB-a(2,3,6,-三碘-8-(4-甲基苯基)-5-牛磺酸取代的氟硼荧)和TB-b (8-(4-甲基苯基)-3,5-双牛磺酸取代的氟硼荧)的合成
(1)室温、氮气保护下向干燥避光反应器中加入吡咯(67.1g,1mol), 4-甲基苯甲醛(6.0g,50mmol),避光搅拌10min后,向体系滴加1.0mL 三氟乙酸,滴加完毕后,搅拌4h后停止反应。用20mL的0.1M NaOH水溶液淬灭反应,100mL乙酸乙酯萃取。将有机相水洗2次后,用无水Na2SO4 干燥,过滤,移走溶剂,减压回收3,4-二甲基吡咯。剩余物用将有机相水洗2次后,用无水Na2SO4干燥,过滤,移走溶剂,减压回收吡咯衍生物。剩余物用CH2Cl2/石油醚/Et3N=100/100/1(v/v/v)柱层析,得黄色固体(粗产品)。将粗产品用乙醇重结晶,得近白色固体中间体2.7g,产率为25%。将得到的中间体溶于80mL甲苯中,加入2,3-二氯-5,6-二氰基对苯二醌(2.83g,12.5mmol),室温搅拌3h后,向反应体系中依次加入12.2mL三乙胺、11.1mL三氟化硼乙醚,继续反应11h,加水淬灭反应,分液。有机相经无水硫酸钠干燥后,过滤,移除溶剂,剩余物以 CH2Cl2/石油醚=1/1(v/v)为洗脱剂柱层析,得绿色固体8-(4-甲苯基) -氟硼荧1.0g,产率为30%。取8-(4-甲苯基)氟硼荧(5.6g,0.02mol), 加入NIS(18g,0.08mol),DMF 50mL,室温下搅拌24h,柱色谱分离,得到2,3,5,6-四碘-8-(4-甲基苯基)氟硼荧15.6g,产率99%。1H NMR(400 MHz,CDCl3):δ=2.40(s,3H),6.91(d,J=8.4Hz,2H),7.27(d, J=8.0Hz,2H),7.31(s,2H)ppm.13C NMR(100MHz,CDCl3):δ= 21.6,90.9,115.9,129.1,129.6,134.0,137.5,139.3,140.5,142.1 ppm.HRMS(ESI+):计算值C16H9BF2I4N2[M+Na]+808.6903,实测值 808.6909。
(2)向干燥的反应器中加入2,3,5,6-四碘-8-(4-甲苯基)氟硼荧(157.14 mg,0.2mmol),牛磺酸(62.6mg,0.5mmol),一水醋酸铜(60.0mg,0.3 mmol),1,2-二(4-吡啶基)乙烷(7.4mg,0.04mmol),醋酸铯(76.8mg, 0.4mmol),乙酸(0.2mL),二氯乙烷(1mL),氮气保护下,在100℃下反应12小时。反应完成后冷至室温,加入10mL二氯甲烷稀释,再经硅藻土过滤并用10~20mL的二氯甲烷洗涤,减压移去溶剂,剩余物用硅胶柱层析(二氯甲烷/石油醚/乙酸乙酯=1/4/1,v/v)分离纯化,真空干燥后得红色固体目标产物TB-a 2,3,6,-三碘-8-(4-甲苯基)-5-牛磺酸取代的氟硼荧TB-a 70.46mg,产率45%。1H NMR(400MHz,CDCl3):δ=2.39(s, 3H),2.85(d,J=8.0Hz,2H),4.14(s,2H),6.25(d,J=8.0Hz,1H),7.19-7.23 (m,1H),7.23-7.36(m,4H),8.81(s,1H)ppm.13C NMR(100MHz,CDCl3):δ=21.7,43.1,48.2,114.2,114.25,117.8,120.6,125.0,126.6,128.2,129.6, 132.0,134.6,136.05,136.1,156.7,159.8ppm.HRMS(ESI+):计算值 C18H15BF2I3N3O3S[M+Na]+802.8951,实测值802.8949。得到红色固体目标产物2,6,-二碘-8-(4-甲苯基)-3,5-双牛磺酸取代的氟硼荧TB-b51.5mg,产率33%。1H NMR(400MHz,CDCl3):δ=2.36(s,3H),2.87(d,J=8.0Hz, 4H),4.16(m,4H),6.84(d,J=8.4Hz,2H),7.21-7.28(m,4H),8.85(s,2H), ppm.13C NMR(100MHz,CDCl3):δ=21.3,43.2,43.5,48.2,48.3,114.2, 117.8,120.6,125.0,126.6,128.2,129.6,132.0,134.6,136.05,136.1,156.7, 159.8ppm.HRMS(ESI+):计算值C20H21BF2I2N4O6S2[M+Na]+805.7927,实测值805.7925。
实施例2
TC-a(3-碘-8-(4-甲氧基苯基)-5-牛磺酸取代的氟硼荧)和TC-b(2,6,- 二碘-8-(4-甲氧基苯基)-3,5-双牛磺酸取代的氟硼荧)的合成
(1)室温、氮气保护下向干燥避光反应器中加入吡咯(67.1g,1mol), 4-甲氧基苯甲醛(7.0g,50mmol),避光搅拌10min后,向体系滴加1.0mL 三氟乙酸,滴加完毕后,搅拌4h后停止反应。用20mL的0.1M NaOH 水溶液淬灭反应,100mL乙酸乙酯萃取。将有机相水洗2次后,用无水 Na2SO4干燥,过滤,移走溶剂,减压回收3,4-二甲基吡咯。剩余物用将有机相水洗2次后,用无水Na2SO4干燥,过滤,移走溶剂,减压回收吡咯衍生物。剩余物用CH2Cl2/石油醚/Et3N=100/100/1(v/v/v)柱层析,得黄色固体(粗产品)。将粗产品用乙醇重结晶,得近白色固体中间体3.9g,产率为31%。将得到的中间体溶于80mL甲苯中,加入2,3-二氯-5,6-二氰基对苯二醌(2.83g,12.5mmol),室温搅拌3h后,向反应体系中依次加入 12.2mL三乙胺、11.1mL三氟化硼乙醚,继续反应11h,加水淬灭反应,分液。有机相经无水硫酸钠干燥后,过滤,移除溶剂,剩余物以CH2Cl2/ 石油醚=1/1(v/v)为洗脱剂柱层析,得绿色固体8-(4-甲氧基苯基)- 氟硼荧1.2g,产率为26%。取8-(4-甲氧基苯基)氟硼荧(5.9g,0.02mol), 加入NIS(9g,0.04mol),DMF 50mL,室温下搅拌24h,柱色谱分离,得到 3,5-二碘-8-(4-甲氧基苯基)氟硼荧10.9g,产率99%。1H NMR(400MHz, CDCl3):δ=3.83(s,3H),5.39(d,J=4.0Hz,1H),6.33(d,J=4.0Hz,1H), 6.46(s,1H),6.94(d,J=4.0Hz,2H),6.99(s,1H),7.24(d,J=8.0Hz,2H)ppm. 13C NMR(100MHz,CDCl3):δ=55.8,66.5,113.3,114.2,114.9,120.8,124.5, 125.2,126.8,132.0,134.6,136.0,159.8ppm.HRMS(ESI+):计算值 C16H11BF2I2N2[M+H]+550.9100,实测值550.9108。
(2)向干燥的反应器中加入3,5-四碘-8-(4-甲氧基苯基)氟硼荧(109.98 mg,0.2mmol),牛磺酸(62.6mg,0.5mmol),一水醋酸铜(60.0mg,0.3 mmol),1,2-二(4-吡啶基)乙烷(7.4mg,0.04mmol),醋酸铯(76.8mg, 0.4mmol),乙酸(0.2mL),二氯乙烷(1mL),氮气保护下,在100℃下反应12小时。反应完成后冷至室温,加入10mL二氯甲烷稀释,再经硅藻土过滤并用10~20mL的二氯甲烷洗涤,减压移去溶剂,剩余物用硅胶柱层析(二氯甲烷/石油醚/乙酸乙酯=1/4/1,v/v)分离纯化,真空干燥后得红色固体目标产物TC-a 3-碘-8-(4-甲氧基苯基)-5-牛磺酸取代的氟硼荧53.61mg,产率49%。1H NMR(400MHz,CDCl3):δ=2.85(d,J=8.0 Hz,2H),3.86(s,3H),4.14(s,2H),6.25(d,J=8.0Hz,1H),7.18-7.23(m,3H), 7.23-7.36(m,4H),8.91(s,1H)ppm.13C NMR(100MHz,CDCl3):δ=43.1, 48.2,55.8,66.5,113.3,114.2,114.9,120.8,124.5,125.2,126.8,132.0,134.6, 135.8.0,160.7ppm.HRMS(ESI+):计算值C18H17BF2IN3O4S[M+H]+ 548.0124,实测值548.0120。得到红色固体目标产物TC-b8-(4-甲氧基苯基)-3,5-双牛磺酸取代的氟硼荧40.26mg,产率37%。1H NMR(400MHz, CDCl3):δ=2.89(d,J=8.0Hz,4H),3.87(s,3H),4.20(m,4H),6.84(d,J= 7.8Hz,2H),7.20-7.26(m,6H),8.85(s,2H),ppm.13C NMR(100MHz, CDCl3):δ=43.2,43.5,48.2,48.3,55.7,114.2,117.8,120.6,125.0,126.6, 128.2,129.6,132.0,134.6,136.05,136.1,156.7,159.8ppm.HRMS(ESI+): 计算值C20H23BF2N4O7S2[M+H]+544.1069,实测值544.1065。
实施例3
将B溶于THF,配成5.0×10-6mol/L溶液,取2.5mL放入比色皿中,测定紫外-可见-近红外吸收以及荧光发射光谱。B的吸收光谱最大吸收峰位于573nm,摩尔消光系数达到2.7×105M-1cm-1(图1)。荧光发射光谱最大吸收峰位于595nm(图2),量子产率为0.11。
实施例4:TB-a的紫外-可见-近红外吸收光谱图和荧光发射谱图
将TB-a溶于THF,配成5.0×10-6mol/L溶液,取2.5mL放入比色皿中,测定紫外-可见-近红外吸收以及荧光发射光谱。TB-a的吸收光谱最大吸收峰位于488nm,摩尔消光系数达到7.8×105M-1cm-1(图3)。荧光发射光谱最大吸收峰位于563nm,(图4),量子产率为0.23。
实施例5:TB-b的紫外-可见-近红外吸收光谱图和荧光发射谱图
将TB-b溶于THF,配成5.0×10-6mol/L溶液,取2.5mL放入比色皿中,测定紫外-可见-近红外吸收以及荧光发射光谱。TB-b的吸收光谱最大吸收峰位于563nm,摩尔消光系数达到4.6×105M-1cm-1(图5)。荧光发射光谱最大吸收峰位于675nm,荧光覆盖波长为577-750nm,半峰宽为 86.5nm(图6),量子产率为0.21。
实施例6:TB-a的水溶性检测
取10mL的去离子水于离心管中,称重,不断加入少量TB-a,震荡2 分钟后以500转每分钟的速度离心5分钟,当离心管底部有少量不溶物时停止加入TB-a,再次称重,两次结果相差10.1mg,说明该化合物的水溶性为10.1mg/mL。
实施例7:TB-b的水溶性检测
取10mL的去离子水于离心管中,称重,不断加入少量TB-b,震荡2 分钟后以500转每分钟的速度离心5分钟,当离心管底部有少量不溶物时停止加入TB-b,再次称重,两次结果相差15.2mg,说明该化合物的水溶性为15.2mg/mL。
实施例8:TB-a产生单线态氧效率图
避光条件下,将产物TB-a配成1×10-6mol/L的THF溶液,鼓入充足的氧气,加入适量的DPBF(单线态氧检测剂),用功率为1W,波长为 405nm的激光灯照射该溶液,DPBF的特征吸收峰随照射时间的变化如图 7。由图可以看出,DPBF在413nm处的特征吸收峰随着光照时间的增长而降低。说明产物TB-a在该条件下能产生单线态氧,结合其良好的水溶性,表明该化合物在光动力学辽法上有潜在应用。
以上所述,仅是本申请的几个实施例,并非对本申请做任何形式的限制,虽然本申请以较佳实施例揭示如上,然而并非用以限制本申请,任何熟悉本专业的技术人员,在不脱离本申请技术方案的范围内,利用上述揭示的技术内容做出些许的变动或修饰均等同于等效实施案例,均属于技术方案范围内。
Claims (10)
1.一类牛磺酸取代的氟硼荧荧光化合物,其特征在于,其结构式如下所示:
R1、R2、R3、R4和R5为氢、氟、氯、溴、碘、烷基、烯基、炔基、烷氧基、苄基、巯基、硫醚基、芳基、取代芳基、杂芳基、取代杂芳基、胺基、酰胺基、酰亚胺基、氰基、醛基、羰基、羧基、磺酸基、酯基中的一种或一种以上,且R1、R2、R3、R4和R5中涉及的碳链为碳个数为1~40的直链或支链。
2.一类牛磺酸取代的氟硼荧荧光化合物,其特征在于,其结构式如下所示:
R1、R2、R3、R4和R5为氢、氟、氯、溴、碘、烷基、烯基、炔基、烷氧基、苄基、巯基、硫醚基、芳基、取代芳基、杂芳基、取代杂芳基、胺基、酰胺基、酰亚胺基、氰基、醛基、羰基、羧基、磺酸基、酯基中的一种或一种以上,且R1、R2、R3、R4和R5中涉及的碳链为碳个数为1~40的直链或支链。
3.一种如权利要求1或2所述的牛磺酸取代的氟硼荧荧光化合物的制备方法,其特征在于,所述制备方法包括:
将8-(4-位取代的苯基)-3,5-二碘-1,2,6,7-四取代的氟硼荧、1,2-二取代的牛磺酸在添加剂、催化剂和溶剂的条件下进行反应,得到8-(4-位取代的苯基)3-碘-5-(2-乙磺酸)胺)-1,2,6,7-四取代的氟硼荧和8-(4-位取代的苯基)3,5-二((2-乙磺酸)胺)-1,2,6,7-四取代的氟硼荧。
4.根据权利要求3所述的牛磺酸取代的氟硼荧荧光化合物的制备方法,其特征在于,所述的制备方法具体包括:
向反应器中加入8-(4-位取代的苯基)-3,5-二碘-1,2,6,7-四取代的氟硼荧、1,2-二取代的牛磺酸、添加剂、催化剂和溶剂,在氮气保护下,在-40~120℃下反应0.1~480小时,冷至室温,加入二氯甲烷,过滤,减压移去溶剂,剩余物用硅胶柱层析分离纯化,真空干燥,得到8-(4-位取代的苯基)3-碘-5-(2-乙磺酸)胺)-1,2,6,7-四取代的氟硼荧和8-(4-位取代的苯基)3,5-二((2-乙磺酸)胺)-1,2,6,7-四取代的氟硼荧。
5.根据权利要求4所述的牛磺酸取代的氟硼荧荧光化合物的制备方法,其特征在于,所述催化剂为三氯化铁、醋酸钴、氯化钴、醋酸镍、氯化镍、氧化铜、醋酸铜、一水醋酸铜、氯化铜、溴化铜、碘化铜、氯化亚铜、碘化亚铜、四(三苯基膦)钯、醋酸钯、氯化钯、氢氧化钯、二(乙腈)二氯化钯、二(苯腈)二氯化钯、二(三苯基膦)二氯化钯、双(二亚苄基丙酮)钯、三(二亚苄基丙酮)二钯、氯化烯丙基钯(II)二聚物、(1,5-环辛二烯)二氯化钯(II)、三氯化铑、醋酸铑、乙酰丙酮三苯基膦羰基铑、双环辛烯氯化铑二聚体、三苯基膦氯化铑、三氯化钌、三苯基膦氯化钌、二氯二羰基双(三苯基膦)钌、双(2-甲基烯丙基)(1,5-环辛二烯)钌(II)中的一种或一种以上组合;所述溶剂为甲醇、乙醇、异丙醇、正丁醇、叔戊醇、乙腈、四氢呋喃、甲酸、乙酸、1,2-二氯乙烷、二氯乙烷、三氯甲烷、乙醚、1,4-二氧六环、二甲基亚砜、苯、氯苯、邻二氯苯、甲苯、二甲苯、均三甲苯、环己烷、石油醚、N,N-二甲基甲酰胺、N,N-二甲基乙酰胺、乙腈中的一种或一种以上组合;所述添加剂为吡啶,2,2’-联吡啶,4,4’-联吡啶,1,2-二(4-吡啶基)乙烷,三苯基膦,三环己基膦,三环己基膦四氟硼酸盐、碳酸钠、醋酸钠、碳酸钾、焦磷酸钾、磷酸钠、醋酸钾、焦磷酸钠、碳酸氢钠、氨水、三乙胺、二乙胺、二异丙基胺、环己二胺、六(亚甲基)四胺、四甲基二乙胺、二甲基二乙胺、甲酸、乙酸、苯甲酸、特戊酸、醋酸铯、特戊酸铯中的一种或一种以上组合。
6.根据权利要求3或4所述的牛磺酸取代的氟硼荧荧光化合物的制备方法,其特征在于,8-(4-位取代的苯基)-3,5-二碘-1,2,6,7-四取代的氟硼荧的反应浓度为0.001~10mol/L;8-(4-位取代的苯基)-3,5-二碘-1,2,6,7-四取代的氟硼荧、1,2-二取代的牛磺酸、添加剂、催化剂的摩尔比为1:(0.01~50):(0.01~10):(0.001~100)。
7.根据权利要求4所述的牛磺酸取代的氟硼荧荧光化合物的制备方法,其特征在于,硅胶柱层析分离纯化时所用的溶剂为石油醚、乙酸乙酯、二氯甲烷、丙酮中的一种或几种。
8.根据权利要求3或4所述的牛磺酸取代的氟硼荧荧光化合物的制备方法,其特征在于,所述的8-(4-位取代的苯基)-3,5-二碘-1,2,6,7-四取代的氟硼荧,其结构通式如下:
其中R1、R2和R5分别为氢、氟、氯、溴、碘、烷基、烯基、炔基、烷氧基、苄基、巯基、硫醚基、芳基、取代芳基、杂芳基、取代杂芳基、胺基、酰胺基、酰亚胺基、氰基、醛基、羰基、羧基、磺酸基、酯基中的一种或一种以上,上述基团中涉及的碳链为碳个数为1~40的直链或支链;
所述的1,2-二取代的牛磺酸的结构通式如下:
其中R3和R4分别为氢、氟、氯、溴、碘、烷基、烯基、炔基、烷氧基、苄基、巯基、硫醚基、芳基、取代芳基、杂芳基、取代杂芳基、胺基、酰胺基、酰亚胺基、氰基、醛基、羰基、羧基、磺酸基、酯基中的一种或一种以上,上述基团中涉及的碳链为碳个数为1~40的直链或支链。
9.根据权利要求1所述的牛磺酸取代的氟硼荧荧光化合物或者按照权利要求3-8中任意一项所述的制备方法制备的牛磺酸取代氟硼荧的荧光化合物作为荧光染料和/或光动力学疗法中的光敏剂的用途。
10.根据权利要求2所述的牛磺酸取代的氟硼荧荧光化合物或者按照权利要求3-8中任意一项所述的制备方法制备的牛磺酸取代氟硼荧的荧光化合物作为近红外荧光染料和/或光动力学疗法中的光敏剂的用途。
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