JPWO2015111647A1 - ホスホール化合物及びそれを含有する蛍光色素 - Google Patents
ホスホール化合物及びそれを含有する蛍光色素 Download PDFInfo
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- JPWO2015111647A1 JPWO2015111647A1 JP2015559100A JP2015559100A JPWO2015111647A1 JP WO2015111647 A1 JPWO2015111647 A1 JP WO2015111647A1 JP 2015559100 A JP2015559100 A JP 2015559100A JP 2015559100 A JP2015559100 A JP 2015559100A JP WO2015111647 A1 JPWO2015111647 A1 JP WO2015111647A1
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- substituted
- aryl group
- alkyl group
- ring
- Prior art date
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- -1 Phosphor compound Chemical class 0.000 title claims abstract description 36
- 239000007850 fluorescent dye Substances 0.000 title abstract description 19
- 125000003118 aryl group Chemical group 0.000 claims description 44
- 125000000217 alkyl group Chemical group 0.000 claims description 42
- 125000000547 substituted alkyl group Chemical group 0.000 claims description 33
- 125000003107 substituted aryl group Chemical group 0.000 claims description 31
- 239000004215 Carbon black (E152) Substances 0.000 claims description 27
- 229930195733 hydrocarbon Natural products 0.000 claims description 27
- 125000001072 heteroaryl group Chemical group 0.000 claims description 26
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 26
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 20
- 125000003277 amino group Chemical group 0.000 claims description 15
- 125000003342 alkenyl group Chemical group 0.000 claims description 9
- 125000003545 alkoxy group Chemical group 0.000 claims description 9
- 125000000304 alkynyl group Chemical group 0.000 claims description 9
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 claims description 8
- DJMUYABFXCIYSC-UHFFFAOYSA-N 1H-phosphole Chemical group C=1C=CPC=1 DJMUYABFXCIYSC-UHFFFAOYSA-N 0.000 claims description 7
- 125000002947 alkylene group Chemical group 0.000 claims description 7
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 7
- 125000001841 imino group Chemical group [H]N=* 0.000 claims description 6
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 5
- 125000001624 naphthyl group Chemical group 0.000 claims description 5
- 229910052731 fluorine Inorganic materials 0.000 claims description 4
- 125000001153 fluoro group Chemical group F* 0.000 claims description 4
- 125000005017 substituted alkenyl group Chemical group 0.000 claims description 4
- 125000004426 substituted alkynyl group Chemical group 0.000 claims description 4
- 125000006615 aromatic heterocyclic group Chemical group 0.000 claims description 2
- 125000001183 hydrocarbyl group Chemical group 0.000 claims 2
- 238000003763 carbonization Methods 0.000 claims 1
- 239000000049 pigment Substances 0.000 claims 1
- 239000002904 solvent Substances 0.000 abstract description 24
- 238000006862 quantum yield reaction Methods 0.000 abstract description 8
- 239000000126 substance Substances 0.000 abstract description 8
- 239000000463 material Substances 0.000 abstract description 6
- 239000000975 dye Substances 0.000 abstract description 4
- 238000010521 absorption reaction Methods 0.000 abstract description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 60
- 239000013256 coordination polymer Substances 0.000 description 43
- 239000000460 chlorine Substances 0.000 description 41
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 40
- 238000005481 NMR spectroscopy Methods 0.000 description 37
- 239000000203 mixture Substances 0.000 description 33
- 150000001875 compounds Chemical class 0.000 description 29
- 229910052799 carbon Inorganic materials 0.000 description 28
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 24
- 239000012043 crude product Substances 0.000 description 24
- 239000000243 solution Substances 0.000 description 22
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 18
- 239000000706 filtrate Substances 0.000 description 18
- 238000010898 silica gel chromatography Methods 0.000 description 17
- 239000012044 organic layer Substances 0.000 description 16
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 15
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 15
- 210000004027 cell Anatomy 0.000 description 15
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 15
- 239000007787 solid Substances 0.000 description 15
- 230000015572 biosynthetic process Effects 0.000 description 14
- 235000019439 ethyl acetate Nutrition 0.000 description 14
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical class O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 14
- 238000003786 synthesis reaction Methods 0.000 description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 13
- 229910052938 sodium sulfate Inorganic materials 0.000 description 12
- 235000011152 sodium sulphate Nutrition 0.000 description 12
- 239000007864 aqueous solution Substances 0.000 description 10
- 229940125904 compound 1 Drugs 0.000 description 10
- 229940125782 compound 2 Drugs 0.000 description 9
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 8
- 229940126214 compound 3 Drugs 0.000 description 8
- 238000001914 filtration Methods 0.000 description 8
- 230000003287 optical effect Effects 0.000 description 8
- 239000011734 sodium Substances 0.000 description 8
- KAFZOLYKKCWUBI-HPMAGDRPSA-N (2s)-2-[[(2s)-2-[[(2s)-1-[(2s)-3-amino-2-[[(2s)-2-[[(2s)-2-(3-cyclohexylpropanoylamino)-4-methylpentanoyl]amino]-5-methylhexanoyl]amino]propanoyl]pyrrolidine-2-carbonyl]amino]-5-(diaminomethylideneamino)pentanoyl]amino]butanediamide Chemical compound N([C@@H](CC(C)C)C(=O)N[C@@H](CCC(C)C)C(=O)N[C@@H](CN)C(=O)N1[C@@H](CCC1)C(=O)N[C@@H](CCCN=C(N)N)C(=O)N[C@@H](CC(N)=O)C(N)=O)C(=O)CCC1CCCCC1 KAFZOLYKKCWUBI-HPMAGDRPSA-N 0.000 description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 7
- 125000005843 halogen group Chemical group 0.000 description 7
- 238000001228 spectrum Methods 0.000 description 7
- 238000001308 synthesis method Methods 0.000 description 7
- VUDZSIYXZUYWSC-DBRKOABJSA-N (4r)-1-[(2r,4r,5r)-3,3-difluoro-4-hydroxy-5-(hydroxymethyl)oxolan-2-yl]-4-hydroxy-1,3-diazinan-2-one Chemical compound FC1(F)[C@H](O)[C@@H](CO)O[C@H]1N1C(=O)N[C@H](O)CC1 VUDZSIYXZUYWSC-DBRKOABJSA-N 0.000 description 6
- COGFELMKDSTKHZ-UHFFFAOYSA-N O=P1C=CC=C1 Chemical compound O=P1C=CC=C1 COGFELMKDSTKHZ-UHFFFAOYSA-N 0.000 description 6
- LNAMMBFJMYMQTO-FNEBRGMMSA-N chloroform;(1e,4e)-1,5-diphenylpenta-1,4-dien-3-one;palladium Chemical compound [Pd].[Pd].ClC(Cl)Cl.C=1C=CC=CC=1\C=C\C(=O)\C=C\C1=CC=CC=C1.C=1C=CC=CC=1\C=C\C(=O)\C=C\C1=CC=CC=C1.C=1C=CC=CC=1\C=C\C(=O)\C=C\C1=CC=CC=C1 LNAMMBFJMYMQTO-FNEBRGMMSA-N 0.000 description 6
- 238000005227 gel permeation chromatography Methods 0.000 description 6
- 238000004128 high performance liquid chromatography Methods 0.000 description 6
- HXITXNWTGFUOAU-UHFFFAOYSA-N phenylboronic acid Chemical compound OB(O)C1=CC=CC=C1 HXITXNWTGFUOAU-UHFFFAOYSA-N 0.000 description 6
- 230000003595 spectral effect Effects 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 5
- 239000012153 distilled water Substances 0.000 description 5
- 239000003480 eluent Substances 0.000 description 5
- 238000002189 fluorescence spectrum Methods 0.000 description 5
- 238000010186 staining Methods 0.000 description 5
- 239000000725 suspension Substances 0.000 description 5
- VGNCBRNRHXEODV-XXVHXNRLSA-N (6r,7r)-1-[(4s,5r)-4-acetyloxy-5-methyl-3-methylidene-6-phenylhexyl]-6-dodecoxy-4,7-dihydroxy-2,8-dioxabicyclo[3.2.1]octane-3,4,5-tricarboxylic acid Chemical compound C([C@@H](C)[C@H](OC(C)=O)C(=C)CCC12[C@H](O)[C@H](C(O2)(C(O)=O)C(O)(C(O1)C(O)=O)C(O)=O)OCCCCCCCCCCCC)C1=CC=CC=C1 VGNCBRNRHXEODV-XXVHXNRLSA-N 0.000 description 4
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 4
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 4
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 4
- 238000002835 absorbance Methods 0.000 description 4
- 229940125898 compound 5 Drugs 0.000 description 4
- YMWUJEATGCHHMB-DICFDUPASA-N dichloromethane-d2 Chemical compound [2H]C([2H])(Cl)Cl YMWUJEATGCHHMB-DICFDUPASA-N 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 4
- 150000002430 hydrocarbons Chemical group 0.000 description 4
- UBJFKNSINUCEAL-UHFFFAOYSA-N lithium;2-methylpropane Chemical compound [Li+].C[C-](C)C UBJFKNSINUCEAL-UHFFFAOYSA-N 0.000 description 4
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 4
- 150000004857 phospholes Chemical class 0.000 description 4
- 238000010791 quenching Methods 0.000 description 4
- 230000000171 quenching effect Effects 0.000 description 4
- VNFWTIYUKDMAOP-UHFFFAOYSA-N sphos Chemical compound COC1=CC=CC(OC)=C1C1=CC=CC=C1P(C1CCCCC1)C1CCCCC1 VNFWTIYUKDMAOP-UHFFFAOYSA-N 0.000 description 4
- UXKLQDCALAWFIU-VKNDCNMPSA-N (6r,7r)-1-[(4s,5r)-4-acetyloxy-5-methyl-3-methylidene-6-phenylhexyl]-4,7-dihydroxy-6-tetradecoxy-2,8-dioxabicyclo[3.2.1]octane-3,4,5-tricarboxylic acid Chemical compound C([C@@H](C)[C@H](OC(C)=O)C(=C)CCC12[C@H](O)[C@H](C(O2)(C(O)=O)C(O)(C(O1)C(O)=O)C(O)=O)OCCCCCCCCCCCCCC)C1=CC=CC=C1 UXKLQDCALAWFIU-VKNDCNMPSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- 239000012300 argon atmosphere Substances 0.000 description 3
- 230000008033 biological extinction Effects 0.000 description 3
- 239000012267 brine Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- PHVXTQIROLEEDB-UHFFFAOYSA-N n-[2-(2-chlorophenyl)ethyl]-4-[[3-(2-methylphenyl)piperidin-1-yl]methyl]-n-pyrrolidin-3-ylbenzamide Chemical compound CC1=CC=CC=C1C1CN(CC=2C=CC(=CC=2)C(=O)N(CCC=2C(=CC=CC=2)Cl)C2CNCC2)CCC1 PHVXTQIROLEEDB-UHFFFAOYSA-N 0.000 description 3
- AICOOMRHRUFYCM-ZRRPKQBOSA-N oxazine, 1 Chemical compound C([C@@H]1[C@H](C(C[C@]2(C)[C@@H]([C@H](C)N(C)C)[C@H](O)C[C@]21C)=O)CC1=CC2)C[C@H]1[C@@]1(C)[C@H]2N=C(C(C)C)OC1 AICOOMRHRUFYCM-ZRRPKQBOSA-N 0.000 description 3
- 125000005010 perfluoroalkyl group Chemical group 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 229920006395 saturated elastomer Polymers 0.000 description 3
- 125000001424 substituent group Chemical group 0.000 description 3
- ILUOEGFLHOEUCF-UHFFFAOYSA-N (3-bromo-1-oxo-1-phenylphosphindol-2-yl)-trimethylsilane Chemical compound BrC=1C2=C(P(C=1[Si](C)(C)C)(C1=CC=CC=C1)=O)C=CC=C2 ILUOEGFLHOEUCF-UHFFFAOYSA-N 0.000 description 2
- KHGHGZPESHUYCR-UHFFFAOYSA-N 1h-phosphindole Chemical group C1=CC=C2PC=CC2=C1 KHGHGZPESHUYCR-UHFFFAOYSA-N 0.000 description 2
- ZSZDMYWEQAZTRY-UHFFFAOYSA-N 2-bromo-1-phenylphosphindole 1-oxide Chemical compound BrC1=CC2=CC=CC=C2P1(=O)C1=CC=CC=C1 ZSZDMYWEQAZTRY-UHFFFAOYSA-N 0.000 description 2
- QDLAABKFYZVHOW-UHFFFAOYSA-N 2-bromo-3-iodonaphthalene Chemical compound C1=CC=C2C=C(I)C(Br)=CC2=C1 QDLAABKFYZVHOW-UHFFFAOYSA-N 0.000 description 2
- QDYFCLVSLUZDHB-UHFFFAOYSA-N 4-ethynyl-n,n-diphenylaniline Chemical group C1=CC(C#C)=CC=C1N(C=1C=CC=CC=1)C1=CC=CC=C1 QDYFCLVSLUZDHB-UHFFFAOYSA-N 0.000 description 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- VGZOYKIGSHGHRK-UHFFFAOYSA-N N,N-dimethyl-4-(1-oxo-1,3-diphenylphosphindol-2-yl)aniline Chemical compound CN(C)C1=CC=C(C=C1)C1=C(C2=C(P1(C1=CC=CC=C1)=O)C=CC=C2)C1=CC=CC=C1 VGZOYKIGSHGHRK-UHFFFAOYSA-N 0.000 description 2
- 229930006000 Sucrose Natural products 0.000 description 2
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 description 2
- NLTUDNKQUJVGKP-UHFFFAOYSA-N [2-(dimethylamino)phenyl]boronic acid Chemical compound CN(C)C1=CC=CC=C1B(O)O NLTUDNKQUJVGKP-UHFFFAOYSA-N 0.000 description 2
- 238000000862 absorption spectrum Methods 0.000 description 2
- 125000005277 alkyl imino group Chemical group 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 125000004467 aryl imino group Chemical group 0.000 description 2
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 2
- 239000012965 benzophenone Substances 0.000 description 2
- 125000004369 butenyl group Chemical group C(=CCC)* 0.000 description 2
- 125000000480 butynyl group Chemical group [*]C#CC([H])([H])C([H])([H])[H] 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- SLLGVCUQYRMELA-UHFFFAOYSA-N chlorosilicon Chemical compound Cl[Si] SLLGVCUQYRMELA-UHFFFAOYSA-N 0.000 description 2
- 125000006165 cyclic alkyl group Chemical group 0.000 description 2
- 210000000805 cytoplasm Anatomy 0.000 description 2
- DMBHHRLKUKUOEG-UHFFFAOYSA-N diphenylamine Chemical compound C=1C=CC=CC=1NC1=CC=CC=C1 DMBHHRLKUKUOEG-UHFFFAOYSA-N 0.000 description 2
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 2
- 238000000799 fluorescence microscopy Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 230000003834 intracellular effect Effects 0.000 description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 125000004368 propenyl group Chemical group C(=CC)* 0.000 description 2
- 125000002568 propynyl group Chemical group [*]C#CC([H])([H])[H] 0.000 description 2
- 239000003586 protic polar solvent Substances 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 238000001953 recrystallisation Methods 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 239000000741 silica gel Substances 0.000 description 2
- 229910002027 silica gel Inorganic materials 0.000 description 2
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 2
- 239000005720 sucrose Substances 0.000 description 2
- 238000004809 thin layer chromatography Methods 0.000 description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 2
- 239000003039 volatile agent Substances 0.000 description 2
- COHWGJMHCMOXLL-UHFFFAOYSA-N (1-bromonaphthalen-2-yl) trifluoromethanesulfonate Chemical compound C1=CC=CC2=C(Br)C(OS(=O)(=O)C(F)(F)F)=CC=C21 COHWGJMHCMOXLL-UHFFFAOYSA-N 0.000 description 1
- ARPVUZQZAKCGMT-UHFFFAOYSA-N (2-amino-3,4-dimethylphenyl)boronic acid Chemical compound CC1=C(C(=C(C=C1)B(O)O)N)C ARPVUZQZAKCGMT-UHFFFAOYSA-N 0.000 description 1
- IGVKWAAPMVVTFX-BUHFOSPRSA-N (e)-octadec-5-en-7,9-diynoic acid Chemical compound CCCCCCCCC#CC#C\C=C\CCCC(O)=O IGVKWAAPMVVTFX-BUHFOSPRSA-N 0.000 description 1
- HMWAJFNEGAJETK-UHFFFAOYSA-N 1-[6-(dimethylamino)naphthalen-2-yl]prop-2-en-1-one Chemical compound C1=C(C(=O)C=C)C=CC2=CC(N(C)C)=CC=C21 HMWAJFNEGAJETK-UHFFFAOYSA-N 0.000 description 1
- OSKVIIXNRQIMNF-UHFFFAOYSA-N 1-bromo-2-[2-(4-chlorophenyl)ethynyl]benzene Chemical compound C1=CC(Cl)=CC=C1C#CC1=CC=CC=C1Br OSKVIIXNRQIMNF-UHFFFAOYSA-N 0.000 description 1
- IUDNRKGPFWUYIC-UHFFFAOYSA-N 2-[2-(2-methoxyethoxy)ethoxy]ethyl 4-methylbenzenesulfonate Chemical compound COCCOCCOCCOS(=O)(=O)C1=CC=C(C)C=C1 IUDNRKGPFWUYIC-UHFFFAOYSA-N 0.000 description 1
- FGXXFXSDTDXNMU-UHFFFAOYSA-N 2-bromo-1,3-diphenylphosphindole 1-oxide Chemical compound BrC1=C(C2=C(P1(C1=CC=CC=C1)=O)C=CC=C2)C1=CC=CC=C1 FGXXFXSDTDXNMU-UHFFFAOYSA-N 0.000 description 1
- KKLCYBZPQDOFQK-UHFFFAOYSA-N 4,4,5,5-tetramethyl-2-phenyl-1,3,2-dioxaborolane Chemical compound O1C(C)(C)C(C)(C)OB1C1=CC=CC=C1 KKLCYBZPQDOFQK-UHFFFAOYSA-N 0.000 description 1
- FTACOUGSJLRMKO-UHFFFAOYSA-N 4-(1-oxo-1,3-diphenylphosphindol-2-yl)-N,N-diphenylaniline Chemical compound C1(=CC=CC=C1)P1(C2=C(C(=C1C1=CC=C(C=C1)N(C1=CC=CC=C1)C1=CC=CC=C1)C1=CC=CC=C1)C=CC=C2)=O FTACOUGSJLRMKO-UHFFFAOYSA-N 0.000 description 1
- XHYNINYKKRIRMX-UHFFFAOYSA-N 4-(1-oxo-1-phenylphosphindol-2-yl)-N,N-diphenylaniline Chemical compound C1(=CC=CC=C1)N(C1=CC=C(C=C1)C1=CC2=C(P1(C1=CC=CC=C1)=O)C=CC=C2)C1=CC=CC=C1 XHYNINYKKRIRMX-UHFFFAOYSA-N 0.000 description 1
- BICZJRAGTCRORZ-UHFFFAOYSA-N 4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenol Chemical compound O1C(C)(C)C(C)(C)OB1C1=CC=C(O)C=C1 BICZJRAGTCRORZ-UHFFFAOYSA-N 0.000 description 1
- ODUCMGWESFPRMC-UHFFFAOYSA-N 7-ethynyl-1-azatricyclo[7.3.1.05,13]trideca-5,7,9(13)-triene Chemical group C1CCN2CCCC3=C2C1=CC(=C3)C#C ODUCMGWESFPRMC-UHFFFAOYSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical group [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- ONZKZSCCIURHEC-UHFFFAOYSA-N BrC=1C2=C(P(C1C1=CC=C(C=C1)Cl)C1=CC=CC=C1)C=CC=C2 Chemical compound BrC=1C2=C(P(C1C1=CC=C(C=C1)Cl)C1=CC=CC=C1)C=CC=C2 ONZKZSCCIURHEC-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- CANDSCJGEUDLNG-UHFFFAOYSA-N C1(=CC=CC=C1)P1C2=C(C(=C1[Si](C)(C)C)C1=CC=CC=C1)C=CC=C2 Chemical compound C1(=CC=CC=C1)P1C2=C(C(=C1[Si](C)(C)C)C1=CC=CC=C1)C=CC=C2 CANDSCJGEUDLNG-UHFFFAOYSA-N 0.000 description 1
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N Furan Chemical group C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- YLPTTXDYAYSWDH-UHFFFAOYSA-N N,N-dimethyl-4-(1-oxo-1-phenylphosphindol-2-yl)aniline Chemical compound CN(C1=CC=C(C=C1)C1=CC2=C(P1(C1=CC=CC=C1)=O)C=CC=C2)C YLPTTXDYAYSWDH-UHFFFAOYSA-N 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical group C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 1
- FZWLAAWBMGSTSO-UHFFFAOYSA-N Thiazole Chemical group C1=CSC=N1 FZWLAAWBMGSTSO-UHFFFAOYSA-N 0.000 description 1
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical group C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 1
- 235000010724 Wisteria floribunda Nutrition 0.000 description 1
- 125000002252 acyl group Chemical group 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- 125000005577 anthracene group Chemical group 0.000 description 1
- 125000002178 anthracenyl group Chemical group C1(=CC=CC2=CC3=CC=CC=C3C=C12)* 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 238000001460 carbon-13 nuclear magnetic resonance spectrum Methods 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 238000004440 column chromatography Methods 0.000 description 1
- 238000012258 culturing Methods 0.000 description 1
- 125000001995 cyclobutyl group Chemical group [H]C1([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 125000001559 cyclopropyl group Chemical group [H]C1([H])C([H])([H])C1([H])* 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 125000004663 dialkyl amino group Chemical group 0.000 description 1
- 125000004986 diarylamino group Chemical group 0.000 description 1
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 125000004672 ethylcarbonyl group Chemical group [H]C([H])([H])C([H])([H])C(*)=O 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 125000002485 formyl group Chemical group [H]C(*)=O 0.000 description 1
- 125000002541 furyl group Chemical group 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000000499 gel Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000002883 imidazolyl group Chemical group 0.000 description 1
- 125000003454 indenyl group Chemical group C1(C=CC2=CC=CC=C12)* 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 125000002510 isobutoxy group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])O* 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000003253 isopropoxy group Chemical group [H]C([H])([H])C([H])(O*)C([H])([H])[H] 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 238000012886 linear function Methods 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 125000004674 methylcarbonyl group Chemical group CC(=O)* 0.000 description 1
- 125000006606 n-butoxy group Chemical group 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000003506 n-propoxy group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])O* 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 125000002971 oxazolyl group Chemical group 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 125000006340 pentafluoro ethyl group Chemical group FC(F)(F)C(F)(F)* 0.000 description 1
- YNPNZTXNASCQKK-UHFFFAOYSA-N phenanthrene Chemical group C1=CC=C2C3=CC=CC=C3C=CC2=C1 YNPNZTXNASCQKK-UHFFFAOYSA-N 0.000 description 1
- 238000001394 phosphorus-31 nuclear magnetic resonance spectrum Methods 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 1
- 125000004076 pyridyl group Chemical group 0.000 description 1
- 125000000168 pyrrolyl group Chemical group 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000000523 sample Substances 0.000 description 1
- 239000012488 sample solution Substances 0.000 description 1
- 125000005920 sec-butoxy group Chemical group 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 235000010265 sodium sulphite Nutrition 0.000 description 1
- MFRIHAYPQRLWNB-UHFFFAOYSA-N sodium tert-butoxide Chemical compound [Na+].CC(C)(C)[O-] MFRIHAYPQRLWNB-UHFFFAOYSA-N 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 125000004213 tert-butoxy group Chemical group [H]C([H])([H])C(O*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 125000001544 thienyl group Chemical group 0.000 description 1
- 210000001519 tissue Anatomy 0.000 description 1
- 150000003613 toluenes Chemical class 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 1
- 238000012800 visualization Methods 0.000 description 1
- 125000005023 xylyl group Chemical group 0.000 description 1
Classifications
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- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
- C07F9/6564—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms
- C07F9/6568—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus atoms as the only ring hetero atoms
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Abstract
Description
1H,13Cおよび31P NMRスペクトルは、核磁気共鳴装置A−400 spectrometer(JEOL)を用いて測定した(共鳴周波数1H:400MHz,13C:100MHz,31P:162MHz)。1H NMRのケミカルシフト値は、重クロロホルムあるいは重ジクロロメタンの残留プロトンのシグナル(δ7.26ppm,δ5.30ppm)を内部標準として決定した。また、13C NMRのケミカルシフト値は重クロロホルムあるいは重ジクロロメタンのシグナル(δ77.16ppm,δ53.8ppm)を内部標準として用いた。31P NMRのケミカルシフト値は、H3PO4のシグナル(δ0.0ppm)を外部標準として用いた。薄層クロマトグラフィー(TLC)はシリカゲル60F254(Merck)を塗布したガラス板を用いて行った。カラムクロマトグラフィーは、PSQ 100B(富士シリシア)を用いて行った。分取リサイクルHPLCには、シリカゲルカラム(和光純薬、Wakosil−II 5−Prep)を備えたLC−918(日本分析工業)を用いた。分取リサイクル型ゲル浸透クロマトグラフィー(GPC)は、ポリスチレンゲルカラム(JAIGEL 1H,日本分析化学工業,移動層:クロロホルム)を備えたLC−918(日本分析化学工業)を使用した。脱水溶媒は、関東化学から購入した溶媒を、有機溶媒精製装置(Glass Contour社製)を用いて精製したものを用いた。脱気した溶媒として、溶媒にアルゴンガスを20分以上吹き込んだものを使用した。反応は特に記述のない限り、アルゴン雰囲気下で行った。
(1)2−[4−(N,N−ジフェニルアミノ)フェニル]−1,3−ジフェニルベンゾ[b]ホスホール−P−オキシド(化合物1)の合成
以下のスキームに従って、化合物1を合成した。
以下のスキームに従って、化合物2を合成した。
以下のスキームに従って、化合物3を合成した。
以下のスキームに従って、化合物4を合成した。
以下のスキームに従って、化合物5を合成した。
以下のスキームに従って、化合物6a−6dを合成した。但し、化合物6aは、合成方法は異なるものの化合物2と同じであるため、以下には代表例として化合物6bの合成方法を詳しく説明する。
2−ブロモ−3−ヨードナフタレン(5mmol), 4−(N,N−ジフェニルアミノ)フェニルアセチレン(5.25mmol),Pd(PPh3)4(0.10mmol),CuI(0.10mmol),トルエン(10mL)及びi−Pr2NH(5mL)の懸濁液を室温で20時間攪拌した。その後、濾過により無機塩を除去し、すべての揮発性物質を減圧下で蒸発させた。シリカゲルクロマトグラフィ(溶出液はヘキサン/CH2Cl2=4/1)により分離したあと、 得られた粗生成物をMeOHから再結晶することにより精製し、白色粉末である合成中間体M8bを収率96%で得た。
合成中間体M8cは、4−(N,N−ジフェニルアミノ)フェニルアセチレンの代わりに2−(2,3,6,7−テトラヒドロ−1H,5H−ベンゾ[ij]キノリジン−9−イル)アセチレンを用いた以外は、合成中間体M8bの合成方法に準じて合成した。また、合成中間体M9cは、合成中間体M8bの代わりに合成中間体M8cを用いた以外は、合成中間体M9bの合成方法に準じて合成した。更に、化合物6cは、合成中間体M9bの代わりに合成中間体M9cを用いた以外は、化合物6bの合成方法に準じて合成した。この化合物6cは、N上のアルキル基がアニリンのベンゼン環に結合してアルキレン鎖(プロピレン鎖)を形成した化合物の一例といえる。化合物6cのスペクトルデータは以下の通り。
合成中間体M8dは、2−ブロモ−3−ヨードナフタレンの代わりに1−ブロモナフタレン−2−イルトリフレートを用いた以外は、合成中間体M8bの合成方法に準じて合成した。また、合成中間体M9dは、合成中間体M8bの代わりに合成中間体M8dを用いた以外は、合成中間体M9bの合成方法に準じて合成した。更に、化合物6dは、合成中間体M9bの代わりに合成中間体M9dを用いた以外は、化合物6bの合成方法に準じて合成した。化合物6dのスペクトルデータは以下の通り。
以下のスキームに従って、化合物7a,7bを合成した。
合成中間体M9a(1.24mmol)を無水トルエン(5mL)に懸濁させた懸濁液へ、HSiCl3(6.24mmol)を室温で一度に加えた。1時間攪拌後、すべての揮発性物質を減圧下で除去した。その後、トルエン(5mL)を加え、得られた懸濁液をアルゴン雰囲気下、セライトプラグを通して濾過し、トルエン(5mL)でリンスした。濾液を濃縮後、得られた固体を無水THF(15mL)に溶かした。この溶液へt−BuLiのペンタン溶液(1.77M,1.47mL,2.60mmol)を−78℃で10分かけて添加した。1時間攪拌後、ベンゾフェノン(2.74mmol)を一度に加え、得られた混合液を室温まで6時間かけてゆっくり温めた。その後、NH4Clの飽和水溶液(2mL)を用いて0℃で反応をクエンチし、続いてH2O2水溶液(1mL,30%)で酸化し、室温で1時間攪拌した。Na2SO3水溶液(20mL,10%)で反応をクエンチした後、混合液をEtOAc(50mL)で2回抽出した。合わせた有機層をH2O(20mL),ブライン(20mL)で洗浄し、その後無水Na2SO4で乾燥し、濾過した。濾液を減圧下で濃縮後、得られた固体をシリカゲルクロマトグラフィ(溶出液はCH2Cl2 からCH2Cl2/EtOAc=2/1へ切り替えた)及びGPC(CHCl3)で精製し、薄黄色の固体である合成中間体M10aを収率51%で得た。
合成中間体M10bは、合成中間体9b(0.500mmol)と4,4’−ビス(トリ(エチレングリコール)モノメチルエーテル)ベンゾフェノン(0.600mmol)を出発原料として、合成中間体M10aと同様にして合成した。また、化合物7bは、合成中間体M10aの代わりに合成中間体M10bを用いた以外は、化合物7aと同様にして合成した。化合物7aのスペクトルデータは以下の通り。
化合物1〜3,6b〜6d,7a及び7bにつき、光物性を測定した。紫外可視吸収スペクトルは紫外可視近赤外分光光度計UV−3150(島津製作所)を、蛍光スペクトルは分光蛍光光度計F−4500(日立)を用いて測定した。絶対蛍光量子収率の測定には、絶対PL量子収率測定装置C9920−02あるいはC11347−01(浜松ホトニクス)を用いた。全ての試料は,ナカライテスク製の蛍光スペクトル測定用溶媒を用いて試料溶液を調製し、1cm角の石英セルを用いて測定した。試料濃度は、吸収スペクトル測定時は約10-5M、蛍光スペクトル測定時は消光が生じないことを確認した濃度の範囲内に設定した。絶対蛍光量子収率を測定する際には、アルゴンを数分間吹き込むことで溶存酸素を除いた。その結果を表1〜表8に示す。なお、表には示さなかったが、ヘキサン、酢酸エチル及びメタノールの配向分極率△fは、それぞれ−0.000518、0.201及び0.309であった。
化合物1〜3につき、表1〜3の結果を用いて、溶媒の配向分極率Δfとストークスシフト値との関係を求めた。その結果を図1に示す。配向分極率Δfは、溶媒の誘電率εと屈折率nを用いて図1に示した式にしたがって算出した。ストークスシフト値は、吸収極大波長λmaxを単位cm-1となるように換算した値から、発光極大波長λexを単位cm-1となるように換算した値を引いた値とした。図1から明らかなように、化合物1〜3は、いずれもストークスシフト値と配向分極率Δfとの関係は直線関係(1次関数)に近似できた。このことから、化合物1〜3を蛍光色素として利用した場合、λmaxとλexを測定してストークスシフト値を求めれば、それに対応した配向分極率Δfを一義的に導くことができる。つまり、ストークスシフト値から、その蛍光色素の周囲の環境がどのような極性であるかを知ることができる。
(1)化合物1を用いた細胞染色実験
ジメチルスルホキシドを0.1%含む化合物1の10mM水溶液中でHeLa細胞を37℃で24時間培養したのち、3%スクロース水溶液で細胞を洗浄し、顕微鏡観察を行った。観察には、ZEISS社の共焦点顕微鏡システム(LSM780)を用いた。その結果、核を除く細胞全体の染色が認められた。ピクセル毎の蛍光スペクトルを取得した結果、530nm、550nm、および565nmに発光極大をもつ3種類のスペクトルに分類できた。細胞の表層付近は主に530nm、細胞質の部分は565nmに極大をもつ発光を示し、細胞質中には550nmに発光極大をもつ箇所が点在していることが認められた。染色された細胞組織の極性環境に依存して発光色が異なることを反映しているものと考えられ、同一の化合物1を用いて細胞内環境のイメージングが可能であることが示された。
ジメチルスルホキシドを0.001%含む化合物3の100nM水溶液中で、HeLa細胞を37℃で1時間培養したのち、3%スクロース水溶液で細胞を洗浄し、顕微鏡観察を行った。観察には、ZEISS社の共焦点顕微鏡システム(LSM780)を用いた。その結果,核を除く細胞全体の染色が認められた。ピクセル毎の蛍光スペクトルを取得した結果、520nmおよび570nmに発光極大波長をもつ2種類のスペクトル分類された。この結果より、染色されている部位に応じて発光波長が異なることが分かった。
化合物1,2(6a),6b,7a,7b及び公知の蛍光色素Alexa−430の各々につき、吸光度が同程度(0.39〜0.44)になるようにアセトニトリル溶液を調製した。溶液中の化合物の濃度は、化合物1:2.35×10-5M,化合物2(6a):2.17×10-5M,化合物6b:1.25×10-5M,化合物7a:3.30×10-5M,化合物7b:2.04×10-5Mであった。Alexa−430は耐光性の高い蛍光色素として知られている。各アセトニトリル溶液につき、溶液調製直後にモル吸光係数を測定した。その後、各アセトニトリル溶液に403nmのレーザ光を20分、60分、120分照射した後のモル吸光係数を測定し、レーザ光照射前(溶液調製直後)のモル吸光係数に対する相対吸光度を求めた。その結果を図2に示す。図2から明らかなように、化合物1,2(6a),6b及び蛍光色素Alexa−430と比べて、化合物7a,6bはレーザ光を120分照射した後も相対吸光度はほぼ1のままであり、非常に高い耐光性を示した。
Claims (7)
- 下記式(1)で表されるホスホール化合物。
- R1はアリール基又は置換アリール基であり、R2は水素原子、アリール基又は置換アリール基であり、R3及びR4は同じものであって、アルキル基、置換アルキル基、アリール基又は置換アリール基であり、Arはベンゼン環又はナフタレン環であり、nはゼロであり、π1はベンゼン環であり、−NR3R4はベンゼン環であるπ1のパラ位に結合している、
請求項1に記載のホスホール化合物。 - R3及びR4は、アルキル基又は置換アルキル基であり、ベンゼン環であるπ1に結合してアルキレン鎖又は置換アルキレン鎖を形成している、
請求項2に記載のホスホール化合物。 - 下記式(2)で表されるホスホール化合物。
- R1はアリール基又は置換アリール基であり、R3及びR4は同じものであって、アルキル基、置換アルキル基、アリール基又は置換アリール基であり、R5及びR6は同じものであって、アルキル基、置換アルキル基、アリール基又は置換アリール基であり、Arはベンゼン環又はナフタレン環であり、nはゼロであり、π1はベンゼン環である、
請求項4に記載のホスホール化合物。 - R3及びR4は、アルキル基又は置換アルキル基であり、ベンゼン環であるπ1に結合してアルキレン鎖又は置換アルキレン鎖を形成している、
請求項5に記載のホスホール化合物。 - 請求項1〜6のいずれか1項に記載のホスホール化合物を含有する蛍光色素。
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