CN104073017A - Organic dye sensitizer, preparation method and application in photoelectric conversion - Google Patents
Organic dye sensitizer, preparation method and application in photoelectric conversion Download PDFInfo
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- CN104073017A CN104073017A CN201410122668.3A CN201410122668A CN104073017A CN 104073017 A CN104073017 A CN 104073017A CN 201410122668 A CN201410122668 A CN 201410122668A CN 104073017 A CN104073017 A CN 104073017A
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- 238000006243 chemical reaction Methods 0.000 title claims abstract description 335
- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- 125000003118 aryl group Chemical group 0.000 claims abstract description 13
- 230000007935 neutral effect Effects 0.000 claims abstract description 13
- 150000001875 compounds Chemical class 0.000 claims description 655
- 238000000034 method Methods 0.000 claims description 454
- 239000002904 solvent Substances 0.000 claims description 164
- PCLIMKBDDGJMGD-UHFFFAOYSA-N N-bromosuccinimide Chemical compound BrN1C(=O)CCC1=O PCLIMKBDDGJMGD-UHFFFAOYSA-N 0.000 claims description 80
- 239000003960 organic solvent Substances 0.000 claims description 76
- 239000003513 alkali Substances 0.000 claims description 75
- 239000007789 gas Substances 0.000 claims description 67
- 229940125782 compound 2 Drugs 0.000 claims description 54
- 238000006467 substitution reaction Methods 0.000 claims description 45
- -1 methoxyl group Chemical group 0.000 claims description 43
- QFLWZFQWSBQYPS-AWRAUJHKSA-N (3S)-3-[[(2S)-2-[[(2S)-2-[5-[(3aS,6aR)-2-oxo-1,3,3a,4,6,6a-hexahydrothieno[3,4-d]imidazol-4-yl]pentanoylamino]-3-methylbutanoyl]amino]-3-(4-hydroxyphenyl)propanoyl]amino]-4-[1-bis(4-chlorophenoxy)phosphorylbutylamino]-4-oxobutanoic acid Chemical compound CCCC(NC(=O)[C@H](CC(O)=O)NC(=O)[C@H](Cc1ccc(O)cc1)NC(=O)[C@@H](NC(=O)CCCCC1SC[C@@H]2NC(=O)N[C@H]12)C(C)C)P(=O)(Oc1ccc(Cl)cc1)Oc1ccc(Cl)cc1 QFLWZFQWSBQYPS-AWRAUJHKSA-N 0.000 claims description 41
- 229940125904 compound 1 Drugs 0.000 claims description 38
- LNUFLCYMSVYYNW-ZPJMAFJPSA-N [(2r,3r,4s,5r,6r)-2-[(2r,3r,4s,5r,6r)-6-[(2r,3r,4s,5r,6r)-6-[(2r,3r,4s,5r,6r)-6-[[(3s,5s,8r,9s,10s,13r,14s,17r)-10,13-dimethyl-17-[(2r)-6-methylheptan-2-yl]-2,3,4,5,6,7,8,9,11,12,14,15,16,17-tetradecahydro-1h-cyclopenta[a]phenanthren-3-yl]oxy]-4,5-disulfo Chemical compound O([C@@H]1[C@@H](COS(O)(=O)=O)O[C@@H]([C@@H]([C@H]1OS(O)(=O)=O)OS(O)(=O)=O)O[C@@H]1[C@@H](COS(O)(=O)=O)O[C@@H]([C@@H]([C@H]1OS(O)(=O)=O)OS(O)(=O)=O)O[C@@H]1[C@@H](COS(O)(=O)=O)O[C@H]([C@@H]([C@H]1OS(O)(=O)=O)OS(O)(=O)=O)O[C@@H]1C[C@@H]2CC[C@H]3[C@@H]4CC[C@@H]([C@]4(CC[C@@H]3[C@@]2(C)CC1)C)[C@H](C)CCCC(C)C)[C@H]1O[C@H](COS(O)(=O)=O)[C@@H](OS(O)(=O)=O)[C@H](OS(O)(=O)=O)[C@H]1OS(O)(=O)=O LNUFLCYMSVYYNW-ZPJMAFJPSA-N 0.000 claims description 33
- 238000006482 condensation reaction Methods 0.000 claims description 30
- 239000003999 initiator Substances 0.000 claims description 24
- 229940125758 compound 15 Drugs 0.000 claims description 23
- 229940125898 compound 5 Drugs 0.000 claims description 23
- AOSZTAHDEDLTLQ-AZKQZHLXSA-N (1S,2S,4R,8S,9S,11S,12R,13S,19S)-6-[(3-chlorophenyl)methyl]-12,19-difluoro-11-hydroxy-8-(2-hydroxyacetyl)-9,13-dimethyl-6-azapentacyclo[10.8.0.02,9.04,8.013,18]icosa-14,17-dien-16-one Chemical compound C([C@@H]1C[C@H]2[C@H]3[C@]([C@]4(C=CC(=O)C=C4[C@@H](F)C3)C)(F)[C@@H](O)C[C@@]2([C@@]1(C1)C(=O)CO)C)N1CC1=CC=CC(Cl)=C1 AOSZTAHDEDLTLQ-AZKQZHLXSA-N 0.000 claims description 22
- 229940126657 Compound 17 Drugs 0.000 claims description 22
- 239000002253 acid Substances 0.000 claims description 22
- SZUVGFMDDVSKSI-WIFOCOSTSA-N (1s,2s,3s,5r)-1-(carboxymethyl)-3,5-bis[(4-phenoxyphenyl)methyl-propylcarbamoyl]cyclopentane-1,2-dicarboxylic acid Chemical compound O=C([C@@H]1[C@@H]([C@](CC(O)=O)([C@H](C(=O)N(CCC)CC=2C=CC(OC=3C=CC=CC=3)=CC=2)C1)C(O)=O)C(O)=O)N(CCC)CC(C=C1)=CC=C1OC1=CC=CC=C1 SZUVGFMDDVSKSI-WIFOCOSTSA-N 0.000 claims description 21
- GCTFWCDSFPMHHS-UHFFFAOYSA-M Tributyltin chloride Chemical compound CCCC[Sn](Cl)(CCCC)CCCC GCTFWCDSFPMHHS-UHFFFAOYSA-M 0.000 claims description 21
- 108010021119 Trichosanthin Proteins 0.000 claims description 21
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- 239000001257 hydrogen Substances 0.000 claims description 21
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- UNILWMWFPHPYOR-KXEYIPSPSA-M 1-[6-[2-[3-[3-[3-[2-[2-[3-[[2-[2-[[(2r)-1-[[2-[[(2r)-1-[3-[2-[2-[3-[[2-(2-amino-2-oxoethoxy)acetyl]amino]propoxy]ethoxy]ethoxy]propylamino]-3-hydroxy-1-oxopropan-2-yl]amino]-2-oxoethyl]amino]-3-[(2r)-2,3-di(hexadecanoyloxy)propyl]sulfanyl-1-oxopropan-2-yl Chemical compound O=C1C(SCCC(=O)NCCCOCCOCCOCCCNC(=O)COCC(=O)N[C@@H](CSC[C@@H](COC(=O)CCCCCCCCCCCCCCC)OC(=O)CCCCCCCCCCCCCCC)C(=O)NCC(=O)N[C@H](CO)C(=O)NCCCOCCOCCOCCCNC(=O)COCC(N)=O)CC(=O)N1CCNC(=O)CCCCCN\1C2=CC=C(S([O-])(=O)=O)C=C2CC/1=C/C=C/C=C/C1=[N+](CC)C2=CC=C(S([O-])(=O)=O)C=C2C1 UNILWMWFPHPYOR-KXEYIPSPSA-M 0.000 claims description 20
- LWLSVNFEVKJDBZ-UHFFFAOYSA-N N-[4-(trifluoromethoxy)phenyl]-4-[[3-[5-(trifluoromethyl)pyridin-2-yl]oxyphenyl]methyl]piperidine-1-carboxamide Chemical compound FC(OC1=CC=C(C=C1)NC(=O)N1CCC(CC1)CC1=CC(=CC=C1)OC1=NC=C(C=C1)C(F)(F)F)(F)F LWLSVNFEVKJDBZ-UHFFFAOYSA-N 0.000 claims description 20
- 150000002431 hydrogen Chemical class 0.000 claims description 20
- ONBQEOIKXPHGMB-VBSBHUPXSA-N 1-[2-[(2s,3r,4s,5r)-3,4-dihydroxy-5-(hydroxymethyl)oxolan-2-yl]oxy-4,6-dihydroxyphenyl]-3-(4-hydroxyphenyl)propan-1-one Chemical compound O[C@@H]1[C@H](O)[C@@H](CO)O[C@H]1OC1=CC(O)=CC(O)=C1C(=O)CCC1=CC=C(O)C=C1 ONBQEOIKXPHGMB-VBSBHUPXSA-N 0.000 claims description 19
- 229940126142 compound 16 Drugs 0.000 claims description 19
- 229940126214 compound 3 Drugs 0.000 claims description 19
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 19
- 239000003795 chemical substances by application Substances 0.000 claims description 18
- GHYOCDFICYLMRF-UTIIJYGPSA-N (2S,3R)-N-[(2S)-3-(cyclopenten-1-yl)-1-[(2R)-2-methyloxiran-2-yl]-1-oxopropan-2-yl]-3-hydroxy-3-(4-methoxyphenyl)-2-[[(2S)-2-[(2-morpholin-4-ylacetyl)amino]propanoyl]amino]propanamide Chemical compound C1(=CCCC1)C[C@@H](C(=O)[C@@]1(OC1)C)NC([C@H]([C@@H](C1=CC=C(C=C1)OC)O)NC([C@H](C)NC(CN1CCOCC1)=O)=O)=O GHYOCDFICYLMRF-UTIIJYGPSA-N 0.000 claims description 16
- 229940125797 compound 12 Drugs 0.000 claims description 16
- 230000021615 conjugation Effects 0.000 claims description 14
- 206010070834 Sensitisation Diseases 0.000 claims description 12
- 230000008313 sensitization Effects 0.000 claims description 12
- 125000001544 thienyl group Chemical group 0.000 claims description 12
- 125000000217 alkyl group Chemical group 0.000 claims description 11
- WGLLSSPDPJPLOR-UHFFFAOYSA-N tetramethylethylene Natural products CC(C)=C(C)C WGLLSSPDPJPLOR-UHFFFAOYSA-N 0.000 claims description 11
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 claims description 11
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 10
- 150000003839 salts Chemical class 0.000 claims description 10
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- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 9
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 9
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- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 8
- ZLVXBBHTMQJRSX-VMGNSXQWSA-N jdtic Chemical compound C1([C@]2(C)CCN(C[C@@H]2C)C[C@H](C(C)C)NC(=O)[C@@H]2NCC3=CC(O)=CC=C3C2)=CC=CC(O)=C1 ZLVXBBHTMQJRSX-VMGNSXQWSA-N 0.000 claims description 8
- IWZSHWBGHQBIML-ZGGLMWTQSA-N (3S,8S,10R,13S,14S,17S)-17-isoquinolin-7-yl-N,N,10,13-tetramethyl-2,3,4,7,8,9,11,12,14,15,16,17-dodecahydro-1H-cyclopenta[a]phenanthren-3-amine Chemical compound CN(C)[C@H]1CC[C@]2(C)C3CC[C@@]4(C)[C@@H](CC[C@@H]4c4ccc5ccncc5c4)[C@@H]3CC=C2C1 IWZSHWBGHQBIML-ZGGLMWTQSA-N 0.000 claims description 7
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- 229910052736 halogen Inorganic materials 0.000 claims description 6
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- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 5
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- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 4
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- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims description 3
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- LQZMLBORDGWNPD-UHFFFAOYSA-N N-iodosuccinimide Substances IN1C(=O)CCC1=O LQZMLBORDGWNPD-UHFFFAOYSA-N 0.000 claims description 2
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 claims description 2
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- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 description 1
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- RFFFKMOABOFIDF-UHFFFAOYSA-N Pentanenitrile Chemical compound CCCCC#N RFFFKMOABOFIDF-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 239000004695 Polyether sulfone Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 229910006404 SnO 2 Inorganic materials 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- NNLVGZFZQQXQNW-ADJNRHBOSA-N [(2r,3r,4s,5r,6s)-4,5-diacetyloxy-3-[(2s,3r,4s,5r,6r)-3,4,5-triacetyloxy-6-(acetyloxymethyl)oxan-2-yl]oxy-6-[(2r,3r,4s,5r,6s)-4,5,6-triacetyloxy-2-(acetyloxymethyl)oxan-3-yl]oxyoxan-2-yl]methyl acetate Chemical compound O([C@@H]1O[C@@H]([C@H]([C@H](OC(C)=O)[C@H]1OC(C)=O)O[C@H]1[C@@H]([C@@H](OC(C)=O)[C@H](OC(C)=O)[C@@H](COC(C)=O)O1)OC(C)=O)COC(=O)C)[C@@H]1[C@@H](COC(C)=O)O[C@@H](OC(C)=O)[C@H](OC(C)=O)[C@H]1OC(C)=O NNLVGZFZQQXQNW-ADJNRHBOSA-N 0.000 description 1
- QLKSCXOGMDNMRI-UHFFFAOYSA-N [Sn].[F+][O-] Chemical compound [Sn].[F+][O-] QLKSCXOGMDNMRI-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- WUOACPNHFRMFPN-UHFFFAOYSA-N alpha-terpineol Chemical compound CC1=CCC(C(C)(C)O)CC1 WUOACPNHFRMFPN-UHFFFAOYSA-N 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- GVFOJDIFWSDNOY-UHFFFAOYSA-N antimony tin Chemical compound [Sn].[Sb] GVFOJDIFWSDNOY-UHFFFAOYSA-N 0.000 description 1
- 239000011260 aqueous acid Substances 0.000 description 1
- 230000006399 behavior Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910000085 borane Inorganic materials 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- ODDBHAGNNBEBEY-UHFFFAOYSA-N boric acid;thiophene Chemical compound OB(O)O.C=1C=CSC=1 ODDBHAGNNBEBEY-UHFFFAOYSA-N 0.000 description 1
- RDHPKYGYEGBMSE-UHFFFAOYSA-N bromoethane Chemical compound CCBr RDHPKYGYEGBMSE-UHFFFAOYSA-N 0.000 description 1
- ANUZKYYBDVLEEI-UHFFFAOYSA-N butane;hexane;lithium Chemical compound [Li]CCCC.CCCCCC ANUZKYYBDVLEEI-UHFFFAOYSA-N 0.000 description 1
- VJYJJHQEVLEOFL-UHFFFAOYSA-N c1c[s]c2c1[s]cc2 Chemical compound c1c[s]c2c1[s]cc2 VJYJJHQEVLEOFL-UHFFFAOYSA-N 0.000 description 1
- 229910000024 caesium carbonate Inorganic materials 0.000 description 1
- HUCVOHYBFXVBRW-UHFFFAOYSA-M caesium hydroxide Chemical class [OH-].[Cs+] HUCVOHYBFXVBRW-UHFFFAOYSA-M 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- ONCCWDRMOZMNSM-FBCQKBJTSA-N compound Z Chemical compound N1=C2C(=O)NC(N)=NC2=NC=C1C(=O)[C@H]1OP(O)(=O)OC[C@H]1O ONCCWDRMOZMNSM-FBCQKBJTSA-N 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- HVMJUDPAXRRVQO-UHFFFAOYSA-N copper indium Chemical compound [Cu].[In] HVMJUDPAXRRVQO-UHFFFAOYSA-N 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000005520 cutting process Methods 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
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- SQIFACVGCPWBQZ-UHFFFAOYSA-N delta-terpineol Natural products CC(C)(O)C1CCC(=C)CC1 SQIFACVGCPWBQZ-UHFFFAOYSA-N 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- CDHICTNQMQYRSM-UHFFFAOYSA-N di(propan-2-yl)alumane Chemical compound CC(C)[AlH]C(C)C CDHICTNQMQYRSM-UHFFFAOYSA-N 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 239000003480 eluent Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 229920001249 ethyl cellulose Polymers 0.000 description 1
- 235000019325 ethyl cellulose Nutrition 0.000 description 1
- YZZNJYQZJKSEER-UHFFFAOYSA-N gallium tin Chemical compound [Ga].[Sn] YZZNJYQZJKSEER-UHFFFAOYSA-N 0.000 description 1
- 239000000499 gel Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000005525 hole transport Effects 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
- 238000005286 illumination Methods 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- MRNHPUHPBOKKQT-UHFFFAOYSA-N indium;tin;hydrate Chemical compound O.[In].[Sn] MRNHPUHPBOKKQT-UHFFFAOYSA-N 0.000 description 1
- 150000004694 iodide salts Chemical class 0.000 description 1
- 239000002608 ionic liquid Substances 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 230000004301 light adaptation Effects 0.000 description 1
- 230000013011 mating Effects 0.000 description 1
- 238000005374 membrane filtration Methods 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 230000029553 photosynthesis Effects 0.000 description 1
- 238000010672 photosynthesis Methods 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920003207 poly(ethylene-2,6-naphthalate) Polymers 0.000 description 1
- 229920000767 polyaniline Polymers 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920006393 polyether sulfone Polymers 0.000 description 1
- 239000011112 polyethylene naphthalate Substances 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920000128 polypyrrole Polymers 0.000 description 1
- 229920000123 polythiophene Polymers 0.000 description 1
- NROKBHXJSPEDAR-UHFFFAOYSA-M potassium fluoride Chemical class [F-].[K+] NROKBHXJSPEDAR-UHFFFAOYSA-M 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- 230000000750 progressive effect Effects 0.000 description 1
- QLNJFJADRCOGBJ-UHFFFAOYSA-N propionamide Chemical compound CCC(N)=O QLNJFJADRCOGBJ-UHFFFAOYSA-N 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 238000002390 rotary evaporation Methods 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- APSBXTVYXVQYAB-UHFFFAOYSA-M sodium docusate Chemical compound [Na+].CCCCC(CC)COC(=O)CC(S([O-])(=O)=O)C(=O)OCC(CC)CCCC APSBXTVYXVQYAB-UHFFFAOYSA-M 0.000 description 1
- 235000010288 sodium nitrite Nutrition 0.000 description 1
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical class [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 description 1
- 239000012265 solid product Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-N succinic acid Chemical compound OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- 229940116411 terpineol Drugs 0.000 description 1
- NMFKEMBATXKZSP-UHFFFAOYSA-N thieno[3,2-b]thiophene Chemical compound S1C=CC2=C1C=CS2.S1C=CC2=C1C=CS2 NMFKEMBATXKZSP-UHFFFAOYSA-N 0.000 description 1
- UZXFOOHHOTUFJA-UHFFFAOYSA-N thiophene;tributyltin Chemical compound C=1C=CSC=1.CCCC[Sn](CCCC)CCCC UZXFOOHHOTUFJA-UHFFFAOYSA-N 0.000 description 1
- 150000003613 toluenes Chemical class 0.000 description 1
- UKTDFYOZPFNQOQ-UHFFFAOYSA-N tributyl(thiophen-2-yl)stannane Chemical compound CCCC[Sn](CCCC)(CCCC)C1=CC=CS1 UKTDFYOZPFNQOQ-UHFFFAOYSA-N 0.000 description 1
- HPTXTUCJAKOFES-UHFFFAOYSA-N tributyl-[4-(trifluoromethyl)phenyl]stannane Chemical compound CCCC[Sn](CCCC)(CCCC)C1=CC=C(C(F)(F)F)C=C1 HPTXTUCJAKOFES-UHFFFAOYSA-N 0.000 description 1
- UORVGPXVDQYIDP-UHFFFAOYSA-N trihydridoboron Substances B UORVGPXVDQYIDP-UHFFFAOYSA-N 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B57/00—Other synthetic dyes of known constitution
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B17/00—Azine dyes
- C09B17/04—Azine dyes of the naphthalene series
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B23/00—Methine or polymethine dyes, e.g. cyanine dyes
- C09B23/10—The polymethine chain containing an even number of >CH- groups
- C09B23/105—The polymethine chain containing an even number of >CH- groups two >CH- groups
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B23/00—Methine or polymethine dyes, e.g. cyanine dyes
- C09B23/14—Styryl dyes
- C09B23/148—Stilbene dyes containing the moiety -C6H5-CH=CH-C6H5
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B57/00—Other synthetic dyes of known constitution
- C09B57/001—Pyrene dyes
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B57/00—Other synthetic dyes of known constitution
- C09B57/004—Diketopyrrolopyrrole dyes
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B57/00—Other synthetic dyes of known constitution
- C09B57/008—Triarylamine dyes containing no other chromophores
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B69/00—Dyes not provided for by a single group of this subclass
- C09B69/10—Polymeric dyes; Reaction products of dyes with monomers or with macromolecular compounds
- C09B69/109—Polymeric dyes; Reaction products of dyes with monomers or with macromolecular compounds containing other specific dyes
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
- H01G9/20—Light-sensitive devices
- H01G9/2059—Light-sensitive devices comprising an organic dye as the active light absorbing material, e.g. adsorbed on an electrode or dissolved in solution
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/60—Organic compounds having low molecular weight
- H10K85/631—Amine compounds having at least two aryl rest on at least one amine-nitrogen atom, e.g. triphenylamine
- H10K85/636—Amine compounds having at least two aryl rest on at least one amine-nitrogen atom, e.g. triphenylamine comprising heteroaromatic hydrocarbons as substituents on the nitrogen atom
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/60—Organic compounds having low molecular weight
- H10K85/649—Aromatic compounds comprising a hetero atom
- H10K85/655—Aromatic compounds comprising a hetero atom comprising only sulfur as heteroatom
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
- H01G9/20—Light-sensitive devices
- H01G9/2027—Light-sensitive devices comprising an oxide semiconductor electrode
- H01G9/2031—Light-sensitive devices comprising an oxide semiconductor electrode comprising titanium oxide, e.g. TiO2
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/40—Organosilicon compounds, e.g. TIPS pentacene
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/60—Organic compounds having low molecular weight
- H10K85/649—Aromatic compounds comprising a hetero atom
- H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/542—Dye sensitized solar cells
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/549—Organic PV cells
Abstract
The invention discloses an organic dye sensitizer, a preparation method and an application of the organic dye sensitizer in photoelectric conversion. The invention provides an organic dye sensitizer having the general formula as shown in formula I, wherein A is an electron-deficient unit, which is an electron acceptor; D is an electron-rich unit, which is an electron donor; N is an electron neutral organic structural unit, which has no significant ability to push and pull the electron; pion is a conjugate structural unit for bonding; Ar is conjugated aromatic ring system chromophoric units or a conjugated combination of two or more of structural units; B refers to a structural unit formed by bonding a nanometer porous surface of the dye-sensitized cell photoanode and transporting electrons excited by irradiating dye-sensitizing agent molecules with the visible and ultraviolet light to form current; and n is 1,2,3,4,5 or 6.
Description
Technical field
The present invention relates to organic dye sensitized dose, preparation method and the application in opto-electronic conversion.
Background technology
The continuous deterioration of the potential collision hazard of the energy and ecotope makes the new and renewable sources of energy of exploitation including sun power become key subjects in worldwide; on the earth, all life is all based on sun power (photosynthesis by phycophyta is realized); electric energy is the widely used one of current human society energy form (realizing by various power stations, battery and electrical equipment) safely and effectively, and photovoltaic energy conversion and energy storage technology are the energy solutions with essence meaning.At present, in photovoltaic cell technical study and Materials, topmost part remains and carries out around crystalline silicon, and the solar cell of silica-base material requires high to material purity, equipment and cost of manufacture costliness; In its suite of equipment manufacturing processed, using the factors such as environmental pollution, old equipment and assembly recycling that material and manufacturing process bring is the Main Bottleneck that this class battery apparatus continues development.In order to adapt to the actual needs of solar cell high-level efficiency, low cost, large-scale production and use, greatly developing non-crystalline silicon, cadmium telluride, copper indium gallium tin, organic semiconductor thin film battery and dye-sensitized solar cells is major domain and the direction of researching and developing.Dye sensitization solar battery (B.O ' Regan, M.
nature, 1991,353,737-740) manufacture craft is relatively simple, manufacturing processed energy consumption is few, and equipment requirements ratio is easier to reach; Its main material cost is cheap, to various intensity light adaptations good (possessing the opto-electronic conversion work capacity under room light and low light condition), in the product orientation advantage that segments market aspect Portable movable electrical equipment and rechargable power supplies, may become the dominance product of the following solar cell of a class.Light-sensitive coloring agent is an important component part of dye sensitization solar battery, and dyestuff performance is most important for the photoelectric transformation efficiency of battery, and using at present more is ruthenium complexe light-sensitive coloring agent N719(M.
et al J.Am.Chem.Soc.1993,115,6382-6390).Substitute in order to find the efficient light-sensitive coloring agent that contains noble ruthenium, various organic photosensitive agent dye molecules are synthesized out (P.Bauerle, et al Angew.Chem.Int.Ed.2009,48,2474-2499).By the design and rational to organic dye sensitized agent molecule structure with rationally cut out, select the fragrant chromophoric group (Ar) of different conjugated structures, conjugated structure connector element and electron rich unit (electron donor(ED), D), electron deficiency unit (electron acceptor(EA), A), or neutral organic structure unit (neutral body, N) construct dye sensitization agent molecule, be expected to rationally change the three-dimensional arrangement of molecule, reduce the nonplanarity that dyes quick agent molecule, thereby reduce dyestuff at TiO
2the pi-pi accumulation effect on surface; The organic dye molecule that can prepare the wider absorption spectrum of possessing of needs, stronger photoelectric current, is beneficial to the locomotivity of enough adjusting electronics in transmission path, improves the photoelectric transformation efficiency of device.Chinese patent CN102816132A and CN102532032A disclose two class novel organic dye sensitizing agents, have enriched the type of organic dye sensitized dose, have embodied organic dye structure and have been full of variety and the good feature of opto-electronic conversion performance.
Summary of the invention
Technical problem to be solved by this invention is that a kind of organic dye sensitized dose, preparation method and the application in opto-electronic conversion are provided in order to overcome the defects such as existing organic dye sensitized dose of light, heat and poor chemical stability.Organic dye sensitized dose of the present invention possesses good light, heat, chemical stability, and the photosensitizer can be used as in commercialization dye-sensitized solar cells product uses.
The invention provides a kind of organic dye sensitized dose, its general formula is suc as formula shown in I: wherein, A(Acceptor) be electron deficiency unit, be electron acceptor(EA); D(Donor) being electron rich unit, is electron donor(ED); N(Neutral) be the neutral organic structure of electronics unit, do not possess obvious push-and-pull electronic capability; π (conjugated link) is for connecting the unit with conjugated structure; Ar is two or more the conjugation molectron in conjugation aromatic ring chromophoric group unit or these structural units; B(Binding Group) for referring to and the nanometer micropore surface phase bonding of dye sensitization battery light electricity anode, thus go out the structural unit of formation electric current by dying electric transmission that quick agent molecule excites after visible and UV-irradiation; N is 1,2,3,4,5 or 6;
In the present invention, described A(Acceptor) be preferably as follows the substituting group form of arbitrary structure:
Wherein, R
1, R
2, R
3, R
6, R
7, R
44, R
47and R
48independently select separately hydrogen, C
1-4alkyl (preferable methyl), C
1-4alkoxyl group (preferably methoxyl group), C
5-10aryl (preferably phenyl), the C that trifluoromethyl replaces
5-10aryl (preferably trifluoromethyl replace phenyl) and trifluoromethyl in one or more; R
4and R
5independently be selected from separately hydrogen, C
1-4alkyl (preferable methyl), C
1-4alkoxyl group (preferably methoxyl group), halogen (preferably F), cyano group, formyl radical and trifluoromethyl in one or more; R
8, R
9, R
10, R
11, R
12, R
13, R
14, R
45and R
46be independently C separately
5-10alkyl (preferably
).
In the present invention, described A(Acceptor) be further preferably as follows the substituting group form of arbitrary structure:
In the present invention, described A(Acceptor) the arbitrary substituting group shown in being further preferably as follows again:
In the present invention, the arbitrary substituting group shown in described A is further preferably as follows again:
In the present invention, described D(Donor) be preferably as follows the substituting group form of arbitrary structure:
Wherein, R
15be selected from hydrogen, C
1-4alkyl, C
1-10alkoxyl group (preferably methoxyl group or
) and
in one or more, the integer that wherein n is 1-10; R
16be selected from C
1-4alkyl (preferable methyl) and C
6-10aryl (preferably phenyl) in one or two; R
17, R
18, R
19and R
20independently be selected from separately hydrogen, C
1-6alkyl (preferably
), C
1-6alkoxyl group (preferably methoxyl group or
) and C
1-6the phenyl that replaces of alkoxyl group (preferably
or
) in one or more; R
21and R
22independently be selected from separately hydrogen, C
1-4alkyl (preferable methyl, ethyl, propyl group, sec.-propyl or the tertiary butyl), C
6-10aryl (preferably phenyl), C
1-4alkoxyl group (preferably methoxyl group, oxyethyl group, propoxy-, isopropoxy or tert.-butoxy) and C
1-4alkylamino (preferably methylamino-, ethylamino-or Propylamino) in one or more; R
23, R
24, R
25, R
26and R
27independently be selected from separately hydrogen, C
1-4alkyl and C
1-4alkoxyl group in one or more.
In the present invention, described D(Donor) be further preferably as follows the substituting group form of arbitrary structure:
In the present invention, described D(Donor) be further preferably as follows again shown in arbitrary substituting group:
In the present invention, described D(Donor) be further preferably as follows again shown in arbitrary substituting group:
In the present invention, described D(Donor) be further preferably as follows again shown in arbitrary substituting group:
In the present invention, described N(Neutral) the arbitrary substituting group shown in being preferably as follows:
C
1-20straight or branched alkyl (preferably
or
), the C that replaced by one or more halogens
1-4the alkyl (C preferably being replaced by one or more fluorine atoms
1-4alkyl, further preferred
c
1-6alkylamino (preferably
), C
1-6alkyl sodium sulfonate (preferably
),
(preferably
),
(preferably
integer that wherein m is 1-10 (preferably 1,2 or 3),
with
wherein R
28for C
1-20straight or branched alkyl.
In the present invention, described N(Neutral) the arbitrary substituting group shown in being further preferably as follows:
In the present invention, described π (conjugated link) is preferably as follows the substituting group form of arbitrary structure:
c
5-10aryl,
Wherein, R
29and R
30independently be selected from separately one or more in hydrogen, phenyl, furyl, pyrryl and thienyl; R
31, R
32and R
33independently be selected from separately hydrogen, C
1-10straight or branched alkyl (preferable methyl, ethyl, propyl group, butyl, amyl group or hexyl), C
1-10straight or branched alkoxyl group (preferably
), thienyl and by C
1-6alkyl replace thienyl in one or more; R
34, R
35, R
36, R
37, R
38and R
39independently be selected from separately hydrogen, C
1-10straight or branched alkyl and C
1-10straight or branched alkoxyl group in one or more.
In the present invention, described π (conjugated link) is further preferably as follows the substituting group form of arbitrary structure:
In the present invention, the arbitrary substituting group shown in described π (conjugated link) is further preferably as follows again:
In the present invention, the arbitrary substituting group shown in described π is further preferably as follows again:
In the present invention, the arbitrary substituting group shown in described π is further preferably as follows again:
In the present invention, described Ar is preferably as follows the substituting group form of arbitrary structure:
In the present invention, the arbitrary substituting group shown in described Ar is further preferably as follows:
In the present invention, the substituting group shown in described Ar is further preferably as follows again:
In the present invention, described B(Binding Group) be preferably as follows the substituting group form of arbitrary structure:
Wherein, R
40and R
41independently be selected from separately hydrogen, carboxyl, hydroxyl, C
2-6alkynyl (preferably ethynyl) and C
1-4carboxyl (preferably
) in one or more; R
42be selected from carboxyl,
cyano group, C
6-10aryl (preferably phenyl), the C being replaced by one or more cyano group
6-10aryl (phenyl preferably being replaced by one or more cyano group) and by the C of one or more carboxyl substituted
6-10aryl (preferably by the phenyl of one or more carboxyl substituted) in one or more; R
43for C
1～C
9straight chain or branched paraffin.
B(binding group described in the present invention) the arbitrary substituting group shown in being further preferably as follows:
In the present invention, described B(binding group) the arbitrary substituting group shown in being further preferably as follows again:
B(binding group described in the present invention) substituting group shown in being further preferably as follows again:
In the present invention, described Ar and described B(binding group) or described π can be connected with reasonable manner by any key; Described D, A or N can be connected with reasonable manner by any key with described π.
In the present invention, described as shown in general formula I organic dye sensitized dose, preferably has the compound of following arbitrary general formula:
Wherein π
1, π
2definition all identical with above-mentioned π definition, π
1with π
2can be the same or different.
In the present invention, described as shown in general formula I organic dye sensitized dose, is further preferably as follows arbitrary compound:
Described in the present invention organic dye sensitized dose can be according to the difference of concrete molecular structure, taking known compound as initial feed, prepare the particular compound in corresponding described organic dye sensitized dose in conjunction with the conventional reaction method of this area and reaction conditions.
It is the preparation method of thienyl, π terthienyl general formula compound 1 while being thienyl that the present invention also provides as Ar, and it comprises the following steps: in organic solvent, by compound 2 with
carry out condensation reaction, obtain compound 1;
Wherein, the definition of A, B and D is all same as above.
The method of preparing compound 1 can adopt ordinary method and the condition of such condensation reaction in this area, particularly preferably following reaction method and condition in the present invention:
Can under gas shield, carry out in the method for preparing compound 1, in the time preparing the method for compound 1 and can carry out under gas shield, one or more in gas preferred nitrogen, argon gas, helium and the neon described in described " under gas shield ".
Preparing in the method for compound 1, described organic solvent optimization acid class organic solvent, the described preferred acetic acid of carboxylic-acid organic solvent.
Preparing in the method for compound 1, the preferred 1mg/mL～100mg/L of mass volume ratio of described compound 2 and described organic solvent, further preferred 1mg/mL～20mg/L.
Preparing in the method for compound 1, described
with the molar ratio of described compound 2 preferably 1～5.
Preparing in the method for compound 1, preferably 0～150 DEG C of the temperature of described condensation reaction, further preferably 100 DEG C～150 DEG C.
Preparing in the method for compound 1, the process of described condensation reaction can adopt the routine monitoring method (for example TLC, HPLC or NMR) in this area to monitor, general with described
when disappearance, be reaction end, preferably 1 hour～24 hours reaction times, further preferably 1 hour～10 hours.
Preparing in the method for compound 1, under the condition that described condensation reaction preferably exists at ammonium acetate, carry out described ammonium acetate and described compound
molar ratio preferably 1～5.
Preferably include following post-processing step in the method for preparing compound 1: after reaction finishes, filtration obtains thick product, column chromatography separates the product obtaining after purifying, and the method that column chromatography separates and condition can adopt ordinary method and the condition of this generic operation in this area.
In the described method of preparing compound, prepared by can adopt method (1) method (2) or the method (3) of described compound 2:
Method (1) preferably includes following steps: in solvent, under the condition that alkali and catalyzer exist, compound 3 and compound 4 are carried out to Suzuki linked reaction, obtain described compound 2;
Method (2) preferably includes following steps: in solvent, under the condition that alkali and catalyzer exist, compound 8 and compound 9 are carried out to Suzuki linked reaction, obtain described compound 2;
Method (3) preferably includes following steps: in organic solvent, compound 11 and acid are carried out to oxidizing reaction and obtain compound 2;
Wherein, the definition of A and D is all same as above.
The method (1) of preparing compound 2 can adopt ordinary method and the condition of such Suzuki linked reaction in this area, particularly preferably following reaction method and condition in the present invention:
Preparing the method (1) of compound 2 can carry out under gas shield; in the time preparing the method (1) of compound 2 and carry out under gas shield, one or more in gas preferred nitrogen, argon gas, helium and the neon described in described " under gas shield ".
In the method (1) of preparing compound 2, the preferred ether solvent of described solvent and/or water, the preferred tetrahydrofuran (THF) of described ether solvent; In the time adopting the mixed solvent of ether solvent and water, described ether solvent and the volume ratio of water preferably 1～10, further preferably 1～5.
In the method (1) of preparing compound 2, the preferred 1mg/mL～100mg/L of mass volume ratio of described compound 4 and described solvent, further preferred 1mg/mL～20mg/L.
In the method (1) of preparing compound 2, the preferred mineral alkali of described alkali, the preferred salt of wormwood of described mineral alkali.
In the method (1) of preparing compound 2, the molar ratio of described alkali and described compound 4 preferably 1～5.
In the method (1) of preparing compound 2, described catalyzer is four triphenyl phosphorus palladiums preferably.
In the method (1) of preparing compound 2, the molar ratio of described catalyzer and described compound 4 preferably 0.01～1, further preferably 0.01～0.1.
In the method (1) of preparing compound 2, the molar ratio of described compound 3 and described compound 4 preferably 1～5.
In the method (1) of preparing compound 2, preferably 0～100 DEG C of the temperature of described Suzuki linked reaction, further preferably 40 DEG C～90 DEG C.
In the method (1) of preparing compound 2, the process of described Suzuki linked reaction can adopt the routine monitoring method (for example TLC, HPLC or NMR) in this area to monitor, general while disappearing taking described compound 4 as reaction end, preferably 1 hour～24 hours reaction times, further preferably 1 hour～10 hours.
Preferably include following post-processing step in the method (1) of preparing compound 2: after reaction finishes, except desolventizing, column chromatography separates the product obtaining after purifying, and the method that column chromatography separates and condition can adopt ordinary method and the condition of this generic operation in this area.
In the described method of preparing compound 1, it preferably includes following steps: in organic solvent, compound 5 and N-bromo-succinimide (NBS) are carried out to substitution reaction, obtain described compound 4;
Wherein, the definition of A, B and D is all same as above.
The method of preparing compound 4 can adopt ordinary method and the condition of such substitution reaction in this area, particularly preferably following reaction method and condition in the present invention:
Preparing in the method for compound 4, described organic solvent preferred amide kind solvent, the preferred DMF of described amide solvent (DMF);
Preparing in the method for compound 4, the preferred 1mg/mL～100mg/L of mass volume ratio of described compound 5 and described organic solvent, further preferred 1mg/mL～20mg/L.
Preparing in the method for compound 4, the molar ratio of described N-bromo-succinimide and described compound 5 preferably 1～3.
Preparing in the method for compound 4, preferably 0～100 DEG C of the temperature of described substitution reaction, further preferably 0 DEG C～40 DEG C.
Preparing in the method for compound 4, the process of described substitution reaction can adopt the routine monitoring method (for example TLC, HPLC or NMR) in this area to monitor, general while disappearing taking described compound 5 as reaction end, preferably 1 hour～48 hours reaction times, further preferably 1 hour～24 hours.
Prepare the method for compound 4 and preferably under the condition of radical initiator existence, carry out, the preferred benzoyl peroxide of described radical initiator or Diisopropyl azodicarboxylate.
The method of preparing compound 4 preferably includes following post-processing step: after reaction finishes, the cancellation that adds water reaction, filters, and obtains compound 4.
In the described method of preparing compound 1, it preferably includes following steps: in solvent, under the condition that alkali and catalyzer exist, compound 6 and compound B-11 are carried out to Suzuki linked reaction, obtain described compound 5;
Wherein, the definition of A, B and D is all same as above.
The method of preparing compound 5 can adopt ordinary method and the condition of such Suzuki linked reaction in this area, particularly preferably following reaction method and condition in the present invention:
Preparing the method for compound 5 can carry out under gas shield, in the time preparing the method for compound 5 and carry out under gas shield, and one or more in gas preferred nitrogen, argon gas, helium and the neon described in described " under gas shield ".
Preparing in the method for compound 5, the preferred ether solvent of described solvent and/or water, the preferred tetrahydrofuran (THF) of described ether solvent; In the time adopting the mixed solvent of ether solvent and water, described ether solvent and the volume ratio of water preferably 1～10, further preferably 1～5.
Preparing in the method for compound 5, the preferred 1mg/mL～100mg/L of mass volume ratio of described compound 6 and described solvent, further preferred 1mg/mL～20mg/L.
Preparing in the method for compound 5, the preferred mineral alkali of described alkali, the preferred salt of wormwood of described mineral alkali.
Preparing in the method for compound 5, the molar ratio of described alkali and described compound 6 preferably 1～5.
Preparing in the method for compound 5, described catalyzer is four triphenyl phosphorus palladiums preferably.
Preparing in the method for compound 5, the molar ratio of described catalyzer and described compound 6 preferably 0.01～1, further preferably 0.01～0.1.
Preparing in the method for compound 5, the molar ratio of described compound 6 and described compound B-11 preferably 1～5.
Preparing in the method for compound 5, preferably 0～100 DEG C of the temperature of described Suzuki linked reaction, further preferably 40 DEG C～90 DEG C.
Preparing in the method for compound 5, the process of described Suzuki linked reaction can adopt the routine monitoring method (for example TLC, HPLC or NMR) in this area to monitor, general while disappearing taking described compound 6 as reaction end, preferably 1 hour～24 hours reaction times, further preferably 1 hour～10 hours.
Preferably include following post-processing step in the method for preparing compound 5: after reaction finishes, except desolventizing, column chromatography separates the product obtaining after purifying, and the method that column chromatography separates and condition can adopt ordinary method and the condition of this generic operation in this area.
In the described method of preparing compound 1, it preferably includes following steps: in organic solvent, under the condition that alkali and catalyzer exist, compound 7 and duplex tetramethyl ethylene ketone boric acid ester (CAS:73183-34-3) are carried out to nucleophilic substitution reaction, obtain described compound 6;
Wherein, the definition of A is same as above.
The method of preparing compound 6 can adopt ordinary method and the condition of such nucleophilic substitution reaction in this area, particularly preferably following reaction method and condition in the present invention:
Preparing in the method for compound 6, the preferred ether solvent of described organic solvent, the preferred Isosorbide-5-Nitrae-dioxane of described ether solvent (diox);
Preparing in the method for compound 6, the preferred 1mg/mL～100mg/L of mass volume ratio of described compound 7 and described organic solvent, further preferred 1mg/mL～20mg/L.
Preparing in the method for compound 6, the molar ratio of described duplex tetramethyl ethylene ketone boric acid ester and described compound 7 preferably 1～3.
Preparing in the method for compound 6, the preferred mineral alkali of described alkali; The preferred Potassium ethanoate of described mineral alkali.
Preparing in the method for compound 6, the molar ratio of described alkali and described compound 7 preferably 1～5.
Preparing in the method for compound 6, described catalyzer is [two (diphenylphosphine) ferrocene of 1,1'-] palladium chloride (Pd (dppf) Cl preferably
2).
Preparing in the method for compound 6, the molar ratio of described catalyzer and described compound 7 preferably 0.01～1, further preferably 0.01～0.1.
Preparing in the method for compound 6, preferably 0～150 DEG C of the temperature of described nucleophilic substitution reaction, further preferably 50 DEG C～100 DEG C.
Preparing in the method for compound 6, the process of described nucleophilic substitution reaction can adopt the routine monitoring method (for example TLC, HPLC or NMR) in this area to monitor, general while disappearing taking described compound 7 as reaction end, preferably 1 hour～24 hours reaction times.
Preferably include following post-processing step in the method for preparing compound 6: after reaction finishes, except desolventizing, column chromatography separates the product obtaining after purifying, and the method that column chromatography separates and condition can adopt ordinary method and the condition of this generic operation in this area.
In the described method of preparing compound 1, it preferably includes following steps: in solvent, under the condition that alkali and catalyzer exist, compound 8 and 2-bromothiophene are carried out to Suzuki linked reaction, obtain described compound 7;
Wherein, the definition of A is all same as above.
The method of preparing compound 7 can adopt ordinary method and the condition of such Suzuki linked reaction in this area, particularly preferably following reaction method and condition in the present invention:
Preparing the method for compound 7 can carry out under gas shield, in the time preparing the method for compound 7 and carry out under gas shield, and one or more in gas preferred nitrogen, argon gas, helium and the neon described in described described " under gas shield ".
Preparing in the method for compound 7, the preferred ether solvent of described solvent and/or water, the preferred tetrahydrofuran (THF) of described ether solvent; In the time adopting the mixed solvent of ether solvent and water, described ether solvent and the volume ratio of water select 1～10, and further preferably 1～5.
Preparing in the method for compound 7, the preferred 1mg/mL～100mg/L of mass volume ratio of described compound 8 and described solvent, further preferred 1mg/mL～20mg/L.
Preparing in the method for compound 7, the preferred mineral alkali of described alkali, the preferred salt of wormwood of described mineral alkali.
Preparing in the method for compound 7, the molar ratio of described alkali and described compound 8 preferably 1～5.
Preparing in the method for compound 7, described catalyzer is four triphenyl phosphorus palladiums preferably.
Preparing in the method for compound 7, the molar ratio of described catalyzer and described compound 8 preferably 0.01～1, further preferably 0.01～0.1.
Preparing in the method for compound 7, the molar ratio of described compound 8 and described 2-bromothiophene preferably 1～5.
Preparing in the method for compound 7, preferably 0～100 DEG C of the temperature of described Suzuki linked reaction, further preferably 40 DEG C～90 DEG C.
Preparing in the method for compound 7, the process of described Suzuki linked reaction can adopt the routine monitoring method (for example TLC, HPLC or NMR) in this area to monitor, while generally disappearance taking described compound 2-bromothiophene as reaction end, preferably 1 hour～24 hours reaction times, further preferably 1 hour～10 hours.
Preferably include following post-processing step in the method for preparing compound 7: after reaction finishes, except desolventizing, column chromatography separates the product obtaining after purifying, and the method that column chromatography separates and condition can adopt ordinary method and the condition of this generic operation in this area.
The method (2) of preparing compound 2 can adopt ordinary method and the condition of such Suzuki linked reaction in this area, particularly preferably following reaction method and condition in the present invention:
Preparing the method (2) of compound 2 can carry out under gas shield, in the time that the described method of preparing compound 2 (2) is carried out under gas shield, and one or more in described gas preferred nitrogen, argon gas, helium and neon.
In the method (2) of preparing compound 2, the preferred ether solvent of described solvent and/or water, the preferred tetrahydrofuran (THF) of described ether solvent; In the time adopting the mixed solvent of ether solvent and water, described ether solvent and the volume ratio of water preferably 1～10, further preferably 1～5.
In the method (2) of preparing compound 2, the preferred 1mg/mL～100mg/L of mass volume ratio of described compound 9 and described solvent, further preferred 1mg/mL～20mg/L.
In the method (2) of preparing compound 2, the preferred mineral alkali of described alkali, the preferred salt of wormwood of described mineral alkali.
In the method (2) of preparing compound 2, the molar ratio of described alkali and described compound 9 preferably 1～5.
In the method (2) of preparing compound 2, described catalyzer is four triphenyl phosphorus palladiums preferably.
In the method (2) of preparing compound 2, the molar ratio of described catalyzer and described compound 9 preferably 0.01～1, further preferably 0.01～0.1.
In the method (2) of preparing compound 2, the molar ratio of described compound 8 and described compound 9 preferably 1～5.
In the method (2) of preparing compound 2, preferably 0～100 DEG C of the temperature of described Suzuki linked reaction, further preferably 40 DEG C～90 DEG C.
In the method (2) of preparing compound 2, the process of described Suzuki linked reaction can adopt the routine monitoring method (for example TLC, HPLC or NMR) in this area to monitor, general while disappearing taking described compound 9 as reaction end, preferably 1 hour～24 hours reaction times, further preferably 1 hour～10 hours.
Preferably include following post-processing step in the method (2) of preparing compound 2: after reaction finishes, except desolventizing, column chromatography separates the product obtaining after purifying, and the method that column chromatography separates and condition can adopt ordinary method and the condition of this generic operation in this area.
In the described method of preparing compound 1, it preferably includes following steps: in solvent, under the condition that alkali and catalyzer exist, by compound Q ' carry out Suzuki linked reaction with compound 3, obtain described compound 9;
Wherein, the definition of D is same as above.
The method of preparing compound 9 can adopt ordinary method and the condition of such Suzuki linked reaction in this area, particularly preferably following reaction method and condition in the present invention:
Preparing the method for compound 9 can carry out under gas shield, in the time preparing the method for compound 9 and carry out under gas shield, and one or more in gas preferred nitrogen, argon gas, helium and the neon described in described " under gas shield ".
Preparing in the method for compound 9, the preferred ether solvent of described solvent and/or water, the preferred tetrahydrofuran (THF) of described ether solvent; In the time adopting the mixed solvent of ether solvent and water, described ether solvent and the volume ratio of water preferably 1～10, further preferably 1～5.
Preparing in the method for compound 9, described compound Q ' with the preferred 1mg/mL～100mg/mL of mass volume ratio of described solvent, further preferred 1mg/mL～20mg/L.
Preparing in the method for compound 9, the preferred mineral alkali of described alkali, the preferred salt of wormwood of described mineral alkali.
Preparing in the method for compound 9, described alkali and described compound Q ' molar ratio preferably 1～5.
Preparing in the method for compound 9, described catalyzer is four triphenyl phosphorus palladiums preferably.
Preparing in the method for compound 9, described catalyzer and described compound Q ' molar ratio preferably 0.01～1, further preferably 0.01～0.1.
Preparing in the method for compound 9, described compound 3 and described compound Q ' molar ratio preferably 1～5.
Preparing in the method for compound 9, preferably 0～100 DEG C of the temperature of described Suzuki linked reaction, further preferably 40 DEG C～90 DEG C.
Preparing in the method for compound 9, the process of described Suzuki linked reaction can adopt the routine monitoring method (for example TLC, HPLC or NMR) in this area to monitor, general while disappearing taking described compound 3 as reaction end, preferably 1 hour～24 hours reaction times, further preferably 1 hour～10 hours.
Preferably include following post-processing step in the method for preparing compound 9: after reaction finishes, except desolventizing, column chromatography separates the product obtaining after purifying, and the method that column chromatography separates and condition can adopt ordinary method and the condition of this generic operation in this area.
In the described method of preparing compound 1, it preferably includes following steps: in organic solvent, compound P ' is carried out to substitution reaction with N-bromo-succinimide (NBS), obtain described compound Q ';
Prepare compound Q ' method can adopt ordinary method and the condition of such substitution reaction in this area, particularly preferably following reaction method and condition in the present invention:
Preparing compound Q ' method in, described organic solvent preferred amide kind solvent, the preferred DMF of described amide solvent (DMF);
Preparing compound Q ' method in, the preferred 1mg/mL～100mg/L of mass volume ratio of described compound P ' and described organic solvent, further preferred 1mg/mL～20mg/L.
Preparing compound Q ' method in, the molar ratio of described N-bromo-succinimide and described compound P ' preferably 1～3.
Preparing compound Q ' method in, preferably 0～100 DEG C of the temperature of described substitution reaction, further preferably 0 DEG C～40 DEG C.
Preparing compound Q ' method in, the process of described substitution reaction can adopt the routine monitoring method (for example TLC, HPLC or NMR) in this area to monitor, general while disappearing taking described compound 11 as reaction end, preferably 1 hour～48 hours reaction times, further preferably 1 hour～24 hours.
Prepare compound Q ' method preferably radical initiator exist condition under carry out, the preferred benzoyl peroxide of described radical initiator or Diisopropyl azodicarboxylate.
Prepare compound Q ' method preferably include following post-processing step: after reaction finishes, the cancellation that adds water reaction, filters, and obtains compound Q '.
In the described method of preparing compound 1, it preferably includes following steps: in solvent, under the condition that alkali and catalyzer exist, compound 10 and compound B-11 are carried out to Suzuki linked reaction, obtain described compound P ';
The method of preparing compound P ' can adopt ordinary method and the condition of such Suzuki linked reaction in this area, particularly preferably following reaction method and condition in the present invention:
Preparing the method for compound P ' can carry out under gas shield, in the time preparing the method for compound P ' and carry out under gas shield, and one or more in gas preferred nitrogen, argon gas, helium and the neon described in described " under gas shield ".
Preparing in the method for compound P ', the preferred ether solvent of described solvent and/or water, the preferred tetrahydrofuran (THF) of described ether solvent; In the time adopting the mixed solvent of ether solvent and water, described ether solvent and the volume ratio of water preferably 1～10, further preferably 1～5.
Preparing in the method for compound P ', the preferred 1mg/mL～100mg/L of mass volume ratio of described compound 10 and described solvent, further preferred 1mg/mL～20mg/L.
Preparing in the method for compound P ', the preferred mineral alkali of described alkali, the preferred salt of wormwood of described mineral alkali.
Preparing in the method for compound P ', the molar ratio of described alkali and described compound 10 preferably 1～5.
Preparing in the method for compound P ', described catalyzer is four triphenyl phosphorus palladiums preferably.
Preparing in the method for compound P ', the molar ratio of described catalyzer and described compound 10 preferably 0.01～1, further preferably 0.01～0.1.
Preparing in the method for compound P ', the molar ratio of described compound B-11 and described compound 10 preferably 1～5.
Preparing in the method for compound P ', preferably 0～100 DEG C of the temperature of described Suzuki linked reaction, further preferably 40 DEG C～90 DEG C.
Preparing in the method for compound P ', the process of described Suzuki linked reaction can adopt the routine monitoring method (for example TLC, HPLC or NMR) in this area to monitor, while generally disappearance taking described compound B-11 as reaction end, preferably 1 hour～24 hours reaction times, further preferably 1 hour～10 hours.
Preferably include following post-processing step in the method for preparing compound P ': after reaction finishes, except desolventizing, column chromatography separates the product obtaining after purifying, and the method that column chromatography separates and condition can adopt ordinary method and the condition of this generic operation in this area.
The method (3) of preparing compound 2 can adopt ordinary method and the condition of such oxidizing reaction in this area, particularly preferably following reaction method and condition in the present invention:
In the method (3) of preparing compound 2, the preferred halogenated hydrocarbon solvent of described solvent, the preferred chlorinated hydrocarbon solvent of described halogenated hydrocarbon solvent, the described preferred methylene dichloride of chlorinated hydrocarbon solvent.
In the method (3) of preparing compound 2, the preferred 1mg/mL～100mg/L of mass volume ratio of described compound 11 and described solvent, further preferred 10mg/mL～50mg/L.
In the method (3) of preparing compound 2, the preferred mineral acid of described acid, the preferred hydrochloric acid of described mineral acid; The mass percentage concentration of described hydrochloric acid preferably 10%～37%, described mass percentage concentration refers to that the quality of hydrogenchloride accounts for the per-cent of hydrochloric acid total mass.
In the method (3) of preparing compound 2, the molar ratio of described acid and described compound 11 preferably 1～5.
In the method (3) of preparing compound 2, preferably 0～100 DEG C of the temperature of described oxidizing reaction, further preferably 0 DEG C～40 DEG C.
In the method (3) of preparing compound 2, the process of described oxidizing reaction can adopt the routine monitoring method (for example TLC, HPLC or NMR) in this area to monitor, general while disappearing taking described compound 11 as reaction end, preferably 1 hour～24 hours reaction times.
Preferably include following post-processing step in the method (3) of preparing compound 2: after reaction finishes, regulate pH to 7 left and right, extraction, obtains thick product and can be directly used in next step reaction.Regulate pH preferably to adopt mineral alkali, the preferred sodium bicarbonate of described mineral alkali.The method of extraction and condition can adopt ordinary method and the condition of this generic operation in this area, the preferred halogenated hydrocarbon solvent of solvent of extraction, the preferred chlorinated hydrocarbon solvent of described halogenated hydrocarbon solvent, the described preferred methylene dichloride of chlorinated hydrocarbon solvent.
In the described method of preparing compound 1,1. it preferably adopt method or 2. method prepares described compound 11:
Method is 1.: in solvent, under the condition that catalyzer exists, compound 12 and compound 13 are carried out to Suzuki linked reaction, obtain described compound 11;
Method is 2.: in solvent, under the condition that alkali and catalyzer exist, compound 17 and compound 3 are carried out to Suzuki linked reaction, obtain described compound 11;
Wherein, the definition of A and D is all same as above.
1. the method for preparing compound 11 can adopt ordinary method and the condition of such Suzuki linked reaction in this area, particularly preferably following reaction method and condition in the present invention:
Prepare the method for compound 11 and 1. can under gas shield, carry out, in the time preparing the method for compound 11 and 1. carry out under gas shield, one or more in gas preferred nitrogen, argon gas, helium and the neon described in described " under gas shield ".
The method of preparing compound 11 1. in, described solvent preferred amide kind solvent, the preferred DMF of described amide solvent and/or N.N-N,N-DIMETHYLACETAMIDE.
The method of preparing compound 11 1. in, the preferred 1mg/mL～100mg/L of mass volume ratio of described compound 12 and described solvent, further preferred 1mg/mL～20mg/L.
The method of preparing compound 11 1. in, described catalyzer is four triphenyl phosphorus palladiums preferably.
The method of preparing compound 11 1. in, the molar ratio of described catalyzer and described compound 12 preferably 0.01～1, further preferably 0.01～0.1.
The method of preparing compound 11 1. in, the molar ratio of described compound 13 and described compound 12 preferably 1～5.
The method of preparing compound 11 1. in, preferably 0～100 DEG C of the temperature of described Suzuki linked reaction, further preferably 40 DEG C～90 DEG C.
The method of preparing compound 11 1. in, the process of described Suzuki linked reaction can adopt the routine monitoring method (for example TLC, HPLC or NMR) in this area to monitor, general while disappearing taking described compound 12 as reaction end, preferably 1 hour～24 hours reaction times.
1. preferably include following post-processing step in the method for preparing compound 11: after reaction finishes, extraction, except desolventizing obtains thick product, thick product column chromatography separates the product obtaining after purifying.The method that column chromatography separates and condition can adopt ordinary method and the condition of this generic operation in this area; The method of extraction and condition can adopt ordinary method and the condition of this generic operation in this area, the preferred esters solvent of solvent of extraction, described esters solvent ethyl acetate.
In the described method of preparing compound 1, it preferably includes following steps: in organic solvent, under the condition that radical initiator exists, compound 14 and tributyltin chloride are carried out to substitution reaction, obtain described compound 13;
The method of preparing compound 13 can adopt ordinary method and the condition of such substitution reaction in this area, particularly preferably following reaction method and condition in the present invention:
Preparing the method for compound 13 can carry out under gas shield, in the time preparing the method for compound 13 and can carry out under gas shield, and the preferred ether solvent of described organic solvent, the preferred tetrahydrofuran (THF) of described ether solvent (THF);
Preparing in the method for compound 13, the preferred 1mg/mL～100mg/mL of mass volume ratio of described compound 14 and described organic solvent, further preferred 1mg/mL～20mg/mL.
Preparing in the method for compound 13, the molar ratio of described tributyltin chloride and described compound 14 preferably 1～3.
Prepare in the method for compound 13 the preferred isopropylmagnesium chloride of described radical initiator.
Prepare in the method for compound 13 molar ratio of described radical initiator and described compound 14 preferably 1～3.
Preparing in the method for compound 13, preferably 0～100 DEG C of the temperature of described substitution reaction, further preferably 0 DEG C～40 DEG C.
Preparing in the method for compound 13, the process of described substitution reaction can adopt the routine monitoring method (for example TLC, HPLC or NMR) in this area to monitor, general taking described compound R ' be reaction end while disappearing, preferably 1 hour～48 hours reaction times, further preferably 1 hour～24 hours.
The method of preparing compound 13 preferably includes following post-processing step: after reaction finishes, and cancellation reaction, extraction, obtains compound 13, can be directly used in next step reaction.The preferred aqueous ammonium chloride solution of reagent that cancellation adopts.Described extraction can adopt the ordinary method of this generic operation in this area, the preferred esters solvent of solvent that described extraction adopts, described esters solvent ethyl acetate.
The method of preparing compound 13 preferably includes following steps: under gas shield; radical initiator is added drop-wise in the solution of compound 14 and organic solvent formation; reaction for some time (preferably 1 hour～3 hours); again tributyltin chloride is added drop-wise in reaction system, carries out substitution reaction and obtain described compound 13.Described preferably-10 DEG C～0 DEG C of temperature in the solution that compound 14 and organic solvent form that radical initiator is added drop-wise to, described preferably-10 DEG C～0 DEG C of temperature in reaction system that tributyltin chloride is added drop-wise to.
In the described method of preparing compound 1, it preferably includes following steps: in organic solvent, under the condition that acid exists, compound 15 and carbonyl-protection base (preferably ethylene glycol) are carried out to condensation reaction, obtain described compound 14;
The method of preparing compound 14 can adopt ordinary method and the condition of such condensation reaction in this area, particularly preferably following reaction method and condition in the present invention:
Preparing in the method for compound 14, described solvent preferred aromatic hydrocarbons kind solvent, the preferred toluene of described aromatic hydrocarbon solvent.
Preparing in the method for compound 14, the preferred 1mg/mL～100mg/mL of mass volume ratio of described compound 15 and described solvent, further preferred 1mg/mL～20mg/L.
Preparing in the method for compound 14, the preferred organic acid of described acid, the preferred tosic acid of described organic acid.
Preparing in the method for compound 14, the molar ratio of described acid and described compound 15 preferably 0.01～0.1.
Preparing in the method for compound 14, described hydroxyl protection reagent preferred diol compounds, the described preferred ethylene glycol of glycols compound.
Preparing in the method for compound 14, the molar ratio of described hydroxyl protection reagent and described compound 15 preferably 1～5.
Preparing in the method for compound 14, preferably 0～150 DEG C of the temperature of described condensation reaction, further preferably 80 DEG C～120 DEG C.
Preparing in the method for compound 14, the process of described condensation reaction can adopt the routine monitoring method (for example TLC, HPLC or NMR) in this area to monitor, general while disappearing taking described compound 15 as reaction end, preferably 1 hour～24 hours reaction times.
Preferably include following post-processing step in the method for preparing compound 14: after reaction finishes, alkali cleaning is to pH7 left and right, and except desolventizing, column chromatography separates the product obtaining after purifying.The preferred mineral alkali of described alkali, the preferred sodium bicarbonate of described mineral alkali.The method that column chromatography separates and condition can adopt ordinary method and the condition of this generic operation in this area.
In the described method of preparing compound 11, it preferably includes following steps: in solvent, under the condition that alkali and catalyzer exist, compound 3 and compound 16 are carried out to Suzuki linked reaction, obtain described compound 15;
Wherein, the definition of D is same as above.
The method of preparing compound 15 can adopt ordinary method and the condition of such Suzuki linked reaction in this area, particularly preferably following reaction method and condition in the present invention:
Preparing the method for compound 15 can carry out under gas shield, in the time preparing the method for compound 15 and carry out under gas shield, and one or more in gas preferred nitrogen, argon gas, helium and the neon described in described " under gas shield ".
Preparing in the method for compound 15, the preferred ether solvent of described solvent and/or water, the preferred tetrahydrofuran (THF) of described ether solvent; In the time adopting the mixed solvent of ether solvent and water, described ether solvent and the volume ratio of water preferably 1～10, further preferably 1～5.
Preparing in the method for compound 15, the preferred 1mg/mL～100mg/L of mass volume ratio of described compound 16 and described solvent, further preferred 1mg/mL～20mg/L.
Preparing in the method for compound 15, the preferred mineral alkali of described alkali, the preferred salt of wormwood of described mineral alkali.
Preparing in the method for compound 15, the molar ratio of described alkali and described compound 16 preferably 1～5.
Preparing in the method for compound 15, described catalyzer is four triphenyl phosphorus palladiums preferably.
Preparing in the method for compound 15, the molar ratio of described catalyzer and described compound 16 preferably 0.01～1, further preferably 0.01～0.1.
Preparing in the method for compound 15, the molar ratio of described compound 3 and described compound 16 preferably 1～5.
Preparing in the method for compound 15, preferably 0～100 DEG C of the temperature of described Suzuki linked reaction, further preferably 40 DEG C～90 DEG C.
Preparing in the method for compound 15, the process of described Suzuki linked reaction can adopt the routine monitoring method (for example TLC, HPLC or NMR) in this area to monitor, general while disappearing taking described compound 16 as reaction end, preferably 1 hour～24 hours reaction times, further preferably 1 hour～10 hours.
Prepare the method for compound 15, preferably include following post-processing step: after reaction finishes, except desolventizing, column chromatography separates the product obtaining after purifying, and the method that column chromatography separates and condition can adopt ordinary method and the condition of this generic operation in this area.
In the described method of preparing compound 1, it preferably includes following steps: in organic solvent, compound B-11 and N-N-iodosuccinimide (NIS) are carried out to substitution reaction, obtain described compound 16;
The method of preparing compound 16 can adopt ordinary method and the condition of such substitution reaction in this area, particularly preferably following reaction method and condition in the present invention:
Preparing in the method for compound 16, described organic solvent preferred amide kind solvent, the preferred DMF of described amide solvent (DMF);
Preparing in the method for compound 16, the preferred 1mg/mL～100mg/L of mass volume ratio of described compound B-11 and described organic solvent, further preferred 1mg/mL～20mg/L.
Preparing in the method for compound 16, the molar ratio of described N-N-iodosuccinimide and described compound B-11 preferably 1～3.
Preparing in the method for compound 16, preferably 0～100 DEG C of the temperature of described substitution reaction, further preferably 0 DEG C～40 DEG C.
Preparing in the method for compound 16, the process of described substitution reaction can adopt the routine monitoring method (for example TLC, HPLC or NMR) in this area to monitor, general while disappearing taking described compound 5 as reaction end, preferably 1 hour～48 hours reaction times, further preferably 1 hour～24 hours.
The method of preparing compound 16 preferably includes following post-processing step: after reaction finishes, the cancellation that adds water reaction, filters, and obtains compound 16.
2. the method for preparing compound 11 can adopt ordinary method and the condition of such Suzuki linked reaction in this area, particularly preferably following reaction method and condition in the present invention:
The method of preparing compound 11 2. in, one or more in gas preferred nitrogen, argon gas, helium and the neon described in described " under gas shield ".
The method of preparing compound 11 2. in, the preferred ether solvent of described solvent and/or water, the preferred tetrahydrofuran (THF) of described ether solvent; In the time adopting the mixed solvent of ether solvent and water, described ether solvent and the volume ratio of water preferably 1～10, further preferably 1～5.
The method of preparing compound 11 2. in, the preferred 1mg/mL～100mg/mL of mass volume ratio of described compound 17 and described solvent, further preferred 1mg/mL～20mg/L.
The method of preparing compound 11 2. in, the preferred mineral alkali of described alkali, the preferred salt of wormwood of described mineral alkali.
The method of preparing compound 11 2. in, the molar ratio of described alkali and described compound 17 preferably 1～5.
The method of preparing compound 11 2. in, described catalyzer is four triphenyl phosphorus palladiums preferably.
The method of preparing compound 11 2. in, the molar ratio of described catalyzer and described compound 17 preferably 0.01～1, further preferably 0.01～0.1.
The method of preparing compound 11 2. in, the molar ratio of described compound 3 and described compound 17 preferably 1～5.
The method of preparing compound 11 2. in, preferably 0～100 DEG C of the temperature of described Suzuki linked reaction, further preferably 40 DEG C～90 DEG C.
The method of preparing compound 11 2. in, the process of described Suzuki linked reaction can adopt the routine monitoring method (for example TLC, HPLC or NMR) in this area to monitor, general while disappearing taking described compound 3 as reaction end, preferably 1 hour～24 hours reaction times, further preferably 1 hour～10 hours.
2. preferably include following post-processing step in the method for preparing compound 11: after reaction finishes, except desolventizing, column chromatography separates the product obtaining after purifying, and the method that column chromatography separates and condition can adopt ordinary method and the condition of this generic operation in this area.
In the described method of preparing compound 11, it preferably includes following steps: in organic solvent, compound 18 and N-bromo-succinimide (NBS) are carried out to substitution reaction, obtain described compound 17;
The method of preparing compound 17 can adopt ordinary method and the condition of such substitution reaction in this area, particularly preferably following reaction method and condition in the present invention:
Preparing in the method for compound 17, described organic solvent preferred amide kind solvent, the preferred DMF of described amide solvent (DMF);
Preparing in the method for compound 17, the preferred 1mg/mL～100mg/L of mass volume ratio of described compound 18 and described organic solvent, further preferred 1mg/mL～20mg/L.
Preparing in the method for compound 17, the molar ratio of described N-bromo-succinimide and described compound 18 preferably 1～3.
Preparing in the method for compound 17, preferably 0～100 DEG C of the temperature of described substitution reaction, further preferably 0 DEG C～40 DEG C.
Preparing in the method for compound 17, the process of described substitution reaction can adopt the routine monitoring method (for example TLC, HPLC or NMR) in this area to monitor, general while disappearing taking described compound 18 as reaction end, preferably 1 hour～48 hours reaction times, further preferably 1 hour～24 hours.
Prepare the method for compound 17 and preferably under the condition of radical initiator existence, carry out, the preferred benzoyl peroxide of described radical initiator or Diisopropyl azodicarboxylate.
The method of preparing compound 17 preferably includes following post-processing step: after reaction finishes, the cancellation that adds water reaction, filters, and obtains compound 17.
In the described method of preparing compound 1, described compound 18 can adopt method I or method II preparation,
It preferably includes following steps method I: in solvent, under the condition that catalyzer exists, by compound S ' carry out Suzuki linked reaction with compound 12, obtain described compound 18;
Method II: in organic solvent, under the condition that catalyzer exists, compound 19 is carried out to Suzuki linked reaction with compound V ', obtain described compound 18;
The method I for preparing compound 18 can carry out under gas shield, in the time preparing the method I of compound 18 and carry out under gas shield, and one or more in gas preferred nitrogen, argon gas, helium and the neon described in described " under gas shield ".
Preparing in the method I of compound 18, described solvent preferred aromatic hydrocarbons kind solvent, the preferred toluene of described aromatic hydrocarbon solvent.
Preparing in the method I of compound 18, the preferred 1mg/mL～100mg/mL of mass volume ratio of described compound 12 and described solvent, further preferred 1mg/mL～20mg/mL.
Preparing in the method I of compound 18, described catalyzer is four triphenyl phosphorus palladiums preferably.
Preparing in the method I of compound 18, the molar ratio of described catalyzer and described compound 12 preferably 0.01～1, further preferably 0.01～0.1.
Preparing in the method I of compound 18, described compound S ' with the molar ratio of described compound 12 preferably 1～5.
Preparing in the method I of compound 18, preferably 0～150 DEG C of the temperature of described Suzuki linked reaction, further preferably 80 DEG C～150 DEG C.
Preparing in the method I of compound 18, the process of described Suzuki linked reaction can adopt the routine monitoring method (for example TLC, HPLC or NMR) in this area to monitor, general while disappearing taking described compound 12 as reaction end, preferably 1 hour～24 hours reaction times.
Preferably include following post-processing step at the method I for preparing compound 18: after reaction finishes, except desolventizing, column chromatography separates the product obtaining after purifying, and the method that column chromatography separates and condition can adopt ordinary method and the condition of this generic operation in this area.
The method II for preparing compound 18 can carry out under gas shield, in the time preparing the method II of compound 18 and carry out under gas shield, and one or more in gas preferred nitrogen, argon gas, helium and the neon described in described " under gas shield ".
Preparing in the method II of compound 18, described organic solvent preferred aromatic hydrocarbons kind solvent, the preferred toluene of described aromatic hydrocarbon solvent.
Preparing in the method II of compound 18, the preferred 1mg/mL～100mg/mL of mass volume ratio of described compound 19 and described solvent, further preferred 1mg/mL～20mg/mL.
Preparing in the method II of compound 18, described catalyzer is four triphenyl phosphorus palladiums preferably.
Preparing in the method II of compound 18, the molar ratio of described catalyzer and described compound 19 preferably 0.01～1, further preferably 0.01～0.1.
Preparing in the method II of compound 18, the molar ratio of described compound V ' and described compound 19 preferably 1～5.
Preparing in the method II of compound 18, preferably 0～150 DEG C of the temperature of described Suzuki linked reaction.
Preparing in the method II of compound 18, the process of described Suzuki linked reaction can adopt the routine monitoring method (for example TLC, HPLC or NMR) in this area to monitor, general while disappearing taking described compound 12 as reaction end, preferably 1 hour～24 hours reaction times.
Preferably include following post-processing step at the method II for preparing compound 18: after reaction finishes, except desolventizing, column chromatography separates the product obtaining after purifying, and the method that column chromatography separates and condition can adopt ordinary method and the condition of this generic operation in this area.
Described prepare compound 1 in, it preferably includes following steps: in organic solvent, under the condition that radical initiator exists, by compound R ' carry out substitution reaction with tributyltin chloride, obtain described compound S ';
Prepare compound S ' method can adopt ordinary method and the condition of such substitution reaction in this area, particularly preferably following reaction method and condition in the present invention:
Preparing compound S ' method in, the preferred ether solvent of described organic solvent, the preferred tetrahydrofuran (THF) of described ether solvent (THF);
Preferred 1mg/mL～the 100mg/mL of mass volume ratio of ' method in, described compound R ' and described organic solvent preparing compound S, further preferred 1mg/mL～20mg/mL.
The molar ratio of ' method in, described tributyltin chloride and described compound R ' preferably 1～3 preparing compound S.
Prepare compound S ' method in, the preferred isopropylmagnesium chloride of described radical initiator.
The prepare compound S molar ratio preferably 1～3 of ' method in, described radical initiator and described compound R '.
Preparing compound S ' method in, preferably 0～100 DEG C of the temperature of described substitution reaction, further preferably 0 DEG C～40 DEG C.
Preparing compound S ' method in, the process of described substitution reaction can adopt the routine monitoring method (for example TLC, HPLC or NMR) in this area to monitor, general taking described compound R ' be reaction end while disappearing, preferably 1 hour～48 hours reaction times, further preferably 1 hour～24 hours.
Prepare compound S ' method preferably include following post-processing step: after reaction finishes, cancellation reaction, extraction, obtains compound S ', can be directly used in next step reaction.The preferred aqueous ammonium chloride solution of reagent that cancellation adopts.Described extraction can adopt the ordinary method of this generic operation in this area, the preferred esters solvent of solvent that described extraction adopts, described esters solvent ethyl acetate.
Prepare compound S ' method preferably include following steps: under gas shield; radical initiator is added drop-wise to compound R ' with organic solvent form solution in; reaction for some time (preferably 1 hour～3 hours); again tributyltin chloride is added drop-wise in reaction system, carries out substitution reaction and obtain described compound S '.Described is added drop-wise to compound R by radical initiator ' preferably-10 DEG C～0 DEG C of temperature in the solution that forms with organic solvent, described preferably-10 DEG C～0 DEG C of temperature in reaction system that tributyltin chloride is added drop-wise to.
In the described method of preparing compound 1, it preferably includes following steps: under the condition that acid exists, compound B-11 and carbonyl-protection base (preferably ethylene glycol) are carried out to condensation reaction, obtain described compound R ';
Prepare compound R ' method can adopt ordinary method and the condition of such condensation reaction in this area, particularly preferably following reaction method and condition in the present invention:
Preparing compound R ' method in, the preferred organic acid of described acid, the preferred tosic acid of described organic acid.
Preparing compound R ' method in, the molar ratio of described acid and described compound B-11 preferably 0.01～0.1.
Preparing compound R ' method in, described hydroxyl protection reagent preferred diol compounds, the described preferred ethylene glycol of glycols compound.
Preparing compound R ' method in, the molar ratio of described hydroxyl protection reagent and described compound B-11 preferably 1～5.
Preparing compound R ' method in, preferably 0～150 DEG C of the temperature of described condensation reaction, further preferably 80 DEG C～120 DEG C.
Preparing compound R ' method in, the process of described condensation reaction can adopt the routine monitoring method (for example TLC, HPLC or NMR) in this area to monitor, general while disappearing taking described compound 17 as reaction end, preferably 1 hour～24 hours reaction times.
The described compound R of preparing ' method, can in organic solvent, carry out, in the time that described condensation reaction is carried out in organic solvent, described solvent preferred aromatic hydrocarbons kind solvent, the preferred toluene of described aromatic hydrocarbon solvent.In the time that described condensation reaction is carried out in organic solvent, the preferred 1mg/mL～100mg/mL of mass volume ratio of described compound B-11 and described organic solvent, further preferred 1mg/mL～20mg/L.
Preparing compound R ' method preferably include following post-processing step: after reaction finishes, alkali cleaning is to about pH7, and except desolventizing, column chromatography separates the product obtaining after purifying.The described preferred mineral alkali of alkali, the preferred sodium bicarbonate of described mineral alkali.The method that column chromatography separates and condition can adopt ordinary method and the condition of this generic operation in this area.
In the described method of preparing compound 12, it preferably includes following steps: in organic solvent, under the condition that radical initiator exists, compound U ' is carried out to substitution reaction with tributyltin chloride, obtain described compound V ';
The method of preparing compound V ' can adopt ordinary method and the condition of such substitution reaction in this area, particularly preferably following reaction method and condition in the present invention:
Preparing in the method for compound V ', the preferred ether solvent of described organic solvent, the preferred tetrahydrofuran (THF) of described ether solvent (THF);
Preparing in the method for compound V ', the preferred 1mg/mL～100mg/mL of mass volume ratio of described compound U ' and described organic solvent, further preferred 1mg/mL～20mg/mL.
Preparing in the method for compound V ', the molar ratio of described tributyltin chloride and described compound U ' preferably 1～3.
Prepare in the method for compound V ' the preferred isopropylmagnesium chloride of described radical initiator.
Prepare in the method for compound V ' molar ratio of described radical initiator and described compound U ' preferably 1～3.
Preparing in the method for compound V ', preferably 0～100 DEG C of the temperature of described substitution reaction, further preferably 0 DEG C～40 DEG C.
Preparing in the method for compound V ', the process of described substitution reaction can adopt the routine monitoring method (for example TLC, HPLC or NMR) in this area to monitor, while generally disappearance taking described compound U ' as reaction end, preferably 1 hour～48 hours reaction times, further preferably 1 hour～24 hours.
The method of preparing compound V ' preferably includes following post-processing step: after reaction finishes, and cancellation reaction, extraction, obtains compound V ', can be directly used in next step reaction.The preferred aqueous ammonium chloride solution of reagent that cancellation adopts.Described extraction can adopt the ordinary method of this generic operation in this area, the preferred esters solvent of solvent that described extraction adopts, described esters solvent ethyl acetate.
The method of preparing compound V ' preferably includes following steps: under gas shield; radical initiator is added drop-wise in the solution of compound U ' and organic solvent formation; reaction for some time (preferably 1 hour～3 hours); again tributyltin chloride is added drop-wise in reaction system, carries out substitution reaction and obtain described compound V '.Described preferably-10 DEG C～0 DEG C of temperature in the solution that compound U ' and organic solvent form that radical initiator is added drop-wise to, described preferably-10 DEG C～0 DEG C of temperature in reaction system that tributyltin chloride is added drop-wise to.
In the described method of preparing compound 1, it preferably includes following steps: under the condition that acid exists, compound T ' is carried out to condensation reaction with carbonyl-protection base (preferably ethylene glycol), obtain described compound U ';
The method of preparing compound U ' can adopt ordinary method and the condition of such condensation reaction in this area, particularly preferably following reaction method and condition in the present invention:
Preparing in the method for compound U ', the preferred organic acid of described acid, the preferred tosic acid of described organic acid.
Preparing in the method for compound U ', the molar ratio of described acid and described compound T ' preferably 0.01～0.1.
Preparing in the method for compound U ', described hydroxyl protection reagent preferred diol compounds, the described preferred ethylene glycol of glycols compound.
Preparing in the method for compound U ', the molar ratio of described hydroxyl protection reagent and described compound T ' preferably 1～5.
Preparing in the method for compound U ', preferably 0～150 DEG C of the temperature of described condensation reaction, further preferably 80 DEG C～120 DEG C.
Preparing in the method for compound U ', the process of described condensation reaction can adopt the routine monitoring method (for example TLC, HPLC or NMR) in this area to monitor, while generally disappearance taking described compound T ' as reaction end, preferably 1 hour～24 hours reaction times.
The described method of preparing compound U ' can be carried out in organic solvent, in the time that described condensation reaction is carried out in organic solvent, and described solvent preferred aromatic hydrocarbons kind solvent, the preferred toluene of described aromatic hydrocarbon solvent.In the time that described condensation reaction is carried out in organic solvent, the preferred 1mg/mL～100mg/mL of mass volume ratio of described compound T ' and described organic solvent, further preferred 1mg/mL～20mg/L.
Preferably include following post-processing step in the method for preparing compound U ': after reaction finishes, alkali cleaning is to pH7 left and right, and except desolventizing, column chromatography separates the product obtaining after purifying.The described preferred mineral alkali of alkali, the preferred sodium bicarbonate of described mineral alkali.The method that column chromatography separates and condition can adopt ordinary method and the condition of this generic operation in this area.
In the described method of preparing compound 1, it preferably includes following steps: in organic solvent, compound 057-1 and N-bromo-succinimide (NBS) are carried out to substitution reaction, obtain described compound T ';
The method of preparing compound T ' can adopt ordinary method and the condition of such substitution reaction in this area, particularly preferably following reaction method and condition in the present invention:
Preparing in the method for compound T ', described organic solvent preferred amide kind solvent, the preferred DMF of described amide solvent (DMF);
Preparing in the method for compound T ', the preferred 1mg/mL～100mg/L of mass volume ratio of described compound 057-1 and described organic solvent, further preferred 1mg/mL～50mg/L.
Preparing in the method for compound T ', the molar ratio of described N-bromo-succinimide and described compound 057-1 preferably 1～3.
Preparing in the method for compound T ', preferably 0～100 DEG C of the temperature of described substitution reaction, further preferably 0 DEG C～40 DEG C.
Preparing in the method for compound T ', the process of described substitution reaction can adopt the routine monitoring method (for example TLC, HPLC or NMR) in this area to monitor, while generally disappearance taking described compound 057-1 as reaction end, preferably 1 hour～48 hours reaction times, further preferably 1 hour～24 hours.
The method of preparing compound T ' preferably includes following post-processing step: after reaction finishes, the cancellation that adds water reaction, filters, and obtains compound T '.
The method of preparing compound T ' preferably includes following steps: the solution of N-bromo-succinimide and organic solvent formation is added drop-wise in the solution of compound 057-1 and organic solvent formation, carries out substitution reaction and obtain compound T '.Preferably-10 DEG C～10 DEG C of the temperature of described " solution that compound 057-1 and organic solvent form ".
In the described method of preparing compound 1, it preferably includes following steps: in solvent, under the condition that alkali and catalyzer exist, compound 20 and compd A 1 are carried out to Suzuki linked reaction, obtain described compound 057-1;
The method of preparing compound 057-1 can adopt ordinary method and the condition of such Suzuki linked reaction in this area, particularly preferably following reaction method and condition in the present invention:
Preparing in the method for compound 057-1, one or more in gas preferred nitrogen, argon gas, helium and the neon described in described " under gas shield ".
Preparing in the method for compound 057-1, the preferred ether solvent of described solvent and/or water, the preferred tetrahydrofuran (THF) of described ether solvent; In the time adopting the mixed solvent of ether solvent and water, described ether solvent and the volume ratio of water preferably 1～10, further preferably 1～5.
Preparing in the method for compound 057-1, the preferred 1mg/mL～100mg/L of mass volume ratio of described compound 20 and described solvent, further preferred 1mg/mL～20mg/L.
Preparing in the method for compound 057-1, the preferred mineral alkali of described alkali, the preferred salt of wormwood of described mineral alkali.
Preparing in the method for compound 057-1, the molar ratio of described alkali and described compound 20 preferably 1～5.
Preparing in the method for compound 057-1, described catalyzer is four triphenyl phosphorus palladiums preferably.
Preparing in the method for compound 057-1, the molar ratio of described catalyzer and described compd A 1 preferably 0.01～1, further preferably 0.01～0.2.
Preparing in the method for compound 057-1, the molar ratio of described compound 20 and described compd A 1 preferably 1～5.
Preparing in the method for compound 057-1, preferably 0～100 DEG C of the temperature of described Suzuki linked reaction, further preferably 40 DEG C～90 DEG C.
Preparing in the method for compound 057-1, the process of described Suzuki linked reaction can adopt the routine monitoring method (for example TLC, HPLC or NMR) in this area to monitor, general while disappearing taking described compd A 1 as reaction end, preferably 1 hour～24 hours reaction times.
Preferably include following post-processing step in the method for preparing compound 057-1: after reaction finishes, except desolventizing, column chromatography separates the product obtaining after purifying, and the method that column chromatography separates and condition can adopt ordinary method and the condition of this generic operation in this area.
The method of preparing compound 1 preferably adopts route one, route two, route three, route four or route five:
Route one:
Route two
Route three
Route four
Route five
The present invention also provides compound 1, compound 2, compound 3, compound 4, compound 5, compound 6, compound 7, compound 8, compound 9, compound 10, compound 11, compound 12, compound 13, compound 14, compound 15, compound 16, compound 17, compound 18, compound 19, compound B-11, compound P ', compound Q ', compound R ', compound S ', compound T ', compound U ', compound V ', compd A 1 or compound 057-1
Wherein, the definition of A, B, D is all same as above.
The present invention also provides the described salt of organic dye sensitized dose, the described preferred described an alkali metal salt of organic dye sensitized dose of the salt of organic dye sensitized dose or the described ammonium salt of organic dye sensitized dose.
The present invention also provide described organic dye sensitized dose 1 or its salt as light-sensitive coloring agent purposes in photoelectric conversion technique.The preferred organic thin film solar cell technology in described photoelectric conversion technique field, dye sensitized nano crystal body solar cell technology or organic photoelectric hydrogen production by water decomposition technology etc., further preferred coloring agent sensitized nanocrystalline body solar cell technology.
Described in the present invention organic dye sensitized dose 1 or its salt are as a kind of novel photosensitizer, and it can be used as pure organic dye photosensitizers and replaces the precious metals complex photosensitizers of reporting in document, can effectively reduce the cost of manufacture of this class battery.
Dye sensitized nano crystal salar battery of the present invention comprises photo cathode, described photo cathode has porous nano sull, described porous nano oxide membranous layer adsorbs or is impregnated with described organic dye sensitized dose, these novel organic dye sensitizing agents can be used as photosensitizers and replace the precious metals complex photosensitizer of reporting in document, can effectively reduce the cost of manufacture of this class battery.Described porous nano sull is one or more in titanium oxide, zinc oxide, stannic oxide.
In the present invention, described absorption or dipping comprise the following steps: first organic dye sensitized dose described in the present invention being dissolved in to organic solvent and being mixed with concentration is 10
-8the solution of～10M, the nanoporous sull of then sintering being annealed later is immersed in this solution, and soak time is one minute to 36 hours, can obtain the photo cathode through sensitization.One or more in the preferred halogenated hydrocarbon solvent of described organic solvent, alcoholic solvent, ether solvent, amide solvent, nitrile solvents, aromatic hydrocarbon solvent and halogenated aryl hydrocarbon kind solvent.The preferred chlorinated hydrocarbon solvent of described halogenated hydrocarbon solvent; One or more in the described preferred methylene dichloride of chlorinated hydrocarbon solvent, chloroform, tetracol phenixin, ethylene dichloride and trichloroethane.The preferred C of described alcoholic solvent
1-8alcoholic solvent; Described C
1-8alcoholic solvent particular methanol, ethanol, propyl alcohol, Virahol and butanols in one or more.One or more in the preferred tetrahydrofuran (THF) of described ether solvent, ether, methyltetrahydrofuran, methyl tertiary butyl ether and isopropyl ether.The preferred acetonitrile of described nitrile solvents.The preferred DMF of described amide solvent.One or more in the preferred benzene of described aromatic hydrocarbon solvent, dimethylbenzene, 4-tert-butyltoluene.The preferred chlorinated aromatic hydrocarbons kind solvent of described halogenated aryl hydrocarbon kind solvent; The described preferred chlorobenzene of chlorinated aromatic hydrocarbons kind solvent.
The present invention also provides a kind of dye sensitized nano crystal body solar cell, and it is mainly made up of following components: transparent substrates layer 1, conductive layer 2, light absorbing zone 3, electrolyte layer 4 and to electrode layer 5; Wherein, light absorbing zone 3 is made up of semi-conductor nano particles 6 and dye coating 7.Described dye coating 7 is made up of as shown in general formula 1 organic dye sensitized dose of the present invention.
In the present invention, described transparent substrates layer 1 preferred glass substrate or plastics; One or more in the preferred polyethylene terephthalate of described plastics, PEN, polycarbonate, polypropylene, poly-propionic acid amide, tri acetyl cellulose and polyethersulfone.
In the present invention, described conductive layer 2 is preferably by tin indium oxide, fluorine oxide tin, ZnO-Ga
2o
3, ZnO-Al
2o
3, any one formation in tin-based oxide, antimony tin and zinc oxide.
In the present invention, described light absorbing zone 3 is preferably made up of semiconductor nano-particles layers 6 and dye coating 7; Preferably, described semiconductor nano-particles layers 6 is connected with conductive layer 2, and dye coating 7 is connected with dielectric substrate 4.
In the present invention, the preferred Si of semi-conductor nano particles of described semiconductor nano-particles layers 6, Ti0
2, SnO
2, ZnO, WO
3, Nb
20
5or TiSrO
3, preferably, the median size <50nm of 0nm< semi-conductor nano particles.
In the present invention, described electrolyte layer 4 preferably by iodine/salt compounded of iodine ionogen, ionic liquid, organic hole transport material (as 2,2-7, tetra-couples of (N of 7-, N-di-p-methoxy aniline)-9,9-spiro-bisfluorene) and inorganic hole mobile material in any one or multiple formation.
In the present invention, described to electrode 5 preferably by any one or multiple composition in Pt, Au, Ni, Cu, Ag, In, Ru, Pd, Rh, Ir, Os, C or conductive polymers; One or more in the preferred polyaniline of described conductive polymers, polypyrrole, Polythiophene, p-phenylene vinylene and polyethers.
Without prejudice to the field on the basis of common sense, above-mentioned each optimum condition, can arbitrary combination, obtains the preferred embodiments of the invention.
Agents useful for same of the present invention and raw material be commercially available obtaining all.
Room temperature in the present invention refers to that envrionment temperature is 10 DEG C～30 DEG C.
Positive progressive effect of the present invention is:
1, in organic dye sensitized agent molecule of the present invention, comprise two or more the conjugation molectron in conjugation aromatic ring chromophoric group unit or these structural units, this aromatic ring directly links two or more electron donor(ED)s, the neutral organic structure of electron acceptor(EA) or electronics unit; The particularly introducing of the neutral organic structure of electron acceptor(EA) and electronics unit, has enriched regulating measure and ability that molecular structure, molecule are inhaled to electronic behavior in wave spectrum scope and molecule.
2, organic dye sensitized dose of the present invention, in its molecule, comprise conjugation aromatic ring and come and dye sensitization battery light electricity anode (TiO by one or more bindinggroup
2, ZnO etc.) and the nanometer micropore surface phase bonding of material, thus go out formation electric current by dying electric transmission that quick agent molecule excites after visible and UV-irradiation.
3, organic dye sensitized agent molecule provided by the invention, the chromophoric group (Ar) that synthetic selected structural unit is general aromatic conjugated structure, the conjugation electron rich unit (electron donor(ED) mating by selection, D), electron deficiency unit (electron acceptor(EA),, or the neutral organic structure unit of electronics (neutral body, N) A), through conjugation link, build conjugation aromatic ring chromophoric group higly branched chain derivatize new dye sensitizing agent.The three-dimensional arrangement of gained molecule is changed, and has improved the nonplanarity that dyes quick agent molecule, has reduced dyestuff at TiO
2the pi-pi accumulation effect on surface; By cutting out conjugation aromatic ring chromophoric group, conjugated structure unit and electron donor(ED), acceptor and neutral body, gained dye sensitizing agent possesses wider absorption spectrum, stronger photoelectric current, can rationally cut out to reach by molecular structure and regulate the locomotivity of electronics in transmission path, the photoelectric transformation efficiency of raising device.Such dye molecule possesses good light, heat, chemical stability, the advantages such as raw material is easy to get, synthetic convenience, molecular diversity, the photoelectric transformation efficiency of gained dye sensitization solar battery reaches the more than 80% of N719 dyestuff, can be used as in commercialization dye-sensitized solar cells product organic photosensitive agent use.
5, the invention discloses the intermediate of organic dye sensitized dose of a class conjugation aromatic ring chromophoric group higly branched chain derivatize, its salt and such organic dye compound, particularly a class band terthienyl conjugation aromatic nucleus modular construction intermediate, its various synthetic methods and rationally organic dye sensitized dose of derivative gained or its salt, their preparation method and they application in opto-electronic conversion field, the precious metals complex photosensitizers of reporting in document or patent can be replaced, the cost of manufacture of this class battery can be effectively reduced.This agents useful for same and all commercially available obtaining of raw material, raw material sources are convenient; Selected synthetic method is general organism unit reaction, and actual preparation and purge process are simple, is suitable for laboratory preparation and suitability for industrialized production.
Brief description of the drawings
Fig. 1 is the structural representation of the dye sensitized nano crystal body solar cell that in effect embodiment 1 prepared by organic dye sensitized dose of I of the present invention, and wherein 1 is transparent substrates; 2 is conductive layer; 3 is light absorbing zone; 4 is electrolyte layer; 5 is to electrode layer.
Fig. 2 is Compound C GTD-DSSC-025 of the present invention, CGTD-DSSC-029, CGTD-DSSC-031, CGTD-DSSC-036, CGTD-DSSC-039, CGTD-DSSC-055, CGTD-DSSC-064, CGTD-DSSC-066, the short-circuit current (Isc) of CGTD-DSSC-069 and N719 and the graph of a relation of current potential (Voc), the wherein graph of a relation of 6 short-circuit currents (Isc) that are CGTD-DSSC-025 and current potential (Voc), 7 is the short-circuit current (Isc) of CGTD-DSSC-029 and the graph of a relation of current potential (Voc), 8 is the short-circuit current (Isc) of CGTD-DSSC-031 and the graph of a relation of current potential (Voc), 9 is the short-circuit current (Isc) of CGTD-DSSC-036 and the graph of a relation of current potential (Voc), 10 is the short-circuit current (Isc) of CGTD-DSSC-039 and the graph of a relation of current potential (Voc), 11 is the short-circuit current (Isc) of CGTD-DSSC-055 and the graph of a relation of current potential (Voc), 12 is the short-circuit current (Isc) of CGTD-DSSC-064 and the graph of a relation of current potential (Voc), 13 is the short-circuit current (Isc) of CGTD-DSSC-066 and the graph of a relation of current potential (Voc), 14 is the short-circuit current (Isc) of CGTD-DSSC-069 and the graph of a relation of current potential (Voc), 15 is the short-circuit current (Isc) of N719 and the graph of a relation of current potential (Voc).
Fig. 3 is Compound C GTD-DSSC-029 of the present invention, CGTD-DSSC-031, CGTD-DSSC-036, CGTD-DSSC-039, CGTD-DSSC-055, CGTD-DSSC-064, CGTD-DSSC-066, the ultraviolet-visible absorption spectroscopy spectrogram of CGTD-DSSC-069, 7 is the ultraviolet-visible absorption spectroscopy spectrogram of CGTD-DSSC-029, 8 is the ultraviolet-visible absorption spectroscopy spectrogram of CGTD-DSSC-031, 9 is the ultraviolet-visible absorption spectroscopy spectrogram of CGTD-DSSC-036, 10 is the ultraviolet-visible absorption spectroscopy spectrogram of CGTD-DSSC-039, 11 is the ultraviolet-visible absorption spectroscopy spectrogram of CGTD-DSSC-055, 12 is the ultraviolet-visible absorption spectroscopy spectrogram of CGTD-DSSC-064, 13 is CGTD-DSSC-066, 14 is the ultraviolet-visible absorption spectroscopy spectrogram of CGTD-DSSC-069.
Embodiment
Mode below by embodiment further illustrates the present invention, but does not therefore limit the present invention among described scope of embodiments.The experimental technique of unreceipted actual conditions in the following example, according to ordinary method and condition, or selects according to catalogue.
Embodiment 1:
1) intermediate A 1 is synthetic: under lucifuge condition; N-bromo-succinimide (1.60 grams, 9 mmoles) is joined to 80 milliliters of N that are dissolved with 3-formyl radical thiophene (1.0 grams, 9 mmoles); in dinethylformamide solution; room temperature reaction 2 days, adds 100 ml waters afterwards, and is extracted with ethyl acetate (100 milliliters; 3 times); organic layer is concentrated, and silica gel is crossed post (sherwood oil: ethyl acetate=50:1) and obtained 1.9 and digest compound A1, productive rate 78.5%.
1H-NMR(400MHz，DMSO-d
6)δ:7.476(s，1H)，9.722(s，1H)。ESI-MS[M+H]
+:267.8。
2) intermediate B 1 is synthetic: in 100 ml flasks, add compd A 1(538 milligram, 2 mmoles), (256 milligrams of thiophene-2-boric acid, 2 mmoles), tetra-triphenylphosphine palladium (232 milligrams, 0.2 mmole) and tetrahydrofuran (THF): 24 milliliters, water (5:1).Under nitrogen protection condition, mixture was 70 DEG C of reactions 8 hours, and after cool to room temperature, concentrated except desolventizing, silica gel column chromatography (sherwood oil: ethyl acetate=50:1) obtains 174 milligrams of compound B-11s, productive rate 31.8%.ESI-MS[M+H]
+:272.7。
3) intermediate C's is synthetic: in 50 ml flasks, add compound 3-hexyl thiophene (842 milligrams, 5 mmoles), 20 milliliters of N-chlorosuccinimide (668 milligrams, 5 mmoles) and DMFs.Under nitrogen protection condition, mixture after 16 hours, adds 20 ml waters at room temperature reaction in reaction solution, is extracted with ethyl acetate (20 milliliters, three times), and organic layer is concentrated obtains 0.98 gram of Compound C, LC-MS purity except desolventizing: 89.02%, and productive rate 97.0%.ESI-MS[M+H]
+：202.2。
4) intermediate D1's is synthetic: in 50 ml flasks, add (909 milligrams of Compound C, 4.5 mmoles), add N-bromo-succinimide (800 milligrams, 4.5 mmoles), room temperature reaction spends the night, in reaction solution, add 20 ml waters, be extracted with ethyl acetate (20 milliliters, three times), organic layer is concentrated digests compound D1 except desolventizing obtains 1.2, LC-MS purity: 100%, productive rate 85.4%.ESI-MS[M+H]
+：281.9。
5) intermediate E is synthetic: in 25 milliliters of there-necked flasks, add Compound D 1(702 milligram, 2.5 mmoles), under-78 DEG C of conditions, drip (1.5 milliliters of n-Butyl Lithiums, 3.75 mmole), under-78 DEG C of conditions, react 1 hour, add sec.-propyl tetramethyl ethylene ketone boric acid ester (744 milligrams, 4 mmoles).Under nitrogen protection condition, mixture reaction 16 hours, adds saturated aqueous ammonium chloride cancellation reaction, and dichloromethane extraction (20 milliliters, three times) concentrates except silica gel chromatographic column after desolventizing separates (sherwood oil) and obtains 450 milligrams of compd Es, productive rate 54.8%.
1H-NMR(400MHz，CDCl
3)δ:0.821(t，3H)，1.237(m，6H),1.255(s，12H),1.501(m，2H),2.481(t，2H)，7.260(s，1H)，ESI-MS[M+H]
+：356.2。
6) intermediate G's is synthetic: in 100 ml flasks, add 50 milliliters of compound F 17-hydroxy-corticosterone (1.67 grams, 6 mmoles), tributyl tin thiophene (2.24 grams, 6 mmoles), tetra-triphenylphosphine palladium (0.694 gram, 0.6 mmole) and tetrahydrofuran (THF)s.Under nitrogen protection condition, mixture was 66 degrees Celsius of reactions 16 hours, after cool to room temperature, concentrated except desolventizing, and silica gel is crossed post (sherwood oil: ethyl acetate=6:1) and obtained 1.5 and digest compound G, LC-MS purity: 98.48%, and productive rate 89%.
1H-NMR(400MHz,DMSO-d
6)δ:3.197(s,3H),3.378(s,3H),7.120(t,1H),7.185(d,1H),7.540(d,2H),7.601(d,1H),7.625(d,1H),ESI-MS(M+H
+):282.0.
7) intermediate H's is synthetic: under lucifuge condition; by (2 grams of NBS; 11.18 mmoles) join the DMF(N of 60 milliliters of compound G (3 grams, 10.65 mmoles), dinethylformamide) in solution; under nitrogen protection, stir and spend the night; in reaction system, add 50 ml waters, solid is separated out, filtration to 2.5g intermediate H; LC-MS purity: 95.77%, productive rate 65.4%.
1H-NMR(400MHz,DMSO-d
6)δ:3.207(s,3H),3.400(s,3H),7.016(d,1H),7.250(d,1H),7.570(m,4H),.ESI-MS(M+H
+)：361.9。
Embodiment 2:
1) intermediate compound I is synthetic: in 25 ml flasks, add 1,1,7,7-tetramethyl-julolidine (91.6 milligrams, 0.4 mmole), 12 milliliters of N-bromo-succinimide (71.2 grams, 0.4 mmole) and methylene dichloride.Under nitrogen protection condition, mixture after 16 hours, adds 12 ml waters at room temperature reaction, and dichloromethane extraction (15 milliliters, 3 times) is concentrated obtains 105 milligrams of Compound I, LC-MS purity except desolventizing: 100%, and productive rate 85.1%.
1H-NMR(400MHz，DMSO-d
6)δ:1.254(s，12H)，1.733(t，4H),3.121(t，4H)，7.083(s，2H)，ESI-MS(M+H
+):310.0。
2) intermediate J's is synthetic: in 50 ml flasks, add (92.4 milligrams of Compound I, 0.3 mmole), (152 milligrams of duplex tetramethyl ethylene ketone boric acid esters, 0.6 mmole), (88.3 milligrams of Potassium ethanoates, 0.9 mmole), [two (diphenylphosphine) ferrocene of 1,1'-] palladium chloride (Pd (dppf) Cl
2) 20 milliliters of (24 milligrams, 0.03 mmole) and dioxs.Under nitrogen protection condition, mixture, 85 DEG C of reactions 16 hours, concentrates except silica gel chromatographic column after desolventizing separates (sherwood oil) and obtains 75 milligrams of compound J, LC-MS purity: 100%, and productive rate 70.4%.
1H-NMR(400MHz,DMSO-d
6)δ:1.231(s，24H)，1.662(t，4H),3.129(t，4H)，7.429(s，2H)，ESI-MS[M+H]
+：356.2。
3) intermediate L's is synthetic: in 50 ml flasks, add (1.07 grams of compound Ks, 3 mmoles), (1.52 grams of compound duplex tetramethyl ethylene ketone boric acid esters, 6 mmoles), Potassium ethanoate (0.882 gram, 9 mmoles), [two (diphenylphosphine) ferrocene of 1,1'-] palladium chloride (Pd (dppf) Cl
2) 20 milliliters of (219 milligrams, 0.3 mmole) and dioxs, be heated to 90 degrees Celsius of stirrings and spend the night, concentrated except desolventizing, silica gel is crossed post (sherwood oil: ethyl acetate=100:1) and is obtained 1.0 grams of compound Ls, LC-MS purity: 98.6%, productive rate 82.3%.
1H-NMR(400MHz，CDCl
3)δ:1.306(s，12H),7.550(m，1H),7.886(d，2H)，7.944(d，1H)，8.025(d，2H)，8.280(s，1H)。ESI-MS[M+H]
+：406.1。
4) intermediate N1's is synthetic: by (364 milligrams of compound M, 1.0 mmoles), 20 milliliters of tetrahydrofuran (THF)s join in 50 milliliters of there-necked flasks, under subzero 78 degrees Celsius, drip (0.48 milliliter of n-Butyl Lithium, 1.2 mmoles), at this temperature, react after 1 hour, drip (390 milligrams of tributyltin chlorides, 1.2 mmoles), dropwise and be slowly warmed up to room temperature reaction 16 hours afterwards, add 20 milliliters, water, be extracted with ethyl acetate (20 milliliters, 3 times), organic layer is concentrated, silica gel is crossed post (sherwood oil: ethyl acetate=50:1) and is obtained 380 milligrams of compound Ns 1, LC-MS purity: 98.47%, productive rate 66.2%.
1H-NMR(400MHz，DMSO-d
6)δ:0.862(t,9H)，1.152(t，6H)，1.335(m，6H)，1.651(m，6H)，7.302(d，1H)，7.750(d，1H)，7.982(d，1H)，8.340(m,2H)。ESI-MS[M+H]
+:576.2。
5) intermediate P's is synthetic: in 100 ml flasks, add compound O(298 milligram, 2 mmoles), (1.28 grams of 4-hexyloxy bromobenzenes, 5 mmoles), (576 milligrams of sodium tert-butoxides, 6 mmoles), (91.5 milligrams of two (dibenzalacetone) palladiums, 0.1 mmole), (116 milligrams of tributyl phosphorus a tetrafluoro borates, 0.4 mmole) and 50 milliliters of toluene, 100 DEG C of reactions hours 16 hours under nitrogen protection condition, concentrate except silica gel chromatographic column after desolventizing separates (sherwood oil: ethyl acetate=100:1) and obtain 800 milligrams of compound P, productive rate 79.8%.
1H-NMR(400MHz，CDCl
3)δ:0.878(t，6H)，1.309(m，8H)，1.406(m，4H)，1.670(m，4H)，3.912(t，4H)6.861(m,4H)，6.949(m,5H)，7.262(m，2H)，7.671(d，1H)，7.783(d，1H)，ESI-MS[M+H]
+：501.1。
6) intermediate Q's is synthetic: in 25 milliliters of there-necked flasks, add compound P(204 milligram, 0.4 mmole), under-78 DEG C of conditions, drip (0.24 milliliter of n-Butyl Lithium, 0.6 mmole), under-78 DEG C of conditions, react 1 hour, add sec.-propyl tetramethyl ethylene ketone boric acid ester (120 milligrams, 0.64 mmole).Under nitrogen protection condition, mixture reaction 16 hours, adds saturated aqueous ammonium chloride cancellation reaction; (20 milliliters of dichloromethane extractions; three times), concentrate except silica gel chromatographic column after desolventizing separates (sherwood oil: ethyl acetate=30:1) and obtain 100 milligrams of compound Qs, productive rate 40%.ESI-MS[M+H]
+：628.2。
7) intermediate R's is synthetic: by bromo-2-9,9-dimethyl-9-(H) (3.30 grams of-fluorenes, 12 mmoles), aniline (440 milligrams, 4.73 mmoles), (180 milligrams of three (dibenzalacetone) two palladiums, 0.2 mmole), tri-butyl phosphine fluoroborate (232 milligrams, 0.8 mmole), sodium tert-butoxide (1.3 grams, 13.5 mmoles) and 20 milliliters of toluene react 4 hours in 100 DEG C under nitrogen atmosphere.Filter, concentrated filtrate, residue is purified (sherwood oil: ethyl acetate=100:1) with silicagel column, obtains 2.0 grams of white solid compound Rs, productive rate 89%.ESI-MS[M+H]
+：478。
8) intermediate S's is synthetic: to being dissolved with (954 milligrams of R, 2.0 mmoles) 50 milliliters of dichloromethane solutions at 0 DEG C, slowly drip (340 milligrams of N-bromo-succinimides (NBS), 1.91 mmoles) be dissolved in the solution of 30 milliliters of methylene dichloride, within 30 minutes, add, finish, continue reaction 30 minutes in 0 DEG C.Remove solvent under reduced pressure, residue purification by silica gel column chromatography (eluent: sherwood oil), obtains 1.02 grams of white solid compound Ss, productive rate 96%.ESI-MS[M+H]
+：478。
9) intermediate T's is synthetic: be dissolved in 20 milliliters of dry tetrahydrofuran solution in the n-Butyl Lithium hexane solution (1.3 milliliters, 2.1 mmoles) of-78 DEG C of dropping 1.6M to compound S (973 milligrams, 1.75 mmoles), finish, remain at-78 DEG C and react 1 hour, add 2-sec.-propyl-4,4-5,5-tetramethyl--1,3,2-dioxo borine (558 milligrams, 3 mmoles), reaction solution was warming up to room temperature naturally, in stirring at room temperature reaction 16 hours.In reaction solution, add 20 milliliters of saturated aqueous ammonium chlorides, ethyl acetate extraction, separates organic layer, is spin-dried for, and purification by silica gel column chromatography (sherwood oil: ethyl acetate=40:1), obtains 630 milligrams of white solid compound T, productive rate: 60%.
1H-NMR(400MHz,CDCl3):δ7.69(d,J=8.0Hz,2H),7.64(d,J=8.0Hz,2H),7.59(d,J=8.0Hz,2H),7.38(d,J=8.0Hz,2H),7.30～7.33(m,2H),7.24～7.28(m,4H),7.15(d,J=8.0Hz,2H),7.09(d,J=8.0Hz,2H),1.40(s,12H),1.35(s,12H)。
10) intermediate V's is synthetic: in 50 ml flasks, add (1.15 grams of compound U, 3 mmoles), (1.52 grams of compound duplex tetramethyl ethylene ketone boric acid esters, 6 mmoles), (0.882 gram of Potassium ethanoate, 9 mmoles), 20 milliliters of the two Diphenyl phosphino ferrocene palladium chlorides (219 milligrams, 0.3 mmole) of 1,1'-and dioxs, being heated to 90 degrees Celsius of stirrings spends the night, concentrated except desolventizing, silica gel is crossed post (sherwood oil: ethyl acetate=100:1) and is obtained 1.0 and digest compound V, productive rate 77.3%.ESI-MS[M+H]
+：431.3。
11) intermediate X is synthetic: in 50 ml flasks, add (1.57 grams of compound W, 3 mmoles), (1.52 grams of compound duplex tetramethyl ethylene ketone boric acid esters, 6 mmoles), (0.882 gram of Potassium ethanoate, 9 mmoles), 20 milliliters of the two Diphenyl phosphino ferrocene palladium chlorides (219 milligrams, 0.3 mmole) of 1,1'-and dioxs, being heated to 95 degrees Celsius of stirrings spends the night, concentrated except desolventizing, silica gel is crossed post (sherwood oil: ethyl acetate=150:1) and is obtained 1.1 and digest compound V, productive rate 64.1%.ESI-MS[M+H]
+：571.6。
Embodiment 3:
1) intermediate Y's is synthetic: in 25 ml flasks, add thieno-[3,2-b] thiophene (140 milligrams, 1 mmole), 12 milliliters of N-bromo-succinimide (480 grams, 0.9 mmole) and methylene dichloride.Under nitrogen protection condition, mixture after 16 hours, adds 12 ml waters at room temperature reaction, and dichloromethane extraction (15 milliliters, 3 times) is concentrated obtains intermediate Y180 milligram except desolventizing.Productive rate 82.1%.ESI-MS(M+H
+):219.8。
2) intermediate Z's is synthetic: in 50 ml flasks, add compound Y(175.2 milligram, 0.8 mmole), compound 3(182.4 milligram, 0.96 mmole), salt of wormwood (331 milligrams, 2.4 mmoles), four (92.6 milligrams of triphenyl phosphorus palladiums, 0.08 mmole), 6 milliliters, 20 milliliters of tetrahydrofuran (THF)s and water.Under nitrogen protection condition, mixture, 68 DEG C of reactions 16 hours, concentrates except silica gel chromatographic column after desolventizing separates (sherwood oil) and obtains intermediate Z170 milligram.Productive rate 74.8%.
1H-NMR(400MHz,DMSO-d
6)δ:7.196(d,1H),7.338(d,1H),7.507(s,1H),7.563(d,2H),7.643(d,2H),ESI-MS(M+H
+):284.3
3) intermediate A ' synthetic: in 100 ml flasks, add (570 milligrams of 4-trifluoromethyl phenylo boric acids, 3 mmoles), 2,3-dibromo thiophene (657 milligrams, 3 mmoles), (1.24 grams, salt of wormwood, 9 mmoles), tetra-triphenylphosphine palladium (347 milligrams, 0.3 mmole), and 25 milliliters of tetrahydrofuran (THF)s, 8 milliliters, water.Under nitrogen protection condition, mixture reacted after 16 hours at 68 DEG C, and after cooling room temperature, concentrated except desolventizing, silica gel chromatographic column separates (petrol ether/ethyl acetate=20/1) and obtains intermediate A ' 700 milligram.Productive rate 62.7%.ESI-MS(M+H
+):372.0。
4) intermediate B ' synthetic: add in 25 ml flasks compd A ' (297.6 milligrams, 0.8 mmole), 25 milliliters of N-bromo-succinimide (142.4 milligrams, 0.8 mmole) and DMFs.Under nitrogen protection condition, mixture reacts after 8 hours under 50 DEG C of conditions, adds 25 ml waters, white solid intermediate B ' 340 milligram to compound 8 of filtration.Productive rate 94.2%.ESI-MS(M+H
+):451.9.
5) intermediate C''s is synthetic: in 50 ml flasks, add (462 milligrams of the bromo-5-trifluoromethyl thiophenes of compound 2-, 2 mmoles), (307.2 milligrams of compound 2-thienyl boric acid, 2.4 mmoles), salt of wormwood (0.828 gram, 6 mmoles), four (232 milligrams of triphenyl phosphorus palladiums, 0.2 mmole), 7 milliliters, 21 milliliters of tetrahydrofuran (THF)s and water.Under nitrogen protection condition, mixture, 68 DEG C of reactions 6 hours, concentrates except silica gel chromatographic column after desolventizing separates (sherwood oil) and obtains intermediate C'400 milligram.Productive rate 85.5%.ESI-MS(M+H
+):233.9。
6) intermediate D''s is synthetic: in 25 ml flasks, add Compound C ' (398 milligrams, 1.7 mmoles), 25 milliliters of N-bromo-succinimide (302 milligrams, 1.7 mmoles) and DMFs.Under nitrogen protection condition, mixture reacts and spends the night under 30 DEG C of conditions, adds 25 ml waters, the white solid intermediate D'340 milligram to compound 4 of filtration.Productive rate 63.9%.ESI-MS(M+H
+):311.9。
7) intermediate E ' synthetic: in 50 ml flasks, add compound 5-methyl-2, (901 milligrams of 1,3-diazosulfides, 6 mmoles), hydrogen bromide (40%, 15 milliliter), after being heated to 120 degree, drip (1 milliliter of bromine, 1 milliliter of hydrogen bromide dissolves), mixture reacts and spends the night under 120 degrees celsius, after cool to room temperature, 15 milliliters of bisulfite saturated aqueous solution of sodium add, remove excessive bromine, filter and obtain yellow solid, ethyl alcohol recrystallization obtains intermediate E ' 1.3 gram.Productive rate 70.3%.ESI-MS(M+H
+):308.8。
8) intermediate F''s is synthetic: in 50 ml flasks, add compd E ' (1.3 grams, 4.2 mmoles), (0.75 gram of N-bromo-succinimide; 4.2 mmoles); Benzoyl Peroxide (50.8 milligrams, 0.21 mmole), 20 milliliters, tetracol phenixin; under nitrogen protection condition; mixture heating reflux reaction spends the night, and solids removed by filtration is used ethyl alcohol recrystallization after filtrate is concentrated; obtain intermediate F'0.92 gram, productive rate 56.6%.ESI-MS(M+H
+):387.2。
9) intermediate G''s is synthetic: in 50 ml flasks, add compound F 17-hydroxy-corticosterone ' (851 milligrams, 2.2 mmoles), (1.1 grams, calcium carbonate, 11 mmoles), and 20 milliliters of dioxan 25 ml waters, be heated to 100 degree reactions and spend the night, after cool to room temperature, remove by filter calcium carbonate, the concentrated intermediate G'0.62 gram that obtains of filtrate.Productive rate 84.5%.ESI-MS(M+H
+):324.2。
10) intermediate H''s is synthetic: in 100 ml flasks, add compound G'(620 milligram, 1.9 mmoles), (1.33 grams of Manganse Dioxide, 15.2 mmole), and 30 milliliters of dioxan, react 1 hour after being heated to 100 degree, after cool to room temperature, remove by filter unreacted Manganse Dioxide, the concentrated intermediate H'400 milligram that obtains of filtrate.Productive rate 64.5%.ESI-MS(M+H
+):321.8。
11) (200 milligrams of intermediate compound I ' synthetic: add in 25 ml flasks compound H ', 0.62 mmole), (293 grams, 2-tributyl tinbase thiophene, 0.78 mmole), four triphenyl phosphorus palladiums (72 milligrams, 0.062 mmole) and 15 milliliters of toluene, after being heated to 95 degrees Celsius, reaction is spent the night, after cool to room temperature, the concentrated toluene of removing, silica gel chromatographic column separates (sherwood oil: ethyl acetate=50:1) and obtains intermediate compound I ' 65 milligram.Productive rate 33.3%.ESI-MS(M+H
+):325.9。
12) intermediate J''s is synthetic: in 25 ml flasks, add (178.3 milligrams of cyclopentyl bithiophenes, 1 mmole), (363 milligrams of n-hexyl bromines, 2.2 mmoles), potassiumiodide (8.3 milligrams, 0.05 mmole), 6 milliliters of dimethyl sulfoxide (DMSO), after stirring at room temperature 10 minutes, add potassium hydroxide (224 milligrams, 4 mmoles).Under nitrogen protection condition, mixture was 20 DEG C of reactions 16 hours, and the cancellation that adds water is reacted and used extracted with diethyl ether (15 milliliters, three times), concentrates and obtains thick product, and silica gel chromatographic column separates (sherwood oil) and obtains intermediate J'300 milligram.Productive rate 86.7%.ESI-MS(M+H
+):346.1。
13) intermediate K''s is synthetic: in 25 milliliters of there-necked flasks, add compound J'(173.3 milligram, 0.5 mmole), 10 milliliters of tetrahydrofuran (THF)s, under subzero 78 degrees celsius, drip n-Butyl Lithium (2.5M, 0.24 milliliter, 0.6 mmole), after dropwising, at this temperature, react 1 hour, under subzero 78 degree conditions, drip (195.3 milligrams of tributyltin chlorides, 0.6 mmole), under nitrogen protection condition, mixture is slowly being warmed up to room temperature and reaction is spent the night, the cancellation that adds water is reacted and is separated which floor has obtained, the concentrated intermediate K'230 milligram that obtains, productive rate 72.3%.ESI-MS(M+H
+):636.2。
14) intermediate L''s is synthetic
In 25 ml flasks, add cyclopentyl bithiophene (178.3 milligrams, 1 mmole), monobromethane (240 milligrams, 2.2 mmoles), potassiumiodide (8.3 milligrams, 0.05 mmole), 8 milliliters of dimethyl sulfoxide (DMSO), after stirring at room temperature 10 minutes, add potassium hydroxide (224 milligrams, 4 mmoles).Under nitrogen protection condition, mixture was 20 DEG C of reactions 17 hours, and the cancellation that adds water is reacted and used extracted with diethyl ether (15 milliliters, three times), concentrates and obtains thick product, and silica gel chromatographic column separates (sherwood oil) and obtains intermediate L'200 milligram.Productive rate 85.5%.ESI-MS(M+H
+):234.1。
15) intermediate M''s is synthetic
In 25 milliliters of there-necked flasks, add compound L ' (550 milligrams; 2.35 mmole); 15 milliliters of tetrahydrofuran (THF)s; under subzero 78 degrees celsius, drip n-Butyl Lithium (2.5M; 1.13 milliliter; 2.82 mmole); after dropwising, at this temperature, react 1 hour, under subzero 78 degree conditions, drip (880 milligrams of tributyltin chlorides; 2.7 mmoles); under nitrogen protection condition, mixture is slowly being warmed up to room temperature and reaction is spent the night, and the cancellation that adds water is reacted and separated which floor has obtained; concentrated 1.02 grams of intermediate M', the productive rate 82.9% of obtaining.ESI-MS(M+H
+):524.2。
16) intermediate N''s is synthetic:
By (450 milligrams of compd Bs, 1.67 mmole), (578 milligrams of N-bromo-succinimides, 3.34 mmoles) be dissolved in trichloromethane (30 milliliters), under ice-water bath, drip acetic acid (10 milliliters), drip and finish, reaction ambient temperature overnight, (30 milliliters of reaction solution difference waters, three times), saturated sodium bicarbonate (20 milliliters), Sulfothiorine (20 milliliters) wash, the concentrated silica gel of organic layer is crossed post (sherwood oil: ethyl acetate=100:1) and is obtained 588 milligrams of intermediate N', LC-MS purity: 99%, and productive rate 88%.ESI-MS[M+H]
+：398.9。
17) intermediate O''s is synthetic:
By intermediate N'(100 milligram, 0.25 mmole), (55 milligrams of 4-isopropoxy phenylo boric acids, 0.3 mmole), (86 milligrams, salt of wormwood, 0.63 mmole) be dissolved in the mixed solvent that fills tetrahydrofuran (THF) (10 milliliters) and water (2 milliliters), under nitrogen protection condition, add (29 milligrams of tetra-triphenylphosphine palladiums, 0.025 mmole), solution spends the night 70 DEG C of reactions, after cool to room temperature, separate organic layer, the concentrated crude product that obtains, silica gel is crossed post (sherwood oil: ethyl acetate=10:1) and is obtained 64 milligrams of intermediate O', LC-MS purity: 96%, productive rate 38%, ESI-MS[M+H+2]
+: 409.0.
18) B of intermediate " synthetic:
By (200 milligrams of compound 055-1,0.279 mmole), (86.5 milligrams of ethylene glycol, 1.39 mmoles), (4.8 milligrams of tosic acid, 0.028 mmole) join in the flask that fills 20 milliliters of toluene, at 130 degrees Celsius of lower fraction water device water-dividings, stirring and refluxing reaction 8 hours, after cool to room temperature, add sodium bicarbonate aqueous solution, regulate pH value to be greater than 8, ethyl acetate extraction is concentrated, and silica gel is crossed post (sherwood oil: ethyl acetate=20:1) and obtained 200 milligrams of compd Bs ".Productive rate 94.3%.ESI-MS(M+H
+)=760.2
19) C of intermediate " synthetic:
Under ice-water bath condition; by isopropylmagnesium chloride (1M; 0.4 milliliter; 0.4 mmole) be added dropwise to fill B " (200 milligrams; 0.263 mmole); in the flask of 10 milliliters of tetrahydrofuran (THF)s; under nitrogen protection condition; 0 degree Celsius of reaction 1 hour; tributyltin chloride (130 milligrams, 0.4 mmole) is added dropwise in flask, react natural intensification reaction overnight after 1 hour under 0 degree Celsius; add aqueous ammonium chloride solution cancellation, ethyl acetate extraction is concentrated to be obtained product and is directly used in next step reaction.Obtain 350 milligrams of Compound C ", TLC purity 60%, productive rate 78.4%.
Embodiment 4:
1) intermediate P''s is synthetic
In 50 ml flasks, add (273 milligrams of compound B-11s; 1 mmole); the chloro-5 boric acid thiophene of 2-(162 milligrams, 1 mmole), (414 milligrams, salt of wormwood; 3 mmoles); tetra-triphenylphosphine palladium (115.8 milligrams, 0.1 mmole) and 20 milliliters of tetrahydrofuran (THF) 4 ml waters, under nitrogen protection, after 65 degree, reaction is spent the night; concentrated except desolventizing after cool to room temperature, silica gel chromatographic column separates (sherwood oil: ethyl acetate=20:1) and obtains intermediate P'280 milligram.Productive rate 90.3%.ESI-MS(M+H
+):310.9。
2) intermediate Q''s is synthetic
In 50 ml flasks, add compound P'(155 milligram, 0.5 mmole), (89 milligrams of N-bromo-succinimides, 0.5 mmole), 20 milliliters of DMFs, 25 degrees Celsius of reactions are spent the night, add water and separate out solid, filter and obtain intermediate Q'175 milligram, productive rate 89.9%.ESI-MS(M+H
+):388.8。
3) intermediate R''s is synthetic:
In a flask of being furnished with water trap, add: compound B-11 (580 milligrams), ethylene glycol (2 milliliters), toluene (30 milliliters), tosic acid (20 milligrams).Reaction solution reflux divides water to spend the night.Be cooled to room temperature, add ethyl acetate dilution, use successively saturated sodium bicarbonate aqueous solution, saturated common salt water washing, anhydrous sodium sulfate drying.Revolve and steam except desolventizing, slightly for product, silica gel column chromatography (petrol ether/ethyl acetate=20:1) purifying obtains oily matter intermediate R'(480 milligram), productive rate 71%.
1H-NMR(400MHz,CDCl
3)δ:7.35(dd,J=1.1Hz,5.4Hz,1H),7.21(dd,J=0.9Hz,3.5Hz,1H),7.18,(s,1H),7.07(dd,J=3.7Hz,5.6Hz,1H),5.82(s,1H),4.14(m,2H),4.00(m,2H)。
4) intermediate S''s is synthetic
Under nitrogen protection, compound R ' (160 milligrams) be dissolved in tetrahydrofuran (THF) (6 milliliters), is cooled to 0 DEG C, stirs the lower isopropylmagnesium chloride (1M tetrahydrofuran solution, 1 milliliter) that drips.Stir 1 hour, add tributyltin chloride (0.32 milliliter), room temperature continues reaction 1 hour.Add saturated aqueous ammonium chloride cancellation, ethyl acetate extraction, saturated common salt water washing, anhydrous sodium sulfate drying.Revolve and steam except desolventizing, slightly for product, silica gel column chromatography (petrol ether/ethyl acetate=20:1) purifying obtains oily matter intermediate S'(200 milligram), productive rate 75%.
1H-NMR(400MHz,CDCl
3)δ:7.32(dd,J=1.2Hz,5.4Hz,1H),7.26,(s,1H),7.22(dd,J=1.0Hz,3.4Hz,1H),7.06(dd,J=3.6Hz,5.4Hz,1H),5.93(s,1H),4.15(m,2H),4.07(m,2H)，1.6(m,6H),1.3(m,6H),1.1(m,6H),0.91(m,9H)。
5) intermediate T''s is synthetic
In 50 ml flasks, add compound 057-1(900 milligram, 3.26 mmoles) 20 milliliters of N, dinethylformamide, under ice bath, slowly drip (580 milligrams of N-bromo-succinimides, 3.26 mmoles) 20 milliliters of DMF solution, be slowly raised to after room temperature, stirring reaction spends the night, and adds water and separates out intermediate T'800 milligram.Productive rate 69.1%.1H-NMR(400MHz,CDCl3):6.961(d,1H),7.000(d,1H),7.163(t,1H),7.308(d,1H),7.501(m,2H),10.073(s,1H).ESI-MS(M+H
+):354.9。
6) intermediate U''s is synthetic
In a flask of being furnished with water trap, add: compound T'(400 milligram), ethylene glycol (2 milliliters), toluene (30 milliliters), tosic acid (20 milligrams).Reaction solution reflux divides water to spend the night.Be cooled to room temperature, add ethyl acetate dilution, use successively saturated sodium bicarbonate aqueous solution, saturated common salt water washing, anhydrous sodium sulfate drying.Revolve and steam except desolventizing, slightly for product, silica gel column chromatography (petrol ether/ethyl acetate=20:1) purifying obtains oily matter intermediate U'(334 milligram), productive rate 71%.
7) intermediate V''s is synthetic
Under nitrogen protection, compound U'(334 milligram) be dissolved in tetrahydrofuran (THF) (8 milliliters), be cooled to 0 DEG C, stir the lower isopropylmagnesium chloride (1M tetrahydrofuran solution, 1.7 milliliters) that drips.Stir 1 hour, add tributyltin chloride (0.54 milliliter), room temperature continues reaction 1 hour.Add saturated aqueous ammonium chloride cancellation, ethyl acetate extraction, saturated common salt water washing, anhydrous sodium sulfate drying.Revolve and steam except desolventizing, slightly for product, silica gel column chromatography (petrol ether/ethyl acetate=20:1) purifying obtains oily matter intermediate V'(420 milligram), productive rate 82%.
1H-NMR(400MHz,CDCl
3)δ:7.34(dd,J=1.0Hz,5.3Hz,1H),7.29(d,J=3.1Hz,1H),7.28(s,1H),7.27(dd,J=1.0Hz,5.4Hz,1H),7.07(dd,J=3.3Hz,5.4Hz,1H),7.06(d,J=3.1Hz,1H),5.89(s,1H),4.20(m,2H),4.03(m,2H)，1.57(m,6H),1.35(m,6H),1.12(m,6H),0.96(t,J=7.2Hz,9H)。
8) intermediate W''s is synthetic
By compound 3 bromo thiophene also [3,2-b] (500 milligrams, thiophene, 2.3 mmoles) be dissolved in tetrahydrofuran (THF) (5 milliliters), under-78 DEG C of conditions, drip (1.76 milliliters of n-Butyl Lithiums, 4.6 mmoles), under-78 DEG C of conditions, react 20 minutes, add N, N-N,N-DIMETHYLACETAMIDE (0.35 milliliter, 4.6 mmoles).Under nitrogen protection condition; mixture reaction 2 hours; add saturated aqueous ammonium chloride cancellation reaction; (20 milliliters of ethyl acetate extractions; three times); concentrate except silica gel chromatographic column after desolventizing separates (sherwood oil: methylene dichloride=1:2) and obtain 200 milligrams of compound W ', LC-MS purity: 100%, productive rate 52%.1H-NMR(400MHz,CDCl3)δ:7.256-7.270(d,1H),7.621-7.634(d,1H),7.876(s,1H),9.099(s,1H)。
9) intermediate X ' synthetic
250 milligrams of W' are dissolved in 10 ml methanol, under stirring, are cooled to 0 DEG C.Add 280 milligrams of sodium borohydrides, react 30 minutes.Revolve to steam and remove most of methyl alcohol, thin up.Ethyl acetate extraction, anhydrous sodium sulfate drying, except after desolventizing, obtain white solid intermediate X ' (250 milligrams), productive rate 99%.
1H-NMR(400MHz,CDCl
3)δ:7.36(d,J=5.3Hz,1H),7.24(d,J=5.3Hz,1H),7.20(s,1H),4.87(s,2H)。
10) intermediate Y''s is synthetic
By X'(200 milligram), NBS(500 milligram) be dissolved in 15 milliliters of tetrahydrofuran (THF)s stirring at room temperature 3 hours.The cancellation that adds water, ethyl acetate extraction, anhydrous sodium sulfate drying.Revolve and steam except desolventizing, thick product purification by silica gel column chromatography (sherwood oil: ethyl acetate=1:2) obtains white solid intermediate Y'(120 milligram), productive rate 31%.
1H-NMR(400MHz,CDCl
3)δ:7.29(s,1H),4.86(d,J=6.3Hz,2H),1.95(t,J=6.2Hz,1H)。
11) intermediate Z''s is synthetic
By Y'(120 milligram), PDC(280 milligram) be dissolved in 10 milliliters of methylene dichloride stirring at room temperature 3 hours.Add diatomite, under vigorous stirring, add ether.Filter, solid is washed by ethyl acetate, and merging filtrate revolves to steam except after desolventizing and obtains green solid intermediate Z'(110 milligram), productive rate 92%.
1H-NMR(400MHz,CDCl
3)δ:10.03(s，1H）7.40(s,1H)。
Embodiment 5:
1) compound 020-1's is synthetic: by (1.39 grams of intermediate H, 3.8 mmoles), (2 grams of intermediate V, 4.56 mmole), (1.6 grams, salt of wormwood, 0.4 mole) join in 250 milliliters of there-necked flasks that fill 100 milliliters of tetrahydrofuran (THF)s and 30 ml waters, under nitrogen protection condition, add (0.448 gram of tetra-triphenylphosphine palladium, 0.4 mmole), solution reacts and spends the night under 68 degrees Celsius, after cool to room temperature, separate organic layer, the concentrated crude product that obtains, silica gel is crossed post (sherwood oil: ethyl acetate=6:1) and is obtained 0.7 and digest compound 020-1, LC-MS purity: 100%, productive rate 38%.
1H-NMR(400MHz,DMSO-d6)δ:3.227(s,3H),3.399(s,3H),3.748(s，6H),6.770(d，2H),6.935(d，4H),7.051(d，4H),7.130(d，1H),7.309(d，1H),7.463(d，2H),7.532(m，2H),7.610(d，1H)。ESI-MS[M+H]
+：584.2。
2) compound 020-2's is synthetic: under nitrogen protection; by compound 020-1(66 milligram; 0.113 mmole); intermediate L(50.3 milligram, 0.125 mmole), (74 milligrams of cesium carbonates; 0.22 mmole); two tri-tert phosphorus palladiums (10 milligrams, 0.011 mmole), and toluene (80 milliliters) is mixed is incorporated under 110 degree stirring reaction 2 hours.After cool to room temperature, concentrated except desolventizing, silica gel column chromatography (sherwood oil: ethyl acetate=2:1) obtains 70 milligrams of compound 020-2, LC-MS purity: 98.6%, and productive rate 74.8%.
1H-NMR(400MHz,DMSO-d6)δ:3.292(s,3H),3.434(s,3H),3.755(s,6H),6.790(d，2H),6.937(d，4H),7.049(d，4H),7.205(d，1H),7.342(d,1H),7.488(d，2H),7.729(d，1H),7.832(m，3H),7.898(d，1H),8.011(d，2H),8.228(d，2H),8.432(d，2H).ESI-MS[M+H]
+：828.2。
3) compound 020-3 is synthetic: under subzero 78 degrees celsius, by (2.5 milliliters of the di-isopropyl aluminum hydride of 1M, 2.5 mmoles) join compound 020-2(414 milligram, 0.5 mmole) tetrahydrofuran (THF) (20 milliliters) solution in, slowly being warming up to room temperature reaction spends the night, in reaction solution, add methylene dichloride (10 milliliters), water (15 milliliters), separate organic layer, concentrated except desolventizing, silica gel column chromatography (sherwood oil: ethyl acetate=5:1) obtains 250 milligrams of compound 020-3, LCMS purity: 99.2%, productive rate 65.1%.
1H-NMR(400MHz,DMSO-d6)3.752(s，6H),6.776(d，2H),6.872(s，1H),6.927(d，4H),7.059(d，4H),7.400(s，1H),7.514(d，2H),7.776(m，2H),7.935(m，3H),8.244(m，3H),8.402(d，2H),10.240(s，1H)。ESI-MS[M+H]
+：769.2。
4) CGTD-DSSC-020's is synthetic: under nitrogen protection; by above-claimed cpd 020-3(192 milligram; 0.25 mmole); (42.5 milligrams of cyanoacetic acids; 0.5 mmole); ammonium acetate (38.5 milligrams, 0.5 mmole), and mixed 125 degrees Celsius of lower stirring reactions 5 hours that are incorporated in of acetic acid (5 milliliters).After cool to room temperature, there is solid to separate out, filter and obtain 104 milligrams of Compound C GTD-DSSC-020, LC-MS purity: 100%, productive rate 50%.
1H-NMR(400MHz,DMSO-d6)3.750(s,6H),6.776(d,2H),6.872(s,1H),6.928(d,4H),7.058(d,4H),7.104(d,1H),7.401(s,1H),7.504(d,2H),7.766(m,2H),7.939(m,3H),8.242(m,3H),8.405(d,2H),12.560(s,1H).ESI-MS[M+H]
+：836.2。
Embodiment 6:
1) compound 021-1's is synthetic: in 50 ml flasks, add (202 milligrams of compound Ls, 0.5 mmole), A1(135 milligram, 0.5 mmole), (58 milligrams of tetra-triphenylphosphine palladiums, 0.05 mmole), 8 milliliters, 15 milliliters of salt of wormwood (208 milligrams, 1.5 mmoles) and tetrahydrofuran (THF)s and water.Under nitrogen protection condition, mixture was 68 degrees Celsius of reactions 2 hours, and after cool to room temperature, concentrated except desolventizing, silica gel is crossed post (sherwood oil: ethyl acetate=10:1) and obtained 150 milligrams of compound 021-1, productive rate 64.1%.
1H-NMR(400MHz,DMSO-d
6)δ:7.632(s,1H),7.830(m，3H),8.242(d，2H),8.438(s，2H),9.762(s，1H)。ESI-MS[M+H]
+：468.0。
2) compound 021-3's is synthetic: in 50 ml flasks, add compound 021-2(135.4 milligram, 0.2 mmole), compound 021-1(93.6 milligram, 0.2 mmole), tetra-triphenylphosphine palladium (25 milligrams, 0.02 mmole) and toluene milliliter.Under nitrogen protection condition, mixture was 90 degrees Celsius of reactions 3 hours, and after cool to room temperature, concentrated except desolventizing, silica gel is crossed post (sherwood oil: ethyl acetate=5:1) and obtained 120 milligrams of compound 021-3, LC-MS purity: 100%, and productive rate 77.5%.
1H-NMR(400MHz,DMSO-d6)3.795(s，6H),6.791(d，2H),6.971(d，4H),7.089(d，4H),7.347(d，1H),7.473(m，3H),7.654(s，1H),7.843(m,3H),8.261(d,2H),8.453(d，2H),9.898(s，1H)。ESI-MS[M+H]
+：775.2。
3) CGTD-DSSC-021's is synthetic: under nitrogen protection; by above-claimed cpd 021-3(120 milligram; 0.155 mmole); (26.4 milligrams of cyanoacetic acids; 0.0.31 mmole); ammonium acetate (23.9 milligrams, 0.31 mmole), and mixed 125 degrees Celsius of lower stirring reactions 5 hours that are incorporated in of acetic acid (5 milliliters).After cool to room temperature, there is solid to separate out, filter and obtain 76 milligrams of Compound C GTD-DSSC-021.LC-MS purity: 100%, productive rate 58.3%.
1H-NMR(400MHz,DMSO-d6)3.748(s,6H),6.730(d，2H),6.824(d，4H),7.035(d，4H),7.289(d，1H),7.330(d，1H),7.445(d,2H),7.644(d，2H),7.763(d，1H),7.981(s，2H),8.212(d，2H),8.389(d，2H),13.920(s，1H).ESI-MS[M+H]
+：842.2。
Embodiment 7:
1) compound 022-1's is synthetic: in 50 ml flasks, add compound 021-2(203 milligram, 0.3 mmole), compd A 1(81 milligram, 0.3 mmole), 20 milliliters of tetra-triphenylphosphine palladium (35 milligrams, 0.03 mmole) and toluene.Under nitrogen protection condition, mixture was 90 degrees Celsius of reactions 16 hours, and after cool to room temperature, concentrated except desolventizing, silica gel is crossed post (sherwood oil: ethyl acetate=20:1) and obtained 90 milligrams of compound 022-1, productive rate 52.2%.
1H-NMR(400MHz,DMSO-d
6)δ:3.753(s,6H),6.762(d，2H),6.937(d，4H),7.079(d，4H),7.432(d，2H),7.546(m，4H),9.955(s，1H),.ESI-MS[M+H]
+：577.1。
2) compound 022-2's is synthetic: in 25 ml flasks, add compound 022-1(90 milligram, 0.156 mmole), (70 milligrams of compound Ls, 0.172 mmole), (18.2 milligrams of tetra-triphenylphosphine palladiums, 0.016 mmole), 5 milliliters, 10 milliliters of salt of wormwood (65 milligrams, 0.47 mmole) and tetrahydrofuran (THF)s and water.Under nitrogen protection condition, mixture is 68 degrees Celsius of reactions 3 hours, after cool to room temperature; separate organic layer, concentrated except desolventizing, silica gel column chromatography (sherwood oil: ethyl acetate=10:1) obtains 65 milligrams of compound 022-2; LC-MS purity: 100%, productive rate 54.2%.
1H-NMR(400MHz,DMSO-d6)3.798(s,6H),6.793(d，2H),6.974(d，4H),7.092(d，4H),7.347(d，1H),7.473(m，3H),7.654(s，1H),7.843(m，3H),8.263(d，2H),8.455(d，2H),9.958(s,1H)。ESI-MS[M+H]
+：775.2。
3) CGTD-DSSC-022's is synthetic: under nitrogen protection; by above-claimed cpd 022-2(65 milligram; 0.084 mmole); (28 milligrams of cyanoacetic acids; 0.34 mmole); ammonium acetate (25 milligrams, 0.34 mmole), and mixed 125 degrees Celsius of lower stirring reactions 5 hours that are incorporated in of acetic acid (5 milliliters).After cool to room temperature, there is solid to separate out, filter and obtain 36 milligrams of Compound C GTD-DSSC-022, LC-MS purity: 100%, productive rate 50.9%.
1H-NMR(400MHz,DMSO-d6)3.762(s，6H),6.762(d,2H),6.846(d,4H),7.072(d,4H),7.297(s,1H),7.480(m,3H),7.805(m,3H),8.172(m,3H),8.265(s,1H),8.395(d,2H),13.820(s,1H)。ESI-MS[M+H]
+：842.2。
Embodiment 8 and embodiment 9:
1) compound 024-2's is synthetic: by (102.8 milligrams of compounds Xs, 0.18 mmole), (100 milligrams of compound 024-1, 0.18 mmole), (75 milligrams, salt of wormwood, 0.54 mole) join in 50 milliliters of there-necked flasks that fill 15 milliliters of tetrahydrofuran (THF)s and 6 ml waters, under nitrogen protection condition, add (21 milligrams of tetra-triphenylphosphine palladiums, 0.018 mmole), solution reacts and spends the night under 68 degrees Celsius, after cool to room temperature, separate organic layer, the concentrated crude product that obtains, silica gel is crossed post (sherwood oil: ethyl acetate=5:1) and is obtained 100 milligrams of compound 024-2, LC-MS purity: 100%, productive rate 60.3%.
1H-NMR(400MHz,DMSO-d6)0.881(t,6H),1.313(m,8H),1.412(m,4H),1.700(m,4H),3.935(t，4H)，6.746(d，2H)，6.916(d，4H),7.041(d，4H),7.439(d，2H),7.508(d,2H),7.608(m,2H),7.745(d,1H),7.795(s,1H),7.918(d,1H),8.348(m,2H),10.063(s,1H)。ESI-MS[M+H]
+：920.2。
2) Compound C GTD-DSSC-024's is synthetic: under nitrogen protection; by above-mentioned compound 024-2(30 milligram; 0.033 mmole); compound 024-3(13.3 milligram; 0.13 mmole); ammonium acetate (10 milligrams, 0.13 mmole), and mixed 125 degrees Celsius of lower stirring reactions 5 hours that are incorporated in of acetic acid (5 milliliters).After cool to room temperature, there is solid to separate out, filter and obtain 25 milligrams of Compound C GTD-DSSC-024, LC-MS purity: 100%, productive rate 69.2%.
1H-NMR(400MHz，DMSO-d
6)0.882(t，6H)，1.306(m，8H)，1.401(m，4H)，1.700(m，4H)，3.926(t，4H),4.679(s,2H)6.726(d,2H),6.898(d，4H),7.016(d，4H),7.300(d，1H),7.442(m,4H),7.575(d,1H),7.686(s,1H),7.843(d,1H),8.276(d,1H),13.818(s,1H).ESI-MS[M+H]
+：1093.2。
3) Compound C GTD-DSSC-025's is synthetic: under nitrogen protection; by above-mentioned compound 024-2(55.3 milligram; 0.06 mmole); (20.4 milligrams of cyanoacetic acids; 0.24 mmole); ammonium acetate (18.5 milligrams, 0.24 mmole), and mixed 125 degrees Celsius of lower stirring reactions 5 hours that are incorporated in of acetic acid (5 milliliters).After cool to room temperature, there is solid to separate out, filter and obtain 50 milligrams of Compound C GTD-DSSC-025, LC-MS purity: 100%, productive rate 84.3%.
1H-NMR(400MHz,DMSO-d
6)0.868(t,6H),1.276(m,8H),1.408(m,4H),1.702(m,4H),3.942(t，4H),6.760(d,2H),6.919(d，4H),7.066(d，4H),7.382(d，1H),7.515(m,4H),7.763(d,1H),7.795(s,1H),8.177(d,1H),8.269(d,1H),8.394(m,2H),13.925(s,1H)。ESI-MS[M+H]
+：987.2。
Embodiment 10:
1) compound 026-2's is synthetic: by (45.7 milligrams of compounds Xs, 0.08 mmole), (51.2 milligrams of compound 026-1, 0.08 mmole), 33 milligrams, salt of wormwood, 0.24 mole) join in 50 milliliters of there-necked flasks that fill 15 milliliters of tetrahydrofuran (THF)s and 6 ml waters, under nitrogen protection condition, add (9.3 milligrams of tetra-triphenylphosphine palladiums, 0.008 mmole), solution reacts and spends the night under 68 degrees Celsius, after cool to room temperature, separate organic layer, the concentrated crude product that obtains, silica gel is crossed post (sherwood oil: ethyl acetate=5:1) and is obtained 45 milligrams of compound 026-2, LC-MS purity: 100%, productive rate 56.3%.
1H-NMR(400MHz,DMSO-d
6)0.870(t,3H),0.931(t,6H),1.246(m,6H),1.365(m,8H),1.466(m,4H),1.654(m,2H),1.735(m,4H),2.664(t，2H),3.973(t，4H),6.825(d,2H),6.929(d，4H),7.077(d，4H),7.412(s,1H),7.506(d，2H),7.637(d,1H),7.771(d,1H),7.844(s,1H),7.949(s,1H),8.300(s,1H),8.383(d,2H),9.834(s,1H)。ESI-MS[M+H]
+：1004.3。
2) Compound C GTD-DSSC-026's is synthetic: under nitrogen protection; by above-mentioned compound 026-2(40 milligram; 0.04 mmole); (13.5 milligrams of cyanoacetic acids; 0.16 mmole); ammonium acetate (12.3 milligrams, 0.16 mmole), and mixed 125 degrees Celsius of lower stirring reactions 5 hours that are incorporated in of acetic acid (5 milliliters).After cool to room temperature, there is solid to separate out, filter and obtain 25 milligrams of Compound C GTD-DSSC-026, LC-MS purity: 100%, yield 58.3%.
1H-NMR(400MHz,DMSO-d
6)0.766(t,3H),0.798(t,6H),1.227(m,8H),1.314(m,8H),1.404(m,4H),1.560(m,2H),1.691(m,4H),3.916(t，4H),6.745(d,2H),6.903(d，4H),7.024(d，4H),7.382(d，1H),7.461(m,4H),7.754(m,2H),7.900(d,1H),8.184(s,1H),8.333(m,2H),13.925(s,1H)。ESI-MS[M+H]
+：1071.3。
Embodiment 11:
1) compound 027-1's is synthetic: in 100 milliliters of there-necked flasks, add compound N 1(200 milligram, 0.34 mmole), intermediate B 1(130 milligram, 0.48 mmole), 10 milliliters of tetra-triphenylphosphine palladium (60 milligrams, 0.05 mmole) and toluene.Under nitrogen protection condition, mixture was 100 DEG C of reactions 16 hours.Concentrated except desolventizing, silica gel is crossed post (sherwood oil: ethyl acetate=10:1) and is obtained 120 milligrams of compound 027-1, productive rate 73%.
1H-NMR(400MHz,CDCl
3)δ:10.10(s,1H),8.28(s,1H),7.96(d,J=8.3Hz,1H),7.69(s，1H),7.60～7.62(m,2H),7.53(dd,J=5.2,1.2Hz,1H),7.35(dd,J=3.6,1.2Hz,1H),7.25(d,J=3.6Hz，2H),7.17～7.19(m,1H)。
2) compound 027-2's is synthetic: (41 milligrams of N-bromo-succinimides; 2.3 mmoles) join (95 milligrams of compound 027-1; 2.0 mmoles) N; in dinethylformamide (8 milliliters) solution; under nitrogen protection, stir and spend the night. there is solid to separate out, filter solid vacuum-drying; obtain 85 milligrams of yellow solid product compound 027-2, productive rate 76%.ESI-MS[M+H]
+：557。
3) compound 027-3's is synthetic: to compound T(30 milligram, 0.05 mmole), compound 027-2(30 milligram, 0.05 mmole), tetra-triphenylphosphine palladium (24 milligrams, 0.02 mmole), (20 milligrams, sodium carbonate, 0.2 mmole) and the mixture of 6 milliliters of tetrahydrofuran (THF)s in, add 1 ml water, reaction mixture reacts 16 hours at 65 DEG C.Remove solvent under reduced pressure, residual purification by silica gel column chromatography (sherwood oil: ethyl acetate=15:1), obtains 30 milligrams of dark red solid compound 027-3, productive rate: 63%.
1H-NMR(400MHz,CDCl
3):δ10.20(s,1H),8.29(s,1H),7.96(d,J=8.0Hz,2H),7.60～7.68(m,7H),7.52(d,J=8.0Hz,2H),7.40(d,J=8.0Hz,2H),7.27～7.35(m,9H),7.21(d,J=8.4Hz,2H),7.14(dd,J=8.4,1.6Hz,2H),1.43(s,12H)。
4) Compound C GTD-DSSC-027's is synthetic: under nitrogen protection; by compound 027-3(30 milligram; 0.03 mmole); (10 milligrams of cyanoacetic acids; 0.12 mmole); ammonium acetate (5 milligrams, 0.07 mmole), and acetic acid (5 milliliters) is mixed is incorporated at 125 DEG C stirring reaction 6 hours.Remove solvent acetic acid under reduced pressure, residue silica gel column chromatography (methylene dichloride: methyl alcohol=20:1) obtains 12 milligrams of bright black solid chemical compound CGTD-DSSC-027, LC-MS purity: 100%, and productive rate: 40%.
1H-NMR(400MHz,DMSO-d
6):δ8.14～8.24（m,3H）,7.99～8.05(m,1H),7.65～7.72(m,5H),7.41～7.49(m,6H),7.18～7.28(m,8H),6.98～7.05(m,4H),1.31(s,12H)。
Embodiment 12:
1) compound 028-2's is synthetic: by (51.2 milligrams of compound T, 0.08 mmole), (48.2 milligrams of compound 028-1, 0.08 mmole), 33 milligrams, salt of wormwood, 0.24 mole) join in 50 milliliters of there-necked flasks that fill 15 milliliters of tetrahydrofuran (THF)s and 6 ml waters, under nitrogen protection condition, add (9.3 milligrams of tetra-triphenylphosphine palladiums, 0.008 mmole), solution reacts and spends the night under 68 degrees Celsius, after cool to room temperature, separate organic layer, the concentrated crude product that obtains, silica gel is crossed post (sherwood oil: ethyl acetate=5:1) and is obtained 60 milligrams of compound 028-2, LC-MS purity: 100%, productive rate 72.3%.ESI-MS[M+H]
+：1036.28。
2) Compound C GTD-DSSC-028's is synthetic: under nitrogen protection; by above-mentioned compound 028-2(52 milligram; 0.05 mmole); (17 milligrams of cyanoacetic acids; 0.2 mmole); ammonium acetate (15.4 milligrams, 0.2 mmole), and mixed 125 degrees Celsius of lower stirring reactions 5 hours that are incorporated in of acetic acid (5 milliliters).After cool to room temperature, there is solid to separate out, filter and obtain 32 milligrams of Compound C GTD-DSSC-028, LC-MS purity: 100%, productive rate 57.9%.
1H-NMR(400MHz,DMSO-d
6)0.784(t,3H),1.176(m,8H),1.355(s,12H),1.589(m，12H),7.049(m,4H),7.263(m，6H),7.504(m，4H),7.604(m，2H),7.729(m,5H),7.832(s,1H),7.904(d，1H),8.196(d,1H),8.33O(s,2H),13.925(s,1H)。ESI-MS[M+H]
+：1071.3。
Embodiment 13:
1) compound 029-2's is synthetic: under nitrogen protection; by (41 milligrams of compound B-11s; 0.15 mmole); compound 029-1(61 milligram, 0.17 mmole), (62 milligrams, salt of wormwood; 0.45 mmole); four triphenyl phosphorus palladiums (18 milligrams, 0.015 mmole), and tetrahydrofuran (THF): water (12 milliliters) is mixed is incorporated at 70 DEG C stirring reaction 8 hours.After cool to room temperature, concentrated except desolventizing, silica gel column chromatography (sherwood oil: ethyl acetate=100:1) obtains 40 milligrams of compound 029-2, LC-MS purity 99.6%, productive rate 63.5%.ESI-MS[M+H]
+：420.8。
2) compound 029-3's is synthetic: by (50 milligrams of compound 029-2,0.12 mmole), (28 milligrams of NBS, 0.15 mmole) join and fill in 10 milliliters of DMF50 milliliter round-bottomed flask bottles, at 32 DEG C, react and spend the night, the cancellation that adds water reaction, has solid to separate out, and suction filtration is dried and obtains 30 milligrams of compound 029-3, LC-MS purity 98.7%, productive rate 50.8%.
1H-NMR(400MHz,CDCl3)δ:7.091-7.136(m,2H),7.219(d,1H),7.329(d,1H),7.585(s,1H),7.636-7.705(m,4H)。
3) compound 029-4's is synthetic: under nitrogen protection; by compound 029-3(30 milligram; 0.06 mmole); compound V(32 milligram, 0.072 mmole), (24 milligrams, salt of wormwood; 0.18 mmole); four triphenyl phosphorus palladiums (7 milligrams, 0.006 mmole), and tetrahydrofuran (THF): water (12 milliliters) is mixed is incorporated at 70 DEG C stirring reaction 8 hours.After cool to room temperature, concentrated except desolventizing, silica gel column chromatography (sherwood oil: ethyl acetate=40:1) obtains 40 milligrams of compound 029-4, LC-MS purity 99.3%, productive rate 90%.ESI-MS[M+H]
+：726.2。
4) compound GTD-DSSC-029's is synthetic: under nitrogen protection; by compound 029-4(40 milligram; 0.06 mmole); (20 milligrams of cyanoacetic acids; 0.24 mmole); ammonium acetate (19 milligrams, 0.24 mmole), and acetic acid (5 milliliters) is mixed is incorporated at 125 DEG C stirring reaction 5 hours.After cool to room temperature, have solid to separate out, filter, filter cake column chromatography for separation (methylene dichloride: methyl alcohol=40:1) obtains 25 milligrams of compound GTD-DSSC-029, LC-MS purity 100%, productive rate 58.1%.
1H-NMR(400MHz,DMSO-d
6)3.747(s,6H),6.753(d,2H),6.924(d,4H),7.050(d,4H),7.216(d,1H),7.049-7.477(m,4H),7.680-7.739(m,3H),7.880(d,2H),7.969(s,1H),8.123(s,1H).ESI-MS[M+H]
+：791.7。
Embodiment 14:
1) compound 030-2's is synthetic: by (59.5 milligrams of intermediate T, 0.1 mmole), (66 milligrams of compound 030-1, 0.11 mmole), (99 milligrams of cesium carbonates, 0.3 mmole), (7.5 milligrams of two (dibenzalacetone) palladiums, 0.005 mmole), (9.6 milligrams of tributyl phosphorus a tetrafluoro borates, 0.02 mmole) join in the there-necked flask that fills 15 milliliters of dioxs, under nitrogen protection condition, solution reacts and spends the night under 109 degrees Celsius, the concentrated crude product that obtains after cool to room temperature, silica gel is crossed post (sherwood oil: ethyl acetate=5:1) and is obtained 40 milligrams of compound 030-2, LC-MS purity: 100%, productive rate 39.2%.ESI-MS[M+H]
+：1036.28。
2) Compound C GTD-DSSC-030's is synthetic: under nitrogen protection; by above-mentioned compound 030-2(40 milligram; 0.038 mmole); (13 milligrams of cyanoacetic acids; 0.15 mmole); ammonium acetate (11.8 milligrams, 0.15 mmole), and mixed 125 degrees Celsius of lower stirring reactions 5 hours that are incorporated in of acetic acid (5 milliliters).After cool to room temperature, there is solid to separate out, filter and obtain 32 milligrams of Compound C GTD-DSSC-030, LC-MS purity: 100%, productive rate 57.9%.
1H-NMR(400MHz,DMSO-d6)：0.787(t，3H),1.176(m,6H),1.334(s，12H),1.542(m,2H),2.602(t,2H),7.014(d,2H),7.038(d,2H),7.095(s,1H),7.254(m,8H),7.378(d,1H),7.485(d,2H),7.632(d,2H),7.698(m,4H),7.800(d,1H),8.042(s,1H),8.176(s,1H),8.222(m,2H),13.925(s,1H).ESI-MS[M+H]
+：1071.3。
Embodiment 15:
1) compound 031-1's is synthetic: under nitrogen protection; by compound 029-3(50 milligram; 0.1 mmole); compounds X (62 milligrams, 0.11 mmole), (40 milligrams, salt of wormwood; 0.3 mmole); four triphenyl phosphorus palladiums (12 milligrams, 0.01 mmole), and tetrahydrofuran (THF): water (12 milliliters) is mixed is incorporated at 68 DEG C stirring reaction 8 hours.After cool to room temperature, concentrated except desolventizing, silica gel column chromatography (sherwood oil: ethyl acetate=50:1) obtains 56 milligrams of compound 031-1, LC-MS purity 98.1%, productive rate 65.1%.ESI-MS[M+H]
+：867.4。
2) Compound C GTD-DSSC-031's is synthetic: under nitrogen protection; by compound 031-1(56 milligram; 0.06 mmole); (20 milligrams of cyanoacetic acids; 0.24 mmole); ammonium acetate (19 milligrams, 0.24 mmole), and acetic acid (10 milliliters) is mixed is incorporated at 125 DEG C stirring reaction 5 hours.After cool to room temperature, have solid to separate out, filter, filter cake column chromatography for separation (methylene dichloride: methyl alcohol=40:1) obtains 27 milligrams of Compound C GTD-DSSC-031, LC-MS purity 100%, productive rate 45%.
1H-NMR(400MHz,DMSO-d6)0.878(t,6H),1.257-1.317(m,8H),1.405(t,4H),1.658-1.728(m,4H),3.921(t,4H),6.741(d,2H),6.896(d,4H),7.016(d,4H),7.217(d,1H),7.403-7.469(m,4H),7.684-7.741(m,3H),7.886(d,2H),7.974(s,1H),8.120(s,1H).ESI-MS[M+H]
+：931.2。
Embodiment 16:
1) compound 032-2's is synthetic: under nitrogen protection; by (100 milligrams of compound 032-1; 0.23 mmole), (71 milligrams of compound B-11s; 0.25 mmole); salt of wormwood (96 milligrams, 0.69 mmole), four (27 milligrams of triphenyl phosphorus palladiums; 0.023 mmole), and tetrahydrofuran (THF): water (12 milliliters) is mixed is incorporated at 70 DEG C stirring reaction 8 hours.After cool to room temperature, concentrated except desolventizing, silica gel column chromatography (sherwood oil: ethyl acetate=100:1) obtains 44 milligrams of compound 032-2, LC-MS purity 100%, productive rate 40%.ESI-MS[M+H]
+：494.1。
2) compound 032-3's is synthetic: by (44 milligrams of compound 032-2,0.09 mmole), (17 milligrams of NBS, 0.095 mmole) join and fill in 10 milliliters of DMF25 milliliter round-bottomed flask bottles, at 27 DEG C, react and spend the night, the cancellation that adds water reaction, has solid to separate out, and silica gel column chromatography (sherwood oil: ethyl acetate=30:1) obtains 40 milligrams of compound 032-3, LC-MS purity 83%, productive rate 78%.ESI-MS[M+H]
+：572.9。
3) compound 032-4's is synthetic: under nitrogen protection; by compound 032-3(40 milligram; 0.07 mmole); compounds X (40 milligrams, 0.07 mmole), (30 milligrams, salt of wormwood; 0.21 mmole); four triphenyl phosphorus palladiums (9 milligrams, 0.007 mmole), and tetrahydrofuran (THF): water (12 milliliters) is mixed is incorporated at 70 DEG C stirring reaction 8 hours.After cool to room temperature, concentrated except desolventizing, silica gel column chromatography (sherwood oil: ethyl acetate=40:1) obtains 40 milligrams of compound 032-4, LC-MS purity 100%, productive rate 61%.ESI-MS[M+H]
+：936.35。
4) Compound C GTD-DSSC-032's is synthetic: under nitrogen protection; by compound 032-4(40 milligram; 0.043 mmole); (15 milligrams of cyanoacetic acids; 0.17 mmole); ammonium acetate (13 milligrams, 0.17 mmole), and acetic acid (5 milliliters) is mixed is incorporated at 125 DEG C stirring reaction 5 hours.After cool to room temperature, have solid to separate out, filter, filter cake column chromatography for separation (methylene dichloride: methyl alcohol=40:1) obtains 25 milligrams of Compound C GTD-DSSC-032, LC-MS purity 100%, productive rate 58.1%.
1H-NMR(400MHz,DMSO-d6)0.853-0.899(t,9H),1.232-1.411(m,18H),1.665-1.733(m,4H),1.797-1.852(m,2H),3.097-3.133(t,2H),3.918-3.950(t,4H),6.751-6.772(d,2H),6.870-6.923(d,4H),7.031-7.053(d,4H),7.226-7.236(d,1H),7.411-7.444(q,2H),7.483-7.505(d,2H),7.664-7.673(d,2H),7.712-7.733(d,2H),7.981(s,1H),8.064-8.107(t,2H),8.240(s,1H)。ESI-MS[M+H]
+：1003.35。
Embodiment 17:
1) compound 034-3's is synthetic: by (48.3 milligrams of compound 034-1, 0.07 mmole), (28 milligrams of compound 034-2, 0.0.077 mmole), (29 milligrams, salt of wormwood, 0.21 mmole), (8.2 milligrams of tetra-triphenylphosphine palladiums, 0.007 mmole) join in the flask that fills 15 milliliters of tetrahydrofuran (THF)s and 6 ml waters, under nitrogen protection condition, solution reacts and spends the night under 69 degrees Celsius, the concentrated crude product that obtains after cool to room temperature, silica gel is crossed post (sherwood oil: ethyl acetate=10:1) and is obtained 30 milligrams of compound 034-3, LC-MS purity: 100%, productive rate 51.1%.ESI-MS[M+H]
+：838.2。
2) Compound C GTD-DSSC-034's is synthetic: under nitrogen protection; by above-mentioned compound 034-3(25 milligram; 0.03 mmole); (10.2 milligrams of cyanoacetic acids; 0.12 mmole); ammonium acetate (9.2 milligrams, 0.12 mmole), and mixed 125 degrees Celsius of lower stirring reactions 5 hours that are incorporated in of acetic acid (5 milliliters).After cool to room temperature, there is solid to separate out, filter and obtain 18 milligrams of Compound C GTD-DSSC-034, LC-MS purity: 100%, productive rate 66.7%.
1H-NMR(400MHz,DMSO-d6)：0.878(t,6H),1.309(m,8H),1.395(m,4H),1.696(m,4H),3.923(t,4H),6.904(d,4H),6.982(m,5H),7.265(s,1H),7.534(m,2H),7.750(m,3H),7.829(d,1H),8.933(d,2H),8.068(s,1H),8.258(s,1H),13.925(s,1H)。ESI-MS[M+H]
+：904.2。
Embodiment 18:
1) compound 035-1's is synthetic: under nitrogen protection; by compound 029-3(50 milligram; 0.10 mmole); compound Q (75 milligrams, 0.12 mmole), (40 milligrams, salt of wormwood; 0.30 mmole); four triphenyl phosphorus palladiums (12 milligrams, 0.01 mmole), and tetrahydrofuran (THF): water (12 milliliters) is mixed is incorporated at 68 DEG C stirring reaction 8 hours.After cool to room temperature, concentrated except desolventizing, silica gel column chromatography (sherwood oil: ethyl acetate=50:1) obtains 55 milligrams of compound 035-1, LC-MS purity 98.5%, productive rate 59.7%.ESI-MS[M+H]
+：923.4。
2) Compound C GTD-DSSC-035's is synthetic: under nitrogen protection; by compound 035-1(55 milligram; 0.06 mmole); (20 milligrams of cyanoacetic acids; 0.24 mmole); ammonium acetate (19 milligrams, 0.24 mmole), and acetic acid (15 milliliters) is mixed is incorporated at 125 DEG C stirring reaction 5 hours.After cool to room temperature, have solid to separate out, filter, filter cake column chromatography for separation (methylene dichloride: methyl alcohol=40:1) obtains 25 milligrams of Compound C GTD-DSSC-035, LC-MS purity 100%, productive rate 42.3%.
1H-NMR(400MHz,DMSO-d6)0.881(t,6H),1.232-1.319(m,8H),1.407(t,4H),1.659-1.711(m,4H),3.915(t,4H),6.873(d,5H),6.969(d,4H),7.179(d,1H),7.266(d,1H),7.435-7.467(m,2H),7.519(s,1H),7.677-7.743(m,4H),7.887(d,2H),7.983(s,1H),8.095(s,1H)。ESI-MS[M+H]
+：987.2。
Embodiment 19:
1) compound 036-2's is synthetic: under nitrogen protection; by (193 milligrams of compound 036-1; 0.46 mmole), (125 milligrams of compound B-11s; 0.46 mmole); salt of wormwood (190 milligrams, 1.38 mmoles), four (55 milligrams of triphenyl phosphorus palladiums; 0.046 mmole), and tetrahydrofuran (THF): water (12 milliliters) is mixed is incorporated at 70 DEG C stirring reaction 8 hours.After cool to room temperature, concentrated except desolventizing, silica gel column chromatography (sherwood oil: ethyl acetate=100:1) obtains 150 milligrams of compound 036-2, LC-MS purity 100%, productive rate 67%.ESI-MS[M+H]
+：487.98。
2) compound 036-3's is synthetic: by (75 milligrams of compound 036-2,0.15 mmole), (30 milligrams of NBS, 0.17 mmole) join and fill in 10 milliliters of DMF25 milliliter round-bottomed flask bottles, at 27 DEG C, react and spend the night, the cancellation that adds water reaction, has solid to separate out, and silica gel column chromatography (sherwood oil: ethyl acetate=30:1) obtains 75 milligrams of compound 036-3, LC-MS purity 100%, productive rate 86%.ESI-MS[M+H]
+：567.89。
3) compound 036-4's is synthetic: under nitrogen protection; by (89 milligrams of compounds Xs; 0.132 mmole); compound 036-3(75 milligram, 0.132 mmole), (55 milligrams, salt of wormwood; 0.4 mmole); four triphenyl phosphorus palladiums (15 milligrams, 0.0132 mmole), and tetrahydrofuran (THF): water (12 milliliters) is mixed is incorporated at 70 DEG C stirring reaction 8 hours.After cool to room temperature, concentrated except desolventizing, silica gel column chromatography (sherwood oil: ethyl acetate=200:3) obtains 86 milligrams of compound 036-4, LC-MS purity 100%, productive rate 70%.ESI-MS[M+H]
+：931.26。
4) Compound C GTD-DSSC-036's is synthetic: under nitrogen protection; by compound 036-4(86 milligram; 0.09 mmole); (32 milligrams of cyanoacetic acids; 0.37 mmole); ammonium acetate (29 milligrams, 0.37 mmole), and acetic acid (10 milliliters) is mixed is incorporated at 125 DEG C stirring reaction 5 hours.After cool to room temperature, have solid to separate out, filter, filter cake column chromatography for separation (methylene dichloride: methyl alcohol=40:1) obtains 50 milligrams of Compound C GTD-DSSC-036, LC-MS purity 100%, productive rate 56.2%.
1H-NMR(400MHz,DMSO-d6)0.852-0.898(t,6H),1.232-1.430(m,12H),1.665-1.717(m,4H),3.919-3.951(t,4H),6.751-6.773(d,2H),6.871(s,1H),6.903-6.925(d,2H),7.035-7.057(d,4H),7.265-7.272(d,2H),7.459-7.475(d,1H),7.490-7.512(d,2H),7.917-7.937(d,1H),8.014(s,1H),8.130-8.154(d,2H),8.189(s,1H)。ESI-MS[M+H]
+：998.27。
Embodiment 20:
1) Compound C GTD-DSSC-018's is synthetic: under nitrogen protection; by compound 018-1(50 milligram; 0.066 mmole); (11.4 milligrams of cyanoacetic acids; 0.132 mmole); ammonium acetate (10.3 milligrams, 0.132 mmole), and mixed 125 degrees Celsius of lower stirring reactions 5 hours that are incorporated in of acetic acid (5 milliliters).After cool to room temperature, there is solid to separate out, filter and obtain 20 milligrams of Compound C GTD-DSSC-018, LC-MS purity: 100%, productive rate 35%.
1H-NMR(400MHz,DMSO-d
6)：3.758(s,6H),6.722(d,2H),6.873(s,1H),6.944(d,4H),7.105(d,4H),7.210(d,2H),7.683(d,1H),7.795(d,2H),7.948(s,2H),8.063(d,2H),8.305(d,2H),13.925(s,1H)。ESI-MS[M+H]
+：816.2。
2) Compound C GTD-DSSC-019's is synthetic: under nitrogen protection; by compound 018-1(30 milligram; 0.04 mmole); compound 019-1(20 milligram; 0.05 mmole); ammonium acetate (3 milligrams, 0.04 mmole), and mixed 125 degrees Celsius of lower stirring reactions 5 hours that are incorporated in of acetic acid (5 milliliters).After cool to room temperature, there is solid to separate out, filter and obtain 13 milligrams of Compound C GTD-DSSC-019, LC-MS purity: 100%.Productive rate 29%.
1H-NMR(400MHz,DMSO-d6):0.855(t,3H),1.296(m,10H),1.591(t,2H),3.758(s,6H),3.973(t,2H),4.180(s,2H),6.722(d,2H),6.878(s,1H),6.949(d,4H),7.102(d,4H),7.206(d,2H),7.780(d,2H),7.949(s,2H),8.068(d,2H),8.308(d,2H),13.930(s,1H)。ESI-MS[M+H]
+：1132.2。
Embodiment 21:
1) compound 023-1's is synthetic: in 25 ml flasks, add 10 milliliters of compound B-11 (96 milligrams, 0.35 mmole), compound N (201 milligrams, 0.35 mmole), tetra-triphenylphosphine palladium (40.5 milligrams, 0.035 mmole) and toluene.Under nitrogen protection condition, mixture was 90 degrees Celsius of reactions 6 hours, and after cool to room temperature, concentrated except desolventizing, silica gel column chromatography (sherwood oil: ethyl acetate=6:1) obtains 130 milligrams of compound 023-1, productive rate 77.9%.
1H-NMR(400MHz,DMSO-d
6)6.872(s,1H),7.274(t,1H),7.620(d,1H),7.654(d,1H),7.816(s,1H),7.876(d,1H),7.945(d,1H),8.361(m,2H),10.012(s,1H)。ESI-MS[M+H]
+：478.0。
2) compound 023-2's is synthetic: under lucifuge condition, by (48 milligrams of N-bromo-succinimides (NBS), 0.27 mmole) join and be dissolved with (129 milligrams of compound 023-1,0.27 mmole) 30 milliliters of N, in dinethylformamide solution, stirred overnight at room temperature, pours reaction solution in 30 milliliters of frozen water into and stirs 30 minutes, filtration obtains 100 milligrams of compound 023-2, productive rate 66.7%.
1H-NMR(400MHz,DMSO-d6)7.318(t,1H),7.432(d,1H),7.546(d,1H),7.798(s,1H),7.854(d,1H),8.184(s,1H),8.298(m,2H),10.005(s,1H)。ESI-MS[M+H]
+：478.0。
3) compound 023-3's is synthetic: by (100 milligrams of compound 023-2, 0.18 mmole), (77.6 grams of compound V, 0.18 mmole), 75 milligrams, salt of wormwood, 0.54 mole) join in 50 milliliters of there-necked flasks that fill 15 milliliters of tetrahydrofuran (THF)s and 6 ml waters, under nitrogen protection condition, add (21 milligrams of tetra-triphenylphosphine palladiums, 0.018 mmole), solution reacts and spends the night under 68 degrees Celsius, after cool to room temperature, separate organic layer, the concentrated crude product that obtains, silica gel is crossed post (sherwood oil: ethyl acetate=5:1) and is obtained 100 milligrams of compound 023-3, LC-MS purity: 100%, productive rate 71.1%.
1H-NMR(400MHz,DMSO-d
6)3.758(s,6H),6.748(d,2H),7.945(d,4H),7.076(d,4H),7.347(d,2H),7.498(m,4H),7.735(d,1H),7.919(d,1H),8.248(s,1H),8.328(d,2H),10.015(s,1H)。ESI-MS[M+H]
+：780.2。
4) Compound C GTD-DSSC-023's is synthetic: under nitrogen protection; by above-mentioned compound 023-3(60 milligram; 0.077 mmole); (26.2 milligrams of cyanoacetic acids; 0.308 mmole); ammonium acetate (23.7 milligrams, 0.308 mmole), and mixed 125 degrees Celsius of lower stirring reactions 5 hours that are incorporated in of acetic acid (5 milliliters).After cool to room temperature, there is solid to separate out, filter and obtain 35 milligrams of Compound C GTD-DSSC-023, LC-MS purity: 100%, productive rate 53.7%.
1H-NMR(400MHz,DMSO-d
6)3.755(s,6H),6.747(d,2H),7.940(d,4H),7.072(d,4H),7.344(d,2H),7.497(m,4H),7.732(d,1H),7.917(d,1H),8.121(s,1H),8.247(s,1H),8.341(d,2H),13.810(s,1H)。ESI-MS[M+H]
+：848.1。
Embodiment 22:
1) compound 039-02's is synthetic: under nitrogen protection; by (137 milligrams of compound 039-01; 0.4 mmole), (120 milligrams of compound B-11s; 0.44 mmole); salt of wormwood (166 milligrams, 1.2 mmoles), four (46 milligrams of triphenyl phosphorus palladiums; 0.04 mmole), and tetrahydrofuran (THF): water (16 milliliters) is mixed is incorporated at 70 DEG C stirring reaction 8 hours.After cool to room temperature, concentrated except desolventizing, silica gel column chromatography (sherwood oil: ethyl acetate=100:1) obtains 113 milligrams of compound 039-02, LC-MS purity 88%, productive rate 70%.ESI-MS[M+H]
+：408.07。
2) compound 039-03's is synthetic: by (113 milligrams of compound 039-02,0.28 mmole), (55 milligrams of NBS, 0.3 mmole) join and fill in 10 milliliters of DMF25 milliliter round-bottomed flask bottles, at 27 DEG C, react and spend the night, the cancellation that adds water reaction, has solid to separate out, and silica gel column chromatography (sherwood oil: ethyl acetate=30:1) obtains 45 milligrams of compound 039-03, LC-MS purity 85%, productive rate 33%.ESI-MS[M+H]
+：487.98。
3) compound 039-04's is synthetic: under nitrogen protection; by (59 milligrams of compounds Xs; 0.09 mmole); compound 039-03(45 milligram, 0.09 mmole), (40 milligrams, salt of wormwood; 0.27 mole); four triphenyl phosphorus palladiums (10 milligrams, 0.009 mmole), and tetrahydrofuran (THF): water (12 milliliters) is mixed is incorporated at 70 DEG C stirring reaction 8 hours.After cool to room temperature, concentrated except desolventizing, silica gel column chromatography (sherwood oil: ethyl acetate=200:3) obtains 50 milligrams of compound 039-04, LC-MS purity 100%, productive rate 67%.ESI-MS[M+H]
+：851.35。
6) Compound C GTD-DSSC-039's is synthetic: under nitrogen protection; by compound 039-04(50 milligram; 0.06 mmole); (20 milligrams of cyanoacetic acids; 0.24 mmole); ammonium acetate (19 milligrams, 0.24 mmole), and acetic acid (5 milliliters) is mixed is incorporated at 125 DEG C stirring reaction 5 hours.After cool to room temperature, have solid to separate out, filter, filter cake column chromatography for separation (methylene dichloride: methyl alcohol=30:1) obtains 30 milligrams of Compound C GTD-DSSC-039, LC-MS purity 100%, productive rate 54.5%.
1H-NMR(400MHz,DMSO-d
6)0.865-0.898(t,6H),1.301-1.322(m,17H),1.396-1.431(m,4H),1.666-1.752(m,4H),3.921-3.952(t,4H),6.753-6.775(d,2H),6.871(s,1H),6.906-6.928(t,4H),7.038-7.060(d,4H),7.247-7.256(d,1H),7.391-7.400(d,1H),7.442-7.462(d,3H),7.493-7.512(d,2H),7.619-7.640(d,2H),7.967(s,1H),8.133(s,1H)。ESI-MS[M+H]
+：918.36。
Embodiment 23
1) compound 045-02's is synthetic: under nitrogen protection; by (103 milligrams of compound 045-01; 0.26 mmole), (70 milligrams of compound B-11s; 0.26 mmole); salt of wormwood (110 milligrams, 0.78 mmole), four (30 milligrams of triphenyl phosphorus palladiums; 0.026 mmole), and tetrahydrofuran (THF): water (16 milliliters) is mixed is incorporated at 70 DEG C stirring reaction 8 hours.After cool to room temperature, concentrated except desolventizing, silica gel column chromatography (sherwood oil: methylene dichloride=1:1) obtains 53 milligrams of compound 045-02, LC-MS purity 97%, productive rate 43%.ESI-MS[M+H]
+：478。
2) compound 045-03's is synthetic: by (53 milligrams of compound 045-02,0.11 mmole), (21 milligrams of NBS, 0.12 mmole) join and fill in 10 milliliters of DMF25 milliliter round-bottomed flask bottles, at 27 DEG C, react and spend the night, the cancellation that adds water reaction, has solid to separate out, and silica gel column chromatography (sherwood oil: methylene dichloride=1:1) obtains 53 milligrams of compound 045-03, LC-MS purity 86%, productive rate 86.8%.ESI-MS[M+H]
+：556。
3) compound 045-04's is synthetic: under nitrogen protection; by (68 milligrams of compounds Xs; 0.114 mmole); compound 045-03(53 milligram, 0.09 mmole), (40 milligrams, salt of wormwood; 0.28 mole); four triphenyl phosphorus palladiums (10 milligrams, 0.009 mmole), and tetrahydrofuran (THF): water (12 milliliters) is mixed is incorporated at 70 DEG C stirring reaction 8 hours.After cool to room temperature, concentrated except desolventizing, silica gel column chromatography (sherwood oil: methylene dichloride=1:1) obtains 58 milligrams of compound 045-04, LC-MS purity 100%, productive rate 66.7%.ESI-MS[M+H]
+：921.28。
4) Compound C GTD-DSSC-045's is synthetic: under nitrogen protection; by compound 045-04(58 milligram; 0.06 mmole); (22 milligrams of cyanoacetic acids; 0.25 mmole); ammonium acetate (19 milligrams, 0.25 mmole), and acetic acid (6 milliliters) is mixed is incorporated at 125 DEG C stirring reaction 5 hours.After cool to room temperature, have solid to separate out, filter, filter cake column chromatography for separation (methylene dichloride: methyl alcohol=30:1) obtains 30 milligrams of Compound C GTD-DSSC-045, LC-MS purity 100%, productive rate 49%.
1H-NMR(400MHz,DMSO-d
6)0.865-0.880(t,6H),1.295-1.511(m,12H),1.677-1.758(m,4H),3.800-3.889(t,4H),4.460-4.479(t,4H),6.694-6.711(d,2H),6.769-6.870(d,4H),6.947-6.964(d,4H),7.116(s,1H),7.328(s,1H),7.379-7.394(d,2H),7.610-7.623(d,2H),7.758-7.781(d,2H),7.889(s,1H),8.088(s,1H).ESI-MS[M+H]
+：988.29。
Embodiment 24:
1) compound 046-2's is synthetic
By (83.6 milligrams of compound 046-1; 0.13 mmole), (89.2 milligrams of X; 0.156 mmole), (54 milligrams, salt of wormwood; 0.39 mmole), (15 milligrams of tetra-triphenylphosphine palladiums; 0.013 mmole) join in the flask that fills 15 milliliters of tetrahydrofuran (THF)s and 6 ml waters; under nitrogen protection condition; solution reacts and spends the night under 69 degrees Celsius; after cool to room temperature, concentrate and obtain crude product, silica gel is crossed post (sherwood oil: ethyl acetate=5:1) and is obtained 67 milligrams of compound 046-2.Productive rate 51.1%.ESI-MS(M+H
+)1007.3。
2) CGTD-DSSC-046's is synthetic
Under nitrogen protection, by the 046-2(50.4 milligram of above-claimed cpd, 0.05 mmole); cyanoacetic acid (17 milligrams, 0.2 mmole), (15.4 milligrams of ammonium acetates; 0.2 mmole), and mixed 125 degrees Celsius of lower stirring reactions 5 hours that are incorporated in of acetic acid (8 milliliters).After cool to room temperature, there is solid to separate out, filter and obtain products C GTD-DSSC-04630 milligram.Productive rate 56.1%.1H-NMR(400MHz,DMSO-d6):0.877(t,6H),1.298(m,8H),1.393(m,4H),1.693(m,4H),3.920(t,4H),6.746(d,2H),6.882(d,4H),7.001(d,4H),7.225(d,1H),7.412(d,1H),7.515(m,6H),7.608(s,1H),7.712(m,4H),8.020(s,1H),8.133(s,1H),13.925(s,1H).ESI-MS(M+H
+)1075.3。
Embodiment 25
1) compound 047-2's is synthetic
By (66 milligrams of compound 047-1; 0.13 mmole), (74 milligrams of X; 0.13 mmole), (54 milligrams, salt of wormwood; 0.39 mmole), (15 milligrams of tetra-triphenylphosphine palladiums; 0.013 mmole) join in the flask that fills 15 milliliters of tetrahydrofuran (THF)s and 6 ml waters; under nitrogen protection condition; solution reacts 7 hours under 68 degrees Celsius; after cool to room temperature, concentrate and obtain crude product, silica gel is crossed post (sherwood oil: ethyl acetate=20:1) and is obtained 72 milligrams of compound 047-2.Productive rate 63.7%.ESI-MS(M+H
+)=870.2。
2) CGTD-DSSC-047's is synthetic
Under nitrogen protection, by the 047-2(43.5 milligram of above-claimed cpd, 0.05 mmole); cyanoacetic acid (17 milligrams, 0.2 mmole), (15.4 milligrams of ammonium acetates; 0.2 mmole), and mixed 125 degrees Celsius of lower stirring reactions 6 hours that are incorporated in of acetic acid (8 milliliters).After cool to room temperature, there is solid to separate out, filter and obtain 34 milligrams of products.Productive rate 72.6%.1H-NMR(400MHz,DMSO-d6):0.878(t,6H),1.310(m,8H),1.408(m,4H),1.696(m,4H),3.924(t,4H),6.730(d,2H),6.889(d,4H),7.012(d,4H),7.242(d,1H),7.400(d,1H),7.422(d,1H),7.490(m,4H),7.690(d,1H),7.962(s,1H),8.142(s,1H),13.925(s,1H).ESI-MS(M+H
+)937.2。
Embodiment 26:
1) compound 048-2's is synthetic
By (106.8 milligrams of compound 048-1; 0.2 mmole), (57 milligrams of 4-trifluoromethyl phenylo boric acids; 0.3 mmole), (83 milligrams, salt of wormwood; 0.6 mmole), (24 milligrams of tetra-triphenylphosphine palladiums; 0.02 mmole) join in the flask that fills 15 milliliters of tetrahydrofuran (THF)s and 6 ml waters; under nitrogen protection condition; solution reacts 8 hours under 68 degrees Celsius; after cool to room temperature, concentrate and obtain crude product, silica gel is crossed post (sherwood oil: ethyl acetate=30:1) and is obtained 84 milligrams of compound 048-2.Productive rate 70.0%.ESI-MS(M+H
+)=600.2。
2) compound 048-3's is synthetic
By (84 milligrams of compound 048-2,0.14 mmole), (28 milligrams of N-bromo-succinimides, 0.154 mmole), join in the flask that fills 15 milliliters of DMFs, under room temperature condition, reaction is spent the night, add 15 ml waters, solid filtering obtains 95 milligrams of 048-3.Productive rate 99.5%.ESI-MS(M+H
+)=678.1。
3) compound 048-4's is synthetic
By (95 milligrams of compound 048-3; 0.14 mmole); (96 milligrams of X; 0.168 mmole), (58 milligrams, salt of wormwood; 0.42 mmole), (16 milligrams of tetra-triphenylphosphine palladiums; 0.014 mmole) join in the flask that fills 10 milliliters of tetrahydrofuran (THF)s and 4 ml waters; under nitrogen protection condition; solution reacts 8 hours under 68 degrees Celsius; after cool to room temperature, concentrate and obtain crude product, silica gel is crossed post (sherwood oil: ethyl acetate=15:1) and is obtained 50 milligrams of compound 048-4.Productive rate 51.2%.ESI-MS(M+H
+)=1043.5。
4) CGTD-DSSC-048's is synthetic
Under nitrogen protection, by the 048-4(50 milligram of above-claimed cpd, 0.047 mmole); cyanoacetic acid (15.1 milligrams, 0.192 mmole), (16.3 milligrams of ammonium acetates; 0.192 mmole), and mixed 125 degrees Celsius of lower stirring reactions 6 hours that are incorporated in of acetic acid (8 milliliters).After cool to room temperature, there is solid to separate out, filter and obtain products C GTD-DSSC-04830 milligram.Productive rate 57.5%.1H-NMR(400MHz,DMSO-d6):0.733(t,6H),0.859(t,6H),0.918(m,4H),1.099(m,12H),1.315(m,8H),1.387(m,4H),1.673(m,4H),1.856(m,4H),3.919(t,4H),6.750(d,2H),6.876(d,4H),6.980(d,4H),7.389(s,1H),7443(m3H),7.855(d,4H),8.274(d,2H),13.916(s,1H).ESI-MS(M+H
+)1110.5。
Embodiment 27:
1) compound 049-2's is synthetic
By (65 milligrams of compound 049-1; 0.2 mmole), (85 milligrams of 029-1; 0.24 mmole), (83 milligrams, salt of wormwood; 0.6 mmole), (24 milligrams of tetra-triphenylphosphine palladiums; 0.02 mmole) join in the flask that fills 15 milliliters of tetrahydrofuran (THF)s and 6 ml waters; under nitrogen protection condition; solution reacts 8 hours under 68 degrees Celsius; after cool to room temperature, concentrate and obtain crude product, silica gel is crossed post (sherwood oil: ethyl acetate=30:1) and is obtained 48 milligrams of compound 049-2.Productive rate 50.8%.ESI-MS(M+H
+)=473.0.
2) compound 049-3's is synthetic
By (47.2 milligrams of compound 049-2,0.1 mmole), (19.6 milligrams of N-bromo-succinimides, 0.11 mmole), join in the flask that fills 15 milliliters of DMFs, under 50 DEG C of conditions, react and spend the night, add 15 ml waters, solid filtering obtains 28 milligrams of 049-3.Productive rate 50.8%.ESI-MS(M+H
+)=550.9.
3) compound 049-4's is synthetic
By (28 milligrams of compound 049-3; 0.0508 mmole); X35 milligram; 0.0609 mmole), (21 milligrams, salt of wormwood; 0.152 mmole), (5.8 milligrams of tetra-triphenylphosphine palladiums; 0.0051 mmole) join in the flask that fills 10 milliliters of tetrahydrofuran (THF)s and 4 ml waters; under nitrogen protection condition; solution reacts 8 hours under 68 degrees Celsius; after cool to room temperature, concentrate and obtain crude product, silica gel is crossed post (sherwood oil: ethyl acetate=10:1) and is obtained 28 milligrams of compound 049-4.Productive rate 60.2%.ESI-MS(M+H
+)=916.3.
4) CGTD-DSSC-049's is synthetic
Under nitrogen protection, by the 049-4(27.6 milligram of above-claimed cpd, 0.03 mmole); cyanoacetic acid (9.24 milligrams, 0.12 mmole), (10.3 milligrams of ammonium acetates; 0.12 mmole), and mixed 125 degrees Celsius of lower stirring reactions 6 hours that are incorporated in of acetic acid (8 milliliters).After cool to room temperature, there is solid to separate out, filter and obtain products C GTD-DSSC-04914 milligram.Productive rate 50.0%.1H-NMR(400MHz,DMSO-d6):0.880(t,6H),1.311(m,8H),1.392(m,4H),1.698(m,4H),3.921(t,4H),6.749(d,2H),6.884(d,4H),7.021(d,4H),7.261(d,1H),7.403(d,1H),7.467(d,2H),7.713(m,3H),7.866(d,2H),8.026(d,1H),8.251(s,1H),8.382(s,1H),13.928(s,1H).ESI-MS(M+H
+)983.3.
Embodiment 28:
1) compound 050-1's is synthetic
By (128 milligrams of compound 048-1; 0.24 mmole), (164 milligrams of X; 0.288 mmole), (99.4 milligrams, salt of wormwood; 0.72 mmole), (28 milligrams of tetra-triphenylphosphine palladiums; 0.024 mmole) join in the flask that fills 15 milliliters of tetrahydrofuran (THF)s and 6 ml waters; under nitrogen protection condition; solution reacts 15 hours under 68 degrees Celsius; after cool to room temperature, concentrate and obtain crude product, silica gel is crossed post (sherwood oil: ethyl acetate=50:1) and is obtained 134 milligrams of compound 050-1.Productive rate 62.0%.ESI-MS(M+H
+)=900.4。
2) compound 050-2's is synthetic
By (134 milligrams of compound 050-1,0.149 mmole), (31.8 milligrams of N-bromo-succinimides, 0.179 mmole), join in the flask that fills 15 milliliters of DMFs, under room temperature condition, reaction is spent the night, add 20 ml waters, solid filtering obtains 120 milligrams of 050-2.Productive rate 82.3%.ESI-MS(M+H
+)=979.4。
3) compound 050-3's is synthetic
By (118 milligrams of compound 050-2; 0.12 mmole); (34.2 milligrams of 4-trifluoromethyl phenylo boric acids; 0.18 mmole), (50 milligrams, salt of wormwood; 0.36 mmole), (14 milligrams of tetra-triphenylphosphine palladiums; 0.012 mmole) join in the flask that fills 10 milliliters of tetrahydrofuran (THF)s and 4 ml waters; under nitrogen protection condition; solution reacts 8 hours under 68 degrees Celsius; after cool to room temperature, concentrate and obtain crude product, silica gel is crossed post (sherwood oil: ethyl acetate=10:1) and is obtained 80 milligrams of compound 050-3.Productive rate 63.9%.ESI-MS(M+H
+)=1043.5。
4) CGTD-DSSC-050's is synthetic
Under nitrogen protection, by the 050-3(50 milligram of above-claimed cpd, 0.047 mmole); cyanoacetic acid (15.1 milligrams, 0.192 mmole), (16.3 milligrams of ammonium acetates; 0.192 mmole), and mixed 125 degrees Celsius of lower stirring reactions 6 hours that are incorporated in of acetic acid (8 milliliters).After cool to room temperature, there is solid to separate out, filter and obtain products C GTD-DSSC-05035 milligram.Productive rate 67%.1H-NMR(400MHz,DMSO-d6):0.751(t,6H),0.876(t,6H),0.893(m,4H),1.099(m,12H),1.315(m,8H),1.387(m,4H),1.673(m,4H),1.856(m,4H),3.919(t,4H),6.750(d,2H),6.899(d,4H),7.002(d,4H),7.389(s,1H),7443(m3H),7.855(d,4H),8.275(d,2H),13.918(s,1H).ESI-MS(M+H
+)1110.5。
Embodiment 29 and embodiment 30:
) compound 051-2 synthetic
By (575 milligrams of compound M '; 1.1 mmoles), 2; (327 milligrams, the bromo-3-formyl radical of 5-bis-thiophene; 1.21 mmoles), tetra-triphenylphosphine palladium (127 milligrams, 0.11 mmole) joins in the flask that fills 20 milliliters of dry toluenes; under nitrogen protection condition; solution reacts 16 hours under 95 degrees Celsius, after cool to room temperature, concentrates and obtains crude product, and silica gel is crossed post (sherwood oil: ethyl acetate=20:1) and obtained 350 milligrams of compound 051-2.Productive rate 75.2%.ESI-MS(M+H
+)=423.9。
2) compound 051-3's is synthetic
By (153 milligrams of compound 051-2; 0.362 mmole), (153.6 milligrams of 029-1; 0.434 mmole), (150 milligrams, salt of wormwood; 1.08 mmoles), (42 milligrams of tetra-triphenylphosphine palladiums; 0.036 mmole) join in the flask that fills 20 milliliters of tetrahydrofuran (THF)s and 8 ml waters; under nitrogen protection condition; solution reacts 8 hours under 68 degrees Celsius; after cool to room temperature, concentrate and obtain crude product, silica gel is crossed post (sherwood oil: ethyl acetate=30:1) and is obtained 120 milligrams of compound 051-3.Productive rate 58.0%.ESI-MS(M+H
+)=570.2
3) compound 051-4's is synthetic
By compound 051-3 (120 milligrams, 0.21 mmole), (45 milligrams of N-bromo-succinimides, 0.253 mmole), join in the flask that fills 15 milliliters of DMFs, under room temperature condition, reaction is spent the night, add 15 ml waters, extracted with diethyl ether (25 milliliters, 3 times) merges organic phase, and anhydrous magnesium sulfate drying filters, concentrate and obtain thick product, silica gel is crossed post (sherwood oil: ethyl acetate=50:1) and is obtained 100 milligrams of compound 051-4.Productive rate 73.3%.ESI-MS(M+H
+)=649.9。
4) compound 051-5's is synthetic
By (100 milligrams of compound 051-4; 0.154 mmole); (97 milligrams of X; 0.17 mmole), (64 milligrams, salt of wormwood; 0.462 mmole), (18 milligrams of tetra-triphenylphosphine palladiums; 0.016 mmole) join in the flask that fills 15 milliliters of tetrahydrofuran (THF)s and 6 ml waters; under nitrogen protection condition; solution reacts 8 hours under 68 degrees Celsius; after cool to room temperature, concentrate and obtain crude product, silica gel is crossed post (sherwood oil: ethyl acetate=10:1) and is obtained 120 milligrams of compound 051-5.Productive rate 76.8%.ESI-MS(M+H
+)=1013.3。
5) CGTD-DSSC-051's is synthetic
Under nitrogen protection, by the 051-5(50 milligram of above-claimed cpd, 0.05 mmole); cyanoacetic acid (17 milligrams, 0.2 mmole), (15 milligrams of ammonium acetates; 0.2 mmole), and mixed 125 degrees Celsius of lower stirring reactions 6 hours that are incorporated in of acetic acid (8 milliliters).After cool to room temperature, there is solid to separate out, filter and obtain products C GTD-DSSC-05128 milligram.Productive rate 55.6%.1H-NMR(400MHz,DMSO-d6):0.594(t,6H),0.881(t,6H),1.236(m,8H),1.393(m,4H),1.698(t,4H),1.856(m,4H),3.927(t,4H),6.757(d,2H),6.886(d,4H),6.988(d,4H),7.366(d,2H),7.456(m3H),7.765(m,3H),7.900(d,2H),7.989(s,1H),8.218(s,1H),13.946(s,1H).ESI-MS(M+H
+)1080.3。
6) CGTD-DSSC-052's is synthetic
Under nitrogen protection, by the 051-5(56 milligram of above-claimed cpd, 0.055 mmole); rhodanine acetic acid (15.7 milligrams, 0.083 mmole), (17 milligrams of ammonium acetates; 0.0.22 mmole), and mixed 125 degrees Celsius of lower stirring reactions 6 hours that are incorporated in of acetic acid (8 milliliters).After cool to room temperature, there is solid to separate out, filter and obtain products C GTD-DSSC-05234 milligram.Productive rate 52.05%.1H-NMR(400MHz,DMSO-d6):0.576(t,6H),0.881(t,6H),1.230(m,4H),1.322(m,8H),1.416(m,4H),1.764(m,4H),3.924t,4H),4.452(s,2H),6.764(d,2H),6.903(d,4H),6.978(d,4H),7.401(m,3H),7.468(d2H),7.554(d,1H),7.735(m,3H),7.787(s,1H),7.895(d,2H),13.938(s,1H).ESI-MS(M+H
+)1186.3。
Embodiment 31 and embodiment 32
1) compound 053-2's is synthetic
By (153 milligrams of compound 053-1; 0.362 mmole), (153.6 milligrams of 029-1; 0.434 mmole), (150 milligrams, salt of wormwood; 1.08 mmoles), (42 milligrams of tetra-triphenylphosphine palladiums; 0.036 mmole) join in the flask that fills 20 milliliters of tetrahydrofuran (THF)s and 8 ml waters; under nitrogen protection condition; solution reacts 8 hours under 68 degrees Celsius; after cool to room temperature, concentrate and obtain crude product, silica gel is crossed post (sherwood oil: ethyl acetate=30:1) and is obtained 120 milligrams of compound 053-2.Productive rate 58.2%.ESI-MS(M+H
+)=570.0。
2) compound 053-3's is synthetic
By (120 milligrams of compound 053-2,0.21 mmole), (45 milligrams of N-bromo-succinimides, 0.253 mmole), join in the flask that fills 20 milliliters of DMFs, under room temperature condition, reaction is spent the night, add 20 ml waters, solid filtering obtains 100 milligrams of 053-3.Productive rate 73.3%.ESI-MS(M+H
+)=650.0。
3) compound 053-4's is synthetic
By (100 milligrams of compound 053-3; 0.154 mmole); (97 milligrams of X; 0.170 mmole), (64 milligrams, salt of wormwood; 0.462 mmole), (18 milligrams of tetra-triphenylphosphine palladiums; 0.0154 mmole) join in the flask that fills 10 milliliters of tetrahydrofuran (THF)s and 4 ml waters; under nitrogen protection condition; solution reacts 8 hours under 68 degrees Celsius; after cool to room temperature, concentrate and obtain crude product, silica gel is crossed post (sherwood oil: ethyl acetate=20:1) and is obtained 120 milligrams of compound 053-4.Productive rate 76.8%.ESI-MS(M+H
+)=1013.3。
4) CGTD-DSSC-053's is synthetic
Under nitrogen protection, by the 053-4(60 milligram of above-claimed cpd, 0.059 mmole); cyanoacetic acid (20.1 milligrams, 0.237 mmole), (18.2 milligrams of ammonium acetates; 0.237 mmole), and mixed 125 degrees Celsius of lower stirring reactions 8 hours that are incorporated in of acetic acid (8 milliliters).After cool to room temperature, there is solid to separate out, filter and obtain products C GTD-DSSC-05335 milligram.Productive rate 52.1%.1H-NMR(400MHz,DMSO-d6):0.595(t,6H),0.882(t,6H),1.355(m,8H),1.410(m,4H),1.678(m,4H),1.910(m,4H),3.578(t,4H)，3.915(t,4H),6.735(d,2H),6.870(d,4H),6.946(d,4H),7.325(s,1H),7420(m4H),7.654(d,1H),7.823(d,1H),8.039(s,1H)8.171(s,1H),8.251(m,2H),13.926(s,1H).ESI-MS(M+H
+)1137.3。
5) CGTD-DSSC-054's is synthetic
Under nitrogen protection, by the 053-4(60 milligram of above-claimed cpd, 0.059 mmole); rhodanine acetic acid (13.5 milligrams, 0.708 mmole), (18.2 milligrams of ammonium acetates; 0.237 mmole), and mixed being incorporated under 125 degrees Celsius of acetic acid (10 milliliters) stirred anti-15 hours.After cool to room temperature, there is solid to separate out, filter and obtain products C GTD-DSSC-05440 milligram.Productive rate 54.5%.ESI-MS(M+H
+)1243.3。
Embodiment 33:
1) compound 055-1's is synthetic
By (114.2 milligrams of compounds Xs; 0.20 mmole), N'(79.8 milligram; 0.20 mmole), (82.8 milligrams, salt of wormwood; 0.6 mmole), (23.2 milligrams of tetra-triphenylphosphine palladiums; 0.02 mmole) join in the flask that fills 20 milliliters of tetrahydrofuran (THF)s and 8 ml waters; under nitrogen protection condition; solution reacts 8 hours under 65 degrees Celsius; after cool to room temperature, concentrate and obtain crude product, silica gel is crossed post (sherwood oil: ethyl acetate=40:1) and is obtained 75 milligrams of compound 055-1.Productive rate 52.3%.ESI-MS(M+H
+)=717.2。
2) compound 055-2's is synthetic
By (71.6 milligrams of compound 055-1; 0.1 mmole); (72.6 milligrams of 061-4; 0.1 mmole), (41.4 milligrams, salt of wormwood; 0.3 mmole), (11.6 milligrams of tetra-triphenylphosphine palladiums; 0.01 mmole) join in the flask that fills 10 milliliters of tetrahydrofuran (THF)s and 3 ml waters; under nitrogen protection condition; solution reacts 16 hours under 68 degrees Celsius; after cool to room temperature, concentrate and obtain crude product, silica gel is crossed post (sherwood oil: ethyl acetate=10:1) and is obtained 92 milligrams of compound 055-2.Productive rate 74.4%.ESI-MS(M+H
+)=1236.6。
3) CGTD-DSSC-055's is synthetic
Under nitrogen protection, by the 055-2(61.8 milligram of above-claimed cpd, 0.05 mmole); cyanoacetic acid (17 milligrams, 0.20 mmole), (17 milligrams of piperidines; 0.20 mmole), and mixed 70 degrees Celsius of lower stirring reactions 48 hours that are incorporated in of tetrahydrofuran (THF) (8 milliliters).Concentratedly after cool to room temperature obtain thick product, silica gel is crossed 35 milligrams of CGTD-DSSC-055 of post (methylene dichloride: methyl alcohol=20:1).Productive rate 53.7%.1H-NMR(400MHz,DMSO-d6):0.751(t,6H),0.866(t,6H),1.135(m,12H),1.335(m,8H),1.412(m,4H),1.701(m,4H),1.987(m,4H),3.736(t,4H)，3.925(t,4H),6.750(d,2H),6.888(d,4H),7.003(d,4H),7.235(m,1H),7394(s，1H),7.435(d,2H),7.724(d,2H),7.783(d,2H),7.923(m,8H)8.132(s,1H),8.222(s,2H),13.946(s,1H).ESI-MS(M+H
+)1137.3
Embodiment 34
1) compound 056-1's is synthetic
By (72.6 milligrams of compound 061-4; 0.1 mmole), (27.3 milligrams of B1; 0.1 mmole), (41.4 milligrams, salt of wormwood; 0.3 mmole), (11.6 milligrams of tetra-triphenylphosphine palladiums; 0.01 mmole) join in the flask that fills 15 milliliters of tetrahydrofuran (THF)s and 6 ml waters; under nitrogen protection condition; solution reacts 8 hours under 65 degrees Celsius; after cool to room temperature, concentrate and obtain crude product, silica gel is crossed post (sherwood oil: ethyl acetate=10:1) and is obtained 65 milligrams of compound 056-1.Productive rate 81.9%.ESI-MS(M+H
+)=792.3。
2) CGTD-DSSC-056's is synthetic
Under nitrogen protection, by the 056-1(36.3 milligram of above-claimed cpd, 0.05 mmole); cyanoacetic acid (17 milligrams, 0.20 mmole), (17 milligrams of piperidines; 0.20 mmole), and mixed 70 degrees Celsius of lower stirring reactions 48 hours that are incorporated in of tetrahydrofuran (THF) (8 milliliters).Concentratedly after cool to room temperature obtain thick product, silica gel is crossed 25 milligrams of CGTD-DSSC-056 of post (methylene dichloride: methyl alcohol=20:1).Productive rate 58.1%.1H-NMR(400MHz,DMSO-d6):0.752(t,6H),1.136(m,12H),1.442(m,4H),3.751(t,4H)，7.242(br,2H),7.793(d,5H),7.942(m,9H),8.251(s,1H),13.946(s,1H).ESI-MS(M+H
+)859.3。
Embodiment 35:
1) compound 057-1's is synthetic
By (486 milligrams of compd As 1; 1.8 mmoles), (576 milligrams of 2-thienyl boric acid; 4.5 mmoles), (1.24 grams, salt of wormwood; 9 mmoles), (417 milligrams of tetra-triphenylphosphine palladiums; 0.36 mmole) join in the flask that fills 30 milliliters of tetrahydrofuran (THF)s and 12 ml waters; under nitrogen protection condition; solution reacts 16 hours under 65 degrees Celsius; after cool to room temperature, concentrate and obtain crude product, silica gel is crossed post (sherwood oil: ethyl acetate=10:1) and is obtained 420 milligrams of compound 057-1.Productive rate 84.5%.ESI-MS(M+H
+)=276.
2) CGTD-DSSC-057's is synthetic
Under nitrogen protection, by the 057-1(55.2 milligram of above-claimed cpd, 0.2 mmole); cyanoacetic acid (68 milligrams, 0.8 mmole), (61.6 milligrams of ammonium acetates; 0.8 mmole), and mixed 125 degrees Celsius of lower stirring reactions 16 hours that are incorporated in of acetic acid (8 milliliters).After cool to room temperature, solid is separated out, and filters and obtains 36 milligrams of CGTD-DSSC-057.Productive rate 52.5%.1H-NMR(400MHz,DMSO-d6):7.167(t,1H),7.313(t,1H),7.419(m,2H),7.663(d,1H),7.905(d,1H),8.017(s,1H),8.230(s,1H),14.031(s,1H).ESI-MS(M+H
+)343.0。
Embodiment 36
1) compound 058-1's is synthetic
By (166 milligrams of compound 057-1,0.6 mmole) join and fill 30 milliliters of N, in the flask of dinethylformamide, under room temperature, add (225 milligrams of N-bromo-succinimides, 1.26 mmoles), solution at room temperature reacts 16 hours, adds 30 ml waters, solid is separated out, filtration to the 058-1 of 245 milligrams.Productive rate 94.04%.ESI-MS(M+H
+)=433.8。
2) CGTD-DSSC-058's is synthetic
Under nitrogen protection, by the 058-1(43.4 milligram of above-claimed cpd, 0.1 mmole); cyanoacetic acid (34 milligrams, 0.4 mmole), (30.8 milligrams of ammonium acetates; 0.4 mmole), and mixed 125 degrees Celsius of lower stirring reactions 16 hours that are incorporated in of acetic acid (8 milliliters).After cool to room temperature, solid is separated out, and filters and obtains 30 milligrams of CGTD-DSSC-058.Productive rate 59.9%.
1H-NMR(400MHz,DMSO-d6):7.257(d,1H),7.302(d,2H),7.449(d,1H),7.946(s,1H),8.128(s,1H),14.090(s,1H).ESI-MS(M+H
+)500.8。
Embodiment 37
1) compound 059-1's is synthetic
By (65.1 milligrams of compound 058-1; 0.15 mmole), (86.4 milligrams of 4-amylbenzene boric acid; 0.45 mmole), (103.5 milligrams, salt of wormwood; 0.75 mmole), (34.7 milligrams of tetra-triphenylphosphine palladiums; 0.03 mmole) join in the flask that fills 20 milliliters of tetrahydrofuran (THF)s and 8 ml waters; under nitrogen protection condition; solution reacts 12 hours under 65 degrees Celsius; after cool to room temperature, concentrate and obtain crude product, silica gel is crossed post (sherwood oil: ethyl acetate=40:1) and is obtained 45 milligrams of compound 059-1.Productive rate 52.7%.ESI-MS(M+H
+)=568.2.
2) CGTD-DSSC-059's is synthetic
Under nitrogen protection, by the 059-1(45 milligram of above-claimed cpd, 0.08 mmole); cyanoacetic acid (27.2 milligrams, 0.32 mmole), (24.6 milligrams of ammonium acetates; 0.32 mmole), and mixed 125 degrees Celsius of lower stirring reactions 16 hours that are incorporated in of acetic acid (8 milliliters).After cool to room temperature, solid is separated out, and filters and obtains 30 milligrams of CGTD-DSSC-059.Productive rate 58.9%.1H-NMR(400MHz,DMSO-d6):0.866(t,6H),1.295(m,8H),1.579(m,4H),2.589(t,4H),7.255(m,4H),7.377(d,2H),7.495(d,1H),7.606(m,5H),7.994(s,1H),8.256(s,1H),14.033(s,1H).ESI-MS(M+H
+)635.2。
Embodiment 38
1) compound 060-1's is synthetic
By (65.1 milligrams of compound 058-1; 0.15 mmole), (214 milligrams of X; 0.375 mmole), (103.5 milligrams, salt of wormwood; 0.75 mmole), (34.7 milligrams of tetra-triphenylphosphine palladiums; 0.03 mmole) join in the flask that fills 20 milliliters of tetrahydrofuran (THF)s and 8 ml waters; under nitrogen protection condition; solution reacts 12 hours under 65 degrees Celsius; the concentrated crude product that obtains after cool to room temperature, silica gel is crossed post (sherwood oil: ethyl acetate=40:1) and is obtained 120 milligrams of compound 060-1.Productive rate 68.8%.ESI-MS(M+H
+)=1162.5.
2) CGTD-DSSC-060's is synthetic
Under nitrogen protection, by the 060-1(58.2 milligram of above-claimed cpd, 0.05 mmole); cyanoacetic acid (17 milligrams, 0.2 mmole), (15.4 milligrams of ammonium acetates; 0.2 mmole), and mixed 125 degrees Celsius of lower stirring reactions 5 hours that are incorporated in of acetic acid (8 milliliters).After cool to room temperature, solid is separated out, and filters and obtains 40 milligrams of CGTD-DSSC-060.Productive rate 65.0%.
1H-NMR(400MHz,DMSO-d6):0.864(t,12H),1.322(m,16H)m,1.412(m,8H),1.718(m,8H),3.936(t,8H),6.748(m,4H),6.926(m,8H),7.051(m,8H),7.263(d,1H),7.346(d,2H),7.458(d,1H),7.492(m,4H),7.931(s,1H),8.153(s,1H),13.936(s,1H).ESI-MS(M+H
+)1229.5。
Embodiment 39
1) compound 061-1's is synthetic:
To be dissolved with (3.84 grams of sodium tert-butoxides, 4.0 mmoles) 2-methyl 2-butanol solution (20 milliliters) be slowly heated to 50 DEG C, at this temperature, add (3.6 grams of 4-bromobenzylcyanides in batches, 20.0 mmole), after adding, temperature is risen to 90 DEG C, to be dissolved with again (2.02 grams of diisopropyl ester amber acids, 10.0 mmoles) 2-methyl-2-butanols (20 milliliters) solution be slowly added drop-wise in reaction solution, after within 3 hours, adding, reaction solution reacts and spends the night at this temperature, then reaction solution is cooled to 50 DEG C, slowly splash into and contain second aqueous acid, reacting liquid filtering, filter cake water and methyl alcohol are washed and are obtained 2.86 grams of red solid 061-1.Productive rate 64%.
2) compound 061-2's is synthetic:
By compound 061-1(1 gram, 2.2 mmoles) be dissolved in DMF (30 milliliters), then by (1.44 grams of hexyl bromide 1 bromohexanes, 8.8 mmoles), cesium carbonate (2.15 grams, 6.6 mmoles) joins in solution, reaction solution spends the night 40 DEG C of reactions.Reacting liquid filtering, adds 200 milliliters of methylene dichloride toward filtrate, washes (50 milliliters, 3 times) with water, and organic layer is concentrated, and silica gel is crossed post (sherwood oil: ethyl acetate=10:1) and obtained 554 milligrams of compound 061-2. productive rates 40.1%.ESI-MS[M+H]
+：615.2。
3) compound 061-3's is synthetic:
By compound 061-2(554 milligram, 0.9 mmole), (171 milligrams of 4-trifluoromethyl phenylo boric acids, 0.9 mmole), (310 milligrams, salt of wormwood, 2.25 mmoles) add in the mixing solutions that is added to tetrahydrofuran (THF) (15 milliliters) and water (3 milliliters), under nitrogen protection condition, add (0.1 gram of tetra-triphenylphosphine palladium, 0.09 mmole), solution was 45 DEG C of reactions 3 hours, after cool to room temperature, separate organic layer, the concentrated crude product that obtains, silica gel is crossed post (sherwood oil: ethyl acetate=10:1) and is obtained 286 milligrams of compound 061-3, LC-MS purity: 100%, productive rate 47%.
1H-NMR(400MHz,CDCl
3)δ:0.857(m,6H),1.213(m,12H),1.572(m,4H),3.758(m,4H),7.512(t,1H),7.683(m,4H),7.705(s,3H),7.755(s,1H),7.784(d,2H),7.532(m,1H),7.911(d,2H)。
4) compound 061-4's is synthetic:
By (286 milligrams of compound 061-3; 0.42 mmole); (267 milligrams of duplex tetramethyl ethylene ketone boric acid esters; 1.05 mmole); (123 milligrams of Potassium ethanoates; 1.26 mmoles) be dissolved in 1; in 4-dioxane (20 milliliters); under nitrogen protection, add the two Diphenyl phosphino ferrocene palladium chlorides (31 milligrams, 0.042 mmole) of 1,1'-; being heated to 90 DEG C spends the night; concentrated except desolventizing, silica gel is crossed post (sherwood oil: methylene dichloride=10:1-1:1) and is obtained 168 milligrams of compound 061-4, productive rate 53.8%.
1H-NMR(400MHz,CDCl
3)δ:0.808-0.838(m,6H),1.241(S,12H),1.261(S,12H),1.646(S,4H),3.751-3.789(m,4H),7.747-7.802(m,8H),7.933-7.979(m,4H)。
5) compound 061-5's is synthetic:
By compound 061-4(118 milligram; 0.16 mmole), compound O'(64 milligram; 0.16 mmole), (55 milligrams, salt of wormwood; 0.4 mmole) be dissolved in the mixed solvent that fills tetrahydrofuran (THF) (20 milliliters) and water (5 milliliters); under nitrogen protection condition, add (18 milligrams of tetra-triphenylphosphine palladiums; 0.01 mmole); solution spends the night 70 DEG C of reactions; after cool to room temperature, separate organic layer; the concentrated crude product that obtains; silica gel is crossed post (sherwood oil: ethyl acetate=3:1) and is obtained 46 milligrams of compound 061-5, LC-MS purity: 100%, and productive rate 38%.
1H-NMR(400MHz,CDCl
3)δ:0.851-0.818(m,6H),1.159(m,6H),1.254(m,12H),1.650(m,4H),3.796-3.825(m,4H),4.582(s,1H),6.735-6.758(d,2H),7.206-7.215(d,1H),7.308-7.317(d,1H),7.518-7.540(d,2H),7.749-7.787(m,8H),7.827(s,1H),7.905-7.963(m,4H),10.229(s,1H).
6) Compound C GTD-DSSC-061's is synthetic:
By compound 061-5(46 milligram; 0.05 mmole), (42 milligrams of cyanoacetic acids; 0.5 mmole), pyridine (0.1 milliliter) is dissolved in the mixed solvent of tetrahydrofuran (THF) (3 milliliters) and acetonitrile (3 milliliters); night is flow through in nitrogen protection next time; cooled and filtered; filtrate is concentrated, and silica gel is crossed post (methylene dichloride: methyl alcohol=100:1) and obtained 13 milligrams of Compound C GTD-DSSC-061.LC-MS purity: 100%, productive rate 27%.
1H-NMR(400MHz,DMSO)δ:0.773-0.741(t,6H),1.118-1.129(m,10H),1.224(s,6H),1.269-1.284(d,6H),3.698-3.709(m,4H),4.596-4.625(m,1H),6.874-6.896(d,2H),7.179(s,1H),7.389-7.396(d,1H),7.477-7.498(d,2H),7.614-7.634(d,2H),7.705-7.726(d,2H),7.762-7.826(m,6H),7.847-7.867(d,2H),8.113-8.160(d,2H)。
Embodiment 40
1) compound 062-1's is synthetic:
By compound 2,4-dimethoxy benzene bromine (5g, 23 mmoles) be dissolved in 50 milliliters of methylene dichloride, under ice-water bath, boron tribromide (20 milliliters) is slowly splashed in solution, drip and finish, under reaction room temperature, stir and spend the night, by methyl alcohol for reaction solution (50 milliliters) cancellation under ice-water bath, the concentrated silica gel of solution after cancellation is crossed post (methylene dichloride: methyl alcohol=50:1-20:1) and is obtained 2.4 and digest compound 062-1, LC-MS purity: 94%, and productive rate 55%.ESI-MS[M+H]
+：190.1。
2) compound 062-2's is synthetic:
By compound 061-1(1.97 gram, 10.4 mmoles) be dissolved in acetonitrile (150 milliliters), then by (4.42 grams of 1-iodohexane; 20.8 mmoles), (6.78 grams of cesium carbonates; 20.8 mmoles) join in solution, under nitrogen protection, reaction solution spends the night 90 DEG C of stirrings.Reacting liquid filtering, adds 100 milliliters of methylene dichloride toward filtrate, washes (50 milliliters, 3 times) with water, and organic layer is concentrated, and silica gel is crossed post (sherwood oil: ethyl acetate=50:1) and obtained 2.8 and digest compound 062-2. productive rate 76%.
1H-NMR(400MHz,CDCl
3)δ:0.888-0.926(t,6H),1.312-1.358(m,8H),1.427-1.511(m,4H),1.742-1.840(m,4H),3.893-3.926(t,2H),3.960-3.993(t,2H),6.348-6.376(dd,1H),6.459-6.466(d,1H),7.358-7.380(d,1H)。
3) compound 062-3's is synthetic:
By compound 062-2(2.8 gram, 7.9 mmoles), (1.97 grams of 4-oil of mirbane boric acid, 11.8 mmole), (1.37 grams of Potassium monofluorides, 23.7 mmoles) be added to glycol dimethyl ether (20 milliliters), toluene (2 milliliters), in the mixing solutions of ethanol (12 milliliters) and water (6 milliliters), under nitrogen protection condition, add (912 milligrams of tetra-triphenylphosphine palladiums, 0.79 mmole), solution is at 110 DEG C of stirring reaction 5h, after cool to room temperature, separate organic layer, the concentrated crude product that obtains, silica gel is crossed post (sherwood oil: ethyl acetate=20:1-20:1) and is obtained 2.1 and digest compound 062-3, LC-MS purity: 95%, productive rate 67%.
1H-NMR(400MHz,CDCl
3)δ:0.782-0.860(tt,6H),1.182-1.290(m,10H),1.374-1.426(m,2H),1.637-1.752(tt,4H),3.877-3.944(m,4H),6.484-6.506(d,2H),7.177-7.197(t,1H),7.599-7.621(d,2H),8.131-8.153(d,2H)。
4) compound 062-4's is synthetic:
By compound 062-3(1.5 gram; 3.76 mmoles), (2.44 grams of zinc powders; 37.6 mmoles), ammonium chloride (3.0 grams, 37.6 mmoles) is added in the mixing solutions of acetone (30 milliliters) and water (6 milliliters), under nitrogen protection condition; solution is at 60 DEG C of stirring reaction 1h; after cool to room temperature, filter, the concentrated crude product that obtains of filtrate, silica gel is crossed post (sherwood oil: methylene dichloride=1:1) and is obtained 1.38 and digest compound 062-4; LC-MS purity: 92%, productive rate 86%.ESI-MS[M+H+2]
+：370.3。
5) compound 062-5's is synthetic:
By compound 062-4(1.0 gram, 2.7 mmoles) be added in the mixing solutions of 9% sulfuric acid (15 milliliters) and acetonitrile (15 milliliters), under ice-water bath, the Sodium Nitrite of water-soluble (3 milliliters) (560 milligrams, 8.1 mmoles) is added drop-wise in solution, drip and finish, stir 30 minutes, the potassiumiodide of water-soluble (5 milliliters) (4.48 grams, 27 mmoles) is joined in reaction solution, drip and finish, 35 DEG C of stirrings of solution are spent the night.After cool to room temperature, saturated sodium thiosulfate solution (20 milliliters) cancellation for reaction solution, neutralize with unsaturated carbonate potassium solution, with dichloromethane extraction (20 milliliters, three times), extraction liquid water (20 milliliters), the concentrated crude product that obtains, silica gel is crossed post (sherwood oil: methylene dichloride=10:1-1:1) and is obtained 860 milligrams of compound 062-5, LC-MS purity: 95%, and productive rate 66%.
1H-NMR(400MHz,CDCl
3)δ:0.861-0.929(m,6H),1.272-1.290(m,4H),1.326-1.393(m,6H),1.452-1.488(tt,2H),1.688-1.808(tt,4H),3.907-3.989(tt,4H),6.508-6.528(m,2H),7.167-7.190(d,2H),7.246-7.266(d,2H),7.661-7.682(d,2H)。
6) compound 062-6's is synthetic:
By compound 062-5(753 milligram; 1.56 mmoles), (90 milligrams of 4-bromanilines; 0.52 mmole), (30 milligrams of cuprous iodides; 0.156 mmole); (28 milligrams of 1.10-phenanthrolines; 0.156 mmole); sodium tert-butoxide (270 milligrams, 2.8 mmoles) is added in toluene (5 milliliters), under nitrogen protection condition; solution is at 125 DEG C of stirring reaction 1h; after cool to room temperature, filter, filtrate is concentrated obtains crude product, and silica gel is crossed post (sherwood oil: methylene dichloride=1:1) and obtained 380 milligrams of compound 062-6; LC-MS purity: 96%, productive rate 83%.
1H-NMR(400MHz,CDCl
3)δ:0.850-0.931(t,12H),1.285-1.303(m,8H),1.339-1.375(m,12H),1.403-1.494(m,4H),1.723-1.813(m,8H),3.935-3.997(m,8H),6.525-6.540(m,4H),7.028-7.049(d,2H),7.097-7.118(d,4H),7.233-7.254(d,3H),7.315-7.336(d,2H),7.423-7.443(d,3H)。
7) compound 062-7's is synthetic:
By compound 062-6(380 milligram, 0.4 mmole) be dissolved in tetrahydrofuran (THF) (5 milliliters), under-78 DEG C of conditions, drip (0.64 milliliter of n-Butyl Lithium, 1.6 mmoles), under-78 DEG C of conditions, react 30 minutes, add sec.-propyl tetramethyl ethylene ketone boric acid ester (298 milligrams, 1.6 mmoles).Under nitrogen protection condition; mixture reaction 16 hours; add saturated aqueous ammonium chloride cancellation reaction; (20 milliliters of dichloromethane extractions; three times); concentrate except silica gel chromatographic column after desolventizing separates (sherwood oil: methylene dichloride=5:1-1:2) and obtain 159 milligrams of compound 062-7, LC-MS purity: 100%, productive rate 40%.
1H-NMR(400MHz,CDCl
3)δ:0.848-0.932(t,12H),1.285-1.303(m,8H),1.334(s,12H),1.348-1.441(m,12H),1.459-1.491(m,4H),1.724-1.815(m,8H),3.935-3.999(m,8H),6.527-6.538(m,4H),7.120-7.153(m,6H),7.246(s,1H),7.269(s,1H),7.426-7.448(d,4H),7.664-7.685(d,2H)。
8) compound 062-8's is synthetic:
By compound 062-7(110 milligram; 0.12 mmole), (50 milligrams of compound 029-3; 0.1 mmole), (41 milligrams, salt of wormwood; 0.3 mmole) be dissolved in the mixed solvent that fills tetrahydrofuran (THF) (9 milliliters) and water (3 milliliters); under nitrogen protection condition, add (11 milligrams of tetra-triphenylphosphine palladiums; 0.01 mmole); solution spends the night 80 DEG C of reactions; after cool to room temperature, separate organic layer; the concentrated crude product that obtains; silica gel is crossed post (sherwood oil: ethyl acetate=3:1) and is obtained 78 milligrams of compound 062-8, LC-MS purity: 100%, and productive rate 64%.
1H-NMR(400MHz,CDCl
3)δ:0.859-0.935(m,12H),1.299-1.317(m,8H),1.344-1.370(m,8H),1.401-1.518(m,8H),1.739-1.821(m,8H),3.951-4.006(m,8H),6.539-6.552(m,4H),7.169-7.190(d,2H),7.220-7.230(d,2H),7.279-7.301(m,5H),7.330-7.340(d,2H),7.464-7.501(m,6H),7.610(s,1H),7.637-7.712(dd,4H),10.185(s,1H).
9) Compound C GTD-DSSC-062's is synthetic:
By compound 062-8(78 milligram; 0.064 mmole), (22 milligrams of cyanoacetic acids; 0.256 mmole), (20 milligrams of ammonium acetates; 0.256 mmole) be dissolved in acetic acid (4 milliliters); under nitrogen protection, reaction solution reacts 4 hours at 125 DEG C, cooled and filtered; filtrate is concentrated, and silica gel is crossed post (methylene dichloride: methyl alcohol=100:1) and obtained 52 milligrams of Compound C GTD-DSSC-062.LC-MS purity: 100%, productive rate 63%.
1H-NMR(400MHz,DMSO)δ:0.774-0.914(m,12H),1.201-1.268(m,12H),1.331-1.377(m,8H),1.398-1.465(m,4H),1.603-1.747(m,8H),3.941-4.019(m,8H),6.554-6.609(m,4H),7.035-7.091(m,6H),7.197-7.225(d,2H),7.260-7.271(d,2H),7.395-7.451(m,6H),7.555-7.584(d,2H),7.631-7.644(d,2H),7.715-7.743(d,2H),7.867-7.893(d,2H),8.021(s,1H),8.1809(s,1H)。
Embodiment 41
1) compound 031-3's is synthetic
By (450 milligrams of compound 031-2; 1.16 mmoles), (660 milligrams of X; 1.16 mmoles), (320 milligrams, salt of wormwood; 2.32 mmoles), (67 milligrams of tetra-triphenylphosphine palladiums; 0.06 mmole) join in the flask that fills 80 milliliters of tetrahydrofuran (THF)s and 20 ml waters; under nitrogen protection condition; solution reacts 8 hours under 68 degrees Celsius; after cool to room temperature, concentrate and obtain crude product, silica gel is crossed post (sherwood oil: ethyl acetate=10:1) and is obtained 100 milligrams of compound 031-3.Productive rate 80%.ESI-MS(M+H
+)=754.2。
2) compound 063-1's is synthetic
By (100 milligrams of compound 031-3, 0.14 mmole), to (26 milligrams of trifluoromethyl phenylo boric acids, 0.14 mmole), (6 milligrams of three (dibenzalacetone) two palladiums, 0.07 mmole), (8 milligrams of tri-butyl phosphine fluoroborates, 0.28 mmole), (130 milligrams of cesium carbonates, 0.4 mmole), join in the flask that fills 15 milliliters of dioxane, under nitrogen protection condition, 120 degrees Celsius are reacted 3 hours, the concentrated crude product that obtains after cool to room temperature, silica gel is crossed post (sherwood oil: ethyl acetate=10:1) and is obtained 85 milligrams of compound 063-1.Productive rate 74%.ESI-MS(M+H
+)=720.3。
3) CGTD-DSSC-063's is synthetic
Under nitrogen protection, by the 063-1(85 milligram of above-claimed cpd, 0.1 mmole); cyanoacetic acid (34 milligrams, 0.4 mmole), (31.2 milligrams of ammonium acetates; 0.4 mmole), and mixed 125 degrees Celsius of lower stirring reactions 6 hours that are incorporated in of acetic acid (5 milliliters).After cool to room temperature, there is solid to separate out, filter and obtain products C GTD-DSSC-06328 milligram.Productive rate 30.0%.1H-NMR(400MHz,DMSO-d6):0.884(t,6H),1.315(m,8H),1.414(m,4H),1.702(m,4H),3.937(t,4H),6.751(d,2H),6.907(d,4H),7.041(d,4H),7.161(t,1H),7.301(d,1H),7.417(s,1H),7.520(m,3H),7.646(d,1H),7.985(s,1H),8.210(s,1H).ESI-MS(M+H
+)=787.3。
Embodiment 42
1) compound 064-2's is synthetic:
By compound 064-1(700 milligram, 1.6 mmoles), (365 milligrams of 4-trifluoromethyl phenylo boric acids, 1.92 mmole), (552 milligrams, salt of wormwood, 4.0 mmoles) be added in the mixing solutions of tetrahydrofuran (THF) (20 milliliters) and water (4 milliliters), under nitrogen protection condition, add (185 milligrams of tetra-triphenylphosphine palladiums, 0.16 mmole), solution was 50 DEG C of stirring reactions 2 days, after cool to room temperature, separate organic layer, the concentrated crude product that obtains, silica gel is crossed post (sherwood oil: ethyl acetate=20:1-20:1) and is obtained 270 milligrams of compound 064-2, LC-MS purity: 98%, productive rate 32%.ESI-MS[M+H+1]
+：507.0。
2) compound 064-3's is synthetic:
By compound 064-2(270 milligram, 0.53 mmole), (81 milligrams of 2-thienyl boric acid, 0.63 mmole), (183 milligrams, salt of wormwood, 1.325 mmoles) be added in the mixing solutions of tetrahydrofuran (THF) (20 milliliters) and water (4 milliliters), under nitrogen protection condition, add (61 milligrams of tetra-triphenylphosphine palladiums, 0.053 mmole), solution spends the night at 70 DEG C of stirring reactions, after cool to room temperature, separate organic layer, the concentrated crude product that obtains, silica gel is crossed post (sherwood oil: methylene dichloride=2:1) and is obtained 210 milligrams of compound 064-3, LC-MS purity: 100%, productive rate 32%.ESI-MS[M+H+1]
+：509.2。
3) compound 064-4's is synthetic:
By compound 064-3(180 milligram, 0.35 mmole), (75 milligrams of N-bromo-succinimides, 0.42 mmole) be dissolved in trichloromethane (15 milliliters), under ice-water bath, drip acetic acid (3 milliliters), drip and finish, reaction is at room temperature stirred 6 hours, (30 milliliters of reaction solution difference waters, three times), saturated sodium bicarbonate (20 milliliters), Sulfothiorine (20 milliliters) wash, the concentrated silica gel of organic layer is crossed post (sherwood oil: methylene dichloride=5:1) and is obtained 205 milligrams of compound 064-4, LC-MS purity: 99%, and productive rate 98%.
1H-NMR(400MHz,CDCl
3)δ:7.077-7.087(d,2H),7.244-7.289(m,3H),7.342-7.360(m,3H),7.468-7.488(m,2H),7.548-7.558(d,1H),7.637-7.661(m,2H),7.690-7.711(d,2H),7.770-7.789(d,1H),7.877-7.897(d,2H),8.098-8.117(d,1H)。
4) compound 064-5's is synthetic:
By compound 064-4(50 milligram, 0.085 mmole), Compound C " (100 milligrams; 0.103 mmole) be dissolved in N,N-dimethylacetamide (3 milliliters), adds tetra-triphenylphosphine palladium (9.8 milligrams; 0.0085 mmole); solution reacts and spends the night at 70 DEG C under nitrogen protection condition, and after cool to room temperature, solution is dissolved in ethyl acetate (30 milliliters); water (10 milliliters; three times) is washed, and organic layer is concentrated obtains crude product, and silica gel is crossed post (sherwood oil: ethyl acetate=1; 25) obtain 38 milligrams of compound 064-5, LC-MS purity: 94%, productive rate 39%.
1H-NMR(400MHz,CDCl
3)δ:0.829-0.861(t,6H),1.256-1.309(m,8H),1.379-1.416(m,4H),1.693-1.730(m,4H),3.856-3.858(t,4H),4.029(m,2H),4.174(m,2H),5.930(s,1H),6.758-6.791(m,4H),63845-6.865(d,2H),7.090(S,1H),7.239-7.253(m,3H),7.338-7.355(m,6H),7.507-7.527(m,4H),7.694-7.736(m,4H),7.769-7.793(m,2H),7.895-7.915(d,2H),8.129-8.150(d,2H)。
5) compound 064-6's is synthetic:
By compound 064-5(38 milligram, 0.032 mmole) be dissolved in methylene dichloride (5 milliliters), under ice-water bath, drip concentrated hydrochloric acid (1 milliliter), drip and finish, solution at room temperature reacts and spends the night.Reaction solution is adjusted to neutrality with saturated sodium bicarbonate solution, and with methylene dichloride (20 milliliters) extraction, extraction liquid water (10 milliliters, three times) is washed, and organic layer is concentrated obtains 52 milligrams of crude product compound 064-6, is directly used in next step reaction.LC-MS purity: 90%, productive rate 140%.
1H-NMR(400MHz,CDCl
3)δ:0.782-0.857(m,6H),1.257-1.3092(m,8H),1.335-1.418(m,4H),1.694-1.7302(m,4H),3.881(m,4H),6.775-6.793(d,4H),6.997(m,4H),7.201-7.229(m,6H),7.334-7.380(m,5H),7.502-7.522(m,2H),7.573(s,1H),7.690-7.722(m,4H),7.760-7.790(m,4H),7.760-7.791(m,2H),7.884-7.905(d,2H),8.130-8.150(d,1H),10.120(s,1H)。
6) Compound C GTD-DSSC-064's is synthetic:
By compound 064-6(52 milligram; 0.045 mmole), (19 milligrams of cyanoacetic acids; 0.225 mmole), (17 milligrams of ammonium acetates; 0.225 mmole) be dissolved in acetic acid (4 milliliters); under nitrogen protection, reaction solution reacts 5 hours at 125 DEG C, cooled and filtered; filtrate is concentrated, and silica gel is crossed post (methylene dichloride: methyl alcohol=50:1) and obtained 19 milligrams of Compound C GTD-DSSC-062.LC-MS purity: 100%, productive rate 34%.
1H-NMR(400MHz,DMSO)δ:0.921(m,6H),1.278-1.482(m,12H),1.745-1.787(m,4H),3.994(m,4H),6.805-6.830(d,2H),6.930-6.996(m,4H),7.038-7.094(m,4H),7.301-7.553(m,10H),7.755(m,2H),7.840-7.863(m,2H),7.971-8.097(m,5H),8.310(s,1H),8.467-8.487(d,1H)。
Embodiment 43
1) compound 065-2's is synthetic
By (500 milligrams of compound 065-1,1.38 mmole), (245.4 milligrams of N-bromo-succinimides, 1.38 mmole), join in the flask that fills 15 milliliters of DMFs, under room temperature condition, react 1 hour, add 60 ml waters, solid filtering obtains 400 milligrams of 065-2.Productive rate 65.7%.ESI-MS(M+H
+)=441.1。
2) compound 065-3's is synthetic
By (400 milligrams of compound 065-2; 0.9 mmole); (475 milligrams, tributyl (4-trifluoromethyl-phenyl) tin; 1.1 mmoles), tetra-triphenylphosphine palladium (55 milligrams, 0.05 mmole) joins in the flask that fills 50 milliliters of toluene solutions; under nitrogen protection; 100 degrees Celsius of reactions are spent the night, and after cool to room temperature, concentrate and obtain crude product, and silica gel is crossed post (sherwood oil=100%) and obtained 410 milligrams of compound 065-3.Productive rate 89%.ESI-MS(M+H
+)=507.2。
3) compound 065-4's is synthetic
By (410 milligrams of compound 065-3,0.81 mmole), (145 milligrams of N-bromo-succinimides, 0.81 mmole), join in the flask that fills 10 milliliters of DMFs, under room temperature condition, react 2 hours, add 60 ml waters, solid filtering obtains 270 milligrams of 065-4.Productive rate 57%.ESI-MS(M+H
+)=585.1。
4) compound 065-5's is synthetic
By (270 milligrams of compound 065-4; 0.46 mmole); (258 milligrams, tributyl (2-thienyl) tin; 0.69 mmole), tetra-triphenylphosphine palladium (30 milligrams, 0.03 mmole) joins in the flask that fills 15 milliliters of toluene solutions; under nitrogen protection; 100 degrees Celsius of reactions are spent the night, and after cool to room temperature, concentrate and obtain crude product, and silica gel is crossed post (sherwood oil=100%) and obtained 240 milligrams of compound 065-5.Productive rate 89%.ESI-MS(M+H
+)=589.2。
5) compound 065-6's is synthetic
By (220 milligrams of compound 065-5,0.37 mmole), (80 milligrams of N-bromo-succinimides, 0.45 mmole), join in the flask that fills 10 milliliters of DMFs, under room temperature condition, react 1 hour, add 60 ml waters, solid filtering obtains 240 milligrams of 065-6.Productive rate 90%.ESI-MS(M+H
+)=667.1。
6) compound 065-7's is synthetic
By (72 milligrams of compound 065-6, 0.11 mmole), (100 milligrams of 055-1b, 0.11 mmole), (10 milligrams of tetra-triphenylphosphine palladiums, 0.01 mmole) join and fill 5 milliliters of N, in the flask of dinethylformamide, under nitrogen protection, 70 degrees Celsius of reactions are spent the night, after cool to room temperature, add 25 ml waters, add again ethyl acetate extraction (20 milliliters of x3), saturated aqueous common salt washing (20 milliliters of x2) for organic phase, anhydrous sodium sulfate drying, filter, the concentrated crude product that obtains of filtrate, silica gel is crossed post (sherwood oil: ethyl acetate=10:1) and is obtained 50 milligrams of compound 065-7.Productive rate 37%.ESI-MS(M+H
+)=1268.4。
7) compound 065-8's is synthetic
By (72 milligrams of compound 065-7,0.04 mmole), join in the flask that fills 10 milliliters of methylene dichloride and 1 milliliter of concentrated hydrochloric acid mixing solutions, under room temperature condition, react 3 hours, add 30 ml waters, then add dichloromethane extraction (20 milliliters of x3), organic phase washes (20 milliliters of x2) with water, anhydrous sodium sulfate drying, filters, and filtrate concentrating obtains 47 milligrams of compound 065-8.Productive rate 98%.ESI-MS(M+H
+)=1224.4。
8) CGTD-DSSC-065's is synthetic
Under nitrogen protection, by the 065-8(40 milligram of above-claimed cpd, 0.032 mmole); cyanoacetic acid (11 milligrams, 0.13 mmole), (10 milligrams of ammonium acetates; 0.13 mmole), and mixed 125 degrees Celsius of lower stirring reactions 12 hours that are incorporated in of acetic acid (5 milliliters).After cool to room temperature, there is solid to separate out, filter and obtain products C GTD-DSSC-0655 milligram.Productive rate 12%.1H-NMR(400MHz,DMSO-d6):0.853(m,12H),1.236(m,20H),1.320(m,8H),1.421(m,4H),1.752(m,4H),3.882(t,4H),6.742(d,2H),6.915(d,4H),7.051(d,4H),7.308(d,1H),7.351(d,1H),7.407(d,1H),7.482(d,1H),7.510(m,3H),7.732(m,4H),7.808(s,1H),7.887(d,2H),7.983(s,1H)，8.188(s,1H).ESI-MS(M+H
+)1291.4。
Embodiment 44
1) compound 066-1's is synthetic
By (110 milligrams of compound Z '; 0.337 mmole), (119 milligrams of 029-1; 0.337 mmole), (139 milligrams, salt of wormwood; 1.01 mmoles), (39 milligrams of tetra-triphenylphosphine palladiums; 0.034 mmole) join in the flask that fills 20 milliliters of tetrahydrofuran (THF)s and 6 ml waters; under nitrogen protection condition; solution reacts 16 hours under 60 degrees Celsius; the concentrated crude product that obtains after cool to room temperature, silica gel is crossed post (sherwood oil: ethyl acetate=20:1) and is obtained 58 milligrams of compound 066-1.Productive rate 36.4%.ESI-MS(M+H
+)=474.7。
2) compound 066-2's is synthetic
By (58 milligrams of compound 066-1; 0.123 mmole), (77 milligrams of X; 0.135 mmole), (51 milligrams, salt of wormwood; 0.369 mmole), (13.9 milligrams of tetra-triphenylphosphine palladiums; 0.012 mmole) join in the flask that fills 10 milliliters of tetrahydrofuran (THF)s and 2 ml waters; under nitrogen protection condition; solution reacts 16 hours under 65 degrees Celsius; the concentrated crude product that obtains after cool to room temperature; silica gel is crossed post (sherwood oil: ethyl acetate=10:1) and is obtained 70 milligrams of compound 066-2, productive rate 68.1%.ESI-MS(M+H
+)=838.3.
3) CGTD-DSSC-066's is synthetic
Under nitrogen protection, by the 066-2(70 milligram of above-claimed cpd, 0.083 mmole); cyanoacetic acid (28.4 milligrams, 0.334 mmole), (25.7 milligrams of ammonium acetates; 0.334 mmole), and mixed 125 degrees Celsius of lower stirring reactions 5 hours that are incorporated in of acetic acid (10 milliliters).After cool to room temperature, solid is separated out, and filters and obtains 40 milligrams of CGTD-DSSC-066.Productive rate 53.25%.1H-NMR(400MHz,DMSO-d6):0.879(t,6H),1.310(m,8H),1.409(m,4H),1.698(m,4H),3.932(t,4H),6.745(d,2H),6.902(d,4H),7.031(d,4H),7.442(d,1H),7.524(d,2H),7.809(m,3H),7.886(d,1H),7.945(d,2H),8.393(s,1H),13.936(s,1H).ESI-MS(M+H
+)905.3。
Embodiment 45
1) compound 067-2's is synthetic
By (230 milligrams of compound 067-1; 1.1 mmoles), (164 milligrams of 2-thienyl boric acid; 1.28 mmoles), (300 milligrams, salt of wormwood; 2.2 mmoles), (20 milligrams of tetra-triphenylphosphine palladiums; 0.02 mmole) join in the flask that fills 50 milliliters of tetrahydrofuran (THF)s and 10 ml waters; under nitrogen protection condition; solution reacts 8 hours under 68 degrees Celsius; after cool to room temperature, concentrate and obtain crude product, silica gel is crossed post (sherwood oil: ethyl acetate=20:1) and is obtained 200 milligrams of compound 067-2.Productive rate 85%.ESI-MS(M+H
+)=219.0。
2) compound 067-3's is synthetic
By (200 milligrams of compound 067-2,0.92 mmole), N-bromo-succinimide (178 milligrams, 1 mmole), join in the flask that fills 10 milliliters of acetic acid and 10 milliliters of trichloromethane mixing solutionss, under room temperature condition, react 2 hours, add 60 ml waters, then add dichloromethane extraction (20 milliliters of x3), organic phase washes (20 milliliters of x2) with water, anhydrous sodium sulfate drying, filters, and filtrate concentrating obtains 245 milligrams of compound 067-3.Productive rate 90%.ESI-MS(M+H
+)=296.9。
3) compound 067-4's is synthetic
By (120 milligrams of compound 067-3, 0.82 mmole), S'(200 milligram, 0.82 mmole), (20 milligrams of tetra-triphenylphosphine palladiums, 0.02 mmole) join and fill 10 milliliters of N, in the flask of dinethylformamide solution, under nitrogen protection, 70 degrees Celsius of reactions are spent the night, after cool to room temperature, add 40 ml waters, add again ethyl acetate extraction (20 milliliters of x3), saturated common salt washing (20 milliliters of x2) for organic phase, anhydrous sodium sulfate drying, filter, the concentrated crude product that obtains of filtrate, silica gel is crossed post (sherwood oil: ethyl acetate=20:1) and is obtained 100 milligrams of compound 067-4.Productive rate 56%.ESI-MS(M+H
+)=455.0。
4) compound 067-5's is synthetic
By (100 milligrams of compound 067-4,0.22 mmole), (43 milligrams of N-bromo-succinimides, 0.24 mmole), join in the flask that fills 8 milliliters of DMFs, under room temperature condition, react 8 hours, add 50 ml waters, solid filtering obtains 118 milligrams of 067-5.Productive rate 100%.ESI-MS(M+H
+)=532.9。
5) compound 067-6's is synthetic
By (118 milligrams of compound 067-5,0.22 mmole), join in the flask that fills 10 milliliters of methylene dichloride and 1 milliliter of concentrated hydrochloric acid mixing solutions, under room temperature condition, react 8 hours, add 30 ml waters, then add dichloromethane extraction (20 milliliters of x3), organic phase washes (20 milliliters of x2) with water, anhydrous sodium sulfate drying, filters, and filtrate concentrating obtains 107 milligrams of compound 067-6.Productive rate 99%.ESI-MS(M+H
+)=490.5。
6) compound 067-7's is synthetic
By (107 milligrams of compound 067-6; 0.22 mmole), (151 milligrams of X; 0.26 mmole), (61 milligrams, salt of wormwood; 0.44 mmole), (20 milligrams of tetra-triphenylphosphine palladiums; 0.02 mmole) join in the flask that fills 50 milliliters of tetrahydrofuran (THF)s and 10 ml waters; under nitrogen protection condition; solution reacts 8 hours under 68 degrees Celsius; after cool to room temperature, concentrate and obtain crude product, silica gel is crossed post (sherwood oil: ethyl acetate=10:1) and is obtained 150 milligrams of compound 067-7.Productive rate 80%.ESI-MS(M+H
+)=854.2。
7) CGTD-DSSC-067's is synthetic
Under nitrogen protection, by the 063-7(150 milligram of above-claimed cpd, 0.175 mmole); cyanoacetic acid (60 milligrams, 0.7 mmole), (54 milligrams of ammonium acetates; 0.7 mmole), and mixed 125 degrees Celsius of lower stirring reactions 8 hours that are incorporated in of acetic acid (5 milliliters).After cool to room temperature, there is solid to separate out, filter and obtain products C GTD-DSSC-06770 milligram.Productive rate 50.0%.1H-NMR(400MHz,DMSO-d6):0.881(t,6H),1.309(m,8H),1.408(m,4H),1.697(m,4H),3.923(t,4H),6.736(d,2H),6.905(d,4H),7.003(d,4H),7.21(s,1H),7.444(m,4H),7.667(s,1H),7.950(m,2H),8.118(m,3H).ESI-MS(M+H
+)=921.2。
Embodiment 46
1) compound 068-2's is synthetic
By (184 milligrams of compound 068-1, 0.42 mmole), S'(220 milligram, 0.42 mmole), (30 milligrams of tetra-triphenylphosphine palladiums, 0.03 mmole) join and fill 10 milliliters of N, in the flask of dinethylformamide solution, under nitrogen protection, 70 degrees Celsius of reactions are spent the night, after cool to room temperature, add 40 ml waters, add again ethyl acetate extraction (20 milliliters of x3), saturated common salt washing (20 milliliters of x2) for organic phase, anhydrous sodium sulfate drying, filter, the concentrated crude product that obtains of filtrate, silica gel is crossed post (sherwood oil: ethyl acetate=10:1) and is obtained 170 milligrams of compound 068-2.Productive rate 68%.ESI-MS(M+H
+)=599.0.
2) compound 068-3's is synthetic
By (170 milligrams of compound 068-2,0.28 mmole), (60 milligrams of N-bromo-succinimides, 0.34 mmole), join in the flask that fills 5 milliliters of DMFs, under room temperature condition, react 2 hours, add 50 ml waters, solid filtering obtains 150 milligrams of 068-3.Productive rate 78%.ESI-MS(M+H
+)=676.9。
3) compound 068-4's is synthetic
By (150 milligrams of compound 068-3,0.22 mmole), join in the flask that fills 10 milliliters of methylene dichloride and 1 milliliter of concentrated hydrochloric acid mixing solutions, under room temperature condition, react 8 hours, add 30 ml waters, then add dichloromethane extraction (20 milliliters of x3), organic phase washes (20 milliliters of x2) with water, anhydrous sodium sulfate drying, filters, and filtrate concentrating obtains 140 milligrams of compound 068-4.Productive rate 98%.ESI-MS(M+H
+)=632.9。
4) compound 068-5's is synthetic
By (40 milligrams of compound 068-4; 0.22 mmole), (126 milligrams of X; 0.22 mmole), (61 milligrams, salt of wormwood; 0.44 mmole), (30 milligrams of tetra-triphenylphosphine palladiums; 0.03 mmole) join in the flask that fills 50 milliliters of tetrahydrofuran (THF)s and 10 ml waters; under nitrogen protection condition; solution reacts 8 hours under 68 degrees Celsius; after cool to room temperature, concentrate and obtain crude product, silica gel is crossed post (sherwood oil: methylene dichloride=1:2) and is obtained 50 milligrams of compound 068-5.Productive rate 23%.ESI-MS(M+H
+)=998.3。
5) CGTD-DSSC-068's is synthetic
Under nitrogen protection, by the 068-5(50 milligram of above-claimed cpd, 0.05 mmole); cyanoacetic acid (17 milligrams, 0.2 mmole), (15.4 milligrams of ammonium acetates; 0.2 mmole), and mixed 125 degrees Celsius of lower stirring reactions 8 hours that are incorporated in of acetic acid (5 milliliters).After cool to room temperature, there is solid to separate out, filter and obtain products C GTD-DSSC-06826 milligram.Productive rate 48.7%.1H-NMR(400MHz,DMSO-d6):0.889(t,6H),1.312(m,8H),1.417(m,4H),1.706(m,4H),3.930(t,4H),6.740(d,2H),6.890(d,4H),7.025(d,4H),7.185(s,1H),7.391(s,1H),7.437(m,3H),7.845(m,3H),7.971(s,1H)，8.131(m,5H).ESI-MS(M+H
+)=1065.3。
Embodiment 47
1) compound 031-3's is synthetic
By compound Q ' (450 milligrams; 1.16 mmoles), (660 milligrams of X; 1.16 mmoles), (320 milligrams, salt of wormwood; 2.32 mmoles), (67 milligrams of tetra-triphenylphosphine palladiums; 0.06 mmole) join in the flask that fills 80 milliliters of tetrahydrofuran (THF)s and 20 ml waters; under nitrogen protection condition; solution reacts 8 hours under 68 degrees Celsius; after cool to room temperature, concentrate and obtain crude product, silica gel is crossed post (sherwood oil: ethyl acetate=10:1) and is obtained 100 milligrams of compound 031-3.Productive rate 80%.ESI-MS(M+H
+)=754.2。
2) compound 031-4's is synthetic
By (50 milligrams of compound 031-3; 0.07 mmole); to (20 milligrams of trifluoromethyl phenylo boric acids; 0.1 mmole); palladium (3 milligrams, 0.01 mmole), 2-dicyclohexyl phosphorus-2; 4; 6-tri isopropyl biphenyl (10 milligrams, 0.02 mmole), (20 milligrams of cesium hydroxides; 0.12 mmole); join in the flask that fills 8 milliliters of propyl carbinols and 2 ml water mixing solutionss, under nitrogen protection condition, room temperature reaction 12 hours; concentrate and obtain crude product, silica gel is crossed post (sherwood oil: ethyl acetate=6:1) and is obtained 20 milligrams of compound 031-4.Productive rate 40%.ESI-MS(M+H
+)=864.2。
3) Compound C GTD-DSSC-031's is synthetic
Under nitrogen protection, by compound 031-4(56 milligram, 0.06 mmole), cyanoacetic acid (20 milligrams, 0.24 mmole), ammonium acetate (19 milligrams, 0.24 mmole), and acetic acid (10 milliliters) is mixed is incorporated at 125 DEG C stirring reaction 5 hours.After cool to room temperature, have solid to separate out, filter, filter cake column chromatography for separation (methylene dichloride: methyl alcohol=40:1) obtains 27 milligrams of Compound C GTD-DSSC-031, LC-MS purity 100%, productive rate 45%.
1H-NMR(400MHz,DMSO-d6)0.878(t,6H),1.257-1.317(m,8H),1.405(t,4H),1.658-1.728(m,4H),3.921(t,4H),6.741(d,2H),6.896(d,4H),7.016(d,4H),7.217(d,1H),7.403-7.469(m,4H),7.684-7.741(m,3H),7.886(d,2H),7.974(s,1H),8.120(s,1H).ESI-MS[M+H]
+：931.2。
Embodiment 48
1) intermediate 069-2's is synthetic
In 50 milliliters of there-necked flasks, add compound 069-1(2.47 gram; 10 mmoles); 2-(tributyl tin) (3.73 grams, thiophene; 10 mmoles); tetra-triphenylphosphine palladium (231 milligrams, 2 mmoles) and 20 milliliters of toluene, under nitrogen protection, 130 degree back flow reaction are spent the night; concentrated except desolventizing after cool to room temperature, silica gel chromatographic column separates (sherwood oil) and obtains intermediate 069-22.47 gram.Productive rate 98.8%, purity 99.5%.1H-NMR(400MHz,DMSO-d6):7.917(m,1H),7.569(m,1H),7.284(t,1H)。
2) intermediate 069-3's is synthetic
In 50 milliliters of single port flasks, add compound 069-2(2.00 gram, 8 mmoles), the DMF of N-bromo-succinimide (2.28 grams, 12.8 mmoles) and 32 milliliters, 25 degree reactions are spent the night, in the frozen water that impouring is 150 milliliters, stir half hour, filter, wash the dry intermediate 069-32.23 gram that obtains three times.Productive rate 84.8%, purity 98.5%.
1H-NMR(400MHz,DMSO-d6):7.404(m,2H).
3) intermediate 069-4's is synthetic
In 5 milliliters of single port flasks, add compound 069-3(75 milligram; 0.228 mmole); compound S ' (120 milligrams; 0.228 mmole); tetra-triphenylphosphine palladium (15 milligrams, 0.023 mmole) and 3 milliliters of toluene, under nitrogen protection, 130 degree back flow reaction are spent the night; concentrated except desolventizing after cool to room temperature, silica gel chromatographic column separates (sherwood oil: ethyl acetate=25:1) and obtains intermediate 069-480 milligram.Productive rate 72.1%, purity 96.5%.1H-NMR(400MHz,DMSO-d6):7.714(m,1H),7.551(m,2H),7.473(s,1H),7.351(t,1H),7.189(m,1H),5.834(s,1H),4.103(m,2H),3.967(m,2H).
4) compound 069-5's is synthetic
In 5 milliliters of single port flasks, add compound 069-4(80 milligram, 0.159 mmole), the DMF of N-bromo-succinimide (29 milligrams, 0.159 mmole) and 2 milliliters, 25 degree reactions are spent the night, in the frozen water that impouring is 10 milliliters, stir half hour, filter, wash the dry product intermediate 069-559 milligram that obtains three times.Productive rate 63.4%.1H-NMR(400MHz,DMSO-d6):7.574(s,2H),7.481(s,1H),7.323(d,1H),7.189(d,1H),5.813(s,1H),4.116(t,2H),3.970(t,2H).
5) compound 069-6's is synthetic
Hydrochloric acid (1M, 1 milliliter, 1.0 mmoles) is joined in 15 milliliters of methylene dichloride that fill 069-5 (56.5 milligrams, 0.1 mmole), react 16 hours under room temperature, dichloromethane extraction concentrates and obtains 52 milligrams of compound 069-6.Productive rate 99.8%.ESI-MS(M+H
+)=520.9.
6) compound 069-7's is synthetic
By (52 milligrams of compound 069-6; 0.1 mmole), (57 milligrams of X; 0.1 mmole), (41.4 milligrams, salt of wormwood; 0.3 mmole), (11.6 milligrams of tetra-triphenylphosphine palladiums; 0.01 mmole) join in the flask that fills 10 milliliters of tetrahydrofuran (THF)s and 2 ml waters; under nitrogen protection condition; solution reacts 16 hours under 65 degrees Celsius; the concentrated crude product that obtains after cool to room temperature, silica gel is crossed post (sherwood oil: ethyl acetate=25:1) and is obtained 60 milligrams of compound 069-7.Productive rate 68.2%.ESI-MS(M+H
+)=886.2。
7) CGTD-DSSC-069's is synthetic
Under nitrogen protection, by the 069-7(26.6 milligram of above-claimed cpd, 0.03 mmole); cyanoacetic acid (10.2 milligrams, 0.12 mmole), (9.24 milligrams of ammonium acetates; 0.12 mmole), and mixed 125 degrees Celsius of lower stirring reactions 5 hours that are incorporated in of acetic acid (6 milliliters).After cool to room temperature, solid is separated out, and filters and obtains 20 milligrams of CGTD-DSSC-069.Productive rate 69.94%.1H-NMR(400MHz,DMSO-d6):0.880(t,6H),1.312(m,8H),1.409(m,4H),1.698(m,4H),3.928(t,4H),6.737(d,2H),6.891(d,4H),7.015(d,4H),7.226(d,1H),7.416(d,1H),7.494(m,3H),7.567(d,1H),8.005(s,1H),8.104(s,1H),13.886(s,1H).ESI-MS(M+H
+)953.3。
Embodiment 49
1) 038-2's is synthetic
Under nitrogen protection; by compound 038-1(90 milligram; 0.19 mmole); X(132 milligram, 0.23 mmole), (79 milligrams, salt of wormwood; 0.57 mmole); four triphenyl phosphorus palladiums (23 milligrams, 0.02 mmole), and tetrahydrofuran (THF): water (15 milliliters) is mixed is incorporated at 68 DEG C stirring reaction 8 hours.After cool to room temperature, concentrated except desolventizing, silica gel column chromatography (sherwood oil: ethyl acetate=100:1) obtains 24 milligrams of 038-2, productive rate 14.9%.ESI-MS(M+H
+):826.2。
2) CGTD-DSSC-038's is synthetic
Under nitrogen protection, by compound 038-2(24 milligram, 0.03 mmole), cyanoacetic acid (13 milligrams, 0.15 mmole), ammonium acetate (12 milligrams, 0.15 mmole), and acetic acid (10 milliliters) is mixed is incorporated at 125 DEG C stirring reaction 5 hours.After cool to room temperature, have solid to separate out, filter, filter cake column chromatography for separation (methylene dichloride: methyl alcohol=30:1) obtains 10 milligrams of products, productive rate 38.4%.1H-NMR(400MHz,DMSO-d6)0.885(s,6H),1.236-1.410(m,12H),1.703(s,4H),3.802(s,3H),3.937(s,4H),6.765(d,2H),6.876-6.927(m,4H),6.993-7.037(m,6H),7.246(s,1H),7.366(s,1H),7.432(d,2H),7.498(d,2H),7.641(d,2H),7.949(s,1H),8.144(s,1H).ESI-MS(M+H
+):893.2。
Effect embodiment 1
The dye sensitized nano crystal body solar cell of organic dye sensitized dose of application of the present invention is by having adsorbed nanocrystal light anode, the ionogen of organic dye sensitized dose and electrode being formed, and its preparation and performance characterization are as follows:
In the present invention, the preparation method of dye sensitized nano crystal body solar cell is as follows:
The preparation of transparent substrates (1) and conductive layer (2) comprises the following steps:
1) conductive glass pre-treatment: take a morsel glass cleaner in water, ultrasonic cleaning 5 minutes.Conductive glass is placed in to intermediate water again, ultrasonic cleaning 5 minutes.Conductive glass is placed in to dehydrated alcohol ultrasonic cleaning 5 minutes again.Hair dryer natural wind 3 minutes.Finally, use high-purity CO
2solid-liquid gas mixture gel pistol aligning conductive glass conducting surface passes through and successively cleans 2 minutes.
The preparation of light absorbing zone (3) comprises the following steps:
2) TiO
2the preparation of slurry: taking business-like P25 powder as raw material, by repeatedly grinding under different conditions, stirring and the method such as ultrasonic, reach and control TiO
2the objects such as granular size, uniformity coefficient and the solid content of slurry.According to this preparation method's feed ratio, once experiment can be prepared the nanometer crystal layer TiO of 20 grams-30 grams
2slurry.Concrete grammar is as follows:
A. get the TiO of 6 grams
2the acetic acid of powder and 1 milliliter mixes, and grinds 5 minutes;
B. the water of 1 milliliter slowly, grinds 1 minute, repeats 5 times;
C. slowly add 1 milliliter of ethanol, grind 1 minute, repeat 15 times;
D. slowly add the ethanol of 2.5 milliliters, grind 1 minute, repeat 6 times;
E. use slowly the ethanol of 100 milliliters, shift TiO
2slurry to one beaker;
F. stir (300rpm) 1 minute with stirrer, intermittently ultrasonic 2 minutes, and then stir (300rpm) 1 minute;
G. slowly add 20 grams of Terpineol 350s;
H. stir (300rpm) 1 minute, intermittently ultrasonic 2 minutes, then continue to stir (300rpm) 1 minute;
I. slowly add 3 grams: ethyl cellulose (1.5 grams of ECl and the 1.5 grams of EC2) ethanolic soln (10%) of 30 grams
J. stir (300rpm) 1 minute, intermittently ultrasonic 2 minutes, then continue to stir (300rpm) 1 minute;
K. repeat 10 step 3 time;
L. under 35 degree, rotary evaporation is slowly removed ethanol;
M. grind 30 minutes with agate mortar.
3) preparation of light-sensitive coloring agent solution:
A. select suitable solvent.
B. prepare the dye solution of finite concentration (as 0.3mM or 0.5mM), the ultrasonic dyestuff that makes dissolves completely.
C. use the millipore filtration membrane filtration dye solution of 0.22 μ m.
D. the dye solution after filtering is placed in to dyestuff and soaks bottle.
E. dye solution is preserved under sealing and darkroom.
The preparation of electrolyte layer (4) comprises the following steps:
4) preparation of high-efficiency electrolytic solution: by absolutely dry acetonitrile and valeronitrile (volume ratio: 1/1) preparation contains 1.0M DMII, 50mM LiI, 30mM I
2, 0.5M tert .-butylpyridine, and the solution of the GuNCS of 0.1M.
Preparation to electrode layer (5) comprises the following steps:
5) to electrode: the conductive glass that sputtering method is plated, with 1N dilute hydrochloric acid ultrasonic cleaning 10 minutes, then use respectively distilled water and dehydrated alcohol ultrasonic cleaning 5 minutes, be placed in baking oven 120 degree lower dry 30 minutes, cooling, is placed in loft drier for subsequent use.
6) battery composition and test: by TiO
2nano-electrode is soaked in the some time in the solution that contains organic dye sensitized dose of the present invention, makes dye composition be adsorbed in TiO
2on the nano particle of electrode, then take out TiO
2electrode, after slightly rinsing and be dried, covers electrode (5) sealing with solvent.Afterwards, electrolytic solution (4) is injected, then by inlet seal, can complete useful area is 0.24cm
2dye sensitization solar battery.The dye sensitization solar battery of gained, under the illumination of AM1.5, is tested to its short-circuit current (Jsc), open circuit voltage (Voc), packing factor (FF), photoelectric transformation efficiency (η).
7) comparative example: make in the same manner described above dye sensitization solar battery, concrete battery structure is shown in Fig. 1.Battery data test is used U.S.'s NEWPORT ORIEL solar simulator and Keithley KEITHLEY data acquisition unit, under the standard light of AM1.5 is irradiated, short-circuit current (Jsc), open circuit voltage (Voc), packing factor (FF), the photoelectric transformation efficiency (η) of test dye respectively, test result representative data is in table 1 and Fig. 2.The uv-visible absorption spectra spectrogram of representative organic dye sensitized agent molecule is shown in Fig. 3.
8) opto-electronic conversion performance measuring result: organic dye sensitized dose of conjugation aromatic ring chromophoric group higly branched chain derivatize of the present invention, the photoelectric transformation efficiency of its dye sensitization solar battery reaches 80% of current the recognized standard dyestuff N719 efficiency.
The representative dyestuff that the commercial N719 of table 1 and embodiment 1-49 obtain is for dye-sensitized nano solar cell properties Data Comparison
| Dyes | V oc/V | J sc/mA?cm 2 | FF/% | Effi./% |
| CGTD-DSSC-025 | 0.67 | 15.15 | 63.63 | 6.44 |
| CGTD-DSSC-029 | 0.70 | 14.85 | 63.04 | 6.58 |
| CGTD-DSSC-031 | 0.71 | 15.51 | 65.15 | 7.17 |
| CGTD-DSSC-036 | 0.74 | 11.96 | 65.80 | 5.81 |
| CGTD-DSSC-039 | 0.69 | 14.83 | 64.45 | 6.64 |
| CGTD-DSSC-55 | 0.69 | 15.85 | 67.78 | 7.41 |
| CGTD-DSSC-64 | 0.68 | 16.69 | 68.09 | 7.60 |
| CGTD-DSSC-66 | 0.57 | 14.64 | 65.30 | 5.46 |
| CGTD-DSSC-69 | 0.65 | 15.02 | 62.71 | 6.11 |
| N719 | 0.70 | 18.76 | 65.80 | 8.62 |
Claims (28)
1. one kind organic dye sensitized dose, it is characterized in that: its general formula is suc as formula shown in I; Wherein, A is electron deficiency unit, is electron acceptor(EA); D is electron rich unit, is electron donor(ED); N is the neutral organic structure of electronics unit; π is the unit connecting with conjugated structure; Ar is two or more the conjugation molectron in conjugation aromatic ring chromophoric group unit or these structural units; B is and the nanometer micropore surface phase bonding of dye sensitization battery light electricity anode, thereby goes out the structural unit of formation electric current by dying electric transmission that quick agent molecule excites after visible and UV-irradiation; N is 1,2,3,4,5 or 6;
2. organic dye sensitized dose as claimed in claim 1, it is characterized in that: the substituting group form that described A is following arbitrary structure:
Wherein, R
1, R
2, R
3, R
6, R
7, R
44, R
47and R
48independently select separately hydrogen, C
1-4alkyl, C
1-4alkoxyl group, C
5-10the C that replaces of aryl, trifluoromethyl
5-10aryl and trifluoromethyl in one or more; R
4and R
5independently be selected from separately hydrogen, C
1-4alkyl, C
1-4alkoxyl group, halogen, cyano group, formyl radical and trifluoromethyl in one or more; R
8, R
9, R
10, R
11, R
12, R
13, R
14, R
45and R
46be independently C separately
5-10alkyl.
3. organic dye sensitized dose as claimed in claim 2, it is characterized in that: described R
1, R
2, R
3, R
6or R
7described in C
1-4alkyl be methyl;
And/or, described R
1, R
2, R
3, R
6, R
7, R
44, R
47and R
48described in C
1-4alkoxyl group be methoxyl group;
And/or, described R
1, R
2, R
3, R
6, R
7, R
44, R
47and R
48described in C
5-10aryl be phenyl;
And/or, described R
1, R
2, R
3, R
6, R
7, R
44, R
47and R
48described in trifluoromethyl replace C
5-10aryl be trifluoromethyl;
And/or, described R
4or R
5described in C
1-4alkyl be methyl;
And/or, described R
4or R
5described in C
1-4alkoxyl group be methoxyl group;
And/or, described R
4or R
5described in halogen be F;
And/or, described R
8, R
9, R
10, R
11, R
12, R
13, R
14, R
45and R
46described in C
5-10alkyl be
4. organic dye sensitized dose as claimed in claim 2, it is characterized in that: the substituting group form that described A is following arbitrary structure:
5. organic dye sensitized dose as claimed in claim 4, it is characterized in that: described A is arbitrary substituting group as follows:
6. organic dye sensitized dose as claimed in claim 1, it is characterized in that: the substituting group form that described D is following arbitrary structure:
Wherein, R
15be selected from hydrogen, C
1-4alkyl, C
1-10alkoxyl group and
in one or more, the integer that wherein n is 1-10; R
16be selected from C
1-4alkyl and C
6-10aryl in one or two; R
17, R
18, R
19and R
20independently be selected from separately hydrogen, C
1-6alkyl, C
1-6alkoxyl group and C
1-6alkoxyl group replace phenyl in one or more; R
21and R
22independently be selected from separately hydrogen, C
1-4alkyl, C
6-10aryl, C
1-4alkoxyl group and C
1-4alkylamino in one or more; R
23, R
24, R
25, R
26and R
27independently be selected from separately hydrogen, C
1-4alkyl and C
1-4alkoxyl group in one or more.
7. organic dye sensitized dose as claimed in claim 6, it is characterized in that: described R
15described in C
1-10alkoxyl group be methoxyl group or
And/or, described R
16described in C
1-4alkyl be methyl;
And/or, described R
16described in C
6-10aryl be phenyl;
And/or, described R
17, R
18, R
19or R
20described in C
1-6alkyl be
And/or, described R
17, R
18, R
19or R
20described in C
1-6alkoxyl group be methoxyl group or
And/or, described R
17, R
18, R
19or R
20described in C
1-6alkoxyl group replace phenyl be
or
And/or, described R
21or R
22described in C
1-4alkyl be methyl, ethyl, propyl group, sec.-propyl or the tertiary butyl;
And/or, described R
21or R
22described in C
6-10aryl be phenyl;
And/or, described R
21or R
22described in C
1-4alkoxyl group be methoxyl group, oxyethyl group, propoxy-, isopropoxy or tert.-butoxy;
And/or, described R
21or R
22described in C
1-4alkylamino be methylamino-, ethylamino-or Propylamino.
8. organic dye sensitized dose as claimed in claim 6, it is characterized in that: the substituting group form that described D is following arbitrary structure:
9. organic dye sensitized dose as claimed in claim 8, it is characterized in that: described D is arbitrary substituting group as follows:
10. organic dye sensitized dose as claimed in claim 1, it is characterized in that: described N is arbitrary substituting group as follows:
C
1-20straight or branched alkyl, the C being replaced by one or more halogens
1-4alkyl, C
1-6alkylamino, C
1-6alkyl sodium sulfonate,
integer that wherein m is 1-10,
with
wherein R
28for C
1-20straight or branched alkyl.
11. organic dye sensitized dose as claimed in claim 10, it is characterized in that: the C described in described N
1-20straight or branched alkyl be
And/or, the C being replaced by one or more halogens described in described N
1-4alkyl be the C being replaced by one or more fluorine atoms
1-4alkyl;
And/or, the C described in described N
1-6alkylamino be
And/or, the C described in described N
1-6alkyl sodium sulfonate be
And/or, described in described N
And/or, described in described N
And/or, described
described in m be 1,2 or 3.
12. organic dye sensitized dose as claimed in claim 11, it is characterized in that: the C being replaced by one or more fluorine atoms described in described N
1-4alkyl be
13. organic dye sensitized dose as claimed in claim 10, it is characterized in that: described N is arbitrary substituting group as follows:
14. organic dye sensitized dose as claimed in claim 1, it is characterized in that: the substituting group form that described π is following arbitrary structure:
c
5-10aryl,
Wherein, R
29and R
30independently be selected from separately one or more in hydrogen, phenyl, furyl, pyrryl and thienyl; R
31, R
32and R
33independently be selected from separately hydrogen, C
1-10straight or branched alkyl, C
1-10straight or branched alkoxyl group, thienyl and by C
1-6alkyl replace thienyl in one or more; R
34, R
35, R
36, R
37, R
38and R
39independently be selected from separately hydrogen, C
1-10straight or branched alkyl and C
1-10straight or branched alkoxyl group in one or more.
15. organic dye sensitized dose as claimed in claim 14, it is characterized in that: the C described in described π
5-10aryl be phenyl;
And/or, described R
31, R
32, R
33or R
38described in C
1-10straight or branched alkyl be methyl, ethyl, propyl group, butyl, amyl group or hexyl;
And/or, described R
31, R
32or R
33described in C
1-10straight or branched alkoxyl group be
16. organic dye sensitized dose as claimed in claim 15, it is characterized in that: the substituting group form that described π is following arbitrary structure:
17. organic dye sensitized dose as claimed in claim 16, it is characterized in that: described π is arbitrary substituting group as follows:
18. organic dye sensitized dose as claimed in claim 1, it is characterized in that: the substituting group form that described Ar is following arbitrary structure:
19. organic dye sensitized dose as claimed in claim 18, it is characterized in that: described Ar is arbitrary substituting group as follows:
20. organic dye sensitized dose as claimed in claim 1, it is characterized in that: the substituting group form that described B is following arbitrary structure:
Wherein, R
40and R
41independently be selected from separately hydrogen, carboxyl, hydroxyl, C
2-6alkynyl and C
1-4carboxyl in one or more; R
42be selected from carboxyl,
cyano group, C
6-10aryl, the C being replaced by one or more cyano group
6-10aryl and by the C of one or more carboxyl substituted
6-10aryl in one or more; R
43for C
1～C
9straight chain or branched paraffin.
21. organic dye sensitized dose as claimed in claim 20, it is characterized in that: described R
40or R
41described in C
2-6alkynyl be ethynyl;
And/or, described R
40or R
41described in C
1-4carboxyl be
And/or, described R
42described in C
6-10aryl be phenyl;
And/or, described R
42described in the C being replaced by one or more cyano group
6-10aryl be the phenyl being replaced by one or more cyano group;
And/or, described R
42described in by the C of one or more carboxyl substituted
6-10aryl be by the phenyl of one or more carboxyl substituted.
22. organic dye sensitized dose as claimed in claim 21, it is characterized in that: described B is arbitrary substituting group as follows:
23. organic dye sensitized dose as claimed in claim 1, it is characterized in that: described as shown in general formula I organic dye sensitized dose, for thering is the compound of following arbitrary general formula:
Wherein π
1, π
2the all definition of the π as described in claim 1,14,15,16 or 17 any one of definition.
24. organic dye sensitized dose as claimed in claim 23, it is characterized in that: described as shown in general formula I organic dye sensitized dose is following arbitrary compound:
25. organic dye sensitized dose or its salt as described in claim 1～24 any one are the purposes of light-sensitive coloring agent in photoelectric conversion technique.
26. organic dye sensitized dose or preparation methods of its salt as described in claim 1～24 any one; it is characterized in that: Ar is the preparation method of thienyl, π terthienyl general formula compound 1 while being thienyl; it comprises the following steps: under gas shield, in organic solvent, by compound 2 with
carry out condensation reaction, obtain compound 1;
Wherein, the definition of A is as described in claim 1～5 any one; The definition of B is as described in claim 1 or 62; The definition of D is as described in claim 1,6,7,8 or 9 any one.
The preparation method of 27. organic dye sensitized dose or its salt as claimed in claim 26, is characterized in that: Ar is the preparation method of thienyl, π terthienyl general formula compound 1 while being thienyl, and it comprises following route:
Route one, comprise the following steps:
Step 1: in solvent, under the condition that alkali and catalyzer exist, compound 8 and 2-bromothiophene are carried out to Suzuki linked reaction, obtain described compound 7;
Step 2: in organic solvent, under the condition that alkali and catalyzer exist, compound 7 and duplex tetramethyl ethylene ketone boric acid ester are carried out to nucleophilic substitution reaction, obtain described compound 6;
Step 3: in solvent, under the condition that alkali and catalyzer exist, compound 6 and compound B-11 are carried out to Suzuki linked reaction, obtain described compound 5;
Step 4: in organic solvent, compound 5 and N-bromo-succinimide are carried out to substitution reaction, obtain described compound 4;
Step 5: in solvent, under the condition that alkali and catalyzer exist, compound 3 and compound 4 are carried out to Suzuki linked reaction, obtain described compound 2;
Step 6: in organic solvent, by compound 2 with
carry out condensation reaction, obtain compound 1;
Route two comprises the following steps:
Step 1: in solvent, under the condition that alkali and catalyzer exist, compound 10 and compound B-11 are carried out to Suzuki linked reaction, obtain described compound P ';
Step 2: in organic solvent, compound P ' is carried out to substitution reaction with N-bromo-succinimide, obtain described compound Q ';
Step 3: in solvent, under the condition that alkali and catalyzer exist, by compound Q ' carry out Suzuki linked reaction with compound 3, obtain described compound 9;
Step 4: in solvent, under the condition that alkali and catalyzer exist, compound 8 and compound 9 are carried out to Suzuki linked reaction, obtain described compound 2;
Step 5: in organic solvent, by compound 2 with
carry out condensation reaction, obtain compound 1;
Route three comprises the following steps:
Step 1: in organic solvent, compound B-11 and N-N-iodosuccinimide are carried out to substitution reaction, obtain described compound 16;
Step 2: in solvent, under the condition that alkali and catalyzer exist, compound 3 and compound 16 are carried out to Suzuki linked reaction, obtain described compound 15;
Step 3: in organic solvent, under the condition that acid exists, compound 15 and carbonyl-protection base are carried out to condensation reaction, obtain described compound 14;
Step 4: in organic solvent, under the condition that radical initiator exists, compound 14 and tributyltin chloride are carried out to substitution reaction, obtain described compound 13;
Step 5: in solvent, under the condition that catalyzer exists, compound 12 and compound 13 are carried out to Suzuki linked reaction, obtain described compound 11;
Step 6: in organic solvent, compound 11 and acid are carried out to oxidizing reaction and obtain compound 2;
Step 7: in organic solvent, by compound 2 with
carry out condensation reaction, obtain compound 1;
Route four comprises the following steps:
Step 1: under the condition that acid exists, compound B-11 and carbonyl-protection base are carried out to condensation reaction, obtain described compound R ';
Step 2: in organic solvent, under the condition that radical initiator exists, by compound R ' carry out substitution reaction with tributyltin chloride, obtain described compound S ';
Step 3: in solvent, under the condition that catalyzer exists, by compound S ' carry out Suzuki linked reaction with compound 12, obtain described compound 18;
Step 4: in organic solvent, compound 18 and N-bromo-succinimide are carried out to substitution reaction, obtain described compound 17;
Step 5: in solvent, under the condition that alkali and catalyzer exist, compound 17 and compound 3 are carried out to Suzuki linked reaction, obtain described compound 11;
Step 6: in organic solvent, compound 11 and acid are carried out to oxidizing reaction and obtain compound 2;
Step 7: in organic solvent, by compound 2 with
carry out condensation reaction, obtain compound 1;
Route five comprises the following steps:
Step 1: in solvent, under the condition that alkali and catalyzer exist, compound 20 and compd A 1 are carried out to Suzuki linked reaction, obtain described compound 057-1;
Step 2: in organic solvent, compound 057-1 and N-bromo-succinimide are carried out to substitution reaction, obtain described compound T ';
Step 3: under the condition that acid exists, compound T ' is carried out to condensation reaction with carbonyl-protection base, obtain described compound U ';
Step 4: in organic solvent, under the condition that radical initiator exists, compound U ' is carried out to substitution reaction with tributyltin chloride, obtain described compound V ';
Step 5: in organic solvent, under the condition that catalyzer exists, compound 19 is carried out to Suzuki linked reaction with compound V ', obtain described compound 18;
Step 6: in organic solvent, compound 18 and N-bromo-succinimide are carried out to substitution reaction, obtain described compound 17;
Step 7: in solvent, under the condition that alkali and catalyzer exist, compound 17 and compound 3 are carried out to Suzuki linked reaction, obtain described compound 11;
Step 8: in organic solvent, compound 11 and acid are carried out to oxidizing reaction and obtain compound 2;
Step 9: in organic solvent, by compound 2 with
carry out condensation reaction, obtain compound 1;
28. compounds 1, compound 2, compound 3, compound 4, compound 5, compound 6, compound 7, compound 8, compound 9, compound 10, compound 11, compound 12, compound 13, compound 14, compound 15, compound 16, compound 17, compound 18, compound 19, compound B-11, compound P ', compound Q ', compound R ', compound S ', compound T ', compound U ', compound V ', compd A 1 or compound 057-1
Wherein, the definition of A is as described in claim 1～5 any one; The definition of B is as described in claim 1 or 62; The definition of D is as described in claim 1,6,7,8 or 9 any one.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410122668.3A CN104073017B (en) | 2013-03-28 | 2014-03-28 | Organic dye sensitized dose, preparation method and the application in photoelectric conversion |
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2013101066497 | 2013-03-28 | ||
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Cited By (7)
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| KR20160111565A (en) * | 2015-03-16 | 2016-09-27 | 부산대학교 산학협력단 | New terthiophen compound and use thereof |
| CN110759899A (en) * | 2019-06-28 | 2020-02-07 | 杭州职业技术学院 | High-rigidity quinoxaline dye sensitizer and preparation method and application thereof |
| KR20200016572A (en) * | 2018-08-07 | 2020-02-17 | 전북대학교산학협력단 | Benzothiadiazole compound and perovskite solar cell comprising the same |
| CN110845489A (en) * | 2019-11-13 | 2020-02-28 | 南京邮电大学 | Asymmetric V-type organic dye sensitizer and preparation method and application thereof |
| CN113896724A (en) * | 2021-10-09 | 2022-01-07 | 吉林大学 | Organic red light micromolecule based on benzothiadiazole-pyreneimidazole and application of organic red light micromolecule in preparation of non-doped organic electroluminescent device |
| CN114014837A (en) * | 2021-10-29 | 2022-02-08 | 南京碳硅人工智能生物医药技术研究院有限公司 | Design and synthesis of novel probe for visually monitoring viscosity fluctuation of living cells |
| CN115160348A (en) * | 2022-07-06 | 2022-10-11 | 中山大学 | Method for direct boronization of aromatic C-H bond under illumination without metal catalysis |
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| CN116217559B (en) * | 2022-12-29 | 2024-04-02 | 浙江工业大学 | Carbazole compound with antenna and preparation method and application thereof |
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| TW201114844A (en) * | 2009-06-19 | 2011-05-01 | Dongjin Semichem Co Ltd | Novel organic dye and preparation thereof |
| CN101602759A (en) * | 2009-07-07 | 2009-12-16 | 武汉大学 | Pyrrole group-containing compound and its production and use |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| KR20160111565A (en) * | 2015-03-16 | 2016-09-27 | 부산대학교 산학협력단 | New terthiophen compound and use thereof |
| KR101699155B1 (en) | 2015-03-16 | 2017-01-24 | 부산대학교 산학협력단 | New terthiophen compound and use thereof |
| KR20200016572A (en) * | 2018-08-07 | 2020-02-17 | 전북대학교산학협력단 | Benzothiadiazole compound and perovskite solar cell comprising the same |
| KR102123902B1 (en) | 2018-08-07 | 2020-06-17 | 전북대학교산학협력단 | Benzothiadiazole compound and perovskite solar cell comprising the same |
| CN110759899A (en) * | 2019-06-28 | 2020-02-07 | 杭州职业技术学院 | High-rigidity quinoxaline dye sensitizer and preparation method and application thereof |
| CN110759899B (en) * | 2019-06-28 | 2020-09-25 | 杭州职业技术学院 | High-rigidity quinoxaline dye sensitizer and preparation method and application thereof |
| CN110845489A (en) * | 2019-11-13 | 2020-02-28 | 南京邮电大学 | Asymmetric V-type organic dye sensitizer and preparation method and application thereof |
| CN113896724A (en) * | 2021-10-09 | 2022-01-07 | 吉林大学 | Organic red light micromolecule based on benzothiadiazole-pyreneimidazole and application of organic red light micromolecule in preparation of non-doped organic electroluminescent device |
| CN113896724B (en) * | 2021-10-09 | 2023-11-24 | 吉林大学 | Organic red light micromolecule based on benzothiadiazole-pyrene imidazole and application thereof in preparation of undoped organic electroluminescent device |
| CN114014837A (en) * | 2021-10-29 | 2022-02-08 | 南京碳硅人工智能生物医药技术研究院有限公司 | Design and synthesis of novel probe for visually monitoring viscosity fluctuation of living cells |
| CN115160348A (en) * | 2022-07-06 | 2022-10-11 | 中山大学 | Method for direct boronization of aromatic C-H bond under illumination without metal catalysis |
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| CN104073017B (en) | 2018-12-14 |
| WO2014154028A1 (en) | 2014-10-02 |
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