CN107964257B - Organic dye compound with quinolinium ion skeleton structure and preparation method and application thereof - Google Patents
Organic dye compound with quinolinium ion skeleton structure and preparation method and application thereof Download PDFInfo
- Publication number
- CN107964257B CN107964257B CN201610915159.5A CN201610915159A CN107964257B CN 107964257 B CN107964257 B CN 107964257B CN 201610915159 A CN201610915159 A CN 201610915159A CN 107964257 B CN107964257 B CN 107964257B
- Authority
- CN
- China
- Prior art keywords
- organic dye
- dye compound
- quinolinium
- quinolinium ion
- skeleton structure
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 150000001875 compounds Chemical class 0.000 title claims abstract description 69
- 238000002360 preparation method Methods 0.000 title description 13
- -1 quinolinium ion Chemical class 0.000 claims abstract description 71
- 125000001424 substituent group Chemical group 0.000 claims abstract description 41
- 125000000026 trimethylsilyl group Chemical group [H]C([H])([H])[Si]([*])(C([H])([H])[H])C([H])([H])[H] 0.000 claims abstract description 10
- 239000011203 carbon fibre reinforced carbon Substances 0.000 claims abstract description 9
- HMDDXIMCDZRSNE-UHFFFAOYSA-N [C].[Si] Chemical compound [C].[Si] HMDDXIMCDZRSNE-UHFFFAOYSA-N 0.000 claims abstract description 4
- 125000001072 heteroaryl group Chemical group 0.000 claims description 38
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 33
- 238000003786 synthesis reaction Methods 0.000 claims description 32
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical group CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 24
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical class N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 claims description 23
- 239000011941 photocatalyst Substances 0.000 claims description 20
- 150000002466 imines Chemical class 0.000 claims description 19
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 18
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 18
- 125000000008 (C1-C10) alkyl group Chemical group 0.000 claims description 17
- 125000003172 aldehyde group Chemical group 0.000 claims description 17
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 17
- 239000010931 gold Substances 0.000 claims description 17
- 229910052737 gold Inorganic materials 0.000 claims description 17
- 238000006243 chemical reaction Methods 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 14
- 125000003368 amide group Chemical group 0.000 claims description 13
- 125000004185 ester group Chemical group 0.000 claims description 13
- 229910052736 halogen Inorganic materials 0.000 claims description 13
- 150000002367 halogens Chemical class 0.000 claims description 13
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 12
- 125000003545 alkoxy group Chemical group 0.000 claims description 12
- 125000002541 furyl group Chemical group 0.000 claims description 12
- 239000003960 organic solvent Substances 0.000 claims description 12
- 125000004076 pyridyl group Chemical group 0.000 claims description 12
- 125000001544 thienyl group Chemical group 0.000 claims description 12
- 239000003054 catalyst Substances 0.000 claims description 11
- 125000001637 1-naphthyl group Chemical group [H]C1=C([H])C([H])=C2C(*)=C([H])C([H])=C([H])C2=C1[H] 0.000 claims description 10
- 125000001622 2-naphthyl group Chemical group [H]C1=C([H])C([H])=C2C([H])=C(*)C([H])=C([H])C2=C1[H] 0.000 claims description 10
- 125000003282 alkyl amino group Chemical group 0.000 claims description 10
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 10
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 10
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 10
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 claims description 10
- 238000006555 catalytic reaction Methods 0.000 claims description 9
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 8
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 8
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 8
- 239000012954 diazonium Substances 0.000 claims description 8
- 150000001989 diazonium salts Chemical class 0.000 claims description 8
- 238000006352 cycloaddition reaction Methods 0.000 claims description 7
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 6
- 230000003197 catalytic effect Effects 0.000 claims description 6
- 229940126214 compound 3 Drugs 0.000 claims description 5
- 125000002943 quinolinyl group Chemical group N1=C(C=CC2=CC=CC=C12)* 0.000 claims description 5
- 230000002194 synthesizing effect Effects 0.000 claims description 5
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 4
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 claims description 4
- 125000002883 imidazolyl group Chemical group 0.000 claims description 4
- 125000001041 indolyl group Chemical group 0.000 claims description 4
- 150000007529 inorganic bases Chemical class 0.000 claims description 4
- 238000006053 organic reaction Methods 0.000 claims description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 4
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 3
- 229910002651 NO3 Inorganic materials 0.000 claims description 3
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 3
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 3
- 125000003118 aryl group Chemical group 0.000 claims description 3
- 150000002343 gold Chemical class 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- VLTRZXGMWDSKGL-UHFFFAOYSA-M perchlorate Inorganic materials [O-]Cl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-M 0.000 claims description 3
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 claims description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 3
- ITMCEJHCFYSIIV-UHFFFAOYSA-M triflate Chemical compound [O-]S(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-M 0.000 claims description 3
- FJDQFPXHSGXQBY-UHFFFAOYSA-L caesium carbonate Chemical compound [Cs+].[Cs+].[O-]C([O-])=O FJDQFPXHSGXQBY-UHFFFAOYSA-L 0.000 claims description 2
- 229910000024 caesium carbonate Inorganic materials 0.000 claims description 2
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 2
- 239000012046 mixed solvent Substances 0.000 claims description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 2
- LPNYRYFBWFDTMA-UHFFFAOYSA-N potassium tert-butoxide Chemical compound [K+].CC(C)(C)[O-] LPNYRYFBWFDTMA-UHFFFAOYSA-N 0.000 claims description 2
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 claims 3
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims 1
- 239000000975 dye Substances 0.000 description 90
- OKKJLVBELUTLKV-VMNATFBRSA-N methanol-d1 Chemical compound [2H]OC OKKJLVBELUTLKV-VMNATFBRSA-N 0.000 description 31
- 230000015572 biosynthetic process Effects 0.000 description 18
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 15
- 238000005160 1H NMR spectroscopy Methods 0.000 description 15
- 239000007787 solid Substances 0.000 description 15
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 10
- 238000004020 luminiscence type Methods 0.000 description 9
- 239000000047 product Substances 0.000 description 8
- ZHNUHDYFZUAESO-UHFFFAOYSA-N Formamide Chemical compound NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 description 6
- 150000001299 aldehydes Chemical class 0.000 description 6
- 125000000524 functional group Chemical group 0.000 description 6
- 239000000463 material Substances 0.000 description 5
- 230000003287 optical effect Effects 0.000 description 5
- 238000006862 quantum yield reaction Methods 0.000 description 5
- 238000011160 research Methods 0.000 description 5
- 230000008859 change Effects 0.000 description 4
- 239000007795 chemical reaction product Substances 0.000 description 4
- 238000013461 design Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000007850 fluorescent dye Substances 0.000 description 4
- 238000003384 imaging method Methods 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- SMWDFEZZVXVKRB-UHFFFAOYSA-O hydron;quinoline Chemical compound [NH+]1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-O 0.000 description 3
- 238000005286 illumination Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- LKUDPHPHKOZXCD-UHFFFAOYSA-N 1,3,5-trimethoxybenzene Chemical compound COC1=CC(OC)=CC(OC)=C1 LKUDPHPHKOZXCD-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 102000053602 DNA Human genes 0.000 description 2
- 108020004414 DNA Proteins 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- NQRYJNQNLNOLGT-UHFFFAOYSA-N Piperidine Chemical compound C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 description 2
- 241000405217 Viola <butterfly> Species 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 150000001345 alkine derivatives Chemical class 0.000 description 2
- 239000007853 buffer solution Substances 0.000 description 2
- 150000004696 coordination complex Chemical class 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- ZBKIUFWVEIBQRT-UHFFFAOYSA-N gold(1+) Chemical compound [Au+] ZBKIUFWVEIBQRT-UHFFFAOYSA-N 0.000 description 2
- CXKWCBBOMKCUKX-UHFFFAOYSA-M methylene blue Chemical compound [Cl-].C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 CXKWCBBOMKCUKX-UHFFFAOYSA-M 0.000 description 2
- 229960000907 methylthioninium chloride Drugs 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000012074 organic phase Substances 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 239000012429 reaction media Substances 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000005556 structure-activity relationship Methods 0.000 description 2
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 238000004293 19F NMR spectroscopy Methods 0.000 description 1
- GODVAYLZXZQBFP-UHFFFAOYSA-N 2-(4-methoxyphenyl)ethynyl-trimethylsilane Chemical compound COC1=CC=C(C#C[Si](C)(C)C)C=C1 GODVAYLZXZQBFP-UHFFFAOYSA-N 0.000 description 1
- GOLORTLGFDVFDW-UHFFFAOYSA-N 3-(1h-benzimidazol-2-yl)-7-(diethylamino)chromen-2-one Chemical compound C1=CC=C2NC(C3=CC4=CC=C(C=C4OC3=O)N(CC)CC)=NC2=C1 GOLORTLGFDVFDW-UHFFFAOYSA-N 0.000 description 1
- BXRFQSNOROATLV-UHFFFAOYSA-N 4-nitrobenzaldehyde Chemical compound [O-][N+](=O)C1=CC=C(C=O)C=C1 BXRFQSNOROATLV-UHFFFAOYSA-N 0.000 description 1
- 235000005811 Viola adunca Nutrition 0.000 description 1
- 240000009038 Viola odorata Species 0.000 description 1
- 235000013487 Viola odorata Nutrition 0.000 description 1
- 235000002254 Viola papilionacea Nutrition 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- 210000004027 cell Anatomy 0.000 description 1
- 230000008602 contraction Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000006880 cross-coupling reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 125000000664 diazo group Chemical group [N-]=[N+]=[*] 0.000 description 1
- 201000010099 disease Diseases 0.000 description 1
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 1
- YQGOJNYOYNNSMM-UHFFFAOYSA-N eosin Chemical compound [Na+].OC(=O)C1=CC=CC=C1C1=C2C=C(Br)C(=O)C(Br)=C2OC2=C(Br)C(O)=C(Br)C=C21 YQGOJNYOYNNSMM-UHFFFAOYSA-N 0.000 description 1
- GNBHRKFJIUUOQI-UHFFFAOYSA-N fluorescein Chemical compound O1C(=O)C2=CC=CC=C2C21C1=CC=C(O)C=C1OC1=CC(O)=CC=C21 GNBHRKFJIUUOQI-UHFFFAOYSA-N 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 150000002391 heterocyclic compounds Chemical class 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- TUEAQGKEELYBCO-UHFFFAOYSA-N indolizine Chemical group C1=CC=CN2C=CC=C21.C1=CC=CN2C=CC=C21 TUEAQGKEELYBCO-UHFFFAOYSA-N 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 230000002438 mitochondrial effect Effects 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 238000011913 photoredox catalysis Methods 0.000 description 1
- GUOHRXPYGSKUGT-UHFFFAOYSA-N quinolizinium Chemical compound C1=CC=CC2=CC=CC=[N+]21 GUOHRXPYGSKUGT-UHFFFAOYSA-N 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 210000000329 smooth muscle myocyte Anatomy 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- ANRHNWWPFJCPAZ-UHFFFAOYSA-M thionine Chemical compound [Cl-].C1=CC(N)=CC2=[S+]C3=CC(N)=CC=C3N=C21 ANRHNWWPFJCPAZ-UHFFFAOYSA-M 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0272—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing elements other than those covered by B01J31/0201 - B01J31/0255
- B01J31/0275—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing elements other than those covered by B01J31/0201 - B01J31/0255 also containing elements or functional groups covered by B01J31/0201 - B01J31/0269
-
- B01J35/39—
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D295/00—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms
- C07D295/16—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms acylated on ring nitrogen atoms
- C07D295/18—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms acylated on ring nitrogen atoms by radicals derived from carboxylic acids, or sulfur or nitrogen analogues thereof
- C07D295/182—Radicals derived from carboxylic acids
- C07D295/192—Radicals derived from carboxylic acids from aromatic carboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic System
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/0803—Compounds with Si-C or Si-Si linkages
- C07F7/081—Compounds with Si-C or Si-Si linkages comprising at least one atom selected from the elements N, O, halogen, S, Se or Te
- C07F7/0812—Compounds with Si-C or Si-Si linkages comprising at least one atom selected from the elements N, O, halogen, S, Se or Te comprising a heterocyclic ring
- C07F7/0814—Compounds with Si-C or Si-Si linkages comprising at least one atom selected from the elements N, O, halogen, S, Se or Te comprising a heterocyclic ring said ring is substituted at a C ring atom by Si
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic System
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/0803—Compounds with Si-C or Si-Si linkages
- C07F7/0825—Preparations of compounds not comprising Si-Si or Si-cyano linkages
- C07F7/083—Syntheses without formation of a Si-C bond
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1018—Heterocyclic compounds
- C09K2211/1025—Heterocyclic compounds characterised by ligands
- C09K2211/1029—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom
Abstract
The invention provides an organic dye compound with a quinolinium ion framework structure, which comprises a quinolinium ion framework structure, trimethylsilyl bonded with the quinolinium ion framework structure through a carbon-silicon single bond, and a substituent connected with the quinolinium ion framework structure through a carbon-carbon bond, wherein the structural general formula of the organic dye compound with the quinolinium ion framework structure is shown in the following structures I, II and III,
Description
Technical Field
The invention belongs to the technical field of organic dyes, and particularly relates to an organic dye compound with a quinolinium ion skeleton structure, and a preparation method and application thereof.
Background
Due to the characteristics of high sensitivity, adjustable properties and strong practicability, the phenomenon of light emission (fluorescence or phosphorescence) of organic molecules has been widely applied in the fields of synthetic chemistry, material science, chemical biology, biomedical science and the like, and has become an indispensable means or tool in academic research, technical development and product manufacturing. Therefore, designing and synthesizing novel organic dyes and studying their optical properties and application prospects have become a popular field of scientific research in recent years. In this field, most of the research is focused on the design and modification of existing luminophore (e.g. fluorescein, fluoroborate, coumarin, cyanine, etc.) derivatives, and relatively few research is focused on new luminophor scaffolds. In 2008 to 2015, Park group synthesized a series of organic light-emitting fuels (Soul-Fluor) based on indolizine (indolizine) skeleton by combining chemical means with computational chemistry aided design and synthesis. By changing the electronic property of the functional group, the light-emitting wavelength and the quantum yield can be effectively controlled. The novel organic dye has been successfully applied to the preparation of various fluorescent probes for live cell contrast imaging. In 2016, the You project group synthesizes a series of novel dyes which can be used for mitochondrial contrast imaging and are named Indazo-Fluor by a palladium-catalyzed oxidation cross-coupling method. Both compounds can realize the adjustability of the luminescent color (from blue to red) in the visible wavelength range by changing the functional groups or structures of the compounds, and have larger application potential.
The organic synthesis of photo-redox-catalyzed (visible light-catalyzed photo-oxygen catalysts) under the action of visible light is a rapidly developing field of heat in recent years. Organic molecules (especially carbon-hydrogen bonds and carbon-carbon bonds) are difficult to activate for organic reactions under low-energy visible light. One effective solution is to utilize some transition-metal complexes or organic dyes (organic dyes) which possess high oxidation or reduction potential under visible light as photocatalysts (photocatalysts) to activate organic molecules by Single Electron Transfer (SET), catalyzing organic reactions. In the selection of the photocatalyst, the use of the metal complex occupies the most part. In contrast, there are few cases where organic dyes have been successfully applied as photocatalysts in the field of organic photoredox catalysis. This is less related to the type of the existing organic photocatalyst and metal complex photocatalyst. Currently, organic photocatalysts which are relatively popular mainly comprise Methylene blue (Methylene blue), Rose Bengal (Rose Bengal) and eosin-y (eosin y), and the like, and have the defects of less selection range, relatively unclear photochemical properties, difficulty in adjusting oxidation or reduction potential by adjusting a structure, and the like. Therefore, if a class of organic dyes with adjustable optical properties and redox potentials can be developed, the organic dye has great significance in the field of organic synthesis of organic photo-induced redox catalysis.
Quinolinium ions (quinolizinium) are heterocyclic compounds which can be used for clinical practice treatment and have important effects on the treatment of smooth muscle cell contraction diseases. Meanwhile, the Ihmels and Viola task group found that quinolinium salt derivatives can also be used as positively charged organic dyes, can efficiently bind to deoxyribonucleic acid (DNA) and produce changes in optical properties. The Ihmels and Viola project group successfully applied quinolinium salt derivatives to the preparation of hydrogen peroxide fluorescent probes by introducing a group containing boric acid. Although there is a certain research on the luminescent property of quinolinium salts in the scientific community, there is no case of synthesizing organic dyes with quinolinium salts as the framework, which have adjustable luminescent property, by a simple method. Therefore, the development of a class of organic dyes which can be used for adjusting the light-emitting wavelength, have high quantum yield and modified structures and can be applied to multiple fields and take the quinolinium salt as the framework has important significance for the property exploration of the quinolinium salt derivatives and the exploration of the light-emitting phenomenon of organic small molecules.
Disclosure of Invention
The invention aims to provide an organic dye compound with a quinolinium ion framework structure and a preparation method thereof, and aims to solve the problem that no organic dye compound with the quinolinium ion framework structure is used as an organic chemical catalyst in the prior art; and the existing preparation method of the organic dye compound has the problems of relatively complex operation and difficulty in realizing adjustable luminescence property of the compound.
The invention also aims to provide application of the organic dye compound with the quinolinium ion skeleton structure.
The invention is realized in such a way that the organic dye compound with the quinolinium ion skeleton structure comprises the quinolinium ion skeleton structure, trimethylsilyl which is bonded with the quinolinium ion skeleton structure through a carbon-silicon single bond and a substituent which is connected with the quinolinium ion skeleton structure through a carbon-carbon bond, wherein the structural general formula of the organic dye compound with the quinolinium ion skeleton structure is shown in the following structures I, II and III,
wherein R is1Selected from phenylSubstituted phenyl, 1-naphthyl, 2-naphthyl, heteroaryl or substituted heteroaryl; the substituent of the substituted phenyl or the substituted heteroaryl is independently C1-C10 alkyl, benzyl, halogen, aldehyde group, carboxyl, ester group, cyano, nitro, hydroxyl, amino, amido, alkoxy, alkylamino or trifluoromethyl, and the number of the substituent is 1-5; the heteroaryl is furyl, thienyl, pyridyl, imidazolyl or indolyl;
R2the aryl group is selected from H, halogen, C1-C10 alkyl, phenyl, substituted phenyl, 1-naphthyl, 2-naphthyl, heteroaryl, benzyl, ester group or amido, wherein the substituent of the substituted phenyl is C1-C10 alkyl, benzyl, halogen, aldehyde group, carboxyl, ester group, cyano, nitro, hydroxyl, amino, amido, alkoxy, alkylamino or trifluoromethyl, the number of the substituents is 1-6, and the heteroaryl is furyl, thienyl or pyridyl;
R3selected from phenyl, substituted phenyl, 1-naphthyl, 2-naphthyl, heteroaryl or substituted heteroaryl; the substituent of the substituted phenyl or the substituted heteroaryl is C1-C10 alkyl, benzyl, halogen, aldehyde group, carboxyl, ester group, cyano, nitro, hydroxyl, amino, amido, alkoxy, alkylamino or trifluoromethyl, and the number of the substituent is 1-4; the heteroaryl is furyl, thienyl or pyridyl;
x is a counterion of the quinolinium salts, selected from chloride, sulfate, nitrate, acetate, perchlorate, tetrafluoroborate, hexafluorophosphate or triflate.
And a preparation method of the organic dye compound with the quinolinium ion skeleton structure, which comprises the following steps:
diazonium salts 1a, 1b and 1c with quinoline structures shown in formulas 1a, 1b and 1c, trimethylsilyl alkyne derivatives shown in formula 2 and monovalent gold complexes are respectively provided;
respectively dissolving the 1a, the 1b and the 1c in an organic solvent, adding the trimethylsilyl alkyne derivative 2, and carrying out catalytic cycloaddition reaction under the conditions of visible light irradiation and room temperature by using the monovalent gold complex as a catalyst to generate the organic dye compound with the quinolinium ion framework structure, wherein the structural general formulas are shown as the following structures I, II and III,
and the application of the organic dye compound with the quinolinium ion framework structure is that the organic dye compound with the quinolinium ion framework structure is used as a photocatalyst for carrying out photo-oxidation-reduction catalysis on organic synthesis reaction of aldehyde group and imine to form amido bond.
The organic dye compound with the quinolinium ion skeleton structure provided by the invention contains trimethylsilyl bonded with the quinolinium ion skeleton structure and a substituent connected with the quinolinium ion skeleton structure through a carbon-carbon bond, and is a new skeleton containing the quinolinium ion structure. The trimethylsilyl improves the hydrophobicity of the quinolinium ions, balances the original hydrophilicity of the quinolinium ions, enables the organic dye to be easily dissolved in an organic phase (such as dichloromethane, acetonitrile or methanol) and to be soluble in water or a buffer solution, and provides conditions for the organic synthesis reaction of aldehyde groups and imine to form amido bonds. The carbon-carbon bond includes R1、R3And a moiety R2The invention can change the substituent R1、R2、R3To adjust the luminescence property (luminescence wavelength) and realize the coverage from blue to red fluorescence. Specifically, when R is1When the electron-donating ability of the dye is enhanced, the red shift of the luminescent wavelength of the dye can be realized; when R is2Or R3When the electron donating ability of (2) is enhanced, blue shift of the emission wavelength of the dye can be realized. Thus, by selecting the appropriate R1、R2、R3As a substituent, an organic dye with the luminescence wavelength in the blue to red fluorescence band (450-700nm) can be selectively obtained. In addition, the organic dye compound with the quinolinium ion skeleton structure provided by the invention can be prepared by changing the substituent R1、R2、R3To adjust the stokes shift and thereby improve the electrical properties. Said quinolinium saltsThe organic dye compound with the ionic framework structure can be used as a catalyst for catalyzing organic synthesis reaction of forming amido bond by aldehyde group and imine through photo-oxidation-reduction. In addition, the organic dye compound with the quinolinium ion skeleton structure can also be used for biological contrast imaging, preparation of molecular fluorescent probes and the field of material science.
The preparation method of the organic dye compound with the quinolinium ion framework structure provided by the invention is used for synthesizing the new quinolinium framework structure by using a visible light and gold double catalytic cycloaddition method, and the method is simple and easy to control. The trimethylsilyl is used as a substituent in alkyne, and extremely high stereoselectivity is realized under the catalysis of visible light and gold, so that the reaction product has high purity, and no isomer is generated except a target product. Meanwhile, the method can rapidly synthesize organic dyes with different luminescent wavelengths and quantum yields and different structures by means of light and gold catalysis and combinatorial chemistry, and can selectively change the luminescent property of the quinolinium salt by simply changing functional groups, thereby breaking through the problems that the prior quinolinium salt luminescent structure-activity relationship is not clear, and new design and quinolinium salt dye synthesis are difficult to select. By adjusting functional groups in molecules, products can be combined into an organic dye library or a photocatalyst library and applied to a plurality of fields.
The application of the organic dye compound with the quinolinium ion framework structure provided by the invention utilizes the novel organic dye compound with the quinolinium ion framework structure as a photocatalyst to catalyze the organic synthesis reaction of aldehyde and imine to form amide. The invention is a brand new field in organic chemistry by using visible light as energy and utilizing an organic photocatalyst to catalyze organic synthesis, and the invention firstly applies the quinolinium salt organic dye in the field and has a pioneering effect.
Detailed Description
In order to make the technical problems, technical solutions and advantageous effects to be solved by the present invention more clearly apparent, the present invention is further described in detail below with reference to the following embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
The embodiment of the invention provides an organic dye compound with a quinolinium ion framework structure, which comprises a quinolinium ion framework structure, a trimethylsilyl group bonded with the quinolinium ion framework structure through a carbon-silicon single bond and a substituent group connected with the quinolinium ion framework structure through a carbon-carbon bond, wherein the structural general formula of the organic dye compound with the quinolinium ion framework structure is shown in the following structures I, II and III,
wherein R is1Selected from phenyl, substituted phenyl, 1-naphthyl, 2-naphthyl, heteroaryl or substituted heteroaryl; the substituent of the substituted phenyl or the substituted heteroaryl is independently C1-C10 alkyl, benzyl, halogen, aldehyde group, carboxyl, ester group, cyano, nitro, hydroxyl, amino, amido, alkoxy, alkylamino or trifluoromethyl, and the number of the substituent is 1-5; the heteroaryl is furyl, thienyl, pyridyl, imidazolyl or indolyl;
R2the aryl group is selected from H, halogen, C1-C10 alkyl, phenyl, substituted phenyl, 1-naphthyl, 2-naphthyl, heteroaryl, benzyl, ester group or amido, wherein the substituent of the substituted phenyl is C1-C10 alkyl, benzyl, halogen, aldehyde group, carboxyl, ester group, cyano, nitro, hydroxyl, amino, amido, alkoxy, alkylamino or trifluoromethyl, the number of the substituents is 1-6, and the heteroaryl is furyl, thienyl or pyridyl;
R3selected from phenyl, substituted phenyl, 1-naphthyl, 2-naphthyl, heteroaryl or substituted heteroaryl; the substituent of the substituted phenyl or the substituted heteroaryl is C1-C10 alkyl, benzyl, halogen, aldehyde group, carboxyl, ester group, cyano, nitro, hydroxyl, amino, amido, alkoxy, alkylamino or trifluoromethyl, and the number of the substituent is 1-4; the heteroaryl is furyl, thienyl or pyridyl;
x is a counterion of the quinolinium salts, selected from chloride, sulfate, nitrate, acetate, perchlorate, tetrafluoroborate, hexafluorophosphate or triflate.
Embodiments of the invention may be practiced by selecting substituent R1、R2、R3To adjust the luminescence property (luminescence wavelength) and realize the coverage from blue to red fluorescence. At the same time, it is possible to modify the substituents R1、R2、R3To adjust the stokes shift and thereby improve the electrical properties.
Preferably, the organic dye compound with the quinolinium ion skeleton structure comprises a compound with the following structure and derivatives thereof,
the organic dye compound with the quinolinium ion framework structure provided by the embodiment of the invention contains trimethylsilyl bonded with the quinolinium ion framework structure and a substituent connected with the quinolinium ion framework structure through a carbon-carbon bond, and is a new framework containing the quinolinium ion structure. The trimethylsilyl improves the hydrophobicity of the quinolinium ions, balances the original hydrophilicity of the quinolinium ions, enables the organic dye to be easily dissolved in an organic phase (such as dichloromethane, acetonitrile or methanol) and to be soluble in water or a buffer solution, and provides conditions for the organic synthesis reaction of aldehyde groups and imine to form amido bonds. The carbon-carbon bond comprises R1, R3 and partial R2 substituent, and the invention can change the substituent R1、R2、R3To adjust the luminescence property (luminescence wavelength) and realize the coverage from blue to red fluorescence. Specifically, when R is1When the electron-donating ability of the dye is enhanced, the red shift of the luminescent wavelength of the dye can be realized; when R is2Or R3When the electron donating ability of (2) is enhanced, blue shift of the emission wavelength of the dye can be realized. Thus, by selecting the appropriate R1、R2、R3As a substituent, an organic dye with the luminescence wavelength in the blue to red fluorescence band (450-700nm) can be selectively obtained. In addition, the invention provides a quinolinium ion skeleton junctionOrganic dye compounds, by varying the substituents R1、R2、R3To adjust the stokes shift and thereby improve the electrical properties. The organic dye compound with the quinolinium ion skeleton structure can be used as a catalyst for photo-oxidation-reduction catalysis of organic synthesis reaction of aldehyde group and imine to form amide bond. In addition, the organic dye compound with the quinolinium ion skeleton structure can also be used for biological contrast imaging, preparation of molecular fluorescent probes and the field of material science.
The organic dye compound with the quinolinium ion skeleton structure provided by the embodiment of the invention can be prepared by the following method.
The embodiment of the invention provides a preparation method of an organic dye compound with a quinolinium ion skeleton structure, which comprises the following steps:
s01, diazonium salts 1a, 1b and 1c with quinoline structures shown in formulas 1a, 1b and 1c, trimethylsilyl alkyne derivatives shown in formula 2 and monovalent gold complexes are respectively provided;
s02, dissolving the 1a, the 1b and the 1c in an organic solvent respectively, adding the trimethylsilyl alkyne derivative 2, and carrying out catalytic cycloaddition reaction under the conditions of visible light irradiation and room temperature by using the monovalent gold complex as a catalyst to generate the organic dye compound with the quinolinium ion framework structure, wherein the structural general formulas are shown as the structures I, II and III,
in the above step S01, the diazonium salts 1a, 1b, 1c having a quinoline structure represented by the formulas 1a, 1b, 1c, and the trimethylsilylalkyne derivatives represented by the formula 2 can be prepared from the prior art documents. The monovalent gold complex, i.e. the gold (I) complex, is commercially available.
Preferably, in order to obtain the organic dye compound with the quinolinium ion skeleton structure with high yield and high purity, the molar ratio of the diazonium salt 1a or 1b or 1c with the quinolinium structure, the trimethylsilyl alkyne derivative 2 and the monovalent gold complex is (1.15-1.25): (0.95-1.05): (0.09-0.11). More preferably, the molar ratio of the diazonium salt 1a or 1b or 1c having a quinoline structure, the trimethylsilyne derivative 2 and the monovalent gold complex is 1.2:1: 0.1.
Preferably, the monovalent gold complex is Ph3PAuCl. The yield of the reaction can be greatly improved by adopting a monovalent gold complex containing triphenylphosphine or derivatives thereof as a ligand, namely a gold (I) complex as a catalyst.
In step S02, it is preferable that the organic solvent is acetonitrile, or the organic solvent is a mixed solvent of acetonitrile and at least one of methanol, ethanol, propanol, isopropanol, butanol, tetrahydrofuran, toluene, dioxane, dichloromethane, and chloroform. The preferred organic solvent is capable of efficiently dissolving the reactants and is safe as a reaction medium without causing chemical reactions with the reaction materials and the reaction products.
The room temperature condition in the embodiment of the present invention refers to a conventional room temperature condition, including a temperature of 10 to 30 ℃, preferably 25 ℃.
The cycloaddition reaction of the embodiment of the present invention can be achieved only under the condition of visible light irradiation (illumination), and preferably, the visible light irradiation uses an LED blue (blue in the subsequent reaction formula), green, white or incandescent lamp as a light source. Specifically, when an LED light source is adopted, the power of the LED light source is more than or equal to 3W; when the incandescent lamp light source is adopted, the power of the incandescent lamp light source is more than or equal to 30W. Only when the light source power meets the conditions, the cycloaddition reaction mechanism can be catalyzed to be opened, and further the organic dye compound with the quinolinium ion framework structure shown in the following structures I, II and III is obtained.
According to the preparation method of the organic dye compound with the quinolinium ion framework structure, provided by the embodiment of the invention, a new quinolinium framework structure is synthesized by a method of double catalytic cycloaddition of visible light and gold, and the method is simple and easy to control. The trimethylsilyl is used as a substituent in alkyne, and extremely high stereoselectivity is realized under the catalysis of visible light and gold, so that the reaction product has high purity, and no isomer is generated except a target product. Meanwhile, the method can rapidly synthesize organic dyes with different luminescent wavelengths and quantum yields and different structures by means of light and gold catalysis and combinatorial chemistry, and can selectively change the luminescent property of the quinolinium salt by simply changing functional groups, thereby breaking through the problems that the prior quinolinium salt luminescent structure-activity relationship is not clear, and new design and quinolinium salt dye synthesis are difficult to select. By adjusting functional groups in molecules, products can be combined into an organic dye library or a photocatalyst library and applied to a plurality of fields.
The embodiment of the invention provides application of the organic dye compound with the quinolinium ion framework structure, wherein the organic dye compound with the quinolinium ion framework structure is used as a photocatalyst and used for carrying out photo-oxidation-reduction catalysis on organic synthesis reaction of aldehyde groups and imine to form amide bonds.
Specifically, the organic dye compound with the quinolinium ion skeleton structure is used as a photocatalyst to catalyze the organic reaction of synthesizing amide bond by oxidizing aldehyde and imine, and comprises the following steps:
q01, providing an aldehyde compound shown in a formula 3, an imine compound shown in a formula 4 and an organic dye compound with the quinolinium ion skeleton structure,
and Q02, dissolving the aldehyde compound 3 and the imine compound 4 in an organic solvent, adding the organic dye compound with the quinolinium ion skeleton structure as a catalyst, and carrying out chemical reaction at room temperature under the conditions of visible light irradiation and alkalinity to generate the amide compound shown in the formula 5, wherein the reaction formula is shown as follows,
wherein, in the formulas 3 and 5, RaSelected from phenyl, substituted phenyl, 1-naphthyl, 2-naphthyl, heteroaryl or substituted heteroaryl; the substituent of the substituted phenyl or the substituted heteroaryl is C1-C10 alkyl, benzyl, halogen, aldehyde group, carboxyl, ester group, cyano, nitro, hydroxyl, amino, amido, alkoxy, alkylamino or trifluoromethyl, and the number of the substituent is 1-5;the heteroaryl is furyl, thienyl, pyridyl, imidazolyl or indolyl;
Rb、Rcrespectively selected from C1-C10 alkyl, cycloalkyl, phenyl, substituted phenyl, 1-naphthyl, 2-naphthyl, heteroaryl or benzyl; the substituent of the substituted phenyl is C1-C10 alkyl and alkoxy, and the number of the substituent is 1-5; the heteroaryl group is furyl, thienyl or pyridyl.
Specifically, in the step Q01, the aldehyde compound represented by formula 3 and the imine compound represented by formula 4 can be obtained by conventional methods, and can be obtained by themselves. The organic dye compound with the quinolinium ion skeleton structure is prepared by the method.
Preferably, in order to obtain a high-yield and high-purity product, the molar ratio of the aldehyde compound 3, the imine compound 4 and the organic dye compound with a quinolinium ion skeleton structure is 1: 2: 0.05.
in the step Q02, the organic solvent is preferably at least one of methanol, ethanol, propanol, isopropanol, butanol, tetrahydrofuran, toluene, dioxane, dichloromethane, and chloroform. The preferred organic solvent is capable of efficiently dissolving the reactants and is safe as a reaction medium without causing chemical reactions with the reaction materials and the reaction products.
The room temperature condition in the embodiment of the present invention refers to a conventional room temperature condition, including a temperature of 10 to 30 ℃, preferably 25 ℃.
In the embodiment of the present invention, the aldehyde compound 3 and the imine compound 4 are used to prepare the amide compound, and the reaction is performed under both the alkaline condition and the visible light irradiation (illumination) condition. Preferably, the alkaline condition is an inorganic base, and the inorganic base comprises at least one of sodium carbonate, potassium carbonate, cesium carbonate, sodium methoxide and potassium tert-butoxide. Preferably, the visible light irradiation is LED blue, green, white or incandescent lamp as a light source. Specifically, when an LED light source is adopted, the power of the LED light source is more than or equal to 3W; when the incandescent lamp light source is adopted, the power of the incandescent lamp light source is more than or equal to 30W. Only when the light source power satisfies the above conditions, the organic dye compound having a quinolinium ion skeleton structure can sufficiently exert a catalytic action to obtain the amide compound represented by formula 5.
The application of the organic dye compound with the quinolinium ion framework structure provided by the embodiment of the invention utilizes the novel organic dye compound with the quinolinium ion framework structure as a photocatalyst to catalyze the organic synthesis reaction of aldehyde and imine to form amide, and has higher yield. The invention is a brand new field in organic chemistry by using visible light as energy and utilizing an organic photocatalyst to catalyze organic synthesis, and the invention firstly applies the quinolinium salt organic dye in the field and has a pioneering effect.
The following description will be given with reference to specific examples.
Example 1: synthesis of organic dye I-1
Diazo salt 1a (0.6mmol), (4-methoxyphenylethynyl) trimethylsilane 2a (0.5mmol), Ph having quinoline structure3PAuCl (0.05mmol) and acetonitrile (5mL) were mixed in a 20mL glass tube and sealed with a rubber stopper. The air in the test tube was removed by a freeze thaw pump cycle and flushed with nitrogen. After the mixture in the test tube is returned to room temperature, the test tube is placed under the irradiation of a blue LED light source for reaction for 16 hours. After completion of the reaction, the solvent was removed and the product was chromatographed to give the product as an orange solid in 69% yield.
1H NMR(400MHz,MeOD)δ9.12(d,J＝9.0Hz,1H),9.02(d,J＝8.5Hz,1H),8.92(d,J＝8.9Hz,1H),8.43(d,J＝8.2Hz,1H),8.24(d,J＝7.2Hz,1H),8.17(t,J＝7.6Hz,1H),8.04(t,J＝7.6Hz,1H),7.72(m,2H),7.48-7.32(m,3H),7.06(d,J＝8.7Hz,2H),3.90(s,3H),0.14(s,9H).
13C NMR(101MHz,MeOD)δ163.17,150.61,148.01,142.64,138.45,138.05,135.19,134.68,134.52,132.40,131.03,130.41,130.20,130.17,129.90,127.85,126.29,119.47,115.80,55.95,1.98.
Example 2: synthesis of organic dye I-2
See example 1 for a yellow solid in 68% yield.
1H NMR(400MHz,MeOD)δ9.16(d,J＝9.0Hz,1H),9.04(d,J＝8.4Hz,1H),8.94(d,J＝8.9Hz,1H),8.46(d,J＝8.3Hz,1H),8.25(d,J＝7.1Hz,1H),8.18(t,J＝7.3Hz,1H),8.06(t,J＝7.7Hz,1H),7.77-7.66(m,2H),7.66-7.58(m,1H),7.52(m,4H),7.39-7.26(m,1H),0.12(s,9H).
13C NMR(101MHz,MeOD)δ150.61,147.87,142.81,139.97,138.26,137.85,135.24,134.94,133.12,131.88,131.20,130.51,130.26,130.19,129.92,127.91,126.40,126.28,119.46,1.88.
Example 3: synthesis of organic dye I-3
See example 1 for a yellow solid in 65% yield.
1H NMR(400MHz,MeOD)δ9.12(d,J＝9.0Hz,1H),9.02(d,J＝8.5Hz,1H),8.92(d,J＝8.9Hz,1H),8.43(d,J＝8.2Hz,1H),8.24(d,J＝7.2Hz,1H),8.17(t,J＝7.6Hz,1H),8.04(t,J＝7.6Hz,1H),7.72(m,2H),7.48-7.32(m,3H),7.06(d,J＝8.7Hz,2H),3.90(s,3H),0.14(s,9H).
13C NMR(101MHz,MeOD)δ150.76,146.82,142.90,138.20,137.76,136.37,135.49,135.40,135.32,135.16,131.29,130.65,130.28,130.02,127.93,126.42,126.32,119.50,117.66,117.44,1.92.
19F NMR(376MHz,MeOD)δ-110.24,-154.92.
Example 4: synthesis of organic dye I-4
See example 1 for a yellow solid in 66% yield.
1H NMR(400MHz,MeOD)δ9.16(d,J＝9.0Hz,1H),9.05(d,J＝8.3Hz,1H),8.96(d,J＝8.9Hz,1H),8.46(d,J＝8.2Hz,1H),8.27(d,J＝7.7Hz,1H),8.19(t,J＝7.5Hz,1H),8.07(t,J＝7.5Hz,1H),7.79-7.63(m,2H),7.55(m,4H),7.49-7.38(m,1H),0.15(s,10H).
13C NMR(101MHz,MeOD)δ150.76,146.60,142.97,138.57,138.15,138.12,137.66,135.33,135.28,134.69,131.35,130.73,130.67,130.30,130.26,130.07,130.05,127.94,126.49,126.31,119.50,1.95.
Example 5: synthesis of organic dye I-5
See example 1 for a yellow solid in 58% yield.
1H NMR(400MHz,MeOD)δ9.16(d,J＝9.0Hz,1H),9.05(d,J＝8.4Hz,1H),8.96(d,J＝8.9Hz,1H),8.46(d,J＝8.2Hz,1H),8.27(d,J＝7.9Hz,1H),8.19(t,J＝7.6Hz,1H),8.07(t,J＝7.7Hz,1H),7.73(m,7.8Hz,4H),7.45(m,8.3Hz,3H),0.15(s,9H).
13C NMR(101MHz,MeOD)δ150.76,146.65,142.97,138.96,138.14,137.65,135.34,135.25,134.83,133.71,131.36,130.76,130.31,130.26,130.09,130.05,127.94,126.50,126.31,126.22,119.49,1.95.
Example 6: synthesis of organic dye I-6
See example 1 for a yellow solid in 31% yield.
1H NMR(400MHz,MeOD)δ9.16(d,J＝8.9Hz,1H),9.04(d,J＝8.3Hz,1H),8.95(d,J＝8.9Hz,1H),8.46(d,J＝8.3Hz,1H),8.27(d,J＝8.0Hz,1H),8.19(t,J＝7.6Hz,1H),8.07(t,J＝7.6Hz,1H),7.91(d,J＝8.3Hz,2H),7.74(m,2H),7.44(t,J＝8.0Hz,1H),7.31(d,J＝8.3Hz,2H),0.15(s,9H).
13C NMR(101MHz,MeOD)δ150.73,146.84,142.95,139.81,139.39,138.16,137.65,135.33,135.21,134.69,131.35,130.77,130.30,130.25,130.10,130.03,127.93,126.50,126.29,119.47,97.84,1.95.
Example 7: synthesis of organic dye I-7
See example 1 for a yellow solid in 56% yield.
1H NMR(400MHz,MeOD)δ9.17(d,J＝9.0Hz,1H),9.06(d,J＝8.4Hz,1H),8.96(d,J＝8.9Hz,1H),8.47(d,J＝8.2Hz,1H),8.26(d,J＝7.8Hz,1H),8.19(t,J＝7.6Hz,1H),8.15-8.03(m,3H),7.76-7.67(m,2H),7.63(d,J＝8.1Hz,2H),7.37(t,J＝7.5Hz,1H),0.13(s,9H).
13C NMR(101MHz,MeOD)δ150.69,147.00,142.99,138.14,137.68,135.32,133.11,131.41,130.79,130.36,130.21,130.09,130.01,127.94,126.47,126.31,119.46,1.96.
Example 8: synthesis of organic dye I-8
See example 1 for a yellow solid in 68% yield.
1H NMR(400MHz,MeOD)δ9.13(d,J＝9.0Hz,1H),9.02(d,J＝8.4Hz,1H),8.95(d,J＝8.9Hz,1H),8.43(d,J＝8.2Hz,1H),8.29(d,J＝8.0Hz,1H),8.18(m,8.5Hz,1H),8.06(d,J＝7.9Hz,1H),7.82(t,J＝7.5Hz,1H),7.68(s,1H),7.60(d,J＝8.5Hz,1H),6.24(s,1H),0.28(s,1H).
13C NMR(101MHz,MeOD)δ150.60,146.90,145.53,142.89,139.56,138.15,137.68,135.85,135.22,131.25,130.94,130.30,130.20,130.15,129.85,127.93,126.31,125.98,125.94,119.48,113.45,2.14.
Example 9: synthesis of organic dye I-9
See example 1 for a yellow solid in 65% yield.
1H NMR(400MHz,MeOD)δ9.13(d,J＝9.0Hz,1H),9.03(d,J＝8.4Hz,1H),8.93(d,J＝8.9Hz,1H),8.44(d,J＝8.2Hz,1H),8.26(d,J＝7.0Hz,1H),8.17(t,J＝7.3Hz,1H),8.05(t,J＝7.6Hz,1H),7.94(dd,J＝2.8,1.0Hz,1H),7.85-7.69(m,2H),7.59(dd,J＝5.0,3.0Hz,1H),7.53-7.36(m,1H),7.00(dd,J＝4.9,0.8Hz,1H),0.20(d,J＝3.1Hz,9H).
13C NMR(101MHz,MeOD)δ150.92,143.27,143.21,140.66,138.65,138.42,135.60,135.57,132.80,131.62,131.43,131.20,130.63,130.56,130.44,130.30,129.59,128.32,126.71,125.57,119.89,2.15.
Example 10: synthesis of organic dye I-10
See example 1 for a specific operation, orange-red solid, 63% yield.
1H NMR(400MHz,MeOD)δ11.03(s,1H),10.65(d,J＝8.3Hz,1H),10.36(d,J＝8.1Hz,1H),10.05(d,J＝8.3Hz,1H),9.78(t,J＝7.6Hz,1H),9.66(t,J＝7.5Hz,1H),9.37(d,J＝9.0Hz,1H),9.29(t,J＝7.7Hz,1H),9.01(d,J＝8.3Hz,1H),8.94(t,J＝7.8Hz,1H),8.62(d,J＝8.8Hz,1H),5.77(s,1H),5.45(s,1H),1.71(s,1H).
13C NMR(101MHz,MeOD)δ165.33,163.22,148.65,139.19,138.37,137.17,135.80,134.58,132.15,131.48,130.30,130.24,130.01,127.80,127.53,126.82,126.41,121.84,115.81,55.95,54.09,1.93.
Example 11: synthesis of organic dye I-11
See example 1 for a specific operation, orange solid, 65% yield.
1H NMR(400MHz,MeOD)δ9.49(s,1H),9.10(d,J＝8.4Hz,1H),8.83(d,J＝8.1Hz,1H),8.50(d,J＝8.3Hz,1H),8.24(t,J＝7.5Hz,1H),8.12(t,J＝7.7Hz,1H),7.95(d,J＝1.8Hz,1H),7.90(d,J＝8.9Hz,1H),7.78(t,J＝7.6Hz,1H),7.60(m,1H),7.45(t,J＝7.7Hz,1H),7.04(d,J＝4.6Hz,1H),4.23(s,3H),0.21(s,9H).
13C NMR(101MHz,MeOD)δ165.33,149.57,143.51,139.94,138.97,138.32,137.56,135.80,132.63,131.65,130.99,130.46,130.36,130.29,129.22,127.87,127.50,126.88,126.44,125.70,121.79,54.10,1.66.
Example 12: synthesis of organic dye I-12
See example 1 for a yellow solid in 46% yield.
1H NMR(400MHz,MeOD)δ9.17(d,J＝9.0Hz,1H),9.06(d,J＝8.4Hz,1H),8.96(d,J＝8.9Hz,1H),8.48(d,J＝8.2Hz,1H),8.28(d,J＝8.2Hz,1H),8.20(t,J＝7.7Hz,1H),8.07(t,J＝7.8Hz,1H),7.74(m,4.7Hz,2H),7.66(d,J＝8.3Hz,2H),7.57(m,2.8Hz,4H),7.51-7.34(m,4H),0.17(s,9H).
13C NMR(101MHz,MeOD)δ150.42,142.65,139.31,137.47,135.03,133.25,133.01,132.98,132.23,131.04,130.46,130.05,129.95,129.82,129.74,129.62,129.20,128.38,127.65,126.93,126.20,123.37,119.21,92.64,88.34,1.74.
Example 13: synthesis of organic dye III-1
See example 1 for a red solid in 34% yield.
1H NMR(400MHz,MeOD)δ10.67(d,J＝8.5Hz,1H),10.58(d,J＝8.4Hz,1H),10.11(m,7.9Hz,2H),9.86(d,J＝7.8Hz,1H),9.82-9.52(m,5H),8.96(d,J＝8.8Hz,2H),8.57(d,J＝8.8Hz,2H),4.70(s,6H),1.80(s,9H).
13C NMR(101MHz,MeOD)δ153.45,149.75,147.01,139.34,135.87,135.56,134.26,134.14,134.01,133.10,132.85,131.31,130.22,128.96,128.91,127.99,125.70,125.50,121.81,120.94,112.92,39.78,1.27.
Example 14: synthesis of organic dye III-2
See example 1 for a yellow solid in 50% yield.
1H NMR(400MHz,MeOD)δ9.12(d,J＝8.5Hz,1H),9.05(d,J＝8.5Hz,1H),8.60(d,J＝8.4Hz,1H),8.40(d,J＝7.4Hz,1H),8.31(d,J＝8.0Hz,1H),8.28-7.96(m,5H),7.56(d,J＝8.6Hz,2H),7.28(d,J＝8.6Hz,2H),3.98(s,3H),0.22(s,9H).
13C NMR(101MHz,MeOD)δ163.39,149.82,145.80,138.97,135.80,135.69,134.62,134.41,133.25,132.91,131.42,130.46,128.96,128.91,128.03,126.58,125.67,125.60,122.05,115.96,55.75,1.18.
Example 15: synthesis of organic dye III-3
See example 1 for a greenish solid in 56% yield.
1H NMR(400MHz,MeOD)δ10.70(d,J＝8.5Hz,1H),10.63(d,J＝8.5Hz,1H),10.18(d,J＝8.3Hz,1H),9.89(d,J＝7.4Hz,2H),9.85-9.54(m,5H),9.27(m,2H),9.07(t,J＝8.6Hz,2H),1.78(s,9H).
13C NMR(101MHz,MeOD)δ150.63,145.34,139.45,136.53,136.33,136.24,135.26,134.08,133.67,132.23,131.69,131.37,129.72,129.65,128.78,126.38,122.97,118.61,118.39,1.83.
Example 16 optical properties of organic dyes I-1 to 12, III-1 to 3.
The organic dyes I-1 to 12, III-1 to 3 synthesized according to the experimental operation can be excited in ultraviolet light or blue-violet visible light wave band to emit fluorescence from blue to red. Specific optical parameters including maximum absorption wavelength, molar absorption coefficient, maximum emission wavelength, stokes shift, and fluorescence quantum yield are shown in table 1 below.
TABLE 1
Example 17
The application of the novel organic dye taking quinolinium salt as a skeleton as a catalyst for catalyzing the synthesis reaction of the amide bond by oxidation.
P-nitrobenzaldehyde 3a (0.1mmol), piperidine 4a (0.2mmol), Na2CO3(0.2mmol), organic photocatalyst (0.005mmol) and acetonitrile (5mL) were mixed in a 20mL glass tube. The tube was placed under illumination by an LED blue light source for 24 hours. After the reaction was completed, 1,3, 5-trimethoxybenzene was used as an internal standard, and the reaction yield was calculated using the nuclear magnetic yield. The results obtained using the different photocatalysts are summarized in table 2 below.
TABLE 2
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents and improvements made within the spirit and principle of the present invention are intended to be included within the scope of the present invention.
Claims (12)
1. A quinolinium ion skeleton structure organic dye compound is characterized by comprising a quinolinium ion skeleton structure, a trimethylsilyl group bonded with the quinolinium ion skeleton structure through a carbon-silicon single bond and a substituent group connected with the quinolinium ion skeleton structure through a carbon-carbon bond, wherein the structural general formula of the quinolinium ion skeleton structure organic dye compound is shown in the following structures I, II and III,
wherein R is1Selected from phenyl, substituted phenyl, 1-naphthyl, 2-naphthyl, heteroaryl or substituted heteroaryl; the substituent of the substituted phenyl or the substituted heteroaryl is independently C1-C10 alkyl, halogen, aldehyde group, carboxyl, ester group, cyano, nitro, hydroxyl, amino, amido, alkoxy, alkylamino or trifluoromethyl, and the number of the substituent is 1-5; the heteroaryl is furyl, thienyl, pyridyl, imidazolyl or indolyl;
R2the aryl group is selected from H, halogen, C1-C10 alkyl, substituted phenyl, heteroaryl, ester group or amido, wherein the substituent of the substituted phenyl is C1-C10 alkyl, halogen, aldehyde group, carboxyl, ester group, cyano, nitro, hydroxyl, amino, amido, alkoxy, alkylamino or trifluoromethyl, the number of the substituents is 1-5, and the heteroaryl is furyl, thienyl or pyridyl;
R3selected from phenyl, substituted phenyl, 1-naphthyl, 2-naphthyl, heteroaryl or substituted heteroaryl; the substituent of the substituted phenyl or the substituted heteroaryl is C1-C10 alkyl, halogen, aldehyde group, carboxyl, ester group, cyano, nitro, hydroxyl, amino, amido, alkoxy, alkylamino or trifluoromethyl, and the number of the substituent is 1-4; the heteroaryl is furyl, thienyl or pyridyl;
x is a counterion of the quinolinium salts, selected from chloride, sulfate, nitrate, acetate, perchlorate, tetrafluoroborate, hexafluorophosphate or triflate,
or the organic dye compound with the quinolinium ion skeleton structure is
2. An organic dye compound with a quinolinium ion skeleton structure, which is characterized by comprising a compound with the following structure,
3. a method for producing the quinolinium ion skeleton structure organic dye compound as described in claim 1 or 2, comprising the steps of:
diazonium salts 1a, 1b and 1c with quinoline structures shown in formulas 1a, 1b and 1c, trimethylsilyl alkyne derivatives shown in formula 2 and monovalent gold complexes are respectively provided;
respectively dissolving the 1a, the 1b and the 1c in an organic solvent, adding the trimethylsilyl alkyne derivative 2, and carrying out catalytic cycloaddition reaction under the conditions of visible light irradiation and room temperature by using the monovalent gold complex as a catalyst to generate the organic dye compound with the quinolinium ion framework structure, wherein the structural general formulas are shown as the following structures I, II and III,
4. the method for preparing an organic dye compound having a quinolinium ion skeleton structure according to claim 3, wherein the molar ratio of said diazonium salt 1a or 1b or 1c having a quinolinium structure, said trimethylsilyl alkyne derivative 2, said monovalent gold complex is (1.15-1.25): (0.95-1.05): 0.09-0.11).
5. The method for preparing an organic dye compound having a quinolinium ion skeleton structure according to claim 4, wherein the molar ratio of the diazonium salt 1a or 1b or 1c having a quinolinium structure, the trimethylsilynyl derivative 2, and the monovalent gold complex is 1.2:1: 0.1.
6. The method according to claim 4, wherein the organic solvent is acetonitrile, or a mixed solvent of acetonitrile and at least one of methanol, ethanol, propanol, isopropanol, butanol, tetrahydrofuran, toluene, dioxane, dichloromethane, and chloroform.
7. The method according to claim 4, wherein the visible light irradiation is conducted using an LED blue, green, white or incandescent lamp as a light source;
when the LED light source is adopted, the power of the LED light source is more than or equal to 3W;
when the incandescent lamp light source is adopted, the power of the incandescent lamp light source is more than or equal to 30W.
8. The method for producing an organic dye compound having a quinolinium ion skeleton structure according to claim 4, wherein the monovalent gold complex is Ph3PAuCl。
9. The application of the organic dye compound with the quinolinium ion framework structure is characterized in that the organic dye compound with the quinolinium ion framework structure is used as a photocatalyst and used for carrying out photo-oxidation-reduction catalysis on organic synthesis reaction of aldehyde group and imine to form amido bond; wherein the structure of the organic dye compound with the quinolinium ion skeleton structure is shown as follows,
10. the use of a quinolinium ion skeletal structure organic dye compound as claimed in claim 9, wherein said quinolinium ion skeletal structure organic dye compound is used as a photocatalyst for catalyzing the organic reaction of aldehyde and imine for synthesizing amide bond, comprising the following steps:
there are provided an aldehyde compound represented by formula 3, an imine compound represented by formula 4, and an organic dye compound having a quinolinium ion skeleton structure according to claim 9,
dissolving the aldehyde compound 3 and the imine compound 4 in an organic solvent, adding the organic dye compound with the quinolinium ion skeleton structure as a catalyst, and carrying out chemical reaction at room temperature under the conditions of visible light irradiation and alkalinity to generate the amide compound shown in the formula 5, wherein the reaction formula is shown as follows,
wherein, in the formulas 3 and 5, RaSelected from phenyl substituted with nitro;
Rb、Rcare respectively selected from cycloalkyl, substituted phenyl, heteroaryl and C1-C10 alkyl; the substituent of the substituted phenyl is alkoxy or C1-C10 alkyl, and the number of the substituents is 1-5; the heteroaryl group is furyl, thienyl or pyridyl.
11. The use of the quinolinium ion skeleton structure organic dye compound according to claim 10, wherein the molar ratio of the aldehyde compound 3, the imine compound 4 and the quinolinium ion skeleton structure organic dye compound is 1: 2: 0.05; and/or
The organic solvent is at least one of methanol, ethanol, propanol, isopropanol, butanol, tetrahydrofuran, toluene, dioxane, dichloromethane and chloroform; and/or
The alkaline condition is inorganic base, and the inorganic base comprises at least one of sodium carbonate, potassium carbonate, cesium carbonate, sodium methoxide and potassium tert-butoxide.
12. Use of a quinolinium ion skeleton structure organic dye compound according to claim 10, wherein the visible light irradiation is with an LED blue, green, white or incandescent lamp as a light source;
when the LED light source is adopted, the power of the LED light source is more than or equal to 3W;
when the incandescent lamp light source is adopted, the power of the incandescent lamp light source is more than or equal to 30W.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610915159.5A CN107964257B (en) | 2016-10-20 | 2016-10-20 | Organic dye compound with quinolinium ion skeleton structure and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610915159.5A CN107964257B (en) | 2016-10-20 | 2016-10-20 | Organic dye compound with quinolinium ion skeleton structure and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN107964257A CN107964257A (en) | 2018-04-27 |
| CN107964257B true CN107964257B (en) | 2021-07-09 |
Family
ID=61996527
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610915159.5A Active CN107964257B (en) | 2016-10-20 | 2016-10-20 | Organic dye compound with quinolinium ion skeleton structure and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN107964257B (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115232120B (en) * | 2021-04-23 | 2023-09-05 | 香港理工大学深圳研究院 | PH fluorescent probe and synthesis method and application thereof |
| CN113402538B (en) * | 2021-05-08 | 2023-12-19 | 香港理工大学深圳研究院 | Fluorescent molecule taking quinolinium ions as framework and labeled polypeptide or protein thereof and preparation method |
| CN113527353B (en) * | 2021-06-25 | 2023-12-15 | 香港理工大学深圳研究院 | Fluorescent probe for detecting active oxygen molecules and preparation method and application thereof |
| CN113354676B (en) * | 2021-06-28 | 2023-09-05 | 香港理工大学深圳研究院 | Cysteine fluorescent probe and preparation method and application thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2000035924A1 (en) * | 1998-12-15 | 2000-06-22 | University Of Pittsburgh | Camptothecin analogs and methods of preparation thereof |
-
2016
- 2016-10-20 CN CN201610915159.5A patent/CN107964257B/en active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2000035924A1 (en) * | 1998-12-15 | 2000-06-22 | University Of Pittsburgh | Camptothecin analogs and methods of preparation thereof |
Non-Patent Citations (2)
| Title |
|---|
| "C-Silyl-Derivate von Chinolizinen";Leonhard Birkofer等;《Chem.Ber.》;19831231;第116卷;2564-2573 * |
| "Synthesis of Indeno-Fused Derivatives of Quinolizinium Salts,Imidazo[1,2-α]pyridine,Pyrido[1,2-α]indole,and 4H-Quinolizin-4-one via Benzannulated Enyne-Allenes";DAI Weixiang等;《J.Org.Chem.》;20050728;第70卷;6647-6652 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN107964257A (en) | 2018-04-27 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107964257B (en) | Organic dye compound with quinolinium ion skeleton structure and preparation method and application thereof | |
| CN110218220B (en) | Functionalized metal-organic framework compound, complex formed by functionalized metal-organic framework compound, and preparation method and application of functionalized metal-organic framework compound | |
| CN106543070B (en) | Carbazole-amides room temperature phosphorimetry molecule and its preparation method and application that N replaces | |
| CN110461820B (en) | Organic luminophores | |
| Chatterjee et al. | Visible-light-induced regioselective synthesis of polyheteroaromatic compounds | |
| Cruz-Navarro et al. | Structural diversity and luminescent properties of coordination complexes obtained from trivalent lanthanide ions with the ligands: tris ((1H-benzo [d] imidazol-2-yl) methyl) amine and 2, 6-bis (1H-benzo [d] imidazol-2-yl) pyridine | |
| CN105936639B (en) | Based on C2vThe group of the lanthanides permeability coordination polymer and its synthetic method of symmetrical ligand and application | |
| CN114040962A (en) | Red fluorescence emitting compounds for organelle imaging | |
| CN108752368A (en) | A kind of zinc-containing metal organic framework materials and its synthetic method and application with fluorescence identifying performance | |
| CN103709202B (en) | Ruthenium (II) complex and preparation method thereof and its it is used as the application of cell fluorescence dyestuff | |
| Liu et al. | Aggregation-induced emission and photocyclization of poly (hexaphenyl-1, 3-butadiene) s synthesized from “1+ 2” polycoupling of internal alkynes and arylboronic acids | |
| Wang et al. | Photocatalytic Approach for Construction of 5, 6-Dihydroimidazo [2, 1-a] isoquinolines and Their Luminescent Properties | |
| Hu et al. | Preparation and fluorescence properties of novel 2-quinolone derivatives and their corresponding Eu (III) complexes | |
| Wessig et al. | Fluorescent Dyes with Large Stokes Shifts Based on Benzo [1, 2‐d: 4, 5‐d'] bis ([1, 3] dithiole)(“S4‐DBD Dyes”) | |
| CN110981892B (en) | Covalent organic framework material with spiropyran molecular switch and preparation method and application thereof | |
| CN113004194A (en) | Circular polarization luminescent organic micro-nano crystal material and preparation method and application thereof | |
| CN110590788B (en) | 2-acyl-9H-pyrrolo [1,2-a]Synthesis method of indole compound | |
| JP2010241874A (en) | Fluorescent solvatochromic dye, and light-emitting film comprising the dye and preparation method therefor, and white light source apparatus comprising the light-emitting film | |
| Zhang et al. | An Optic/Proton Dual‐Controlled Fluorescence Switch based on Novel Photochromic Bithienylethene Derivatives | |
| CN112939936B (en) | Carbonyl azetidine substituted naphthalimide fluorescent dye and synthetic method and application thereof | |
| CN113501836A (en) | Star BODIPY near-infrared fluorescent dye and preparation method thereof | |
| CN106947469A (en) | Miscellaneous fluorescent dye of iso-indoles boron and its preparation method and application | |
| Shishlikova et al. | Directed Synthesis of Regioisomeric Monoaryl‐Substituted Pyridines Containing a Tricyanobutadiene Fragment and Study on Their Optical Properties | |
| Das et al. | Photoinduced Synthesis of 2-Trifluoromethylated Indoles through Oxidative Trifluoromethylation Using Langlois’ Reagent in the Absence of External Photocatalyst | |
| CN111620898B (en) | N 2 O-BOBPY fluorescent dye and preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |