CN108148086B - The preparation method of organic triplet photosensitizer with Host-guest Recognition group - Google Patents
The preparation method of organic triplet photosensitizer with Host-guest Recognition group Download PDFInfo
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- CN108148086B CN108148086B CN201810077194.3A CN201810077194A CN108148086B CN 108148086 B CN108148086 B CN 108148086B CN 201810077194 A CN201810077194 A CN 201810077194A CN 108148086 B CN108148086 B CN 108148086B
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- methylene chloride
- triplet
- photosensitizer
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- 239000003504 photosensitizing agent Substances 0.000 title claims abstract description 65
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 150000001875 compounds Chemical class 0.000 claims abstract description 204
- -1 Hexamethylene diamine Chemical class 0.000 claims abstract description 8
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 269
- 238000006243 chemical reaction Methods 0.000 claims description 81
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 72
- 239000002904 solvent Substances 0.000 claims description 60
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 56
- 238000000034 method Methods 0.000 claims description 52
- 238000004587 chromatography analysis Methods 0.000 claims description 48
- 238000000746 purification Methods 0.000 claims description 48
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 45
- 230000008569 process Effects 0.000 claims description 39
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 claims description 36
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 36
- LVTJOONKWUXEFR-FZRMHRINSA-N protoneodioscin Natural products O(C[C@@H](CC[C@]1(O)[C@H](C)[C@@H]2[C@]3(C)[C@H]([C@H]4[C@@H]([C@]5(C)C(=CC4)C[C@@H](O[C@@H]4[C@H](O[C@H]6[C@@H](O)[C@@H](O)[C@@H](O)[C@H](C)O6)[C@@H](O)[C@H](O[C@H]6[C@@H](O)[C@@H](O)[C@@H](O)[C@H](C)O6)[C@H](CO)O4)CC5)CC3)C[C@@H]2O1)C)[C@H]1[C@H](O)[C@H](O)[C@H](O)[C@@H](CO)O1 LVTJOONKWUXEFR-FZRMHRINSA-N 0.000 claims description 35
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 34
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 claims description 32
- LQZMLBORDGWNPD-UHFFFAOYSA-N N-iodosuccinimide Chemical compound IN1C(=O)CCC1=O LQZMLBORDGWNPD-UHFFFAOYSA-N 0.000 claims description 31
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 31
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 30
- FSYKKLYZXJSNPZ-UHFFFAOYSA-N sarcosine Chemical compound C[NH2+]CC([O-])=O FSYKKLYZXJSNPZ-UHFFFAOYSA-N 0.000 claims description 30
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims description 26
- JNGZXGGOCLZBFB-IVCQMTBJSA-N compound E Chemical compound N([C@@H](C)C(=O)N[C@@H]1C(N(C)C2=CC=CC=C2C(C=2C=CC=CC=2)=N1)=O)C(=O)CC1=CC(F)=CC(F)=C1 JNGZXGGOCLZBFB-IVCQMTBJSA-N 0.000 claims description 26
- 239000000047 product Substances 0.000 claims description 26
- 238000003756 stirring Methods 0.000 claims description 20
- 239000012043 crude product Substances 0.000 claims description 19
- MFFMQGGZCLEMCI-UHFFFAOYSA-N 2,4-dimethyl-1h-pyrrole Chemical compound CC1=CNC(C)=C1 MFFMQGGZCLEMCI-UHFFFAOYSA-N 0.000 claims description 18
- PAPNRQCYSFBWDI-UHFFFAOYSA-N DMP Natural products CC1=CC=C(C)N1 PAPNRQCYSFBWDI-UHFFFAOYSA-N 0.000 claims description 18
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 18
- 238000002156 mixing Methods 0.000 claims description 18
- RGHHSNMVTDWUBI-UHFFFAOYSA-N 4-hydroxybenzaldehyde Chemical compound OC1=CC=C(C=O)C=C1 RGHHSNMVTDWUBI-UHFFFAOYSA-N 0.000 claims description 17
- 235000019441 ethanol Nutrition 0.000 claims description 17
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 17
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 16
- 229910052760 oxygen Inorganic materials 0.000 claims description 16
- 238000010898 silica gel chromatography Methods 0.000 claims description 16
- 239000000243 solution Substances 0.000 claims description 16
- 239000000126 substance Substances 0.000 claims description 16
- 108010077895 Sarcosine Proteins 0.000 claims description 15
- 229910052757 nitrogen Inorganic materials 0.000 claims description 15
- 229940043230 sarcosine Drugs 0.000 claims description 15
- 229960005070 ascorbic acid Drugs 0.000 claims description 13
- 235000010323 ascorbic acid Nutrition 0.000 claims description 13
- 239000011668 ascorbic acid Substances 0.000 claims description 13
- 239000005457 ice water Substances 0.000 claims description 13
- 239000003480 eluent Substances 0.000 claims description 12
- PXIPVTKHYLBLMZ-UHFFFAOYSA-N sodium azide Substances [Na+].[N-]=[N+]=[N-] PXIPVTKHYLBLMZ-UHFFFAOYSA-N 0.000 claims description 12
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 11
- 239000001301 oxygen Substances 0.000 claims description 11
- 239000003054 catalyst Substances 0.000 claims description 10
- 239000011259 mixed solution Substances 0.000 claims description 10
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 9
- 239000007789 gas Substances 0.000 claims description 9
- 238000006073 displacement reaction Methods 0.000 claims description 8
- 239000012044 organic layer Substances 0.000 claims description 8
- 229940126062 Compound A Drugs 0.000 claims description 7
- NLDMNSXOCDLTTB-UHFFFAOYSA-N Heterophylliin A Natural products O1C2COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC2C(OC(=O)C=2C=C(O)C(O)=C(O)C=2)C(O)C1OC(=O)C1=CC(O)=C(O)C(O)=C1 NLDMNSXOCDLTTB-UHFFFAOYSA-N 0.000 claims description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 6
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 6
- 239000007795 chemical reaction product Substances 0.000 claims description 6
- 239000003795 chemical substances by application Substances 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 6
- 239000012046 mixed solvent Substances 0.000 claims description 6
- 239000000741 silica gel Substances 0.000 claims description 6
- 229910002027 silica gel Inorganic materials 0.000 claims description 6
- 229960001866 silicon dioxide Drugs 0.000 claims description 6
- 230000009471 action Effects 0.000 claims description 5
- 238000013019 agitation Methods 0.000 claims description 5
- 230000003197 catalytic effect Effects 0.000 claims description 5
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 5
- 229910000366 copper(II) sulfate Inorganic materials 0.000 claims description 5
- 238000004090 dissolution Methods 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 5
- 229940087646 methanolamine Drugs 0.000 claims description 5
- LWIHDJKSTIGBAC-UHFFFAOYSA-K tripotassium phosphate Chemical compound [K+].[K+].[K+].[O-]P([O-])([O-])=O LWIHDJKSTIGBAC-UHFFFAOYSA-K 0.000 claims description 5
- 229910000404 tripotassium phosphate Inorganic materials 0.000 claims description 5
- 238000010792 warming Methods 0.000 claims description 5
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical class [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 4
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 4
- 229910052799 carbon Inorganic materials 0.000 claims description 4
- 238000001914 filtration Methods 0.000 claims description 4
- 239000010410 layer Substances 0.000 claims description 4
- 239000003208 petroleum Substances 0.000 claims description 4
- 230000008859 change Effects 0.000 claims description 3
- 235000011152 sodium sulphate Nutrition 0.000 claims description 3
- 229940125904 compound 1 Drugs 0.000 claims description 2
- 230000015572 biosynthetic process Effects 0.000 abstract description 12
- 238000003786 synthesis reaction Methods 0.000 abstract description 11
- 238000012546 transfer Methods 0.000 abstract description 9
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 abstract description 3
- 230000037361 pathway Effects 0.000 abstract description 2
- 238000001338 self-assembly Methods 0.000 abstract description 2
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 10
- 239000002994 raw material Substances 0.000 description 10
- 238000001228 spectrum Methods 0.000 description 10
- 239000007832 Na2SO4 Substances 0.000 description 7
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 description 6
- 238000005160 1H NMR spectroscopy Methods 0.000 description 5
- 229910015900 BF3 Inorganic materials 0.000 description 5
- 230000005281 excited state Effects 0.000 description 5
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- 238000009792 diffusion process Methods 0.000 description 4
- 230000005284 excitation Effects 0.000 description 4
- 238000000605 extraction Methods 0.000 description 4
- 239000000543 intermediate Substances 0.000 description 4
- 239000003960 organic solvent Substances 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- PAAZPARNPHGIKF-UHFFFAOYSA-N 1,2-dibromoethane Chemical compound BrCCBr PAAZPARNPHGIKF-UHFFFAOYSA-N 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 150000004985 diamines Chemical class 0.000 description 3
- 229920001971 elastomer Polymers 0.000 description 3
- 239000000499 gel Substances 0.000 description 3
- 230000003993 interaction Effects 0.000 description 3
- 239000013067 intermediate product Substances 0.000 description 3
- 239000002808 molecular sieve Substances 0.000 description 3
- CPELXLSAUQHCOX-UHFFFAOYSA-N Hydrogen bromide Chemical compound Br CPELXLSAUQHCOX-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 238000012984 biological imaging Methods 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- NEHMKBQYUWJMIP-UHFFFAOYSA-N chloromethane Chemical class ClC NEHMKBQYUWJMIP-UHFFFAOYSA-N 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- WGLUMOCWFMKWIL-UHFFFAOYSA-N dichloromethane;methanol Chemical group OC.ClCCl WGLUMOCWFMKWIL-UHFFFAOYSA-N 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 230000005283 ground state Effects 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 238000006386 neutralization reaction Methods 0.000 description 2
- FEMOMIGRRWSMCU-UHFFFAOYSA-N ninhydrin Chemical compound C1=CC=C2C(=O)C(O)(O)C(=O)C2=C1 FEMOMIGRRWSMCU-UHFFFAOYSA-N 0.000 description 2
- 239000012074 organic phase Substances 0.000 description 2
- 230000020477 pH reduction Effects 0.000 description 2
- 230000001699 photocatalysis Effects 0.000 description 2
- 238000007146 photocatalysis Methods 0.000 description 2
- 238000002428 photodynamic therapy Methods 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 229910052761 rare earth metal Inorganic materials 0.000 description 2
- 150000002910 rare earth metals Chemical class 0.000 description 2
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- 125000005931 tert-butyloxycarbonyl group Chemical group [H]C([H])([H])C(OC(*)=O)(C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- 238000004809 thin layer chromatography Methods 0.000 description 2
- 125000003944 tolyl group Chemical group 0.000 description 2
- DWNBOPVKNPVNQG-LURJTMIESA-N (2s)-4-hydroxy-2-(propylamino)butanoic acid Chemical compound CCCN[C@H](C(O)=O)CCO DWNBOPVKNPVNQG-LURJTMIESA-N 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- 206010070834 Sensitisation Diseases 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 150000001345 alkine derivatives Chemical class 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 230000002146 bilateral effect Effects 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
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- RDHPKYGYEGBMSE-UHFFFAOYSA-N bromoethane Chemical compound CCBr RDHPKYGYEGBMSE-UHFFFAOYSA-N 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 229910052927 chalcanthite Inorganic materials 0.000 description 1
- 239000007806 chemical reaction intermediate Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000011097 chromatography purification Methods 0.000 description 1
- 238000004440 column chromatography Methods 0.000 description 1
- 238000012790 confirmation Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 125000003963 dichloro group Chemical group Cl* 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000007850 fluorescent dye Substances 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 239000004519 grease Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 229910000042 hydrogen bromide Inorganic materials 0.000 description 1
- 150000005204 hydroxybenzenes Chemical class 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 230000000873 masking effect Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 238000006053 organic reaction Methods 0.000 description 1
- 238000006552 photochemical reaction Methods 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 238000006862 quantum yield reaction Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000008313 sensitization Effects 0.000 description 1
- 231100000489 sensitizer Toxicity 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229920002379 silicone rubber Polymers 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- XHFLOLLMZOTPSM-UHFFFAOYSA-M sodium;hydrogen carbonate;hydrate Chemical class [OH-].[Na+].OC(O)=O XHFLOLLMZOTPSM-UHFFFAOYSA-M 0.000 description 1
- 239000011343 solid material Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
Classifications
-
- 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
- C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic Table
- C07F5/02—Boron compounds
- C07F5/022—Boron compounds without C-boron linkages
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1003—Carbocyclic compounds
- C09K2211/1007—Non-condensed systems
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1003—Carbocyclic compounds
- C09K2211/1011—Condensed systems
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- 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
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1018—Heterocyclic compounds
- C09K2211/1025—Heterocyclic compounds characterised by ligands
- C09K2211/1044—Heterocyclic compounds characterised by ligands containing two nitrogen atoms as heteroatoms
- C09K2211/1055—Heterocyclic compounds characterised by ligands containing two nitrogen atoms as heteroatoms with other heteroatoms
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- 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
- C09K2211/1059—Heterocyclic compounds characterised by ligands containing three nitrogen atoms as heteroatoms
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- 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
- C09K2211/1092—Heterocyclic compounds characterised by ligands containing sulfur as the only heteroatom
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- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Plural Heterocyclic Compounds (AREA)
Abstract
The preparation method of the invention discloses a kind of organic triplet photosensitizer with Host-guest Recognition group, belongs to photosensitizer synthesis technical field.The present invention passes through in C60Hexamethylene diamine is introduced in the organic triplet photosensitizer of-Bodipy binary compound on the middle position benzene ring position of Bodipy as supermolecule binding site, self assembly is carried out in the solution by the triplet photosensitizer with hyperon binding site and the supermolecule main block containing triplet receptor, within the scope of space length to molecular dimension between the triplet that furthers photosensitizer and triplet receptor, so that triplet photosensitizer need not be spread within the scope of useful life just can transmit energy, reduce the probability that triplet exciton is inactivated by non-radiative pathway, improve the energy transfer efficiency between photosensitizer and receptor, and then improve upper transfer efficiency.
Description
Technical field
The present invention relates to photosensitizer technical fields, and in particular to a kind of organic triplet light with Host-guest Recognition group
Quick dose of preparation method.
Background technique
With the rapid development of society, the worldwide energy shortage epoch quietly arrive, fossil fuel it is a large amount of
The mankind are driven increasingly to pay close attention to this inexhaustible safe environment protection type energy of solar energy using caused environmental problem
Source.The utilization efficiency for improving solar energy is the unremitting pursuit of each subject scientist.
Upper switch technology is that energy photons can be changed into a technology of high-energy photons, is improving Solar use
Efficiency field has important value, has a wide range of applications in fields such as photovoltaic, photocatalysis, biological imagings at present.It is real
Now there are many upper method converted, such as upper conversion can be achieved using rare earth metal, two-photon absorption dyestuff and mineral crystal.
Although conversion method has the characteristics that respective and special application field on these, there is also defects, such as rare earth
The absorbing ability of material is weaker, and operation wavelength is not easy to adjust, upper conversion quantum low efficiency etc.；Two-photon fluorescent dye (TPA) needs
High-intensitive exciting light is wanted, MW cm is generally required-2Rank is 10,000,000 times of sunlight intensity.These disadvantages make these skills
Art is restricted in the application of the emerging fields such as solar battery.
Conversion (Triplet-triplet annihilation upconversion, letter on T-T annihilation
Claim to convert on TTA), exciting light energy density needed for having because of it small (sunlight can be used as excitation light source), photosensitizer are to visible
The operation wavelength of strong, the upper conversion of the absorbability of light can facilitate the advantages that adjustable and receive significant attention.Triplet excited state, TTA:
T-T annihilation (between acceptor molecule), 1A*: the singlet excited of receptor.The upper converting system of TTA includes two parts:
Triplet photosensitizer (energy donor) and triplet receptor (burying in oblivion agent) reach its excitation after triplet sensitiser absorption exciting light
Singlet state reaches its excited triplet state by intersystem crossing (ISC)；Photosensitizer molecule in excited triplet state is in photosensitizer
When close with acceptor molecule, the triplet of acceptor molecule is transferred energy to by colliding, i.e. generation triplet-triplet energies
It shifts (TTET), so that the triplet excited state of acceptor molecule be made to obtain population；Two acceptor molecules in triplet excited state touch
It hits, buries in oblivion, the singlet excited of an acceptor molecule is generated with certain probability, another then returns to ground state；In substance
The acceptor molecule of excitation state (S1) is returned to ground state (S0) in the form of radiation transistion, the fluorescence converted in sending.
Triplet photosensitizer is mainly used as energy donor and causes new a photochemistry and photophysical process, such as sends out
Raw triplet-triplet energies transmitting or electron transmission etc..Ideal triplet photosensitizer should have strong visible light to inhale
Receipts ability, high ISC efficiency guarantee that molecule has higher triplet quantum yield, and the long triplet excited state service life is to guarantee to have foot
The enough time occurs energy transmission, participates in the features such as various optical physics, photochemical reaction.Molecule triplet excited state obtains effective cloth
In electroluminescent, phosphorescent biological imaging or molecule sensing, photodynamic therapy, (PDT, sensitization generate the triplet photosensitizer of office
Singlet oxygen, 1O2), photocatalysis organic reaction, the fields such as convert on T-T annihilation and have extensive use.
As can be seen that triplet photosensitizer is conversion skill on such from the introduction that the above triplet buries in oblivion upper switching mechanism
The indispensable a part of art, the photophysical property of triplet photosensitizer bury in oblivion upper transfer efficiency to triplet and play important work
With.Up to the present, the triplet photosensitizer with supermolecule binding site has not been reported.With supermolecule binding site
Triplet photosensitizer buries in oblivion upper transfer efficiency with very important influence for improving triplet.
Bury in oblivion upper switching mechanism from triplet to learn, in generation conversion need two component parts-triplet photosensitizer with
Receptor collaboration is completed, and energy can be transmitted by needing to diffuse near receptor after the excitation of triplet photosensitizer light, this is in certain molecules
It is very fatal defect in the system such as solid material of diffusion limited.
Summary of the invention
The preparation side of the purpose of the present invention is to provide a kind of organic triplet photosensitizer with Host-guest Recognition group
Method, to solve the problems, such as that existing photosensitizer transfer efficiency is low.
The technical scheme to solve the above technical problems is that
A kind of organic triplet photosensitizer with Host-guest Recognition group, has the following structure:
Its molecular formula are as follows: C102H57BF2N8O3S。
A kind of preparation method of organic triplet photosensitizer with Host-guest Recognition group, comprising:
(1) prepare compound F:
(11) compound A and 1 being utilized, 2- Bromofume synthesizes compound B, wherein compound A is parahydroxyben-zaldehyde,
The structure of compound B are as follows:
(12) compound B is reacted in shading environment in inert atmosphere with 2,4- dimethyl pyrrole and trifluoroacetic acid,
After reaction, DDQ, triethylamine and BF are sequentially added3·OEt2The reaction was continued, and compound C, the structure of compound C is made are as follows:
(13) compound D, the structure of compound D are synthesized using compound C and N-iodosuccinimide are as follows:
(14) compound D is mixed with 5- aldehyde radical -2- thienyl boric acid, K is then added3PO4·3H2O, then in indifferent gas
At catalyst Pd (OAc) in atmosphere2Under the action of synthesize compound E, the structure of compound E are as follows:
(15) compound E and NaN are utilized3Synthesize compound F, the structure of compound F are as follows:
(2) prepare compound c:
(21) 1,6- hexamethylene diamine and (BOC) are utilized2O synthesizes compound b, the structure of compound b are as follows:
(22) compound c, the structure of compound c is made using compound b and 3- propargyl bromide are as follows:
(3) compound F made from step (1) is mixed with compound c made from step (2), is added in an inert atmosphere
CuSO4·5H2O and ascorbic acid reaction, are made compound G, the structure of compound G are as follows:
(4) by compound G and C60It is mixed in inert atmosphere and reacts with sarcosine, organic triplet photosensitizer is made.
Further, in preferred embodiments of the present invention, prepare compound F includes process in detail below:
(11) hydroxy benzaldehyde is dissolved in ethyl alcohol, it is anti-at 75-80 DEG C that 1,2- Bromofume and potassium carbonate is then added
7.5-8.5h is answered, after confirming fully reacting using thin-layered chromatography, is filtered, compound B is made in purification；Wherein, hydroxy benzenes first
The molar ratio of aldehyde, 1,2- Bromofume and potassium carbonate is 1:(4.8-5.5): (1.0-1.2), the expansion used in thin-layered chromatography
Agent is methylene chloride；
(12) in an inert atmosphere, compound B and methylene chloride are added into reactor, while using and vacuumizing displacement nitrogen
The mode of gas removes the oxygen of dissolution in methylene chloride, and 2,4- dimethyl pyrrole and trifluoroacetic acid is then added in shading environment
Middle reaction 8-12h；After confirming fully reacting using thin-layered chromatography, DDQ stirring is added, reacts cooling reactant after 0.8-1.5h
System；Continue that triethylamine is added after stirring 10-20min, continues that BF is added dropwise after stirring 0.4-0.6h3·OEt2, mention after complete reaction
It is pure, compound C is made；Wherein, the molar ratio of compound B, 2,4- dimethyl pyrrole and DDQ are 1:2:1, triethylamine, BF3·
OEt2It is 10:10:1 with the molar ratio of compound B, trifluoroacetic acid is catalytic amount, and the solvent used in thin-layered chromatography is two
Chloromethanes and n-hexane are mixed according to the volume ratio of 1:1；
(13) compound C is dissolved in methylene chloride, under the conditions of ice-water bath, is added dropwise dissolved with N-iodosuccinimide
Dry methylene chloride solution reacts 0.8-1.2h, and after confirming fully reacting with thin-layered chromatography, compound D is made in purification；Its
In, the molar ratio of compound C and N-iodosuccinimide is 1:1, and the solvent used in thin-layered chromatography is methylene chloride
It is mixed with n-hexane according to the volume ratio of 1:1；
(14) compound D and 5- aldehyde radical -2- thienyl boric acid is dissolved in the in the mixed solvent that toluene and ethyl alcohol are constituted, stirring is equal
K is added after even3PO4·3H2Catalyst Pd (OAc) is added in inert atmosphere in O2The back flow reaction 7.5-8.5h at 75-85 DEG C,
After confirming fully reacting with thin-layered chromatography, stop heating, be cooled to room temperature, compound E is made after purification；Wherein, compound
D, 5- aldehyde radical -2- thienyl boric acid, K3PO4·3H2O and Pd (OAc)2Molar ratio be 1:3:2:0.05, use in thin-layered chromatography
Solvent be that methylene chloride and n-hexane are mixed according to the volume ratio of 1:1；
(15) by NaN3It is dissolved in DMSO, compound E is then added dropwise and reacts 8-12min, after complete reaction, purify, system
Obtain compound F；Wherein, compound F and NaN3Molar ratio be 0.4:1.
It should be noted that potassium carbonate is used for neutralization reaction product hydrogen bromide in step (11)；In step (12),
Methylene chloride is not particularly limited as solvent, dosage, and " shading environment " is also understood to be dark surrounds or dark
Case.
Further, in preferred embodiments of the present invention, in step (12), purification includes process in detail below:
The solvent in reaction product is removed with Rotary Evaporators, then is further purified with silica gel chromatographic column, purification is obtained
A crude product cleaned with saturated sodium bicarbonate solution, be then extracted with dichloromethane, merge organic layer, it is dry with sodium sulphate
Afterwards, it filters, obtained secondary crude product is purified with silica gel column chromatography again, obtains compound C by concentration；Wherein, silicagel column is adopted
Eluant, eluent is by methylene chloride: petroleum ether is mixed according to the volume ratio of 1:1.
Further, in preferred embodiments of the present invention, prepare compound c includes process in detail below:
(21) by (BOC)2O, which is dissolved in methylene chloride, to be mixed, after 2-3h, by mixed solution be added dropwise to ice-water bath 1,6- oneself
In diamines, 23-25h is reacted at room temperature, and after confirming fully reacting with solvent, compound b is made in purification；Wherein, 1,6- oneself
Diamines and (BOC)2The molar ratio of O is (6-8): 1 solvent is the volume of methylene chloride, methanol and triethylamine according to 100:10:1
Than mixing；
(22) compound b and 3- propargyl bromide is dissolved in ethyl alcohol, K is then added2CO3, it is heated to 35- under agitation
45 DEG C of reaction 2.5-3.5h, after confirming fully reacting with solvent, compound c is made in purification；Wherein, compound b, 3- bromine third
Alkynes and K2CO3Molar ratio be 1:1:(2.5-3), solvent be methylene chloride and methanol according to the volume ratio mixing of 20:1 and
At.
Further, in preferred embodiments of the present invention, step (3) includes process in detail below:
Compound F and compound c are dissolved in methylene chloride, CuSO is added under an inert atmosphere4·5H2O and ascorbic acid
Reaction after confirming fully reacting with thin-layered chromatography, is taken out product and is refrigerated, compound G is made；Wherein, compound F, chemical combination
Object c, CuSO4·5H2The molar ratio of O and ascorbic acid is 1:1:0.3:0.6, and the solvent used in thin-layered chromatography is dichloro
Methane and methanol are mixed according to the volume ratio of 30:1.
Further, in preferred embodiments of the present invention, step (4) includes process in detail below:
By compound G, C60After sarcosine mixing, toluene mixing is added, mixed solution is warming up in an inert atmosphere
105-120 DEG C of back flow reaction 1.5-2.5h, then cools to room temperature, and organic triplet photosensitizer is made in purification；Wherein, chemical combination
Object G, C60Molar ratio with sarcosine is 1:1:4.
In step (4), toluene is not particularly limited as solvent, dosage.The C that the present invention uses60Toluene solution,
Its concentration is preferably 1mg/ml.
Further, in preferred embodiments of the present invention, inert atmosphere passes through the method for vacuumizing displacement nitrogen and obtains.
The invention has the following advantages:
Organic triplet photosensitizer of the invention has Host-guest Recognition site in chemical structure, passes through the identification position
With the triplet receptor for being combined with supermolecule host-guest interaction occurs for point, and can further photosensitizer and receptor in diffusion limited system
Space length, upper transfer efficiency is improved in diffusion limited system to realize.
Organic triplet photosensitizer that the present invention synthesizes is the noval chemical compound that do not report, with Host-guest Recognition group:
The middle position benzene ring position of Bodipy is reacted by Click introduces one end by tertbutyloxycarbonyl protection hexamethylene diamine as supermolecule combination
The purpose of one end amido protecting is the stability in order to improve photosensitizer by site, tertbutyloxycarbonyl, convenient for its preservation, the protection
Group can remove in acid condition, and acid condition can make protonated amino simultaneously, and hexamethylene diamine and cucurbit after protonating
[6] urea has strong host-guest interaction, Formation constants > 108M.Such photosensitizer and modify the three of aforementioned body molecule
When weight state receptor combines, the energy transfer efficiency between triplet photosensitizer and triplet receptor can be improved, and then improve three
Weight state triplet buries in oblivion the efficiency of upper conversion.
Organic triplet photosensitizer of the invention passes through in C60In the organic triplet photosensitizer of-Bodipy binary compound
Hexamethylene diamine is introduced on the middle position benzene ring position of Bodipy as supermolecule binding site, light object of the position to triplet photosensitizer
Rationality matter does not influence, and passes through the triplet photosensitizer with hyperon binding site and the supermolecule master containing triplet receptor
Body carries out self assembly in the solution, the space length between the triplet that furthers photosensitizer and triplet receptor to molecular dimension range
It is interior, so that containing C with bigger molecule size60Organic triplet photosensitizer need not spread within the scope of useful life and just can pass
Pass energy, to reduce the probability that triplet exciton is inactivated by non-radiative pathway, improve triplet photosensitizer and triplet by
Energy transfer efficiency between body, and then improve upper transfer efficiency.
The present invention, by building the reaction environment being protected from light, avoids in the step when synthesizing key intermediate compound C
One of raw material used: 2,4- dimethyl pyrrole light or oxygen and situation apt to deteriorate and cause yield to reduce；And
The feed ratio of strict control compound B and 2,4- dimethyl pyrrole of the present invention is 1:2；Under the stringent control of two conditions,
So that the yield of compound C is obviously improved.In addition, the present invention is washed with saturated sodium bicarbonate water in subsequent purification step,
To which the remaining boron trifluoride ether for being difficult to separate with chromatographic column after reaction be removed by acid-base neutralization, improving
The product purity of object C is closed, to improve compound C integral product quality, lays base for the subsequent organic triplet photosensitizer of synthesis
Plinth provides guarantee for final product quality.
Detailed description of the invention
Fig. 1 is the synthetic route chart of compound F；
Fig. 2 is the synthetic route chart of compound c；
Fig. 3 is organic triplet photosensitizer: the synthetic route chart of compound H；
Fig. 4 is the nmr spectrum chart of compound C；
Fig. 5 is the nmr spectrum chart of compound D；
Fig. 6 is the nmr spectrum chart of compound E；
Fig. 7 is the nmr spectrum chart of compound F；
Fig. 8 is the nmr spectrum chart of compound b；
Fig. 9 is the nmr spectrum chart of compound c；
Figure 10 is the nmr spectrum chart of compound d；
Figure 11 is organic triplet photosensitizer: the nmr spectrum chart of compound H.
Specific embodiment
The principle and features of the present invention will be described below with reference to the accompanying drawings, and the given examples are served only to explain the present invention, and
It is non-to be used to limit the scope of the invention.The person that is not specified actual conditions in embodiment, according to normal conditions or the item suggested of manufacturer
Part carries out.Reagents or instruments used without specified manufacturer is the conventional products that can be obtained by commercially available purchase.
Embodiment 1
The preparation method of organic triplet photosensitizer with Host-guest Recognition group of the present embodiment, comprising:
(1) prepare compound F:
Synthetic route is as shown in Figure 1.
(11) compound B is synthesized using compound A and glycol dibromide.Detailed process is as follows:
Hydroxy benzaldehyde is dissolved in ethyl alcohol, the reaction 8h of 1,2- Bromofume and potassium carbonate at 78 DEG C is then added, benefit
It after confirming fully reacting with thin-layered chromatography, filters, compound B is made in purification；Wherein, hydroxy benzaldehyde, 1,2- Bromofume
Molar ratio with potassium carbonate is 1:5:1, and the solvent used in thin-layered chromatography is methylene chloride.The specific mistake of this step purification
Journey are as follows: reaction product is extracted with dichloromethane, merges organic phase, uses anhydrous Na2SO4It is dry and organic with Rotary Evaporators removing
Obtained crude product silica gel column chromatography is purified (eluant, eluent: methylene chloride) by solvent.
The yield of compound B is 30.4%.
(12) compound B is reacted in shading environment in inert atmosphere with 2,4- dimethyl pyrrole and trifluoroacetic acid,
After reaction, DDQ, triethylamine and BF is successively added3·OEt2The reaction was continued, and compound C is made.Detailed process is as follows:
In an inert atmosphere, compound B and dry methylene chloride are added into reactor, while using and vacuumizing displacement nitrogen
The mode of gas removes the oxygen of dissolution in methylene chloride, and 2,4- dimethyl pyrrole and trifluoroacetic acid is then added in shading environment
Middle reaction 10h；After confirming fully reacting using thin-layered chromatography, DDQ stirring is added, reacts cooling reaction system after 1h；Continue
Triethylamine is added after stirring 15min, continues that BF is added dropwise after stirring 0.5h3·OEt2, it purifies after complete reaction, it is apparent when having
After fluorescence-causing substance point generates, show fully reacting, compound C is made；Wherein, compound B, 2,4- dimethyl pyrrole and DDQ
Molar ratio is 1:2:1, triethylamine, BF3·OEt2Molar ratio with compound B is 10:10:1, and trifluoroacetic acid is catalytic amount, thin layer
The solvent used in chromatography mixes for methylene chloride and n-hexane according to the volume ratio of 1:1.This step purifies
Process in detail below: it further purifies, will purify with the solvent in Rotary Evaporators removal reaction product, then with silica gel chromatographic column
An obtained crude product is cleaned with saturated sodium bicarbonate solution, is then extracted with dichloromethane, and is merged organic layer, is used sodium sulphate
It after drying, filters, obtained secondary crude product is purified with silica gel column chromatography again, obtains compound C by concentration；Wherein, silica gel
The eluant, eluent that column uses is methylene chloride: petroleum ether is mixed according to the volume ratio of 1:1.
Compound C is orange-yellow, yield 11.4%.
(13) compound D is synthesized using compound C and N-iodosuccinimide.Detailed process is as follows:
Compound C is dissolved in dry methylene chloride, under the conditions of ice-water bath, is added dropwise dissolved with N-iodosuccinimide
Dry methylene chloride solution reacts 1h, and after confirming fully reacting with thin-layered chromatography, compound D is made in purification；Wherein, chemical combination
The molar ratio of object C and N-iodosuccinimide is 1:1, and the solvent used in thin-layered chromatography is methylene chloride and n-hexane
It is mixed according to the volume ratio of 1:1.The purification of this step includes process in detail below: removing reaction product with Rotary Evaporators
Organic solvent, by obtained crude product silica gel column chromatography separating-purifying.
Compound D is orange-yellow, yield 55.9%.
(14) compound D is mixed with 5- aldehyde radical -2- thienyl boric acid, K is then added3PO4·3H2O, then in indifferent gas
At catalyst Pd (OAc) in atmosphere2Under the action of synthesize compound E.Detailed process is as follows:
Compound D and 5- aldehyde radical -2- thienyl boric acid is dissolved in the in the mixed solvent that toluene and ethyl alcohol are constituted, after mixing evenly
K is added3PO4·3H2Catalyst Pd (OAc) is added in inert atmosphere in O2Back flow reaction 8h, uses thin-layered chromatography at 80 DEG C
After confirming fully reacting, stop heating, be cooled to room temperature, compound E is made after purification；Wherein, compound D, 5- aldehyde radical -2- thiophene
Pheno boric acid, K3PO4·3H2O and Pd (OAc)2Molar ratio be 1:3:2:0.05, the solvent used in thin-layered chromatography is two
Chloromethanes and n-hexane are mixed according to the volume ratio of 1:1.The purification of this step includes process in detail below: reaction is obtained
The purification of crude product purified by silica gel column chromatography, eluant, eluent is methylene chloride: n-hexane=1:1.
Compound E is red powder, yield 14.2%.
(15) compound E and NaN are utilized3Synthesize compound F.Detailed process is as follows:
By NaN3It is dissolved in DMSO, compound E is then added dropwise and reacts 10min, after complete reaction, chemical combination is made in purification
Object F；Wherein, compound F and NaN3Molar ratio be 0.4:1.The purification of this step includes process in detail below: determining that raw material is basic
After having reacted, at once plus water is washed, and milkiness shape occurs in solution at this time, and suitable NaCl is then added and goes to emulsify, then uses CH2Cl2
Extraction, collected organic layer Na2SO4It after drying, is spin-dried for, crude product silica gel column chromatography separating-purifying.
Compound F is red product, yield 85.4%.
(2) prepare compound c:
Synthetic route is as shown in Figure 2.
(21) 1,6- hexamethylene diamine and (BOC) are utilized2O synthesizes compound b.Detailed process is as follows:
By (BOC)2O, which is dissolved in methylene chloride, to be mixed, and after 2-3h, mixed solution is added dropwise to 1, the 6- hexamethylene diamine of ice-water bath
In, it reacts at room temperature for 24 hours, after confirming fully reacting with solvent, compound b is made in purification；Wherein, 1,6- hexamethylene diamine with
(BOC)2The molar ratio of O is 7.7:1, and solvent is that methylene chloride, methanol and triethylamine are mixed according to the volume ratio of 100:10:1
It forms.The purification of this step includes process in detail below: suitable quantity of water being added into product and washes away unreacted 1,6- hexamethylene diamine, mistake
Filter, filtrate use CH2Cl2Extraction, organic layer Na2SO4After drying, solvent is removed with Rotary Evaporators, slightly uses product rubber column gel column color
Spectrum purification (eluant, eluent is methylene chloride: methanol: triethylamine=100:10:1), is developed the color with ninhydrin.
Compound b is colourless liquid, yield 17.9%.
(22) compound c is made using compound b and 3- propargyl bromide.Detailed process is as follows:
Compound b and 3- propargyl bromide is dissolved in ethyl alcohol, K is then added2CO3, it is heated to 40 DEG C of reactions under agitation
3h, after confirming fully reacting with solvent, compound c is made in purification；Wherein, compound b, 3- propargyl bromide and K2CO3Rub
, than being 1:1:2.8, solvent is that methylene chloride and methanol are mixed according to the volume ratio of 20:1 for you.This step purification include with
Lower detailed process: removing the organic solvent in product with Rotary Evaporators, and the separation of obtained crude product silica gel column chromatography is mentioned
Pure (washing and dehydrating integrated machine CH2Cl2: CH3OH=20:1).
Compound c is yield 26.6%.
(3) prepare compound G:
Synthetic route is as shown in Figure 3.
Compound F and compound c are dissolved in methylene chloride, CuSO is added under an inert atmosphere4·5H2O and ascorbic acid
Reaction after confirming fully reacting with thin-layered chromatography, is taken out product and is refrigerated, compound G is made；Wherein, compound F, chemical combination
Object c, CuSO4·5H2The molar ratio of O and ascorbic acid is 1:1:0.3:0.6, the solvent used in thin-layered chromatography is dichloro
Methane methanol is mixed according to the volume ratio of 30:1.
(4) compound G and C60It is reacted with sarcosine
By compound G, C60After sarcosine mixing, toluene mixing is added, mixed solution is warming up in an inert atmosphere
110 DEG C of back flow reaction 2h, then cool to room temperature, and organic triplet photosensitizer is made in purification；Wherein, compound G, C60And flesh
The molar ratio of propylhomoserin is 1:1:4.The purification of this step includes process in detail below: it is gone out product solvent with Rotary Evaporators, it is thick to produce
Product are purified with silica gel column chromatography, and eluant, eluent is toluene: n-hexane=5:1.
Red product H is organic triplet photosensitizer.
Embodiment 2
The present embodiment is specific as follows the difference from embodiment 1 is that the reaction condition of each step is slightly different:
The preparation method of organic triplet photosensitizer with Host-guest Recognition group of the present embodiment, comprising:
(1) prepare compound F:
(11) compound B is synthesized using compound A and glycol dibromide.Detailed process is as follows:
Hydroxy benzaldehyde is dissolved in ethyl alcohol, the reaction 7.5h of 1,2- Bromofume and potassium carbonate at 75 DEG C is then added,
It after confirming fully reacting using thin-layered chromatography, filters, compound B is made in purification；Wherein, hydroxy benzaldehyde, 1,2- dibromo second
The molar ratio of alkane and potassium carbonate is 1:4.8:1, and the solvent used in thin-layered chromatography is methylene chloride.
(12) compound B is reacted in shading environment in inert atmosphere with 2,4- dimethyl pyrrole and trifluoroacetic acid,
After reaction, DDQ, triethylamine and BF is successively added3·OEt2The reaction was continued, and compound C is made.Detailed process is as follows:
In an inert atmosphere, compound B and dry methylene chloride are added into reactor, while using and vacuumizing displacement nitrogen
The mode of gas removes the oxygen of dissolution in methylene chloride, and 2,4- dimethyl pyrrole and trifluoroacetic acid is then added in shading environment
Middle reaction 8h；After confirming fully reacting using thin-layered chromatography, DDQ stirring is added, reacts cooling reaction system after 0.8h；Continue
Triethylamine is added after stirring 10min, continues that BF is added dropwise after stirring 0.4h3·OEt2, it purifies after complete reaction, it is apparent when having
After fluorescence-causing substance point generates, show fully reacting, compound C is made；Wherein, compound B, 2,4- dimethyl pyrrole and DDQ
Molar ratio is 1:2:1, triethylamine, BF3·OEt2Molar ratio with compound B is 10:10:1, and trifluoroacetic acid is catalytic amount, thin layer
The solvent used in chromatography mixes for methylene chloride and n-hexane according to the volume ratio of 1:1.
(13) compound D is synthesized using compound C and N-iodosuccinimide.Detailed process is as follows:
Compound C is dissolved in dry methylene chloride, under the conditions of ice-water bath, is added dropwise dissolved with N-iodosuccinimide
Dry methylene chloride solution reacts 0.8h, and after confirming fully reacting with thin-layered chromatography, compound D is made in purification；Wherein, change
The molar ratio for closing object C and N-iodosuccinimide is 1:1, the solvent used in thin-layered chromatography for methylene chloride and just oneself
Alkane is mixed according to the volume ratio of 1:1.
(14) compound D is mixed with 5- aldehyde radical -2- thienyl boric acid, K is then added3PO4·3H2O, then in indifferent gas
At catalyst Pd (OAc) in atmosphere2Under the action of synthesize compound E.Detailed process is as follows:
Compound D and 5- aldehyde radical -2- thienyl boric acid is dissolved in the in the mixed solvent that toluene and ethyl alcohol are constituted, after mixing evenly
K is added3PO4·3H2Catalyst Pd (OAc) is added in inert atmosphere in O2Back flow reaction 7.5h, uses thin-layer chromatography at 75 DEG C
After method confirms fully reacting, stop heating, be cooled to room temperature, compound E is made after purification；Wherein, compound D, 5- aldehyde radical -2-
Thienyl boric acid, K3PO4·3H2O and Pd (OAc)2Molar ratio be 1:3:2:0.05, the solvent used in thin-layered chromatography for
Methylene chloride and n-hexane are mixed according to the volume ratio of 1:1.
(15) compound E and NaN are utilized3Synthesize compound F.Detailed process is as follows:
By NaN3It is dissolved in DMSO, compound E is then added dropwise and reacts 8min, after complete reaction, compound is made in purification
F；Wherein, compound F and NaN3Molar ratio be 0.4:1.
(2) prepare compound c:
(21) 1,6- hexamethylene diamine and (BOC) are utilized2O synthesizes compound b.Detailed process is as follows:
By (BOC)2O, which is dissolved in methylene chloride, to be mixed, and after 2h, mixed solution is added dropwise to 1, the 6- hexamethylene diamine of ice-water bath
In, 23h is reacted at room temperature, and after confirming fully reacting with solvent, compound b is made in purification；Wherein, 1,6- hexamethylene diamine with
(BOC)2The molar ratio of O be 6:1 solvent be methylene chloride, methanol and triethylamine according to the volume ratio mixing of 100:10:1 and
At.
(22) compound c is made using compound b and 3- propargyl bromide.Detailed process is as follows:
Compound b and 3- propargyl bromide is dissolved in ethyl alcohol, K is then added2CO3, it is heated to 35 DEG C of reactions under agitation
2.5h, after confirming fully reacting with solvent, compound c is made in purification；Wherein, compound b, 3- propargyl bromide and K2CO3's
Molar ratio is 1:1:2.5, and solvent is that methylene chloride and methanol are mixed according to the volume ratio of 20:1.
(3) prepare compound G:
Compound F and compound c are dissolved in methylene chloride, CuSO is added under an inert atmosphere4·5H2O and ascorbic acid
Reaction after confirming fully reacting with thin-layered chromatography, is taken out product and is refrigerated, compound G is made；Wherein, compound F, chemical combination
Object c, CuSO4·5H2The molar ratio of O and ascorbic acid is 1:1:0.3:0.6, and the solvent used in thin-layered chromatography is dichloro
Methane methanol is mixed according to the volume ratio of 30:1.
(4) compound G and C60It is reacted with sarcosine
By compound G, C60After sarcosine mixing, toluene mixing is added, mixed solution is warming up in an inert atmosphere
105 DEG C of back flow reaction 1.5h, then cool to room temperature, and organic triplet photosensitizer is made in purification；Wherein, compound G, C60With
The molar ratio of sarcosine is 1:1:4.
Embodiment 3
The present embodiment is specific as follows the difference from embodiment 1 is that the reaction condition of each step is slightly different:
The preparation method of organic triplet photosensitizer with Host-guest Recognition group of the present embodiment, comprising:
(1) prepare compound F:
(11) compound B is synthesized using compound A and glycol dibromide.Detailed process is as follows:
Hydroxy benzaldehyde is dissolved in ethyl alcohol, the reaction 8.5h of 1,2- Bromofume and potassium carbonate at 80 DEG C is then added,
It after confirming fully reacting using thin-layered chromatography methylene chloride, filters, compound B is made in purification；Wherein, hydroxy benzaldehyde, 1,
The molar ratio of 2- Bromofume and potassium carbonate is 1:5.5:1.2, and the solvent used in thin-layered chromatography is methylene chloride.
(12) compound B is reacted in shading environment in inert atmosphere with 2,4- dimethyl pyrrole and trifluoroacetic acid,
After reaction, DDQ, triethylamine and BF is successively added3·OEt2The reaction was continued, and compound C is made.Detailed process is as follows:
In an inert atmosphere, compound B and dry methylene chloride are added into reactor, while using and vacuumizing displacement nitrogen
The mode of gas removes the oxygen of dissolution in methylene chloride, and 2,4- dimethyl pyrrole and trifluoroacetic acid is then added in shading environment
Middle reaction 12h；After confirming fully reacting using thin-layered chromatography, DDQ stirring is added, reacts cooling reaction system after 1.5h；After
Triethylamine is added after continuous stirring 20min, continues that BF is added dropwise after stirring 0.6h3·OEt2, it purifies after complete reaction, it is obvious when having
Fluorescence-causing substance point generate after, show fully reacting, be made compound C；Wherein, compound B, 2,4- dimethyl pyrrole and DDQ
Molar ratio be 1:2:1, triethylamine, BF3·OEt2Molar ratio with compound B is 10:10:1, and trifluoroacetic acid is catalytic amount, thin
The solvent used in layer chromatography mixes for methylene chloride and n-hexane according to the volume ratio of 1:1.
(13) compound D is synthesized using compound C and N-iodosuccinimide.Detailed process is as follows:
Compound C is dissolved in dry methylene chloride, under the conditions of ice-water bath, is added dropwise dissolved with N-iodosuccinimide
Dry methylene chloride solution reacts 1.2h, and after confirming fully reacting with thin-layered chromatography, compound D is made in purification；Wherein, change
The molar ratio for closing object C and N-iodosuccinimide is 1:1, the solvent used in thin-layered chromatography for methylene chloride and just oneself
Alkane is mixed according to the volume ratio of 1:1.
(14) compound D is mixed with 5- aldehyde radical -2- thienyl boric acid, K is then added3PO4·3H2O, then in indifferent gas
At catalyst Pd (OAc) in atmosphere2Under the action of synthesize compound E.Detailed process is as follows:
Compound D and 5- aldehyde radical -2- thienyl boric acid is dissolved in the in the mixed solvent that toluene and ethyl alcohol are constituted, after mixing evenly
K is added3PO4·3H2Catalyst Pd (OAc) is added in inert atmosphere in O2Back flow reaction 8.5h, uses thin-layer chromatography at 85 DEG C
After method confirms fully reacting, stop heating, be cooled to room temperature, compound E is made after purification；Wherein, compound D, 5- aldehyde radical -2-
Thienyl boric acid, K3PO4·3H2O and Pd (OAc)2Molar ratio be 1:3:2:0.05, the solvent used in thin-layered chromatography for
Methylene chloride and n-hexane are mixed according to the volume ratio of 1:1.
(15) compound E and NaN are utilized3Synthesize compound F.Detailed process is as follows:
By NaN3It is dissolved in DMSO, compound E is then added dropwise and reacts 12min, after complete reaction, chemical combination is made in purification
Object F；Wherein, compound F and NaN3Molar ratio be 0.4:1.
(2) prepare compound c:
(21) 1,6- hexamethylene diamine and (BOC) are utilized2O synthesizes compound b.Detailed process is as follows:
By (BOC)2O, which is dissolved in methylene chloride, to be mixed, and after 3h, mixed solution is added dropwise to 1, the 6- hexamethylene diamine of ice-water bath
In, 25h is reacted at room temperature, and after confirming fully reacting with solvent, compound b is made in purification；Wherein, 1,6- hexamethylene diamine with
(BOC)2The molar ratio of O be 8:1 solvent be methylene chloride, methanol and triethylamine according to the volume ratio mixing of 100:10:1 and
At.
(22) compound c is made using compound b and 3- propargyl bromide.Detailed process is as follows:
Compound b and 3- propargyl bromide is dissolved in ethyl alcohol, K is then added2CO3, it is heated to 45 DEG C of reactions under agitation
3.5h, after confirming fully reacting with solvent, compound c is made in purification；Wherein, compound b, 3- propargyl bromide and K2CO3's
Molar ratio is 1:1:3, and solvent is that methylene chloride and methanol are mixed according to the volume ratio of 20:1.
(3) prepare compound G:
Compound F and compound c are dissolved in methylene chloride, CuSO is added under an inert atmosphere4·5H2O and ascorbic acid
Reaction after confirming fully reacting with thin-layered chromatography, is taken out product and is refrigerated, compound G is made；Wherein, compound F, chemical combination
Object c, CuSO4·5H2The molar ratio of O and ascorbic acid is 1:1:0.3:0.6, and the solvent used in thin-layered chromatography is dichloro
Methane and methanol are mixed according to the volume ratio of 30:1.
(4) compound G and C60It is reacted with sarcosine
By compound G, C60After sarcosine mixing, toluene mixing is added, mixed solution is warming up in an inert atmosphere
120 DEG C of back flow reaction 2.5h, then cool to room temperature, and organic triplet photosensitizer is made in purification；Wherein, compound G, C60With
The molar ratio of sarcosine is 1:1:4.
Embodiment 4
The preparation method of organic triplet photosensitizer with Host-guest Recognition group of the present embodiment, comprising:
1. the synthesis of compound B
Parahydroxyben-zaldehyde (6.0g, 49.2mmol) is dissolved in 60mL ethyl alcohol in three-necked flask, 1,2- bis- is added
Bromoethane (46.2g, 21.0mL, 246.0mmol) and potassium carbonate (6.6g, 47.0mmol) heat 78 DEG C instead after being sufficiently stirred
It answers, about reacts 8 hours.After TCL (methylene chloride is solvent) confirms that parahydroxyben-zaldehyde fundamental reaction is complete, filtering, so
After be extracted with dichloromethane, merge organic phase, use anhydrous Na2SO4Drying simultaneously removes organic solvent with Rotary Evaporators, obtains
Crude product purifies (eluant, eluent: methylene chloride) with silica gel column chromatography, obtains product B (3.4g).Yield: 30.4%.
2. the synthesis of compound C
The oxygen in reaction system is removed with the method for vacuumizing displacement nitrogen, compound B is added under nitrogen protection
(2.3g, 10.0mmol) adds the 400.0mL methylene chloride dry with molecular sieve into three-necked flask, then vacuumizes displacement
The method of nitrogen removes the oxygen dissolved in methylene chloride, sufficiently takes 2,4- dimethyl pyrrole with 5mL syringe after removing oxygen
(2.2mL, 20.0mmol) is injected into reaction flask, trifluoroacetic acid 0.2mL then is added with same method again, in rubber stopper
Vacuum grease is coated at pin hole, and reaction system is then encased shading with masking foil and reacts an evening.TCL (solvent: dichloromethane
Alkane) confirm that raw material has reacted rear and DDQ (2.3g, 10.0mmol) is added, it stirs 1 hour, then uses ice-water bath cooling reaction system,
It is lower after stirring 15 minutes that 12mL triethylamine is added, continue to stir 0.5h, then 12.0mL BF is added dropwise with dropper3·OEt2, after
Continuous reaction a period of time, confirmation reaction intermediate raw material have almost reacted and have had stopping after apparent fluorescence-causing substance point anti-
It answers, is slightly purified after then removing a part of solvent with Rotary Evaporators with silica gel column chromatography, remove a large amount of impurity, then obtaining
Crude product with saturation NaHCO3It is extracted with dichloromethane after solution washing, merges organic layer, use Na2SO4After drying, filtering is dense
Contracting, crude product are purified with silica gel column chromatography, and eluant, eluent is (methylene chloride: petroleum ether=1:1), obtain orange product C
(510.0mg), yield 11.4%.
Compound C:1HNMR (400MHz, CDCl3): 7.20 (d, 2H, J=8.64Hz), 7.04 (d, 2H, J=
8.62Hz), 6.00 (s, 2H), 4.38 (t, 2H, J=6.21Hz), 3.71 (t, 2H, J=6.23Hz), 2.57 (s, 6H), 1.45
(s,6H).
3. the synthesis of compound D
Compound C (200.0mg, 44.6mmol) is dissolved in the dry CH of 30mL molecular sieve2Cl2In, ice-water bath condition
Under, with constant pressure funnel the 50mL molecular sieve for being dissolved with N-iodosuccinimide (NIS) (100.4mg, 44.6mmol)
Dry CH2Cl2Solution is slowly added dropwise in compound C solution, and about 1h is added dropwise to complete, and the reaction was continued a hour, then uses
After TCL (solvent is methylene chloride: n-hexane=1:1) confirms raw material fully reacting.Organic solvent is removed with Rotary Evaporators,
Crude product silica gel column chromatography separating-purifying obtains orange product D (143.0mg), yield: 55.9%.
Compound D:1HNMR (400MHz, CDCl3): 7.19 (d, 2H, J=8.65Hz), 7.05 (d, 2H, J=
8.66Hz), 6.07 (s, 1H), 4.39 (t, 2H, J=6.22Hz), 3.72 (t, 2H, J=6.25Hz), 2.65 (s, 3H), 2.59
(s,H),1.46(s,6H).
4. the synthesis of compound E
5- aldehyde radical -2- thienyl boric acid (228.7mg, 1.5mmol) and intermediate D (251.9mg, 0.5mmol) are dissolved in
K is added after being sufficiently stirred in the in the mixed solvent of 10mL toluene and 10mL ethyl alcohol3PO4·3H2O (260mg, 1.0mmol), then makes
With the deoxidation method for vacuumize-replacing nitrogen, it is catalyzed being added after the oxygen in this operation circulation 3~5 times sufficiently system of going out
Agent Pd (OAc)2(6.4mg, 0.03mmol), then mixed liquor is heated to 80 DEG C of back flow reactions 8 hours, and (solvent is dichloro to TCL
Methane: n-hexane=1:1) determine that raw material fundamental reaction is complete after, stop reaction, be cooled to room temperature, crude product purified by silica gel column chromatography
Purification, eluant, eluent is methylene chloride: n-hexane=1:1, obtains red powder product (544.0mg), yield: 14.2%.
Compound E:1HNMR (400MHz, CDCl3): 9.87 (s, 1H), 7.73 (d, 1H, J=3.54), 7.20 (d, 2H, J
=8.05Hz), 7.04 (d, 2H, J=8.02Hz), 6.94 (d, 1H, J=3.51Hz), 6.07 (s, 1H), 4.36 (t, 2H, J=
6.16Hz), 3.69 (t, 2H, J=6.11Hz), 2.59 (d, 6H, J=8.16Hz), 1.46 (s, 6H)
5. the synthesis of compound F
By NaN3(15.2mg, 0.2mmol) is dissolved in 10mL DMSO, be then added dropwise to intermediate E (44.0mg,
About 10min or so is reacted in 0.08mmol), after determining that raw material fundamental reaction is complete, at once plus there is milkiness shape in water washing, solution,
Suitable NaCl is added to go to emulsify, then uses CH2Cl2Extraction, collected organic layer Na2SO4It after drying, is spin-dried for, crude product silicon
Rubber column gel column chromatographic purification.Finally obtain red product F (34.6mg), yield: 85.4%.
Compound F:1HNMR (400MHz, CDCl3): 9.89 (s, 1H), 7.75 (d, 1H, J=3.85Hz), 7.23 (d,
2H, J=8.61Hz), 7.08 (d, 2H, J=8.62Hz), 6.97 (d, 1H, J=3.83Hz), 6.10 (s, 1H), 4.24 (t, 2H,
), J=5.03Hz 3.69 (t, 2H, J=4.91Hz), 2.62 (d, 6H, J=8.28Hz), 1.48 (d, 6H, J=2.02Hz)
6. the synthesis of compound b
By (BOC)2O (1.0g, 4.6mmol) is dissolved in 12mL CH2Cl2It is middle about 2.5h be added dropwise to ice-water bath 1,6- oneself
In diamines (4.1g, 35.6mmol), then react at room temperature for 24 hours, TCL (solvent is methylene chloride: methanol: triethylamine=
After 100:10:1) determining reaction raw materials a reaction to a certain extent, suitable quantity of water is then added and washes away unreacted 1,6- hexamethylene diamine,
Filtering, filtrate use CH2Cl2Extraction, organic layer Na2SO4After drying, solvent is removed with Rotary Evaporators, slightly uses product rubber column gel column
Chromatography purity (eluant, eluent is methylene chloride: methanol: triethylamine=100:10:1), is developed the color with ninhydrin.Separating-purifying obtains nothing
Color liquid b (1.4g), yield 17.9%.
Compound b:1HNMR (400MHz, CDCl3): 4.59 (s, 1H), 3.10 (d, 2H, J=6.08Hz), 2.70 (t,
2H, J=7.01Hz), 2.11 (s, 2H), 1.48-1.44 (m, 3H), 1.39-1.28 (m, 4H)
7. the synthesis of compound c, d
Intermediate b (1.3g, 6.4mmol) and 3- propargyl bromide (0.8g, 6.4mmol) is dissolved in 20mL by the equivalent of 1:1
Ethyl alcohol in, while K is added2CO3(2.5g,18.2mmol).It is heated to 40 DEG C under stirring conditions to react 3 hours, TCL (exhibition
Opening agent is methylene chloride: methanol=20:1) confirm that raw material fully reacting stops reacting later, it is removed with Rotary Evaporators organic molten
Agent, crude product is with silica gel column chromatography separating-purifying (washing and dehydrating integrated machine CH2Cl2: CH3OH=20:1), collect and obtain bilateral product d
(274.0mg), yield: 33.1%；Obtain unilateral product c (200.0mg), yield: 26.6%.
8. the synthesis of compound G
Intermediate product F (34.6mg, 0.07mmol) and intermediate product c (16.0mg, 0.07mmol) is molten by the equivalent of 1:1
CH of the solution in 6mL2Cl2In, it then vacuumizes-replaces nitrogen and remove oxygen, CuSO is added under nitrogen protection4·5H2O(5mg)
With ascorbic acid (8mg).Solvent is (CH2Cl2: MeOH=30:1), it determines and stops reaction after raw material has reacted, at room temperature
It is spin-dried for contact plate and determines to be dissolved in CH after product G is purer2Cl2Middle placement refrigerator saves stand-by (easy to become due to product less stable
Matter is so fail to weigh up quality)
9. the synthesis of compound H
By above-mentioned intermediate product G (0.05mmol), C60(37.7mmol, 0.05mmol) and sarcosine (16.2mg,
It 0.2mmol) is added in bis- mouthfuls of bottles of 100mL, 35mL toluene is being added, nitrogen is then being vacuumized-replace three times, in nitrogen protection
Under, mixed liquor is to slowly warm up to 110 DEG C, then back flow reaction 2h is down to room temperature, it is gone out solvent with Rotary Evaporators, crude product
It is purified with silica gel column chromatography, eluant, eluent is toluene: n-hexane=5:1.Obtain red product H.
Fig. 4 to Figure 11 is the nmr spectrum chart for the compound that above-described embodiment 4 is synthesized in each step, according to map
Determine the chemical structure of each compound.
Compound H prepared by the present invention is quasi- to be used as triplet photosensitizer, leads with the triplet receptor for being connected with supermolecule
Object interaction realizes that triplet buries in oblivion upper conversion to realize in diffusion limited system.Organic triplet of the invention
Photosensitizer in use, it is carried out acidification with trifluoroacetic acid at room temperature, then again with the triplet that is connected with supermolecule
Receptor combines.Excessive trifluoroacetic acid is removed by Rotary Evaporators after acidification.
The foregoing is merely presently preferred embodiments of the present invention, is not intended to limit the invention, it is all in spirit of the invention and
Within principle, any modification, equivalent replacement, improvement and so on be should all be included in the protection scope of the present invention.
Claims (7)
1. the preparation method of organic triplet photosensitizer with Host-guest Recognition group, which is characterized in that
Organic triplet photosensitizer has the following structure formula:
Preparation method includes the following steps:
(1) prepare compound F:
(11) compound A and 1 being utilized, 2- Bromofume synthesizes compound B, wherein the compound A is parahydroxyben-zaldehyde,
The structure of the compound B are as follows:
(12) the compound B is reacted in shading environment in inert atmosphere with 2,4- dimethyl pyrrole and trifluoroacetic acid,
After reaction, DDQ, triethylamine and BF are sequentially added3·OEt2The reaction was continued, and compound C, the structure of the compound C is made
Are as follows:
(13) compound D, the structure of the compound D are synthesized using the compound C and N-iodosuccinimide are as follows:
(14) the compound D is mixed with 5- aldehyde radical -2- thienyl boric acid, K is then added3PO4·3H2O, then in indifferent gas
At catalyst Pd (OAc) in atmosphere2Under the action of synthesize compound E, the structure of the compound E are as follows:
(15) the compound E and NaN is utilized3Synthesize compound F, the structure of the compound F are as follows:
(2) prepare compound c:
(21) 1,6- hexamethylene diamine and (BOC) are utilized2O synthesizes compound b, the structure of the compound b are as follows:
(22) compound c, the structure of the compound c is made using the compound b and 3- propargyl bromide are as follows:
(3) the compound F made from step (1) is mixed with the compound c made from step (2), in an inert atmosphere
CuSO is added4·5H2O and ascorbic acid reaction, are made compound G, the structure of the compound G are as follows:
(4) by the compound G and C60It is mixed in inert atmosphere and reacts with sarcosine, organic triplet photosensitizer is made.
2. the preparation method of organic triplet photosensitizer according to claim 1 with Host-guest Recognition group, special
Sign is that prepare compound F includes process in detail below:
(11) hydroxy benzaldehyde is dissolved in ethyl alcohol, the reaction of 1,2- Bromofume and potassium carbonate at 75-80 DEG C is then added
7.5-8.5h, after confirming fully reacting using thin-layered chromatography, is filtered, and compound B is made in purification；Wherein, hydroxy benzaldehyde,
The molar ratio of 1,2- Bromofume and potassium carbonate is 1:(4.8-5.5): (1.0-1.2), the solvent used in thin-layered chromatography
For methylene chloride；
(12) in an inert atmosphere, compound B and methylene chloride are added into reactor, while replacing nitrogen using vacuumizing
Mode removes the oxygen of dissolution in methylene chloride, and it is anti-in shading environment that 2,4- dimethyl pyrrole and trifluoroacetic acid is then added
Answer 8-12h；After confirming fully reacting using thin-layered chromatography, DDQ stirring is added, reacts cooling reaction system after 0.8-1.5h；
Continue that triethylamine is added after stirring 10-20min, continues that BF is added dropwise after stirring 0.4-0.6h3·OEt2, it purifies after complete reaction,
Compound C is made；Wherein, the molar ratio of compound B, 2,4- dimethyl pyrrole and DDQ are 1:2:1, triethylamine, BF3·OEt2With
The molar ratio of compound B is 10:10:1, and trifluoroacetic acid is catalytic amount, and the solvent used in thin-layered chromatography is methylene chloride
It is mixed with n-hexane according to the volume ratio of 1:1；
(13) compound C is dissolved in methylene chloride, under the conditions of ice-water bath, the drying dissolved with N-iodosuccinimide is added dropwise
Dichloromethane solution reacts 0.8-1.2h, and after confirming fully reacting with thin-layered chromatography, compound D is made in purification；Wherein, change
The molar ratio for closing object C and N-iodosuccinimide is 1:1, the solvent used in thin-layered chromatography for methylene chloride and just oneself
Alkane is mixed according to the volume ratio of 1:1；
(14) compound D and 5- aldehyde radical -2- thienyl boric acid is dissolved in the in the mixed solvent that toluene and ethyl alcohol are constituted, after mixing evenly
K is added3PO4·3H2Catalyst Pd (OAc) is added in inert atmosphere in O2Back flow reaction 7.5-8.5h, use are thin at 75-85 DEG C
After layer chromatography confirms fully reacting, stop heating, be cooled to room temperature, compound E is made after purification；Wherein, compound D, 5-
Aldehyde radical -2- thienyl boric acid, K3PO4·3H2O and Pd (OAc)2Molar ratio be 1:3:2:0.05, the exhibition used in thin-layered chromatography
Opening agent is that methylene chloride and n-hexane are mixed according to the volume ratio of 1:1；
(15) by NaN3It is dissolved in DMSO, compound E is then added dropwise and reacts 8-12min, after complete reaction, chemical combination is made in purification
Object F；Wherein, compound F and NaN3Molar ratio be 0.4:1.
3. the preparation method of organic triplet photosensitizer according to claim 2 with Host-guest Recognition group, special
Sign is, in step (12), purification includes process in detail below:
The solvent in reaction product is removed with Rotary Evaporators, then is further purified with silica gel chromatographic column, one obtained will be purified
Secondary crude product is cleaned with saturated sodium bicarbonate solution, is then extracted with dichloromethane, and organic layer is merged, after sodium sulphate drying,
Filtering, concentration, obtained secondary crude product is purified with silica gel column chromatography again, obtains compound C；Wherein, silicagel column uses
Eluant, eluent by methylene chloride: petroleum ether is mixed according to the volume ratio of 1:1.
4. the preparation method of organic triplet photosensitizer according to claim 1 with Host-guest Recognition group, special
Sign is that prepare compound c includes process in detail below:
(21) by (BOC)2O, which is dissolved in methylene chloride, to be mixed, and after 2-3h, mixed solution is added dropwise to 1, the 6- hexamethylene diamine of ice-water bath
In, 23-25h is reacted at room temperature, and after confirming fully reacting with solvent, compound b is made in purification；Wherein, 1,6- hexamethylene diamine
With (BOC)2The molar ratio of O is (6-8): 1 solvent is that methylene chloride, methanol and triethylamine are mixed according to the volume ratio of 100:10:1
It closes；
(22) compound b and 3- propargyl bromide is dissolved in ethyl alcohol, K is then added2CO3, it is heated to 35-45 DEG C under agitation
2.5-3.5h is reacted, after confirming fully reacting with solvent, compound c is made in purification；Wherein, compound b, 3- propargyl bromide with
And K2CO3Molar ratio be 1:1:(2.5-3), solvent is that methylene chloride and methanol are mixed according to the volume ratio of 20:1.
5. the preparation side of organic triplet photosensitizer according to claim 1-4 with Host-guest Recognition group
Method, which is characterized in that step (3) includes process in detail below:
Compound F and compound c are dissolved in methylene chloride, CuSO is added under an inert atmosphere4·5H2O and ascorbic acid are anti-
It answers, after confirming fully reacting with thin-layered chromatography, takes out product and refrigerate, compound G is made；Wherein, compound F, compound
c、CuSO4·5H2The molar ratio of O and ascorbic acid is 1:1:0.3:0.6, and the solvent used in thin-layered chromatography is dichloromethane
Alkane and methanol are mixed according to the volume ratio of 30:1.
6. the preparation method of organic triplet photosensitizer according to claim 5 with Host-guest Recognition group, special
Sign is that step (4) includes process in detail below:
By compound G, C60After sarcosine mixing, toluene mixing is added, mixed solution is warming up to 105- in an inert atmosphere
120 DEG C of back flow reaction 1.5-2.5h, then cool to room temperature, and organic triplet photosensitizer is made in purification；Wherein, compound G,
C60Molar ratio with sarcosine is 1:1:4.
7. the preparation method of organic triplet photosensitizer according to claim 6 with Host-guest Recognition group, special
Sign is that the inert atmosphere passes through the method for vacuumizing displacement nitrogen and obtains.
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