CN109485582A - A kind of Fluorenone base organogel molecule and its preparation method and application - Google Patents
A kind of Fluorenone base organogel molecule and its preparation method and application Download PDFInfo
- Publication number
- CN109485582A CN109485582A CN201811325579.3A CN201811325579A CN109485582A CN 109485582 A CN109485582 A CN 109485582A CN 201811325579 A CN201811325579 A CN 201811325579A CN 109485582 A CN109485582 A CN 109485582A
- Authority
- CN
- China
- Prior art keywords
- tri
- alkoxy
- present
- base
- fluorenone
- Prior art date
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- YLQWCDOCJODRMT-UHFFFAOYSA-N fluoren-9-one Chemical compound C1=CC=C2C(=O)C3=CC=CC=C3C2=C1 YLQWCDOCJODRMT-UHFFFAOYSA-N 0.000 title claims abstract description 31
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims abstract description 88
- 238000001514 detection method Methods 0.000 claims abstract description 21
- 239000000463 material Substances 0.000 claims abstract description 19
- 238000006243 chemical reaction Methods 0.000 claims description 89
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 70
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 63
- 239000002585 base Substances 0.000 claims description 52
- 125000003545 alkoxy group Chemical group 0.000 claims description 49
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 48
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 claims description 38
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 36
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 36
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 34
- -1 3- dimethylamino-propyl Chemical group 0.000 claims description 32
- 235000019441 ethanol Nutrition 0.000 claims description 30
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 claims description 30
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 28
- VHYFNPMBLIVWCW-UHFFFAOYSA-N 4-Dimethylaminopyridine Chemical compound CN(C)C1=CC=NC=C1 VHYFNPMBLIVWCW-UHFFFAOYSA-N 0.000 claims description 24
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 24
- 229910052796 boron Inorganic materials 0.000 claims description 24
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 claims description 24
- 241000790917 Dioxys <bee> Species 0.000 claims description 23
- QPJVMBTYPHYUOC-UHFFFAOYSA-N methyl benzoate Chemical class COC(=O)C1=CC=CC=C1 QPJVMBTYPHYUOC-UHFFFAOYSA-N 0.000 claims description 23
- 208000032825 Ring chromosome 2 syndrome Diseases 0.000 claims description 22
- 229910052757 nitrogen Inorganic materials 0.000 claims description 22
- FYEFHYMUEWRCRF-UHFFFAOYSA-N 2,7-dibromofluoren-1-one Chemical compound BrC1=CC=C2C3=CC=C(Br)C(=O)C3=CC2=C1 FYEFHYMUEWRCRF-UHFFFAOYSA-N 0.000 claims description 21
- 239000002253 acid Substances 0.000 claims description 21
- KXDAEFPNCMNJSK-UHFFFAOYSA-N Benzamide Chemical compound NC(=O)C1=CC=CC=C1 KXDAEFPNCMNJSK-UHFFFAOYSA-N 0.000 claims description 20
- 239000005711 Benzoic acid Substances 0.000 claims description 19
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 19
- 235000010233 benzoic acid Nutrition 0.000 claims description 19
- 150000003839 salts Chemical class 0.000 claims description 19
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 15
- 230000004913 activation Effects 0.000 claims description 14
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 14
- LEXBBZCFWJNTGC-UHFFFAOYSA-N gallicin Natural products C1CC(=C)C(O)CCC(C)=CC2OC(=O)C(C)C21 LEXBBZCFWJNTGC-UHFFFAOYSA-N 0.000 claims description 12
- 239000000758 substrate Substances 0.000 claims description 12
- ONIKNECPXCLUHT-UHFFFAOYSA-N 2-chlorobenzoyl chloride Chemical compound ClC(=O)C1=CC=CC=C1Cl ONIKNECPXCLUHT-UHFFFAOYSA-N 0.000 claims description 11
- 229910001511 metal iodide Inorganic materials 0.000 claims description 11
- 238000005917 acylation reaction Methods 0.000 claims description 10
- 238000002156 mixing Methods 0.000 claims description 10
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 claims description 10
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical class ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 claims description 9
- 150000008044 alkali metal hydroxides Chemical class 0.000 claims description 9
- 150000004703 alkoxides Chemical class 0.000 claims description 9
- COQOYMRZIFLJII-UHFFFAOYSA-N boron;2,3-dimethylbutane-2,3-diol Chemical compound [B].CC(C)(O)C(C)(C)O COQOYMRZIFLJII-UHFFFAOYSA-N 0.000 claims description 9
- 239000002052 molecular layer Substances 0.000 claims description 9
- FVAUCKIRQBBSSJ-UHFFFAOYSA-M sodium iodide Chemical group [Na+].[I-] FVAUCKIRQBBSSJ-UHFFFAOYSA-M 0.000 claims description 9
- 229940095102 methyl benzoate Drugs 0.000 claims description 8
- 239000003960 organic solvent Substances 0.000 claims description 8
- AVXFJPFSWLMKSG-UHFFFAOYSA-N 2,7-dibromo-9h-fluorene Chemical class BrC1=CC=C2C3=CC=C(Br)C=C3CC2=C1 AVXFJPFSWLMKSG-UHFFFAOYSA-N 0.000 claims description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 7
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical group [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 7
- 238000007254 oxidation reaction Methods 0.000 claims description 7
- 238000006069 Suzuki reaction reaction Methods 0.000 claims description 6
- 238000005660 chlorination reaction Methods 0.000 claims description 6
- 238000005859 coupling reaction Methods 0.000 claims description 6
- 230000007062 hydrolysis Effects 0.000 claims description 6
- 238000006460 hydrolysis reaction Methods 0.000 claims description 6
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 claims description 6
- 125000001246 bromo group Chemical group Br* 0.000 claims description 5
- KMUONIBRACKNSN-UHFFFAOYSA-N potassium dichromate Chemical compound [K+].[K+].[O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O KMUONIBRACKNSN-UHFFFAOYSA-N 0.000 claims description 5
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 4
- NXQGGXCHGDYOHB-UHFFFAOYSA-L cyclopenta-1,4-dien-1-yl(diphenyl)phosphane;dichloropalladium;iron(2+) Chemical compound [Fe+2].Cl[Pd]Cl.[CH-]1C=CC(P(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1.[CH-]1C=CC(P(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 NXQGGXCHGDYOHB-UHFFFAOYSA-L 0.000 claims description 4
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 4
- KZPYGQFFRCFCPP-UHFFFAOYSA-N 1,1'-bis(diphenylphosphino)ferrocene Chemical compound [Fe+2].C1=CC=C[C-]1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=C[C-]1P(C=1C=CC=CC=1)C1=CC=CC=C1 KZPYGQFFRCFCPP-UHFFFAOYSA-N 0.000 claims description 3
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 3
- 150000004702 methyl esters Chemical class 0.000 claims description 3
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 3
- 235000009518 sodium iodide Nutrition 0.000 claims description 3
- MHABMANUFPZXEB-UHFFFAOYSA-N O-demethyl-aloesaponarin I Natural products O=C1C2=CC=CC(O)=C2C(=O)C2=C1C=C(O)C(C(O)=O)=C2C MHABMANUFPZXEB-UHFFFAOYSA-N 0.000 claims description 2
- 229940113088 dimethylacetamide Drugs 0.000 claims description 2
- 229910052763 palladium Inorganic materials 0.000 claims description 2
- 125000003698 tetramethyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims 2
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims 1
- 150000001447 alkali salts Chemical class 0.000 claims 1
- 125000000217 alkyl group Chemical group 0.000 claims 1
- 229910021529 ammonia Inorganic materials 0.000 claims 1
- 235000019253 formic acid Nutrition 0.000 claims 1
- 125000006303 iodophenyl group Chemical group 0.000 claims 1
- BXGTVNLGPMZLAZ-UHFFFAOYSA-N n'-ethylmethanediimine;hydrochloride Chemical compound Cl.CCN=C=N BXGTVNLGPMZLAZ-UHFFFAOYSA-N 0.000 claims 1
- RPGWZZNNEUHDAQ-UHFFFAOYSA-N phenylphosphine Chemical compound PC1=CC=CC=C1 RPGWZZNNEUHDAQ-UHFFFAOYSA-N 0.000 claims 1
- 238000010521 absorption reaction Methods 0.000 abstract description 3
- 230000027756 respiratory electron transport chain Effects 0.000 abstract description 3
- 238000010791 quenching Methods 0.000 abstract description 2
- 230000000171 quenching effect Effects 0.000 abstract description 2
- 238000005232 molecular self-assembly Methods 0.000 abstract 1
- 239000012265 solid product Substances 0.000 description 57
- 238000000034 method Methods 0.000 description 51
- 239000000243 solution Substances 0.000 description 49
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 36
- 239000000741 silica gel Substances 0.000 description 32
- 229910002027 silica gel Inorganic materials 0.000 description 32
- 229960001866 silicon dioxide Drugs 0.000 description 32
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 30
- 238000005406 washing Methods 0.000 description 30
- 238000001816 cooling Methods 0.000 description 29
- 229960004756 ethanol Drugs 0.000 description 27
- 230000015572 biosynthetic process Effects 0.000 description 24
- 238000003786 synthesis reaction Methods 0.000 description 24
- 239000000499 gel Substances 0.000 description 22
- 239000012074 organic phase Substances 0.000 description 19
- 238000005160 1H NMR spectroscopy Methods 0.000 description 18
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 18
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 18
- 238000001953 recrystallisation Methods 0.000 description 16
- 239000012153 distilled water Substances 0.000 description 15
- 238000000926 separation method Methods 0.000 description 15
- 239000007787 solid Substances 0.000 description 15
- 238000000967 suction filtration Methods 0.000 description 15
- 238000001035 drying Methods 0.000 description 13
- 238000003810 ethyl acetate extraction Methods 0.000 description 13
- 239000007788 liquid Substances 0.000 description 13
- 239000000203 mixture Substances 0.000 description 13
- CEJSFFKDFWPORO-UHFFFAOYSA-N 3,4,5-tridodecoxybenzoic acid Chemical compound CCCCCCCCCCCCOC1=CC(C(O)=O)=CC(OCCCCCCCCCCCC)=C1OCCCCCCCCCCCC CEJSFFKDFWPORO-UHFFFAOYSA-N 0.000 description 12
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 12
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 12
- 238000004140 cleaning Methods 0.000 description 12
- 238000000605 extraction Methods 0.000 description 12
- 238000012544 monitoring process Methods 0.000 description 12
- DCAYPVUWAIABOU-UHFFFAOYSA-N alpha-n-hexadecene Natural products CCCCCCCCCCCCCCCC DCAYPVUWAIABOU-UHFFFAOYSA-N 0.000 description 10
- 239000012043 crude product Substances 0.000 description 10
- 238000012360 testing method Methods 0.000 description 10
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 9
- 239000011521 glass Substances 0.000 description 9
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 9
- 230000005311 nuclear magnetism Effects 0.000 description 9
- FPQQSJJWHUJYPU-UHFFFAOYSA-N 3-(dimethylamino)propyliminomethylidene-ethylazanium;chloride Chemical compound Cl.CCN=C=NCCCN(C)C FPQQSJJWHUJYPU-UHFFFAOYSA-N 0.000 description 8
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 8
- 239000002904 solvent Substances 0.000 description 8
- 239000000047 product Substances 0.000 description 7
- 238000000746 purification Methods 0.000 description 7
- 238000010992 reflux Methods 0.000 description 7
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 6
- 239000000706 filtrate Substances 0.000 description 6
- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical compound [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 6
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical class CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 5
- 125000006306 4-iodophenyl group Chemical group [H]C1=C([H])C(*)=C([H])C([H])=C1I 0.000 description 5
- 235000002597 Solanum melongena Nutrition 0.000 description 5
- 244000061458 Solanum melongena Species 0.000 description 5
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Natural products C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 5
- 150000001412 amines Chemical class 0.000 description 5
- 229960000935 dehydrated alcohol Drugs 0.000 description 5
- TXCDCPKCNAJMEE-UHFFFAOYSA-N dibenzofuran Chemical class C1=CC=C2C3=CC=CC=C3OC2=C1 TXCDCPKCNAJMEE-UHFFFAOYSA-N 0.000 description 5
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000012512 characterization method Methods 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 229940117975 chromium trioxide Drugs 0.000 description 3
- WGLPBDUCMAPZCE-UHFFFAOYSA-N chromium trioxide Inorganic materials O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 3
- GAMDZJFZMJECOS-UHFFFAOYSA-N chromium(6+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Cr+6] GAMDZJFZMJECOS-UHFFFAOYSA-N 0.000 description 3
- 239000002274 desiccant Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 235000011056 potassium acetate Nutrition 0.000 description 3
- 238000001338 self-assembly Methods 0.000 description 3
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- ZHNUHDYFZUAESO-UHFFFAOYSA-N Formamide Chemical compound NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- KRVSOGSZCMJSLX-UHFFFAOYSA-L chromic acid Substances O[Cr](O)(=O)=O KRVSOGSZCMJSLX-UHFFFAOYSA-L 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- SNRUBQQJIBEYMU-UHFFFAOYSA-N dodecane Chemical compound CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 2
- 238000000295 emission spectrum Methods 0.000 description 2
- 239000000284 extract Substances 0.000 description 2
- 238000002189 fluorescence spectrum Methods 0.000 description 2
- AWJWCTOOIBYHON-UHFFFAOYSA-N furo[3,4-b]pyrazine-5,7-dione Chemical compound C1=CN=C2C(=O)OC(=O)C2=N1 AWJWCTOOIBYHON-UHFFFAOYSA-N 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
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- 239000001257 hydrogen Substances 0.000 description 2
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- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
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- 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
- VMKOFRJSULQZRM-UHFFFAOYSA-N 1-bromooctane Chemical compound CCCCCCCCBr VMKOFRJSULQZRM-UHFFFAOYSA-N 0.000 description 1
- GCDPERPXPREHJF-UHFFFAOYSA-N 1-iodododecane Chemical compound CCCCCCCCCCCCI GCDPERPXPREHJF-UHFFFAOYSA-N 0.000 description 1
- HPJFXFRNEJHDFR-UHFFFAOYSA-N 22291-04-9 Chemical compound C1=CC(C(N(CCN(C)C)C2=O)=O)=C3C2=CC=C2C(=O)N(CCN(C)C)C(=O)C1=C32 HPJFXFRNEJHDFR-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- UEXCJVNBTNXOEH-UHFFFAOYSA-N Ethynylbenzene Chemical group C#CC1=CC=CC=C1 UEXCJVNBTNXOEH-UHFFFAOYSA-N 0.000 description 1
- 206010016825 Flushing Diseases 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- WINTXHPCODMMRI-UHFFFAOYSA-N benzene naphthalene Chemical compound C1=CC=CC=C1.C1=CC=CC=C1.C1=CC=CC2=CC=CC=C21 WINTXHPCODMMRI-UHFFFAOYSA-N 0.000 description 1
- QQEXMHVHLWKOQT-UHFFFAOYSA-N benzene;formamide Chemical compound NC=O.C1=CC=CC=C1 QQEXMHVHLWKOQT-UHFFFAOYSA-N 0.000 description 1
- 125000003236 benzoyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C(*)=O 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000004087 circulation Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
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- 125000000058 cyclopentadienyl group Chemical group C1(=CC=CC1)* 0.000 description 1
- 238000001212 derivatisation Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 229910000071 diazene Inorganic materials 0.000 description 1
- 125000003963 dichloro group Chemical group Cl* 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- ZSWFCLXCOIISFI-UHFFFAOYSA-N endo-cyclopentadiene Natural products C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- XYIBRDXRRQCHLP-UHFFFAOYSA-N ethyl acetoacetate Chemical compound CCOC(=O)CC(C)=O XYIBRDXRRQCHLP-UHFFFAOYSA-N 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000011010 flushing procedure Methods 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 238000004108 freeze drying Methods 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000004770 highest occupied molecular orbital Methods 0.000 description 1
- DKAGJZJALZXOOV-UHFFFAOYSA-N hydrate;hydrochloride Chemical compound O.Cl DKAGJZJALZXOOV-UHFFFAOYSA-N 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- SVEUVITYHIHZQE-UHFFFAOYSA-N n-methylpyridin-2-amine Chemical compound CNC1=CC=CC=N1 SVEUVITYHIHZQE-UHFFFAOYSA-N 0.000 description 1
- 239000012044 organic layer Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 125000001820 oxy group Chemical group [*:1]O[*:2] 0.000 description 1
- 239000003002 pH adjusting agent Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000011540 sensing material Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000007779 soft material Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 150000003462 sulfoxides Chemical class 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000002371 ultraviolet--visible spectrum Methods 0.000 description 1
- 239000012855 volatile organic compound Substances 0.000 description 1
- 230000010148 water-pollination Effects 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C235/00—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by oxygen atoms
- C07C235/42—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by oxygen atoms having carbon atoms of carboxamide groups bound to carbon atoms of six-membered aromatic rings and singly-bound oxygen atoms bound to the same carbon skeleton
- C07C235/44—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by oxygen atoms having carbon atoms of carboxamide groups bound to carbon atoms of six-membered aromatic rings and singly-bound oxygen atoms bound to the same carbon skeleton with carbon atoms of carboxamide groups and singly-bound oxygen atoms bound to carbon atoms of the same non-condensed six-membered aromatic ring
- C07C235/56—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by oxygen atoms having carbon atoms of carboxamide groups bound to carbon atoms of six-membered aromatic rings and singly-bound oxygen atoms bound to the same carbon skeleton with carbon atoms of carboxamide groups and singly-bound oxygen atoms bound to carbon atoms of the same non-condensed six-membered aromatic ring having the nitrogen atom of at least one of the carboxamide groups bound to a carbon atom of a six-membered aromatic ring
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- C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
- G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
- G01N21/64—Fluorescence; Phosphorescence
- G01N21/6428—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes"
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- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
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- C07C2603/02—Ortho- or ortho- and peri-condensed systems
- C07C2603/04—Ortho- or ortho- and peri-condensed systems containing three rings
- C07C2603/06—Ortho- or ortho- and peri-condensed systems containing three rings containing at least one ring with less than six ring members
- C07C2603/10—Ortho- or ortho- and peri-condensed systems containing three rings containing at least one ring with less than six ring members containing five-membered rings
- C07C2603/12—Ortho- or ortho- and peri-condensed systems containing three rings containing at least one ring with less than six ring members containing five-membered rings only one five-membered ring
- C07C2603/18—Fluorenes; Hydrogenated fluorenes
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- G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
- G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
- G01N21/64—Fluorescence; Phosphorescence
- G01N21/6428—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes"
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Abstract
The present invention provides a kind of Fluorenone base organogel molecules and its preparation method and application, belong to gel rubber material technical field.The fluorescence sense film that Fluorenone base organogel molecule provided by the invention is prepared can be used for the detection of aniline steam.Between the Fluorenone base organogel molecular self assembly occurs for the present invention when preparing sense film, is built into three-dimensional space net structure, increases film itself specific surface area, enhances its absorption to aniline steam；So that the fluorescence of fluorescence sense film is quenched, and with the increase of aniline vapour concentration, degree aggravation is quenched in the aniline steam and the intermolecular generation Photo-induced electron transfer of Fluorenone base organogel being adsorbed.Concentration of aniline is detected by concentration of aniline and the relationship of fluorescence sense film fluorescent quenching.
Description
Technical field
The present invention relates to gel rubber material technical field, in particular to a kind of Fluorenone base organogel molecule and preparation method thereof
And application.
Background technique
Low molecular weight organic gel (LMOGs) is by noncovalent interaction, such as hydrogen bond, coordination metal, pi-pi accumulation, Fan De
A kind of soft material between solid and liquid that the interactions such as Hua Li, electrostatic force, hydrophobic-hydrophobic and hydrophily are formed,
It has been widely used in the fields such as flexible electronic, organizational engineering, optics, catalysis, Molecular Detection, drug control and release.Closely
Nian Lai gives more concerns to the detection of volatile organic compounds using molecular gel strategy.
Aniline is widely applied in chemistry, pharmacy and food industry.Excessive organic amine can seriously destroy ecology in air
Environment constitutes a serious threat to human health.
The material of amine steam is detected by a variety of, such as: zang et al. reports the net of the 3D with a kind of based on derivative and ties
Nanofiber is made in structure, enhances fluorescence sense technology (" the Expedient Vapor Probing of Organic of aniline steam
Amines Using Fluorescent Nanofibers Fabricated from an n-Type Organic
Semiconductor ", zang etc., Nano.Letters.2008；8:2219-23).Xue project has been combined into a kind of hydrogen bond and has made
For the bi-component gel of main drive, and realize by electric charge transfer reversible the detection (" Strong to aniline molecule
Fluorescent Smart Organogel as a Dual Sensing Material for Volatile Acid and
Organic Amine Vapors ", Xue etc., Chem-A Eur is J.2015；21:17508-15.).Recently, room analogy etc. develops
A kind of aniline steam detection material, MOLECULE DESIGN are mainly extended altogether by introducing two phenylacetylene structures on benzene-naphthalene diimide
The HOMO energy level that yoke degree adjusts molecule adapts to the testing requirements of aniline, and introduces three (dodecane of the conventional gel factor in end
Oxygroup) benzamide group, with assign it can gelatination property, and using the molecular self-assembling ability of itself prepare light stablize
The good nano fibrous membrane of property, reversible detection (" the Functionality-Oriented Derivatization for aniline
of Naphthalene Diimide:A Molecular Gel Strategy-Based Fluorescent Film for
Aniline Vapor Detection ", room analogy etc., ACS Appl.Mater.Interfaces 2016；8:18584-
18592)。
Although having much to the detection report of aniline, Fluorenone base gel molecular is used for aniline detection, and there has been no correlations
Report.
Summary of the invention
In view of this, it is an object of that present invention to provide a kind of Fluorenone base organogel molecules and its preparation method and application.
The fluorescence sense film that Fluorenone base organogel molecule provided by the invention is prepared can be used for the detection of aniline steam.
The present invention provides a kind of Fluorenone base organogel molecule with structure shown in Formulas I:
The present invention also provides the preparations with Fluorenone base organogel molecule shown in Formulas I described in a kind of claim 1
Method, comprising the following steps:
1) gallicin, brominated alkanes, alkaline metal iodide, strong base-weak acid salt and organic solvent are mixed, in nothing
Alkoxide is carried out under oxygen environment, obtains 3,4,5- tri- (alkoxy) methyl benzoates；The brominated alkanes are the monobromo of C4~C16
For alkane；
2) 3,4,5- tri- (alkoxy) methyl benzoate, alkali metal hydroxide and the ethyl alcohol for obtaining the step 1) are mixed
Reaction is hydrolyzed in conjunction, obtains 3,4,5- tri- (alkoxy) benzoic acid；
3) obtain the step 2) 3,4,5- tri- (alkoxy) benzoic acid are mixed with thionyl chloride carries out chlorination,
Obtain 3,4,5- tri- (alkoxy) chlorobenzoyl chloride；
4) 3,4,5- tri- (alkoxy) chlorobenzoyl chloride, paraiodoaniline, 1- (the 3- dimethylamino for obtaining the step 3)
Propyl) -3- ethyl-carbodiimide hydrochloride, 4-dimethylaminopyridine and 1,2- dichloroethanes, which mixes, carries out acylation reaction, obtains
To 3,4,5- tri- (alkoxy)-N- (4- iodophenyl) benzamide；
5) 2,7- dibromo fluorenes, potassium bichromate and acetic acid are mixed and carries out oxidation reaction, obtain 2,7- dibromo fluorenone；
6) 2,7- dibromo fluorenone, connection the boron pinacol ester, [1,1 '-bis- (diphenylphosphinos) two obtained the step 5)
Luxuriant iron] palladium chloride, acetate and n,N-Dimethylformamide carry out coupling reaction under oxygen-free environment, obtain 2,7- it is bis- (4,
Penta ring -2- base of 4,5,5- tetramethyl -1,3,2- dioxy boron) -9H- fluorenes -9- ketone；
7) 3,4,5- tri- (alkoxy)-N- (4- iodophenyl) benzamide for obtaining the step 4), the step 6)
Bis- (penta ring -2- base of 4,4,5,5- tetramethyl -1,3,2- dioxy the boron) -9H- fluorenes -9- ketone of obtained 2,7-, tetrakis triphenylphosphine palladium,
Strong base-weak acid salt, water and toluene mixing carry out suzuki reaction, obtain with Fluorenone base organogel molecule shown in Formulas I.
Preferably, alkaline metal iodide is sodium iodide and/or potassium iodide in the step 1)；The strong base-weak acid salt is carbon
Sour sodium and/or potassium carbonate；The organic solvent is N,N-dimethylformamide or DMAC N,N' dimethyl acetamide.
Preferably, gallicin, brominated alkanes, alkaline metal iodide, strong base-weak acid salt and have in the step 1)
The mass ratio of the material of solvent are as follows: 1:4~10:0.1:8~15:50~100.
Preferably, 3,4,5- tri- (alkoxy) methyl benzoates in the step 2), alkali metal hydroxide and ethyl alcohol
The mass ratio of the material is 1:1~4:50~150.
Preferably, paraiodoaniline in the step 4), 1- (3- dimethylamino-propyl) -3- ethyl-carbodiimide hydrochloride,
The amount of the substance of 3,4,5- tri- (alkoxy) benzoic acid in 4-dimethylaminopyridine, 1,2- dichloroethanes and the step 3)
Than for 1~3:1~3::0.5~2:210~420:1.
Preferably, 2,7- dibromo fluorenone, connection boron pinacol ester, [1,1 '-bis- (diphenylphosphinos) two cyclopentadienyl in the step 6)
Iron] palladium chloride, acetate and N,N-dimethylformamide the mass ratio of the material be 1:1~3:0.01~0.1:5~10:115
~145.
Preferably, in the step 7) 3,4,5- tri- (alkoxy)-N- (4- iodophenyl) benzamides, 2,7- it is bis- (4,4,
Penta ring -2- base of 5,5- tetramethyl -1,3,2- dioxy boron) -9H- fluorenes -9- ketone, tetrakis triphenylphosphine palladium, strong base-weak acid salt, Shui Hejia
The mass ratio of the material of benzene is 2~3:1:0.1~0.2:10~15:240~480:245~285.
The present invention also provides a kind of fluorescence sense film, the film successively includes gel molecular layer and the quartzy glass of activation
Glass substrate, the gel molecular layer include the gel molecular with structure shown in Formulas I.
The present invention also provides application of the above-mentioned fluorescence sense film in the detection of aniline steam.
Advantageous effects: the present invention provides a kind of Fluorenone base organogel molecules and its preparation method and application.This
The fluorescence sense film that the Fluorenone base organogel molecule that invention provides is prepared can be used for the detection of aniline steam.The present invention exists
When preparing sense film, self assembly occurs between the Fluorenone base organogel molecular, is built into three-dimensional space net structure,
Increase film itself specific surface area, enhances its absorption to aniline steam；The aniline steam and Fluorenone base being adsorbed are organic
Photo-induced electron transfer occurs between gel molecular, so that the fluorescence of fluorescence sense film is quenched, and dense with aniline steam
Degree aggravation is quenched in the increase of degree.Concentration of aniline is carried out by concentration of aniline and the relationship of fluorescence sense film fluorescent quenching
Detection.
For this phenomenon, the relationship for discussing concentration of aniline and DOF film fluorescence and being quenched of system, and done a series of
Experiment, has obtained concentration of aniline in 220ppm or less, the line style relationship y=that efficiency (QE) is quenched of concentration of aniline and DOF
0.0044x+0.2023。
Detailed description of the invention:
Fig. 1 is UV-vis absorption spectrum of the DOF in tetrahydrofuran in embodiment 1；
Fig. 2 is normalized emission spectra of the DOF in tetrahydrofuran in embodiment 1；
Fig. 3 is that sol-gel of the DOF in N,N-dimethylformamide solvent converts figure in embodiment 1；
Fig. 4 is the fluorescence spectra of fluorescence sense film in the case where the aniline steam of various concentration in embodiment 3；
Fig. 5 is that the aniline steam detection of fluorescence sense film in embodiment 4 repeats linearity curve.
Specific embodiment
The present invention provides a kind of Fluorenone base organogel molecule with structure shown in Formulas I:
The present invention also provides the preparations with Fluorenone base organogel molecule shown in Formulas I described in a kind of claim 1
Method, comprising the following steps:
1) gallicin, brominated alkanes, alkaline metal iodide, strong base-weak acid salt and organic solvent are mixed, in nothing
Alkoxide is carried out under oxygen environment, obtains 3,4,5- tri- (alkoxy) methyl benzoates；The brominated alkanes are the monobromo of C4~C16
For alkane；
2) 3,4,5- tri- (alkoxy) methyl benzoate, alkali metal hydroxide and the ethyl alcohol for obtaining the step 1) are mixed
Reaction is hydrolyzed in conjunction, obtains 3,4,5- tri- (alkoxy) benzoic acid；
3) obtain the step 2) 3,4,5- tri- (alkoxy) benzoic acid are mixed with thionyl chloride carries out chlorination,
Obtain 3,4,5- tri- (alkoxy) chlorobenzoyl chloride；
4) 3,4,5- tri- (alkoxy) chlorobenzoyl chloride, paraiodoaniline, 1- (the 3- dimethylamino for obtaining the step 3)
Propyl) -3- ethyl-carbodiimide hydrochloride, 4-dimethylaminopyridine and 1,2- dichloroethanes, which mixes, carries out acylation reaction, obtains
3,4,5- tri- (alkoxy)-N- (4- iodophenyl) benzamide；
5) 2,7- dibromo fluorenes, potassium bichromate and acetic acid are mixed and carries out oxidation reaction, obtain 2,7- dibromo fluorenone；
6) 2,7- dibromo fluorenone, connection the boron pinacol ester, [1,1 '-bis- (diphenylphosphinos) two obtained the step 5)
Luxuriant iron] palladium chloride, acetate and n,N-Dimethylformamide carry out coupling reaction under oxygen-free environment, obtain 2,7- it is bis- (4,
Penta ring -2- base of 4,5,5- tetramethyl -1,3,2- dioxy boron) -9H- fluorenes -9- ketone；
7) 3,4,5- tri- (alkoxy)-N- (4- iodophenyl) benzamide for obtaining the step 4), the step 6)
Bis- (penta ring -2- base of 4,4,5,5- tetramethyl -1,3,2- dioxy the boron) -9H- fluorenes -9- ketone of obtained 2,7-, tetrakis triphenylphosphine palladium,
Strong base-weak acid salt, water and toluene mixing carry out suzuki reaction, obtain with Fluorenone base organogel molecule shown in Formulas I.
Gallicin, brominated alkanes, alkaline metal iodide, strong base-weak acid salt and organic solvent are blended in by the present invention
Alkoxide reaction is carried out under oxygen-free environment, obtains 3,4,5- tri- (alkoxy) methyl benzoates；The brominated alkanes are C4~C16
Bromoalkanes hydrocarbon.
In the present invention, the bromoalkanes hydrocarbon of the C4~C16 is preferably C4H9Br、C8H17Br、 C10H21Br、C12H25Br
Or C16H33Br。
In the present invention, the alkaline metal iodide is preferably sodium iodide and/or potassium iodide, and the strong base-weak acid salt is preferred
For sodium carbonate and/or potassium carbonate, the organic solvent is preferably n,N-Dimethylformamide or n,N-dimethylacetamide.
In the present invention, the gallicin, brominated alkanes, alkaline metal iodide, strong base-weak acid salt and organic molten
The mass ratio of the material of agent is preferably 1:4~10:0.1:8~15:50~100, more preferably 1:4.15~7:0.1:10~13:
57~80.
In the present invention, the alkaline metal iodide is in alkoxide reaction process by C12H25Br is converted into C12H25I, more
Be conducive to the progress of alkoxide reaction, the strong base-weak acid salt provides alkaline environment, converts-O for-OH-, be conducive to alcoxyl
Change the progress of reaction.
In the present invention, the oxygen-free environment is preferably provided by nitrogen.
In the present invention, the temperature of the alkoxide reaction is preferably 70~100 DEG C, and more preferably 80~90 DEG C；It is described
The time of alkoxide reaction is preferably 15~30h, more preferably 20~for 24 hours.
Whether present invention preferably employs TLC monitoring reactions to terminate.
In the present invention, after alkoxide reaction, further preferably include gained reaction solution is successively carried out cool down, be filtered,
Extraction, washing, dry, silicagel column purification and recrystallization, obtain white solid product.
In the present invention, the cooling is preferably cooled to room temperature.The present invention is not particularly limited cooling method, choosing
With cooling means well known to those skilled in the art, such as natural cooling.
The present invention is not particularly limited the method for suction filtration, selects suction filtration method well known to those skilled in the art.
In the present invention, the washing preferably washes gained filtrate after suction filtration.Method of the present invention to washing
It is not particularly limited, selects method for washing well known to those skilled in the art.
In the present invention, the extraction preferably extracts gained liquid after washing.The extractant of the extraction is excellent
It is selected as ethyl acetate.The present invention is not particularly limited the specific method of the extraction, selects well known to those skilled in the art
Extracting process.
In the present invention, the drying is preferably dried gained organic phase after the extraction.The desiccant is excellent
It is selected as anhydrous sodium sulfate.
In the present invention, the silicagel column purification preferably carries out silicagel column purification to the organic phase after the drying.This
The specific method that invention purifies silicagel column is not particularly limited, and selects silicagel column method of purification well known to those skilled in the art
?.
In the present invention, the recrystallization preferably recrystallizes products therefrom after silicagel column purification.At this
In invention, the recrystallization is preferably ethyl alcohol recrystallization.The present invention is not particularly limited the specific method of ethyl alcohol recrystallization, choosing
With ethyl alcohol recrystallization method well known to those skilled in the art.
After obtaining 3,4,5- tri- (alkoxy) methyl benzoates, 3,4,5- tri- (alkoxy) benzene first that the present invention will obtain
Sour methyl esters, alkali metal hydroxide and ethyl alcohol mixing carry out hydrolysis, obtain 3,4,5- tri- (alkoxy) benzoic acid.
In the present invention, the alkali metal hydroxide is preferably sodium hydroxide or potassium hydroxide.In the present invention, described
Alkali metal hydroxide provides alkaline condition, is conducive to hydrolysis of ester group.
In the present invention, the substance of described 3,4,5- tri- (alkoxy) methyl benzoates, alkali metal hydroxide and ethyl alcohol
Amount than being preferably 1:1~4:50~150, more preferably 1:3:105~130.
In the present invention, the temperature of the hydrolysis is preferably 60~80 DEG C, and more preferably 70~75 DEG C；The hydrolysis
The time of reaction is preferably 15~25h, more preferably 20~for 24 hours.
In the present invention, further preferably successively include after the hydrolysis gained reaction solution is adjusted pH value to 1~1.5,
Cooling, suction filtration and recrystallization, obtain 3,4,5- tri- (alkoxy) benzoic acid.
In the present invention, the pH adjusting agent for adjusting pH value is preferably dilute hydrochloric acid.The present invention does not have the concentration of dilute hydrochloric acid
There is particular determination, selects concentration well known to those skilled in the art.
In the present invention, gained liquid is cooled to room temperature after the cooling will preferably adjust pH value.The present invention is to described
Cooling method and rate is not particularly limited, and selects method and rate well known to those skilled in the art, such as naturally cold
But.
In the present invention, described filter preferably filters gained liquid after cooling.Method of the present invention to suction filtration
It is not particularly limited, selects method well known to those skilled in the art.
In the present invention, the recrystallization preferably recrystallizes gained filter residue after suction filtration.In the present invention, described
Recrystallization is preferably ethyl alcohol recrystallization.The present invention is not particularly limited the method for ethyl alcohol recrystallization, selects those skilled in the art
Method known to member.
After obtaining 3,4,5- tri- (alkoxy) benzoic acid, 3,4,5- tri- (alkoxy) benzoic acid and two that the present invention will obtain
The mixing of chlorine sulfoxide carries out chlorination, obtains 3,4,5- tri- (alkoxy) chlorobenzoyl chlorides.
In the present invention, described 3, the mass ratio of the material of 4,5- tri- (alkoxy) benzoic acid and thionyl chloride is preferably 1:
115~185, more preferably 1:138~150.
In the present invention, the temperature of the chlorination is preferably 70~80 DEG C, and more preferably 75~79 DEG C, the reaction
Time be 10~15h, more preferably 12h.
It in the present invention, further preferably include successively being cooled down and being removed dichloro to gained reaction solution after the chlorination
Sulfoxide obtains 3,4,5- tri- (alkoxy) chlorobenzoyl chlorides.
In the present invention, the cooling is preferably cooled to room temperature.The present invention does not have the method and rate of the cooling
Particular determination selects cooling means and rate well known to those skilled in the art.
In the present invention, the removing thionyl chloride preferably rotates.
After obtaining 3,4,5- tri- (alkoxy) chlorobenzoyl chlorides, 3,4,5- tri- (alkoxy) benzoyls that the present invention will obtain
Chlorine, paraiodoaniline, 1- (3- dimethylamino-propyl) -3- ethyl-carbodiimide hydrochloride, 4-dimethylaminopyridine and 1,2- dichloro
Ethane mixing carries out acylation reaction, obtains 3,4,5- tri- (alkoxy)-N- (4- iodophenyl) benzamides.
In the present invention, the paraiodoaniline, 1- (3- dimethylamino-propyl) -3- ethyl-carbodiimide hydrochloride, 4- bis-
The mass ratio of the material of methylamino pyridine, 1,2- dichloroethanes and the 3,4,5- tri- (alkoxy) benzoic acid be preferably 1~3:1~
3:0.5~2:210~420:1, more preferably 1.2~2:1.2~2:0.8~1.5:250~350:1.
In the present invention, 1- (3- the dimethylamino-propyl) -3- ethyl-carbodiimide hydrochloride is condensing agent and crosslinking
Agent, the 4-dimethylaminopyridine are the catalyst of acylation reaction, and 1, the 2- dichloroethanes is solvent.
In the present invention, the temperature of the acylation reaction is preferably 20~50 DEG C, and more preferably 25~35 DEG C；It is described
The time of acylation reaction is preferably 10~15h, more preferably 12h.
In the present invention, the acylation reaction preferably carries out under agitation, and the present invention does not have the rate of stirring
Particular determination selects stirring rate well known to those skilled in the art.
Whether present invention preferably uses TLC monitoring acylation reactions to terminate.
It in the present invention, further preferably successively include except 1,2- dichloroethanes, methylene chloride dissolution, water after the acylation reaction
It washes and is spin-dried for, obtain 3,4,5- tri- (alkoxy)-N- (4- iodophenyl) benzamides.
In the present invention, the method for removing 1,2- dichloroethanes preferably rotates.
In the present invention, products therefrom after 1,2- dichloroethanes is preferably dissolved in dichloromethane by the methylene chloride dissolution
In alkane, mixed liquor is obtained.The present invention is not particularly limited the dosage of methylene chloride, selects amount well known to those skilled in the art
?.
In the present invention, the washing preferably washes obtained mixed liquor.The present invention does not have the method for washing
There is particular determination, selects method for washing well known to those skilled in the art.
In the present invention, described to be spin-dried for preferably being spin-dried for gained liquid after washing.In the present invention, described to be spin-dried for
Temperature be preferably 45~55 DEG C, more preferably 50~55 DEG C.
2,7- dibromo fluorenes, potassium bichromate and acetic acid are mixed and carry out oxidation reaction by the present invention, obtain 2,7- dibromo fluorenone.
In the present invention, the mass ratio of the material of 2, the 7- dibromo fluorenes, potassium bichromate and acetic acid is preferably 1:2~3:105
~210, more preferably 1:2.4~2.8:126~150.
In the present invention, the temperature of the oxidation reaction is preferably 20~50 DEG C, and more preferably 25~35 DEG C；The oxidation
The time of reaction is preferably 10~15h, more preferably 12h.
It in the present invention, further preferably include successively cool down to gained reaction solution, filtering, wash after the oxidation reaction
And recrystallization, obtain 2,7- dibromo fluorenone.
In the present invention, the cooling is preferably cooled to room temperature.The present invention is not special to cooling method and rate
It limits, cooling means well known to those skilled in the art is selected, such as natural cooling.
In the present invention, the suction filtration preferably filters reaction solution after cooling.Method of the present invention to suction filtration
It is not particularly limited, selects suction filtration method well known to those skilled in the art.
In the present invention, the washing preferably successively washes gained filter residue after suction filtration with acetic acid, water and dilute hydrochloric acid
It washs, obtains crude product.The present invention is not particularly limited the concentration of dilute hydrochloric acid, selects concentration well known to those skilled in the art i.e.
It can.The present invention is not particularly limited the specific method of washing, selects washing methods well known to those skilled in the art.
In the present invention, the recrystallization preferably crystallizes gained crude product after washing.The crystallization is preferably
Ethyl alcohol recrystallization.The present invention is not particularly limited the specific method of ethyl alcohol recrystallization, selects well known to those skilled in the art
Ethyl alcohol recrystallization method.
After obtaining 2,7- dibromo fluorenone, the present invention by obtained 2,7- dibromo fluorenone, connection boron pinacol ester, [1,1 '-is bis-
(diphenylphosphino) ferrocene] palladium chloride, acetate and n,N-Dimethylformamide carry out coupling reaction under oxygen-free environment,
Obtain bis- (penta ring -2- base of 4,4,5,5- tetramethyl -1,3,2- dioxy the boron) -9H- fluorenes -9- ketone of 2,7-.
In the present invention, 2, the 7- dibromo fluorenone, connection boron pinacol ester, [1,1 '-bis- (diphenylphosphino) ferrocene]
The mass ratio of the material of palladium chloride, acetate and N,N-dimethylformamide is preferably 1:1~3:0.01~0.1:5~10:
115~145, more preferably 1:1.5~2.4:0.05~0.08:8:120~130.
In the present invention, the temperature of the coupling reaction is preferably 80~100 DEG C, and more preferably 85~90 DEG C, the idol
The time of connection reaction is preferably 8~15h, more preferably 10~12h.
It in the present invention, further preferably include successively cooling down, extracting to gained reaction solution, washing, doing after the coupling reaction
It is dry, be spin-dried for silica gel post separation, obtain bis- (4,4,5,5- tetramethyls -1,3, penta ring -2- base of 2- dioxy the boron) -9H- fluorenes -9- of 2,7-
Ketone.
In the present invention, the cooling is preferably cooled to room temperature.The present invention does not have the method and rate of the cooling
Particular determination selects method and rate well known to those skilled in the art.
In the present invention, the extractant of the extraction is preferably ethyl acetate.The present invention does not have the method for the extraction
Particular determination selects extracting process well known to those skilled in the art.
In the present invention, the washing preferably washes gained reaction solution after cooling.The present invention is to the washing
Method be not particularly limited, select method for washing well known to those skilled in the art.
In the present invention, the desiccant of the drying is preferably that anhydrous sodium sulfate is dry.Side of the present invention to the drying
Method is not particularly limited, and selects drying means well known to those skilled in the art.
In the present invention, described to be spin-dried for preferably being spin-dried for gained organic phase after extraction.In the present invention, the rotation
Dry temperature is preferably 45~55 DEG C, and more preferably 50~55 DEG C.
In the present invention, silica gel post separation preferably carries out silica gel post separation to being spin-dried for rear products therefrom.The present invention is to silicon
The method of rubber column gel column separation is not particularly limited, and selects method well known to those skilled in the art.
After obtaining 3,4,5- tri- (alkoxy)-N- (4- iodophenyl) benzamides, the present invention will obtain 3,4,5- tri-
Bis- (penta ring-the 2- of 4,4,5,5- tetramethyl -1,3,2- dioxy boron of (alkoxy)-N- (4- iodophenyl) benzamide, the 2,7-
Base) -9H- fluorenes -9- ketone, tetrakis triphenylphosphine palladium, strong base-weak acid salt, water and toluene mixing progress suzuki reaction, it obtains with Formulas I
Shown in Fluorenone base organogel molecule.
In the present invention, the strong base-weak acid salt is preferably sodium carbonate or potassium carbonate.In the present invention, the strong base weak acid
Salt is used to adjust pH, increases reactivity.
In the present invention, described 3,4,5- tri- (alkoxy)-N- (4- iodophenyl) benzamides, 2,7- bis- (4,4,5,5-
Penta ring -2- base of tetramethyl -1,3,2- dioxy boron) -9H- fluorenes -9- ketone, tetrakis triphenylphosphine palladium, strong base-weak acid salt, water and toluene
The mass ratio of the material is preferably 2~3:1:0.1~0.2:10~15:240~480:245~285, more preferably 2.5:1:0.15:
12:288~350:250~260.
In the present invention, the temperature of the suzuki reaction is preferably 100~130 DEG C, and more preferably 111~120 DEG C；Institute
The time for stating reaction is preferably 15~25, more preferably 20~for 24 hours.
In the present invention, further preferably successively include to the cooling of gained reaction solution after the suzuki reaction, extraction, washing, do
It is dry, be spin-dried for silica gel post separation, obtain with Fluorenone base organogel molecule shown in Formulas I.
In the present invention, the cooling is preferably cooled to room temperature.The present invention does not have the method and rate of the cooling
Particular determination selects method and rate well known to those skilled in the art.
In the present invention, the extraction preferably extracts gained liquid after washing.In the present invention, the extraction
Extractant be preferably ethyl acetate.
The present invention is not particularly limited the method for washing, selects method for washing well known to those skilled in the art.
In the present invention, the desiccant of the drying is preferably that anhydrous sodium sulfate is dry.Side of the present invention to the drying
Method is not particularly limited, and selects drying means well known to those skilled in the art.
In the present invention, described to be spin-dried for preferably being spin-dried for gained organic layer after extraction.In the present invention, the rotation
Dry temperature is preferably 45~55 DEG C, and more preferably 50~55 DEG C.
In the present invention, the silica gel post separation preferably carries out silica gel post separation to being spin-dried for rear products therefrom.The present invention
The method of silica gel post separation is not particularly limited, silicagel column separation method well known to those skilled in the art is selected.
The present invention also provides a kind of fluorescence sense film, the film successively includes gel molecular layer and the quartzy glass of activation
Glass substrate, the gel molecular layer include the gel molecular with structure shown in Formulas I.
In the present invention, the thickness of the gel molecular layer is preferably 10~1000 μm, and more preferably 100~500 μm；
The thickness of the activation quartz glass substrate is preferably 0.1~2mm, more preferably 1~1.8mm.
The present invention also provides a kind of preparation methods of fluorescence sense film, comprising the following steps:
The Fluorenone base organogel molecule with structure shown in Formulas I is mixed with n,N-Dimethylformamide, is obtained
Mixed liquor；The concentration of Fluorenone base organogel molecule is 5 × 10 in the mixed liquor-4~8 × 10-4mol/L；
The mixed liquor is spun on activation one side surface of quartz glass substrate, forms gel molecular layer, obtains fluorescence biography
Feel film.
The present invention heats the Fluorenone base organogel molecule with structure shown in Formulas I and N,N-dimethylformamide
Mixing, obtains mixed liquor；The concentration of Fluorenone base organogel molecule is 5 × 10 in the mixed liquor-4~8 × 10-4Mol/L,
Preferably 6 × 10-4~7 × 10-4mol/L.In the present invention, described to heat mixed preferably 130~170 DEG C of temperature, more preferably
150~160 DEG C.
After obtaining mixed liquor, the present invention in activation one side surface of quartz glass substrate, forms obtained mixing drop solidifying
Glue obtains fluorescence sense film after freeze-dried.
In the present invention, the thickness of the gel molecular layer wet film obtained after the dropwise addition is preferably 10~1000 μm, more excellent
It is selected as 100~500 μm.
It in the present invention, further include being freeze-dried to gel molecular wet film after the spin coating.In the present invention, described
The temperature of freeze-drying is preferably -30~-20 DEG C, and more preferably -28~-23 DEG C.
The present invention is not particularly limited the method for the dropwise addition, selects spin coating method well known to those skilled in the art i.e.
It can.
In the present invention, the preparation method of the activation quartz glass plate preferably includes following steps:
Quartz glass plate is impregnated 1~3 day in butyric acid solution, obtains pretreatment quartz glass plate；
The pretreatment quartz glass plate is immersed in 1~3h of activation in the mixed liquor of the concentrated sulfuric acid and hydrogen peroxide, is lived
Change glass substrate；The mass concentration of the concentrated sulfuric acid is preferably 96~98%, and the dense quality of the hydrogen peroxide is preferably 28
~30%, the volume ratio of the concentrated sulfuric acid and hydrogen peroxide is 2~3:1.
The present invention impregnates quartz glass plate 1~3 day in butyric acid solution, obtains pretreatment quartz glass plate.In this hair
It further preferably successively include washing and drying after the immersion in bright.The present invention is not particularly limited the method for washing, selects this
Method for washing known to the technical staff of field.Such as rinsed with a large amount of clear water.The present invention does not have special limit to dry method
It is fixed, select drying means well known to those skilled in the art.
After obtaining pretreatment quartz glass plate, obtained pretreatment quartz glass plate is immersed in the concentrated sulfuric acid and hydrogen peroxide
1~3h is activated in mixed liquor, obtains activation glass substrate；The mass concentration of the concentrated sulfuric acid is 96~98%, the hydrogen peroxide
Quality it is dense be 28~30%, the volume ratio of the concentrated sulfuric acid and hydrogen peroxide is 2~3:1.
In the present invention, the temperature of the activation is preferably 80~100 DEG C, and more preferably 85~90 DEG C.
It in the present invention, further preferably successively include that glass substrate is cooled to room temperature, wash and is dried after the activation.
The present invention is not particularly limited the method and rate of the cooling, selects cooling well known to those skilled in the art
Method and rate, such as natural cooling.
The present invention is not particularly limited the method for washing, selects method for washing well known to those skilled in the art,
Such as rinsed with a large amount of clear water.
The present invention is not particularly limited dry method, selects drying means well known to those skilled in the art.
The present invention also provides application of the above-mentioned fluorescence sense film in the detection of aniline steam.
When preparing sense film, the intermolecular generation self assembly of Fluorenone base organogel is built into the netted knot of three-dimensional space
Structure increases film itself specific surface area, enhances its absorption to aniline steam；The aniline steam being adsorbed has with Fluorenone base
Photo-induced electron transfer occurs between machine gel molecular, so that the fluorescence of DOF film is quenched, and with aniline vapour concentration
Increase, degree aggravation is quenched.The detection of aniline steam is carried out according to the relationship that amine concentration and DOF film fluorescence are quenched.
For a better understanding of the present invention, below with reference to the embodiment content that the present invention is furture elucidated, but it is of the invention
Content is not limited solely to the following examples.
Embodiment 1
1) synthesis of 3,4,5- tri- (dodecyloxy) methyl benzoate (2)
It weighs respectively gallicin (5.00g, 27.17mmol), potassium carbonate (38g, 275.5mmol), potassium iodide
120mL n,N-Dimethylformamide and 27mL bromo 12 is added in the three-necked flask of 250mL in (0.45g, 2.71mmol)
Alkane.System is in N2Under protection, 70 DEG C of reactions are for 24 hours.TLC monitoring is cooled to room temperature after reaction.The filtrate obtained after suction filtration adds
Enter washing, adds ethyl acetate extraction, merge organic phase, it is dry with anhydrous sodium sulfate.Crude product after silicagel column purifies again
Ethyl alcohol recrystallizes, and obtains white solid product.
The nuclear-magnetism characterize data of gained white solid is as follows:
1H NMR(400MHz,CDCl3,δ):7.24(s,2H；CH),3.96-4.01(m,6H；CH2), 1.81-1.77(m,
6H；CH2),1.34-1.46(m,6H；CH2),1.16-1.39(m,48H；CH2),0.86 (m,9H；CH3)。
By above-mentioned data it is found that above-mentioned white solid is 3,4,5- tri- (dodecyloxy) methyl benzoates, yield is
88.3%.
2) synthesis of 3,4,5- tri- (dodecyloxy) benzoic acid (3)
Weigh 3,4,5- tri- (dodecyloxy) methyl benzoates (13.5g, 19.6mmol) and potassium hydroxide (2.20g,
39.2mmol) in the three-necked flask of 250mL, system flows back 24 hours after 120mL dehydrated alcohol is added.TLC monitoring reaction knot
Shu Hou is added dilute hydrochloric acid and adjusts pH to 1.Reaction solution filters after being cooled to room temperature, and filter residue recrystallizes white in the ethyl alcohol of heat
Solid product.
White solid product nuclear-magnetism characterize data it is as follows:1H NMR(400MHz, CDCl3,δ):7.24(s,
2H；CH),3.96-4.01(m,6H；CH2),1.81-1.77(m,6H；CH2), 1.34-1.46(m,6H；CH2),1.16-1.39
(m,48H；CH2),0.86(m,9H；CH3)
By above-mentioned data it is found that gained white solid product is 3,4,5- tri- (dodecyloxy) benzoic acid, yield is
87.6%.
3) 3,4,5- tri- (dodecyloxy) chlorobenzoyl chloride (4) and 3,4,5- tri- (dodecyloxy)-N- (4- iodophenyl)
The synthesis of benzamide (5)
3,4,5- tri- (dodecyloxy) benzoic acid (2.00g, 2.96mmol) are weighed in the single port eggplant type bottle of 100mL,
System is cooled to room temperature and removes the thionyl chloride in system after system reflux 12h after addition 30mL thionyl chloride.It weighs respectively
Paraiodoaniline (0.77g, 3.52mmol), 1- (3- dimethylamino-propyl) -3- ethyl-carbodiimide hydrochloride (0.68g,
3.54mmol), 4-dimethylaminopyridine (0.29g, 2.38mmol) is added in system, then 50mL 1,2- is added into system
Dichloroethanes makees solvent, and system is stirred at room temperature overnight.TLC is monitored after reaction, by 1, the 2- dichloroethanes in system
It removes.Reaction solution to be poured into beaker after methylene chloride is added and distilled water cleaning reaction solution is added, liquid separation merges organic phase,
It is spin-dried for, obtained mixture obtains white solid product with silicagel column separating-purifying.
The characterize data of gained white solid product is as follows:
1H NMR(400MHz,CDCl3) δ 8.59 (s, 1H, NH), 7.56 (d, J=9.0Hz, 2H, CH), 7.43 (d, J=
9.0Hz, 2H, CH), 6.95 (s, 2H, CH), 3.95 (t, J=5.0Hz, 2H, OCH2), 3,81 (t, J=6.0Hz, 4H, OCH2),
1.71-1.78(m,60H,CH2), 0.88 (t, J=6.0 Hz, 9H, CH3)。
By above-mentioned data it is found that gained white solid product is 3,4,5- tri- (dodecyloxy)-N- (4- iodophenyl) benzene
Formamide, yield 56.6%.
4) synthesis of 2,7- dibromo fluorenone (10)
2,7- dibromo fluorenes (5.00g, 15.5mmol) is weighed respectively, and chromium trioxide (3.72g, 37.2mmol) is in 100mL's
In three-necked flask, 60mL anhydrous acetic acid is added, system is stirred at room temperature 12 hours.After reaction, reaction solution is cooled to
Room temperature filters, and filter residue is successively cleaned with acetic acid, water, dilute hydrochloric acid, and obtained crude product recrystallizes to obtain yellow solid production with ethyl alcohol
Object.
The data characterization of the yellow solid product is as follows:
1H NMR(400MHz,CDCl3): δ 7.78 (d, J=2.0Hz, 1H), 7.67 (d, J=7.2Hz, 1H), 7.62 (d,
J=6.4Hz, 1H), 7.51-7.52 (m, 2H), 7.41 (d, J=7.6Hz, 1H), 7.30-7.35 (m, 1H).
By above-mentioned data it is found that gained yellow solid product is 2,7- dibromo fluorenone, yield 82.3%.
5) synthesis of bis- (penta ring -2- base of 4,4,5,5- tetramethyl -1,3,2- dioxy the boron) -9H- fluorenes -9- ketone (11) of 2,7-
2, the 7- dibromo fluorenone (3.00g, 8.93mmol) prepared is taken, is joined boron pinacol ester (5.45g, 21.4mmol),
[1,1 '-bis- (diphenylphosphino) ferrocene] palladium chloride (0.33g, 0.45mmol), potassium acetate (5.25g, 53.6mmol) in
In two mouthfuls of flasks of 100mL, the n,N-Dimethylformamide of 80mL is added, system is reacted 12 hours for 90 DEG C under nitrogen protection.
TLC is monitored after reaction, and system is cooled to room temperature, and reaction solution is poured into beaker, a large amount of distilled water cleaning reaction solutions are added,
Ethyl acetate extraction is added into system again, separates organic phase, is spin-dried for.Obtained mixture silicagel column separating-purifying, obtains yellow
Color solid product.
The characterize data of gained yellow solid product is as follows:
1H NMR(400MHz,CDCl3) δ ppm8.12 (s, 2H), 7.95 (d, J=7.4Hz, 2H), 7.56 (d, J=
7.4Hz,2H),1.35(s,24H)。
By above-mentioned data it is found that gained yellow solid product is 2,7- bis- (4,4,5,5- tetramethyls -1,3,2- dioxy boron penta
Ring -2- base) -9H- fluorenes -9- ketone, yield 55.8%.
6) N, N'- ((9- oxa- -9H- fluorenes -2,7- diyl) bis- (4,1- styrene)) bis- (3,4,5- tri- (dodecyloxy)
Benzamide) (DOF) synthesis
Bis- (penta ring -2- base of 4,4,5,5- tetramethyl -1,3,2- dioxy the boron) -9H- fluorenes -9- ketone of 2,7- are weighed respectively
(1.00g, 2.31mmol), 3,4,5- tri- (dodecyloxy)-N- (4- iodophenyl) benzamides (2.02g, 2.31mmol),
Tetrakis triphenylphosphine palladium (0.27g, 0.23mmol), potassium carbonate (3.16g, 23.1mmol) add in two mouthfuls of flasks of 100mL
Enter 12mL distilled water and 60mL toluene, system flows back 24 hours under nitrogen protection.After reaction, by the reaction solution in system
It pours into beaker, a large amount of water cleaning reaction solutions is added, then ethyl acetate extraction is added into system, organic phase is separated, after being spin-dried for
Obtained mixture obtains brown-red solid product with silicagel column separating-purifying.
The nuclear-magnetism characterize data of gained brown-red solid product is as follows:
1H NMR(400MHz,CDCl3) δ ppm7.90 (d, J=7.5Hz, 3H), 7.77-7.70 (m, 5H), 7.62 (dd, J
=17.8,8.2Hz, 6H), 7.08 (s, 4H), 4.03 (q, J=6.7Hz, 12H), 1.64 (s, 10H), 1.47 (d, J=
5.9Hz, 12H), 1.27 (s, 98H), 0.88 (t, J=6.7Hz, 18H). HRMS(ESI)m/z calcd for C111H171N2O9 +(M+H)+1676.2979,found 1676.3544.
By above-mentioned data it is found that gained brown-red solid product is DOF, yield 43.5%.
Embodiment 2
20 small test tubes are taken, are divided into two groups, every group ten, is separately added into 2mg embodiment 1 in one group of small test tube and prepares
Then obtained DOF is separately added into petroleum ether, n-hexane, toluene, methylene chloride, chloroform, second into the small test tube of group again
Acetoacetic ester, ethyl alcohol, methanol, N,N-dimethylformamide and dimethyl sulfoxide 2mL.Test tube is heated to test tube solution reflux 2min
Afterwards, solution natural cooling in seed bottle in test tube is taken to cool down, experimental phenomena is as shown in Figure 3.
As shown in Figure 3: by taking DOF forms gel in n,N-Dimethylformamide as an example, 2mgDOF and 2mL N, N- diformazan
Base formamide is heated to reflux two minutes to obtain sol solution, is transferred to natural cooling in seed bottle and cools down, declines with temperature, DOF points
It is self-assembly of one-dimensional fiber stick between son, then mutually tangles the tridimensional network to be formed throughout entire liquid environment, it is molten
Agent molecule is locked in reticular structure, and liquid is prevented to flow, and forms the phenomenon that right figure seed bottle is inverted without sliding.
Embodiment 3
Compound DOF obtained in embodiment 1 is dissolved in n,N-Dimethylformamide, being prepared into concentration is 5 × 10-4's
Stock solution takes 10~20 μ L stock solutions to drop evenly in clean, activation quartz glass substrate surface, is stored at room temperature 5~10
Hour, it spontaneously dries 20~30 hours, fluorescence sense film is prepared, seal spare.
The method of above-mentioned activation glass substrate is:
Quartz glass plate is cut into 2cm × 1cm size, is impregnated 3 days in the chromic acid solution newly prepared, with a large amount of after taking-up
The chromic acid solution that distilled water will indicate that is cleaned, and it is 98%H that mass fraction is immersed into after 100 DEG C of drying2SO4And mass fraction
For 30%H2O2In the mixed solution being made by the volume ratio of 2~3:1, mixed solution is heated to 70 DEG C, it is naturally cold when activating 1
But to room temperature, with a large amount of distilled water flushings, 90~100 DEG C of drying, obtained cleaning, activation glass substrate after cooling.
Embodiment 4
Aniline steam detects at 25 DEG C: placed one layer of gauze containing aniline in the bottom of a quartz colorimetric utensil.
Then the quartz colorimetric utensil of the fluorescence sense film aniline vapor injection of certain volume prepared to one containing embodiment 3
In.The emission spectrum of concentration of aniline dependence of the DOF fluorescent film in the case where incident light is 355nm, test result such as Fig. 4 institute are obtained
Show.As shown in Figure 4, with the increase of concentration of aniline, the emissive porwer of DOF is gradually reduced, and until film adsorption saturation, transmitting is strong
Degree no longer declines；When concentration of aniline is in 220ppm or less, line style relationship y is presented in be quenched efficiency (QE) of concentration of aniline and DOF
=0.0044x+0.2023.
Embodiment 5
The aniline steam test experience in embodiment 4 is carried out to fluorescence sense film first, film is then placed on 30~
It is purged 3 minutes under the conditions of 50 DEG C of hot wind, then carries out the scanning of fluorescence spectrum, respectively the maximum emission intensity of record purging front and back
Numerical value, and carry out 10 as above operations.It finally draws the DOF fluorescence sense film aniline steam detection of Fig. 5 such as and repeats linearity curve.
As shown in Figure 5, it records initial emission intensity and is set to 1, then carry out aniline detection and heating desorbs, record transmitted value, reach
It still can reach 90% of initial strength or more after 10 circulations, illustrate it with good repeatability.
Embodiment 6
1) synthesis of 3,4,5- tri- (dodecyloxy) methyl benzoate (2)
It weighs respectively gallicin (1.00g, 5.434mmol), potassium carbonate (9.12g, 66.12mmol), potassium iodide
70mL n,N-Dimethylformamide and 6.5mL bromo 12 is added in the three-necked flask of 100mL in (0.09g, 0.542mmol)
Alkane.System is in N2Under protection, 70 DEG C of reactions are for 24 hours.TLC monitoring is cooled to room temperature after reaction.The filtrate obtained after suction filtration adds
Enter washing, adds ethyl acetate extraction, merge organic phase, it is dry with anhydrous sodium sulfate.Crude product after silicagel column purifies again
Ethyl alcohol recrystallizes, and obtains white solid product.
The nuclear-magnetism characterize data of gained white solid is as follows:
1H NMR(400MHz,CDCl3,δ):7.24(s,2H；CH),3.96-4.01(m,6H；CH2), 1.81-1.77(m,
6H；CH2),1.34-1.46(m,6H；CH2),1.16-1.39(m,48H；CH2),0.86 (m,9H；CH3)。
By above-mentioned data it is found that above-mentioned white solid is 3,4,5- tri- (dodecyloxy) methyl benzoates, yield is
85.6%.
2) synthesis of 3,4,5- tri- (dodecyloxy) benzoic acid (3)
Weigh 3,4,5- tri- (dodecyloxy) methyl benzoates (2.025g, 2.94mmol) and potassium hydroxide (0.44g,
7.84mmol) in the three-necked flask of 100mL, system flows back 24 hours after 18mL dehydrated alcohol is added.TLC monitoring reaction terminates
Afterwards, dilute hydrochloric acid is added and adjusts pH to 1.Reaction solution filters after being cooled to room temperature, and filter residue recrystallizes white solid in the ethyl alcohol of heat
Body product.
White solid product nuclear-magnetism characterize data it is as follows:1H NMR(400MHz, CDCl3,δ):7.24(s,
2H；CH),3.96-4.01(m,6H；CH2),1.81-1.77(m,6H；CH2), 1.34-1.46(m,6H；CH2),1.16-1.39
(m,48H；CH2),0.86(m,9H；CH3)
By above-mentioned data it is found that gained white solid product is 3,4,5- tri- (dodecyloxy) benzoic acid, yield is
83.2%.
3) 3,4,5- tri- (dodecyloxy) chlorobenzoyl chloride (4) and 3,4,5- tri- (dodecyloxy)-N- (4- iodophenyl)
The synthesis of benzamide (5)
3,4,5- tri- (dodecyloxy) benzoic acid (1.20g, 1.78mmol) are weighed in the single port eggplant type bottle of 100mL,
System is cooled to room temperature and removes the thionyl chloride in system after system reflux 12h after addition 18mL thionyl chloride.It weighs respectively
Paraiodoaniline (0.55g, 2.53mmol), 1- (3- dimethylamino-propyl) -3- ethyl-carbodiimide hydrochloride (0.49g,
2.55mmol), 4-dimethylaminopyridine (0.24g, 1.99mmol) is added in system, then 42mL 1,2- is added into system
Dichloroethanes makees solvent, and system is stirred at room temperature overnight.TLC is monitored after reaction, by 1, the 2- dichloroethanes in system
It removes.Reaction solution to be poured into beaker after methylene chloride is added and distilled water cleaning reaction solution is added, liquid separation merges organic phase,
It is spin-dried for, obtained mixture obtains white solid product with silicagel column separating-purifying.
The characterize data of gained white solid product is as follows:
1H NMR(400MHz,CDCl3) δ 8.59 (s, 1H, NH), 7.56 (d, J=9.0Hz, 2H, CH), 7.43 (d, J=
9.0Hz, 2H, CH), 6.95 (s, 2H, CH), 3.95 (t, J=5.0Hz, 2H, OCH2), 3,81 (t, J=6.0Hz, 4H, OCH2),
1.71-1.78(m,60H,CH2), 0.88 (t, J=6.0 Hz, 9H, CH3)。
By above-mentioned data it is found that gained white solid product is 3,4,5- tri- (dodecyloxy)-N- (4- iodophenyl) benzene
Formamide, yield 55.2%.
4) synthesis of 2,7- dibromo fluorenone (10)
2,7- dibromo fluorenes (3.00g, 9.3mmol) is weighed respectively, and chromium trioxide (2.68g, 26.8mmol) is in 100mL's
In three-necked flask, 43mL anhydrous acetic acid is added, system is stirred at room temperature 12 hours.After reaction, reaction solution is cooled to
Room temperature filters, and filter residue is successively cleaned with acetic acid, water, dilute hydrochloric acid, and obtained crude product recrystallizes to obtain yellow solid production with ethyl alcohol
Object.
The data characterization of the yellow solid product is as follows:
1H NMR(400MHz,CDCl3): δ 7.78 (d, J=2.0Hz, 1H), 7.67 (d, J=7.2Hz, 1H), 7.62 (d,
J=6.4Hz, 1H), 7.51-7.52 (m, 2H), 7.41 (d, J=7.6Hz, 1H), 7.30-7.35 (m, 1H).
By above-mentioned data it is found that gained yellow solid product is 2,7- dibromo fluorenone, yield 80%.
5) synthesis of bis- (penta ring -2- base of 4,4,5,5- tetramethyl -1,3,2- dioxy the boron) -9H- fluorenes -9- ketone (11) of 2,7-
Take 2, the 7- dibromo fluorenone (7.21g, 21.43mmol) prepared, connection boron pinacol ester (15.69g,
61.6mmol), [1,1 '-bis- (diphenylphosphino) ferrocene] palladium chloride (0.95g, 1.29mmol), potassium acetate (12.6g,
128.63mmol) in two mouthfuls of flasks of 250mL, the N of 190mL is added, N- dimethylformamide, system is under nitrogen protection
90 DEG C are reacted 12 hours.TLC is monitored after reaction, and system is cooled to room temperature, and reaction solution is poured into beaker, a large amount of steam is added
Distilled water cleans reaction solution, then ethyl acetate extraction is added into system, separates organic phase, is spin-dried for.Obtained mixture silica gel
Post separation purification, obtains yellow solid product.
The characterize data of gained yellow solid product is as follows:
1H NMR(400MHz,CDCl3) δ ppm8.12 (s, 2H), 7.95 (d, J=7.4Hz, 2H), 7.56 (d, J=
7.4Hz,2H),1.35(s,24H)。
By above-mentioned data it is found that gained yellow solid product is 2,7- bis- (4,4,5,5- tetramethyls -1,3,2- dioxy boron penta
Ring -2- base) -9H- fluorenes -9- ketone, yield 53.1%.
6) N, N'- ((9- oxa- -9H- fluorenes -2,7- diyl) bis- (4,1- styrene)) bis- (3,4,5- tri- (dodecyloxy)
Benzamide) (DOF) synthesis
Bis- (penta ring -2- base of 4,4,5,5- tetramethyl -1,3,2- dioxy the boron) -9H- fluorenes -9- ketone of 2,7- are weighed respectively
(0.6g, 1.38mmol), 3,4,5- tri- (dodecyloxy)-N- (4- iodophenyl) benzamides (1.45g, 1.65mmol), four
(triphenylphosphine) palladium (0.19g, 0.16mmol), potassium carbonate (2.28g, 16.63mmol) are added in two mouthfuls of flasks of 100mL
8.6mL distilled water and 43mL toluene, system flow back 24 hours under nitrogen protection.After reaction, by the reaction solution in system
It pours into beaker, a large amount of water cleaning reaction solutions is added, then ethyl acetate extraction is added into system, organic phase is separated, after being spin-dried for
Obtained mixture obtains brown-red solid product with silicagel column separating-purifying.
The nuclear-magnetism characterize data of gained brown-red solid product is as follows:
1H NMR(400MHz,CDCl3) δ ppm7.90 (d, J=7.5Hz, 3H), 7.77-7.70 (m, 5H), 7.62 (dd, J
=17.8,8.2Hz, 6H), 7.08 (s, 4H), 4.03 (q, J=6.7Hz, 12H), 1.64 (s, 10H), 1.47 (d, J=
5.9Hz, 12H), 1.27 (s, 98H), 0.88 (t, J=6.7Hz, 18H). HRMS(ESI)m/z calcd for C111H171N2O9 +(M+H)+1676.2979,found 1676.3544.
By above-mentioned data it is found that gained brown-red solid product is DOF, yield 44.8%.
Embodiment 7
1) synthesis of 3,4,5- tri- (dodecyloxy) methyl benzoate (2)
It weighs respectively gallicin (3.30g, 17.93mmol), potassium carbonate (32.6g, 236.4mmol), potassium iodide
80mL n,N-Dimethylformamide and 19mL bromo 12 is added in the three-necked flask of 250mL in (0.33g, 1.97mmol)
Alkane.System is in N2Under protection, 70 DEG C of reactions are for 24 hours.TLC monitoring is cooled to room temperature after reaction.The filtrate obtained after suction filtration adds
Enter washing, adds ethyl acetate extraction, merge organic phase, it is dry with anhydrous sodium sulfate.Crude product after silicagel column purifies again
Ethyl alcohol recrystallizes, and obtains white solid product.
The nuclear-magnetism characterize data of gained white solid is as follows:
1H NMR(400MHz,CDCl3,δ):7.24(s,2H；CH),3.96-4.01(m,6H；CH2), 1.81-1.77(m,
6H；CH2),1.34-1.46(m,6H；CH2),1.16-1.39(m,48H；CH2),0.86 (m,9H；CH3)。
By above-mentioned data it is found that above-mentioned white solid is 3,4,5- tri- (dodecyloxy) methyl benzoates, yield is
88.3%.
2) synthesis of 3,4,5- tri- (dodecyloxy) benzoic acid (3)
Weigh 3,4,5- tri- (dodecyloxy) methyl benzoates (6.8g, 9.8mmol) and potassium hydroxide (1.10g,
19.6mmol) in the three-necked flask of 250mL, system flows back 14 hours after 120mL dehydrated alcohol is added.TLC monitoring reaction knot
Shu Hou is added dilute hydrochloric acid and adjusts pH to 1.Reaction solution filters after being cooled to room temperature, and filter residue recrystallizes white in the ethyl alcohol of heat
Solid product.
White solid product nuclear-magnetism characterize data it is as follows:1H NMR(400MHz, CDCl3,δ):7.24(s,
2H；CH),3.96-4.01(m,6H；CH2),1.81-1.77(m,6H；CH2), 1.34-1.46(m,6H；CH2),1.16-1.39
(m,48H；CH2),0.86(m,9H；CH3)
By above-mentioned data it is found that gained white solid product is 3,4,5- tri- (dodecyloxy) benzoic acid, yield is
88%.
3) 3,4,5- tri- (dodecyloxy) chlorobenzoyl chloride (4) and 3,4,5- tri- (dodecyloxy)-N- (4- iodophenyl)
The synthesis of benzamide (5)
3,4,5- tri- (dodecyloxy) benzoic acid (1.00g, 1.46mmol) are weighed in the single port eggplant type bottle of 100mL,
System is cooled to room temperature and removes the thionyl chloride in system after system reflux 11h after addition 14mL thionyl chloride.It weighs respectively
Paraiodoaniline (0.37g, 1.81mmol), 1- (3- dimethylamino-propyl) -3- ethyl-carbodiimide hydrochloride (0.34g,
1.72mmol), 4-dimethylaminopyridine (0.15g, 1.19mmol) is added in system, then 25mL 1,2- is added into system
Dichloroethanes makees solvent, and system is stirred at room temperature overnight.TLC is monitored after reaction, by 1, the 2- dichloroethanes in system
It removes.Reaction solution to be poured into beaker after methylene chloride is added and distilled water cleaning reaction solution is added, liquid separation merges organic phase,
It is spin-dried for, obtained mixture obtains white solid product with silicagel column separating-purifying.
The characterize data of gained white solid product is as follows:
1H NMR(400MHz,CDCl3) δ 8.59 (s, 1H, NH), 7.56 (d, J=9.0Hz, 2H, CH), 7.43 (d, J=
9.0Hz, 2H, CH), 6.95 (s, 2H, CH), 3.95 (t, J=5.0Hz, 2H, OCH2), 3,81 (t, J=6.0Hz, 4H, OCH2),
1.71-1.78(m,60H,CH2), 0.88 (t, J=6.0 Hz, 9H, CH3)。
By above-mentioned data it is found that gained white solid product is 3,4,5- tri- (dodecyloxy)-N- (4- iodophenyl) benzene
Formamide, yield 51.6%.
4) synthesis of 2,7- dibromo fluorenone (10)
2,7- dibromo fluorenes (2.50g, 7.7mmol) is weighed respectively, and chromium trioxide (1.86g, 18.6mmol) is in 100mL's
In three-necked flask, 30mL anhydrous acetic acid is added, system is stirred at room temperature 14 hours.After reaction, reaction solution is cooled to
Room temperature filters, and filter residue is successively cleaned with acetic acid, water, dilute hydrochloric acid, and obtained crude product recrystallizes to obtain yellow solid production with ethyl alcohol
Object.
The data characterization of the yellow solid product is as follows:
1H NMR(400MHz,CDCl3): δ 7.78 (d, J=2.0Hz, 1H), 7.67 (d, J=7.2Hz, 1H), 7.62 (d,
J=6.4Hz, 1H), 7.51-7.52 (m, 2H), 7.41 (d, J=7.6Hz, 1H), 7.30-7.35 (m, 1H).
By above-mentioned data it is found that gained yellow solid product is 2,7- dibromo fluorenone, yield 78.3%.
5) synthesis of bis- (penta ring -2- base of 4,4,5,5- tetramethyl -1,3,2- dioxy the boron) -9H- fluorenes -9- ketone (11) of 2,7-
Take 2, the 7- dibromo fluorenone (1.50g, 4.45mmol) prepared, connection boron pinacol ester (2.72g,
10.07mmol), [1,1 '-bis- (diphenylphosphino) ferrocene] palladium chloride (0.16g, 0.23mmol), potassium acetate (2.65g,
26.7mmol) in two mouthfuls of flasks of 100mL, it is added the n,N-Dimethylformamide of 40mL, 100 DEG C under nitrogen protection of system
Reaction 14 hours.TLC is monitored after reaction, and system is cooled to room temperature, and reaction solution is poured into beaker, a large amount of distilled water are added
Reaction solution is cleaned, then ethyl acetate extraction is added into system, organic phase is separated, is spin-dried for.Obtained mixture silicagel column point
From purification, yellow solid product is obtained.
The characterize data of gained yellow solid product is as follows:
1H NMR(400MHz,CDCl3) δ ppm8.12 (s, 2H), 7.95 (d, J=7.4Hz, 2H), 7.56 (d, J=
7.4Hz,2H),1.35(s,24H)。
By above-mentioned data it is found that gained yellow solid product is 2,7- bis- (4,4,5,5- tetramethyls -1,3,2- dioxy boron penta
Ring -2- base) -9H- fluorenes -9- ketone, yield 52.8%.
6) N, N'- ((9- oxa- -9H- fluorenes -2,7- diyl) bis- (4,1- styrene)) bis- (3,4,5- tri- (dodecyloxy)
Benzamide) (DOF) synthesis
Bis- (penta ring -2- base of 4,4,5,5- tetramethyl -1,3,2- dioxy the boron) -9H- fluorenes -9- ketone of 2,7- are weighed respectively
(0.52g, 1.65mmol), 3,4,5- tri- (dodecyloxy)-N- (4- iodophenyl) benzamides (1.02g, 1.65mmol),
Tetrakis triphenylphosphine palladium (0.13g, 0.12mmol), potassium carbonate (1.61g, 12.1mmol) add in two mouthfuls of flasks of 100mL
Enter 6mL distilled water and 30mL toluene, system flows back 21 hours under nitrogen protection.After reaction, by the reaction solution in system
It pours into beaker, a large amount of water cleaning reaction solutions is added, then ethyl acetate extraction is added into system, organic phase is separated, after being spin-dried for
Obtained mixture obtains brown-red solid product with silicagel column separating-purifying.
The nuclear-magnetism characterize data of gained brown-red solid product is as follows:
1H NMR(400MHz,CDCl3) δ ppm7.90 (d, J=7.5Hz, 3H), 7.77-7.70 (m, 5H), 7.62 (dd, J
=17.8,8.2Hz, 6H), 7.08 (s, 4H), 4.03 (q, J=6.7Hz, 12H), 1.64 (s, 10H), 1.47 (d, J=
5.9Hz, 12H), 1.27 (s, 98H), 0.88 (t, J=6.7Hz, 18H). HRMS(ESI)m/z calcd for C111H171N2O9 +(M+H)+1676.2979,found 1676.3544.
By above-mentioned data it is found that gained brown-red solid product is DOF, yield 44.2%.
Embodiment 8
1) synthesis of 3,4,5- tri- (normal octane oxygroup) methyl benzoate
It weighs respectively gallicin (5.00g, 27.17mmol), potassium carbonate (38g, 275.5mmol), potassium iodide
120mL n,N-Dimethylformamide and 21mL bromooctane is added in the three-necked flask of 250mL in (0.45g, 2.71mmol).Body
Tie up to N2Under protection, 70 DEG C of reactions are for 24 hours.TLC monitoring is cooled to room temperature after reaction.Water is added in the filtrate obtained after suction filtration
It washes, adds ethyl acetate extraction, merge organic phase, it is dry with anhydrous sodium sulfate.Crude product ethyl alcohol again after silicagel column purifies
It recrystallizes, obtains white solid product.
It will test it is found that above-mentioned white solid is 3,4,5- tri- (normal octane oxygroup) methyl benzoates, yield is
84.6%.
2) synthesis of 3,4,5- tri- (normal octane oxygroup) benzoic acid
Weigh 3,4,5- tri- (normal octane oxygroup) methyl benzoates (10.2g, 19.6mmol) and potassium hydroxide (2.20g,
39.2mmol) in the three-necked flask of 250mL, system flows back 24 hours after 120mL dehydrated alcohol is added.TLC monitoring reaction knot
Shu Hou is added dilute hydrochloric acid and adjusts pH to 1.Reaction solution filters after being cooled to room temperature, and filter residue recrystallizes white in the ethyl alcohol of heat
Solid product.
Through, it is found that gained white solid product is 3,4,5- tri- (normal octane oxygroup) benzoic acid, yield is known to detection
80.1%.
3) 3,4,5- tri- (normal octane oxygroup) chlorobenzoyl chloride (4) and 3,4,5- tri- (normal octane oxygroup)-N- (4- iodophenyl)
The synthesis of benzamide (5)
3,4,5- tri- (normal octane oxygroup) benzoic acid (1.49g, 2.96mmol) are weighed in the single port eggplant type bottle of 100mL,
System is cooled to room temperature and removes the thionyl chloride in system after system reflux 12h after addition 30mL thionyl chloride.It weighs respectively
Paraiodoaniline (0.77g, 3.52mmol), 1- (3- dimethylamino-propyl) -3- ethyl-carbodiimide hydrochloride (0.68g,
3.54mmol), 4-dimethylaminopyridine (0.29g, 2.38mmol) is added in system, then 50mL 1,2- is added into system
Dichloroethanes makees solvent, and system is stirred at room temperature overnight.TLC is monitored after reaction, by 1, the 2- dichloroethanes in system
It removes.Reaction solution to be poured into beaker after methylene chloride is added and distilled water cleaning reaction solution is added, liquid separation merges organic phase,
It is spin-dried for, obtained mixture obtains white solid product with silicagel column separating-purifying.
By above-mentioned data it is found that gained white solid product is 3,4,5- tri- (normal octane oxygroup)-N- (4- iodophenyl) benzene
Formamide, yield 46.7%.
4) bis- (penta ring -2- of 4,4,5,5- tetramethyl -1,3,2- dioxy boron of 2,7- obtained in embodiment 1 are weighed respectively
Base) -9H- fluorenes -9- ketone (1.00g, 2.31mmol), 3,4,5- tri- (normal octane oxygroup)-N- (4- iodophenyl) benzamides
(2.31mmol), tetrakis triphenylphosphine palladium (0.27g, 0.23mmol), potassium carbonate (3.16g, 23.1mmol) is in the two of 100mL
In mouth flask, 12mL distilled water is added and 60mL toluene, system flow back 24 hours under nitrogen protection.After reaction, by body
Reaction solution in system pours into beaker, a large amount of water cleaning reaction solutions is added, then ethyl acetate extraction is added into system, has separated
Machine phase, the mixture obtained after being spin-dried for obtain brown-red solid product with silicagel column separating-purifying.Through detecting, the rufous is solid
Body product is N, N'- ((9- oxa- -9H- fluorenes -2,7- diyl) bis- (4,1- styrene)) bis- (3,4,5- tri- (normal octane oxygroup)
Benzamide.Yield is 46%.
Embodiment 9
1) synthesis of 3,4,5- tri- (hexadecane epoxide) methyl benzoate
It weighs respectively gallicin (5.00g, 27.17mmol), potassium carbonate (38g, 275.5mmol), potassium iodide
120mL n,N-Dimethylformamide and 27mL bromo 12 is added in the three-necked flask of 250mL in (0.45g, 2.71mmol)
Alkane.System is in N2Under protection, 70 DEG C of reactions are for 24 hours.TLC monitoring is cooled to room temperature after reaction.The filtrate obtained after suction filtration adds
Enter washing, adds ethyl acetate extraction, merge organic phase, it is dry with anhydrous sodium sulfate.Crude product after silicagel column purifies again
Ethyl alcohol recrystallizes, and obtains white solid product.Through detection it is found that above-mentioned white solid is 3,4,5- tri- (hexadecane epoxide) benzene first
Sour methyl esters, yield 88.3%.
2) synthesis of 3,4,5- tri- (hexadecane epoxide) benzoic acid
Weigh 3,4,5- tri- (hexadecane epoxide) methyl benzoates (16.78g, 19.6mmol) and potassium hydroxide (2.20g,
39.2mmol) in the three-necked flask of 250mL, system flows back 24 hours after 120mL dehydrated alcohol is added.TLC monitoring reaction knot
Shu Hou is added dilute hydrochloric acid and adjusts pH to 1.Reaction solution filters after being cooled to room temperature, and filter residue recrystallizes white in the ethyl alcohol of heat
Solid product.It is found that gained white solid product is 3,4,5- tri- (hexadecane epoxide) benzoic acid known to being detected, yield is
87.6%.
3) 3,4,5- tri- (hexadecane epoxide) chlorobenzoyl chloride (4) and 3,4,5- tri- (hexadecane epoxide)-N- (4- iodophenyl)
The synthesis of benzamide (5)
3,4,5- tri- (hexadecane epoxide) benzoic acid (2.49g, 2.96mmol) are weighed in the single port eggplant type bottle of 100mL,
System is cooled to room temperature and removes the thionyl chloride in system after system reflux 12h after addition 30mL thionyl chloride.It weighs respectively
Paraiodoaniline (0.77g, 3.52mmol), 1- (3- dimethylamino-propyl) -3- ethyl-carbodiimide hydrochloride (0.68g,
3.54mmol), 4-dimethylaminopyridine (0.29g, 2.38mmol) is added in system, then 50mL 1,2- is added into system
Dichloroethanes makees solvent, and system is stirred at room temperature overnight.TLC is monitored after reaction, by 1, the 2- dichloroethanes in system
It removes.Reaction solution to be poured into beaker after methylene chloride is added and distilled water cleaning reaction solution is added, liquid separation merges organic phase,
It is spin-dried for, obtained mixture obtains white solid product with silicagel column separating-purifying.Through detecting it is found that gained white solid product is
3,4,5- tri- (hexadecane epoxide)-N- (4- iodophenyl) benzamides, yield 57.6%.
4) bis- (penta ring -2- of 4,4,5,5- tetramethyl -1,3,2- dioxy boron of 2,7- obtained in embodiment 1 are weighed respectively
Base) -9H- fluorenes -9- ketone (1.00g, 2.31mmol), 3,4,5- tri- (hexadecane epoxide)-N- (4- iodophenyl) benzamides
(2.31mmol), tetrakis triphenylphosphine palladium (0.27g, 0.23mmol), potassium carbonate (3.16g, 23.1mmol) is in the two of 100mL
In mouth flask, 12mL distilled water is added and 60mL toluene, system flow back 24 hours under nitrogen protection.After reaction, by body
Reaction solution in system pours into beaker, a large amount of water cleaning reaction solutions is added, then ethyl acetate extraction is added into system, has separated
Machine phase, the mixture obtained after being spin-dried for obtain brown-red solid product with silicagel column separating-purifying.Through detecting, the rufous is solid
Body product is N, N'- ((9- oxa- -9H- fluorenes -2,7- diyl) bis- (4,1- styrene)) bis- (3,4,5- tri- (normal octane oxygroup) benzene
Formamide.Yield is 46%.
The above is only a preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art
For member, various improvements and modifications may be made without departing from the principle of the present invention, these improvements and modifications are also answered
It is considered as protection scope of the present invention.
Claims (10)
1. a kind of Fluorenone base organogel molecule with structure shown in Formulas I:
The R is the alkyl of C4~C16.
2. a kind of preparation method of the Fluorenone base organogel molecule described in claim 1 with structure shown in Formulas I, including with
Lower step:
1) gallicin, brominated alkanes, alkaline metal iodide, strong base-weak acid salt and organic solvent are mixed, in anaerobic ring
Alkoxide reaction is carried out under border, obtains 3,4,5- tri- (alkoxy) methyl benzoates；The brominated alkanes are the monobromo of C4~C16
For alkane；
2) 3,4,5- tri- (alkoxy) methyl benzoate, alkali metal hydroxide and ethyl alcohol that the step 1) obtains are mixed into
Row hydrolysis obtains 3,4,5- tri- (alkoxy) benzoic acid；
3) obtain the step 2) 3,4,5- tri- (alkoxy) benzoic acid are mixed with thionyl chloride carries out chlorination, obtains
3,4,5- tri- (alkoxy) chlorobenzoyl chloride；
4) 3,4,5- tri- (alkoxy) chlorobenzoyl chloride, paraiodoaniline, the 1- (3- dimethylamino-propyl)-obtained the step 3)
3- ethyl-carbodiimide hydrochloride, 4-dimethylaminopyridine and 1, the mixing of 2- dichloroethanes carry out acylation reaction, obtain 3,4,
5- tri- (alkoxy)-N- (4- iodophenyl) benzamide；
5) 2,7- dibromo fluorenes, potassium bichromate and acetic acid are mixed and carries out oxidation reaction, obtain 2,7- dibromo fluorenone；
6) 2,7- dibromo fluorenone, connection the boron pinacol ester, [1,1 '-bis- (diphenylphosphino) ferrocene] obtained the step 5)
Palladium chloride, acetate and n,N-Dimethylformamide carry out coupling reaction under oxygen-free environment, obtain 2,7- bis- (4,4,5,5-
Penta ring -2- base of tetramethyl -1,3,2- dioxy boron) -9H- fluorenes -9- ketone；
7) 3,4,5- tri- (alkoxy)-N- (4- iodophenyl) benzamide that the step 4) obtains, the step 6) are obtained
2,7- bis- (penta ring -2- base of 4,4,5,5- tetramethyl -1,3,2- dioxy boron) -9H- fluorenes -9- ketone, tetrakis triphenylphosphine palladium, highly basic
Salt of weak acid, water and toluene mixing carry out suzuki reaction, obtain with Fluorenone base organogel molecule shown in Formulas I.
3. preparation method according to claim 2, which is characterized in that alkaline metal iodide is sodium iodide in the step 1)
And/or potassium iodide；The strong base-weak acid salt is sodium carbonate and/or potassium carbonate；The organic solvent is N,N-dimethylformamide
Or DMAC N,N' dimethyl acetamide.
4. preparation method according to claim 2 or 3, which is characterized in that gallicin, bromo in the step 1)
The mass ratio of the material of alkane, alkaline metal iodide, strong base-weak acid salt and organic solvent are as follows: 1:4~10:0.1:8~15:50~
100。
5. preparation method according to claim 2, which is characterized in that 3,4,5- tri- (alkoxy) benzene first in the step 2)
The mass ratio of the material of sour methyl esters, alkali metal hydroxide and ethyl alcohol is 1:1~4:50~150.
6. preparation method according to claim 2, which is characterized in that paraiodoaniline, 1- (3- diformazan ammonia in the step 4)
Base propyl) -3- ethyl-carbodiimide hydrochloride, 4-dimethylaminopyridine, 1,2- dichloroethanes and 3,4,5- tri- (alkoxy) benzene
The mass ratio of the material of formic acid is 1~3:1~3:0.5~2:210~420:1.
7. according to preparation method as claimed in claim 2, which is characterized in that 2,7- dibromo fluorenone in the step 6), connection boron frequency that
The mass ratio of the material of alcohol ester, [1,1 '-bis- (diphenylphosphino) ferrocene] palladium chloride, acetate and N,N-dimethylformamide
For 1:1~3:0.01~0.1:5~10:115~145.
8. according to preparation method as claimed in claim 2, which is characterized in that 3,4,5- tri- (alkoxy)-N- (4- in the step 7)
Iodophenyl) benzamide, 2,7- bis- (penta ring -2- base of 4,4,5,5- tetramethyl -1,3,2- dioxy boron) -9H- fluorenes -9- ketone, four (three
Phenylphosphine) palladium, strong base-weak acid salt, water and toluene the mass ratio of the material be 2~3:1:0.1~0.2:10~15:240~480:
245~285.
9. a kind of fluorescence sense film, the fluorescence sense film successively includes gel molecular layer and activation quartz glass substrate,
The gel molecular layer includes the gel molecular described in claim 1 with structure shown in Formulas I.
10. application of the fluorescence sense film as claimed in claim 9 in the detection of aniline steam.
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|---|---|---|---|---|
| CN110006887A (en) * | 2019-04-29 | 2019-07-12 | 南京工程学院 | A kind of novel organic amine gas detection film and preparation method thereof |
| CN114436923A (en) * | 2022-01-06 | 2022-05-06 | 宁波大学 | Small-molecule antibacterial gel for promoting wound healing after infection of antibiotic drug-resistant bacteria |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7157124B2 (en) * | 2003-01-06 | 2007-01-02 | Chisso Petrochemical Corporation | Polymerizable compounds and their polymers |
| CN101040028A (en) * | 2004-10-13 | 2007-09-19 | 罗利克有限公司 | Photocrosslinkable materials |
| CN105693539A (en) * | 2016-01-12 | 2016-06-22 | 湖南工业大学 | High-planarity diamine monomer containing fluorene or fluorenone structure and synthesis method and application thereof |
| CN105713018A (en) * | 2014-12-05 | 2016-06-29 | 中国石油化工股份有限公司 | Metal organic skeleton material and preparation method thereof |
-
2018
- 2018-11-08 CN CN201811325579.3A patent/CN109485582B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7157124B2 (en) * | 2003-01-06 | 2007-01-02 | Chisso Petrochemical Corporation | Polymerizable compounds and their polymers |
| CN101040028A (en) * | 2004-10-13 | 2007-09-19 | 罗利克有限公司 | Photocrosslinkable materials |
| CN105713018A (en) * | 2014-12-05 | 2016-06-29 | 中国石油化工股份有限公司 | Metal organic skeleton material and preparation method thereof |
| CN105693539A (en) * | 2016-01-12 | 2016-06-22 | 湖南工业大学 | High-planarity diamine monomer containing fluorene or fluorenone structure and synthesis method and application thereof |
Non-Patent Citations (4)
| Title |
|---|
| GALEN L. EAKINSA，等: "Tuning HOMO–LUMO levels: trends leading to the design of 9‐fluorenone scaffolds with predictable electronic and optoelectronic properties", 《JOURNAL OF PHYSICAL ORGANIC CHEMISTRY》 * |
| JIAYUN FAN，等: "Functionality Oriented Derivatization of Naphthalenediimide: A Molecular Gel Strategy-Based Fluorescent Film for Aniline Vapor Detection", 《ACS APPLIED MATERIALS & INTERFACES》 * |
| JINYANG HU，等: "AIE-active molecule-based self-assembled nano-fibrous films for sensitive detection of volatile organic amines", 《JOURNAL OF MATERIALS CHEMISTRY C》 * |
| VAISHALI SAMANT，等: "Dynamics of intermolecular electron transfer from amines to the excited states of 9-fluorenone", 《JOURNAL OF PHOTOCHEMISTRY AND PHOTOBIOLOGY A: CHEMISTRY》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110006887A (en) * | 2019-04-29 | 2019-07-12 | 南京工程学院 | A kind of novel organic amine gas detection film and preparation method thereof |
| CN114436923A (en) * | 2022-01-06 | 2022-05-06 | 宁波大学 | Small-molecule antibacterial gel for promoting wound healing after infection of antibiotic drug-resistant bacteria |
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| CN109485582B (en) | 2020-07-17 |
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