CN104277065A - Complex, preparation method thereof, fluorine ion sensor and method for detecting fluorine ion - Google Patents
Complex, preparation method thereof, fluorine ion sensor and method for detecting fluorine ion Download PDFInfo
- Publication number
- CN104277065A CN104277065A CN201410443247.0A CN201410443247A CN104277065A CN 104277065 A CN104277065 A CN 104277065A CN 201410443247 A CN201410443247 A CN 201410443247A CN 104277065 A CN104277065 A CN 104277065A
- Authority
- CN
- China
- Prior art keywords
- unsubstituted
- replacement
- title complex
- solution
- group
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 238000002360 preparation method Methods 0.000 title claims abstract description 56
- 238000000034 method Methods 0.000 title claims abstract description 40
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 title claims abstract description 26
- 125000001072 heteroaryl group Chemical group 0.000 claims abstract description 24
- 239000000126 substance Substances 0.000 claims abstract description 23
- 229910052805 deuterium Inorganic materials 0.000 claims abstract description 20
- YZCKVEUIGOORGS-OUBTZVSYSA-N Deuterium Chemical compound [2H] YZCKVEUIGOORGS-OUBTZVSYSA-N 0.000 claims abstract description 18
- YZCKVEUIGOORGS-NJFSPNSNSA-N Tritium Chemical compound [3H] YZCKVEUIGOORGS-NJFSPNSNSA-N 0.000 claims abstract description 18
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract description 18
- 125000004093 cyano group Chemical group *C#N 0.000 claims abstract description 18
- 229910052722 tritium Inorganic materials 0.000 claims abstract description 18
- 229910052736 halogen Inorganic materials 0.000 claims abstract description 16
- 150000002367 halogens Chemical class 0.000 claims abstract description 16
- 230000008859 change Effects 0.000 claims description 56
- 238000000862 absorption spectrum Methods 0.000 claims description 47
- -1 nitro, hydroxyl Chemical group 0.000 claims description 44
- 238000002189 fluorescence spectrum Methods 0.000 claims description 30
- 239000000203 mixture Substances 0.000 claims description 21
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 19
- 238000002156 mixing Methods 0.000 claims description 19
- 238000006243 chemical reaction Methods 0.000 claims description 18
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 17
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 15
- 230000008569 process Effects 0.000 claims description 15
- ILAHWRKJUDSMFH-UHFFFAOYSA-N boron tribromide Chemical compound BrB(Br)Br ILAHWRKJUDSMFH-UHFFFAOYSA-N 0.000 claims description 8
- 125000005913 (C3-C6) cycloalkyl group Chemical group 0.000 claims description 7
- 230000015572 biosynthetic process Effects 0.000 claims description 7
- 239000002904 solvent Substances 0.000 claims description 7
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 claims description 6
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 6
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 6
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 6
- 125000006650 (C2-C4) alkynyl group Chemical group 0.000 claims description 5
- 125000003601 C2-C6 alkynyl group Chemical group 0.000 claims description 5
- 238000003786 synthesis reaction Methods 0.000 claims description 5
- 229920000137 polyphosphoric acid Polymers 0.000 claims description 4
- 125000003118 aryl group Chemical group 0.000 abstract description 8
- 125000000304 alkynyl group Chemical group 0.000 abstract description 6
- 125000003545 alkoxy group Chemical group 0.000 abstract description 3
- 125000004104 aryloxy group Chemical group 0.000 abstract description 3
- 125000000753 cycloalkyl group Chemical group 0.000 abstract description 3
- 125000004185 ester group Chemical group 0.000 abstract description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 abstract description 2
- 125000000923 (C1-C30) alkyl group Chemical group 0.000 abstract 1
- 125000000739 C2-C30 alkenyl group Chemical group 0.000 abstract 1
- 125000003277 amino group Chemical group 0.000 abstract 1
- 125000001033 ether group Chemical group 0.000 abstract 1
- 125000005245 nitryl group Chemical group [N+](=O)([O-])* 0.000 abstract 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 50
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 32
- 239000003446 ligand Substances 0.000 description 17
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 16
- 125000000217 alkyl group Chemical group 0.000 description 15
- 238000005481 NMR spectroscopy Methods 0.000 description 14
- 125000004432 carbon atom Chemical group C* 0.000 description 14
- 239000007787 solid Substances 0.000 description 14
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 11
- 229910052799 carbon Inorganic materials 0.000 description 11
- 238000001514 detection method Methods 0.000 description 11
- 150000002500 ions Chemical class 0.000 description 11
- 230000000694 effects Effects 0.000 description 10
- 238000010521 absorption reaction Methods 0.000 description 8
- 239000013078 crystal Substances 0.000 description 8
- FPGGTKZVZWFYPV-UHFFFAOYSA-M tetrabutylammonium fluoride Chemical compound [F-].CCCC[N+](CCCC)(CCCC)CCCC FPGGTKZVZWFYPV-UHFFFAOYSA-M 0.000 description 8
- FLIQZZAJPCIEKH-UHFFFAOYSA-N COC1=CC(=C(C=C1)C(=O)O)OCl Chemical compound COC1=CC(=C(C=C1)C(=O)O)OCl FLIQZZAJPCIEKH-UHFFFAOYSA-N 0.000 description 7
- ICVPMDZOZGOFSB-UHFFFAOYSA-N carbonyl dichloride methyl benzoate Chemical compound COC(C1=CC=CC=C1)=O.C(=O)(Cl)Cl ICVPMDZOZGOFSB-UHFFFAOYSA-N 0.000 description 7
- 125000001624 naphthyl group Chemical group 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- 238000005160 1H NMR spectroscopy Methods 0.000 description 6
- ILUJQPXNXACGAN-UHFFFAOYSA-N O-methylsalicylic acid Chemical compound COC1=CC=CC=C1C(O)=O ILUJQPXNXACGAN-UHFFFAOYSA-N 0.000 description 6
- 238000004458 analytical method Methods 0.000 description 6
- 229960004756 ethanol Drugs 0.000 description 6
- QPJVMBTYPHYUOC-UHFFFAOYSA-N methyl benzoate Chemical compound COC(=O)C1=CC=CC=C1 QPJVMBTYPHYUOC-UHFFFAOYSA-N 0.000 description 6
- 239000000843 powder Substances 0.000 description 6
- 150000003839 salts Chemical class 0.000 description 6
- 238000010586 diagram Methods 0.000 description 5
- 238000011156 evaluation Methods 0.000 description 5
- 125000002769 thiazolinyl group Chemical group 0.000 description 5
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- 150000001555 benzenes Chemical group 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 230000003993 interaction Effects 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 239000012046 mixed solvent Substances 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 125000001424 substituent group Chemical group 0.000 description 4
- 230000016776 visual perception Effects 0.000 description 4
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 125000004450 alkenylene group Chemical group 0.000 description 3
- 125000001118 alkylidene group Chemical group 0.000 description 3
- 125000004419 alkynylene group Chemical group 0.000 description 3
- 125000003968 arylidene group Chemical group [H]C(c)=* 0.000 description 3
- 125000001995 cyclobutyl group Chemical group [H]C1([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 3
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 3
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 3
- 125000001559 cyclopropyl group Chemical group [H]C1([H])C([H])([H])C1([H])* 0.000 description 3
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical group C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 3
- 125000001207 fluorophenyl group Chemical group 0.000 description 3
- 229940095102 methyl benzoate Drugs 0.000 description 3
- 125000004430 oxygen atom Chemical group O* 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- FKASFBLJDCHBNZ-UHFFFAOYSA-N 1,3,4-oxadiazole Chemical group C1=NN=CO1 FKASFBLJDCHBNZ-UHFFFAOYSA-N 0.000 description 2
- GNYCSXNVIRAAEC-UHFFFAOYSA-N 5-chloro-2-methoxybenzohydrazide Chemical compound COC1=CC=C(Cl)C=C1C(=O)NN GNYCSXNVIRAAEC-UHFFFAOYSA-N 0.000 description 2
- 241000972773 Aulopiformes Species 0.000 description 2
- WPQKONYBICXUFR-UHFFFAOYSA-N CCOC(C(C=C1OCl)=CC=C1OC)=O Chemical compound CCOC(C(C=C1OCl)=CC=C1OC)=O WPQKONYBICXUFR-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- 125000005428 anthryl group Chemical group [H]C1=C([H])C([H])=C2C([H])=C3C(*)=C([H])C([H])=C([H])C3=C([H])C2=C1[H] 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- PASDCCFISLVPSO-UHFFFAOYSA-N benzoyl chloride Chemical compound ClC(=O)C1=CC=CC=C1 PASDCCFISLVPSO-UHFFFAOYSA-N 0.000 description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 125000001309 chloro group Chemical group Cl* 0.000 description 2
- 125000000000 cycloalkoxy group Chemical group 0.000 description 2
- 229960000935 dehydrated alcohol Drugs 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 230000005284 excitation Effects 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 125000005843 halogen group Chemical group 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 125000000623 heterocyclic group Chemical group 0.000 description 2
- 125000000717 hydrazino group Chemical group [H]N([*])N([H])[H] 0.000 description 2
- 125000005597 hydrazone group Chemical group 0.000 description 2
- 125000005647 linker group Chemical group 0.000 description 2
- 238000004020 luminiscence type Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 125000005186 naphthyloxy group Chemical group C1(=CC=CC2=CC=CC=C12)O* 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 125000002080 perylenyl group Chemical group C1(=CC=C2C=CC=C3C4=CC=CC5=CC=CC(C1=C23)=C45)* 0.000 description 2
- CSHWQDPOILHKBI-UHFFFAOYSA-N peryrene Natural products C1=CC(C2=CC=CC=3C2=C2C=CC=3)=C3C2=CC=CC3=C1 CSHWQDPOILHKBI-UHFFFAOYSA-N 0.000 description 2
- 125000005561 phenanthryl group Chemical group 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 230000004044 response Effects 0.000 description 2
- 235000019515 salmon Nutrition 0.000 description 2
- 229910002027 silica gel Inorganic materials 0.000 description 2
- 239000000741 silica gel Substances 0.000 description 2
- 229960001866 silicon dioxide Drugs 0.000 description 2
- 238000000967 suction filtration Methods 0.000 description 2
- 230000007704 transition Effects 0.000 description 2
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- YBYIRNPNPLQARY-UHFFFAOYSA-N 1H-indene Natural products C1=CC=C2CC=CC2=C1 YBYIRNPNPLQARY-UHFFFAOYSA-N 0.000 description 1
- HIXDQWDOVZUNNA-UHFFFAOYSA-N 2-(3,4-dimethoxyphenyl)-5-hydroxy-7-methoxychromen-4-one Chemical compound C=1C(OC)=CC(O)=C(C(C=2)=O)C=1OC=2C1=CC=C(OC)C(OC)=C1 HIXDQWDOVZUNNA-UHFFFAOYSA-N 0.000 description 1
- RAAGZOYMEQDCTD-UHFFFAOYSA-N 2-fluorobenzoyl chloride Chemical compound FC1=CC=CC=C1C(Cl)=O RAAGZOYMEQDCTD-UHFFFAOYSA-N 0.000 description 1
- WLPATYNQCGVFFH-UHFFFAOYSA-N 2-phenylbenzonitrile Chemical group N#CC1=CC=CC=C1C1=CC=CC=C1 WLPATYNQCGVFFH-UHFFFAOYSA-N 0.000 description 1
- PPWNCLVNXGCGAF-UHFFFAOYSA-N 3,3-dimethylbut-1-yne Chemical group CC(C)(C)C#C PPWNCLVNXGCGAF-UHFFFAOYSA-N 0.000 description 1
- USCSRAJGJYMJFZ-UHFFFAOYSA-N 3-methyl-1-butyne Chemical group CC(C)C#C USCSRAJGJYMJFZ-UHFFFAOYSA-N 0.000 description 1
- RKIDDEGICSMIJA-UHFFFAOYSA-N 4-chlorobenzoyl chloride Chemical compound ClC(=O)C1=CC=C(Cl)C=C1 RKIDDEGICSMIJA-UHFFFAOYSA-N 0.000 description 1
- 125000000590 4-methylphenyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)C([H])([H])[H] 0.000 description 1
- SKDHHIUENRGTHK-UHFFFAOYSA-N 4-nitrobenzoyl chloride Chemical compound [O-][N+](=O)C1=CC=C(C(Cl)=O)C=C1 SKDHHIUENRGTHK-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 1
- 206010016818 Fluorosis Diseases 0.000 description 1
- AXKJOWVRUHGNBD-UHFFFAOYSA-N Oc1ccccc1-c1nnc(-c2ccccc2)[o]1 Chemical compound Oc1ccccc1-c1nnc(-c2ccccc2)[o]1 AXKJOWVRUHGNBD-UHFFFAOYSA-N 0.000 description 1
- 208000001132 Osteoporosis Diseases 0.000 description 1
- SQYDLQWSDHXLIG-UHFFFAOYSA-N [O-][N+](c(cc1)ccc1-c1nnc(-c2ccccc2O)[o]1)=O Chemical compound [O-][N+](c(cc1)ccc1-c1nnc(-c2ccccc2O)[o]1)=O SQYDLQWSDHXLIG-UHFFFAOYSA-N 0.000 description 1
- DQMGZCOKSYOUNY-UHFFFAOYSA-N [O].C1=CC=CC2=CC3=CC=CC=C3C=C21 Chemical compound [O].C1=CC=CC2=CC3=CC=CC=C3C=C21 DQMGZCOKSYOUNY-UHFFFAOYSA-N 0.000 description 1
- INKDAKMSOSCDGL-UHFFFAOYSA-N [O].OC1=CC=CC=C1 Chemical compound [O].OC1=CC=CC=C1 INKDAKMSOSCDGL-UHFFFAOYSA-N 0.000 description 1
- 125000004062 acenaphthenyl group Chemical group C1(CC2=CC=CC3=CC=CC1=C23)* 0.000 description 1
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 125000005605 benzo group Chemical group 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 125000004369 butenyl group Chemical group C(=CCC)* 0.000 description 1
- 125000002837 carbocyclic group Chemical group 0.000 description 1
- XEVRDFDBXJMZFG-UHFFFAOYSA-N carbonyl dihydrazine Chemical compound NNC(=O)NN XEVRDFDBXJMZFG-UHFFFAOYSA-N 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 238000005352 clarification Methods 0.000 description 1
- 238000010668 complexation reaction Methods 0.000 description 1
- 125000004802 cyanophenyl group Chemical group 0.000 description 1
- 125000001352 cyclobutyloxy group Chemical group C1(CCC1)O* 0.000 description 1
- 125000001887 cyclopentyloxy group Chemical group C1(CCCC1)O* 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 208000004042 dental fluorosis Diseases 0.000 description 1
- 125000004188 dichlorophenyl group Chemical group 0.000 description 1
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 1
- 125000003983 fluorenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3CC12)* 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 230000006870 function Effects 0.000 description 1
- 125000002192 heptalenyl group Chemical group 0.000 description 1
- ACJRMEVDTSKFDP-UHFFFAOYSA-N heptaphene Chemical compound C1=CC=C2C=C(C=C3C4=CC5=CC6=CC=CC=C6C=C5C=C4C=CC3=C3)C3=CC2=C1 ACJRMEVDTSKFDP-UHFFFAOYSA-N 0.000 description 1
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 125000001633 hexacenyl group Chemical group C1(=CC=CC2=CC3=CC4=CC5=CC6=CC=CC=C6C=C5C=C4C=C3C=C12)* 0.000 description 1
- PKIFBGYEEVFWTJ-UHFFFAOYSA-N hexaphene Chemical compound C1=CC=C2C=C3C4=CC5=CC6=CC=CC=C6C=C5C=C4C=CC3=CC2=C1 PKIFBGYEEVFWTJ-UHFFFAOYSA-N 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 description 1
- 239000005457 ice water Substances 0.000 description 1
- 125000002883 imidazolyl group Chemical group 0.000 description 1
- 125000003454 indenyl group Chemical group C1(C=CC2=CC=CC=C12)* 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000005956 isoquinolyl group Chemical group 0.000 description 1
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000003261 o-tolyl group Chemical group [H]C1=C([H])C(*)=C(C([H])=C1[H])C([H])([H])[H] 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000001715 oxadiazolyl group Chemical group 0.000 description 1
- 125000002971 oxazolyl group Chemical group 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 125000003933 pentacenyl group Chemical group C1(=CC=CC2=CC3=CC4=CC5=CC=CC=C5C=C4C=C3C=C12)* 0.000 description 1
- GUVXZFRDPCKWEM-UHFFFAOYSA-N pentalene Chemical compound C1=CC2=CC=CC2=C1 GUVXZFRDPCKWEM-UHFFFAOYSA-N 0.000 description 1
- JQQSUOJIMKJQHS-UHFFFAOYSA-N pentaphene Chemical compound C1=CC=C2C=C3C4=CC5=CC=CC=C5C=C4C=CC3=CC2=C1 JQQSUOJIMKJQHS-UHFFFAOYSA-N 0.000 description 1
- 125000004115 pentoxy group Chemical group [*]OC([H])([H])C([H])([H])C([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 description 1
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 125000004368 propenyl group Chemical group C(=CC)* 0.000 description 1
- LNKHTYQPVMAJSF-UHFFFAOYSA-N pyranthrene Chemical compound C1=C2C3=CC=CC=C3C=C(C=C3)C2=C2C3=CC3=C(C=CC=C4)C4=CC4=CC=C1C2=C34 LNKHTYQPVMAJSF-UHFFFAOYSA-N 0.000 description 1
- 125000003226 pyrazolyl group Chemical group 0.000 description 1
- 125000001725 pyrenyl group Chemical group 0.000 description 1
- 125000002098 pyridazinyl group Chemical group 0.000 description 1
- 125000004076 pyridyl group Chemical group 0.000 description 1
- 125000000714 pyrimidinyl group Chemical group 0.000 description 1
- 125000005493 quinolyl group Chemical group 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000002390 rotary evaporation Methods 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 125000000335 thiazolyl group Chemical group 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- 239000011573 trace mineral Substances 0.000 description 1
- 235000013619 trace mineral Nutrition 0.000 description 1
- 125000004306 triazinyl group Chemical group 0.000 description 1
- 125000001425 triazolyl group Chemical group 0.000 description 1
- PGXOVVAJURGPLL-UHFFFAOYSA-N trinaphthylene Chemical group C1=CC=C2C=C3C4=CC5=CC=CC=C5C=C4C4=CC5=CC=CC=C5C=C4C3=CC2=C1 PGXOVVAJURGPLL-UHFFFAOYSA-N 0.000 description 1
- 238000000825 ultraviolet detection Methods 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 230000003313 weakening effect Effects 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention provides a complex as shown in a chemical formula 1 in the specification, a preparation method of the complex, a fluorine ion sensor and a method for detecting a fluorine ion. In the chemical formula 1, m is an integer from 0 to 5, n is an integer from 0 to 4, R1, R2 and R3 are independently selected from a group composed of deuterium, tritium, halogen, a cyano group, an amino group, nitryl, hydroxyl, carboxyl, substituted or unsubstituted C2-C30 ether groups, substituted or unsubstituted C2-C30 ester groups, substituted or unsubstituted C1-C30 alkyls, substituted or unsubstituted C2-C30 alkenyls, substituted or unsubstituted C2-C30 alkynyls, substituted or unsubstituted C3-C30 cycloalkyls, substituted or unsubstituted C1-C30 alkoxyl groups, substituted or unsubstituted C3-C30 cycloalkoxyls, substituted or unsubstituted C5-C30 aryls, substituted or unsubstituted C5-C30 aryloxys and substituted or unsubstituted C3-C30 heteroaryls.
Description
Technical field
The present invention relates to a kind of title complex and preparation method thereof, particularly a kind ofly can be used as title complex of fluorine ion sensing device and preparation method thereof.
Background technology
Negatively charged ion has great importance in biology, medical science and environmental science, and the design and synthesis about negatively charged ion receptor has caused the broad interest of people.In recent decades, the various negatively charged ion receptor of people's design and synthesis, optionally identifies some important negatively charged ion.Fluorion is as minimum negatively charged ion, and having unique chemical property, is the trace element of needed by human, and such as significant to the clinical treatment of the control of carious tooth and osteoporosis etc., incorrect picked-up then causes fluorosis.The detection identification of fluorion all has great significance to medical science, environmental science and Food science.
Summary of the invention
One object of the present invention is to provide a kind of title complex.
Another object of the present invention is to provide a kind of title complex that can be used as fluorine ion sensing device.
Another object of the present invention is to provide a kind of preparation method that can be used as the title complex of fluorine ion sensing device.
Another object of the present invention is to provide a kind of method detecting fluorion.
Title complex according to the present invention is represented by chemical formula 1:
Chemical formula 1:
In chemical formula 1, m is the integer of 0-5, and n is the integer of 0-4, R
1, R
2and R
3all independently selected from deuterium, tritium, halogen, cyano group, amino, nitro, hydroxyl, carboxyl, replacement or unsubstituted C
2-C
30ether, replacement or unsubstituted C
2-C
30ester group, replacement or unsubstituted C
1-C
30alkyl, replacement or unsubstituted C
2-C
30thiazolinyl, replacement or unsubstituted C
2-C
30alkynyl, replacement or unsubstituted C
3-C
30cycloalkyl, replacement or unsubstituted C
1-C
30alkoxyl group, replacement or unsubstituted C
3-C
30cycloalkyloxy, replacement or unsubstituted C
5-C
30aryl, replacement or unsubstituted C
5-C
30aryloxy and replacement or unsubstituted C
3-C
30the group of heteroaryl composition.
R
1, R
2and R
3all can independently selected from deuterium, tritium, halogen, cyano group, amino, nitro, hydroxyl, carboxyl, replacement or unsubstituted C
2-C
6ether, replacement or unsubstituted C
2-C
6ester group, replacement or unsubstituted C
1-C
6alkyl, replacement or unsubstituted C
2-C
6thiazolinyl, replacement or unsubstituted C
2-C
6alkynyl, replacement or unsubstituted C
3-C
10cycloalkyl, replacement or unsubstituted C
1-C
6alkoxyl group, replacement or unsubstituted C
3-C
10cycloalkyloxy, replacement or unsubstituted C
5-C
20aryl, replacement or unsubstituted C
5-C
20aryloxy and replacement or unsubstituted C
3-C
20the group of heteroaryl composition.
R
1, R
2and R
3all can independently selected from deuterium, tritium, halogen, cyano group, amino, nitro, hydroxyl, carboxyl, replacement or unsubstituted C
2-C
4ether, replacement or unsubstituted C
2-C
4ester group, replacement or unsubstituted C
1-C
4alkyl, replacement or unsubstituted C
2-C
4thiazolinyl, replacement or unsubstituted C
2-C
4alkynyl, replacement or unsubstituted C
3-C
6cycloalkyl, replacement or unsubstituted C
1-C
4alkoxyl group, replacement or unsubstituted C
3-C
6cycloalkyloxy, replacement or unsubstituted C
5-C
12aryl, replacement or unsubstituted C
5-C
12aryloxy and replacement or unsubstituted C
3-C
12the group of heteroaryl composition.
R
1and R
3all can independently selected from-F ,-Cl ,-NH
2,-NO
2,-OR
4with-COOR
4the group of composition, R
2can be selected from the group of methyl, ethyl and propyl group composition, wherein, R
4c
1-C
30alkyl, C
3-C
30cycloalkyl or C
5-C
30aryl.Further, R
4can be C
1-C
6alkyl, C
3-C
10cycloalkyl, C
5-C
20aryl.Closer, R
4can be C
1-C
4alkyl, C
3-C
6cycloalkyl, C
5-C
12aryl, such as methyl, ethyl, propyl group, butyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, phenyl, naphthyl.
Preparation method according to title complex of the present invention comprises: make part
with AlCl
3with alcohol R
2oH is obtained by reacting described title complex.
This preparation method also can comprise and prepare part
step, prepare part
step comprise: make
intermediate 1 is obtained with ethanol synthesis; Intermediate 1 and hydrazine reaction is made to obtain intermediate 2; Make intermediate 2 with
be obtained by reacting intermediate 3; Intermediate 3 and polyphosphoric acid is made to be obtained by reacting intermediate 4; Intermediate 4 and boron tribromide is made to be obtained by reacting part
Fluorine ion sensing device according to the present invention comprises above-mentioned title complex.
Comprise according to the method for fluorion in detection solution of the present invention: described title complex is joined in described solution; Measure ultraviolet-visible or the ultra-violet absorption spectrum of described solution, or measure the fluorescence spectrum of described solution, or observe the color of described solution; Colour-change according to ultraviolet-visible or the change of ultra-violet absorption spectrum, the change of fluorescence spectrum or described solution determines that described solution contains fluorion.
Comprise according to the method for fluorion in detection solution of the present invention: described title complex is dissolved in a solvent, to obtain the first solution; Second solution is added gradually in the first solution, to obtain mixing solutions; In the process adding the first solution gradually, measure ultraviolet-visible or the ultra-violet absorption spectrum of mixing solutions, or measure the fluorescence spectrum of mixing solutions, or observe the color of mixing solutions; Colour-change according to ultraviolet-visible or the change of ultra-violet absorption spectrum, the change of fluorescence spectrum or mixing solutions determines that the second solution contains fluorion.
Accompanying drawing explanation
Fig. 1 shows the CH to ligand 1 according to the present invention
2cl
2/ CH
3constantly F is dripped in CN (1:2, v/v) solution
-the uv-visible absorption spectra obtained, illustration is wherein wavelength is 320nm and 416nm place, and absorbancy is along with adding F
-the changing trend diagram of equivalent value;
Fig. 2 shows the CH to part 2 according to the present invention
2cl
2/ CH
3constantly F is dripped in CN (1:2, v/v) solution
-the uv-visible absorption spectra obtained, illustration is wherein wavelength is 327nm and 423nm place, and absorbancy is along with adding F
-the changing trend diagram of equivalent value;
Fig. 3 shows the CH to part 3 according to the present invention
2cl
2/ CH
3constantly F is dripped in CN (1:2, v/v) solution
-the ultra-violet absorption spectrum obtained;
Fig. 4 shows the CH to part 4 according to the present invention
2cl
2/ CH
3constantly F is dripped in CN (1:2, v/v) solution
-the ultra-violet absorption spectrum obtained;
Fig. 5 shows the CH to part 5 according to the present invention
2cl
2/ CH
3constantly F is dripped in CN (1:2, v/v) solution
-the ultra-violet absorption spectrum obtained;
Fig. 6 shows the CH to part 7 according to the present invention
2cl
2/ CH
3constantly F is dripped in CN (1:2, v/v) solution
-the ultra-violet absorption spectrum obtained;
Fig. 7 shows the CH to part 8 according to the present invention
2cl
2/ CH
3constantly F is dripped in CN (1:2, v/v) solution
-the ultra-violet absorption spectrum obtained;
Fig. 8 shows the CH to ligand 1 according to the present invention
2cl
2/ CH
3constantly F is dripped in CN (1:2, v/v) solution
-the fluorescence spectrum figure obtained, illustration is wherein wavelength is 386nm, 399nm and 411nm place, and fluorescence intensity is along with adding F
-the changing trend diagram of equivalent value;
Fig. 9 shows the CH to part 3 according to the present invention
2cl
2/ CH
3constantly F is dripped in CN (1:2, v/v) solution
-the fluorescence spectrum figure obtained;
Figure 10 shows the CH to part 4 according to the present invention
2cl
2/ CH
3constantly F is dripped in CN (1:2, v/v) solution
-the fluorescence spectrum figure obtained, in figure, the photo in left side demonstrates and does not drip F
-time solution, in figure, the photo on right side demonstrates and has dripped F
-time solution;
Figure 11 shows the CH to part 5 according to the present invention
2cl
2/ CH
3constantly F is dripped in CN (1:2, v/v) solution
-the fluorescence spectrum figure obtained;
Figure 12 shows the CH to part 8 according to the present invention
2cl
2/ CH
3constantly F is dripped in CN (1:2, v/v) solution
-the fluorescence spectrum figure obtained;
Figure 13 shows the CH to part 2 according to the present invention
2cl
2/ CH
3the F of 3.8eq (equivalent) is added respectively in CN (1:2, v/v) solution
-, Br
-, I
-, H
2pO
4 -and CH
3cOO
-after the uv-visible absorption spectra that obtains, and show the CH of part 2
2cl
2/ CH
3cN (1:2, v/v) solution and add the F of 3.8eq
-, Br
-, I
-, H
2pO
4 -and CH
3cOO
-after the photo of solution;
Figure 14 shows the CH to title complex 1 according to the present invention
2cl
2/ CH
3[Bu is dripped respectively in CN (1:2, v/v) solution
4n] R (R=Br
-, I
-, F
-, H
2pO
4 -and CH
3cOO
-) after the uv-visible absorption spectra that obtains, and show the CH of title complex 1
2cl
2/ CH
3cN (1:2, v/v) solution and add F
-, Br
-, I
-, H
2pO
4 -and CH
3cOO
-after the photo of solution;
Figure 15 shows the CH to title complex 1 according to the present invention
2cl
2/ CH
3constantly F is dripped in CN (1:2, v/v) solution
-the uv-visible absorption spectra obtained, illustration is wherein wavelength is 368nm and 423nm place, and absorbancy is along with adding F
-the changing trend diagram of equivalent value;
Figure 16 shows the CH to title complex 5 according to the present invention
2cl
2/ CH
3constantly F is dripped in CN (1:2, v/v) solution
-the ultra-violet absorption spectrum obtained;
Figure 17 shows the CH to title complex 1 (2 μMs) according to the present invention
2cl
2/ CH
3constantly F is dripped in CN (1:2, v/v) solution
-the fluorescence spectrum figure (excitation wavelength is 285nm) obtained, illustration is wherein wavelength is that 374nm and 508nm place fluorescence intensity is along with adding F
-the changing trend diagram of equivalent value, in figure, the photo in left side demonstrates and does not drip F
-time solution, in figure, the photo on right side demonstrates and has dripped F
-time solution;
Figure 18 shows the CH to title complex 5 (2 μMs) according to the present invention
2cl
2/ CH
3constantly F is dripped in CN (1:2, v/v) solution
-the fluorescence spectrum figure (excitation wavelength is 370nm) obtained, in figure, the photo in left side demonstrates and does not drip F
-time solution, in figure, the photo on right side demonstrates and has dripped F
-time solution.
Embodiment
Title complex according to the present invention is represented by chemical formula 1, and it is a kind of double-core bridging aluminum complex.
chemical formula 1:
In chemical formula 1, m is the integer of 0-5, (R
1)
mrepresent m R of the hydrogen atom on substituted benzene ring
1substituting group.When m equals 0, there is not the substituent R of the hydrogen atom on substituted benzene ring
1.M can be 1,2,3,4 or 5.
R
1can be selected from deuterium, tritium, halogen, cyano group, amino, nitro, hydroxyl, carboxyl, replacement or unsubstituted C
2-C
30ether, replacement or unsubstituted C
2-C
30ester group, replacement or unsubstituted C
1-C
30alkyl, replacement or unsubstituted C
2-C
30thiazolinyl, replacement or unsubstituted C
2-C
30alkynyl, replacement or unsubstituted C
3-C
30cycloalkyl, replacement or unsubstituted C
1-C
30alkoxyl group, replacement or unsubstituted C
3-C
30cycloalkyloxy, replacement or unsubstituted C
5-C
30aryl, replacement or unsubstituted C
5-C
30aryloxy and replacement or unsubstituted C
3-C
30the group of heteroaryl composition.
In one exemplary embodiment, R
1can be selected from deuterium, tritium, halogen, cyano group, amino, nitro, hydroxyl, carboxyl, replacement or unsubstituted C
2-C
6ether, replacement or unsubstituted C
2-C
6ester group, replacement or unsubstituted C
1-C
6alkyl, replacement or unsubstituted C
2-C
6thiazolinyl, replacement or unsubstituted C
2-C
6alkynyl, replacement or unsubstituted C
3-C
10cycloalkyl, replacement or unsubstituted C
1-C
6alkoxyl group, replacement or unsubstituted C
3-C
10cycloalkyloxy, replacement or unsubstituted C
5-C
20aryl, replacement or unsubstituted C
5-C
20aryloxy and replacement or unsubstituted C
3-C
20the group of heteroaryl composition.
In one exemplary embodiment, R
1can be selected from deuterium, tritium, halogen, cyano group, amino, nitro, hydroxyl, carboxyl, replacement or unsubstituted C
2-C
4ether, replacement or unsubstituted C
2-C
4ester group, replacement or unsubstituted C
1-C
4alkyl, replacement or unsubstituted C
2-C
4thiazolinyl, replacement or unsubstituted C
2-C
4alkynyl, replacement or unsubstituted C
3-C
6cycloalkyl, replacement or unsubstituted C
1-C
4alkoxyl group, replacement or unsubstituted C
3-C
6cycloalkyloxy, replacement or unsubstituted C
5-C
12aryl, replacement or unsubstituted C
5-C
12aryloxy and replacement or unsubstituted C
3-C
12the group of heteroaryl composition.
In chemical formula 1, n is the integer of 0-4, (R
3)
nrepresent n R of the hydrogen atom on substituted benzene ring
3substituting group.When n equals 0, there is not the substituent R of the hydrogen atom on substituted benzene ring
3.M can be 1,2,3 or 4.
R
3can be selected from deuterium, tritium, halogen, cyano group, amino, nitro, hydroxyl, carboxyl, replacement or unsubstituted C
2-C
30ether, replacement or unsubstituted C
2-C
30ester group, replacement or unsubstituted C
1-C
30alkyl, replacement or unsubstituted C
2-C
30thiazolinyl, replacement or unsubstituted C
2-C
30alkynyl, replacement or unsubstituted C
3-C
30cycloalkyl, replacement or unsubstituted C
1-C
30alkoxyl group, replacement or unsubstituted C
3-C
30cycloalkyloxy, replacement or unsubstituted C
5-C
30aryl, replacement or unsubstituted C
5-C
30aryloxy and replacement or unsubstituted C
3-C
30the group of heteroaryl composition.
In one exemplary embodiment, R
3can be selected from deuterium, tritium, halogen, cyano group, amino, nitro, hydroxyl, carboxyl, replacement or unsubstituted C
2-C
6ether, replacement or unsubstituted C
2-C
6ester group, replacement or unsubstituted C
1-C
6alkyl, replacement or unsubstituted C
2-C
6thiazolinyl, replacement or unsubstituted C
2-C
6alkynyl, replacement or unsubstituted C
3-C
10cycloalkyl, replacement or unsubstituted C
1-C
6alkoxyl group, replacement or unsubstituted C
3-C
10cycloalkyloxy, replacement or unsubstituted C
5-C
20aryl, replacement or unsubstituted C
5-C
20aryloxy and replacement or unsubstituted C
3-C
20the group of heteroaryl composition.
In one exemplary embodiment, R
3can be selected from deuterium, tritium, halogen, cyano group, amino, nitro, hydroxyl, carboxyl, replacement or unsubstituted C
2-C
4ether, replacement or unsubstituted C
2-C
4ester group, replacement or unsubstituted C
1-C
4alkyl, replacement or unsubstituted C
2-C
4thiazolinyl, replacement or unsubstituted C
2-C
4alkynyl, replacement or unsubstituted C
3-C
6cycloalkyl, replacement or unsubstituted C
1-C
4alkoxyl group, replacement or unsubstituted C
3-C
6cycloalkyloxy, replacement or unsubstituted C
5-C
12aryl, replacement or unsubstituted C
5-C
12aryloxy and replacement or unsubstituted C
3-C
12the group of heteroaryl composition.
In chemical formula 1, R
2can be selected from deuterium, tritium, halogen, cyano group, amino, nitro, hydroxyl, carboxyl, replacement or unsubstituted C
2-C
30ether, replacement or unsubstituted C
2-C
30ester group, replacement or unsubstituted C
1-C
30alkyl, replacement or unsubstituted C
2-C
30thiazolinyl, replacement or unsubstituted C
2-C
30alkynyl, replacement or unsubstituted C
3-C
30cycloalkyl, replacement or unsubstituted C
1-C
30alkoxyl group, replacement or unsubstituted C
3-C
30cycloalkyloxy, replacement or unsubstituted C
5-C
30aryl, replacement or unsubstituted C
5-C
30aryloxy and replacement or unsubstituted C
3-C
30the group of heteroaryl composition.
In one exemplary embodiment, R
2can be selected from deuterium, tritium, halogen, cyano group, amino, nitro, hydroxyl, carboxyl, replacement or unsubstituted C
2-C
6ether, replacement or unsubstituted C
2-C
6ester group, replacement or unsubstituted C
1-C
6alkyl, replacement or unsubstituted C
2-C
6thiazolinyl, replacement or unsubstituted C
2-C
6alkynyl, replacement or unsubstituted C
3-C
10cycloalkyl, replacement or unsubstituted C
1-C
6alkoxyl group, replacement or unsubstituted C
3-C
10cycloalkyloxy, replacement or unsubstituted C
5-C
20aryl, replacement or unsubstituted C
5-C
20aryloxy and replacement or unsubstituted C
3-C
20the group of heteroaryl composition.
In one exemplary embodiment, R
2can be selected from deuterium, tritium, halogen, cyano group, amino, nitro, hydroxyl, carboxyl, replacement or unsubstituted C
2-C
4ether, replacement or unsubstituted C
2-C
4ester group, replacement or unsubstituted C
1-C
4alkyl, replacement or unsubstituted C
2-C
4thiazolinyl, replacement or unsubstituted C
2-C
4alkynyl, replacement or unsubstituted C
3-C
6cycloalkyl, replacement or unsubstituted C
1-C
4alkoxyl group, replacement or unsubstituted C
3-C
6cycloalkyloxy, replacement or unsubstituted C
5-C
12aryl, replacement or unsubstituted C
5-C
12aryloxy and replacement or unsubstituted C
3-C
12the group of heteroaryl composition.
In one exemplary embodiment, R
1and R
3all can independently selected from-F ,-Cl ,-NH
2,-NO
2,-OR
4with-COOR
4the group of composition, wherein, R
4c
1-C
30alkyl, C
3-C
30cycloalkyl or C
5-C
30aryl, R
2can be selected from the group of methyl, ethyl and propyl group composition.Further, R
4can be C
1-C
6alkyl, C
3-C
10cycloalkyl, C
5-C
20aryl.Closer, R
4can be C
1-C
4alkyl, C
3-C
6cycloalkyl, C
5-C
12aryl, such as methyl, ethyl, propyl group, butyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, phenyl, naphthyl.
Unsubstituted C described here
1-C
30the example of alkyl includes but not limited to methyl, ethyl, propyl group, isobutyl-, sec-butyl, amyl group, isopentyl, hexyl, heptyl, octyl group, nonyl and dodecyl.C
1-C
30at least one hydrogen atom of alkyl can by D atom (deuterium, tritium), halogen atom, cyano group, amino, amidino groups, nitro, hydroxyl, diazanyl, hydrazone group, carboxyl or its salt, sulfonic group or its salt, phosphoric acid or its salt, C
1-C
30alkyl, C
1-C
30alkoxyl group, C
2-C
30thiazolinyl, C
2-C
30alkynyl, C
5-C
20aryl, C
3-C
20heteroaryl ,-N (Q
1) (Q
2) or-Si (Q
3) (Q
4) (Q
5) replace.Here, Q
1to Q
5can be all hydrogen atom, D atom (deuterium, tritium), halogen atom, cyano group, amino, amidino groups, nitro, hydroxyl, diazanyl, hydrazone group, carboxyl or its salt, sulfonic group or its salt, phosphoric acid or its salt, C independently
1-C
30alkyl, C
1-C
30alkoxyl group, C
2-C
30thiazolinyl, C
2-C
30alkynyl, C
5-C
20aryl or C
3-C
20heteroaryl.
Unsubstituted C described here
2-C
30the example of thiazolinyl comprises vinyl, propenyl, butenyl etc.Unsubstituted C
2-C
30at least one hydrogen atom in thiazolinyl can the C of referenced replacement
1-C
30the substituting group that alkyl describes replaced.
Unsubstituted C described here
2-C
30the example of alkynyl comprises ethynyl, proyl, phenylene-ethynylene, naphthyl acetylene base, isopropyl-acetylene base, tert-butyl acetylene base and dibenzenyl base.Unsubstituted C
2-C
30at least one hydrogen atom in alkynyl can the C of referenced replacement
1-C
30the substituting group that alkyl describes replaced.
C described here
3-C
30the example of cycloalkyl comprises cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl and suberyl.Unsubstituted C
3-C
30at least one hydrogen atom in cycloalkyl can the C of referenced replacement
1-C
30the substituting group that alkyl describes replaced.
Unsubstituted C described here
1-C
30the example of alkoxyl group comprises methoxyl group, oxyethyl group, propoxy-, isopropoxy, butoxy and pentyloxy.C
1-C
30at least one hydrogen atom of alkoxyl group can the C of referenced replacement
1-C
30the substituting group that alkyl describes replaced.
Unsubstituted C described here
3-C
30the example of cycloalkyloxy comprises ring propoxy-, cyclobutoxy group and cyclopentyloxy.C
3-C
30at least one hydrogen atom of cycloalkyloxy can the C of referenced replacement
1-C
30the substituting group that alkyl describes replaced.
Unsubstituted C described here
5-C
30aryl refers to the carbocyclic, aromatic systems containing at least one ring.At least two rings can condense each other, maybe can be connected to each other by singly-bound.Term " aryl " refers to aroma system, such as phenyl, naphthyl or anthryl.C
5-C
30at least one hydrogen atom in aryl can the C of referenced replacement
1-C
30the substituting group that alkyl describes replaced.Replace or unsubstituted C
5-C
30the example of aryl includes but not limited to: phenyl, C
1-C
10alkyl phenyl (such as, ethylphenyl), halogenophenyl (such as, adjacent fluorophenyl, a fluorophenyl, to fluorophenyl, dichlorophenyl), cyano-phenyl, dicyano phenyl, Trifluoromethoxyphen-l, xenyl, halogenated biphenyl base, cyanobiphenyl base, C
1-C
10alkyl biphenyl base, C
1-C
10alkoxyl group xenyl, o-tolyl, a tolyl and p-methylphenyl, adjacent cumyl, a cumyl and to cumyl,
base, Phenoxyphenyl, (α, alpha-alpha-dimethyl benzene) phenyl, (N, N'-dimethyl) aminophenyl, (N, N'-phenylbenzene) aminophenyl, pentalene base, indenyl, naphthyl, halo naphthyl (such as, fluoro naphthyl), C
1-C
10alkyl naphthyl (such as, methyl naphthyl), C
1-C
10alkoxyl group naphthyl (such as, methoxyl group naphthyl), cyanonaphthyl, anthryl,
base, heptalenyl, acenaphthenyl, all naphthyls, fluorenyl, anthraquinonyl, methylanthryl, phenanthryl, benzo [9,10] phenanthryl, pyrenyl, 1,2-benzo phenanthryl, ethyl-1,2-benzo phenanthryl, Pi base, perylene base, chlorine are for perylene base, pentaphene base, pentacenyl, neighbours' phenylene, hexaphene base, hexacenyl, rubicenyl, guan base, trinaphthylene base, heptaphene base, heptaphenyl and pyranthrene base.
Unsubstituted C described here
5-C
30the example of aryloxy comprises phenoxy group, naphthyloxy, biphenylyloxy, connection naphthyloxy, anthracene oxygen base etc.C
5-C
30at least one hydrogen atom of aryloxy can the C of referenced replacement
1-C
30the substituting group that alkyl describes replaced.
Unsubstituted C described here
3-C
30heteroaryl comprises at least one heteroatoms selected from N, O, P and S.At least two rings can condense each other, maybe can be connected to each other by singly-bound.Unsubstituted C
3-C
30the example of heteroaryl can comprise pyrazolyl, imidazolyl, oxazolyl, thiazolyl, triazolyl, tetrazyl, oxadiazolyl, pyridyl, pyridazinyl, pyrimidyl, triazinyl, carbazyl, indyl, quinolyl and isoquinolyl.C
3-C
30at least one hydrogen atom in heteroaryl can the C of referenced replacement
1-C
30the substituting group that alkyl describes replaced.
Unsubstituted ether described here has-A
1-O-A
2the group of structure, wherein ,-A
2unsubstituted alkyl, unsubstituted thiazolinyl, unsubstituted alkynyl, unsubstituted aryl or unsubstituted heteroaryl ,-A
1-be unsubstituted alkylidene group, unsubstituted alkenylene, unsubstituted alkynylene, unsubstituted arylidene or unsubstituted inferior heteroaryl.At least one hydrogen atom in ether can the C of referenced replacement
1-C
30the substituting group that alkyl describes replaced.
Unsubstituted ester group described here has-A
3cOOA
4or A
5cOOA
6the group of-structure, wherein ,-A
4unsubstituted alkyl, unsubstituted thiazolinyl, unsubstituted alkynyl, unsubstituted aryl or unsubstituted heteroaryl ,-A
3-be singly-bound, unsubstituted alkylidene group, unsubstituted alkenylene, unsubstituted alkynylene, unsubstituted arylidene or unsubstituted inferior heteroaryl ,-A
5unsubstituted alkyl, unsubstituted thiazolinyl, unsubstituted alkynyl, unsubstituted aryl or unsubstituted heteroaryl ,-A
6-be singly-bound, unsubstituted alkylidene group, unsubstituted alkenylene, unsubstituted alkynylene, unsubstituted arylidene or unsubstituted inferior heteroaryl.At least one hydrogen atom in ester group can the C of referenced replacement
1-C
30the substituting group that alkyl describes replaced.
In chemical formula 1, R
1be connected on phenyl ring.Specifically, R
1the carbon atom of any position in 2,3,4,5 or 6 of phenyl ring can be connected to.Preferably, R
1be connected to the carbon atom of 4 on phenyl ring, be in the R of this position
1sterically hindered less, and be easy to manufacture according to title complex of the present invention.Less preferred, R
1be connected to the carbon atom of a position in 3 and 5 on phenyl ring.More less preferred, R
1be connected to the carbon atom of a position in 2 and 6 on phenyl ring.
In chemical formula 1, R
3be connected on phenyl ring.Specifically, R
3the carbon atom of any position in the ortho position of the C atom that O atom is connected to, a position, contraposition can be connected to.Preferably, R
3be connected to the carbon atom of contraposition, be in the R of this position
3sterically hindered less, and be easy to manufacture according to title complex of the present invention.Less preferred, R
3be connected to the carbon atom of ortho position or a position on phenyl ring.
Can be any one in title complex 1 to title complex 6 below according to title complex of the present invention.
Title complex 1:
Title complex 2:
Title complex 3:
Title complex 4:
Title complex 5:
Title complex 6:
Preparation method according to title complex of the present invention is described below.Can prepare according to title complex of the present invention according to reaction scheme 1 below.
reaction scheme 1:
More particularly, part is made
with AlCl
3with alcohol R
2oH is obtained by reacting according to title complex of the present invention.
Part can be prepared according to reaction scheme 2 below
reaction scheme 2:
More particularly, make as raw material
obtain intermediate 1 with ethanol synthesis, then make intermediate 1 and hydrazine reaction generate intermediate 2, intermediate 2 and as raw material
reaction generates intermediate 3, then makes intermediate 3 and polyphosphoric acid react and generates intermediate 4, and last intermediate 4 reacts with boron tribromide and generates part
Anion sensors mainly comprises antenna group (or being called conjugated group), linker and chromophore (or being called signal group).Antenna group and sensing ion (negatively charged ion) interact or in conjunction with sensing ion, that is, Received signal strength.(namely chromophore is receiving the signal of antenna group, with antenna Interaction of substituents) after, there is color change, spectrum change (such as visible-ultra-violet absorption spectrum or change in fluorescence) or electrochemical properties change, by instrument or naked eyes direct feeling to this change, to reach the object of identification to relevant ions and detection.Linker is in order to antenna group and chromophore to be coupled together.
The Main Function of antenna group is that measured ion is treated in induction, needs and treats that measured ion has strong interaction, and not having an effect with other similar ions.For the preparation of the part of title complex of the present invention
there is the phenolic hydroxyl group as antenna group, and control the stability of hydrogen bond by ring hydrogen bond, solely to F
-response, and not with other ionic interactions.
Chromophore mainly produces the group of colour-change, visible-ultra-violet absorption spectrum or change in fluorescence, and these changes can be arrived by instrument or direct visual perception, so just can by antenna group and F
-interaction be converted into discernible signal, reach F
-identification and detection.For the preparation of the part of title complex of the present invention
have the heterocycle of 1,3,4-oxadiazoles group as chromophore, its obvious color change, absorbancy and change in fluorescence are observed simply by naked eyes and instrument.Obvious color change caused by chromophore arrives by direct visual perception, absorbancy change is observed by spectrograph, and change in fluorescence detects by fluorescent optical sensor, part for the preparation of title complex of the present invention takes into account this several respects, efficient, the high sensing selectively achieved fluorion.
For the preparation of the R in the above-mentioned part of title complex of the present invention
1and/or R
3selection substantial effect is not had to above-described fluorine ion sensing performance, only may have the effect of fine setting to above-mentioned color change, visible-ultra-violet absorption spectrum or change in fluorescence.In addition, described above is R
1the carbon atom of any position in 2,3,4,5 or 6 of phenyl ring can be connected to, R
3the carbon atom of any position in the ortho position of the C atom that O atom is connected to, a position, contraposition can be connected to.R
1the position be connected to and/or R
3the above-described fluorine ion sensing performance of the position be connected to described part does not have substantial effect, only may have the effect of fine setting to above-mentioned color change, visible-ultra-violet absorption spectrum or change in fluorescence.
In addition, title complex according to the present invention has the phenol oxygen base as antenna group, and controls the stability of hydrogen bond by ring hydrogen bond, solely to F
-response, and not with other ionic interactions.Title complex according to the present invention has the heterocycle of 1,3,4-oxadiazoles group as chromophore, and its obvious color change, absorbancy and change in fluorescence are observed simply by naked eyes and instrument.Obvious color change caused by chromophore arrives by direct visual perception, absorbancy change is observed by spectrograph, and change in fluorescence detects by fluorescent optical sensor, title complex according to the present invention takes into account this several respects, efficient, the high sensing selectively achieved fluorion.
Substituent R in chemical formula 1
1, R
2and/or R
3selection substantial effect is not had to above-described fluorine ion sensing performance, only may have the effect of fine setting to above-mentioned color change, visible-ultra-violet absorption spectrum or change in fluorescence.In addition, described above is in chemical formula 1, R
1the carbon atom of any position in 2,3,4,5 or 6 of phenyl ring can be connected to, R
3the carbon atom of any position in the ortho position of the C atom that O atom is connected to, a position, contraposition can be connected to.R
1the position be connected to and/or R
3the fluorine ion sensing performance of the position be connected to title complex of the present invention does not have substantial effect, only may have the effect of fine setting to above-mentioned color change, visible-ultra-violet absorption spectrum or change in fluorescence.
Fluorine ion sensing device according to the present invention can comprise according to title complex of the present invention.Fluorine ion sensing device according to the present invention can be according to title complex of the present invention.
Can comprise according to the method for fluorion in detection solution of the present invention: title complex of the present invention (such as, as a solution) is joined in described solution; Adopt ultraviolet-visual spectrometer to measure ultraviolet-visible or the ultra-violet absorption spectrum of described solution, or measure the fluorescence spectrum of described solution by fluorescence spectrophotometer, or the color of the described solution that detects by an unaided eye; Colour-change according to ultraviolet-visible or the change of ultra-violet absorption spectrum, the change of fluorescence spectrum or described solution determines that described solution contains fluorion.
Can comprise according to the method for fluorion in detection solution of the present invention: title complex of the present invention is dissolved in a solvent, to obtain the first solution; Second solution is added in the first solution, to obtain mixing solutions; Ultraviolet-visual spectrometer is adopted to measure the ultraviolet-visible of mixing solutions or the ultraviolet-visible of ultra-violet absorption spectrum relative to the first solution or the change of ultra-violet absorption spectrum, or measure the change of fluorescence spectrum relative to the fluorescence spectrum of the first solution of mixing solutions by fluorescence spectrophotometer, or the color of the mixing solutions that detects by an unaided eye is relative to the change of the color of the first solution; Change according to ultraviolet-visible or the change of ultra-violet absorption spectrum, the change of fluorescence spectrum or color determines that the second solution contains fluorion.
Can comprise according to the method for fluorion in detection solution of the present invention: title complex of the present invention is dissolved in a solvent, to obtain the first solution; Second solution is added gradually in the first solution, to obtain mixing solutions; In the process adding the first solution gradually, adopt ultraviolet-visual spectrometer to measure ultraviolet-visible or the ultra-violet absorption spectrum of mixing solutions, or measure the fluorescence spectrum of mixing solutions by fluorescence spectrophotometer, or the color of the mixing solutions that detects by an unaided eye; Colour-change according to ultraviolet-visible or the change of ultra-violet absorption spectrum, the change of fluorescence spectrum or mixing solutions determines that the second solution contains fluorion.
Describe in more detail according to title complex of the present invention and preparation method thereof in conjunction with example hereinafter.
preparation example 1: the preparation of part 2
Part 2 is prepared according to reaction scheme 3 below.
reaction scheme 3:
First, according to following step synthetic intermediate 1-1 (5-chloro-O-Anisic Acid ethyl ester): take the chloro-O-Anisic Acid 5g (0.027mmol) of 5-in 250mL bis-neck bottle, add 90mL dehydrated alcohol, vitriol oil 14mL, reflux 24 hours, be extracted with ethyl acetate and obtain yellow oily liquid 5.4g, productive rate 90%.
Then, according to following step synthetic intermediate 2-1 (5-chloro-2-methoxybenzoyl hydrazine): take 5-chloro-O-Anisic Acid ethyl ester 5.4g (0.023mmol) in 250mL bis-neck bottle, add 90mL dehydrated alcohol, 80% hydrazine hydrate 3.6mL, N
2protection backflow 24 hours, obtain yellow oily liquid with dichloromethane extraction, (elutriant is CH to too short silicagel column
2cl
2and sherwood oil), obtain faint yellow solid 3.9g, productive rate 85%.
1H?NMR(400MHz；CDCl
3)，δ：8.9(s,1H),8.19-8.17(m,1H),7.47-7.43(t,1H),7.09-7.06(t,1H),6.97-6.95(m,1H),4.2(s,2H),3.9(s,3H)。
Then, according to following step synthetic intermediate 3-1 (4-(2-(5-chloro-2-p-methoxy-phenyl) carbohydrazide) methyl benzoate): take 5-chloro-2-methoxybenzoyl hydrazine 4.0g (0.02mol) and to carbonyl chloride methyl benzoate 3g (0.02mol) in 250mL bis-neck bottle, add anhydrous THF 80mL, oil bath reacting by heating 3h is proceeded to after ice-water bath reaction 1h, be cooled to room temperature, add water and produce a large amount of precipitation, suction filtration, by recrystallizing methanol, obtain white needle-like crystals 5.8g, productive rate 80%.
1H?NMR(400MHz；CDCl
3),δ：11.05(s,1H),10.34(s,1H),8.14-8.08(q,3H),7.99-7.97(m,2H),7.54-7.50(t,lH),7.11-7.07(t,1H),4.13(s,3H),3.95(s,3H).ESI,m/z:362.1。
Afterwards, according to following step synthetic intermediate 4-1 (4-(5-(the chloro-2-p-methoxy-phenyl of 5-)-1,3,4-oxadiazoles-2-) methyl benzoate): take intermediate 3-1 (1.11g, 0.003mol) and 10g polyphosphoric acid in two neck bottles, add 1,4-dioxane 60mL reacting by heating 24h, is cooled to room temperature, adds water and produces a large amount of precipitation, suction filtration, (elutriant is CH to too short silicagel column
2cl
2and sherwood oil), obtain white powder 0.5g, productive rate 50%.
1H?NMR(400MHz；CDCl
3),δ:8.23-8.21(t,4H),8.02(s,1H),7.51-7.48(d,lH),7.05-7.03(d,1H),4.01(s,3H),3.98(s,3H)。
13C?NMR(CDCl
3):166.08,163.81,162.68,156.54,132.89,132.78,130.22,129.88,127.65,126.86,125.85,114.01,113.42,56.42,52.45.ESI,m/z:345.2。
Finally, according to following step synthetic ligands 2 (4-(5-(5-chlorine-2-hydroxyl phenyl)-1,3,4-oxadiazoles-2-) methyl benzoate): take intermediate 4-1 (0.3g, 1mmol) in two neck bottles, add methylene dichloride 30mL.Drip the dichloromethane solution 20mL of boron tribromide 1mL (2mmol) in ice bath, time for adding is 10-20min, and lucifuge reaction 3h, obtains white opacity liquid.After completion of the reaction, a small amount of methyl alcohol of careful dropping and 20mL water in white opacity liquid, use 30mL dichloromethane extraction, rotary evaporation falls solvent and obtains white powder, obtains white crystal 0.2g by recrystallizing methanol, productive rate 70%.Mp.142-144 DEG C.
1h NMR (400MHz; DMSO-d
6): δ 10.65 (s, 1H ,-OH), 8.26 (d, J=8.0Hz, 2H, phenyl), 8.17 (d, J=8.0Hz, 2H, phenyl), 7.97 (s, 1H, phenyl), 7.53 (d, J=12.0Hz, lH, phenyl), 7.13 (d, J=8.0Hz, 1H, phenyl), 3.91 (s, 3H ,-COOCH
3).
13c NMR (125MHz, CDCl
3): δ 170.65,168.19,167.93,160.57,138.36,137.56,135.46,135.34,133.43,132.37,132.28,132.15,128.34,124.31,116.35.Ultimate analysis measured value (C
16h
12clN
2o
4calculated value, %) C, 58.13 (58.11); H, 3.72 (3.35); N, 8.39 (8.47); ESI, m/z:330.
preparation example 2: the preparation of ligand 1
Replace except using O-Anisic Acid in the process preparing intermediate 1-1, except the chloro-O-Anisic Acid of 5-, preparing ligand 1 according to the method substantially identical with preparation example 1.Product is white needles (70%).Mp.140-142 DEG C.
1h NMR (400MHz; CDCl
3): δ 10.13 (s, 1H ,-OH), 8.23 (s, 4H, phenyl), 7.89 (d, J=12.0Hz, 1H, phenyl), 7.48 (t, J=1.6Hz, 1H, phenyl), 7.16 (d, J=8.0Hz, lH, phenyl), 7.06 (t, J=0.4Hz, 1H, phenyl), 3.91 (s, 3H ,-COOCH
3).
13c NMR (125MHz, CDCl
3): δ 165.98,164.67,162.49,157.82,134.01,133.21,130.36,127.04,126.95,126.58,120.02,117.74,107.83,52.521.Ultimate analysis measured value (C
16h
12n
2o
4calculated value, %) C, 65.13 (64.86); H, 4.68 (4.08); N, 9.42 (9.46); ESI, m/z:296.
Ligand 1:
preparation example 3: the preparation of part 3
The chloro-O-Anisic Acid of 5-is replaced except using O-Anisic Acid in the process preparing intermediate 1-1, in the process preparing intermediate 3-1, use Benzoyl chloride to replace outside carbonyl chloride methyl benzoate, prepare part 3 according to the method substantially identical with preparation example 1.Product is white needles (80%).
1h NMR (400MHz; CDCl
3): δ 10.19 (s, 1H ,-OH), 8.15 (d, J=2H), 8.13 (d, J=12.0Hz, 1H, phenyl), 7.8 (t, J=1.6Hz, 3H, phenyl), 7.46 (d, J=8.0Hz, lH, phenyl), 7.06 (t, J=0.4Hz, 1H, phenyl), 7.02 (s, 1H); ESI, m/z:238.
Part 3:
preparation example 4: the preparation of part 4
Except using Benzoyl chloride to replace except carbonyl chloride methyl benzoate in the process preparing intermediate 3-1, prepare part 4 according to the method substantially identical with preparation example 1.Product is pale pink needle-like solid (75%).
1h NMR (400MHz; CDCl
3): δ 10.19 (s, 1H ,-OH), 8.15 (d, J=2H), 8.13 (d, J=12.0Hz, 1H, phenyl), 7.8 (t, J=1.6Hz, 3H, phenyl), 7.46 (d, J=8.0Hz, lH, phenyl), 7.06 (t, J=0.4Hz, 1H, phenyl), 7.02 (s, 1H); ESI, m/z:272.
Part 4:
preparation example 5: the preparation of part 5
The chloro-O-Anisic Acid of 5-is replaced except using O-Anisic Acid in the process preparing intermediate 1-1, in the process preparing intermediate 3-1, use p-benzoyl chloro for outside carbonyl chloride methyl benzoate, prepare part 5 according to the method substantially identical with preparation example 1.Product is pale yellow powder (70%).
1h NMR (400MHz; CDCl
3): δ 10.19 (s, 1H ,-OH), 7.86 (d, J=2H), 7.76 (d, J=12.0Hz, 1H, phenyl), 7.37 (t, J=1.6Hz, 1H, phenyl), 7.06 (d, J=8.0Hz, lH, phenyl), 6.96 (t, J=0.4Hz, 1H, phenyl), 6.70 (s, 1H), 4.01 (s, 2H ,-NH
2); ESI, m/z:253.
Part 5:
preparation example 6: the preparation of part 6
The chloro-O-Anisic Acid of 5-is replaced except using O-Anisic Acid in the process preparing intermediate 1-1, in the process preparing intermediate 3-1, use paranitrobenzoyl chloride to replace outside carbonyl chloride methyl benzoate, prepare part 6 according to the method substantially identical with preparation example 1.Product is pale yellow powder (75%).
1h NMR (400MHz; CDCl
3): δ 9.97 (s, 1H ,-OH), 8.36 (d, 4H), 7.81 (d, J=12.0Hz, 1H, phenyl), 7.45 (t, J=1.6Hz, 1H, phenyl), 7.1 (d, J=8.0Hz, lH, phenyl), 6.99 (t, J=0.4Hz, 1H, phenyl), 6.70 (s, 1H); ESI, m/z:283.
Part 6:
preparation example 7: the preparation of part 7
The chloro-O-Anisic Acid of 5-is replaced except using O-Anisic Acid in the process preparing intermediate 1-1, in the process preparing intermediate 3-1, use parachlorobenzoyl chloride to replace outside carbonyl chloride methyl benzoate, prepare part 7 according to the method substantially identical with preparation example 1.Product is white powder (80%).
1h NMR (400MHz; CDCl
3): δ 10.11 (s, 1H ,-OH), 8.07 (d, 2H), 7.75 (d, J=12.0Hz, 1H, phenyl), 7.50 (t, J=1.6Hz, 3H, phenyl), 7.34 (d, J=8.0Hz, lH, phenyl), 7.02 (t, J=0.4Hz, 1H, phenyl); ESI, m/z:272.
Part 7:
preparation example 8: the preparation of part 8
The chloro-O-Anisic Acid of 5-is replaced except using O-Anisic Acid in the process preparing intermediate 1-1, use in the process preparing intermediate 3-1 and fluorobenzoyl chloride is replaced outside carbonyl chloride methyl benzoate, prepare part 8 according to the method substantially identical with preparation example 1.Product is khaki color powder (74%).
1h NMR (400MHz; CDCl
3): δ 10.08 (s, 1H ,-OH), 8.08 (d, 3H), 7.78 (d, J=12.0Hz, 1H, phenyl), 7.41 (t, J=1.6Hz, 1H, phenyl), 7.19 (d, J=8.0Hz, lH, phenyl), 7.07 (t, J=0.4Hz, 1H, phenyl), 7.97 (t, J=0.4Hz, 1H, phenyl); ESI, m/z:256.
Part 8:
preparation example 9: the preparation of title complex 1
Take 0.13g (0.4mmol) ligand 1, add methyl alcohol 30mL, be heated to solution clarification, slowly drip containing 0.027g (0.2mmol) AlCl
3methanol solution 20mL, stirring reaction 1h, regulator solution pH=6, have a large amount of white precipitate to generate immediately, filtered while hot, obtains light yellow solid; In the chloroformic solution of light yellow solid, slowly spread methyl alcohol, obtain yellow bulk crystals 0.1g, productive rate 76%.
1HNMR(400MHz；CDCl
3)：8.10-8.08(d,8H),7.60-7.58(d,12H),7.33-7.29(t,4H),6.79-6.72(m,8H),4.07(s,12H),3.51(s,6H)。Ultimate analysis measured value (C
66h
50al
2n
8o
18calculated value, %): C, 60.92 (61.11); H, 4.02 (3.89); N, 8.42 (8.64).ESI，m/z:617[Al(C
16H
12N
2O
4)
2]
+，648[Al(C
16H
12N
2O
4)
2(CH
3O)]
+，706[Al
2(C
16H
12N
2O
4)
2(CH
3O)
2]
+。
preparation example 10: the preparation of title complex 2
Except using ethanol to replace methyl alcohol as except solvent, prepare salmon coloured solid according to the method substantially identical with preparation example 9; In the chloroformic solution of salmon coloured solid, slowly spread ethanol, obtain yellow bulk crystals 0.1g, productive rate 78%.
1HNMR(400MHz；CDCl
3)：8.04-8.02(d,8H),7.69-7.52(d,12H),7.32-7.26(t,4H),6.76-6.73(m,8H),4.06(s,12H),3.52-3.48(q,4H),0.82-0.80(t,6H)。Ultimate analysis measured value (C
68h
54al
2n
8o
18calculated value, %): C, 61.25 (61.63); H, 4.11 (4.11); N, 8.92 (8.46) .ESI, m/z:617 [Al (C
16h
12n
2o
4)
2]
+, 719 [Al
2(C
16h
12n
2o
4)
2(CH
3cH
2o) (CH
2o)]
+, 1016 [Al
2(C
16h
12n
2o
4)
3(CH
3cH
2o) (CH
2o)]
+.
preparation example 11: the preparation of title complex 3
Except using part 3 to replace except ligand 1, prepare pink solid according to the method substantially identical with preparation example 9; In the chloroformic solution of pink solid, slowly spread methyl alcohol, obtain light yellow bulk crystals 0.08g, productive rate 78%.
1HNMR(400MHz；CDCl
3)：8.16-8.15(d,3H),7.88-7.87(d,2H),7.60-7.52(m,22H),7.43-7.39(t,9H),3.51(s,6H)。Ultimate analysis measured value (C
58h
42al
2n
8o
10calculated value, %): C, 65.45 (65.41); H, 3.93 (3.98); N, 10.67 (10.52).ESI,m/z：501[Al(C
14H
10N
2O
2)
2]
+，532[Al(C
14H
10N
2O
2)
2(CH
3O)]
+，590[Al
2(C
14H
10N
2O
2)
2(CH
3O)
2]
+。
preparation example 12: the preparation of title complex 4
Replace ligand 1 except using part 3 and use ethanol to replace methyl alcohol as except solvent, preparing light pink solid according to the method substantially identical with preparation example 9; In the chloroformic solution of light pink solid, slowly spread ethanol, obtain light yellow bulk crystals 0.08g, productive rate 79%.
1HNMR(400MHz；CDCl
3)：8.15-8.13(d,3H),7.58-7.56(d,2H),7.52-7.38(m,22H),7.17-6.73(t,9H),3.51(q,4H),0.82-0.80(t,6H)。Ultimate analysis measured value (C
60h
46al
2n
8o
10calculated value, %): C, 65.93 (66.13); H, 4.24 (4.11); N, 10.25 (10.54).ESI,m/z:501[Al(C
14H
10N
2O
2)
2]
+，1094[Al(C
14H
10N
2O
2)
4(CH
3?CH
2O)
2]
+。
preparation example 13: the preparation of title complex 5
Except using part 4 to replace except ligand 1, prepare orange solids according to the method substantially identical with preparation example 9; In the chloroformic solution of orange solids, slowly spread methyl alcohol, obtain yellow bulk crystals 0.1g, productive rate 80%.
1HNMR(400MHz；CDCl
3)：δ8.08(d,8H),7.93(d,8H),7.85(s,4H),7.82(t,4H),7.49(d,4H),7.40(s,4H),3.53(s,6H)。ESI,m/z:569[Al(C
14H
8ClN
2O
2)
2]
+。
preparation example 14: the preparation of title complex 6
Except using part 7 to replace except ligand 1, prepare orange solids according to the method substantially identical with preparation example 9; In the chloroformic solution of orange solids, slowly spread methyl alcohol, obtain yellow bulk crystals 0.1g, productive rate 81%.
1HNMR(400MHz；CDCl
3)：δ8.02(d,8H),7.93(d,8H),7.91(d,4H),7.65(t,4H),7.48(t,4H),7.39(d,4H),3.51(s,6H)。ESI,m/z:569[Al(C
14H
8ClN
2O
2)
2]
+。
evaluation Example 1: the ultraviolet-visible of ligand 1,2,3,4,5,7 and 8 pairs of fluorions detects or purple
outer detection
Each with 10 by ligand 1,2,3,4,5,7 and 8
-5~ 10
-6mol/L (such as 10
-5mol/L) concentration is dissolved in CH
2cl
2/ CH
3cN (1:2, v/v) in mixed solvent with obtained solution, then in each solution, constantly tetrabutyl ammonium fluoride is dripped, adopt ultraviolet-visual spectrometer (UV-Vis) to measure ultraviolet-visible or the ultra-violet absorption spectrum of each solution simultaneously, thus obtain the ultraviolet-visible shown in Fig. 1 to Fig. 7 or ultra-violet absorption spectrum.Arrow in Fig. 1 to Fig. 7 all represents the increase along with content of fluoride ion in solution, the change of absorbancy.
As shown in Figures 1 to 7, along with the increase of content of fluoride ion, the visible ultra-violet absorption spectrum of system is in regular change.Wherein, absorption peak (π-π * transition) strength degradation between 300 ~ 350nm, and between 350 ~ 450nm, there is new absorption peak (n-π * transition), and strengthen gradually.In addition, the color of solution also from colourless become light yellow.This illustrates that ligand 1,2,3,4,5,7 and 8 all has sensing and recognition reaction to fluorion, is a kind of well fluorion chemical sensor.This sensing effect not only can be detected by instrument, and can be arrived by direct visual perception.
evaluation Example 2: the fluoroscopic examination of ligand 1,3,4,5 and 8 pairs of fluorions
Each with 10 by ligand 1,3,4,5 and 8
-5~ 10
-6mol/L (such as 10
-5mol/L) concentration is dissolved in CH
2cl
2/ CH
3with obtained solution in CN (1:2, v/v) mixed solvent, then in each solution, constantly drip tetrabutyl ammonium fluoride, adopt fluorescence spectrophotometer to measure the fluorescence spectrum of each solution simultaneously, thus obtain the fluorescence spectrum shown in Fig. 8 to Figure 12.Arrow in Fig. 8 to Figure 12 all represents the increase along with content of fluoride ion in solution, the change of emissive porwer.
As shown in Fig. 8 to Figure 12, along with the increase of content of fluoride ion, the fluorescence spectrum of system is in regular change.This illustrates ligand 1,3,4,5 and 8 pairs of fluorions have sensing and recognition reaction, is a kind of well fluorion chemical sensor.Especially part 4, is not dripping F
-time, solution launches blue-fluorescence substantially; Drip F
-afterwards, moving to right appears in fluorescence spectrum and the emissive porwer of green area obviously increases, and makes solution transmitting green fluorescence on the whole.This illustrates that part 4 can be used as a kind of fluorion chemical sensor efficiently.
evaluation Example 3: the Selective recognition of part 2 pairs of fluorions and sensing
To the CH of part 2 according to the present invention
2cl
2/ CH
3cN (1:2, v/v) solution (concentration 10
-5~ 10
-6mol/L, such as 10
-5mol/L) F is dripped respectively in
-, Br
-, I
-, H
2pO
4 -and CH
3cOO
-after (solution added is colourless), adopts ultraviolet-visual spectrometer (UV-Vis) to measure the uv-visible absorption spectra of each solution, thus obtain the uv-visible absorption spectra shown in Figure 13.
As shown in figure 13, the CH of part 2 indicated by the solid line
2cl
2/ CH
3cN solution and add Br
-, I
-, H
2pO
4 -and CH
3cOO
-after the uv-visible absorption spectra of solution substantially mutually the same on profile, and add F
-after the uv-visible absorption spectra of solution there is noticeable change (shown in dotted line).In addition, the CH of part 2
2cl
2/ CH
3cN solution and add Br
-, I
-, H
2pO
4 -and CH
3cOO
-after solution be colourless, and add F
-after solution be faint yellow.This illustrates that part 2 pairs of fluorions have high selectivity, and this high selectivity makes F
-detection by the interference of other ion.Identify fluorion quickly and easily by solution colour change, without the need to by any analytical instrument, this is also the advantage of part of the present invention.
evaluation Example 4: the ultraviolet detection of title complex 1 and 5 pairs of fluorions and title complex 1 pair of fluorion
selective recognition and sensing
Each with 10 by title complex 1 and 5
-5~ 10
-6mol/L (such as 10
-5mol/L) concentration is dissolved in CH
2cl
2/ CH
3cN (1:2, v/v) in mixed solvent with obtained solution, then in each solution, constantly tetrabutyl ammonium fluoride is dripped, adopt ultraviolet-visual spectrometer (UV-Vis) to measure the uv-visible absorption spectra of each solution simultaneously, thus obtain the uv-visible absorption spectra shown in Figure 15 and Figure 16.Arrow in Figure 15 and Figure 16 all represents the increase along with content of fluoride ion in solution, the change of absorbancy.
As shown in Figure 15 and Figure 16, along with the increase of content of fluoride ion, the absorption spectrum of system is in regular change.Wherein, the absorption peak near 360nm declines, and the absorption peak of about 400nm strengthens, and this illustrates that title complex 1 and 5 pairs of fluorions have sensing and recognition reaction, is a kind of well fluorion chemical sensor.
To the CH of title complex 1 according to the present invention
2cl
2/ CH
3[Bu is added respectively in CN (1:2, v/v) solution
4n] R (R=Br
-, I
-, F
-, H
2pO
4 -and CH
3cOO
-), then adopt ultraviolet-visual spectrometer (UV-Vis) to measure the uv-visible absorption spectra of each solution, thus obtain the uv-visible absorption spectra shown in Figure 14.
As shown in figure 14, the CH of title complex 1
2cl
2/ CH
3cN solution and add Br
-, I
-and H
2pO
4 -after the ultra-violet absorption spectrum of solution roughly the same on profile, and add CH
3cOO
-and F
-after the ultra-violet absorption spectrum of solution there is noticeable change.Add CH
3cOO
-and F
-after the change of solution be different.Along with CH
3cOO
-add, decline gradually at the absorption peak at 360nm place, and occur new absorption peak at 320nm place and strengthen gradually.And along with F
-add, the absorption peak at 360nm place significantly declines, and occurs new absorption peak at 400nm place and increase gradually.In addition, the CH of title complex 1
2cl
2/ CH
3cN solution and add Br
-, I
-, H
2pO
4 -and CH
3cOO
-after solution be colourless, and add F
-after solution be faint yellow.This illustrates that title complex 1 pair of fluorion has high selectivity, identifying fluorion quickly and easily by solution colour change, without the need to by any analytical instrument.In addition, also by the change of absorption spectrum, to CH
3cOO
-carry out identifying and detecting.
evaluation Example 5: the fluoroscopic examination of title complex 1 and 5 pairs of fluorions
Each concentration with 2 μMs in title complex 1 and 5 is dissolved in CH
2cl
2/ CH
3with obtained solution in CN (1:2, v/v) mixed solvent, then in each solution, constantly drip tetrabutyl ammonium fluoride, adopt fluorescence spectrophotometer to measure the fluorescence spectrum of each solution simultaneously, thus obtain the fluorescence spectrum shown in Figure 17 and Figure 18.Arrow in Figure 17 and Figure 18 all represents the increase along with content of fluoride ion in solution, the change of emissive porwer.
As shown in figs. 17 and 18, along with the increase of content of fluoride ion, the fluorescence spectrum of system is in regular change.This illustrates that title complex 1 and 5 pairs of fluorions have sensing and recognition reaction, is a kind of well fluorion chemical sensor.
About title complex 1, as shown in figure 17, along with F
-add, it reduces gradually in the luminescence at 508nm place, and strengthens gradually at the new emission peak of 374nm place formation one.From the glow color of outside, do not dripping F
-time, solution launches blue-green fluorescent on the whole; Drip F
-afterwards, blue-green fluorescent disappears, and solution almost no longer launches visible ray, but launches sightless 374nm ultraviolet.This illustrates that title complex 1 can be used as a kind of fluoride ion fluorescent sensor efficiently.
About title complex 5, as shown in figure 18, along with F
-add, its luminescence at 423nm place reduces gradually and weakens, and strengthens gradually at the new emission peak of 508nm place formation one, and the degree of this enhancing will be far smaller than weakening of 423nm place.From the glow color of outside, do not dripping F
-time, solution shows strong blue-fluorescence; Drip F
-afterwards, moving to right appears in fluorescence spectrum and the emissive porwer of green area obviously increases, and makes solution transmitting green fluorescence on the whole.This illustrates that title complex 5 can be used as a kind of fluoride ion fluorescent sensor efficiently.
Claims (10)
1. a title complex, is characterized in that described title complex is represented by chemical formula 1:
Chemical formula 1:
In chemical formula 1, m is the integer of 0-5, and n is the integer of 0-4, R
1, R
2and R
3all independently selected from deuterium, tritium, halogen, cyano group, amino, nitro, hydroxyl, carboxyl, replacement or unsubstituted C
2-C
30ether, replacement or unsubstituted C
2-C
30ester group, replacement or unsubstituted C
1-C
30alkyl, replacement or unsubstituted C
2-C
30thiazolinyl, replacement or unsubstituted C
2-C
30alkynyl, replacement or unsubstituted C
3-C
30cycloalkyl, replacement or unsubstituted C
1-C
30alkoxyl group, replacement or unsubstituted C
3-C
30cycloalkyloxy, replacement or unsubstituted C
5-C
30aryl, replacement or unsubstituted C
5-C
30aryloxy and replacement or unsubstituted C
3-C
30the group of heteroaryl composition.
2. title complex according to claim 1, is characterized in that R
1, R
2and R
3all independently selected from deuterium, tritium, halogen, cyano group, amino, nitro, hydroxyl, carboxyl, replacement or unsubstituted C
2-C
6ether, replacement or unsubstituted C
2-C
6ester group, replacement or unsubstituted C
1-C
6alkyl, replacement or unsubstituted C
2-C
6thiazolinyl, replacement or unsubstituted C
2-C
6alkynyl, replacement or unsubstituted C
3-C
10cycloalkyl, replacement or unsubstituted C
1-C
6alkoxyl group, replacement or unsubstituted C
3-C
10cycloalkyloxy, replacement or unsubstituted C
5-C
20aryl, replacement or unsubstituted C
5-C
20aryloxy and replacement or unsubstituted C
3-C
20the group of heteroaryl composition.
3. title complex according to claim 1, is characterized in that R
1, R
2and R
3all independently selected from deuterium, tritium, halogen, cyano group, amino, nitro, hydroxyl, carboxyl, replacement or unsubstituted C
2-C
4ether, replacement or unsubstituted C
2-C
4ester group, replacement or unsubstituted C
1-C
4alkyl, replacement or unsubstituted C
2-C
4thiazolinyl, replacement or unsubstituted C
2-C
4alkynyl, replacement or unsubstituted C
3-C
6cycloalkyl, replacement or unsubstituted C
1-C
4alkoxyl group, replacement or unsubstituted C
3-C
6cycloalkyloxy, replacement or unsubstituted C
5-C
12aryl, replacement or unsubstituted C
5-C
12aryloxy and replacement or unsubstituted C
3-C
12the group of heteroaryl composition.
4. title complex according to claim 1, is characterized in that R
1and R
3all independently selected from-F ,-Cl ,-NH
2,-NO
2,-OR
4with-COOR
4the group of composition, R
2be selected from the group of methyl, ethyl and propyl group composition, wherein, R
4c
1-C
30alkyl, C
3-C
30cycloalkyl or C
5-C
30aryl.
5. title complex according to claim 1, is characterized in that described title complex is any one in title complex 1 to title complex 6 below:
Title complex 1:
Title complex 2:
Title complex 3:
Title complex 4:
Title complex 5:
Title complex 6:
6. the preparation method of title complex according to claim 1, is characterized in that comprising: make part
with AlCl
3with alcohol R
2oH is obtained by reacting title complex according to claim 1.
7. preparation method according to claim 6, characterized by further comprising and prepare part
step, prepare part
step comprise:
Make
intermediate 1 is obtained with ethanol synthesis;
Intermediate 1 and hydrazine reaction is made to obtain intermediate 2;
Make intermediate 2 with
be obtained by reacting intermediate 3;
Intermediate 3 and polyphosphoric acid is made to be obtained by reacting intermediate 4;
Intermediate 4 and boron tribromide is made to be obtained by reacting part
Intermediate 1:
Intermediate 2:
Intermediate 3:
Intermediate 4:
8. a fluorine ion sensing device, is characterized in that comprising title complex according to claim 1.
9. detect a method for fluorion in solution, it is characterized in that described method comprises:
Title complex according to claim 1 is joined in described solution;
Measure ultraviolet-visible or the ultra-violet absorption spectrum of described solution, or measure the fluorescence spectrum of described solution, or observe the color of described solution;
Colour-change according to ultraviolet-visible or the change of ultra-violet absorption spectrum, the change of fluorescence spectrum or described solution determines that described solution contains fluorion.
10. detect a method for fluorion in solution, it is characterized in that described method comprises:
Title complex according to claim 1 is dissolved in a solvent, to obtain the first solution;
Second solution is added gradually in the first solution, to obtain mixing solutions;
In the process adding the first solution gradually, measure ultraviolet-visible or the ultra-violet absorption spectrum of mixing solutions, or measure the fluorescence spectrum of mixing solutions, or observe the color of mixing solutions;
Colour-change according to ultraviolet-visible or the change of ultra-violet absorption spectrum, the change of fluorescence spectrum or mixing solutions determines that the second solution contains fluorion.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410443247.0A CN104277065B (en) | 2014-09-02 | 2014-09-02 | Coordination compound, its preparation method, fluorine ion sensing device and the method for detection fluorion |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410443247.0A CN104277065B (en) | 2014-09-02 | 2014-09-02 | Coordination compound, its preparation method, fluorine ion sensing device and the method for detection fluorion |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104277065A true CN104277065A (en) | 2015-01-14 |
| CN104277065B CN104277065B (en) | 2016-08-24 |
Family
ID=52252460
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410443247.0A Expired - Fee Related CN104277065B (en) | 2014-09-02 | 2014-09-02 | Coordination compound, its preparation method, fluorine ion sensing device and the method for detection fluorion |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104277065B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113603610A (en) * | 2021-07-13 | 2021-11-05 | 上海应用技术大学 | Naphthalimide organogelator and preparation method and application thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1730485A (en) * | 2005-08-05 | 2006-02-08 | 南京大学 | Fluorion sensing test paper for visual colorimetry and its uses |
| US20110294229A1 (en) * | 2010-05-28 | 2011-12-01 | Florida State University Research Foundation, Inc. | Colorimetric and fluorimetric fluoride sensing |
| CN103159762A (en) * | 2013-03-25 | 2013-06-19 | 华东理工大学 | Epindolidione derivative and application thereof |
-
2014
- 2014-09-02 CN CN201410443247.0A patent/CN104277065B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1730485A (en) * | 2005-08-05 | 2006-02-08 | 南京大学 | Fluorion sensing test paper for visual colorimetry and its uses |
| US20110294229A1 (en) * | 2010-05-28 | 2011-12-01 | Florida State University Research Foundation, Inc. | Colorimetric and fluorimetric fluoride sensing |
| CN103159762A (en) * | 2013-03-25 | 2013-06-19 | 华东理工大学 | Epindolidione derivative and application thereof |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113603610A (en) * | 2021-07-13 | 2021-11-05 | 上海应用技术大学 | Naphthalimide organogelator and preparation method and application thereof |
| CN113603610B (en) * | 2021-07-13 | 2023-09-26 | 上海应用技术大学 | Naphthalene hydrazide organic gel factor and preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN104277065B (en) | 2016-08-24 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103865290A (en) | Fluorine-boron fluorescent dye as well as preparation method and application thereof | |
| CN101646744A (en) | Time-temperature indicator based on oligomeric spiroaromatics | |
| PL227162B1 (en) | New, highly fluorescent heterocyclic substances and their preparation | |
| CN109762000A (en) | Based on the spirooxazine H-like ion fluorescent probe compounds and its synthetic method of 1,8- naphthalimide unit and application | |
| Nandhini et al. | Spectroscopic and DFT/TD-DFT studies on selective and sensitive fluorescent detection of Al (III) ion | |
| Wang et al. | Highly efficient and selective turn-off quenching of ligand-sensitized luminescence from europium imidazo [4, 5-f]-1, 10-phenanthroline complex by fluoride ion | |
| CN104277065A (en) | Complex, preparation method thereof, fluorine ion sensor and method for detecting fluorine ion | |
| Raju et al. | Synthesis, photophysical characterisation and photostability studies of NIR probes with aliphatic, aromatic and chlorinated terminals in 5-and 9-amino positions of benzo [a] phenoxazines | |
| CN104277010A (en) | Compound and preparation method thereof, fluoride ion sensor and fluorine ion detection method | |
| Tan et al. | Photophysical studies of novel lanthanide (Eu3+ and Tb3+) luminescent hydrogels | |
| CN103936631B (en) | A kind of Biphenyl carbamide compound containing oximido and its preparation method and application | |
| CN111825645B (en) | Naphtho-coumarin compound, preparation method and application of naphthocoumarin compound as photoluminescence material | |
| Aggarwal et al. | Synthesis and application of an indenoquinoline dione conjugate as a dual fluorescent and colorimetric pH sensor | |
| Fadda et al. | Some studies in cyanine dyes incorporating pyridine rings endowed with pharmaceutical potency | |
| Rufchahi et al. | 6-Butyl-4-hydroxyquinolin-2-(1H)-one as an enol type coupling component for the synthesis of some new azo disperse dyes | |
| CN108409757B (en) | Zinc complex and preparation method and application thereof | |
| CN104211649A (en) | Preparation method of quinazoline-4(3H)-ketone and application | |
| CN106554770A (en) | A kind of preparation and its application of triazole derivatives | |
| CN107556228B (en) | Nitrogen heterocyclic derivative and application thereof | |
| CN103275017B (en) | 2-substituted quinazolinone compound, its synthesis method and application | |
| US5266700A (en) | Bipyridyls and their use as inks | |
| CN102816454B (en) | Ester group containing 1,8-naphthalimide fluorescent dichroic dye, preparation method and application thereof | |
| Mac et al. | Photophysical properties of some donor–acceptor 1H-pyrazolo [3, 4-b] quinolines: Radiative versus non-radiative electron transfer processes | |
| Jlaiel et al. | Experimental and theoretical studies of photophysical properties of N-Substituted iminocoumarins | |
| Kammoun et al. | Reactivity of 3‐cyano‐N‐ethoxycarbonyl‐iminocoumarin with hydrazides as N‐nucleophiles |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20160824 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |