CN115260182B - Thiazole coupling quinolyl phenol benzenesulfonate enhanced fluorescent probe for detecting hydrogen sulfide and preparation method and application thereof - Google Patents
Thiazole coupling quinolyl phenol benzenesulfonate enhanced fluorescent probe for detecting hydrogen sulfide and preparation method and application thereof Download PDFInfo
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- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 title claims abstract description 40
- 229910000037 hydrogen sulfide Inorganic materials 0.000 title claims abstract description 39
- 239000007850 fluorescent dye Substances 0.000 title claims abstract description 29
- -1 quinolyl phenol benzenesulfonate Chemical compound 0.000 title claims abstract description 22
- FZWLAAWBMGSTSO-UHFFFAOYSA-N Thiazole Chemical compound C1=CSC=N1 FZWLAAWBMGSTSO-UHFFFAOYSA-N 0.000 title claims abstract description 18
- 230000008878 coupling Effects 0.000 title claims abstract description 11
- 238000010168 coupling process Methods 0.000 title claims abstract description 11
- 238000005859 coupling reaction Methods 0.000 title claims abstract description 11
- 238000002360 preparation method Methods 0.000 title abstract description 14
- 150000001875 compounds Chemical class 0.000 claims abstract description 46
- NLFBCYMMUAKCPC-KQQUZDAGSA-N ethyl (e)-3-[3-amino-2-cyano-1-[(e)-3-ethoxy-3-oxoprop-1-enyl]sulfanyl-3-oxoprop-1-enyl]sulfanylprop-2-enoate Chemical compound CCOC(=O)\C=C\SC(=C(C#N)C(N)=O)S\C=C\C(=O)OCC NLFBCYMMUAKCPC-KQQUZDAGSA-N 0.000 claims abstract description 30
- HTSGKJQDMSTCGS-UHFFFAOYSA-N 1,4-bis(4-chlorophenyl)-2-(4-methylphenyl)sulfonylbutane-1,4-dione Chemical compound C1=CC(C)=CC=C1S(=O)(=O)C(C(=O)C=1C=CC(Cl)=CC=1)CC(=O)C1=CC=C(Cl)C=C1 HTSGKJQDMSTCGS-UHFFFAOYSA-N 0.000 claims abstract description 23
- XZFDKWMYCUEKSS-UHFFFAOYSA-N 6,6-Dimethylbicyclo[3.1.1]heptan-2-one Chemical compound C1C2C(C)(C)C1CCC2=O XZFDKWMYCUEKSS-UHFFFAOYSA-N 0.000 claims abstract description 22
- RGHHSNMVTDWUBI-UHFFFAOYSA-N 4-hydroxybenzaldehyde Chemical compound OC1=CC=C(C=O)C=C1 RGHHSNMVTDWUBI-UHFFFAOYSA-N 0.000 claims abstract description 16
- 238000002189 fluorescence spectrum Methods 0.000 claims abstract description 13
- SSFSNKZUKDBPIT-UHFFFAOYSA-N 2,4-dinitrobenzenesulfonyl chloride Chemical compound [O-][N+](=O)C1=CC=C(S(Cl)(=O)=O)C([N+]([O-])=O)=C1 SSFSNKZUKDBPIT-UHFFFAOYSA-N 0.000 claims abstract description 8
- USFZMSVCRYTOJT-UHFFFAOYSA-N Ammonium acetate Chemical compound N.CC(O)=O USFZMSVCRYTOJT-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000005695 Ammonium acetate Substances 0.000 claims abstract description 8
- 229940043376 ammonium acetate Drugs 0.000 claims abstract description 8
- 235000019257 ammonium acetate Nutrition 0.000 claims abstract description 8
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 claims abstract description 8
- CUONGYYJJVDODC-UHFFFAOYSA-N malononitrile Chemical compound N#CCC#N CUONGYYJJVDODC-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000002994 raw material Substances 0.000 claims abstract description 7
- 238000007363 ring formation reaction Methods 0.000 claims abstract description 6
- VRVRGVPWCUEOGV-UHFFFAOYSA-N 2-aminothiophenol Chemical compound NC1=CC=CC=C1S VRVRGVPWCUEOGV-UHFFFAOYSA-N 0.000 claims abstract description 5
- 238000001514 detection method Methods 0.000 claims abstract description 5
- 238000005886 esterification reaction Methods 0.000 claims abstract description 4
- 238000006243 chemical reaction Methods 0.000 claims description 51
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 30
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 20
- 239000000243 solution Substances 0.000 claims description 19
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 18
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 claims description 12
- 239000012074 organic phase Substances 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 11
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 9
- 239000012043 crude product Substances 0.000 claims description 9
- 238000006555 catalytic reaction Methods 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 7
- 238000012544 monitoring process Methods 0.000 claims description 7
- 238000005406 washing Methods 0.000 claims description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 6
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 6
- 239000007864 aqueous solution Substances 0.000 claims description 6
- 239000012295 chemical reaction liquid Substances 0.000 claims description 6
- 239000008367 deionised water Substances 0.000 claims description 6
- 229910021641 deionized water Inorganic materials 0.000 claims description 6
- 239000012153 distilled water Substances 0.000 claims description 6
- 239000000741 silica gel Substances 0.000 claims description 6
- 229910002027 silica gel Inorganic materials 0.000 claims description 6
- HRZFUMHJMZEROT-UHFFFAOYSA-L sodium disulfite Chemical compound [Na+].[Na+].[O-]S(=O)S([O-])(=O)=O HRZFUMHJMZEROT-UHFFFAOYSA-L 0.000 claims description 6
- 229940001584 sodium metabisulfite Drugs 0.000 claims description 6
- 235000010262 sodium metabisulphite Nutrition 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 5
- 238000010992 reflux Methods 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- 125000005605 benzo group Chemical group 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
- 238000002390 rotary evaporation Methods 0.000 claims description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 3
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical class [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 3
- 238000007865 diluting Methods 0.000 claims description 3
- 230000007935 neutral effect Effects 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- UONNCRCRHHFOAA-UHFFFAOYSA-N phenyl 2,4-dinitrobenzenesulfonate Chemical compound [O-][N+](=O)C1=CC([N+](=O)[O-])=CC=C1S(=O)(=O)OC1=CC=CC=C1 UONNCRCRHHFOAA-UHFFFAOYSA-N 0.000 claims description 3
- AHZJKOKFZJYCLG-UHFFFAOYSA-K trifluoromethanesulfonate;ytterbium(3+) Chemical compound [Yb+3].[O-]S(=O)(=O)C(F)(F)F.[O-]S(=O)(=O)C(F)(F)F.[O-]S(=O)(=O)C(F)(F)F AHZJKOKFZJYCLG-UHFFFAOYSA-K 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 2
- 238000000967 suction filtration Methods 0.000 claims description 2
- QWXYZCJEXYQNEI-OSZHWHEXSA-N intermediate I Chemical compound COC(=O)[C@@]1(C=O)[C@H]2CC=[N+](C\C2=C\C)CCc2c1[nH]c1ccccc21 QWXYZCJEXYQNEI-OSZHWHEXSA-N 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 claims 1
- 238000006170 formylation reaction Methods 0.000 abstract description 3
- 238000007079 thiolysis reaction Methods 0.000 abstract description 3
- IAZDPXIOMUYVGZ-WFGJKAKNSA-N Dimethyl sulfoxide Chemical compound [2H]C([2H])([2H])S(=O)C([2H])([2H])[2H] IAZDPXIOMUYVGZ-WFGJKAKNSA-N 0.000 description 16
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 8
- 235000013305 food Nutrition 0.000 description 5
- 238000003786 synthesis reaction Methods 0.000 description 5
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 4
- 238000005160 1H NMR spectroscopy Methods 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 239000003480 eluent Substances 0.000 description 4
- 230000002452 interceptive effect Effects 0.000 description 4
- 239000003208 petroleum Substances 0.000 description 4
- 229910021642 ultra pure water Inorganic materials 0.000 description 4
- 239000012498 ultrapure water Substances 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 239000000523 sample Substances 0.000 description 3
- 206010061218 Inflammation Diseases 0.000 description 2
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- 235000013601 eggs Nutrition 0.000 description 2
- 238000001506 fluorescence spectroscopy Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 230000004054 inflammatory process Effects 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- LATPRGOTJGNZTM-UHFFFAOYSA-N 2-amino-3-phenylbenzenethiol Chemical compound NC1=C(S)C=CC=C1C1=CC=CC=C1 LATPRGOTJGNZTM-UHFFFAOYSA-N 0.000 description 1
- 208000024827 Alzheimer disease Diseases 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- 208000024172 Cardiovascular disease Diseases 0.000 description 1
- 206010028813 Nausea Diseases 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 230000002159 abnormal effect Effects 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000006907 apoptotic process Effects 0.000 description 1
- 230000008953 bacterial degradation Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- ZYGHJZDHTFUPRJ-UHFFFAOYSA-N benzo-alpha-pyrone Natural products C1=CC=C2OC(=O)C=CC2=C1 ZYGHJZDHTFUPRJ-UHFFFAOYSA-N 0.000 description 1
- 150000001591 beta-pinene derivatives Chemical class 0.000 description 1
- 230000008827 biological function Effects 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 201000011529 cardiovascular cancer Diseases 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 235000001671 coumarin Nutrition 0.000 description 1
- 125000000332 coumarinyl group Chemical class O1C(=O)C(=CC2=CC=CC=C12)* 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 206010012601 diabetes mellitus Diseases 0.000 description 1
- 201000010099 disease Diseases 0.000 description 1
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 239000010842 industrial wastewater Substances 0.000 description 1
- 230000003914 insulin secretion Effects 0.000 description 1
- 230000006371 metabolic abnormality Effects 0.000 description 1
- 230000004770 neurodegeneration Effects 0.000 description 1
- 208000015122 neurodegenerative disease Diseases 0.000 description 1
- 230000036542 oxidative stress Effects 0.000 description 1
- SCOAVUHOIJMIBW-UHFFFAOYSA-N phenanthrene-1,2-dione Chemical class C1=CC=C2C(C=CC(C3=O)=O)=C3C=CC2=C1 SCOAVUHOIJMIBW-UHFFFAOYSA-N 0.000 description 1
- 230000035790 physiological processes and functions Effects 0.000 description 1
- 238000004451 qualitative analysis Methods 0.000 description 1
- 238000004445 quantitative analysis Methods 0.000 description 1
- 239000007843 reactive sulfur species Substances 0.000 description 1
- 235000020095 red wine Nutrition 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 230000005062 synaptic transmission Effects 0.000 description 1
- 150000003505 terpenes Chemical class 0.000 description 1
- 235000007586 terpenes Nutrition 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- 150000003573 thiols Chemical class 0.000 description 1
- 239000002341 toxic gas Substances 0.000 description 1
- 238000003828 vacuum filtration Methods 0.000 description 1
- 230000024883 vasodilation Effects 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 235000014101 wine Nutrition 0.000 description 1
- 150000003732 xanthenes Chemical class 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D417/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00
- C07D417/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing two hetero rings
- C07D417/10—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing two hetero rings linked by a carbon chain containing aromatic rings
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- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- 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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- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
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- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
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- C09K2211/1018—Heterocyclic compounds
- C09K2211/1025—Heterocyclic compounds characterised by ligands
- C09K2211/1029—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom
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- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1018—Heterocyclic compounds
- C09K2211/1025—Heterocyclic compounds characterised by ligands
- C09K2211/1029—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom
- C09K2211/1037—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom with sulfur
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Abstract
The invention discloses a thiazole coupling quinolyl phenol benzenesulfonate enhanced fluorescent probe for detecting hydrogen sulfide, and a preparation method and application thereof. The invention takes nopinone as a raw material, and carries out cyclization reaction with malononitrile, p-hydroxybenzaldehyde and ammonium acetate to obtain a compound I; carrying out formylation reaction on the compound I and urotropine to obtain a compound II; cyclizing the compound II with o-amino thiophenol to obtain a compound III; and (3) carrying out esterification reaction on the compound III and 2, 4-dinitrobenzenesulfonyl chloride to obtain the compound NPS. The NPS can selectively generate thiolysis reaction with hydrogen sulfide, so that 2, 4-dinitrobenzenesulfonyl is completely removed from NPS molecules and a compound III with yellow fluorescence is released, the fluorescence spectrum of the compound III is rapidly enhanced, the compound III can be used as a specific enhanced fluorescent probe for detecting hydrogen sulfide, the detection limit reaches 8.3 multiplied by 10 ‑8 M, and the compound III has good application prospect.
Description
Technical Field
The invention belongs to the technical field of fine organic synthesis, and relates to a thiazole coupling quinolyl phenol benzenesulfonate enhanced fluorescent probe for detecting hydrogen sulfide, and a preparation method and application thereof.
Background
Hydrogen sulfide (H 2 S) is a colorless, malodorous, highly toxic gas, called the third endogenous gas transporter next to nitric oxide and carbon monoxide in the living system. H 2 S, an active sulfur species (reactive sulfur species, RSS), is an essential thiol-containing molecule and plays a multifunctional role in resisting oxidative stress and maintaining normal physiological functions of organisms, including neurotransmission, vasodilation, insulin secretion, apoptosis and inflammation. In addition, abnormal fluctuations in H 2 S levels and concentrations are associated with a range of diseases such as metabolic abnormalities, neurodegenerative diseases, diabetes, alzheimer' S disease, cardiovascular diseases, cancer and inflammation. In addition, hydrogen sulfide has been demonstrated to be present in many food and industrial wastewater. The discharged wastewater containing hydrogen sulfide can seriously pollute water environment and food, and cause serious harm to human health. In general, spoiled eggs contain a certain amount of H 2 S gas, which is produced by bacterial degradation of various sulfides and gives off a nausea-causing odor of the rotten eggs. In addition, H 2 S is also considered as one of the important indicators for judging the quality of red wine, and poor quality wine generally contains a higher concentration of H 2 S. Therefore, the fluctuating level of H 2 S is an important indicator for monitoring the freshness and quality of food. In view of the important biological functions of H 2 S and its important effects on food quality, it is necessary to accurately evaluate H 2 S concentrations in food samples and organisms.
There are many reports of synthesis studies on organic fluorescent probes for detecting hydrogen sulfide, and the synthesis studies generally include: fluorescent probes such as xanthenes, coumarins, phenanthrenequinones, and cyanines. And the organic fluorescent probe for hydrogen sulfide detection is synthesized by adopting renewable natural terpene as a raw material, so that the related report is less, and the fluorescent probe technology has great research value and development prospect.
Disclosure of Invention
Aiming at the defects existing in the prior art, the technical problem to be solved by the invention is to provide the thiazole coupling quinolyl phenol benzenesulfonate enhanced fluorescent probe for detecting hydrogen sulfide, which can specifically react with hydrogen sulfide, and the fluorescence spectrum of the probe is rapidly enhanced to perform qualitative and quantitative analysis on the hydrogen sulfide. The invention aims to provide a preparation method of the thiazole coupling quinolyl phenol benzenesulfonate enhanced fluorescent probe for detecting hydrogen sulfide. The invention also solves the other technical problem of providing an application of the thiazole coupling quinolyl phenol benzenesulfonate enhanced fluorescent probe for detecting hydrogen sulfide.
In order to solve the technical problems, the invention adopts the following technical scheme:
The thiazole coupling quinolyl phenol benzenesulfonate enhanced fluorescent probe for detecting hydrogen sulfide is named as 4- (2 '-amino-3' -cyano-7 ',7' -dimethyl-5 ',6',7',8' -tetrahydro-6 ',8' -methanoquinolin-4 '-yl) -2- (benzo [ d ] thiazol-2' -yl) phenol 2, 4-dinitrobenzenesulfonate, NPS for short, and has the structural formula:
the preparation method of the thiazole coupling quinolyl phenol benzenesulfonate enhanced fluorescent probe for detecting hydrogen sulfide comprises the following specific synthesis steps:
1) Taking nopinone as a raw material, and performing cyclization reaction with malononitrile, parahydroxybenzaldehyde and ammonium acetate to obtain a 4- (2 ' -amino-3 ' -cyano-7 ',7' -dimethyl-5 ',6',7',8' -tetrahydro-6 ',8' -methanoquinolin-4 ' -yl) phenol compound I;
2) Under the catalysis of trifluoroacetic acid, formylating the compound I with urotropine to obtain 3-formyl-4- (2 ' -amino-3 ' -cyano-7 ',7' -dimethyl-5 ',6',7',8' -tetrahydro-6 ',8' -methanoquinolin-4 ' -yl) phenol compound II;
3) Under the catalysis of sodium metabisulfite, the compound II and o-aminophenylsulfnol undergo cyclization reaction to obtain a 4- (2 '-amino-3' -cyano-7 ',7' -dimethyl-5 ',6',7',8' -tetrahydro-6 ',8' -methanoquinolin-4 '-yl) -2- (benzo [ d ] thiazol-2' -yl) phenol compound III;
4) The compound III and 2, 4-dinitrobenzenesulfonyl chloride are subjected to esterification reaction under the catalysis of triethylamine to prepare a compound 4- (2 '-amino-3' -cyano-7 ',7' -dimethyl-5 ',6',7',8' -tetrahydro-6 ',8' -methanoquinolin-4 '-yl) -2- (benzo [ d ] thiazole-2' -yl) phenol 2, 4-dinitrobenzenesulfonate compound NPS.
In the step 1), under the catalysis of ytterbium trifluoromethane sulfonate, the raw materials nopinone, malononitrile, parahydroxybenzaldehyde and ammonium acetate undergo cyclization reaction to obtain a compound I, and the specific preparation steps are as follows:
(1) Adding 10mmol of nopinone, 10-15 mmol of malononitrile, 10-15 mmol of p-hydroxybenzaldehyde, 15-30 mmol of ammonium acetate and 30-50 mL of ethanol into a three-necked flask, adding 0.5-1 mmol of ytterbium triflate, heating and refluxing for reaction for 6-12 h, and tracking and monitoring the reaction progress by using a TLC method until the nopinone conversion rate reaches 100%, and stopping the reaction;
(2) The reaction solution is cooled, filtered under reduced pressure, washed by cold ethanol and dried to obtain the compound I.
In the step 2), under the action of trifluoroacetic acid, the compound I and urotropine are subjected to formylation reaction to obtain a compound II, and the specific preparation steps are as follows:
(1) Adding 1mmol of compound I, 2-4 mmol of urotropine and 5-15 mL of trifluoroacetic acid into a three-necked flask, carrying out reflux reaction for 4-8 h, monitoring the reaction progress by TLC until the compound I is completely reacted, adding 5-15 mL of 1M dilute hydrochloric acid aqueous solution into the reaction solution, continuously stirring for 1h, cooling to room temperature and stopping the reaction;
(2) The reaction solution is extracted by ethyl acetate, and the organic phase is washed to be neutral by saturated sodium bicarbonate aqueous solution and distilled water; the organic phase is dried by anhydrous sodium sulfate, filtered and distilled to remove the solvent, and then the crude product of the compound II is obtained;
(3) The crude product of compound II was separated by a silica gel column (200-300 mesh, eluent petroleum ether/ethyl acetate=6:1, v/v) to give compound II.
In the step 3), the compound II is cyclized with o-aminophenylsulfnol under the catalysis of sodium metabisulfite to obtain a compound III, and the specific preparation steps are as follows:
(1) Adding 1mmol of compound II, 1-1.5 mmol of o-amino thiophenol and 1-1.5 mmol of sodium metabisulfite into 5-10 mLN, N-dimethylformamide, and reacting for 2-4 h at 110 ℃;
(2) And (3) cooling the reaction liquid to room temperature, adding 10-30 mL of ice deionized water into the reaction liquid, performing reduced pressure suction filtration on the obtained reaction liquid, washing with ethanol and deionized water for several times, and drying to obtain the compound III.
In the step 4), under the catalysis of triethylamine, the compound III and 2, 4-dinitrobenzene sulfonyl chloride undergo substitution reaction to obtain a compound NPS, and the specific preparation steps are as follows:
(1) Under the protection of nitrogen, adding 1mmol of compound III, 2-4 mmol of triethylamine and 5-15 mmol of dichloromethane into a three-neck flask, stirring at 0 ℃ for reaction, dropwise adding 2-3 mmol of 2, 4-dinitrobenzenesulfonyl chloride into the flask, continuously reacting for 4-6 h at room temperature, and monitoring the reaction progress by TLC until the compound III is reacted completely, and stopping the reaction;
(2) Diluting the reaction solution with water, extracting with ethyl acetate, and washing the organic phase with distilled water to neutrality; the organic phase was dried over anhydrous sodium sulfate, filtered, and the solvent was removed by rotary evaporation, and the crude product was separated by a silica gel column (200-300 mesh, eluent petroleum ether/ethyl acetate=4:1, v/v) to give compound NPS.
Use of the compound NPS for detecting hydrogen sulfide. Can react with hydrogen sulfide specifically, the fluorescence spectrum is enhanced rapidly, and the detection limit reaches 8.3X10 -8 M.
The invention takes nopinone as a raw material, and carries out cyclization reaction with malononitrile, p-hydroxybenzaldehyde and ammonium acetate to obtain a compound I; carrying out formylation reaction on the compound I and urotropine to obtain a compound II; cyclizing the compound II with o-amino thiophenol to obtain a compound III; and (3) carrying out esterification reaction on the compound III and 2, 4-dinitrobenzenesulfonyl chloride to obtain a final compound NPS. The compound NPS can selectively generate a thiolysis reaction with hydrogen sulfide to form a compound III, the fluorescence spectrum of the compound NPS is rapidly enhanced, and the compound NPS can be used as a specific enhanced fluorescent probe for detecting the hydrogen sulfide.
The beneficial effects are that: compared with the prior art, the thiazole coupling quinolyl phenol benzenesulfonate enhanced fluorescent probe compound NPS prepared by using the natural renewable resource beta-pinene derivative nopanone as a raw material can selectively generate thiolysis reaction with hydrogen sulfide, so that 2, 4-dinitrobenzenesulfonyl completely detaches from NPS molecules and releases a compound III with yellow fluorescence, the fluorescence spectrum of the compound III is rapidly enhanced, and the compound III can be used as a specific fluorescent probe for detecting the hydrogen sulfide, the detection limit reaches 8.3X10 -8 M, and the performance is excellent.
Drawings
FIG. 1 is a graph of fluorescence emission spectra of NPS compounds each acting with a different interfering compound;
FIG. 2 is a graph showing fluorescence spectra of NPS compounds in pure water with different concentrations of hydrogen sulfide, respectively.
Detailed Description
The invention will be further illustrated with reference to specific examples.
Example 1
The synthetic route of compound NPS is:
The specific synthesis steps are as follows:
1) Preparation of Compound I
10Mmol of nopinone, 10mol of malononitrile, 10mol of p-hydroxybenzaldehyde, 15mmol of ammonium acetate and 30mL of ethanol are added into a three-necked flask, 1mL of 10% volume fraction aqueous acetic acid solution is added, the mixture is heated and refluxed for 6h, the progress of the reaction is tracked and monitored by a TLC method, and the reaction is stopped until the conversion rate of the nopinone reaches 100%. Cooling the reaction solution, vacuum filtering, washing with cold ethanol, and drying to obtain compound I with the yield of 73％.1H NMR(600MHz,DMSO-d6)δ：9.71(s,1H),7.16(d,J＝8.3Hz,2H),6.87 (d,J＝8.3Hz,2H),6.52(s,2H),2.70(t,J＝5.6Hz,1H),2.59(dd,J＝9.5,5.8Hz, 1H),2.50-2.48(m,1H),2.40(dd,J＝16.5,2.7Hz,1H),2.19(tt,J＝6.1,3.0Hz,1H), 1.33(s,3H),1.20(d,J＝9.5Hz,1H),0.65(s,3H).13C NMR(150MHz,DMSO-d6) δ：169.49,158.74,157.72,152.37,129.58,126.43,117.27,115.75,115.39,86.82, 50.18,38.46,29.50,29.20,25.65,21.12.
2) Preparation of Compound II
1Mmol of compound I, 2mmol of urotropine and 10mL of trifluoroacetic acid are added into a three-necked flask, reflux reaction is carried out for 4h, the reaction progress is monitored by TLC until the reaction of the compound I is complete, 10mL of 1M dilute hydrochloric acid aqueous solution is added into the reaction solution, stirring reaction is continued for 1h, cooling to room temperature is carried out, and the reaction is stopped. The reaction solution is extracted by ethyl acetate, and the organic phase is washed to be neutral by saturated sodium bicarbonate aqueous solution and distilled water; the organic phase was dried over anhydrous sodium sulfate, filtered, and the solvent was removed by rotary evaporation to give a crude product of compound II. Separating the crude product of the compound II by a silica gel column (200-300 meshes, eluent petroleum ether/ethyl acetate=6:1, v/v) to obtain an intermediate II with the yield of 57％.1H NMR(600MHz,DMSO-d6)δ11.04(s,1H),10.32(s,1H), 7.62(d,J＝2.4Hz,1H),7.53(dd,J＝8.5,2.4Hz,1H),7.13(d,J＝8.5Hz,1H),6.62 (s,2H),2.71(t,J＝5.6Hz,1H),2.59(dt,J＝9.5,5.8Hz,1H),2.47(d,J＝3.1Hz, 1H),2.38(dd,J＝16.5,2.7Hz,1H),2.18(tt,J＝5.7,2.8Hz,1H),1.33(s,3H),1.21 (d,J＝9.5Hz,1H),0.65(s,3H).13C NMR(150MHz,DMSO-d6)δ191.00,169.82, 160.84,158.74,150.92,136.28,128.72,127.01,122.23,117.76,117.02,115.63, 86.38,64.94,50.18,38.49,29.41,29.02,25.62,21.13.
3) Preparation of Compound III
1Mmol of compound II, 1mmol of o-aminophenylthiophenol, 1mmol of sodium metabisulfite were added to 10mL of N, N-dimethylformamide and reacted at 110℃for 4h. Cooling the reaction solution to room temperature, adding 30mL of ice deionized water into the reaction solution, performing vacuum filtration on the obtained reaction solution, washing with ethanol and deionized water for several times, and drying to obtain a compound III with the yield of 92％.1H NMR(600MHz,DMSO-d6)δ：11.80 (s,1H),8.21(d,J＝2.3Hz,1H),8.14(d,J＝8.0Hz,1H),8.05(d,J＝8.1Hz,1H), 7.53(t,J＝7.5Hz,1H),7.43(q,J＝9.2,8.4Hz,2H),7.22(d,J＝8.4Hz,1H),6.65(s, 2H),2.72(s,1H),2.62-2.54(m,2H),2.43(d,J＝16.6Hz,1H),2.18(td,J＝6.6,6.1, 3.2Hz,1H),1.33(s,3H),1.25(d,J＝9.4Hz,1H),0.68(s,3H).13C NMR(150MHz, DMSO-d6)δ：169.78,163.76,158.77,156.27,151.41,151.37,134.83,132.20,128.14, 127.34,126.44,125.09,122.29,122.00,118.91,117.27,117.16,115.72,86.56,50.20, 38.49,29.46,29.12,25.62,21.13,14.09.
4) Preparation of Compound NPS
Under the protection of nitrogen, 1mmol of compound III, 3mmol of triethylamine and 15mmol of dichloromethane are added into a three-neck flask, the mixture is stirred at 0 ℃ for reaction, 2mmol of 2, 4-dinitrobenzenesulfonyl chloride is added into the flask dropwise, the reaction is continued for 6 hours at room temperature, and the reaction progress is monitored by TLC until the reaction of the intermediate III is stopped after the reaction is completed. Diluting the reaction solution with water, extracting with ethyl acetate, and washing the organic phase with distilled water to neutrality; the organic phase is dried by anhydrous sodium sulfate, filtered, and the solvent is removed by rotary evaporation, and the crude product is separated by a silica gel column (200-300 meshes, eluent petroleum ether/ethyl acetate=4:1, v/v) to obtain the compound NPS with the yield of 58％.1H NMR (600MHz,DMSO-d6)δ：8.97(d,J＝2.3Hz,1H),8.34(dd,J＝8.7,2.3Hz,1H),8.24 (d,J＝8.7Hz,1H),8.12(d,J＝7.9Hz,2H),7.98(d,J＝8.1Hz,1H),7.70(dd,J＝ 8.5,2.2Hz,1H),7.54(t,J＝7.9Hz,2H),7.50-7.44(m,1H),6.76(s,2H),2.74(t,J＝ 5.6Hz,1H),2.63(dt,J＝9.4,5.8Hz,1H),2.56(dd,J＝16.5,3.2Hz,1H),2.43(dd,J ＝16.5,2.7Hz,1H),2.23(tt,J＝6.0,3.0Hz,1H),1.35(s,3H),1.28(d,J＝9.3Hz, 1H),0.70(s,3H).13C NMR(150MHz,DMSO-d6)δ：170.34,170.16,160.67,158.67, 152.23,150.88,149.63,147.71,145.75,136.57,135.32,133.07,131.52,131.01, 127.25,127.08,126.82,126.10,124.29,123.21,122.27,120.76,116.75,115.48, 85.87,59.76,38.59,28.89,25.64,21.20,20.76,14.08.
Example 2
The compound NPS was dissolved in ethanol to prepare a solution at a concentration of 1mM, and diluted to 20. Mu.M with ultrapure water for fluorescence spectrum test. The fluorescence spectra of the different interfering compounds on the probe compound NPS were measured by fluorescence spectrometry using the different interfering compounds dissolved in ultrapure water and diluted to 20. Mu.M, as shown in FIG. 1. The results show that only hydrogen sulfide can cause a significant change in the fluorescence spectrum intensity of the compound compared to other interfering compounds, indicating that the compound NPS can specifically recognize hydrogen sulfide.
Example 3
The compound NPS was dissolved in ethanol to prepare a 1mM solution, and diluted to 10. Mu.M with ultrapure water for use. Hydrogen sulfide was also dissolved in ultrapure water and prepared into solutions having concentrations of 0,2, 4, 6, 8, 10, 12, 14, 16, 18, 20 μm, respectively. Fluorescence spectra of hydrogen sulfide at different concentrations on the probe compound NPS were measured using fluorescence spectrometry, as shown in fig. 2. The result shows that the fluorescence spectrum of the fluorescent probe compound NPS is changed regularly, which indicates that the fluorescent probe compound NPS can be used as an enhanced fluorescent probe for detecting hydrogen sulfide.
Claims (8)
1. A thiazole coupling quinolyl phenol benzenesulfonate enhanced fluorescent probe for detecting hydrogen sulfide is characterized by comprising the following structural formula:
。
2. The method for preparing a thiazole-coupled quinolinyl phenol benzenesulfonate enhanced fluorescent probe for detecting hydrogen sulfide as set forth in claim 1, comprising the steps of:
1) Taking nopinone as a raw material, and carrying out cyclization reaction with malononitrile, parahydroxybenzaldehyde and ammonium acetate to obtain a compound I;
2) Under the catalysis of trifluoroacetic acid, formylating the compound I with urotropine to obtain a compound II;
3) Under the catalysis of sodium metabisulfite, cyclizing the compound II with o-amino thiophenol to obtain a compound III;
4) The compound III is catalyzed by triethylamine to perform esterification reaction with 2, 4-dinitrobenzenesulfonyl chloride to prepare 4- (2 '-amino-3' -cyano-7 ',7' -dimethyl-5 ',6',7',8' -tetrahydro-6 ',8' -methanoquinolin-4 '-yl) -2- (benzo [ d ] thiazole-2' -yl) phenol 2, 4-dinitrobenzenesulfonate; the specific reaction formula is as follows:
。
3. The method for preparing the thiazole coupled quinolinyl phenol benzenesulfonate enhanced fluorescent probe for detecting hydrogen sulfide as in claim 2, wherein in step 1), the specific process for preparing the compound I is as follows:
(1) Adding 10mmol of nopinone, 10-15 mmol of malononitrile, 10-15 mmol of p-hydroxybenzaldehyde, 15-30 mmol of ammonium acetate and 30-50 mL of ethanol into a three-necked flask, adding 0.5-1 mmol of ytterbium triflate, heating and refluxing for reaction for 6-12 h, and tracking and monitoring the reaction progress by using a TLC method until the nopinone conversion rate reaches 100%, and stopping the reaction;
(2) The reaction solution is cooled, filtered under reduced pressure, washed by cold ethanol and dried to obtain the compound I.
4. The method for preparing the thiazole-coupled quinolinyl phenol benzenesulfonate enhanced fluorescent probe for detecting hydrogen sulfide as set forth in claim 2, wherein in step 2), the specific procedure for preparing the compound II is as follows:
(1) Adding 1mmol of intermediate I, 2-4 mmol of urotropine and 5-15 mL of trifluoroacetic acid into a three-necked flask, carrying out reflux reaction for 4-8 h, monitoring the reaction progress by TLC until the reaction of the compound I is complete, adding 5-15 mL of 1M dilute hydrochloric acid aqueous solution into the reaction solution, continuously stirring for 1h, cooling to room temperature and stopping the reaction;
(2) The reaction solution is extracted by ethyl acetate, and the organic phase is washed to be neutral by saturated sodium bicarbonate aqueous solution and distilled water; the organic phase is dried by anhydrous sodium sulfate, filtered and distilled to remove the solvent, and then the crude product of the compound II is obtained;
(3) The crude product of the compound II is separated by a silica gel column to obtain the compound II.
5. The method for preparing a thiazole coupled quinolinyl phenol benzenesulfonate enhanced fluorescent probe for detecting hydrogen sulfide as in claim 2, wherein in step 3), the specific procedure for preparing the compound III is as follows:
(1) Adding 1mmol of compound II, 1-1.5 mmol of o-amino thiophenol and 1-1.5 mmol of sodium metabisulfite into 5-10 mLN, N-dimethylformamide, and reacting for 2-4 h at 110 ℃;
(2) And (3) cooling the reaction liquid to room temperature, adding 10-30 mL of ice deionized water into the reaction liquid, performing reduced pressure suction filtration on the obtained reaction liquid, washing with ethanol and deionized water for several times, and drying to obtain the compound III.
6. The method for preparing the thiazole-coupled quinolinyl phenol benzenesulfonate enhanced fluorescent probe for detecting hydrogen sulfide as in claim 2, wherein in step 4), the specific procedure for preparing NPS is as follows:
(1) Under the protection of nitrogen, adding 1mmol of compound III, 2-4 mmol of triethylamine and 5-15 mmol of dichloromethane into a three-neck flask, stirring at 0 ℃ for reaction, dropwise adding 2-3 mmol of 2, 4-dinitrobenzenesulfonyl chloride into the flask, continuing to react at room temperature for 4-6 hours, and monitoring the reaction progress by TLC until the compound III is reacted completely, and stopping the reaction;
(2) Diluting the reaction solution with water, extracting with ethyl acetate, and washing the organic phase with distilled water to neutrality; the organic phase was dried over anhydrous sodium sulfate, filtered, and the solvent was removed by rotary evaporation, and the crude product was separated by a silica gel column to give compound NPS.
7. Use of the thiazole-coupled quinolinyl phenol benzenesulfonate enhanced fluorescent probe for detecting hydrogen sulfide as in claim 1 for detecting hydrogen sulfide.
8. The use according to claim 7, wherein the thiazole-coupled quinolinylphenol benzenesulfonate enhanced fluorescent probe is capable of selectively generating thiolytic reaction with hydrogen sulfide to completely release 2, 4-dinitrobenzenesulfonyl from NPS molecule and release compound III having yellow fluorescence, so that its fluorescence spectrum is rapidly enhanced, and can be used as a specific fluorescent probe for detecting hydrogen sulfide with a detection limit of 8.3×10 -8 M; the structural formula of the compound III is as follows:
。
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| CN111777572A (en) * | 2020-07-13 | 2020-10-16 | 湖南科技大学 | Benzothiazole-based hydrogen sulfide fluorescent probe and preparation method and application thereof |
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| CN111233876A (en) * | 2020-02-27 | 2020-06-05 | 湖南科技大学 | Fluorescent probe for rapidly detecting hydrogen sulfide and preparation method and application thereof |
| CN111777572A (en) * | 2020-07-13 | 2020-10-16 | 湖南科技大学 | Benzothiazole-based hydrogen sulfide fluorescent probe and preparation method and application thereof |
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