CN105315264A - N'-(quinoiline-2-methylene)-7-diethylamine coumarin-3-formylhydrazine and preparation method and application thereof - Google Patents
N'-(quinoiline-2-methylene)-7-diethylamine coumarin-3-formylhydrazine and preparation method and application thereof Download PDFInfo
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Abstract
The invention belongs to the technical field of chemical sensing, particularly relates to a coumarin compound N'-(quinoiline-2-methylene)-7-diethylamine coumarin-3-formylhydrazine with metal ion recognizing groups and a preparation method and application of the coumarin compound, and aims at providing the coumarin compound N'-(quinoiline-2-methylene)-7-diethylamine coumarin-3-formylhydrazine high in sensitivity, selectivity and water solubility. The compound is obtained by introducing a diethylamino group to the 7th site of a coumarin mother nucleus benzopyran structure to serve as the electron donating group and introducing an aldehyde quinoline structure with copper iron specificity combining capacity to the 3rd site of the coumarin mother nucleus benzopyran structure through the Schiff's base reaction. The compound can be used as a fluorescent agent for fluorescent detection of metal ions and particularly used for fluorescent detection of Cu2+.
Description
Technical field
The invention belongs to chemical sensitisation technical field, be specifically related to coumarin kind compound N '-(quinoline-2-methylene radical)-7-diethylaminocoumarin-3-formyl hydrazine containing metal ion recognition group and its preparation method and application.
Background technology
Tonka bean camphor formal name used at school benzopyrone, extensively there is the important natural crossing cyclic cpds of a class of occurring in nature in coumarin kind compound, has unique biological activity and excellent optical characteristics.Under UV-irradiation, tonka bean camphor has the physical properties of blue-fluorescence.The existence of tonka bean camphor is easily recognized by fluorescence.Introduce electron-donating group in the C-7 position of tonka bean camphor, electron-withdrawing group is introduced in C-3 or C-4 position, forms " pushing away-La " electron system, fluorescence can be made to strengthen, even if under visible light, also can observe fluorescence.
Summary of the invention
The object of this invention is to provide a kind of highly sensitive, selectivity good, the coumarin kind compound N ' of good water solubility-(quinoline-2-methylene radical)-7-diethylaminocoumarin-3-formyl hydrazine.
The present invention also provides the preparation method and application of this N '-(quinoline-2-methylene radical)-7-diethylaminocoumarin-3-formyl hydrazine.
Technical scheme of the present invention is:
A kind of N '-(quinoline-2-methylene radical)-7-diethylaminocoumarin-3-formyl hydrazine, the structure of wherein N '-(quinoline-2-methylene radical)-7-diethylaminocoumarin-3-formyl hydrazine is as follows:
The preparation method of N ' of the present invention-(quinoline-2-methylene radical)-7-diethylaminocoumarin-3-formyl hydrazine comprises the following steps:
(1) ratio getting amount of substance is that the 4-diethylin salicylic aldehyde of 1:1.2 ~ 2 and diethyl malonate are in reaction flask, add dehydrated alcohol 4-diethylin salicylic aldehyde and diethyl malonate are dissolved, then the ratio adding 10 ~ 20mL piperidines according to the 4-diethylin salicylic aldehyde of 1moL adds catalyzer piperidines, be heated to 88 ~ 91 DEG C, stirring and refluxing 4 ~ 6h, after thin-layer chromatography detection reaction completes, stopped reaction, rotary evaporation concentration of reaction solution, cool sherwood oil that rear volume ratio is 3:1 and greenish yellow solid 7-N is made in ethyl acetate mixtures extraction, N dimethylamine butylcoumariii-3-ethyl formate,
(2) ratio getting amount of substance is the 7-N of 1:2 ~ 3, N dimethylamine butylcoumariii-3-ethyl formate and hydrazine hydrate are in reaction flask, add anhydrous methanol by 7-N, N dimethylamine butylcoumariii-3-ethyl formate and hydrazine hydrate dissolve, and are heated to 30 DEG C, stirring and refluxing 20 ~ 40min, after thin-layer chromatography detection reaction completes, stopped reaction, cools sherwood oil that rear volume ratio is 2:1 and ethyl acetate mixtures extraction makes yellow solid 7-N, N dimethylamine butylcoumariii-3-formyl hydrazine;
(3) ratio getting amount of substance is the 7-N of 1:1.2 ~ 1.4, N dimethylamine butylcoumariii-3-formyl hydrazine and quinoline-2-formaldehyde are in reaction flask, add dehydrated alcohol by 7-N, N dimethylamine butylcoumariii-3-formyl hydrazine and quinoline-2-dissolve formaldehyde, be heated to 65-80 DEG C, stirring and refluxing 2 ~ 3h, after thin-layer chromatography detection reaction completes, stopped reaction, cools sherwood oil that rear volume ratio is 2:1 and yellow solid N '-(quinoline-2-methylene radical)-7-diethylaminocoumarin-3-formyl hydrazine is made in ethyl acetate mixtures extraction;
Concrete reaction equation is:
N ' of the present invention-(quinoline-2-methylene radical)-7-diethylaminocoumarin-3-formyl hydrazine is applied to the fluoroscopic examination of metal ion as fluorescent reagent.
Further, N ' of the present invention-(quinoline-2-methylene radical)-7-diethylaminocoumarin-3-formyl hydrazine is applied to acetone/H
2cu in O medium
2+fluoroscopic examination, N '-(quinoline-2-methylene radical)-7-diethylaminocoumarin-3-formyl hydrazine that namely the present invention prepares as fluorescent reagent, can be applied to 80% (v/v) H
2cu in O/ medium-acetone
2+fluoroscopic examination, be at 80% (v/v) H
2cu in the aqueous solution is detected in O/ medium-acetone
2+highly sensitive, highly selective fluorescent reagent.
Further, N ' of the present invention-(quinoline-2-methylene radical)-7-diethylaminocoumarin-3-formyl hydrazine is containing comprising Ag
+, Al
3+, Ba
2+, Ca
2+, Cd
2+, Co
3+, Cr
3+, Cu
2+, Fe
3+, Hg
2+, K
+, Mg
2+, Mn
2+, Na
+, Ni
2+, Pb
2+, Zn
2+in environment Deng metal ion, there is good recognition performance to cupric ion, show as quenching of fluorescence.
The preparation method of compound provided by the invention, technique is simple, requires low, only need common heating reflux just to can be mass-produced for experimental installation.Preparation condition environmental protection of the present invention, purify easily, reaction yield is high, can be very fast take pure target compound.
Accompanying drawing explanation
Fig. 1 is 7-N of the present invention, the infrared spectrogram of N dimethylamine butylcoumariii-3-ethyl formate;
Fig. 2 is 7-N of the present invention, the carbon-13 nmr spectra figure of N dimethylamine butylcoumariii-3-ethyl formate;
Fig. 3 is 7-N of the present invention, the hydrogen nuclear magnetic resonance spectrogram of N dimethylamine butylcoumariii-3-ethyl formate;
Fig. 4 is 7-N of the present invention, the mass spectrum of N dimethylamine butylcoumariii-3-ethyl formate;
Fig. 5 is 7-N of the present invention, the infrared spectrogram of N dimethylamine butylcoumariii-3-formyl hydrazine;
Fig. 6 is 7-N of the present invention, the carbon-13 nmr spectra figure of N dimethylamine butylcoumariii-3-formyl hydrazine;
Fig. 7 is 7-N of the present invention, the hydrogen nuclear magnetic resonance spectrogram of N dimethylamine butylcoumariii-3-formyl hydrazine;
Fig. 8 is 7-N of the present invention, the mass spectrum of N dimethylamine butylcoumariii-3-formyl hydrazine;
Fig. 9 is the infrared spectrogram of N ' of the present invention-(quinoline-2-methylene radical)-7-diethylaminocoumarin-3-formyl hydrazine;
Figure 10 is the carbon-13 nmr spectra figure of N ' of the present invention-(quinoline-2-methylene radical)-7-diethylaminocoumarin-3-formyl hydrazine;
Figure 11 is the hydrogen nuclear magnetic resonance spectrogram of N ' of the present invention-(quinoline-2-methylene radical)-7-diethylaminocoumarin-3-formyl hydrazine;
Figure 12 is the mass spectrum of N ' of the present invention-(quinoline-2-methylene radical)-7-diethylaminocoumarin-3-formyl hydrazine;
Figure 13 be N '-(quinoline-2-methylene radical)-7-diethylaminocoumarin-3-formyl hydrazine of example 6 as fluorescent reagent at 80% (v/v) H
2ag is added respectively in O/ medium-acetone
+, Al
3+, Ba
2+, Ca
2+, Cd
2+, Co
3+, Cr
3+, Cu
2+, Fe
3+, Hg
2+, K
+, Mg
2+, Mn
2+, Na
+, Ni
2+, Pb
2+, Zn
2+fluorescence pattern;
Figure 14 be N '-(quinoline-2-methylene radical)-7-diethylaminocoumarin-3-formyl hydrazine of example 7 as fluorescent reagent at 80% (v/v) H
2fluorescence spectrum figure during ion coexist is detected in O/ medium-acetone;
Figure 15 be N '-(quinoline-2-methylene radical)-7-diethylaminocoumarin-3-formyl hydrazine of example 8 as fluorescent reagent at 80% (v/v) H
2lower concentration Cu is detected in O/ medium-acetone
2+time fluorescence spectrum figure;
Figure 16 be N '-(quinoline-2-methylene radical)-7-diethylaminocoumarin-3-formyl hydrazine of example 8 as fluorescent reagent at 80% (v/v) H
2lower concentration Cu is detected in O/ medium-acetone
2+time linear relationship chart.
Embodiment
Embodiment 1
A kind of N '-(quinoline-2-methylene radical)-7-diethylaminocoumarin-3-formyl hydrazine, its structure is as follows:
Embodiment 2
A kind of preparation method of N '-(quinoline-2-methylene radical)-7-diethylaminocoumarin-3-formyl hydrazine, its step is as follows:
(1) in 250mL reaction flask, 4-diethylin salicylic aldehyde (3.96g is added, 20mmol) with diethyl malonate (4mL, 24mmol) add 30mL dehydrated alcohol heated and stirred to dissolve, then 0.16mL piperidines is added, be heated to 91 DEG C, stirring and refluxing 6h, stopped reaction after thin-layer chromatography detection reaction completes, namely extract reaction solution with kapillary and to drip and material solution is added on respectively and is about on the zero line at 1cm place from thin layer plate one end, dry up rearmounted thin layer plate in the separation chamber filling developping agent, immersion depth is 0.5cm, when to be deployed dose of forward position is about near 1cm far from top, chromatosheet is taken out, develop the color under ultraviolet lamp after drying, there is obvious product point, raw material point is reduced to and does not substantially change, rotary evaporation concentration of reaction solution, then 150mL petrol ether/ethyl acetate solution (3/1 is dropwise joined, v/v) in solution, yellow solid is separated out after leaving standstill 1h, suction filtration, obtain yellow solid, then petrol ether/ethyl acetate solution (3/1 is used, v/v) solution washing, obtain 4.88g greenish yellow solid 7-N, N dimethylamine butylcoumariii-3-ethyl formate, productive rate 85.1%,
(2) in 250mL round-bottomed flask, 7-N is added, N dimethylamine butylcoumariii-3-ethyl formate (2.89g, 10mmol), add 25mL anhydrous methanol heated and stirred to dissolve, then hydrazine hydrate (1mL is added, 20mmol), be heated to 30 DEG C, stirring and refluxing reaction 20min, faint yellow solid is had to separate out, after thin-layer chromatography detection reaction completes, appropriate distilled water is added in reaction solution, cooling, suction filtration, wash filter cake with water three times, dry, faint yellow solid is through purification by silica gel column chromatography, elutriant is petrol ether/ethyl acetate solution (2/1, v/v), yellow solid 7-N is obtained after drying, N dimethylamine butylcoumariii-3-formyl hydrazine 2.21g,
(3) intermediate 7-N is taken, N dimethylamine butylcoumariii-3-formyl hydrazine (0.62g, 2.25mmol), be dissolved in 25mL ethanol, add quinoline-2-formaldehyde (0.42g again, 2.67mmol), heat 70 DEG C of back flow reaction 2h, after thin-layer chromatography detection reaction completes, cooling, suction filtration, obtain yellow powdery solid, then be the aqueous ethanolic solution solution washing 3 times of 1:1 by the volume ratio that temperature is 0 ~ 10 DEG C, after drying, yellow solid is through purification by silica gel column chromatography, elutriant is petrol ether/ethyl acetate solution (2/1, v/v), yellow solid N '-(quinoline-2-methylene radical)-7-diethylaminocoumarin-3-formyl hydrazine 0.73g is obtained after drying, after testing, fusing point is 262 ~ 264 DEG C.
The product of the present invention to the present embodiment three steps detects, specific as follows:
1, the present invention is to the target product 7-N of step (1), and N dimethylamine butylcoumariii-3-ethyl formate has carried out infrared spectra, carbon-13 nmr spectra, proton nmr spectra, mass spectrum and ultimate analysis inspection and detected, specific as follows:
Infrared spectra: see Fig. 1, uses KBr compressing tablet, and Perkin-Elmer682 infrared spectrometer records the infrared spectra of target product, FTIR (KBr)
/ cm
-1, detect the absorption peak that there is following functional group in spectrogram: 3454cm
-1for the absorption peak of ester group-C=O, 2974cm
-1for the absorption peak of-CH3,1755cm
-1for the absorption peak of lactone C=O, 1701cm
-1for the absorption peak of C=O in-COEt, 1621cm
-1, 1587cm
-1and 1513cm
-1for the absorption peak of phenyl ring skeleton, 1417cm
-1for the absorption peak of-C=CH-, 1219cm
-1for the absorption peak of-C-O-, the existence of the functional group that these absorption peaks prove and target product 7-N, the functional group that N dimethylamine butylcoumariii-3-ethyl formate has is identical;
Carbon-13 nmr spectra: see Fig. 2, with CDCl
3for solvent, TMS is interior mark, Bruker company AVANCE400MHz nuclear magnetic resonance analyser records carbon spectrum, shows below data in spectrogram:
13cNMR (100MHz, CDCl
3) 12.41,14.37,45.08,61.13,76.69,77.01,77.33,96.72,107.67,108.99,109.47,130.99,149.16,152.81,158.26,158.43,164.25, the detection data in spectrogram and target product 7-N, N dimethylamine butylcoumariii-3-ethyl formate matches;
Proton nmr spectra: see Fig. 3, with CDCl
3for solvent, TMS is interior mark, Bruker company AVANCE400MHz nuclear magnetic resonance analyser records hydrogen spectrum, shows below data in spectrogram:
1hNMR (400MHz, CDCl
3) δ 8.41 (s, 1H ,-C=CH), 7.34 (d, J=8.9Hz, 1H, ArH), 6.59 (d, J=8.8Hz, 1H, ArH), 6.45 (s, 1H, ArH), 4.36 (q, J=7.1Hz, 2H ,-CH
2-), 3.43 (q, J=7.1Hz, 4H ,-CH
2-), 1.38 (t, J=7.1Hz, 3H ,-CH
3), 1.22 (t, J=7.1Hz, 6H ,-CH
3), the detection data in spectrogram and target product 7-N, N dimethylamine butylcoumariii-3-ethyl formate matches;
Mass spectrum: see Fig. 4, concrete detected result is as follows: ESI-MS, m/z:290.1 [M+H]
+.
Ultimate analysis detected result is as follows: ultimate analysis (C
16h
19nO
4) measured value (%; Theoretical value): C66.50 (66.42), N4.89 (4.84), H6.66 (6.62).
2, the present invention is to the target product 7-N of step (2), and N dimethylamine butylcoumariii-3-formyl hydrazine has carried out infrared spectra, carbon-13 nmr spectra, proton nmr spectra, mass spectrum and ultimate analysis inspection and detected, specific as follows:
Infrared spectra: see Fig. 5, uses KBr compressing tablet, and Perkin-Elmer682 infrared spectrometer records the infrared spectra of target product, FT-IR (KBr compressing tablet)
/ cm
-1detect the absorption peak that there is following functional group in spectrogram: 2976 is-CH3 absorption peak, 1688 is lactone C=O absorption peak, 1619,1580,1517 is phenyl ring skeleton absorption peak, and 1418 is-C=CH-absorption peak, and 1239 have-C-O-absorption peak, 3302 is the absorption peak of primary amine-C-N, 3203 is the absorption peak of secondary amine-C-N, the existence of the functional group that these absorption peaks prove and target product 7-N, and the functional group that N dimethylamine butylcoumariii-3-formyl hydrazine has is identical;
Carbon-13 nmr spectra: see Fig. 6, with CDCl
3for solvent, TMS is interior mark, Bruker company AVANCE400MHz nuclear magnetic resonance analyser records carbon spectrum, shows below data in spectrogram:
13cNMR (100MHz, CDCl
3) 12.39,45.07,96.56,108.29,109.05,109.96,131.09,147.96,152.63,157.57,162.05,163.81, the detection data in spectrogram and target product 7-N, N dimethylamine butylcoumariii-3-formyl hydrazine matches;
Proton nmr spectra: see Fig. 7, with CDCl
3for solvent, TMS is interior mark, Bruker company AVANCE400MHz nuclear magnetic resonance analyser records hydrogen spectrum, shows below data in spectrogram:
1hNMR (400MHz, CDCl
3) δ 9.67 (s, 1H ,-NH-), 8.63 (s, 1H ,-C=CH), 7.39 (d, J=8.9Hz, 1H, ArH), 6.61 (dd, J=8.9,1.3Hz, 1H, ArH), 6.45 (s, 1H, ArH), 4.11 (s, 2H ,-NH
2), 3.42 (q, J=7.0Hz, 4H ,-CH
2-), 1.20 (t, J=7.1Hz, 6H ,-CH
3), the detection data in spectrogram and target product 7-N, N dimethylamine butylcoumariii-3-formyl hydrazine matches;
Mass spectrum: see Fig. 8, concrete detected result is as follows: ESI-MS, m/z:276.1 [M+H]
+.
Ultimate analysis (C
14h
17n
3o
3) measured value (%; Theoretical value): C61.01 (61.08), N15.24 (15.26), H6.26 (6.22).
3, target product N '-(quinoline-2-the methylene radical)-7-diethylaminocoumarin-3-formyl hydrazine of the present invention to step (3) has carried out infrared spectra, carbon-13 nmr spectra, proton nmr spectra, mass spectrum and ultimate analysis inspection detection, specific as follows:
Infrared spectra: see Fig. 9, uses KBr compressing tablet, and Perkin-Elmer682 infrared spectrometer records the infrared spectra of target product, FT-IR (KBr compressing tablet)
/ cm
-1detect the absorption peak that there is following functional group in spectrogram: 2969 is-CH3 absorption peak, 1698 is lactone C=O absorption peak, 1616,1587,1556 is phenyl ring skeleton absorption peak, 1417-C=CH-absorption peaks, 1266 have-C-O-absorption peak, and the existence of the functional group that these absorption peaks prove and the functional group that target product N '-(quinoline-2-methylene radical)-7-diethylaminocoumarin-3-formyl hydrazine has are identical;
Carbon-13 nmr spectra: see Figure 10, with CDCl
3for solvent, TMS is interior mark, Bruker company AVANCE400MHz nuclear magnetic resonance analyser records carbon spectrum, shows below data in spectrogram:
13cNMR (100MHz, CDCl
3) 12.41,45.19,96.58,108.60,110.28,118.60,127.22,127.66,128.44,129.44,129.71,131.48,136.20,147.91,148.90,149.32,153.07,153.54,157.89,160.19,162.70, the detection data in spectrogram and target product N '-(quinoline-2-methylene radical)-7-diethylaminocoumarin-3-formyl hydrazine match;
Proton nmr spectra: see Figure 11, with CDCl
3for solvent, TMS is interior mark, Bruker company AVANCE400MHz nuclear magnetic resonance analyser records hydrogen spectrum, shows below data in spectrogram:
1hNMR (400MHz, CDCl
3) δ 12.15 (s, 1H,-N-H), 8.82 (s, 1H,-N=C-H), 8.42 (s, 1H,-C=C-H), 8.34 (d, J=8.6Hz, 1H), 8.16 (d, J=8.6Hz, 1H), 8.07 (d, J=8.5Hz, 1H, ArH), 7.81 (d, J=8.1Hz, 1H, ArH), 7.70 (t, J=7.6Hz, 1H, ArH), 7.54 (t, J=7.5Hz, 1H, ArH), 7.45 (d, J=8.9Hz, 1H, ArH), 6.66 (d, J=8.9Hz, 1H, ArH), 6.49 (s, 1H, ArH), 3.45 (q, J=7.0Hz, 4H,-CH
2-), 1.23 (t, J=7.0Hz, 6H ,-CH
3), the detection data in spectrogram and target product N '-(quinoline-2-methylene radical)-7-diethylaminocoumarin-3-formyl hydrazine match,
Mass spectrum: see Figure 12, concrete detected result is as follows: ESI-MS, m/z:415.2 [M+H]
+.
Ultimate analysis (C
24h
22n
4o
3) measured value (%; Theoretical value): C69.67 (69.55), N13.71 (13.52), H5.42 (5.35).
Embodiment 3
5.0 × 10 are added in the colorimetric cylinder of 10mL
-7n '-(quinoline-2-methylene radical)-7-diethylaminocoumarin-3-formyl hydrazine acetone soln 2mL of mol/L, adds different metal ion (Ag respectively with transfer pipet
+, Al
3+, Ba
2+, Ca
2+, Cd
2+, Co
3+, Cr
3+, Cu
2+, Fe
3+, Hg
2+, K
+, Mg
2+, Mn
2+, Na
+, Ni
2+, Pb
2+, Zn
2+), be 2mL, concentration 1.0 × 10
-6mol/L, uses redistilled water constant volume, in λ
ex/ λ
em=438nm/480nm place surveys its fluorescence spectrum, and see Figure 13, as can be seen from the figure probe N '-(quinoline-2-methylene radical)-7-diethylaminocoumarin-3-formyl hydrazine is to Cu
2+there is good selectivity, show as quenching of fluorescence.
Embodiment 4
In order to determine the range of application of fluorescent probe N '-(quinoline-2-methylene radical)-7-diethylaminocoumarin-3-formyl hydrazine, the present embodiment carries out ion interference experiment.Specific as follows: at Cu
2+(2.0 × 10
-7and be in excess in Cu mol/L)
2+other metal ions (5.0 × 10
-7mol/L), under common existence, be 1.0 × 10 to concentration
-7n '-(quinoline-2-methylene radical)-7-diethylaminocoumarin-3-formyl hydrazine solution of mol/L carries out fluorescence spectrum test.See Figure 14, as can be seen from the figure Ag
+, Al
3+, Ba
2+, Ca
2+, Cd
2+, Co
3+, Cr
3+, Fe
3+, Hg
2+, K
+, Mg
2+, Mn
2+, Na
+, Ni
2+, Pb
2+, Zn
2+affect very faint, so when testing metal ion and coexisting, N '-(quinoline-2-methylene radical)-7-diethylaminocoumarin-3-formyl hydrazine is to Cu
2+identification there is certain reliability.
Embodiment 5
5.0 × 10 are added in the colorimetric cylinder of 10mL
-7n '-(quinoline-2-methylene radical)-7-diethylaminocoumarin-3-formyl hydrazine acetone soln 2mL of mol/L, adds 1.0 × 10 of different volumes with transfer pipet
-6mol/L metal ion Cu
2+, use redistilled water constant volume, in λ
ex/ λ
em=438nm/480nm place surveys its fluorescence spectrum, sees Figure 15, as can be seen from the figure along with Cu
2+the increase fluorescence intensity of concentration weakens gradually, and fluorescence intensity level is 2.0 × 10
-8mol/L ~ 2.0 × 10
-7present good linear relationship within the scope of mol/L, fluorescence intensity is F=238.97-119.85C at linear equation, linearly dependent coefficient R
2=0.9928 (n=3), is specifically shown in Figure 16.
Embodiment 6
5.0 × 10 are added in the colorimetric cylinder of 10mL
-7n '-(quinoline-2-methylene radical)-7-diethylaminocoumarin-3-formyl hydrazine acetone soln 2mL of mol/L, adds 3mL with transfer pipet and makes metal ion mixed solution by oneself, use redistilled water constant volume, in λ
ex/ λ
em=438nm/480nm place surveys its fluorescence spectrum, and utilizes the linear equation of embodiment 5 to calculate copper ion concentration, and concrete outcome is in table 1:
The detected result of cupric ion in metal ion mixed solution made by oneself by table 1
Note:
Sample 1:Cu
2+(5.0 × 10
-8mol/L); Mn
2+, Al
2+, K
+, Pb
2+, Na
+, Ca
2+, Ag
+(1.0 × 10
-7mol/L)
Sample 2:Cu
2+(8.0 × 10
-8mol/L); Mn
2+, Al
2+, K
+, Pb
2+, Na
+, Ca
2+, Ag
+(1.0 × 10
-7mol/L).
Claims (4)
1. N '-(quinoline-2-methylene radical)-7-diethylaminocoumarin-3-formyl hydrazine, is characterized in that the structure of N '-(quinoline-2-methylene radical)-7-diethylaminocoumarin-3-formyl hydrazine is as follows:
2. the preparation method of N ' according to claim 1-(quinoline-2-methylene radical)-7-diethylaminocoumarin-3-formyl hydrazine, is characterized in that comprising the following steps:
(1) ratio getting amount of substance is that the 4-diethylin salicylic aldehyde of 1:1.2 ~ 2 and diethyl malonate are in reaction flask, add dehydrated alcohol 4-diethylin salicylic aldehyde and diethyl malonate are dissolved, then the ratio adding 10 ~ 20mL piperidines according to the 4-diethylin salicylic aldehyde of 1moL adds catalyzer piperidines, be heated to 88 ~ 91 DEG C, stirring and refluxing 4 ~ 6h, after thin-layer chromatography detection reaction completes, stopped reaction, rotary evaporation reaction solution, cool sherwood oil that rear volume ratio is 3:1 and greenish yellow solid 7-N is made in ethyl acetate mixtures extraction, N dimethylamine butylcoumariii-3-ethyl formate,
(2) ratio getting amount of substance is the 7-N of 1:2 ~ 3, N dimethylamine butylcoumariii-3-ethyl formate and hydrazine hydrate are in reaction flask, add anhydrous methanol by 7-N, N dimethylamine butylcoumariii-3-ethyl formate and hydrazine hydrate dissolve, and are heated to 30 DEG C, stirring and refluxing 20 ~ 40min, after thin-layer chromatography detection reaction completes, stopped reaction, cools sherwood oil that rear volume ratio is 2:1 and ethyl acetate mixtures extraction makes yellow solid 7-N, N dimethylamine butylcoumariii-3-formyl hydrazine;
(3) ratio getting amount of substance is the 7-N of 1:1.2 ~ 1.4, N dimethylamine butylcoumariii-3-formyl hydrazine and quinoline-2-formaldehyde are in reaction flask, add dehydrated alcohol by 7-N, N dimethylamine butylcoumariii-3-formyl hydrazine and quinoline-2-dissolve formaldehyde, be heated to 65-80 DEG C, stirring and refluxing 2 ~ 3h, after thin-layer chromatography detection reaction completes, stopped reaction, cools sherwood oil that rear volume ratio is 2:1 and yellow solid N '-(quinoline-2-methylene radical)-7-diethylaminocoumarin-3-formyl hydrazine is made in ethyl acetate mixtures extraction.
3. the application of N ' according to claim 1-(quinoline-2-methylene radical)-7-diethylaminocoumarin-3-formyl hydrazine, is characterized in that the fluoroscopic examination being applied to metal ion as fluorescent reagent.
4. the application of N ' according to claim 3-(quinoline-2-methylene radical)-7-diethylaminocoumarin-3-formyl hydrazine, is characterized in that being applied to acetone/H as fluorescent reagent
2cu in O medium
2+fluoroscopic examination.
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| CN107382981A (en) * | 2017-07-05 | 2017-11-24 | 河南理工大学 | A kind of fluorescence probe based on the double hydazone derivatives of pyrroles's cumarin and its preparation method and application |
| CN107417675A (en) * | 2017-08-15 | 2017-12-01 | 新乡医学院 | A kind of novel coumarin class Schiff base derivatives, preparation method and its application in copper ion fluorescence and cell imaging detection |
| CN108484583A (en) * | 2018-03-30 | 2018-09-04 | 湖南师范大学 | Cu in a kind of colorimetric determination water2+And Ni2+The synthesis and application of probe |
| CN111253386A (en) * | 2020-02-14 | 2020-06-09 | 中北大学 | Naked eye recognition Cu2+Fluorescent probe and preparation method and application thereof |
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| CN115322180A (en) * | 2022-07-26 | 2022-11-11 | 南京医科大学康达学院 | Coumarin pyrazolone fluorescent probe and preparation method and application thereof |
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| CN107417675A (en) * | 2017-08-15 | 2017-12-01 | 新乡医学院 | A kind of novel coumarin class Schiff base derivatives, preparation method and its application in copper ion fluorescence and cell imaging detection |
| CN108484583A (en) * | 2018-03-30 | 2018-09-04 | 湖南师范大学 | Cu in a kind of colorimetric determination water2+And Ni2+The synthesis and application of probe |
| CN108484583B (en) * | 2018-03-30 | 2021-03-02 | 湖南师范大学 | Colorimetric method for detecting Cu in water2+And Ni2+Synthesis and application of probe |
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| CN112920175A (en) * | 2020-12-17 | 2021-06-08 | 吉林大学 | Coumarin-based palladium ion fluorescent probe compound and preparation method thereof |
| CN112920175B (en) * | 2020-12-17 | 2022-05-31 | 吉林大学 | Coumarin-based palladium ion fluorescent probe compound and preparation method thereof |
| CN113248430A (en) * | 2021-05-21 | 2021-08-13 | 西北师范大学 | Quinoline derivative-based fluorescence sensor, synthesis thereof and application thereof in aluminum ion detection |
| CN114426534A (en) * | 2021-12-15 | 2022-05-03 | 南京师范大学 | Reversible fluorescent probe for detecting copper ions and preparation method thereof |
| CN114426534B (en) * | 2021-12-15 | 2023-01-31 | 南京师范大学 | Reversible fluorescent probe for detecting copper ions and preparation method thereof |
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