CN103320118A - Schiff base cooper ion fluorescence probe and preparation method thereof - Google Patents
Schiff base cooper ion fluorescence probe and preparation method thereof Download PDFInfo
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- CN103320118A CN103320118A CN2013101663816A CN201310166381A CN103320118A CN 103320118 A CN103320118 A CN 103320118A CN 2013101663816 A CN2013101663816 A CN 2013101663816A CN 201310166381 A CN201310166381 A CN 201310166381A CN 103320118 A CN103320118 A CN 103320118A
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Abstract
The present invention relates to a Schiff base copper ion fluorescence probe and a preparation method thereof, and belongs to the technical field of Schiff base synthesis. The structure general formula of the Schiff base copper ion fluorescence probe is the formula (I), wherein a substituting group R is hydrogen atom or N,Ndiethylamino. The synthesis method comprises that: p-aminoacetophenone reacts with 4-diethylaminobenzaldehyde to produce an intermediate, and the intermediate reacts with substituted salicylaldehyde to produce the corresponding Schiff base. The Schiff base copper ion fluorescence probe has the following characteristics that: the structure of the Schiff base copper ion fluorescence probe is different from the structure of the existing Schiff base; and the probe provides good response to copper ions, wherein fluorescence intensity is increased by about four times when the probe contacts the cooper ions, such that the detection result is easily obtained with the Schiff base copper ion fluorescence probe in the case of low fluorescence intensity.
Description
Technical field
The present invention relates to a kind of schiff bases copper ion fluorescence probe and preparation method thereof, belong to the synthesis technical field of schiff bases.
Background technology
Cupric ion is one of indispensable trace element of organism normal activities, but its excessive concentration or the too low disorder that all causes Living system, thereby cause relevant disease, such as Wilson disease (Menkes Wilson disease) alzheimer's Alzheimer's disease (Alzheimer ' s disease), prion disease (Prion diseases).Therefore the detection of the cupric ion in organism and environment is followed the tracks of and is seemed especially important
.
Schiff bases, English name: Schiff's base also claims western Buddhist alkali; Be the more stable imines that a class is connected with alkyl or aryl on nitrogen-atoms, its general formula is R
1r
2c=N-R
3, R
3for aryl or alkyl, rather than hydrogen.The half amine aldehyde that nucleophilic addition generates similar hemiacetal first occurs with carbonyl compound (aldehyde, ketone) by aromatic amine in fragrant schiff bases usually, then dehydration reaction generation imines occurs and obtain.Due to schiff base compounds have good photophysical property, with the better bonding action of cupric ion there is special physiologically active, therefore this compounds can be applied to the field such as copper ion probe and bio-imaging and can be that preparation is antibacterial, sterilization, the new selection of drug provision such as antitumor, antiviral.
Summary of the invention
The object of the present invention is to provide the schiff bases copper ion fluorescence probe that a kind of structure is different from existing schiff bases.
Another object of the present invention is to provide the preparation method of above-mentioned schiff bases copper ion probe.
Technical scheme of the present invention:
A kind of schiff bases copper ion fluorescence probe, its structure is:
Described R is hydrogen atom or 4-N, the N diethylamino group.
A kind of preparation method of above-mentioned schiff bases copper ion fluorescence probe, comprise the steps
(1) para-aminoacetophenone and the reaction of 4-diethylamide benzaldehyde, obtain intermediate A;
(2) R-salicylic aldehyde and intermediate A reaction, obtain the schiff bases copper ion fluorescence probe;
Intermediate A is 1-(4-amino-benzene)-3-(4-diethylin benzene)-acrylketone, and its structural formula is:
In the present invention, described para-aminoacetophenone, its English name: 4'-Aminoacetophenone; Described 4-diethylamide benzaldehyde, its English name: 4-Diethylaminobenzaldehyde; The structure of described R-salicylic aldehyde is
; R is H or N, the N diethylin.It when R is H, is salicylic aldehyde (salicylaldehyde); When R is 4-N, during the N diethylin, be 4-(diethylin) salicylic aldehyde (4-(Diethylamino) salicylaldehyde).
Preparation method's of the present invention synthetic route is:
Above-mentioned preparation method:
Step (1) adopts following method to complete: para-aminoacetophenone and 4-diethylamide organic solvent dissolution for benzaldehyde, take the sodium hydroxide ethanolic soln/and potassium hydroxide-ethanol solution be alkaline conditioner, room temperature, stirring reaction more than 9 hours, separating-purifying; In alkaline conditioner the massfraction of alkali be 8% ~ 20%, with the volume ratio of organic solvent be 3-5:6;
Step (2) adopts following method to complete: intermediate A and R-salicylic aldehyde organic solvent dissolution, and 85-90 ° of C refluxed more than 6 hours, then separating-purifying;
The reaction of step (1) and (2) is the reaction that mol ratio is 1:1, can make in actual mechanical process that wherein any raw material is excessive, does not affect reaction; As long as the consumption of solvent can make the raw material complete miscibility.
In step (1):
Described organic solvent is preferably ethanol; Preferred, the ratio of para-aminoacetophenone/4-diethylamide benzaldehyde and organic solvent ethanol is 1mmol:2mL.Described alkaline conditioner is preferably the sodium hydroxide ethanolic soln of 8-14%.Reaction times is preferably 18 hours.Described separating and purifying method is: pour mixture after completion of the reaction into frozen water, then use dichloromethane extraction, then extraction liquid is purified with silica gel chromatographic column.The elutriant of purification use is preferably methylene dichloride/sherwood oil [V (methylene dichloride)/V (sherwood oil)=1:1.
In step (2):
Described organic solvent is preferably ethanol; Preferred, the ratio of R-salicylic aldehyde/intermediate A and organic solvent ethanol is 2.73mmol:100mL.Return time is preferably 12 hours.Described separating and purifying method: remove organic solvent with Rotary Evaporators, by solid suction filtration, the recrystallization of separating out.
Beneficial effect
Schiff bases copper ion fluorescence probe of the present invention, its structure is different from the structure of existing schiff bases; Cupric ion is had to good response, there is the function that detects cupric ion; A kind of means of new detection cupric ion are provided.When existing schiff bases runs into cupric ion, its fluorescence intensity reduces; When schiff bases copper ion fluorescence probe of the present invention runs into cupric ion, its fluorescence intensity has improved four times of left and right; Therefore, in the situation that fluorescence intensity is lower, schiff bases copper ion fluorescence probe of the present invention more easily obtains detected result.
Preparation method of the present invention, to temperature require lowly, easily control, product is easy to separate, yield is high, purity is high.
The accompanying drawing explanation
The proton nmr spectra that Fig. 1 is the prepared intermediate A of embodiment 1;
The proton nmr spectra that Fig. 2 is the prepared schiff bases copper ion fluorescence probe of embodiment 1;
The carbon-13 nmr spectra that Fig. 3 is the prepared schiff bases copper ion fluorescence probe of embodiment 1;
The proton nmr spectra that Fig. 4 is the prepared schiff bases copper ion fluorescence probe of embodiment 6;
The carbon-13 nmr spectra that Fig. 5 is the prepared schiff bases copper ion fluorescence probe of embodiment 6;
Fig. 6 is the absorption spectrum that the prepared schiff bases copper ion fluorescence probe of embodiment 1 detects cupric ion;
Fig. 7 is the absorption spectrum that the prepared schiff bases copper ion fluorescence probe of embodiment 6 detects cupric ion;
The fluorescence spectrum of the schiff bases copper ion fluorescence probe cupric ion that Fig. 8 embodiment 1 is prepared;
The fluorescence spectrum of the schiff bases copper ion fluorescence probe cupric ion that Fig. 9 embodiment 6 is prepared.
Embodiment
(1) prepare 1-(4-amino-benzene)-3-(4-diethylin benzene)-acrylketone (intermediate
a)
2.0g (15mmol) para-aminoacetophenone and 2.7g (15mmol) 4-diethyl amino benzaldehyde are added in the single port bottle that contains the 30mL dehydrated alcohol, then the sodium hydroxide ethanolic soln that to drip the 20mL massfraction be 10%, under room temperature, stir 18 hours, product in flask is poured in frozen water, with dichloromethane extraction (3 * 30mL).With silica gel chromatographic column, purify, elutriant is that [V (methylene dichloride)/V (sherwood oil)=1:1, obtain the sorrel compound and be intermediate A, productive rate 46.1% methylene dichloride/sherwood oil.Intermediate A is carried out to the nuclear magnetic resonance map analysis,
1h NMR (400MHz, CDCl
3): 1.19 (t,
j=7.2Hz, 6H), 3.40 (q,
j=7.2Hz, 4H), 4.12 (s, 2H), 6.65 (d,
j=8.4Hz, 2H), 6.69 (d,
j=8.4Hz, 2H), 7.34 (d,
j=15.2Hz, 1H), 7.52 (d,
j=8.8Hz, 2H), 7.76 (d,
j=15.2Hz, 1H), 7.92 (d,
j=8.8Hz, 2H).
(2) prepare salicylic aldehyde schiff bases (schiff bases copper ion fluorescence probe)
By 0.1g (0.82mmol) salicylic aldehyde, 0.24g (0.82mmol) intermediate
awith 30 mL ethanol, add in 50 mL single necked round bottom flask, mixed solution is heated to 85 ℃, backflow 12h.After being cooled to room temperature, with Rotary Evaporators, most of solvent is removed, had solid to separate out, suction filtration obtains the sorrel powder, with dehydrated alcohol and methylene dichloride mixing solutions recrystallization, obtains the reddish-brown crystal, productive rate 60%.
Step (2) gained reddish-brown crystal is carried out to the nuclear magnetic resonance map analysis,
1h NMR (400MHz, CDCl
3): 1.22 (t,
j=7.2Hz, 6H), 3.43 (q,
j=7.2Hz, 4H), 6.67 (d,
j=8.0Hz, 1H), 6.97 (t,
j=7.6Hz, 1H), 7.05 (d,
j=8.0Hz, 1H), 7.32-7.40 (m, 3H), 7.43 (d,
j=7.6Hz, 2H), 7.55 (d,
j=8.8Hz, 2H), 7.82 (d,
j=15.6Hz, 1H), 8.10 (d,
j=8.4Hz, 2H), 8.67 (s, 1H), 13.04 (s, 1H).
13c NMR (100MHz, CDCl
3), 12.72,44.67,111.45,116.09,117.51,119.21,119.38,121.37,129.94,130.95,132.75,133.83,137.61,146.11,151.85,161.42,163.95,189.43 (18peaks).
Embodiment 2-5
According to table 1: get the sodium hydroxide ethanolic soln, the consumption of other materials and the operational condition salicylic aldehyde schiff bases of all preparing reddish-brown lenticular identical with embodiment 1;
Table 1
| ? | The massfraction of sodium hydroxide ethanolic soln | Consumption | |
| Embodiment | |||
| 2 | 8％ | 20mL | 41% |
| |
14％ | 20mL | 43% |
| |
10％ | |
40% |
| |
10％ | |
45% |
Preparation 4-diethylin salicylic aldehyde schiff bases (schiff bases copper ion fluorescence probe)
Intermediate by 0.16g (0.82mmol) 4-(diethylin) salicylic aldehyde, 0.24g (0.82mmol) embodiment 1 preparation
awith 30 mL ethanol, add in 50 mL single necked round bottom flask, mixed solution is heated to 90 ℃, backflow 12h.After being cooled to room temperature, with Rotary Evaporators, most of solvent is removed, had solid to separate out, suction filtration obtains the sorrel powder, with dehydrated alcohol and methylene dichloride mixing solutions recrystallization, obtains the reddish-brown crystal, productive rate 83%.
Step gained reddish-brown crystal is carried out to the nuclear magnetic resonance map analysis,
1h NMR (400MHz, CDCl
3): 1.22 (t,
j=6.8Hz, 12H), 3.42 (q,
j=6.8Hz, 8H), 6.22 (s, 1H), 6.28 (d,
j=8.4Hz, 1H), 6.67 (d,
j=8.4Hz, 2H), 7.19 (d,
j=8.8Hz, 1H), 7.31 (d,
j=8.4Hz, 2H), 7.35 (d,
j=15.6Hz, 1H), 7.55 (d,
j=8.8Hz, 2H), 7.81 (d,
j=15.2Hz, 1H), 8.06 (d,
j=8.4Hz, 2H), 8.45 (s, 1H), 13.61 (s, 1H).
13c NMR (100MHz, CDCl
3), 12.76,12.88,44.68,44.85,97.93,104.42,109.27,111.47,116.33,120.83,120.96,122.17,129.99,130.04,130.88,134.42,136.26,145.67,149.81,152.59,161.05,164.66,189.41 (23peaks).
Optical physics by the schiff bases copper ion fluorescence probe of embodiment 1 and 6 preparations to cupric ion detects.
Add the absorption peak blue shift 18nm of 1 equivalent cupric ion salicylic aldehyde schiff bases (embodiment 1 preparation) at the 453nm place, the absorption peak of 4-diethylin salicylic aldehyde schiff bases (embodiment 6 preparations) at the 467nm place reduces, blue shift 30nm, a new absorption peak appears in the 351nm place simultaneously.The fluorescence spectrum of salicylic aldehyde schiff bases (embodiment 1 preparation) is along with cupric ion adds, and fluorescence intensity has improved 4 times of left and right, and fluorescence peak has the small blue shift of 4nm.The fluorescence of 4-diethylin salicylic aldehyde schiff bases (embodiment 6 preparations) strengthens, fluorescence peak blue shift 51nm.This shows that they have good response to cupric ion, have the function that detects cupric ion.
Claims (8)
1. a schiff bases copper ion fluorescence probe, is characterized in that, its structure is:
Described R is hydrogen atom or 4-N, the N diethylamino group.
2. the preparation method of a schiff bases copper ion fluorescence probe claimed in claim 1, is characterized in that, comprises the steps
(1) para-aminoacetophenone and the reaction of 4-diethylamide benzaldehyde, obtain intermediate A;
(2) R-salicylic aldehyde and intermediate A reaction, obtain the schiff bases copper ion fluorescence probe;
Intermediate A is 1-(4-amino-benzene)-3-(4-diethylin benzene)-acrylketone, and its structural formula is:
3. preparation method according to claim 2 is characterized in that:
Step (1) adopts following method to complete: para-aminoacetophenone and 4-diethylamide organic solvent dissolution for benzaldehyde, take the sodium hydroxide ethanolic soln/and potassium hydroxide-ethanol solution be alkaline conditioner, room temperature, stirring reaction more than 9 hours, separating-purifying; In alkaline conditioner the massfraction of alkali be 8% ~ 20%, with the volume ratio of organic solvent be 3-5:6.
4. according to the described preparation method of claim 2 or 3, it is characterized in that:
Step (2) adopts following method to complete: intermediate A and R-salicylic aldehyde organic solvent dissolution, 85-90 ° of C refluxed more than 6 hours, then separating-purifying.
5. preparation method according to claim 3 is characterized in that:
Described organic solvent is ethanol; The sodium hydroxide ethanolic soln that described alkaline conditioner is 8-14%.
6. preparation method according to claim 4, it is characterized in that: described separating and purifying method is: pour mixture after completion of the reaction into frozen water, then use dichloromethane extraction, then extraction liquid is purified with silica gel chromatographic column.
7. preparation method according to claim 6, it is characterized in that: described organic solvent is ethanol; Described separating and purifying method: remove organic solvent with Rotary Evaporators, by solid suction filtration, the recrystallization of separating out.
8. preparation method according to claim 7, it is characterized in that: the ratio of para-aminoacetophenone/4-diethylamide benzaldehyde and organic solvent ethanol is 1mmol:2mL; The ratio of R-salicylic aldehyde/intermediate A and organic solvent ethanol is 2.73mmol:100mL.
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Non-Patent Citations (1)
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| 张妍等: "一种新型极性荧光探针的合成与应用", 《分析试验室》 * |
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| CN104177321A (en) * | 2014-08-06 | 2014-12-03 | 济南大学 | Copper ion fluorescence probe based on benzopyran diketone and preparation method of copper iron fluorescence probe |
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| CN106278957A (en) * | 2016-10-11 | 2017-01-04 | 温州医科大学 | A kind of novel copper ion fluorescent molecular probe and application thereof |
| CN106278957B (en) * | 2016-10-11 | 2017-11-28 | 温州医科大学 | A kind of new copper ion fluorescent molecular probe and its application |
| CN107082751A (en) * | 2017-04-11 | 2017-08-22 | 安徽大学 | One kind has Cu2+Two-photon fluorescence probe of identification function and its production and use |
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| CN108863984A (en) * | 2017-10-22 | 2018-11-23 | 德州学院 | For detecting Mg2+、Fe3+、Cu2+Azacrown ether containing sulfur-fluorenes schiff bases fluorescent molecular probe and preparation method |
| CN108863984B (en) * | 2017-10-22 | 2021-05-18 | 德州学院 | For detecting Mg2+、Fe3+、Cu2+Sulfur aza crown ether-fluorene Schiff base fluorescent molecular probe and preparation method thereof |
| CN108586382A (en) * | 2018-04-08 | 2018-09-28 | 山西大学 | A kind of schiff base compound and its preparation and the application in copper ion detection |
| CN108586382B (en) * | 2018-04-08 | 2021-09-28 | 山西大学 | Schiff base compound, preparation thereof and application thereof in copper ion detection |
| CN109970634A (en) * | 2019-03-27 | 2019-07-05 | 福建师范大学 | A kind of pyridine schiff base structure fluorescence probe and the preparation method and application thereof for detecting copper ion |
| CN109970634B (en) * | 2019-03-27 | 2022-03-15 | 福建师范大学 | Pyridine Schiff base structure fluorescent probe for detecting copper ions and preparation method and application thereof |
| CN109781694A (en) * | 2019-03-29 | 2019-05-21 | 上海应用技术大学 | The rapid detection method of metal ion in a kind of grape wine |
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