CN103320118B - 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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- CN103320118B CN103320118B CN201310166381.6A CN201310166381A CN103320118B CN 103320118 B CN103320118 B CN 103320118B CN 201310166381 A CN201310166381 A CN 201310166381A CN 103320118 B CN103320118 B CN 103320118B
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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 base cooper ion fluorescence probe and preparation method thereof, belong to the synthesis technical field of schiff bases.
Background technology
Copper ion is one of indispensable trace element of organism normal activities, but its excessive concentration or the too low disorder all causing life system, thus cause relevant disease, such as Wilson disease (Menkes Wilson disease) alzheimer's presenile dementia (Alzheimer ' s disease), prion disease (Prion diseases).Therefore the detecting and tracking of the copper ion in organism and environment is seemed especially important
.
Schiff bases, English name: Schiff's base, also claims Schiff 's base; 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, instead of hydrogen.Usually first there is with carbonyls (aldehyde, ketone) the half amine aldehyde that nucleophilic addition generates similar hemiacetal by aromatic amine in fragrant schiff bases, then dehydration reaction generation imines occurs and obtains.Due to schiff base compounds have good photophysical property, with the better bonding action of copper ion there is special physiologically active, therefore this compounds can be applied to that the domain variability such as copper ion probe and bio-imaging can be that preparation is antibacterial, sterilization, the medicine such as antitumor, antiviral provide new selection.
Summary of the invention
The object of the present invention is to provide the Schiff base cooper ion fluorescence probe that a kind of structure is different from existing schiff bases.
Another object of the present invention is to the preparation method that above-mentioned schiff bases copper ion probe is provided.
Technical scheme of the present invention:
A kind of Schiff base cooper ion fluorescence probe, its structure is:
；
Described R is hydrogen atom or 4-N, N diethylamino group.
A preparation method for above-mentioned Schiff base cooper ion fluorescence probe, comprises the steps
(1) para aminoacetophenone and the reaction of 4-diethylamide benzaldehyde, obtain intermediate A;
(2) R-salicylide and intermediate A reaction, obtain Schiff base cooper ion fluorescence probe;
Intermediate A is 1-(4-aminobenzene)-3-(4-diethylin benzene)-propenone, 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-salicylide is
; R is H or N, N diethylin.It is salicylide (salicylaldehyde) when R is H; Be 4-(diethylin) salicylide (4-(Diethylamino) salicylaldehyde) when R is 4-N, N diethylin.
The synthetic route of preparation method of the present invention is:
。
Above-mentioned preparation method:
Step (1) adopts following method to complete: para aminoacetophenone and 4-diethylamide benzaldehyde organic solvent dissolution, with NaOH ethanolic solution/and potassium hydroxide-ethanol solution for alkaline conditioner, room temperature, stirring reaction more than 9 hours, separating-purifying; In alkaline conditioner, the mass fraction of alkali is 8% ~ 20%, is 3-5:6 with the volume ratio of organic solvent;
Step (2) adopts following method to complete: intermediate A and R-salicylide organic solvent dissolution, and 85-90 ° of C refluxes more than 6 hours, then separating-purifying;
The reaction of step (1) and (2) is the reaction that mol ratio is 1:1, and can making wherein in actual mechanical process, any one raw material is excessive, does not affect reaction; As long as the consumption of solvent can make 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 NaOH ethanolic solution of 8-14%.Reaction time is preferably 18 hours.Described process for separation and purification is: pour mixture after completion of the reaction into frozen water, then use dichloromethane extraction, then is purified by extract silica gel chromatographic column.The eluent of purification is preferably carrene/benzinum [V (carrene)/V (benzinum)=1:1.
In step (2):
Described organic solvent is preferably ethanol; Preferred, the ratio of R-salicylide/intermediate A and organic solvent ethanol is 2.73mmol:100mL.Return time is preferably 12 hours.Described process for separation and purification: remove organic solvent with Rotary Evaporators, by solid suction filtration, the recrystallization of separating out.
Beneficial effect
Schiff base cooper ion fluorescence probe of the present invention, its structure is different from the structure of existing schiff bases; There is good response to copper ion, there is the function detecting copper ion; Provide a kind of means of detection copper ion newly.When existing schiff bases runs into copper ion, its fluorescence intensity reduces; When Schiff base cooper ion fluorescence probe of the present invention runs into copper ion, its fluorescence intensity improves about four times; Therefore, when fluorescence intensity is lower, Schiff base cooper ion fluorescence probe of the present invention more easily obtains testing result.
Preparation method of the present invention, low to the requirement of temperature, easily control, product is easy to separation, yield is high, purity is high.
Accompanying drawing explanation
The proton nmr spectra of the intermediate A of Fig. 1 prepared by embodiment 1;
The proton nmr spectra of the Schiff base cooper ion fluorescence probe of Fig. 2 prepared by embodiment 1;
The carbon-13 nmr spectra of the Schiff base cooper ion fluorescence probe of Fig. 3 prepared by embodiment 1;
The proton nmr spectra of the Schiff base cooper ion fluorescence probe of Fig. 4 prepared by embodiment 6;
The carbon-13 nmr spectra of the Schiff base cooper ion fluorescence probe of Fig. 5 prepared by embodiment 6;
The Schiff base cooper ion fluorescence probe of Fig. 6 prepared by embodiment 1 detects the absorption spectrum of copper ion;
The Schiff base cooper ion fluorescence probe of Fig. 7 prepared by embodiment 6 detects the absorption spectrum of copper ion;
The fluorescence spectrum of the Schiff base cooper ion fluorescence probe copper ion prepared by Fig. 8 embodiment 1;
The fluorescence spectrum of the Schiff base cooper ion fluorescence probe copper ion prepared by Fig. 9 embodiment 6.
Detailed description of the invention
Embodiment 1
(1) 1-(4-aminobenzene)-3-(4-diethylin benzene)-propenone (intermediate is prepared
a)
2.0g (15mmol) para aminoacetophenone and 2.7g (15mmol) 4-diethyl amino benzaldehyde are added in the single port bottle containing 30mL absolute ethyl alcohol, then the NaOH ethanolic solution that 20mL mass fraction is 10% is dripped, stirred at ambient temperature 18 hours, product in flask is poured in frozen water, with dichloromethane extraction (3 × 30mL).Purify with silica gel chromatographic column, eluent is that [V (carrene)/V (benzinum)=1:1, obtains bronzing compound and be intermediate A, productive rate 46.1% carrene/benzinum.Nuclear magnetic resonance map analysis is carried out to intermediate A,
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) salicylide schiff bases (Schiff base cooper ion fluorescence probe) is prepared
By 0.1g (0.82mmol) salicylide, 0.24g (0.82mmol) intermediate
aadd in 50 mL single necked round bottom flask with 30 mL ethanol, mixed liquor is heated to 85 DEG C, backflow 12h.After being cooled to room temperature, removed by most of solvent with Rotary Evaporators, have solid to separate out, suction filtration obtains Red-brown powder, obtains red-brown crystals, productive rate 60% with absolute ethyl alcohol and carrene mixed solution recrystallization.
Nuclear magnetic resonance map analysis is carried out to step (2) gained red-brown crystals,
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 NaOH ethanolic solution, the consumption of other materials and the operating condition salicylide schiff bases of all having prepared red-brown crystals shape identical with embodiment 1;
Table 1
| The mass fraction of NaOH ethanolic solution | Consumption | Productive rate | |
| Embodiment 2 | 8％ | 20mL | 41% |
| Embodiment 3 | 14％ | 20mL | 43% |
| Embodiment 4 | 10％ | 15mL | 40% |
| Embodiment 5 | 10％ | 25mL | 45% |
Embodiment 6
Preparation 4-diethylin salicylide schiff bases (Schiff base cooper ion fluorescence probe)
By the intermediate of 0.16g (0.82mmol) 4-(diethylin) salicylide, the preparation of 0.24g (0.82mmol) embodiment 1
aadd in 50 mL single necked round bottom flask with 30 mL ethanol, mixed liquor is heated to 90 DEG C, backflow 12h.After being cooled to room temperature, removed by most of solvent with Rotary Evaporators, have solid to separate out, suction filtration obtains Red-brown powder, obtains red-brown crystals, productive rate 83% with absolute ethyl alcohol and carrene mixed solution recrystallization.
Nuclear magnetic resonance map analysis is carried out to step gained red-brown crystals,
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).
Schiff base cooper ion fluorescence probe prepared by embodiment 1 and 6 is detected the optical physics of copper ion.
Add 1 equivalent copper ion salicylide schiff bases (prepared by embodiment 1) the absworption peak blue shift 18nm at 453nm place, 4-diethylin salicylide schiff bases (prepared by the embodiment 6) absworption peak at 467nm place reduces, blue shift 30nm, the new absworption peak of 351nm place appearance one simultaneously.The fluorescence spectrum of salicylide schiff bases (prepared by embodiment 1) adds along with copper ion, and fluorescence intensity improves about 4 times, fluorescence peak has the small blue shift of 4nm.The Fluorescence Increasing of 4-diethylin salicylide schiff bases (prepared by embodiment 6), fluorescence peak blue shift 51nm.This shows that they have good response to copper ion, there is the function detecting copper ion.
Claims (7)
1. a Schiff base cooper ion fluorescence probe, is characterized in that, its structure is:
；
Described R is hydrogen atom or 4-N, N diethylamino group.
2. a preparation method for Schiff base cooper ion fluorescence probe according to claim 1, is characterized in that, comprises the steps
(1) para aminoacetophenone and the reaction of 4-diethylamide benzaldehyde, obtain intermediate A;
(2) R-salicylide and intermediate A reaction, obtain Schiff base cooper ion fluorescence probe;
Intermediate A is 1-(4-aminobenzene)-3-(4-diethylin benzene)-propenone, 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 benzaldehyde organic solvent dissolution, with NaOH ethanolic solution/and potassium hydroxide-ethanol solution for alkaline conditioner, room temperature, stirring reaction more than 9 hours, separating-purifying; In alkaline conditioner, the mass fraction of alkali is 8% ~ 20%, is 3-5:6 with the volume ratio of organic solvent.
4. the preparation method according to Claims 2 or 3, is characterized in that:
Step (2) adopts following method to complete: intermediate A and R-salicylide organic solvent dissolution, and 85-90 ° of C refluxes more than 6 hours, then separating-purifying.
5. preparation method according to claim 4, is characterized in that: described process for separation and purification is: pour mixture after completion of the reaction into frozen water, then use dichloromethane extraction, then is purified by extract silica gel chromatographic column.
6. preparation method according to claim 5, is characterized in that: described organic solvent is ethanol; Described process for separation and purification: remove organic solvent with Rotary Evaporators, by solid suction filtration, the recrystallization of separating out.
7. preparation method according to claim 6, is characterized in that: the ratio of para aminoacetophenone/4-diethylamide benzaldehyde and organic solvent ethanol is 1mmol:2mL; The ratio of R-salicylide/intermediate A and organic solvent ethanol is 2.73mmol:100mL.
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| CN104177321B (en) * | 2014-08-06 | 2015-10-21 | 济南大学 | A kind of copper ion fluorescence probe based on chromene diketone and preparation method thereof |
| CN104961647A (en) * | 2015-06-26 | 2015-10-07 | 西北师范大学 | Fluorescent recognition cupper ion (CU2+) sensor molecules and composition and application thereof |
| CN105044061A (en) * | 2015-07-25 | 2015-11-11 | 渤海大学 | High-selectivity method for detecting p-phenylenediamine in aqueous solution |
| 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 |
| CN107082751B (en) * | 2017-04-11 | 2018-10-23 | 安徽大学 | Has Cu2+Two-photon fluorescent probe with identification function and preparation method and application thereof |
| CN107056779B (en) * | 2017-04-25 | 2019-03-12 | 三峡大学 | A kind of schiff bases fluorescence probe QCS and preparation method thereof |
| 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 |
| CN108586382B (en) * | 2018-04-08 | 2021-09-28 | 山西大学 | Schiff base compound, preparation thereof and application thereof in copper ion detection |
| 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 |
| CN109781694B (en) * | 2019-03-29 | 2021-09-24 | 上海应用技术大学 | Rapid detection method for metal ions in wine |
| CN110092771A (en) * | 2019-04-19 | 2019-08-06 | 深圳大学 | A kind of fluorescence probe and preparation method thereof for human serum albumins detection, Fluorescence kit |
| CN113698353B (en) * | 2021-08-27 | 2023-05-05 | 桂林理工大学 | Imidazolyl Schiff base fluorescence sensor for detecting copper (II) particles in aqueous solution and synthesis method thereof |
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