CN104829526B - Fluorescent probe compounds and its preparation method and application - Google Patents
Fluorescent probe compounds and its preparation method and application Download PDFInfo
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- C07D215/00—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems
- C07D215/02—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom
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Abstract
The present invention relates to organic synthesis field, in particular to a kind of fluorescent probe compounds and its preparation method and application.The compound that the present invention is provided is 2 (2 methylol) phenylchinolines, and its preparation method includes：2 bromoquinolines, 2 carbethoxyl group phenyl boric acids, cesium carbonate and catalyst are added in DMF solution, are stirred, obtain reactant mixture；By reactant mixture is by extraction, washing and dries concentration, 2 (2 carbethoxyl group) phenylchinolines are obtained；And be added drop-wise in the mixed solution being made up of lithium aluminium hydride reduction and tetrahydrofuran, continue to stir complete to the reaction of 2 (2 carbethoxyl group) phenylchinolines, after reaction solution ice-water bath is cooled down, filtered after ethyl acetate is added dropwise, and filtrate is obtained final product by rotary evaporation concentration, silica gel column chromatography purification and petrol ether/ethyl acetate mixed liquor drip washing.The compound can facilitate organophosphorus pesticide or detection of heavy metal ion as the fluorescent probe compounds in fluorescence detection method.
Description
Technical field
The present invention relates to organic synthesis field, in particular to a kind of fluorescent probe compounds and preparation method thereof and
Using.
Background technology
Organic phosphorus compound agricultural chemicals, is a kind phosphate ester class compound or its derivative.This kind of material is to acetylcholine
Esterase (acetylcholinesterase, AchE) activity has strong inhibitory action, causes acetylcholine mistake in people, animal body
, so as to cause cholinergic nerve system function serious diseases, there is poisoning symptom in amount accumulation.Therefore, this kind of material has toxicity
By force, the characteristics of acting on fast, improper use can cause very big threat to human health or even life.
Specifically, in organophosphorus pesticide, a class is often acted on nerve gas, is commonly used for chemical weapons during war.Most
Representative four nerve toxicants are tabun (Tabun), sarin (Sarin), soman (Soman) and VX (VX).
Contain P-CN keys and P-F keys or P-SCH in their molecular structure2CH2N(R)2Key.
An other organophosphorus compounds are commonly used for insecticide, are insecticide of the China using extensive consumption maximum, mainly
Including DDVP, parathion, thimet, demeton, Rogor, metrifonate, malathion etc..Organophosphorus pesticide (OPPs) is used as one
Class is efficient, the insecticide of wide spectrum is being widely used in the aspects such as the anti-evil and family, storage insecticidal of agricultural, but,
Rear serious harm environment is largely used, its detection has turned into the important content of food safety detection.Conventional organophosphor agriculture at present
Medicine residue analysis method chromatogram or chromaticness on-line method, such as GC, HPLC and GC-MS etc., but these detection method complex operations and
It is higher to equipment requirement, it is unfavorable for onsite application.
Fluoroscopic examination is one of effective way of the inexpensive easy detection of realization, during fluoroscopic examination, You Jifen
Sub- fluorescence probe has sensitivity high, response fast, design and can cut out many special natures such as connecing property is strong, therefore research and development
New organic molecule fluorescence probe has become people's technical problem urgently to be resolved hurrily.
In view of this, it is special to propose the present invention.
The content of the invention
The first object of the present invention is to provide a kind of fluorescent probe compounds, and the compound is special due to its structure
Property, it can occur intermolecular interaction with phosphate pesticide or heavy metal ion, final to realize detection agricultural chemicals or a huge sum of money
Belong to the purpose of ion.Therefore organophosphorus pesticide or heavy metal can be facilitated as the fluorescent probe compounds in fluorescence detection method
Ion detection.
It is another object of the present invention to provide the preparation method of above-mentioned fluorescent probe compounds, the method is with 2- bromines
Quinoline, 2- carbethoxyl group phenyl boric acids etc. are reactant, by controlling reaction condition and system, realize 2- (2- methylols) phenyl
The synthesis of quinoline, for the application of the compound provides the foundation, additionally, the method is easily operated, required equipment is also more simple.
The third object of the present invention is the purposes of the fluorescent probe compounds for providing above-mentioned.
In order to realize the above object spy of the present invention uses following technical scheme：
This fluorescent probe compounds that the present invention is provided, its chemical structural formula is：
Entitled 2- (2- methylols) phenylchinoline of the compound, the probe has specific chemical constitution, and it can be with
There is intermolecular interaction in phosphate pesticide or heavy metal ion so that the fluorescence of detection architecture is converted, and finally
Realize the purpose of detection phosphate pesticide or heavy metal ion.
The embodiment of the present invention additionally provides a kind of preparation method according to above-claimed cpd, comprises the following steps：
1), 2- bromoquinolines, 2- carbethoxyl groups phenyl boric acid, cesium carbonate and catalyst are added in DMF solution, are stirred
Mix, obtain reactant mixture；
2) reactant mixture, is sequentially passed through into extraction, washing and concentration is dried, 2- (2- carbethoxyl groups) benzene is obtained
Base quinoline；
3), the 2- (2- carbethoxyl groups) phenylchinoline is added drop-wise to the mixing being made up of lithium aluminium hydride reduction and tetrahydrofuran molten
In liquid, continue to stir complete to the reaction of 2- (2- carbethoxyl groups) phenylchinoline, obtain reaction solution；
4) after, the reaction solution ice-water bath is cooled down, filtered after ethyl acetate is added dropwise, and the filtrate that will be obtained is by rotation
After evaporation and concentration, silica gel column chromatography purification and petrol ether/ethyl acetate mixed liquor drip washing, fluorescent probe compounds are obtained.
Optionally, in step 1) in, the catalyst is dppf palladium chlorides.
Dppf palladium chlorides, because it has specific chemical constitution, therefore can promote as the catalyst of coupling reaction
The generation of 2- (2- carbethoxyl groups) phenylchinoline.
Optionally, step 1) in：The stirring is carried out under the protection of nitrogen.
Nitrogen is relatively stable due to its chemical property, therefore, under the protection of nitrogen, can avoid due to some active gas
Body participates in reacting and causing response path to change.
Optionally, in step 1) in, specifically include：
2- bromoquinolines, 2- carbethoxyl groups phenyl boric acid, cesium carbonate and dppf palladium chlorides are added under the protection of nitrogen
To in the mixed liquor, and liquid was stirred in 75-85 DEG C, obtained reactant mixture；
Wherein, the 2- bromoquinolines, the mol ratio of 2- carbethoxyl group phenyl boric acids are (2.9-3.1)：(3.2-3.4).
During reaction system is built, the used in amounts to each reactant will be controlled strictly, if usage amount is controlled
It is improper, then then to cause synthetic reaction to fail, it is impossible to obtain product.Thus, in step 1) in, it is preferable that 2- bromoquinolines, 2-
The mol ratio of carbethoxyl group phenyl boric acid is (2.9-3.1)：(3.2-3.4).After mixing with mixed liquor, during stirring, preferably
Temperature is 75-85 DEG C, to improve reaction speed and promote reaction complete.
Optionally, in step 2) in, specifically include：
In the mixed liquor that reactant mixture addition is constituted containing isometric water and EtOAc, after after point liquid, by water
Layer is extracted at twice with EtOAc, and merged and washed with sodium-chloride water solution successively after organic phase, use anhydrous Na2SO4Dry, then pass through
Rotary Evaporators are concentrated, and obtain 2- (2- carbethoxyl groups) phenylchinoline.
During synthesis, due to 2- (2- carbethoxyl groups) phenylchinoline for obtaining, typically mostly crude product, Er Qieqi
Unstable chemcial property.Therefore, in extracting, washing and dry concentration process, great care is answered.Preferably, in order to improve
The yield of 2- (2- carbethoxyl groups) phenylchinoline, reactant mixture is first added to isometric water and EtOAc constitute before extraction
Mixed liquor in, after mixing, treat its point of liquid, and water layer EtOAc extracts (to realize that extraction is complete as much as possible) at twice, closes
And after organic phase, washed with sodium-chloride water solution successively, use anhydrous Na2SO4Dry, then the concentration of rotated evaporimeter.
Optionally, in step 3) in, specifically include：
By the 2- (2- carbethoxyl groups) phenylchinolines temperature be less than under conditions of 10 DEG C be added drop-wise to by lithium aluminium hydride reduction and
In the mixed solution of tetrahydrofuran composition, reaction system is warming up to room temperature, continues to stir 28-32 hours, treat 2- (2- ethoxy carbonyls
Base) phenylchinoline reaction is complete, obtains reaction solution.
In step 2) in, compound 2- (2- carbethoxyl groups) phenylchinoline for obtaining, it is very unstable as intermediate
It is fixed and more sensitive to temperature, therefore need to be added drop-wise to what is be made up of lithium aluminium hydride reduction and tetrahydrofuran (less than 10 DEG C) at low temperature
Mixed solution；After completion of dropping, the temperature of reaction system is increased to room temperature, promotes reaction to occur, it is however generally that, stirring reaction
After 28-32 hours, 2- (2- carbethoxyl groups) phenylchinoline exhausts, and reaction tends to complete.
Optionally, in step 4) in, the outlet temperature of the cooling is 0-1 DEG C.
Before filtration, in order to prevent the product in reaction solution unstable and recurring structure transformation；Reaction solution is made
0 DEG C is cooled to ice-water bath so that reaction can terminate, and keep product structure stabilization.After filtering, filtrate is steamed by rotation
After hair concentration, silica gel column chromatography purification and petrol ether/ethyl acetate mixed liquor drip washing, yellow powder fluorescence probe is obtained
Compound.
Optionally, step 4) in：In the petrol ether/ethyl acetate mixed liquor, the volume of petroleum ether and ethyl acetate
It is (9-10)：1.
By after silica gel column chromatography proposition, in order to realize preferable drip washing effect, in petrol ether/ethyl acetate mixed liquor,
Petroleum ether is (9-10) with the volume of ethyl acetate：1.
For the preparation method of above-mentioned fluorescent probe compounds, i.e. the synthetic method of 2- (2- methylols) phenylchinoline,
All response paths are as follows：
Wherein：
A is：2- bromoquinolines；B is：2- carbethoxyl group phenyl boric acids；C is：2- (2- carbethoxyl groups) phenylchinoline；D is：2-
(2- methylols) phenylchinoline.
Described fluorescent probe compounds as detection organophosphorus pesticide, heavy metal ion, especially in conduct
Detection DDVP and Cr3+Organic molecule fluorescent probe compounds in application.
Brief description of the drawings
In order to illustrate more clearly of the specific embodiment of the invention or technical scheme of the prior art, below will be to specific
The accompanying drawing to be used needed for implementation method or description of the prior art is briefly described, it should be apparent that, in describing below
Accompanying drawing is some embodiments of the present invention, for those of ordinary skill in the art, before creative work is not paid
Put, other accompanying drawings can also be obtained according to these accompanying drawings.
UV absorption figures of the Fig. 1 for the fluorescent probe compounds for providing of the invention after acid adding；
UV absorption figures of the Fig. 2 for the fluorescent probe compounds for providing of the invention after metrifonate is added；
Fig. 3 adds the fluorescence emission spectrogram of compound after DDVP for the fluorescent probe compounds that the present invention is provided；
Fig. 4 adds the fluorescence emission spectrogram of compound after chlopyrifos for the fluorescent probe compounds that the present invention is provided；
The figure of the fluorescence emission spectrum after the fluorescent probe compounds addition Rogor that Fig. 5 is provided for the present invention；
Fig. 6 adds the fluorescence emission spectrogram of compound after flolimat for the fluorescent probe compounds that the present invention is provided；
Fig. 7 adds the fluorescence emission spectrogram of compound after parathion-methyl for the fluorescent probe compounds that the present invention is provided；
After Fig. 8 is heated for the fluorescent probe compounds that provide of the present invention and formic acid fluorescence emission spectrogram of compound；
Fig. 9 adds the fluorescence emission spectrogram of compound after zinc chloride for the fluorescent probe compounds that the present invention is provided；
Figure 10 adds the fluorescence emission spectrogram of compound after copper sulphate for the fluorescent probe compounds that the present invention is provided；
Figure 11 adds the fluorescence emission spectrogram of compound after chromium chloride for the fluorescent probe compounds that the present invention is provided；
Fluorescence emission spectrogram of compound after the fluorescent probe compounds elder generation acid adding that Figure 12 is provided for the present invention plus after alkali；
The 1H-NMR collection of illustrative plates of the fluorescent probe compounds that Figure 13 is provided for the present invention.
Specific embodiment
To make the object, technical solutions and advantages of the present invention clearer, technical scheme will be carried out below
Clear, complete description, based on the specific embodiment in the present invention, those of ordinary skill in the art are not making creativeness
Resulting all other implementation method on the premise of work, belongs to the scope that the present invention is protected.
The preparation method of this fluorescent probe compounds that the present invention is provided, comprises the following steps：
S1：2- bromoquinolines, 2- carbethoxyl groups phenyl boric acid, cesium carbonate and catalyst are added in DMF solution, are stirred
Mix, obtain reactant mixture；
In this step, for the architectural feature and physicochemical property of two kinds of reactants, and then preferred original has been filtered out
Material weight proportion and reaction condition, such as：Catalyst is dppf palladium chlorides.Meanwhile, 2- bromoquinolines, 2- carbethoxyl group phenyl boric acids
Mol ratio be (2.9-3.1)：(3.2-3.4).In addition, in order to prevent some active gases from participating in reaction, in stirring reaction
During, preferably carried out under the protection of nitrogen stable in properties.
S2：The reactant mixture is sequentially passed through into extraction, washing and concentration is dried, 2- (2- carbethoxyl groups) benzene is obtained
Base quinoline；
Preferably, above-mentioned steps 102 can be carried out according to following operation：The reactant mixture is added containing isometric
Water and EtOAc compositions mixed liquor in, after after point liquid, water layer is extracted at twice with EtOAc (equal with mixeding liquid volume),
Washed twice with sodium-chloride water solution (volume is 1.5 times of EtOAc) successively after merging organic phase, use anhydrous Na2SO4Dry, then
Rotated evaporimeter concentration, obtains 2- (2- carbethoxyl groups) phenylchinoline.
Through measure, by step 2) operation so that the yield of compound 2- (2- carbethoxyl groups) phenylchinoline is reachable
To more than 80%.
S3：The 2- (2- carbethoxyl groups) phenylchinoline is added drop-wise to the mixing being made up of lithium aluminium hydride reduction and tetrahydrofuran molten
In liquid, continue to stir complete to the reaction of 2- (2- carbethoxyl groups) phenylchinoline, obtain reaction solution.
Preferably, in this step, 2- (2- carbethoxyl groups) phenylchinolines are added drop-wise under conditions of temperature is less than 10 DEG C
In the mixed solution be made up of lithium aluminium hydride reduction and tetrahydrofuran, and after completion of dropping, the temperature of reaction system is increased to room temperature,
Reaction is promoted to occur.
S4：After the reaction solution ice-water bath is cooled down, filtered after ethyl acetate is added dropwise, and the filtrate that will be obtained is by rotation
After evaporation and concentration, silica gel column chromatography purification and petrol ether/ethyl acetate mixed liquor drip washing, fluorescent probe compounds are obtained.
In the step, it is preferably that the temperature of reaction system is cooled into 0 DEG C that ice-water bath cooling is specific, terminates anti-with rapid
Should, and prevent product recurring structure from changing.In addition, during using petrol ether/ethyl acetate mixed liquor drip washing, preferably
Ground, petroleum ether is (9-10) with the volume of ethyl acetate：1.
Next, with reference to above-mentioned content, implementation in detail below is provided to the preparation method of fluorescent probe compounds
Example：
Embodiment one
The first step：By compound A (3.12g, 0.015mol), compound B (3.21g, 0.0165mol), alkali Cs2CO3
(0.0405mol) and catalyst Pd (dppf) Cl2Under the protection of (0.0008mol) nitrogen, 80 DEG C are stirred overnight in DMF solution,
Obtain reactant mixture.
After reactant mixture is cooled to room temperature, it is added in the mixed liquor containing 100mL water and 100mL EtOAc.Divide liquid
Afterwards, water layer is extracted at twice with 200mL EtOAc, merges organic phase, washed at twice with the sodium-chloride water solution of 300mL,
And use anhydrous Na2SO4Dry, then rotated evaporimeter is concentrated to give dark brown oil, the i.e. crude product of compound C.
Second step：It is under 0 DEG C, nitrogen protective condition, the lithium aluminium hydride reduction of 1.1g (0.03mol) is dried with 30mL
Tetrahydrofuran mixes.
Compound C is dissolved in the dried tetrahydrofuran solutions of 10mL, control temperature (T<10 DEG C) it is added dropwise to instead
In answering container.Completion of dropping, temperature of reaction system is warmed to room temperature, and continues to stir 30min.Monitored with TLC, when compound C consumptions
When to the greatest extent, reaction system ice-water bath is cooled to 0 DEG C, is added dropwise over 10mL EtOAc and filters.By the concentration of filtrate rotary evaporation,
And purified with silica gel column chromatography, with petrol ether/ethyl acetate=10:1 mixed liquor drip washing, obtains yellow powder compound D
(420mg).In addition, the 1H-NMR collection of illustrative plates of compound that the method is made is as shown in figure 13.
Embodiment two
The first step：By compound A (0.0145mol), compound B (0.016mol), alkali Cs2CO3(0.04mol) and catalysis
Agent Pd (dppf) Cl2Under the protection of (0.00075mol) nitrogen, 75 DEG C are stirred overnight in DMF solution, obtain reactant mixture.
After reactant mixture is cooled to room temperature, it is added in the mixed liquor containing 100mL water and 100mL EtOAc.Divide liquid
Afterwards, water layer is extracted at twice with 200mL EtOAc, merges organic phase, washed at twice with the sodium-chloride water solution of 300mL,
And use anhydrous Na2SO4Dry, then rotated evaporimeter is concentrated to give dark brown oil, the i.e. crude product of compound C.
Second step：Under 0 DEG C, nitrogen protective condition, 1g lithium aluminium hydride reductions are mixed with the dried tetrahydrofuran of 25mL.
Compound C is dissolved in the dried tetrahydrofuran solutions of 10mL, control temperature (T<10 DEG C) it is added dropwise to instead
In answering container.Completion of dropping, temperature of reaction system is warmed to room temperature, and continues to stir 28min.Monitored with TLC, when compound C consumptions
When to the greatest extent, reaction system ice-water bath is cooled to 0 DEG C, is added dropwise over 10mL EtOAc and filters.By the concentration of filtrate rotary evaporation,
And purified with silica gel column chromatography, with petrol ether/ethyl acetate=10:1 mixed liquor drip washing, obtains yellow powder compound D.
Embodiment three
The first step：By compound A (0.01505mol), compound B (0.017mol), alkali Cs2CO3(0.041mol) and urge
Agent Pd (dppf) Cl2Under the protection of (0.00085mol) nitrogen, 85 DEG C are stirred overnight in DMF solution, obtain reactant mixture.
After reactant mixture is cooled to room temperature, it is added in the mixed liquor containing 100mL water and 100mL EtOAc.Divide liquid
Afterwards, water layer is extracted at twice with 200mL EtOAc, merges organic phase, washed at twice with the sodium-chloride water solution of 300mL,
And use anhydrous Na2SO4Dry, then rotated evaporimeter is concentrated to give dark brown oil, the i.e. crude product of compound C.
Second step：Under 0 DEG C, nitrogen protective condition, by 1.2g lithium aluminium hydride reductions and 35mL by dried tetrahydrofuran
Mixing.
Compound C is dissolved in the dried tetrahydrofuran solutions of 10mL, control temperature (T<10 DEG C) it is added dropwise to instead
In answering container.Completion of dropping, temperature of reaction system is warmed to room temperature, and continues to stir 32min.Monitored with TLC, when compound C consumptions
When to the greatest extent, reaction system ice-water bath is cooled to 0 DEG C, is added dropwise over 10mL EtOAc and filters.By the concentration of filtrate rotary evaporation,
And purified with silica gel column chromatography, with petrol ether/ethyl acetate=10:1 mixed liquor drip washing, obtains yellow powder compound D.
The composite result of the various embodiments of the present invention of table 1
| Project | Embodiment 1 | Embodiment 2 | Embodiment 3 |
| Product | 420mg | 418mg | 425mg |
| Yield | 11.91% | 12.261% | 12.01% |
| Purity | 96.20% | 97.65% | 97.60% |
It is pointed out that in above-mentioned all of embodiment, A is：2- bromoquinolines；B is：2- carbethoxyl group phenyl boric acids；C
For：2- (2- carbethoxyl groups) phenylchinoline；D is：2- (2- methylols) phenylchinoline.
In addition, the fluorescent probe compounds that the preferred embodiments of the present invention one are provided, its methanol solution is with sour (HCl)
Add, uv absorption spectra is as indicated with 1.
Fig. 1 shows, in the methanol solution of probe -2 (fluorescent probe compounds), with the addition of hydrochloric acid, probe -2
Absworption peak red shift, reason be probably because the N atoms on quinoline ring have alkalescence, can be with binding hydrogen ions, so as to cause probe point
Sub- absworption peak red shift.
Additionally, by detect the present invention provide fluorescent probe compounds (prepared by embodiment 1, hereinafter referred to as probe -2) its
Under conditions of difference (50 DEG C of heating, acid adding, plus phosphorous agricultural chemicals, add metal ion etc.) fluorescence emission peak change (detection
Process is using conventional fluorescence detection method), so as to verify that it is examined as phosphorous agricultural chemicals and part metals ion fluorescence
Application effect in probing pin.
Application examples 1：
Influence of the metrifonate to the fluorescence intensity of probe -2, as a result as shown in Fig. 2 being illustrated by Fig. 2,5 × 10-4mol/L
Metrifonate is gradually added into the methanol solution of probe -2, the fluorescent emission change of probe substantially, during heating does not change also unobvious.
Application examples 2：
Influence of the DDVP to the fluorescence intensity of probe -2, as a result as shown in figure 3,5 × 10-4The methyl alcohol of mol/L probes -2
DDVP is gradually added into solution, dimethyl dichlorovinyl phosphate content is less during beginning, the fluorescent emission change of probe is not obvious, but
When DDVP concentration increases to 1.2 μ g/mL, fluorescence emission spectral position there occurs red shift, illustrate that probe has identification to DDVP
Function.
Application examples 3：
Influence of the chlopyrifos to the fluorescence intensity of probe -2, as a result as shown in figure 4, as seen in Figure 4, with chlopyrifos
Addition, probe fluorescent emission change not substantially, during heating change it is also unobvious.
Application examples 4：
Influence of the Rogor to the fluorescence intensity of probe -2, as a result as shown in figure 5, as seen in Figure 5, with Rogor plus
Enter, the fluorescent emission change of probe substantially, during heating does not change also unobvious.
Application examples 5：
Influence of the flolimat to the fluorescence intensity of probe -2, as a result as shown in fig. 6, as seen in Figure 6, with oxidation
The addition of Rogor, the fluorescent emission change of probe substantially, during heating does not change also unobvious.
Application examples 6：
Influence of the parathion-methyl to the fluorescence intensity of probe -2, as a result as shown in fig. 7,5 × 10-4Mol/L probes -2
With the addition of parathion-methyl in methanol solution, the fluorescent emission change of probe substantially, during heating does not change also unobvious.
Application examples 7：
The influence of heating and acid to the fluorescence intensity of probe -2, as a result as shown in figure 8,5 × 10-4The methyl alcohol of mol/L probes -2
, with 50 DEG C of extensions of heat time, the fluorescent emission change of probe is not obvious, but when adding hydrochloric acid, emission spectrum occurs for solution
Obvious red shift, emissive porwer is also remarkably reinforced, and this explanation adds the N atoms after hydrochloric acid in probe molecule to be combined with H atom, leads
Probe structure is caused to change, so that emission spectrum also changes therewith.
Application examples 8：
Various concentrations zinc chloride is to probe-2The influence of fluorescence intensity, as a result as shown in figure 9, as seen in Figure 9, with
The addition of zinc chloride, the fluorescent emission change of probe is not obvious.
Application examples 9：
Influence of the various concentrations copper sulphate to the fluorescence intensity of probe -2, shown in result figure 10, from fig. 10 it can be seen that with
The addition of copper sulphate, the fluorescent emission change of probe substantially, does not illustrate that -2 pairs of copper ions of probe do not have recognition reaction.
Application examples 10：
Influence of the various concentrations chromium chloride to the fluorescence intensity of probe -2, as a result as shown in figure 11.It can be seen from figure 11 that with
The addition of chromium chloride, the fluorescence emission peak red shift of probe -2, emissive porwer is remarkably reinforced, and illustrates the presence of chromium to the glimmering of material
Light transmitting influence is larger, and the material can be used to detect Cr3+Presence.
Application examples 11：
HCl and NaOH are to 5 × 10-4The influence of the fluorescence intensity of mol/L probes -2, as a result as shown in figure 12, wherein, according to suction
Peak order from top to bottom is received, the methanol solution of probe -2, probe -2+ hydrochloric acid 0.016mol/L, probe -2+ hydrochloric acid is followed successively by
0.048mol/L, probe -2+ hydrochloric acid 0.048mol/L+ NaOH 0.032mol/L, probe -2+ hydrochloric acid 0.048mol/L+ hydrogen
The condition of sodium oxide molybdena 0.064mol/L, probe -2+ hydrochloric acid 0.048mol/L+ NaOH 0.096mol/L.
It can be recognized from fig. 12 that with the addition of hydrochloric acid, there is red shift in the fluorescent emission of material, and peak shape also there occurs
Change, the shape of main peak plus shoulder seam is changed into from obvious Two peak emission, because there is N atoms in probe 2 can be with H ions
With reference to, the structure of probe 2 is have impact on, so as to have impact on the change of its emission spectrum, red shift is launched in energy gap reduction；Simultaneously at this
NaOH is added in solution, transmitting collection of illustrative plates gradually reverts to original state, it is one reversible to illustrate that material adds the reaction of acid
Process.
In sum, the preparation method of this fluorescent probe compounds that the present invention is provided, its operation is easy, and yield compared with
It is high；2- (2- methylols) phenylchinoline being prepared from, it may apply to DDVP, Cr3+Deng fluorescent detection probe.
The preferred embodiments of the present invention are the foregoing is only, is not intended to limit the invention, for the skill of this area
For art personnel, the present invention can have various modifications and variations.It is all within the spirit and principles in the present invention, made any repair
Change, equivalent, improvement etc., should be included within the scope of the present invention.
Claims (10)
1. a kind of fluorescent probe compounds, it is characterised in that the compound it is entitled：2- (2- methylols) phenylchinoline, its
Chemical structural formula is：
2. the preparation method of the fluorescent probe compounds described in a kind of claim 1, it is characterised in that comprise the following steps：
1), 2- bromoquinolines, 2- carbethoxyl groups phenyl boric acid, cesium carbonate and catalyst are added in DMF solution, are stirred,
Obtain reactant mixture；
2) reactant mixture, is sequentially passed through into extraction, washing and concentration is dried, 2- (2- carbethoxyl groups) phenyl quinazoline is obtained
Quinoline；
3), the 2- (2- carbethoxyl groups) phenylchinoline is added drop-wise to the mixed solution being made up of lithium aluminium hydride reduction and tetrahydrofuran
In, continue to stir complete to the reaction of 2- (2- carbethoxyl groups) phenylchinoline, obtain reaction solution；
4) after, the reaction solution ice-water bath is cooled down, filtered after ethyl acetate is added dropwise, and the filtrate that will be obtained is by rotary evaporation
After concentration, silica gel column chromatography purification and petrol ether/ethyl acetate mixed liquor drip washing, fluorescent probe compounds are obtained.
3. the preparation method of fluorescent probe compounds according to claim 2, it is characterised in that in step 1) in, it is described
Catalyst is dppf palladium chlorides.
4. the preparation method of fluorescent probe compounds according to claim 3, it is characterised in that step 1) in, it is described to stir
Mix is carried out under the protection of nitrogen.
5. the preparation method of fluorescent probe compounds according to claim 4, it is characterised in that in step 1) in, specifically
Including：
2- bromoquinolines, 2- carbethoxyl groups phenyl boric acid, cesium carbonate and dppf palladium chlorides are added to institute under the protection of nitrogen
In stating DMF solution, and liquid was stirred in 75-85 DEG C, obtained reactant mixture；
Wherein, the 2- bromoquinolines, the mol ratio of 2- carbethoxyl group phenyl boric acids are (2.9-3.1)：(3.2-3.4).
6. the preparation method of fluorescent probe compounds according to claim 5, it is characterised in that in step 2) in, specifically
Including：
The reactant mixture is added in the mixed liquor for containing isometric water and EtOAc compositions, after after point liquid, water layer is used
EtOAc is extracted at twice, and merged and washed with sodium-chloride water solution successively after organic phase, use anhydrous Na2SO4Dry, then it is rotated
Evaporimeter is concentrated, and obtains 2- (2- carbethoxyl groups) phenylchinoline.
7. the preparation method of the fluorescent probe compounds according to claim any one of 2-6, it is characterised in that in step 3)
In, specifically include：
The 2- (2- carbethoxyl groups) phenylchinolines are less than under conditions of 10 DEG C in temperature and are added drop-wise to by lithium aluminium hydride reduction and tetrahydrochysene
In the mixed solution of furans composition, reaction system is warming up to room temperature, continues to stir 28-32min, treat 2- (2- carbethoxyl groups) benzene
The reaction of base quinoline is complete, obtains reaction solution.
8. the preparation method of fluorescent probe compounds according to claim 7, it is characterised in that in step 4) in, it is described
The outlet temperature of cooling is 0-1 DEG C.
9. the preparation method of fluorescent probe compounds according to claim 8, it is characterised in that step 4) in：
In the petrol ether/ethyl acetate mixed liquor, petroleum ether is (9-10) with the volume ratio of ethyl acetate：1.
10. the fluorescent probe compounds described in claim 1 as detection organophosphorus pesticide, heavy metal ion it is organic
Application in fluorescence probe.
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