CN104829526A - Fluorescent probe compound and preparation method and application of fluorescent probe compound - Google Patents
Fluorescent probe compound and preparation method and application of fluorescent probe compound Download PDFInfo
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Abstract
The invention relates to the field of organic synthesis, in particular to a fluorescent probe compound and a preparation method and an application of the fluorescent probe compound. The compound is 2-(2-hydroxymethyl) phenychinoline. The preparation method comprises the following steps of adding 2-bromoquinoline, 2-ethoxycarbonylphenylboronic acid, cesium carbonate and a catalyst in DMF (dimethyl formamide) solution and stirring to obtain a reaction mixture; extracting and washing the reaction mixture and performing dry concentration on the reaction mixture to obtain 2-(2-ethoxycarbonyl) phenychinoline; and dripping the 2-(2-ethoxycarbonyl) phenychinoline in a mixed solution consisting of lithium aluminum hydride and tetrahydrofuran, stirring until the 2-(2-ethoxycarbonyl) phenychinoline reacts completely, cooling down reaction liquid in an ice-water bath manner, dripping ethyl acetate in the reaction liquid, filtering the reaction liquid, performing rotary evaporation concentration on filter liquor, purifying the filter liquor by using silica gel column chromatography and leaching the filter liquor by using petroleum ether/ethyl acetate mixed liquid to obtain the compound. The compound can serve as the fluorescent probe compound in a fluorescent detection method, and detection on organophosphorus pesticide or heavy metal ions is facilitated.
Description
Technical field
The present invention relates to organic synthesis field, in particular to a kind of fluorescent probe compounds and its preparation method and application.
Background technology
Organo phosphorous compounds agricultural chemicals is a kind phosphate ester compounds or its derivative.This kind of material is to acetylcholinesterase (acetylcholinesterase, AchE) activity has strong restraining effect, cause vagusstoff excessive accumulation in people, animal body, thus cause cholinergic nerve system function serious diseases, occur toxicity symptom.Therefore, this kind of material has strong toxicity, acts on fast feature, and improper use can cause very large threat to human health and even life.
Concrete, in organophosphorus pesticide, a class often has nerve gas effect, is commonly used for chemical weapons during war.Representational four nerve toxicants of most are tabun (Tabun), sarin (Sarin), soman (Soman) and VX (VX).Containing P-CN key and P-F key or P-SCH in their molecular structure
2cH
2n (R)
2key.
An other organophosphorus compounds is commonly used for sterilant, is the sterilant that China uses extensively, consumption is maximum, mainly comprises SD-1750, thiophos, phorate, Systox, Rogor, Trichlorphon, Malathion etc.Organophosphorus pesticide (OPPs) is efficient as a class, the sterilant of wide spectrum is being widely used in agricultural anti-evil and the aspect such as family, storage insecticidal, but, serious harm environment after a large amount of use, it detects the important content having become food safety detection.At present conventional organophosphorus pesticide analytical procedure chromatogram or chromaticness on-line method, as GC, HPLC and GC-MS etc., but these detection method complicated operations and higher to equipment requirements, be unfavorable for onsite application.
Fluoroscopic examination is one of effective way realizing low cost easy detection, in the process of fluoroscopic examination, organic molecule fluorescent probe have highly sensitive, response is fast, designability and can cut out many special propertys such as connecing property is strong, that therefore researches and develops novel organic molecule fluorescent probe becomes people's technical problem urgently to be resolved hurrily.
In view of this, special proposition the present invention.
Summary of the invention
The first object of the present invention is to provide a kind of fluorescent probe compounds, this compound due to the singularity of its structure, its can with phosphate pesticide or heavy metal ion generation molecular interaction, final realize the object detecting agricultural chemicals or heavy metal ion.Therefore can be used as the fluorescent probe compounds in fluorescence detection method, facilitate organophosphorus pesticide or detection of heavy metal ion.
Another object of the present invention is to provide the preparation method of above-mentioned fluorescent probe compounds, the method with 2-bromoquinoline, 2-ethoxycarbonyl phenylo boric acid etc. for reactant, by controlling reaction conditions and system, achieve the synthesis of 2-(2-methylol) phenylquinoline, for the application of this compound provides the foundation, in addition, the method easy handling, required equipment is also comparatively simple and easy.
The third object of the present invention is to provide the purposes of above-mentioned fluorescent probe compounds.
In order to realize above object, spy of the present invention by the following technical solutions:
This fluorescent probe compounds provided by the invention, its chemical structural formula is:
The name of this compound is called 2-(2-methylol) phenylquinoline, this probe has specific chemical structure, its can with phosphate pesticide or heavy metal ion generation molecular interaction, the fluorescence of detection system is converted, and the final object realizing 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), by 2-bromoquinoline, 2-ethoxycarbonyl phenylo boric acid, cesium carbonate and catalyzer join in DMF solution, stir, obtain reaction mixture;
2), by described reaction mixture concentrate through extraction, washing and drying successively, obtain 2-(2-ethoxycarbonyl) phenylquinoline;
3), by described 2-(2-ethoxycarbonyl) phenylquinoline be added drop-wise in the mixing solutions be made up of lithium aluminum hydride and tetrahydrofuran (THF), continue to be stirred to 2-(2-ethoxycarbonyl) phenylquinoline and react completely, obtain reaction solution;
4), by after described reaction solution ice-water bath cooling, filter after dripping ethyl acetate, and concentrated through rotary evaporation for the filtrate obtained, silica gel column chromatography are purified and after the drip washing of petrol ether/ethyl acetate mixed solution, obtains fluorescent probe compounds.
Optionally, in step 1) in, described catalyzer is dppf palladium chloride.
Dppf palladium chloride, because it has specific chemical structure, therefore can be used as the catalyzer of linked reaction, promotes the generation of 2-(2-ethoxycarbonyl) phenylquinoline.
Optionally, step 1) in: described in be stirred in the protection of nitrogen under carry out.
Nitrogen due to its chemical property comparatively stable, therefore, under the protection of nitrogen, can avoid due to some reactive gass participate in react and cause response path to change.
Optionally, in step 1) in, specifically comprise:
2-bromoquinoline, 2-ethoxycarbonyl phenylo boric acid, cesium carbonate and dppf palladium chloride are joined in described mixed solution under the protection of nitrogen, and carries out stirred liquid in 75-85 DEG C, obtain reaction mixture;
Wherein, the mol ratio of described 2-bromoquinoline, 2-ethoxycarbonyl phenylo boric acid is (2.9-3.1): (3.2-3.4).
In the process building reaction system, strictly to control the used in amounts of each reactant, if usage quantity control is improper, so then can causes building-up reactions failure, cannot product be obtained.Thus, in step 1) in, preferably, the mol ratio of 2-bromoquinoline, 2-ethoxycarbonyl phenylo boric acid is (2.9-3.1): (3.2-3.4).After mixing with mixed solution, in the process of stirring, preferable temperature is 75-85 DEG C, to improve speed of response and to promote to react completely.
Optionally, in step 2) in, specifically comprise:
Described reaction mixture is added containing isopyknic water and EtOAc composition mixed solution in, after separatory, water layer EtOAc is extracted at twice, and after merging organic phase successively with aqueous NaCl wash, use anhydrous Na
2sO
4drying, then concentrate through Rotary Evaporators, obtain 2-(2-ethoxycarbonyl) phenylquinoline.
In the process of synthesis, due to 2-(2-ethoxycarbonyl) phenylquinoline obtained, mostly generally be crude product, and its unstable chemcial property.Therefore, in extraction, washing and dry concentration process, great care is answered.Preferably, in order to improve the productive rate of 2-(2-ethoxycarbonyl) phenylquinoline, first reaction mixture is added in the mixed solution of isopyknic water and EtOAc composition before extraction, after mixing, treat its separatory, and water layer EtOAc extracts (to realize extraction as much as possible completely) at twice, after merging organic phase, successively with aqueous NaCl wash, use anhydrous Na
2sO
4drying, then concentrate through Rotary Evaporators.
Optionally, in step 3) in, specifically comprise:
Described 2-(2-ethoxycarbonyl) phenylquinoline is added drop-wise in the mixing solutions be made up of lithium aluminum hydride and tetrahydrofuran (THF) under temperature is less than the condition of 10 DEG C, reaction system is warming up to room temperature, continue to stir 28-32 hour, treat that 2-(2-ethoxycarbonyl) phenylquinoline reacts completely, obtain reaction solution.
In step 2) in, compound 2-(2-ethoxycarbonyl) phenylquinoline obtained, it is as intermediate, very unstable, and comparatively responsive to temperature, therefore need at low temperatures (being less than 10 DEG C) to be added drop-wise to the mixing solutions be made up of lithium aluminum hydride and tetrahydrofuran (THF); After dropwising, the temperature of reaction system is increased to room temperature, impel reaction to occur, generally speaking, after stirring reaction 28-32 hour, 2-(2-ethoxycarbonyl) phenylquinoline exhausts, and reaction is tending towards complete.
Optionally, in step 4) in, the terminal temperature of described cooling is 0-1 DEG C.
Before filtration, the recurring structure transformation in order to prevent the reaction product in reaction solution unstable; Used by reaction solution ice-water bath to be cooled to 0 DEG C, reaction can be stopped, and keep product structure to stablize.After filtration, filtrate is concentrated through rotary evaporation, silica gel column chromatography is purified and after the drip washing of petrol ether/ethyl acetate mixed solution, is obtained yellow powder fluorescent probe compounds.
Optionally, step 4) in: in described petrol ether/ethyl acetate mixed solution, the volume of sherwood oil and ethyl acetate is (9-10): 1.
After silica gel column chromatography proposes, in order to realize good drip washing effect, in petrol ether/ethyl acetate mixed solution, the volume of sherwood oil and ethyl acetate is (9-10): 1.
For the preparation method of above-mentioned fluorescent probe compounds, i.e. the synthetic method of 2-(2-methylol) phenylquinoline, all response paths are as follows:
Wherein:
A is: 2-bromoquinoline; B is: 2-ethoxycarbonyl phenylo boric acid; C is: 2-(2-ethoxycarbonyl) phenylquinoline; D is: 2-(2-methylol) phenylquinoline.
Described fluorescent probe compounds as detection organophosphorus pesticide, heavy metal ion, especially as detection SD-1750 and Cr
3+organic molecule fluorescent probe compounds in application.
Accompanying drawing explanation
In order to be illustrated more clearly in the specific embodiment of the invention or technical scheme of the prior art, be briefly described to the accompanying drawing used required in embodiment or description of the prior art below, apparently, accompanying drawing in the following describes is some embodiments of the present invention, for those of ordinary skill in the art, under the prerequisite not paying creative work, other accompanying drawing can also be obtained according to these accompanying drawings.
Fig. 1 is the uv-absorbing figure of fluorescent probe compounds provided by the invention after acid adding;
Fig. 2 is the uv-absorbing figure of fluorescent probe compounds provided by the invention after adding Trichlorphon;
Fig. 3 is the fluorescence emission spectrogram after fluorescent probe compounds provided by the invention adds SD-1750;
Fig. 4 is the fluorescence emission spectrogram after fluorescent probe compounds provided by the invention adds Chlorpyrifos 94;
Fig. 5 is the figure that fluorescent probe compounds provided by the invention adds the fluorescence emission spectrum after Rogor;
Fig. 6 is the fluorescence emission spectrogram after fluorescent probe compounds provided by the invention adds omethoate;
Fig. 7 is the fluorescence emission spectrogram after fluorescent probe compounds provided by the invention adds parathion-methyl;
Fig. 8 is after fluorescent probe compounds provided by the invention heating and the fluorescence emission spectrogram of formic acid;
Fig. 9 is the fluorescence emission spectrogram after fluorescent probe compounds provided by the invention adds zinc chloride;
Figure 10 is the fluorescence emission spectrogram after fluorescent probe compounds provided by the invention adds copper sulfate;
Figure 11 is the fluorescence emission spectrogram after fluorescent probe compounds provided by the invention adds chromium chloride;
Figure 12 is the fluorescence emission spectrogram after adding alkali after the first acid adding of fluorescent probe compounds provided by the invention;
Figure 13 is the 1H-NMR collection of illustrative plates of fluorescent probe compounds provided by the invention.
Embodiment
For making the object, technical solutions and advantages of the present invention clearly; clear, complete description is carried out below by technical scheme of the present invention; based on the embodiment in the present invention; other embodiments all that those of ordinary skill in the art obtain under the prerequisite not making creative work, all belong to the scope that the present invention protects.
The preparation method of this fluorescent probe compounds provided by the invention, comprises the following steps:
S1: 2-bromoquinoline, 2-ethoxycarbonyl phenylo boric acid, cesium carbonate and catalyzer are joined in DMF solution, stirs, obtain reaction mixture;
In this step, for constitutional features and the physicochemical property of two kinds of reactants, and then filter out preferred raw material weight proportioning and reaction conditions, as: catalyzer is dppf palladium chloride.Meanwhile, the mol ratio of 2-bromoquinoline, 2-ethoxycarbonyl phenylo boric acid is (2.9-3.1): (3.2-3.4).In addition, in order to prevent some reactive gass from participating in reaction, in the process of stirring reaction, preferably carry out under the protection of the nitrogen of stable in properties.
S2: described reaction mixture is concentrated through extraction, washing and drying successively, obtains 2-(2-ethoxycarbonyl) phenylquinoline;
Preferably, above-mentioned steps 102 can be carried out according to following operation: added by described reaction mixture in the mixed solution formed containing isopyknic water and EtOAc, after separatory, water layer EtOAc (equal with mixeding liquid volume) is extracted at twice, after merging organic phase, uses sodium chloride aqueous solution (volume is 1.5 times of EtOAc) to wash twice, use anhydrous Na successively
2sO
4drying, then concentrate through Rotary Evaporators, obtain 2-(2-ethoxycarbonyl) phenylquinoline.
Through mensuration, by step 2) operation, make the productive rate of compound 2-(2-ethoxycarbonyl) phenylquinoline to reach more than 80%.
S3: be added drop-wise in the mixing solutions be made up of lithium aluminum hydride and tetrahydrofuran (THF) by described 2-(2-ethoxycarbonyl) phenylquinoline, continues to be stirred to 2-(2-ethoxycarbonyl) phenylquinoline and reacts completely, obtain reaction solution.
Preferably, in this step, 2-(2-ethoxycarbonyl) phenylquinoline is added drop-wise in the mixing solutions be made up of lithium aluminum hydride and tetrahydrofuran (THF) under temperature is less than the condition of 10 DEG C, and after dropwising, the temperature of reaction system is increased to room temperature, impels reaction to occur.
S4: after described reaction solution ice-water bath cooling, filter after dripping ethyl acetate, and concentrated through rotary evaporation for the filtrate obtained, silica gel column chromatography are purified and after the drip washing of petrol ether/ethyl acetate mixed solution, obtains fluorescent probe compounds.
In this step, the temperature of reaction system specifically preferably can be cooled to 0 DEG C by ice-water bath cooling, with rapid termination reaction, and prevents product recurring structure from changing.In addition, in the process utilizing the drip washing of petrol ether/ethyl acetate mixed solution, preferably, the volume of sherwood oil and ethyl acetate is (9-10): 1.
Next, in conjunction with above-mentioned content, following specific embodiment is provided to the preparation method of fluorescent probe compounds:
Embodiment one
The first step: by compd A (3.12g, 0.015mol), compd B (3.21g, 0.0165mol), alkali Cs
2cO3 (0.0405mol) and catalyst P d (dppf) Cl
2(0.0008mol), under nitrogen protection, in DMF solution, 80 DEG C of stirrings are spent the night, and obtain reaction mixture.
After reaction mixture cool to room temperature, join in the mixed solution containing 100mL water and 100mLEtOAc.After separatory, water layer 200mL EtOAc is extracted at twice, merge organic phase, wash at twice with the sodium chloride aqueous solution of 300mL, and use anhydrous Na
2sO
4drying, then obtain dark brown oil, i.e. the crude product of Compound C through Rotary Evaporators is concentrated.
Second step: 0 DEG C, under nitrogen protection condition, the lithium aluminum hydride of 1.1g (0.03mol) is mixed with the dried tetrahydrofuran (THF) of 30mL.
Compound C be dissolved in the dried tetrahydrofuran solution of 10mL, control temperature (T<10 DEG C) is added dropwise in reaction vessel.Dropwise, temperature of reaction system is risen to room temperature, continue to stir 30min.With TLC monitoring, when Compound C exhausts, reaction system ice-water bath is cooled to 0 DEG C, dropwise adds 10mL EtOAc and filter.Filtrate rotary evaporation is concentrated, and purifies with silica gel column chromatography, with petrol ether/ethyl acetate=10:1 mixed solution drip washing, obtain yellow powder Compound D (420mg).In addition, the 1H-NMR collection of illustrative plates of compound made of the method as shown in figure 13.
Embodiment two
The first step: by compd A (0.0145mol), compd B (0.016mol), alkali Cs
2cO
3(0.04mol) with catalyst P d (dppf) Cl
2(0.00075mol), under nitrogen protection, in DMF solution, 75 DEG C of stirrings are spent the night, and obtain reaction mixture.
After reaction mixture cool to room temperature, join in the mixed solution containing 100mL water and 100mLEtOAc.After separatory, water layer 200mL EtOAc is extracted at twice, merge organic phase, wash at twice with the sodium chloride aqueous solution of 300mL, and use anhydrous Na
2sO
4drying, then obtain dark brown oil, i.e. the crude product of Compound C through Rotary Evaporators is concentrated.
Second step: 0 DEG C, under nitrogen protection condition, 1g lithium aluminum hydride is mixed with the dried tetrahydrofuran (THF) of 25mL.
Compound C be dissolved in the dried tetrahydrofuran solution of 10mL, control temperature (T<10 DEG C) is added dropwise in reaction vessel.Dropwise, temperature of reaction system is risen to room temperature, continue to stir 28min.With TLC monitoring, when Compound C exhausts, reaction system ice-water bath is cooled to 0 DEG C, dropwise adds 10mL EtOAc and filter.Filtrate rotary evaporation is concentrated, and purifies with silica gel column chromatography, with petrol ether/ethyl acetate=10:1 mixed solution drip washing, obtain yellow powder Compound D.
Embodiment three
The first step: by compd A (0.01505mol), compd B (0.017mol), alkali Cs
2cO
3(0.041mol) with catalyst P d (dppf) Cl
2(0.00085mol), under nitrogen protection, in DMF solution, 85 DEG C of stirrings are spent the night, and obtain reaction mixture.
After reaction mixture cool to room temperature, join in the mixed solution containing 100mL water and 100mLEtOAc.After separatory, water layer 200mL EtOAc is extracted at twice, merge organic phase, wash at twice with the sodium chloride aqueous solution of 300mL, and use anhydrous Na
2sO
4drying, then obtain dark brown oil, i.e. the crude product of Compound C through Rotary Evaporators is concentrated.
Second step: 0 DEG C, under nitrogen protection condition, 1.2g lithium aluminum hydride is mixed through dried tetrahydrofuran (THF) with 35mL.
Compound C be dissolved in the dried tetrahydrofuran solution of 10mL, control temperature (T<10 DEG C) is added dropwise in reaction vessel.Dropwise, temperature of reaction system is risen to room temperature, continue to stir 32min.With TLC monitoring, when Compound C exhausts, reaction system ice-water bath is cooled to 0 DEG C, dropwise adds 10mL EtOAc and filter.Filtrate rotary evaporation is concentrated, and purifies with silica gel column chromatography, with petrol ether/ethyl acetate=10:1 mixed solution drip washing, obtain yellow powder Compound D.
The synthesis result of table 1 various embodiments of the present invention
| 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 A is in above-mentioned all embodiments: 2-bromoquinoline; B is: 2-ethoxycarbonyl phenylo boric acid; C is: 2-(2-ethoxycarbonyl) phenylquinoline; D is: 2-(2-methylol) phenylquinoline.
In addition, the fluorescent probe compounds that the preferred embodiments of the present invention one provide, its methanol solution adds along with acid (HCl), and uv absorption spectra as indicated with 1.
Fig. 1 shows, in the methanol solution of probe-2 (fluorescent probe compounds), along with adding of hydrochloric acid, the absorption peak red shift of probe-2, reason may be because the atom N on quinoline ring has alkalescence, can binding hydrogen ions, thus causes the red shift of probe molecule absorption peak.
In addition, by detecting fluorescent probe compounds provided by the invention, (prepared by embodiment 1, hereinafter referred to as probe-2) change (testing process all adopts conventional fluorescence detection method) of its fluorescence emission peak of (50 DEG C of heating, acid adding, add phosphorous agricultural chemicals, add metal ion etc.) under different conditions, thus verify that it is as the effect in phosphorous agricultural chemicals and part metals ion fluorescence detection probes.
Application examples 1:
Trichlorphon is on the impact of probe-2 fluorescence intensity, and result as shown in Figure 2, is illustrated by Fig. 2,5 × 10
-4add Trichlorphon gradually in the methanol solution of mol/L probe-2, the fluorescent emission change of probe is not obvious, and during heating, change is also not obvious.
Application examples 2:
SD-1750 on the impact of probe-2 fluorescence intensity, result as shown in Figure 3,5 × 10
-4sD-1750 is added gradually in the methanol solution of mol/L probe-2, during beginning, dimethyl dichlorovinyl phosphate content is less, and the fluorescent emission change of probe is not obvious, but when SD-1750 concentration increases to 1.2 μ g/mL, fluorescence emission spectral position there occurs red shift, illustrates that probe has recognition function to SD-1750.
Application examples 3:
Chlorpyrifos 94 is on the impact of probe-2 fluorescence intensity, and as shown in Figure 4, as seen in Figure 4, along with adding of Chlorpyrifos 94, the fluorescent emission change of probe is not obvious, and during heating, change is also not obvious for result.
Application examples 4:
Rogor is on the impact of probe-2 fluorescence intensity, and as shown in Figure 5, as seen in Figure 5, along with adding of Rogor, the fluorescent emission change of probe is not obvious, and during heating, change is also not obvious for result.
Application examples 5:
Omethoate is on the impact of probe-2 fluorescence intensity, and as shown in Figure 6, as seen in Figure 6, along with adding of omethoate, the fluorescent emission change of probe is not obvious, and during heating, change is also not obvious for result.
Application examples 6:
Parathion-methyl on the impact of probe-2 fluorescence intensity, result as shown in Figure 7,5 × 10
-4adding along with parathion-methyl in the methanol solution of mol/L probe-2, the fluorescent emission change of probe is not obvious, and during heating, change is also not obvious.
Application examples 7:
Heating and acid on the impact of probe-2 fluorescence intensity, result as shown in Figure 8,5 × 10
-4the methanol solution of mol/L probe-2 is along with the prolongation of 50 DEG C of heat-up times, the fluorescent emission change of probe is not obvious, but when adding hydrochloric acid, emmission spectrum there occurs obvious red shift, emissive porwer also obviously strengthens, atom N after this explanation adds hydrochloric acid in probe molecule is combined with H atom, cause probe structure to change, thus emmission spectrum also changes thereupon.
Application examples 8:
Different concns zinc chloride is to probe
-2the impact of fluorescence intensity, as shown in Figure 9, as seen in Figure 9, along with adding of zinc chloride, the fluorescent emission change of probe is not obvious for result.
Application examples 9:
Different concns copper sulfate is on the impact of probe-2 fluorescence intensity, and shown in result Figure 10, as can be seen from Figure 10, along with adding of copper sulfate, the fluorescent emission change of probe is not obvious, illustrates that probe-2 pairs of cupric ions do not have recognition reaction.
Application examples 10:
Different concns chromium chloride is on the impact of probe-2 fluorescence intensity, and result as shown in figure 11.As can be seen from Figure 11, along with adding of chromium chloride, the fluorescence emission peak red shift of probe-2, emissive porwer obviously strengthens, and illustrate that the fluorescent emission impact of the existence of chromium on material is comparatively large, this material can be used for detecting Cr
3+existence.
Application examples 11:
HCl and NaOH is to 5 × 10
-4the impact of mol/L probe-2 fluorescence intensity, result as shown in figure 12, wherein, according to absorption peak order from top to bottom, be followed successively by the condition of probe-2 methanol solution, probe-2+ hydrochloric acid 0.016mol/L, probe-2+ hydrochloric acid 0.048mol/L, probe-2+ hydrochloric acid 0.048mol/L+ sodium hydroxide 0.032mol/L, probe-2+ hydrochloric acid 0.048mol/L+ sodium hydroxide 0.064mol/L, probe-2+ hydrochloric acid 0.048mol/L+ sodium hydroxide 0.096mol/L.
As can be seen from Figure 12, along with adding of hydrochloric acid, the fluorescent emission generation red shift of material, and peak shape also there occurs change, become from obvious Two peak emission the shape that main peak adds shoulder seam, this is because exist in probe 2 atom N can with H ionic bond, have impact on the structure of probe 2, thus have impact on the change of its emmission spectrum, energy gap reduces, and launches red shift; Simultaneously in this solution, add sodium hydroxide again, launch collection of illustrative plates and revert to original state gradually, illustrating that material adds sour reaction is a reversible process.
In sum, the preparation method of this fluorescent probe compounds provided by the invention, its processing ease, and productive rate is higher; 2-(2-methylol) phenylquinoline be prepared from, it can be applied to SD-1750, Cr
3+deng fluorescent detection probe.
The foregoing is only the preferred embodiments of the present invention, be not limited to the present invention, for a person skilled in the art, the present invention can have various modifications and variations.Within the spirit and principles in the present invention all, any amendment done, equivalent replacement, improvement etc., all should be included within protection scope of the present invention.
Claims (10)
1. a fluorescent probe compounds, is characterized in that, the name of this compound is called: 2-(2-methylol) phenylquinoline, and its chemical structural formula is:
2. a preparation method for fluorescent probe compounds according to claim 1, is characterized in that, comprises the following steps:
1), by 2-bromoquinoline, 2-ethoxycarbonyl phenylo boric acid, cesium carbonate and catalyzer join in DMF solution, stir, obtain reaction mixture;
2), by described reaction mixture concentrate through extraction, washing and drying successively, obtain 2-(2-ethoxycarbonyl) phenylquinoline;
3), by described 2-(2-ethoxycarbonyl) phenylquinoline be added drop-wise in the mixing solutions be made up of lithium aluminum hydride and tetrahydrofuran (THF), continue to be stirred to 2-(2-ethoxycarbonyl) phenylquinoline and react completely, obtain reaction solution;
4), by after described reaction solution ice-water bath cooling, filter after dripping ethyl acetate, and concentrated through rotary evaporation for the filtrate obtained, silica gel column chromatography are purified and after the drip washing of petrol ether/ethyl acetate mixed solution, obtains fluorescent probe compounds.
3. the preparation method of fluorescent probe compounds according to claim 2, is characterized in that, in step 1) in, described catalyzer is dppf palladium chloride.
4. the preparation method of fluorescent probe compounds according to claim 3, is characterized in that, step 1) in, described in be stirred in the protection of nitrogen under carry out.
5. the preparation method of fluorescent probe compounds according to claim 4, is characterized in that, in step 1) in, specifically comprise:
2-bromoquinoline, 2-ethoxycarbonyl phenylo boric acid, cesium carbonate and dppf palladium chloride are joined in described DMF solution under the protection of nitrogen, and carries out stirred liquid in 75-85 DEG C, obtain reaction mixture;
Wherein, the mol ratio of described 2-bromoquinoline, 2-ethoxycarbonyl phenylo boric acid is (2.9-3.1): (3.2-3.4).
6. the preparation method of fluorescent probe compounds according to claim 5, is characterized in that, in step 2) in, specifically comprise:
Described reaction mixture is added containing isopyknic water and EtOAc composition mixed solution in, after separatory, water layer EtOAc is extracted at twice, and after merging organic phase successively with aqueous NaCl wash, use anhydrous Na
2sO
4drying, then concentrate through Rotary Evaporators, obtain 2-(2-ethoxycarbonyl) phenylquinoline.
7. the preparation method of the fluorescent probe compounds according to any one of claim 2-6, is characterized in that, in step 3) in, specifically comprise:
Described 2-(2-ethoxycarbonyl) phenylquinoline is added drop-wise in the mixing solutions be made up of lithium aluminum hydride and tetrahydrofuran (THF) under temperature is less than the condition of 10 DEG C, reaction system is warming up to room temperature, continue to stir 28-32min, treat that 2-(2-ethoxycarbonyl) phenylquinoline reacts completely, obtain reaction solution.
8. the preparation method of fluorescent probe compounds according to claim 7, is characterized in that, in step 4) in, the terminal temperature of described cooling is 0-1 DEG C.
9. the preparation method of fluorescent probe compounds according to claim 8, is characterized in that, step 4) in:
In described petrol ether/ethyl acetate mixed solution, the volume of sherwood oil and ethyl acetate is (9-10): 1.
10. the application of fluorescent probe compounds according to claim 1 in the organic molecule fluorescent probe as detection organophosphorus pesticide, heavy metal ion.
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| CN105503915B (en) * | 2015-12-16 | 2017-05-03 | 西北大学 | Europium metal-organic framework compound with fluorescent recognition function and preparation method and application |
| CN117304029A (en) * | 2023-09-26 | 2023-12-29 | 山东信发瑞捷新材料科技有限公司 | 4,16- [2.2] cyclophenyl diester and 4- [2.2] cyclophenyl monoester, one-pot synthesis preparation method and application thereof |
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| AASIF HELAL等: ""Fluorescence Sensing Properties of 2-(2"-Hydroxyphenyl)quinoline and Derivatives"", 《BULL. KOREAN CHEM. SOC.》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105503915B (en) * | 2015-12-16 | 2017-05-03 | 西北大学 | Europium metal-organic framework compound with fluorescent recognition function and preparation method and application |
| CN117304029A (en) * | 2023-09-26 | 2023-12-29 | 山东信发瑞捷新材料科技有限公司 | 4,16- [2.2] cyclophenyl diester and 4- [2.2] cyclophenyl monoester, one-pot synthesis preparation method and application thereof |
| CN117304029B (en) * | 2023-09-26 | 2024-04-26 | 山东信发瑞捷新材料科技有限公司 | 4,16- [2.2] Cyclophenyl diester and 4- [2.2] cyclophenyl monoester, one-pot synthesis preparation method and application thereof |
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