CN104876863A - Fluorescent probe compound and preparation method and application thereof - Google Patents

Fluorescent probe compound and preparation method and application thereof Download PDF

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CN104876863A
CN104876863A CN201510287947.XA CN201510287947A CN104876863A CN 104876863 A CN104876863 A CN 104876863A CN 201510287947 A CN201510287947 A CN 201510287947A CN 104876863 A CN104876863 A CN 104876863A
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fluorescent probe
ethoxycarbonyl
preparation
probe compounds
phenylquinoline
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CN104876863B (en
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贾临芳
魏朝俊
赵建庄
梁丹
吴昆明
曲江兰
何文豪
聂晓庆
郭丽媛
李西
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Beijing University of Agriculture
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • 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
    • C07D215/12—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 with substituted hydrocarbon radicals attached to ring carbon atoms
    • C07D215/14—Radicals substituted by oxygen atoms
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
    • G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
    • G01N21/64—Fluorescence; Phosphorescence
    • G01N21/6428—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes"
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/10—Non-macromolecular compounds
    • C09K2211/1018—Heterocyclic compounds

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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 application thereof. The compound is of 8-(2-hydroxymethyl) phenyl quinoline; the preparation method includes adding 8-bromoquinoline, 2-ethoxycarbonyl phenyl boric acid, sodium carbonate and a catalyst into a mixture solution composed of dioxane, ethanol and water, mixing and obtaining a reaction mixture; after extracting, washing, drying and concentrating the reaction mixture and acquiring the 8-(2-hydroxymethyl) phenyl quinoline, dropping the 8-(2-hydroxymethyl) phenyl quinoline into a mixture solution composed of lithium aluminum hydride and tetrahydrofuran, stirring continuously till complete reaction, obtaining the reaction fluid, cooling through iced water, adding ethyl acetate and filtering, and obtaining the finished product after rotary filtrate evaporating and concentrating, silicon column chromatography purifying and leaching. The intermolecular interaction can be performed on the compound and phosphate pesticides or heavy metal ions, and the compound can be applied to organophosphorus pesticide or heavy metal ion detection.

Description

Fluorescent probe compounds and its preparation method and application
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, and this compound is due to the singularity of its structure, and it with phosphate pesticide or heavy metal ion, intermolecular interaction can occur, the final object realizing detection 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 8-bromoquinoline, 2-ethoxycarbonyl phenylo boric acid etc. for reactant, by controlling reaction conditions and system, achieve the synthesis of 8-(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 8-(2-methylol) phenylquinoline, this probe has specific chemical structure, intermolecular interaction can be there is in it with phosphate pesticide or heavy metal ion, 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 8-bromoquinoline, 2-ethoxycarbonyl phenylo boric acid, sodium carbonate and catalyzer join in the mixed solution be made up of diox, second alcohol and water, stir, obtain reaction mixture;
2), by described reaction mixture concentrate through extraction, washing and drying successively, obtain 8-(2-ethoxycarbonyl) phenylquinoline;
3), by described 8-(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 8-(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 tetrakis triphenylphosphine palladium.
Tetrakis triphenylphosphine palladium, because it has specific chemical structure, therefore can be used as the catalyzer of linked reaction, promotes the generation of 8-(2-ethoxycarbonyl) phenylquinoline.
Optionally, step 1) in: in described mixed solution, the volume ratio of diox, second alcohol and water is (3-5): 1:1.
After each reactant and catalyst mix, in order to provide reactive system well, each reactant and catalyzer etc. are joined in the mixed solution formed by diox, second alcohol and water that volume ratio is (3-5): 1:1, be convenient to realize component mixed solution component part on the one hand dissolve each other, be also convenient to itself and each reactant and catalyst mix on the other hand even.
Optionally, in step 1) in, specifically comprise:
8-bromoquinoline, 2-ethoxycarbonyl phenylo boric acid, sodium carbonate and tetrakis triphenylphosphine palladium 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 8-bromoquinoline, 2-ethoxycarbonyl phenylo boric acid, sodium carbonate and tetrakis triphenylphosphine palladium is (2.9-3.1): (3.2-3.4): (8-8.2): (0.15-0.17).
In the process building reaction system, strictly to control the used in amounts of each reactant and catalyzer, if usage quantity control is improper, so then can causes building-up reactions failure, cannot product be obtained.Therefore, in step 1) in, preferably, the mol ratio of 8-bromoquinoline, 2-ethoxycarbonyl phenylo boric acid, sodium carbonate and tetrakis triphenylphosphine palladium is (2.9-3.1): (3.2-3.4): (8-8.2): (0.15-0.17).And, this several material is joined mixed solution and carry out in the process of reacting, cause interference in order to prevent some reactive gass to reaction and destroy, the comparatively stable nitrogen of preferred character of use carries out shielding gas; 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 8-(2-ethoxycarbonyl) phenylquinoline.
In the process of synthesis, due to 8-(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 8-(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 8-(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 8-(2-ethoxycarbonyl) phenylquinoline reacts completely, obtain reaction solution.
In step 2) in, compound 8-(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, 8-(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 scarlet pulpous state 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 8-(2-methylol) phenylquinoline, all response paths are as follows:
Wherein:
A is: 8-bromoquinoline; B is: 2-ethoxycarbonyl phenylo boric acid; C is: 8-(2-ethoxycarbonyl) phenylquinoline; D is: 8-(2-methylol) phenylquinoline;
The application of described fluorescent probe compounds in the organic molecule fluorescent probe as detection organophosphorus pesticide, heavy metal ion.
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 alkali;
Fig. 3 is the fluorescence emission spectrogram after fluorescent probe compounds provided by the invention adds acetone;
Fig. 4 is the fluorescence emission spectrogram after fluorescent probe compounds provided by the invention adds Rogor;
Fig. 5 is the fluorescence emission spectrogram after fluorescent probe compounds provided by the invention adds SD-1750;
Fig. 6 is the fluorescence emission spectrogram after fluorescent probe compounds provided by the invention adds Chlorpyrifos 94;
Fig. 7 is the fluorescence emission spectrogram after fluorescent probe compounds provided by the invention adds parathion-methyl;
Fig. 8 is the fluorescence emission spectrogram after fluorescent probe compounds provided by the invention adds copper sulfate;
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 chromium chloride;
Figure 11 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: 8-bromoquinoline, 2-ethoxycarbonyl phenylo boric acid, sodium carbonate and catalyzer are joined in the mixed solution be made up of diox, second alcohol and water, 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 tetrakis triphenylphosphine palladium; Meanwhile, in mixed solution, the volume ratio of diox, second alcohol and water is (3-5): 1:1.And the mol ratio of 8-bromoquinoline, 2-ethoxycarbonyl phenylo boric acid, sodium carbonate and tetrakis triphenylphosphine palladium is (2.9-3.1): (3.2-3.4): (8-8.2): (0.15-0.17).
S2: described reaction mixture is concentrated through extraction, washing and drying successively, obtains 8-(2-ethoxycarbonyl) phenylquinoline;
Preferably, step 102 can be carried out according to following operation:
Described reaction mixture is added 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, use anhydrous Na successively 2sO 4drying, then concentrate through Rotary Evaporators, obtain 8-(2-ethoxycarbonyl) phenylquinoline.
Through mensuration, by step 2) operation, make the productive rate of compound 8-(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 8-(2-ethoxycarbonyl) phenylquinoline, continues to be stirred to 8-(2-ethoxycarbonyl) phenylquinoline and reacts completely, obtain reaction solution.
Preferably, in this step, 8-(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 Na 2cO 3(4.3g, 0.0405mol) and catalyst P d (PPh 3) 4under (0.95g, 0.0008mol) nitrogen protection, in 90mL (diox: ethanol: water=4:1:1) 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 5.5g, 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 60mL.
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 stirring 30 hours.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 scarlet soup compound D (820mg).In addition, the 1H-NMR collection of illustrative plates of this compound as shown in figure 11.
Embodiment two
The first step: by compd A (0.0145mol), compd B (0.016mol), alkali Na 2cO 3(0.04mol) with catalyst P d (PPh 3) 4(0.00075mol), under nitrogen protection, in 90mL (diox: ethanol: water=3:1:1) 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 55mL.
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 stirring 28 hours.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 scarlet soup compound D.
Embodiment three
The first step: by compd A (0.01505mol), compd B (0.017mol), alkali Na 2cO 3(0.041mol) with catalyst P d (PPh 3) 4(0.00085mol), under nitrogen protection, in 95mL (diox: ethanol: water=4:1:1) 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 65mL.
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 stirring 32 hours.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 scarlet soup compound D.
It is pointed out that A is in above-mentioned all embodiments: 8-bromoquinoline; B is: 2-ethoxycarbonyl phenylo boric acid; C is: 8-(2-ethoxycarbonyl) phenylquinoline; D is: 8-(2-methylol) phenylquinoline.
The synthesis result of table 1 various embodiments of the present invention
Project Embodiment 1 Embodiment 2 Embodiment 3
Product 820mg 816mg 822mg
Yield 23.26％ 23.94％ 23.24％
Purity 96.08％ 96.53％ 95.30％
In addition, the fluorescent probe compounds that the preferred embodiments of the present invention one provide, it is along with acid, the adding of alkali, and uv absorption spectra is as shown in 1 and 2.
Fig. 1 shows, adds the methanol solution of hydrochloric acid in the methanol solution of fluorescent probe compounds (hereinafter referred to as probe-1), finds its absorption peak red shift, and absorption intensity strengthens.Fig. 2 illustrates, add the solution of acid, then add alkali sodium hydroxide, the absorption spectrum of probe-1 can return to original shape again, and it is reversible for illustrating that probe-1 there occurs change under the action of an acid.The generation of this process may have lone-pair electron relevant with the nitrogen-atoms on quinoline ring.
In addition, by detecting fluorescent probe compounds provided by the invention, (prepared by embodiment one, hereinafter referred to as probe-1) fluorescence intensity change (detection method adopt conventional fluorescence detection method) of its (different solvents, potential of hydrogen, phosphorous agricultural chemicals and metal ion) 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:
Acetone is on the impact of probe-1 fluorescence intensity, and result as shown in Figure 3, illustrates, 5 × 10 -4add acetone gradually in the methanol solution of mol/L probe-1, do not find the considerable change of launching collection of illustrative plates, illustrate that the fluorescent emission of acetone to probe-1 does not have a significant effect.
Application examples 2:
Rogor on the impact of probe-1 fluorescence intensity, result as shown in Figure 4,5 × 10 -4add the acetone soln of Rogor in the methanol solution of mol/L probe-1 gradually, the emission spectrum of probe is almost constant.Test the impact on probe-1 of Trichlorphon, thiophos, omethoate and diethyl chloro-phosphate successively, result shows, to add Rogor similar, probe-1 fluorescent emission collection of illustrative plates does not all have considerable change.
Application examples 3:
SD-1750 on the impact of probe-1 fluorescence intensity, result as shown in Figure 5, as seen in Figure 5, along with the add-on of SD-1750 increases gradually, do not affect the fluorescent emission of probe-1 during beginning, along with the increase of add-on, emissive porwer occurs suddenly significantly to weaken; Illustrate that this fluorescent probe compounds may be used in the detection of SD-1750.
Application examples 4:
Chlorpyrifos 94 on the impact of probe-1 fluorescence intensity, result as shown in Figure 6, as seen in Figure 6, along with the add-on of Chlorpyrifos 94 increases gradually, the fluorescent emission of probe-1 first strengthens and weakens afterwards, and along with the increase of add-on, emissive porwer occurs suddenly significantly to weaken.Illustrate that this fluorescent probe compounds may be used in the detection of Chlorpyrifos 94.
Application examples 5:
Parathion-methyl on the impact of probe-1 fluorescence intensity, result as shown in Figure 7, as seen in Figure 7, along with the add-on of first class thiophos increases gradually, do not affect the fluorescent emission of probe-1 during beginning, along with the increase of add-on, emissive porwer occurs suddenly significantly to weaken.Illustrate that this fluorescent probe compounds may be used in the detection of parathion-methyl agricultural chemicals.
Application examples 6:
Copper sulfate on the impact of probe-1 fluorescence intensity, result as shown in Figure 8,5 × 10 -4add the methanol solution of copper sulfate in the methanol solution of mol/L probe-1 gradually, the emission spectrum of probe is almost constant.
Application examples 7:
Zinc chloride on the impact of probe-1 fluorescence intensity, result as shown in Figure 9,5 × 10 -4add the methanol solution of zinc chloride in the methanol solution of mol/L probe-1 gradually, the emission spectrum of probe-1 is at about 500nm, and fluorescent emission slightly increases.Illustrate that this fluorescent probe compounds may be used in the detection of zinc chloride.
Application examples 8:
Chromium chloride on the impact of probe-1 fluorescence intensity, result as shown in Figure 10, as seen in Figure 10,5 × 10 -4the methanol solution of chromium chloride is added gradually in the methanol solution of mol/L probe-1, the fluorescent emission of emission spectrum between 500nm-600nm of probe-1 obviously increases, and weaken at the absorption peak of about 400nm, illustrate that probe-1 pair of chromium chloride has reasonable recognition reaction.
The preparation method of this fluorescent probe compounds provided by the invention, its processing ease, and productive rate is higher; 8-(2-methylol) phenylquinoline be prepared from, it can be applied to SD-1750, Cr 3+deng fluorescent detection probe; Thus overcoming GC common in prior art, the methods such as HPLC and GC-MC detect SD-1750, Chlorpyrifos 94, parathion-methyl agricultural chemicals, zinc chloride, Cr 3+time, there is complicated operation, high and be unfavorable for the defect of onsite application to equipment requirements.
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: 8-(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 8-bromoquinoline, 2-ethoxycarbonyl phenylo boric acid, sodium carbonate and catalyzer join in the mixed solution be made up of diox, second alcohol and water, stir, obtain reaction mixture;
2), by described reaction mixture concentrate through extraction, washing and drying successively, obtain 8-(2-ethoxycarbonyl) phenylquinoline;
3), by described 8-(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 8-(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 tetrakis triphenylphosphine palladium.
4. the preparation method of fluorescent probe compounds according to claim 3, is characterized in that, step 1) in:
In described mixed solution, the volume ratio of diox, second alcohol and water is (3-5): 1:1.
5. the preparation method of fluorescent probe compounds according to claim 4, is characterized in that, in step 1) in, specifically comprise:
8-bromoquinoline, 2-ethoxycarbonyl phenylo boric acid, sodium carbonate and tetrakis triphenylphosphine palladium 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 8-bromoquinoline, 2-ethoxycarbonyl phenylo boric acid, sodium carbonate and tetrakis triphenylphosphine palladium is (2.9-3.1): (3.2-3.4): (8-8.2): (0.15-0.17).
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 8-(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 8-(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 8-(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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