CN104031108B - A kind of fluorescent chemicals and preparation method thereof and the methods and applications utilizing this fluorescent chemicals to prepare sense film - Google Patents
A kind of fluorescent chemicals and preparation method thereof and the methods and applications utilizing this fluorescent chemicals to prepare sense film Download PDFInfo
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Abstract
The invention discloses a kind of fluorescent chemicals and preparation method thereof and the methods and applications utilizing this fluorescent chemicals to prepare sense film, cholesterol and sugared structure are introduced oligomerization phenylacetylene simultaneously, and the hydrophobicity of cholesterol and the wetting ability of sugared structure make again the fluorescent chemicals synthesized have the more assembly behavior of horn of plenty.With the sense film that this compound prepares, there is the microtexture of uniform, controllable, and good stability, long service life, highly sensitive to the identification of hydrogenchloride steam.This kind of film and Commercial optical instrument conbined usage can be realized the Sensitive Detection to hydrogen chloride vapors.In addition, through sense film device, hydrogenchloride steam special detector can also be developed.
Description
Technical field
The invention belongs to fluorescent chemicals preparing technical field, be specifically related to a kind of fluorescent chemicals and preparation method thereof and the methods and applications utilizing this fluorescent chemicals to prepare sense film.
Background technology
Along with increasingly sharpening of global environmental pollution and ecological degradation, environmental problem more and more becomes the important factor of relation mankind life quality, has thus caused the extensive concern of domestic and international scientist to the detection of atmospheric polluting material.Hydrogen chloride gas, as common are harmful gas, has strong impulse effect to eye and respiratory mucosa, and long-term higher concentration contact, can cause chronic bronchitis, gastrointestinal dysfunction and dental erosion etc.; In addition, plant also has certain tolerance limit to hydrogen cloride concentration, once exceed this threshold concentration, the biological cells and tissues organ of plant will come to harm, and physiological function is obstructed with growing, and finally causes death; Meanwhile, in air, hydrogen cloride concentration is too high, also can cause acid rain, thus causes the corrosion of soil acidification and buildings.
MasanobuMatsuguchi group adopts the method for atom transfer radical polymerization to prepare PNIPAM nanoparticle, and be coated on quartz resonator, successfully achieve the sensitive reversible detection to 1ppm hydrogen chloride gas by QCM (Quartz Crystal Microbalance) technology; Aniline and formaldehyde copolymer are obtained nano composite material by Prafull group, and prepare with iron and aluminium doping the film utilizing electrochemical signals to detect hydrogen chloride gas; MyungHwaKim seminar then introduces Trimethylamine in poly-diacetylene, and resulting polymers and polyvinyl alcohol is adulterated and prepare electrostatic spinning, and first passage material fluorescence color changes the Visual retrieval achieved hydrogen chloride gas.Although these methods achieve the Sensitive Detection to hydrogen chloride gas to a certain extent, also Shortcomings part, such as: the time of response is long, selectivity is low, is difficult to device etc.Fluorescence membrane due to its high sensitivity, selectivity and simple to operate, to advantages such as instrument requirements are lower, by increasing for sensor research.Prior art discloses side chain cholesterol being introduced conjugation fluorescence molecule, and this molecule is polymerized with diamines, obtain the polymkeric substance containing cholesterol with fluorescence property, effectively achieve the highly sensitive detection to hydrogen chloride gas.But this film assembling property is poor, and can not reuse, this just hinders its practical application greatly.
Summary of the invention
The object of the present invention is to provide a kind of fluorescent chemicals and preparation method thereof and the method utilizing this fluorescent chemicals to prepare sense film, this fluorescent chemicals possesses the advantage such as supramolecule characteristic and easy assembling, and the sense film thus prepared by this fluorescent chemicals can realize the Sensitive Detection to hydrogenchloride steam.
The present invention is achieved through the following technical solutions:
A kind of fluorescent chemicals, the structural formula of this fluorescent chemicals is as follows:
Wherein, m=0,1 or 2, n=5,8,10 or 12.
A preparation method for fluorescent chemicals, comprises the following steps:
1) under nitrogen protection, sugared pentaacetate and acetic acid hydrazine are dissolved in DMF, stir 2 ~ 4 hours at 50 ~ 60 DEG C, in the reaction solution obtained, add ethyl acetate after washing, collect organic phase, except desolventizing obtains colorless oil, i.e. compound 1;
2) under argon shield, compound 1, Trichloroacetonitrile and cesium carbonate are dissolved in anhydrous methylene chloride in 0 DEG C, 0 DEG C of insulation reaction 1 ~ 3 hour, by the solid filtering that reaction produces, filtrate is condensed into oily matter, and oily matter is carried out pillar layer separation, obtains compound 2;
3) under argon shield, compound 5 and aminoethoxyethanol substituent are dissolved in methylene dichloride, stir 16 ~ 20 hours at 40 ~ 50 DEG C; naturally cool to room temperature, add sodium borohydride, stirring at normal temperature reaction 1 ~ 2 hour; reaction terminates after washing; use dichloromethane extraction again, collect organic phase, then that organic phase is dry and filter; filtrate is removed desolventizing and is carried out pillar layer separation; obtain greenish yellow solid 6, wherein, the structural formula of described compound 5 is:
The structural formula of described aminoethoxyethanol substituent is:
4) under argon shield, greenish yellow solid 6 and compound 2 are dissolved in anhydrous methylene chloride, add trimethylsilyl trifluoromethanesulfonic acid fat, ice bath stirred after 2 ~ 4 hours, washed, with dichloromethane extraction with the sodium bicarbonate aqueous solution that mass concentration is 5%, collect organic phase, then organic phase is dry and filter, filtrate, except the laggard row pillar layer separation of desolventizing, obtains flaxen compound 7;
5) under argon shield; compound 7 is dissolved in the mixed solvent of methyl alcohol and tetrahydrofuran (THF); drip sodium methoxide solution; stirred at ambient temperature 4 ~ 6 hours; adding acidic cation-exchange resin to reaction solution is neutrality, obtains mixed solution, by this mixed solution except the laggard row pillar layer separation of desolventizing; obtain greenish yellow solid, i.e. fluorescent chemicals.
Step 1) in, the mol ratio of sugared pentaacetate, acetic acid hydrazine and DMF is 1:(1 ~ 1.3).
Described sugared pentaacetate is β-D alpha-glucose pentaacetate, α-D alpha-glucose pentaacetate, β-D semi-lactosi pentaacetate, β-L semi-lactosi pentaacetate or α-D Mannose pentaacetate.
Step 2) in, the mol ratio of compound 1, Trichloroacetonitrile and cesium carbonate is 1:(2 ~ 4): (0.2 ~ 0.4); Step 2) described in pillar layer separation adopt ethyl acetate: the eluent that the volume ratio mixing of sherwood oil=1:1 is obtained is separated.
Step 3) in, the mol ratio of compound 5, aminoethoxyethanol substituent and sodium borohydride is 1:(2.5 ~ 4): (3 ~ 5); Step 3) described in pillar layer separation adopt methylene dichloride: the eluent that the volume ratio mixing of methyl alcohol=10:1 is obtained is separated.
Step 4) in, the mol ratio of compound 6, compound 2 and trimethylsilyl trifluoromethanesulfonic acid fat is 1:(2 ~ 4): (0.1 ~ 0.3); Step 4) described pillar layer separation employing methylene dichloride: the eluent that the volume ratio mixing of methyl alcohol=15:1 is obtained is separated.
Step 5) in, in compound 7, sodium methoxide solution, the mol ratio of sodium methylate, methyl alcohol and tetrahydrofuran (THF) is 1:(0.8 ~ 1.6): (500 ~ 600): (100 ~ 150); Step 5) described pillar layer separation employing methylene dichloride: the eluent that the volume ratio mixing of methyl alcohol=4:1 is obtained is separated.
Adopt fluorescent chemicals to prepare a method for fluorescence sense film, comprise the following steps:
1) fluorescent chemicals is dissolved in trichloromethane, makes the storing solution that concentration is 0.18mg/mL ~ 1.80mg/mL;
2) in relative humidity be 60% ~ 75% atmosphere under, be that the storing solution of 0.18mg/mL ~ 1.80mg/mL is coated in clean glass matrix surface uniformly by concentration, leave standstill 20 ~ 60min, obtained fluorescence sense film.
A kind of fluorescence sense film is preparing the application in fluorescence sense device.
Compared with prior art, the present invention has following useful technique effect:
The synthetic method of fluorescent chemicals of the present invention, introduces oligomerization phenylacetylene by cholesterol and sugared structure simultaneously.Wherein cholesterol has the advantages such as rigid-skeleton, multichiral center and strong Van der Waals accumulation; Sugar structure then has multiple hydrogen bonding sites and good biocompatibility.Fluorescent chemicals prepared in the present invention introduces cholesterol and sugared structure in oligomerization phenylacetylene simultaneously, this just not give only the above-mentioned all supramolecule characteristics of target compound, more because of the hydrophobicity of cholesterol and the wetting ability of sugared structure made this compound have the more assembly behavior of horn of plenty.With the fluorescence sense film that this compound prepares, there is the microtexture of uniform, controllable, and good stability, long service life, highly sensitive to the identification of hydrogen chloride vapors, what is more important, detect completely reversibility, this has just laid solid foundation for it for the preparation of fluorescence sense device.This kind of film and Commercial optical instrument conbined usage can be realized the Sensitive Detection to environment hydrogen chloride gas, in addition, by sense film device, also can develop hydrogen chloride gas special detector.
Accompanying drawing explanation
Fig. 1 is the excitation-emission spectrogram of the fluorescence sense film that the present invention obtains;
Fig. 2 is the micro-structure diagram of fluorescence sense film;
Fig. 3 is the fluorescence sense figure of fluorescence sense film in different concns hydrogen chloride gas;
Fig. 4 is the recovery of fluorescence sense film to hydrogen chloride gas;
Fig. 5 is that different sour gas and common solvents steam are to the quencher efficiency diagram of film fluorescence;
Fig. 6 is the mass spectrum of the fluorescent chemicals that the embodiment of the present invention 1 obtains.
Embodiment
Below in conjunction with specific embodiment, the present invention is described in further detail, and the explanation of the invention is not limited.
The preparation method of fluorescent chemicals of the present invention, comprises the following steps:
1, compound 5 (be specifically the Chinese invention patent of CN102604140A see publication number) is prepared
1. the iodo-Isosorbide-5-Nitrae-two of 2,5-bis-(methoxyl group)-benzene is synthesized
Under nitrogen protection, to the mixture adding iodine, Potassium Iodate and water and the vitriol oil in the acetum of anisole respectively; 80 DEG C are reacted 8 ~ 12 hours, and suction filtration, vacuum-drying, obtains white solid, i.e. 2,5-bis-iodo-Isosorbide-5-Nitrae-two (methoxyl group)-benzene.Wherein, be 1:(0.8 ~ 1.2 to the mol ratio of anisole, iodine, Potassium Iodate, water and the vitriol oil): (0.2 ~ 0.6): (150 ~ 190): (1 ~ 3).Its reaction equation is as follows:
2. the iodo-Isosorbide-5-Nitrae-two of 2,5-bis-(hydroxyl)-benzene is synthesized
Under nitrogen protection, iodo-for 2,5-bis-Isosorbide-5-Nitrae-two (methoxyl group)-benzene is dissolved in methylene dichloride, and under-78 DEG C of conditions, in solution, drips boron tribromide; Reaction stirring 14 ~ 18 hours, suction filtration, vacuum-drying, obtains white solid, i.e. 2,5-bis-iodo-Isosorbide-5-Nitrae-two (hydroxyl)-benzene.Wherein, the mol ratio of the iodo-Isosorbide-5-Nitrae-two of 2,5-bis-(methoxyl group)-benzene, boron tribromide and methylene dichloride is 1:(2 ~ 4): (30 ~ 50).Its reaction equation is as follows:
3. synthetic compound 3
Under argon shield; cholesterol, dibromo substituted straight chain alkane and potassium hydroxide are dissolved in anhydrous tetrahydro furan; react 14 ~ 18 hours at 80 DEG C; rotary evaporation is except desolventizing; be washed to neutrality; recrystallizing methanol, finally uses methylene dichloride: sherwood oil=1:1 carries out pillar layer separation, obtains white solid.Wherein the mol ratio of cholesterol, dibromo substituted straight chain alkane, potassium hydroxide and tetrahydrofuran (THF) is 1:(4 ~ 6): (3 ~ 7): (30 ~ 50).Reaction equation is:
In formula, the value of n is 5 or 8 or 10 or 12.
4. synthetic compound 4
Under argon shield, iodo-for compound 3,2,5-bis-Isosorbide-5-Nitrae-two (hydroxyl)-benzene, salt of wormwood are dissolved in anhydrous DMF, react 14 ~ 18 hours at 160 DEG C.Reaction terminates, and is poured into by solution in large water gaging and separates out precipitation, suction filtration, vacuum-drying, with methylene dichloride: sherwood oil=3:2 carries out pillar layer separation, obtains white solid.Wherein, the mol ratio of the iodo-Isosorbide-5-Nitrae-two of 2,5-bis-(hydroxyl)-benzene, compound 3, salt of wormwood and DMF is 1:(2 ~ 4): (20 ~ 30): (150 ~ 180).Reaction equation is:
5. synthetic compound 5
Under argon shield, by compound 4, be dissolved in anhydrous Diisopropylamine and dry toluene to alkynyl phenyl aldehyde, cuprous iodide, tetraphenylphosphonium palladium, react 10 ~ 14 hours at 70 DEG C.After reaction terminates, be cooled to room temperature, washing dichloromethane extraction, collect organic phase, rotary evaporation is to remove solvent.Resulting brown oil recrystallizing methanol obtains yellow solid, with methylene dichloride: methyl alcohol=100:1 carries out pillar layer separation, obtains greenish yellow solid, i.e. compound 5.Wherein, compound 4, to the mol ratio of alkynyl phenyl aldehyde, cuprous iodide, tetraphenylphosphonium palladium, Diisopropylamine and toluene be: 1:(2 ~ 4): (0.04 ~ 0.06): (0.04 ~ 0.06): (40 ~ 60): (60 ~ 80).Reaction equation is:
Preferably, the step of synthesis 2,5-bis-iodo-Isosorbide-5-Nitrae-two (methoxyl group)-benzene 1. in, be 1:0.4:1:170:2 to the mol ratio of anisole and Potassium Iodate, iodine, Glacial acetic acid, sulfuric acid;
Preferably, the step of synthesis 2,5-bis-iodo-Isosorbide-5-Nitrae-two (hydroxyl)-benzene 2. in, the mol ratio of 2,5-bis-iodo-Isosorbide-5-Nitrae-two (methoxyl group)-benzene and boron tribromide, methylene dichloride is 1:3:40;
Preferably, synthetic compound 3 step 3. in, the mol ratio of cholesterol and potassium hydroxide, dibromo substituted straight chain alkane, tetrahydrofuran (THF) is 1:5:5:40;
Preferably, synthetic compound 4 step 4. in, the mol ratio of 2,5-bis-iodo-Isosorbide-5-Nitrae-two (hydroxyl)-benzene and compound 3, salt of wormwood, DMF is 1:3:25:170;
Preferably, synthetic compound 5 step 5. in, compound 4 be 1:3:0.05:0.05:50:70 to the mol ratio of ethynylbenzaldehyde, tetraphenylphosphonium palladium, cuprous iodide, Diisopropylamine, toluene;
2, fluorescent chemicals is prepared
6. synthetic compound 1
Under nitrogen protection, sugared pentaacetate and acetic acid hydrazine are dissolved in DMF, in 55 DEG C of reactions 2 ~ 4 hours.Reaction terminates, in reaction solution, add ethyl acetate, by massive laundering, collects organic phase, except desolventizing obtains colorless oil.Wherein, the mol ratio of sugared pentaacetate, acetic acid hydrazine and DMF is 1:(1 ~ 1.3): (50 ~ 70), reaction equation is as follows:
7. synthetic compound 2
Under argon shield, compound 1, Trichloroacetonitrile and cesium carbonate are dissolved in anhydrous methylene chloride in 0 DEG C.Ice bath stirs 1 ~ 3 hour, and by the solid filtering that reaction produces, filtrate rotary evaporation, gained oily matter is with ethyl acetate: sherwood oil=1:1 is that post crossed by developping agent, obtains pale yellow oil.Wherein the mol ratio of compound 1, Trichloroacetonitrile, cesium carbonate and methylene dichloride is 1:(2 ~ 4): (0.2 ~ 0.4): (40 ~ 70), reaction equation is as follows:
8. synthetic compound 6
Under argon shield, be dissolved in methylene dichloride by compound 5 and aminoethoxyethanol substituent, 45 DEG C are reacted 16 ~ 20 hours.Naturally cool to room temperature, add sodium borohydride, stirring at normal temperature 1 hour, rotary evaporation, with except desolventizing, washes dichloromethane extraction, collects organic phase, anhydrous MgSO
4drying, filters, by filtrate rotary evaporation, and gained solid with methylene chloride: methyl alcohol=10:1 carries out pillar layer separation as developping agent, obtains greenish yellow solid.Wherein, the mol ratio of compound 5, aminoethoxyethanol substituent, sodium borohydride and methylene dichloride is 1:(2.5 ~ 4): (3 ~ 5): (140 ~ 180).Reaction equation is:
Wherein the value of m is 0 or 1 or 2, n=5,8,10 or 12.
9. synthetic compound 7
Under argon shield, be dissolved in anhydrous methylene chloride by compound 6 and compound 2, carefully add trimethylsilyl trifluoromethanesulfonic acid fat, ice bath stirs 2 ~ 4 hours.Reaction terminates, and washes, dichloromethane extraction with 5% sodium bicarbonate aqueous solution, collects organic phase, anhydrous MgSO
4drying, filters, by filtrate rotary evaporation, and gained solid with methylene chloride: methyl alcohol=15:1 crosses post, obtains faint yellow solid, i.e. compound 7.Wherein, the mol ratio of compound 6, compound 2, trimethylsilyl trifluoromethanesulfonic acid fat and methylene dichloride is 1:(2 ~ 4): (0.1 ~ 0.3): (130 ~ 150).Reaction equation is:
10. fluorescent chemicals is synthesized
Under argon shield, be dissolved in by compound 7 in the mixed solvent of methyl alcohol and tetrahydrofuran (THF), drip sodium methoxide solution, the concentration of sodium methoxide solution is 0.2mmol/mL; Stirring at room temperature 4 ~ 6 hours, add acidic cation-exchange resin to reaction solution for neutral, by mixed solution rotary evaporation, gained solid with methylene chloride: methyl alcohol=4:1 is that post crossed by developping agent, obtains greenish yellow solid, i.e. target product fluorescent chemicals.Wherein, the mol ratio of compound 7, sodium methylate, methyl alcohol, tetrahydrofuran (THF) is 1:(0.8 ~ 1.6): (500 ~ 600): (100 ~ 150).Reaction equation is:
Preferably, the step of synthetic compound 1 6. in, the mol ratio of sugared pentaacetate, acetic acid hydrazine and DMF is 1:1.1:60;
Preferably, the step of synthetic compound 2 7. in, the mol ratio of compound 1, Trichloroacetonitrile, cesium carbonate and methylene dichloride is 1:3:0.3:50;
Preferably, synthetic compound 6 step 8. in, the mol ratio of compound 5,2-(2-amino ethoxy) ethanol, sodium borohydride and methylene dichloride is 1:3:4:160;
Preferably, the step of synthetic compound 7 9. in, the mol ratio of compound 6, compound 2, trimethylsilyl trifluoromethanesulfonic acid fat and methylene dichloride is 1:3:0.2:140;
Preferably, the step of synthesis target product fluorescent chemicals 10. in, the mol ratio of compound 7, sodium methylate, methyl alcohol, tetrahydrofuran (THF) is 1:1.1:540:135.
3, the method for fluorescence sense film is prepared
Fluorescent chemicals is dissolved in trichloromethane, is prepared into the storing solution of 0.18mg/mL ~ 1.80mg/mL.Get 30 ~ 50 μ L storing solutions under the atmosphere of relative humidity 60% ~ 75%, be evenly coated in clean glass matrix surface, place and within 20 ~ 60 minutes, treat that its solvent evaporates is complete, sealing is preserved, and prepares fluorescence sense film.
Preferably, fluorescent chemicals is dissolved in trichloromethane, is prepared into the storing solution of 1.80mg/mL.Get 30 μ L storing solutions at every turn under the atmosphere of relative humidity 75%, be evenly coated in clean glass matrix surface, place and within 20 ~ 60 minutes, treat that its solvent evaporates is complete, sealing is preserved, and prepares fluorescence sense film.
Embodiment 1
1, preparation contains the fluorescent chemicals of cholesterol and sugared structure
1. the iodo-Isosorbide-5-Nitrae-two of 2,5-bis-(methoxyl group)-benzene is synthesized
Under nitrogen protection, in 140mL acetum, the aqueous sulfuric acid 15mL of 2.0g to anisole, 4.0g iodine, 1.22g Potassium Iodate and massfraction 10% is added respectively.80 DEG C are stirred 10 hours, and by a large amount of solid suction filtrations produced, vacuum-drying, obtains white solid, i.e. 2,5-bis-iodo-Isosorbide-5-Nitrae-two (methoxyl group)-benzene.Wherein to the mol ratio 1:1:0.4:170:2 of anisole, iodine, Potassium Iodate, acetic acid and the vitriol oil;
2. the iodo-Isosorbide-5-Nitrae-two of 2,5-bis-(hydroxyl)-benzene is synthesized
Under nitrogen protection, iodo-for 7.8g2,5-bis-Isosorbide-5-Nitrae-two (methoxyl group)-benzene is dissolved in 50mL methylene dichloride, and under-78 DEG C of conditions, in solution, drips 5.58mL boron tribromide.After being added dropwise to complete, stirring at room temperature 16 hours, by a large amount of solid suction filtrations produced, vacuum-drying, obtains white solid, is the iodo-Isosorbide-5-Nitrae-two of 2,5-bis-(hydroxyl)-benzene.Wherein, the mol ratio of the iodo-Isosorbide-5-Nitrae-two of 2,5-bis-(methoxyl group)-benzene, boron tribromide and methylene dichloride is 1:3:40;
3. synthetic compound 3
Under argon shield, by 6.0g cholesterol, 21.0g1,8-bis-bromooctane and 4.4g potassium hydroxide are dissolved in 50mL anhydrous tetrahydro furan, stir 16 hours at 80 DEG C, and rotary evaporation is except desolventizing, washing dichloromethane extraction, rotary evaporation obtains yellow oil, recrystallizing methanol, with methylene dichloride: sherwood oil=1:1 carries out pillar layer separation, obtain white solid, be compound 3; Wherein, the mol ratio of cholesterol, 1,8-bis-bromooctane, potassium hydroxide and tetrahydrofuran (THF) is 1:5:5:40;
4. synthetic compound 4
Under argon shield, 4.0g compound 3, the iodo-Isosorbide-5-Nitrae of 0.85g2,5-bis--two (hydroxyl)-benzene, 8.0g salt of wormwood are dissolved in the anhydrous DMF of 30mL, stir 16 hours at 160 DEG C.Reaction terminates, and is poured into water by solution, has a large amount of Precipitation, suction filtration, vacuum-drying, with methylene dichloride: sherwood oil=3:2 carries out pillar layer separation, obtains white solid, i.e. compound 4; Wherein, the mol ratio of the iodo-Isosorbide-5-Nitrae-two of 2,5-bis-(hydroxyl)-benzene, compound 3, salt of wormwood and DMF is 1:3:25:170;
5. synthetic compound 5
Under argon shield, 1.5g compound 4,0.43g are dissolved in the anhydrous Diisopropylamine of 7.8mL and 8.2mL dry toluene to ethynylbenzaldehyde, 0.01g cuprous iodide, 0.064g tetraphenylphosphonium palladium, stir 12 hours at 70 DEG C.After reaction terminates, be cooled to room temperature, washing dichloromethane extraction, by organic phase rotary evaporation, recrystallizing methanol, gained yellow solid methylene dichloride: methyl alcohol=100:1 carries out pillar layer separation, obtains greenish yellow solid, is compound 5; Wherein compound 4, to the mol ratio of ethynylbenzaldehyde, cuprous iodide, tetraphenylphosphonium palladium, Diisopropylamine and toluene be: 1:3:0.05:0.05:50:70;
6. synthetic compound 1
Under nitrogen protection, 4.0g β-D-Glucose pentaacetate and 0.99g acetic acid hydrazine are dissolved in 47mLN, in dinethylformamide, stir 3 hours in 55 DEG C.Reaction terminates, washing extraction into ethyl acetate, and collect organic phase, rotary evaporation obtains colorless oil, is compound 1; Wherein, the mol ratio of β-D alpha-glucose pentaacetate, acetic acid hydrazine and DMF is 1:1.1:60;
7. synthetic compound 2
Under argon shield, 1.5g compound 1,1.85g Trichloroacetonitrile and 0.42g cesium carbonate are dissolved in 13.7mL anhydrous methylene chloride in 0 DEG C.Condition of ice bath stirs 3 hours, by solid filtering, and filtrate rotary evaporation, gained oily matter ethyl acetate: sherwood oil=1:1 is that post crossed by developping agent, obtains pale yellow oil, is compound 2; Wherein the mol ratio of compound 1, Trichloroacetonitrile, cesium carbonate and methylene dichloride is 1:3:0.3:50;
8. synthetic compound 6
Under argon shield, by 0.8g compound 5 and 0.186g2-(2-amino ethoxy) dissolve with ethanol in 6mL methylene dichloride, 45 DEG C are stirred 10 hours.Naturally cool to room temperature, add 0.09g sodium borohydride, stirring at normal temperature 1 hour.Wash reaction solution with water dichloromethane extraction, collect organic phase, anhydrous MgSO
4drying, filters, and filtrate rotary evaporation is also with methylene dichloride: methyl alcohol=10:1 carries out pillar layer separation as developping agent, obtains greenish yellow solid, is compound 6.Wherein, the mol ratio of compound 5,2-(2-amino ethoxy) ethanol, sodium borohydride and methylene dichloride is: 1:3:4:160;
9. synthetic compound 7
Under argon shield, be dissolved in 3mL anhydrous methylene chloride by 0.5g compound 6 and 0.5g compound 2, carefully add 0.014g trimethylsilyl trifluoromethanesulfonic acid fat, condition of ice bath stirs 3 hours.Reaction terminates, and washes, dichloromethane extraction with 5% sodium bicarbonate aqueous solution, collects organic phase, anhydrous MgSO
4drying, filters, by filtrate rotary evaporation, and gained solid with methylene chloride: methyl alcohol=15:1 crosses post, obtains faint yellow solid.Wherein, the mol ratio of compound 6, compound 2, trimethylsilyl trifluoromethanesulfonic acid fat and methylene dichloride is 1:3:0.2:140;
10. target product is synthesized---fluorescent chemicals
Under argon shield; 0.2g compound 7 is dissolved in the mixed solvent of 2mL methyl alcohol and 1mL tetrahydrofuran (THF); add sodium methylate 0.0070g; stirring at room temperature 5 hours; add acidic cation-exchange resin to reaction solution for neutral; by mixed solution rotary evaporation also with methylene dichloride: methyl alcohol=4:1 is that post crossed by developping agent, obtains greenish yellow solid, fluorescent chemicals.Wherein the mol ratio of compound 7, sodium methylate, methyl alcohol, tetrahydrofuran (THF) is 1:1.2:540:135.
The fusing point of obtained fluorescent chemicals is: 93-95 DEG C.
Ir data is IR (KBr, cm
-1): 3438,2935,1052.
Mass spectrum MS (ESI, m/2z): calculated value: 931.6532, measured value: 931.6533.
Fig. 6 is the mass spectrogram of fluorescent chemicals, as can be seen from the X-coordinate of spectrogram, actually records nuclear-cytoplasmic ratio and theoretical value is basically identical, illustrates and obtain target product fluorescent chemicals.
2, fluorescence sense film is prepared
Fluorescent chemicals is dissolved in trichloromethane, is prepared into the storing solution of 1.80mg/mL.Get 30 μ L storing solutions under the atmosphere of relative humidity 75%, be evenly coated in clean glass matrix surface, place and within 30 minutes, treat that its solvent evaporates is complete, sealing is preserved, and prepares fluorescence sense film.
3, proof test:
The detection of function fluorescent chemicals to hydrogen chloride gas containing cholesterol, β-D glucose synthesized in embodiment 1 is explored.
Accompanying drawing 1 is the excitation-emission spectrogram of fluorescent chemicals, and wherein a is excitation spectrum, and b is emmission spectrum.As seen from the figure, maximum excitation wavelength is 375nm, and maximum emission wavelength is 494nm.
Accompanying drawing 2 is the assembling assumption diagram of the fluorescence sense film that embodiment 1 obtains, and the shows fluorescent microscopy images that (a) is film, (b) is its scanning electron microscope (SEM) photograph.As seen from the figure, film by packaging assembly evenly and have and form compared with the ball-like structure of bigger serface, this just make film and analysans can large, the permeability of contact area well, for its Sensitive Detection has established solid foundation.
Accompanying drawing 3 is that the obtained fluorescence sense film of embodiment 1 is to the fluorescence sense figure of hydrogen chloride gas.Detect hydrogen cloride concentration used and be respectively 4.4ppb, 8.8ppb, 13.2ppb, 17.6ppb, 22.0ppb, 26.4ppb, 30.8ppb, 35.2ppb, 44.0ppb, 52.8ppb, 61.6ppb, 79.2ppb.In figure, curve a is blank, the fluorescent emission intensity curve of curve b to be chlorine hydride gas concentration be 4.4ppb, the fluorescent emission intensity curve of curve c to be chlorine hydride gas concentration be 8.8ppb, the fluorescent emission intensity curve of curve d to be chlorine hydride gas concentration be 13.2ppb, the fluorescent emission intensity curve of curve e to be chlorine hydride gas concentration be 17.6ppb, the fluorescent emission intensity curve of curve f to be chlorine hydride gas concentration be 22.0ppb, the fluorescent emission intensity curve of curve g to be chlorine hydride gas concentration be 26.4ppb, the fluorescent emission intensity curve of curve h to be chlorine hydride gas concentration be 30.8ppb, the fluorescent emission intensity curve of curve i to be chlorine hydride gas concentration be 52.8ppb.Show the increase along with hydrogen cloride concentration by figure, film fluorescence intensity is by remarkable quencher.When hydrogen chloride gas is 4.4ppb, film fluorescence quencher degree just reaches 24%, and when hydrogen cloride concentration reaches 52.8ppb, fluorescence intensity no longer reduces, and quencher degree reaches maximum.
Accompanying drawing 4 is that fluorescence sense film is verified the recovery of hydrogen chloride gas.44.0ppb, 88.0ppb, 880.0ppb, 15.4ppm, 154.0ppm, 616.0ppm, 1540.0ppm and saturated hydrogen chloride vapors is selected to carry out quencher to film respectively, then reply with saturated ammonia, result shows that film can recover initial fluorescence intensity, has good reversibility.
Accompanying drawing 5 be the obtained fluorescence sense film of embodiment 1 to the quencher efficiency diagram of the steams such as hydrogenchloride and formic acid, acetic acid, methylene dichloride, tetrahydrofuran (THF), wherein hydrogen chloride gas used concentration is 66.0ppb, and other gas concentration is 66.0ppm.As seen from the figure, this film can realize the selective enumeration method to hydrogen chloride vapors.
Comprehensive above proof test can be found out, the fluorescence sense film that the present invention obtains possesses good fluorescence characteristic, has the microtexture of uniform, controllable, highly sensitive to hydrogen chloride vapors identification, and detects reversible, therefore, is highly suitable for preparing fluorescence sense device.
Embodiment 2
1. the iodo-Isosorbide-5-Nitrae-two of 2,5-bis-(methoxyl group)-benzene is synthesized
Under nitrogen protection, add the aqueous sulfuric acid 15mL of 2.0g to anisole, 3.2g iodine, 1.22g Potassium Iodate and massfraction 10% in 140mL acetum respectively, 80 DEG C are stirred 10 hours.By a large amount of solid suction filtrations produced, vacuum-drying, obtains white solid.Be wherein 1:0.8:0.4:170:2 to the mol ratio of anisole, iodine, Potassium Iodate, acetic acid and the vitriol oil;
2. the iodo-Isosorbide-5-Nitrae-two of 2,5-bis-(hydroxyl)-benzene is become
Under nitrogen protection, iodo-for 7.8g2,5-bis-Isosorbide-5-Nitrae-two (methoxyl group)-benzene is dissolved in 50mL methylene dichloride, and under-78 DEG C of conditions, in solution, drips 3.72mL boron tribromide.By a large amount of solid suction filtrations produced, vacuum-drying, obtains white solid, is the iodo-Isosorbide-5-Nitrae-two of 2,5-bis-(hydroxyl)-benzene.Wherein the mol ratio of 2,5-bis-iodo-Isosorbide-5-Nitrae-two (methoxyl group)-benzene, boron tribromide and methylene dichloride is 1:2:40;
3. synthetic compound 3
Under argon shield, by 6.0g cholesterol, 12.6g1,8 two bromooctanes and 4.4g potassium hydroxide are dissolved in 50mL anhydrous tetrahydro furan, react 16 hours at 80 DEG C.Rotary evaporation is except desolventizing, and washing dichloromethane extraction, rotary evaporation obtains yellow oil, recrystallizing methanol, with methylene dichloride: sherwood oil=1:1 carries out pillar layer separation, obtains white solid.Wherein cholesterol, 1, the mol ratio of 8 two bromooctanes, potassium hydroxide and tetrahydrofuran (THF) is 1:3:5:40;
4. synthetic compound 4
Under argon shield, 2.67g compound 3, the iodo-Isosorbide-5-Nitrae of 0.85g2,5-bis--two (hydroxyl)-benzene, 8.0g salt of wormwood are dissolved in the anhydrous DMF of 30mL, react 16 hours at 160 DEG C.Reaction terminates, and is poured into water by solution, has a large amount of Precipitation, suction filtration, vacuum-drying, with methylene dichloride: sherwood oil=3:2 carries out pillar layer separation, obtains white solid.Wherein the mol ratio of 2,5-bis-iodo-Isosorbide-5-Nitrae-two (hydroxyl)-benzene, compound 3, salt of wormwood and DMF is 1:2:25:170;
5. synthetic compound 5
Under argon shield, 1.5g compound 4,0.29g are dissolved in the anhydrous Diisopropylamine of 7.8mL and 8.2mL dry toluene alkynyl phenyl aldehyde, 0.01g cuprous iodide, 0.064g tetraphenylphosphonium palladium.React 12 hours at 70 DEG C.After reaction terminates, be cooled to room temperature, washing dichloromethane extraction, by organic phase rotary evaporation, recrystallizing methanol, gained yellow solid methylene dichloride: methyl alcohol=100:1 carries out pillar layer separation, obtains greenish yellow solid.Wherein compound 4, to the mol ratio of ethynylbenzaldehyde, cuprous iodide, tetraphenylphosphonium palladium, Diisopropylamine and toluene be: 1:2:0.05:0.05:50:70;
6. synthetic compound 1
Under nitrogen protection, 4g β-D alpha-glucose pentaacetate and 0.9g acetic acid hydrazine are dissolved in 47mLN, in dinethylformamide, in 55 DEG C of reactions 3 hours.Reaction terminates, and washing extraction into ethyl acetate, collect organic phase, rotary evaporation obtains colorless oil.Wherein the mol ratio of β-D alpha-glucose pentaacetate, acetic acid hydrazine and DMF is 1:1:60;
7. synthetic compound 2
Under argon shield, 1.5g compound 1,1.23g Trichloroacetonitrile and 0.42g cesium carbonate are dissolved in 13.7mL anhydrous methylene chloride in 0 DEG C.Ice bath stirs 3 hours, by solid filtering, and filtrate rotary evaporation, gained oily matter ethyl acetate: sherwood oil=1:1 is that post crossed by developping agent, obtains pale yellow oil.Wherein the mol ratio of compound 1, Trichloroacetonitrile, cesium carbonate and methylene dichloride is 1:2:0.3:50;
8. synthetic compound 6
Under argon shield, by 0.8g compound 5 and 0.124g2-(2-amino ethoxy) dissolve with ethanol in 6mL methylene dichloride, 45 DEG C of reactions 10 hours.Naturally cool to room temperature, add 0.09g sodium borohydride, stirring at normal temperature 1 hour.Wash reaction solution with water dichloromethane extraction, collect organic phase, anhydrous MgSO
4drying, filters, and filtrate rotary evaporation is also with methylene dichloride: methyl alcohol=10:1 carries out pillar layer separation as developping agent, obtains greenish yellow solid.Wherein the mol ratio of compound 5,2-(2-amino ethoxy) ethanol, sodium borohydride and methylene dichloride is: 1:2:4:160;
9. synthetic compound 7
Under argon shield, be dissolved in 3mL anhydrous methylene chloride by 0.5g compound 6 and 0.33g compound b, carefully add 0.014g trimethylsilyl trifluoromethanesulfonic acid fat, ice bath stirs 3 hours.Reaction terminates, and washes, dichloromethane extraction with 5% sodium bicarbonate aqueous solution, collects organic phase, anhydrous MgSO
4drying, filters, by filtrate rotary evaporation, and gained solid with methylene chloride: methyl alcohol=15:1 crosses post, obtains faint yellow solid.Wherein the mol ratio of compound 6, compound 2, trimethylsilyl trifluoromethanesulfonic acid fat and methylene dichloride is 1:2:0.2:140.
10. fluorescent chemicals is synthesized
Under argon shield; 0.2g compound 7 is dissolved in the mixed solvent of 2mL methyl alcohol and 1mL tetrahydrofuran (THF); add sodium methylate 0.0093g; stirring at room temperature 5 hours; add acidic cation-exchange resin to reaction solution for neutral; be spin-dried for, with methylene dichloride: methyl alcohol=4:1 is that post crossed by developping agent, obtains greenish yellow solid.Wherein the mol ratio of compound 7, sodium methylate, methyl alcohol, tetrahydrofuran (THF) is 1:1.6:540:135.
2, fluorescence sense film is prepared
Compound VI is dissolved in trichloromethane, is prepared into the storing solution of 0.18mg/mL.Get 30 μ L storing solutions under the atmosphere of relative humidity 75%, be evenly coated in clean glass matrix surface, place and within 20 minutes, treat that its solvent evaporates is complete, sealing is preserved, and prepares fluorescence sense film.
Embodiment 3
1. the iodo-Isosorbide-5-Nitrae-two of 2,5-bis-(methoxyl group)-benzene is synthesized
Under nitrogen protection atmosphere, in 140mL acetum, add the aqueous sulfuric acid 15mL of 2.0g to anisole, 5g iodine, 0.61g Potassium Iodate and massfraction 10% respectively.80 DEG C are stirred 10 hours, and by a large amount of solid suction filtrations produced, vacuum-drying, obtains white solid.Be wherein 1:1:0.2:170:2 to the mol ratio of anisole, iodine, Potassium Iodate, acetic acid and the vitriol oil.
2. the iodo-Isosorbide-5-Nitrae-two of 2,5-bis-(hydroxyl)-benzene is synthesized
Under nitrogen protection, iodo-for 7.8g2,5-bis-Isosorbide-5-Nitrae-two (methoxyl group)-benzene is dissolved in 50mL methylene dichloride, and under-78 DEG C of conditions, in solution, drips 7.44mL boron tribromide.After being added dropwise to complete, stirring at room temperature 12 hours, by a large amount of solid suction filtrations produced, vacuum-drying, obtains white solid.Wherein, the mol ratio of the iodo-Isosorbide-5-Nitrae-two of 2,5-bis-(methoxyl group)-benzene, boron tribromide and methylene dichloride is 1:4:40;
3. synthetic compound 3
Under argon shield, by 6.0g cholesterol, 25.3g1,8 two bromooctanes and 4.4g potassium hydroxide are dissolved in 50mL anhydrous tetrahydro furan, react 16 hours at 80 DEG C.Rotary evaporation is except desolventizing, and washing dichloromethane extraction, rotary evaporation obtains yellow oil, recrystallizing methanol, with methylene dichloride: sherwood oil=1:1 carries out pillar layer separation, obtains white solid.Wherein cholesterol, 1, the mol ratio of 8 two bromooctanes, potassium hydroxide and tetrahydrofuran (THF) is 1:6:5:40;
4. synthetic compound 4
Under argon shield, 5.4g compound 3, the iodo-Isosorbide-5-Nitrae of 0.85g2,5-bis--two (hydroxyl)-benzene, 8.0g salt of wormwood are dissolved in the anhydrous DMF of 30mL, react 16 hours at 160 DEG C.Reaction terminates, and is poured into water by solution, has a large amount of Precipitation, suction filtration, vacuum-drying, with methylene dichloride: sherwood oil=3:2 carries out pillar layer separation, obtains white solid.Wherein, the mol ratio of the iodo-Isosorbide-5-Nitrae-two of 2,5-bis-(hydroxyl)-benzene, compound 3, salt of wormwood and DMF is 1:4:25:170;
5. synthetic compound 5
Under argon shield, 1.5g compound 4,0.58g are dissolved in the anhydrous Diisopropylamine of 7.8mL and 8.2mL dry toluene alkynyl phenyl aldehyde, 0.01g cuprous iodide, 0.064g tetraphenylphosphonium palladium.React 12 hours at 70 DEG C.After reaction terminates, be cooled to room temperature, washing dichloromethane extraction, by organic phase rotary evaporation, recrystallizing methanol, gained yellow solid methylene dichloride: methyl alcohol=100:1 carries out pillar layer separation, obtains greenish yellow solid.Wherein compound 4, be 1:4:0.05:0.05:50:70 to the mol ratio of ethynylbenzaldehyde, cuprous iodide, tetraphenylphosphonium palladium, Diisopropylamine and toluene;
6. synthetic compound 1
Under nitrogen protection, 4g β-D alpha-glucose pentaacetate and 1.17g acetic acid hydrazine are dissolved in 47mLN, in dinethylformamide, in 55 DEG C of reactions 3 hours.Reaction terminates, and washing extraction into ethyl acetate, collect organic phase, rotary evaporation obtains colorless oil.Wherein the mol ratio of β-D alpha-glucose pentaacetate, acetic acid hydrazine and DMF is 1:1.3:60;
7. synthetic compound 2
Under argon shield, 1.5g compound 1,2.46g Trichloroacetonitrile and 0.42g cesium carbonate are dissolved in 13.7mL anhydrous methylene chloride in 0 DEG C.Ice bath stirs 3 hours, by solid filtering, and filtrate rotary evaporation, gained oily matter ethyl acetate: sherwood oil=1:1 is that post crossed by developping agent, obtains pale yellow oil.Wherein the mol ratio of compound 1, Trichloroacetonitrile, cesium carbonate and methylene dichloride is 1:4:0.3:50;
8. synthetic compound 6
Under argon shield, by 0.8g compound 5 and 0.248g2-(2-amino ethoxy) dissolve with ethanol in 6mL methylene dichloride, 45 DEG C of reactions 10 hours.Naturally cool to room temperature, add 0.09g sodium borohydride, stirring at normal temperature 1 hour.Wash reaction solution with water dichloromethane extraction, collect organic phase, anhydrous MgSO
4drying, filters, and filtrate rotary evaporation is also with methylene dichloride: methyl alcohol=10:1 carries out pillar layer separation as developping agent, obtains greenish yellow solid.Wherein the mol ratio of compound 5,2-(2-amino ethoxy) ethanol, sodium borohydride and methylene dichloride is 1:4:4:160;
9. synthetic compound 7
Under argon shield, be dissolved in 3mL anhydrous methylene chloride by 0.5g compound 6 and 0.66g compound 2, carefully add 0.014g trimethylsilyl trifluoromethanesulfonic acid fat, ice bath stirs 3 hours.Reaction terminates, and washes, dichloromethane extraction with 5% sodium bicarbonate aqueous solution, collects organic phase, anhydrous MgSO
4drying, filters, by filtrate rotary evaporation, and gained solid with methylene chloride: methyl alcohol=15:1 crosses post, obtains faint yellow solid.Wherein the mol ratio of compound 6, compound 2, trimethylsilyl trifluoromethanesulfonic acid fat and methylene dichloride is 1:4:0.2:140.
10. fluorescent chemicals is synthesized
Under argon shield; 0.2g compound 7 is dissolved in the mixed solvent of 2mL methyl alcohol and 1mL tetrahydrofuran (THF); add sodium methylate 0.0039g; stirring at room temperature 5 hours; add acidic cation-exchange resin to reaction solution for neutral; be spin-dried for, with methylene dichloride: methyl alcohol=4:1 is that post crossed by developping agent, obtains greenish yellow solid.Wherein the mol ratio of compound 7, sodium methylate, methyl alcohol, tetrahydrofuran (THF) is 1:0.8:540:135.
2, fluorescence sense film is prepared
By compound dissolution in trichloromethane, be prepared into the storing solution of 1.8mg/mL.Get 50 μ L storing solutions under the atmosphere of relative humidity 75%, be evenly coated in clean glass matrix surface, place and within 60 minutes, treat that its solvent evaporates is complete, sealing is preserved, and prepares fluorescence sense film.
Embodiment 4
In embodiment 1 ~ 3 preparation containing cholesterol, sugared structure fluorescent chemicals synthetic compound 3 step 3. in, the equimolar pentamethylene bromide of dibromo substituted straight chain alkane used is replaced, and other steps of this step are identical with corresponding embodiment, prepare compound 3, in formula, the value of n is 5.Synthetic compound 7 step 8. in, 2-(2-amino ethoxy) ethanol used equimolar 2-[2-(2-amino ethoxy)] replaces, in formula, the value of m is 2, and other steps of this step are identical with corresponding embodiment, prepare compound 7.Synthetic compound 1 step 6. in, the equimolar α-D alpha-glucose pentaacetate of β-D alpha-glucose pentaacetate used is replaced, and prepares compound 1.
Other steps are identical with embodiment 1 ~ 3.
Embodiment 5
In embodiment 1 ~ 3 preparation containing cholesterol, sugared structure fluorescent chemicals synthetic compound 3 step 3. in, 1,8-bis-bromooctane used is with equimolar 1,10-dibromo-decane is replaced, other steps of this step are identical with corresponding embodiment, prepare compound 3, and in formula, the value of n is 10.Synthetic compound 7 step 8. in, the equimolar 2-monoethanolamine of 2-(2-amino ethoxy) ethanol used is replaced, and in formula, the value of m is 0.Other steps of this step are identical with corresponding embodiment, prepare compound 7.Synthetic compound 1 step 6. in, the equimolar β-D semi-lactosi pentaacetate of β-D alpha-glucose pentaacetate used is replaced, and prepares compound 1.
Other steps are identical with embodiment 1 ~ 3.
Embodiment 6
In embodiment 1 ~ 3 preparation containing cholesterol, sugared structure fluorescent chemicals synthetic compound 3 step 3. in, 1,8-bis-bromooctane used is with equimolar 1,12-dibromo-dodecane is replaced, other steps of this step are identical with corresponding embodiment, prepare compound 3, and in formula, the value of n is 12.Synthetic compound 1 step 6. in, the equimolar β-L semi-lactosi pentaacetate of β-D alpha-glucose pentaacetate used is replaced, and prepares compound 1.Other steps are identical with embodiment 1 ~ 3.
Embodiment 7
In embodiment 1 ~ 3 preparation containing cholesterol, sugared structure fluorescent chemicals synthetic compound 1 step 6. in, the equimolar α-D Mannose pentaacetate of β-D alpha-glucose pentaacetate used is replaced, and prepares compound 1.Other steps are identical with embodiment 1 ~ 3.
Embodiment 8
Prepare in fluorescence sense film step 2 in embodiment 1 ~ 3, storing solution solvent for use trichloromethane tetrahydrofuran (THF) is replaced.Other steps are identical with embodiment 1 ~ 3.
Embodiment 9
Prepare in fluorescence sense film step 2 in embodiment 1 ~ 3, by clean glass matrix used at 98%H
2sO
4(21mL) and 30%H
2o
2(9mL), in mixing solutions, heat 1 hour under slight boiling condition, rinse with a large amount of intermediate water after cooling, dry up stand-by.Other steps are identical with embodiment 1 ~ 3.
Claims (8)
1. a fluorescent chemicals, is characterized in that, the structural formula of this fluorescent chemicals is as follows:
Wherein, m=0,1 or 2, n=5,8,10 or 12.
2. the preparation method of fluorescent chemicals described in claim 1, is characterized in that, comprises the following steps:
1) under nitrogen protection, sugared pentaacetate and acetic acid hydrazine are dissolved in DMF, stir 2 ~ 4 hours at 50 ~ 60 DEG C, in the reaction solution obtained, add ethyl acetate after washing, collect organic phase, except desolventizing obtains colorless oil, i.e. compound 1;
Step 1) in, the mol ratio of sugared pentaacetate, acetic acid hydrazine and DMF is 1:(1 ~ 1.3): (50 ~ 70); Described sugared pentaacetate is β-D alpha-glucose pentaacetate, α-D alpha-glucose pentaacetate, β-D semi-lactosi pentaacetate, β-L semi-lactosi pentaacetate or α-D Mannose pentaacetate;
2) under argon shield, compound 1, Trichloroacetonitrile and cesium carbonate are dissolved in anhydrous methylene chloride in 0 DEG C, 0 DEG C of insulation reaction 1 ~ 3 hour, by the solid filtering that reaction produces, filtrate is condensed into oily matter, and oily matter is carried out pillar layer separation, obtains compound 2;
3) under argon shield, compound 5 and aminoethoxyethanol substituent are dissolved in methylene dichloride, stir 16 ~ 20 hours at 40 ~ 50 DEG C; naturally cool to room temperature, add sodium borohydride, stirring at normal temperature reaction 1 ~ 2 hour; reaction terminates after washing; use dichloromethane extraction again, collect organic phase, then that organic phase is dry and filter; filtrate is removed desolventizing and is carried out pillar layer separation; obtain greenish yellow solid 6, wherein, the structural formula of described compound 5 is:
N=5,8,10 or 12;
The structural formula of described aminoethoxyethanol substituent is:
M=0,1 or 2;
4) under argon shield, greenish yellow solid 6 and compound 2 are dissolved in anhydrous methylene chloride, add trimethylsilyl trifluoromethanesulfonic acid fat, ice bath stirred after 2 ~ 4 hours, washed, with dichloromethane extraction with the sodium bicarbonate aqueous solution that mass concentration is 5%, collect organic phase, then organic phase is dry and filter, filtrate, except the laggard row pillar layer separation of desolventizing, obtains flaxen compound 7;
5) under argon shield; compound 7 is dissolved in the mixed solvent of methyl alcohol and tetrahydrofuran (THF); drip sodium methoxide solution; stirred at ambient temperature 4 ~ 6 hours; adding acidic cation-exchange resin to reaction solution is neutrality, obtains mixed solution, by this mixed solution except the laggard row pillar layer separation of desolventizing; obtain greenish yellow solid, i.e. fluorescent chemicals according to claim 1.
3. the preparation method of a kind of fluorescent chemicals according to claim 2, is characterized in that, step 2) in, the mol ratio of compound 1, Trichloroacetonitrile and cesium carbonate is 1:(2 ~ 4): (0.2 ~ 0.4); Step 2) described in pillar layer separation adopt ethyl acetate: the eluent that the volume ratio mixing of sherwood oil=1:1 is obtained is separated.
4. the preparation method of a kind of fluorescent chemicals according to claim 2, is characterized in that, step 3) in, the mol ratio of compound 5, aminoethoxyethanol substituent and sodium borohydride is 1:(2.5 ~ 4): (3 ~ 5); Step 3) described in pillar layer separation adopt methylene dichloride: the eluent that the volume ratio mixing of methyl alcohol=10:1 is obtained is separated.
5. the preparation method of a kind of fluorescent chemicals according to claim 2, is characterized in that, step 4) in, the mol ratio of compound 6, compound 2 and trimethylsilyl trifluoromethanesulfonic acid fat is 1:(2 ~ 4): (0.1 ~ 0.3); Step 4) described pillar layer separation employing methylene dichloride: the eluent that the volume ratio mixing of methyl alcohol=15:1 is obtained is separated.
6. the preparation method of a kind of fluorescent chemicals according to claim 2, it is characterized in that, step 5) in, in compound 7, sodium methoxide solution, the mol ratio of sodium methylate, methyl alcohol and tetrahydrofuran (THF) is 1:(0.8 ~ 1.6): (500 ~ 600): (100 ~ 150); Chromatographic column is separated and adopts methylene dichloride: the eluent that the volume ratio mixing of methyl alcohol=4:1 is obtained is separated.
7. adopt fluorescent chemicals according to claim 1 to prepare a method for fluorescence sense film, it is characterized in that, comprise the following steps:
1) fluorescent chemicals is dissolved in trichloromethane, makes the storing solution that concentration is 0.18mg/mL ~ 1.80mg/mL;
2) in relative humidity be 60% ~ 75% atmosphere under, be that the storing solution of 0.18mg/mL ~ 1.80mg/mL is coated in clean glass matrix surface uniformly by concentration, leave standstill 20 ~ 60min, obtained fluorescence sense film.
8. a fluorescence sense film according to claim 7 is preparing the application in fluorescence sense device.
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