CN103709069B - 6'-hydroxyl naphthyl-2-cyanoacrylate and application thereof - Google Patents
6'-hydroxyl naphthyl-2-cyanoacrylate and application thereof Download PDFInfo
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Abstract
The invention belongs to the field of organic chemistry, and in particular relates to 6'-hydroxyl naphthyl-2-cyanoacrylate. The chemical structure of the 6'-hydroxyl naphthyl-2-cyanoacrylate is shown in formula (I) which is as shown in the description, wherein R is methyl, ethyl, propyl and butyl, 2-(2-methoxy ethyoxyl) ethyoxyl or 2-(N,N-dimethyl) aminoethyl. The 6'-hydroxyl naphthyl-2-cyanoacrylate is obtained by performing reaction on 6'-hydroxyl-2-naphthaldehyde and 2-cyan-acetic ester. The 6'-hydroxyl naphthyl-2-cyanoacrylate has fluorine ion fluorescence recognition performance and can be used for detecting fluorine ions in cells.
Description
Technical field
The invention belongs to organic chemistry filed, relate to acrylic ester compound, be specifically related to 2-cyanoacrylate.
Background technology
Negatively charged ion plays key player in life science and chemical process, all plays an important role in fields such as biology, pathology and environmental monitorings.Wherein fluorion is conducive to dental health and treatment osteoporosis, and meanwhile, it also can cause the diseases such as urinary calculi.Therefore the fluorion probe that design and synthesis selectivity is good, highly sensitive has been a great concern in recent years.
The Imaging-PAM that development in recent years is got up has quick nondestructive, and intuitively, sensitivity high, has been widely used in detection fluorion.Such as, a series of 1,5-diaryl-3-(the 2-hydroxyl-4 of the design and synthesis such as Wang Ping Xiang; 6-Dimethoxyphenyl)-2-pyrazoline compounds; find that this compounds optionally identifies fluorion in DMSO, can as fluorescent probe (Wu Jing, the Xu Zhuxiong identifying fluorion; Wang Ping Xiang; SCI, 2010, V31; No11,2201).Fluorion has low radius/charge ratio, and its solvation tendency is strong, and polarity is high, when causing most of fluorion fluorescent probe to detect fluorion in aqueous solution, there is selectivity low, the shortcoming that sensitivity is weak, the application of restriction fluorion fluorescent probe.Meanwhile, the cytotoxicity of most of fluorion fluorescent probe is high, and cell-penetrating performance is poor, causes fluorion fluorescent probe can not detect intracellular fluorion.
Naphthyl-2 cyanoacrylate is widely used in biological field, amyloid (the K.Cao that can be used in fluoroscopic examination brain, M.Farahi, M.Dakanali, W.M.Chang, C.J.Sigurdson, E.A.Theodorakis and J.Yang, J.Am.Chem.Soc., 2012,134,17338.).But have no it for detecting the report of fluorion in the aqueous solution and intracellular fluorion.
Summary of the invention
The object of this invention is to provide a kind of 6 '-hydroxynaphenyl-2 cyanoacrylate, this 6 '-hydroxynaphenyl-2-cyanoacrylate can detect fluorion in the aqueous solution, especially can detect intracellular fluorion.
The technical scheme that the present invention solves the problem is:
A kind of 6 '-hydroxynaphenyl-2-cyanoacrylate, its structural formula is for shown in (I):
In formula (I), R is methyl, ethyl, propyl group, butyl, 2-(2-(2-methoxy ethoxy) oxyethyl group) ethyl or 2-(N, N-dimethyl) amido ethyl.
In 6 '-hydroxynaphenyl-2 cyanoacrylate compound of the present invention, R is preferably 2-(2-(2-methoxy ethoxy) oxyethyl group) ethyl.
6 '-hydroxynaphenyl-2 cyanoacrylate of the present invention adopts this area common method synthesis, e.g., 6-hydroxyl naphthalene 2-formaldehyde and 2-cyan-acetic ester is obtained by reacting as adopted the method shown in lower formula II:
In formula (II), R is methyl, ethyl, propyl group, butyl, 2-(2-(2-methoxy ethoxy) oxyethyl group) ethyl or 2-(N, N-dimethyl) amido ethyl.
In the preparation method that reaction formula II of the present invention represents, 2-cyan-acetic ester can carry out esterification by 2-Malonic mononitrile and corresponding alcohol by following formula (III) and obtain:
In formula (III), R is methyl, ethyl, propyl group, butyl, 2-(2-(2-methoxy ethoxy) oxyethyl group) ethyl or 2-(N, N-dimethyl) amido ethyl.
6 '-hydroxynaphenyl-2 cyanoacrylate of the present invention is combined with fluorion, and the fluorescence color of the aqueous solution of 6 '-hydroxynaphenyl-2-cyanoacrylate can be made to change.
The method that 6 '-hydroxynaphenyl-2-cyanoacrylate of the present invention detects fluorion in the aqueous solution is made up of following steps:
(1) 6 '-hydroxynaphenyl-2-cyanoacrylate is dissolved in hydrophilic organic solvent, then the water that volume multiple is 99 is added, prepare the aqueous solution containing 6 '-hydroxynaphenyl-2-cyanoacrylate, wherein said hydrophilic organic solvent is acetonitrile, THF, DMF or DMSO;
(2) drip detected sample, under wavelength is 365nm optical excitation, observes aqueous solution fluorescence color and whether change, if aqueous solution fluorescence color becomes blue by green, then contain fluorion in interpret sample.
The fluorescence spectrum of 6 '-hydroxynaphenyl-2-cyanoacrylate of the present invention demonstrates an absorption peak at 490nm place, and fluorescence color is green; After adding fluorion, its fluorescent absorption peak is displaced to 450nm, and fluorescence color is then blue.Its principle is, fluorion with the phenolic hydroxyl group generation deprotonation on 6 '-hydroxynaphenyl-2-cyanoacrylate, can affect the conjugation effect of 6 '-hydroxynaphenyl-2-cyanoacrylate, cause fluorescence color to change.
The present invention has the following advantages relative to prior art: 6 '-hydroxynaphenyl-2-cyanoacrylate of the present invention not only can detect the fluorion in the aqueous solution, but also can carry out fluoroscopic examination to intracellular fluorion.
Accompanying drawing explanation
Fig. 1 is the Cytotoxic bar graph of 6 '-hydroxynaphenyl-2-alpha-cyanoacrylate 2-(2-(2-methoxy ethoxy) oxyethyl group) ethyl ester.
Embodiment
With specific embodiment, preparation method of the present invention and effect thereof are described in further detail below.
Embodiment 1
The preparation of 1.6 '-hydroxynaphenyl-2-alpha-cyanoacrylate 2-(2-(2-methoxy ethoxy) oxyethyl group) ethyl ester
In 100ml flask, add 3.44g 6-hydroxyl-2-naphthaldehyde, 4.62g2-(2-(2-methoxy ethoxy) oxyethyl group) 2-cyan-acetic ester and 0.5g N, N-dimethyl-4-aminopyridine, then add 30ml anhydrous tetrahydro furan.React under room temperature after 24 hours, underpressure distillation is except desolventizing, and residual solids silicagel column consists of ethyl acetate at elutriant: under normal hexane=1:1 (v/v), purifying obtains yellow solid 7.24g.Productive rate 94%.
2. the sign of compound
Mp 137.0～138.5℃.
1H NMR(400MHz,DMSO-d
6):δ3.22(s,3H),3.37～3.44(m,4H),3.52～3.56(m,10H),3.60～3.63(m,2H),3.74～3.76(m,2H),4.40～4.43(m,1H),7.23(s,2H),7.85～7.90(dd,J＝9.16Hz,J＝21.16Hz,2H),8.13～8.16(dd,J＝1.39,J＝8.32Hz,1H),8.42～8.46(d,J＝13.53Hz 2H),10.45(s,1H).
13C NMR(100MHz,DMSO-d
6):δ57.98,65.32,68.06,69.59,69.73,69.90,71.24,99.49,109.19,116.09,120.03,124.76,131.52,135.22,137.22,155.27,158.80,162.34.
IR(cm
-1,KBr):3330,2962,2878,1898,1719,1617,1589,1517,1481,1351,1191,1144,930,817,744,631.
Elemental analysis:Anal.Calcd for C
21H
23NO
6:C,65.44；H,6.02；N,3.63；O,24.91.Found:C,65.82；H,6.08；N,3.71.
Above-mentioned detected result confirms that the compound of preparation is 6 '-hydroxynaphenyl-2-alpha-cyanoacrylate 2-(2-(2-methoxy ethoxy) oxyethyl group) ethyl ester, and its chemical structure is as shown in the formula shown in (IV):
3. compliance test result
3.1. fluorion in the detection aqueous solution
(1) compound concentration is 6 '-hydroxynaphenyl-2-alpha-cyanoacrylate 2-(2-(2-methoxy ethoxy) oxyethyl group) the ethyl ester DMSO solution of 30mM, get 10 μ l 6 '-hydroxynaphenyl-2-alpha-cyanoacrylate 2-(2-(2-methoxy ethoxy) oxyethyl group) ethyl ester DMSO solution respectively, adding distil water is rare to 10ml, obtains 10 parts of 6 '-hydroxynaphenyl-2-alpha-cyanoacrylate 2-(2-(2-methoxy ethoxy) oxyethyl group) the ethyl ester aqueous solution;
(2) compound concentration is the aqueous solution of the Sodium Fluoride of 30mM, Sodium Bromide, SODIUMNITRATE, sodium-chlor, sodium pyrosulfate, sodium carbonate, sodium azide, Sodium Thiocyanate 99, sodium disulfide and sodium-acetate respectively;
(3) in every a 6 '-hydroxynaphenyl-2-alpha-cyanoacrylate 2-(2-(2-methoxy ethoxy) oxyethyl group) ethyl ester aqueous solution, drip a kind of aqueous solution 0.1ml that step (2) is prepared respectively, after mixing, under 365nm optical excitation, observe the fluorescence color change of 6 '-hydroxynaphenyl-2-alpha-cyanoacrylate 2-(2-(2-methoxy ethoxy) oxyethyl group) ethyl ester aqueous solution.
Result shows, after adding sodium fluoride aqueous solution, the fluorescence color of 6 '-hydroxynaphenyl-2-alpha-cyanoacrylate 2-(2-(2-methoxy ethoxy) oxyethyl group) the ethyl ester aqueous solution becomes blue by green, and after adding the aqueous solution of Sodium Bromide, SODIUMNITRATE, sodium-chlor, sodium pyrosulfate, sodium carbonate, sodium azide, Sodium Thiocyanate 99, sodium disulfide and sodium-acetate, the fluorescence color of 6 '-hydroxynaphenyl-2-alpha-cyanoacrylate 2-(2-(2-methoxy ethoxy) oxyethyl group) the ethyl ester aqueous solution all remains unchanged.This result shows, 6 '-hydroxynaphenyl-2-alpha-cyanoacrylate 2-(2-(2-methoxy ethoxy) oxyethyl group) ethyl ester can at fluoroscopic examination fluorion under aqueous conditions.
The present inventor is also studied the fluorescence spectrum that 6 '-hydroxynaphenyl-2-alpha-cyanoacrylate 2-(2-(2-methoxy ethoxy) oxyethyl group) the ethyl ester aqueous solution drips before and after step (2) aqueous solution prepared.Found that, in the process dripping sodium fluoride aqueous solution, the fluorescence spectrum of solution is by 490nm blue shift to 450nm, and in the process dripping other aqueous solution, the fluorescence spectrum of solution changes less.This result of study illustrates, 6 '-hydroxynaphenyl-2-alpha-cyanoacrylate 2-(2-(2-methoxy ethoxy) oxyethyl group) ethyl ester demonstrates good selectivity to fluorion.
3.2.MTT method detects cells growth activity
By PC3 or HeLa cell with every hole 6X10
3individual cell is inoculated in 96 orifice plates, overnight incubation, use concentration instead and be respectively 5, the cell culture fluid containing 6 '-hydroxynaphenyl-2-alpha-cyanoacrylate 2-(2-(2-methoxy ethoxy) oxyethyl group) ethyl ester of 10,15,20 μm of ol/ml, after continuing to cultivate 24h, supernatant liquor is abandoned in suction, and every hole adds 200 μ l MTT reagent (5mg/ml prepares with PBS); Continue to cultivate 4h, discard nutrient solution, every hole adds 150 μ l DMSO, is placed in cell shaking table 10min, dissolves completely to blue particle.By microplate reader (the full-automatic microplate reader of ELX800, Bao Te Instrument Ltd. of the U.S.) under excitation wavelength is 490nm condition, measure each hole absorbance, with the nutrient solution containing cell and MTT for control group, only to add the nutrient solution of equivalent and MTT for blank well.Calculate cell survival rate according to the following equation: cell survival rate (%)=(experimental port absorbance-blank well absorbance)/(control wells absorbance-blank well absorbance) × 100%.Take cell survival rate as ordinate zou, compound 6 '-hydroxynaphenyl-2-alpha-cyanoacrylate 2-(2-(2-methoxy ethoxy) oxyethyl group) ethyl ester concentration is the cytotoxicity bar graph that X-coordinate draws 6 '-hydroxynaphenyl-2-alpha-cyanoacrylate 2-(2-(2-methoxy ethoxy) oxyethyl group) ethyl ester, and result as shown in Figure 1.The cytotoxicity that Fig. 1 shows 6 '-hydroxynaphenyl-2-alpha-cyanoacrylate 2-(2-(2-methoxy ethoxy) oxyethyl group) ethyl ester is low.
3.3. cell cultures and imaging
The PC3 cell of taking the logarithm vegetative period is inoculated in and is equipped with in 6 orifice plates, overnight incubation, after the RPMI-1640 used instead containing 10 μm of ol/ml6 '-hydroxynaphenyl-2-alpha-cyanoacrylate 2-(2-(2-methoxy ethoxy) oxyethyl group) ethyl ester continues to cultivate 30min, clean 6 orifice plate 3 times with phosphate buffered saline buffer, remove excessive 6 '-hydroxynaphenyl-2-alpha-cyanoacrylate 2-(2-(2-methoxy ethoxy) oxyethyl group) ethyl ester.The RPMI-1640 continuing to add propidium iodide (10 μ g/ml) cleans 6 orifice plate 3 times with phosphate buffered saline buffer, removes excessive propidium iodide after continuing to cultivate 30min.Observe under cell being placed in laser confocal microscope, there is green fluorescence in the cell after 6 '-hydroxynaphenyl-2-alpha-cyanoacrylate 2-(2-(2-methoxy ethoxy) oxyethyl group) ethyl ester process in tenuigenin.Result shows that 6 '-hydroxynaphenyl-2-alpha-cyanoacrylate 2-(2-(2-methoxy ethoxy) oxyethyl group) ethyl ester has good Cell permeable, may be used for preparing the fluorescent probe detecting fluorion in cell.
The PC3 cell of taking the logarithm vegetative period is inoculated in and is equipped with in 6 orifice plates, overnight incubation, after the RPMI-1640 used instead containing 10 μm of ol/ml 6 '-hydroxynaphenyl-2-alpha-cyanoacrylate 2-(2-(2-methoxy ethoxy) oxyethyl group) ethyl esters continues to cultivate 30min, clean 6 orifice plate 3 times with phosphate buffered saline buffer, remove excessive 6 '-hydroxynaphenyl-2-alpha-cyanoacrylate 2-(2-(2-methoxy ethoxy) oxyethyl group) ethyl ester.The DMEM nutrient solution used instead containing 100 μm of ol/ml NaF cleans 6 orifice plate 3 times with phosphate buffered saline buffer, removes excessive fluorion after continuing to cultivate 30min.After using the RPMI-1640 continuation cultivation 30min containing propidium iodide (10 μ g/ml) instead, clean 6 orifice plate 3 times with phosphate buffered saline buffer, remove excessive propidium iodide.Observe under cell being placed in laser confocal microscope.Result shows, and after fluorion enters cell, changes the fluorescence color that the cell after 6 '-hydroxynaphenyl-2-alpha-cyanoacrylate 2-(2-(2-methoxy ethoxy) oxyethyl group) ethyl ester process shows in tenuigenin into blueness.Result shows that 6 '-hydroxynaphenyl-2-alpha-cyanoacrylate 2-(2-(2-methoxy ethoxy) oxyethyl group) ethyl ester can detect intracellular fluorion.
Embodiment 2
The preparation of 1.6 '-hydroxynaphenyl-2-Methyl 2-cyanoacrylate
In 100ml flask, add 3.44g 6-hydroxyl-2-naphthaldehyde, 1.98g 2-malonic methyl ester nitrile and 0.5g N, N-dimethyl-4-aminopyridine, then add 30ml anhydrous tetrahydro furan.React under room temperature after 24 hours, underpressure distillation is except desolventizing, and residual solids silicagel column consists of ethyl acetate at elutriant: under normal hexane=1:4 (v/v), purifying obtains yellow solid 4.08g.Productive rate 81%.
2. the sign of compound
1H NMR(400MHz,DMSO-d
6):δ3.71(s,3H),4.08～4.13(m,1H),7.23(s,2H),7.81～7.88(dd,2H),8.01～8.05(dd,1H),8.40～8.43(d,2H),10.56(s,1H).
13C NMR(100MHz,DMSO-d
6):δ52.11,100.34，109.11,117.22,121.13,123.41,132.50,136.32,137.62,155.17,157.55,161.31.
Above-mentioned detected result confirms that the compound of preparation is 6 '-hydroxynaphenyl-2-Methyl 2-cyanoacrylate.
3. detect fluorion in the aqueous solution
(1) compound concentration is 6 '-hydroxynaphenyl-2-Methyl 2-cyanoacrylate acetonitrile solution of 30mM, get 10 μ l 6 '-hydroxynaphenyl-2-Methyl 2-cyanoacrylate acetonitrile solutions respectively, add distilled water rare to 10ml, obtain 10 parts of 6 '-hydroxynaphenyl-2-alpha-cyanoacrylate aqueous solution of ester;
(2) compound concentration is the aqueous solution of the Sodium Fluoride of 30mM, Sodium Bromide, SODIUMNITRATE, sodium-chlor, sodium pyrosulfate, sodium carbonate, sodium azide, Sodium Thiocyanate 99, sodium disulfide and sodium-acetate respectively;
(3) in every a 10ml 6 '-hydroxynaphenyl-2-Methyl 2-cyanoacrylate aqueous solution, drip a kind of aqueous solution 0.1ml that step (2) is prepared respectively, after mixing, under 365nm optical excitation, observe the fluorescence color change of 6 '-hydroxynaphenyl-2-Methyl 2-cyanoacrylate aqueous solution.
Result shows, after adding sodium fluoride aqueous solution, the fluorescence color of 6 '-hydroxynaphenyl-2-Methyl 2-cyanoacrylate aqueous solution becomes blue by green, and after adding the aqueous solution of Sodium Bromide, SODIUMNITRATE, sodium-chlor, sodium pyrosulfate, sodium carbonate, sodium azide, Sodium Thiocyanate 99, sodium disulfide and sodium-acetate, the fluorescence color of 6 '-hydroxynaphenyl-2-Methyl 2-cyanoacrylate aqueous solution all remains unchanged.This result shows, 6 '-hydroxynaphenyl-2-Methyl 2-cyanoacrylate demonstrates selectivity and fluorescence identifying ability to fluorion.
Embodiment 3
The preparation of 1.6 '-hydroxynaphenyl-2-cyanacrylate
In 100ml flask, add 3.44g 6-hydroxyl-2-naphthaldehyde, 2.26g2-ethyl cyanoacetate and 0.5g N, N-dimethyl-4-aminopyridine, then add 30ml anhydrous tetrahydro furan.React under room temperature after 24 hours, underpressure distillation is except desolventizing, and residual solids silicagel column consists of ethyl acetate at elutriant: under normal hexane=1:4 (v/v), purifying obtains yellow solid 4.65g.Productive rate 87%.
2. the sign of compound
1H NMR(400MHz,DMSO-d
6):δ1.03(s,3H),4.11～4.13(m,2H),4.55～4.58(m,1H),7.11(s,2H),7.74～7.78(dd,2H),7.89～7.92(dd,1H),8.10～8.14(d,2H),10.77(s,1H).
13C NMR(100MHz,DMSO-d
6):δ11.44,56.11,103.11，109.53,116.92,121.73,123.81,131.97,136.71,137.23,155.51,158.44,162.89.
Above-mentioned detected result confirms that the compound of preparation is 6 '-hydroxynaphenyl-2-cyanacrylate.
3. detect fluorion in the aqueous solution
6 '-hydroxynaphenyl-2-cyanacrylate is dissolved in DMF, make 6 '-hydroxynaphenyl-2-Methyl 2-cyanoacrylate DMF solution that concentration is 30mM, the method 6 '-hydroxynaphenyl-2-cyanacrylate then adopting embodiment 2 same detects fluorion in the aqueous solution.Result shows, after adding sodium fluoride aqueous solution, the fluorescence color of 6 '-hydroxynaphenyl-2-cyanacrylate aqueous solution becomes blue by green, and after adding the aqueous solution of Sodium Bromide, SODIUMNITRATE, sodium-chlor, sodium pyrosulfate, sodium carbonate, sodium azide, Sodium Thiocyanate 99, sodium disulfide and sodium-acetate, the fluorescence color of 6 '-hydroxynaphenyl-2-cyanacrylate aqueous solution all remains unchanged.This result shows, 6 '-hydroxynaphenyl-2-cyanacrylate demonstrates selectivity and fluorescence identifying ability to fluorion.
Embodiment 4
6 '-hydroxynaphenyl-2-cyanoacrylate propyl propionate
The preparation of 1.6 '-hydroxynaphenyl-2-cyanoacrylate propyl propionate
In 100ml flask, add 3.44g 6-hydroxyl-2-naphthaldehyde, 2.54g 2-Malonic mononitrile propyl ester and 0.5g N, N-dimethyl-4-aminopyridine, then add 30ml anhydrous tetrahydro furan.React under room temperature after 24 hours, underpressure distillation is except desolventizing, and residual solids silicagel column consists of ethyl acetate at elutriant: under normal hexane=1:4 (v/v), purifying obtains yellow solid 4.38g.Productive rate 78%.
2. the sign of compound
1H NMR(400MHz,DMSO-d
6):δ1.03(s,3H),1.32～1.34(m,2H),3.81～3.84(m,2H),4.11～4.13(m,1H),7.05(s,2H),7.51～7.55(dd,2H),7.71～7.75(dd,1H),8.22～8.25(d,2H),10.17(s,1H).
13C NMR(100MHz,DMSO-d
6):δ11.14,15.44,59.41,102.91，110.23,117.15,122.03,125.11,131.67,135.81,137.43,156.01,158.14,162.11.
Above-mentioned detected result confirms that the compound of preparation is 6 '-hydroxynaphenyl-2-cyanoacrylate propyl propionate.
3. detect fluorion in the aqueous solution
6 '-hydroxynaphenyl-2-cyanacrylate is dissolved in DMSO, make 6 '-hydroxynaphenyl-2-Methyl 2-cyanoacrylate DMSO solution that concentration is 30mM, the method 6 '-hydroxynaphenyl-2-cyanacrylate then adopting embodiment 2 same detects fluorion in the aqueous solution.Result shows, after adding sodium fluoride aqueous solution, the fluorescence color of 6 '-hydroxynaphenyl-2-cyanacrylate aqueous solution becomes blue by green, and after adding the aqueous solution of Sodium Bromide, SODIUMNITRATE, sodium-chlor, sodium pyrosulfate, sodium carbonate, sodium azide, Sodium Thiocyanate 99, sodium disulfide and sodium-acetate, the fluorescence color of 6 '-hydroxynaphenyl-2-cyanacrylate aqueous solution all remains unchanged.This result shows, 6 '-hydroxynaphenyl-2-cyanacrylate demonstrates selectivity and fluorescence identifying ability to fluorion.
Embodiment 5
6 '-hydroxynaphenyl-2-Tisuacryl
The preparation of 1.6 '-hydroxynaphenyl-2-Tisuacryl
In 100ml flask, add 3.44g 6-hydroxyl-2-naphthaldehyde, 2.82g 2-Malonic mononitrile butyl ester and 0.5g N, N-dimethyl-4-aminopyridine, then add 30ml anhydrous tetrahydro furan.React under room temperature after 24 hours, underpressure distillation is except desolventizing, and residual solids silicagel column consists of ethyl acetate at elutriant: under normal hexane=1:4 (v/v), purifying obtains yellow solid 5.37g.Productive rate 791%.
2. the sign of compound
1H NMR(400MHz,DMSO-d
6):δ0.98(s,3H),1.21～1.23(m,2H),1.44～1.46(m,2H),3.97～4.01(m,2H),4.51～4.54(m,1H),7.13(s,2H),7.62～7.65(dd,2H),7.78～7.83(dd,1H),8.31～8.36(d,2H),11.06(s,1H).
13C NMR(100MHz,DMSO-d
6):δ11.55,13.77,16.64,58.01,102.77，110.10,116.89,121.88,125.19,131.41,135.42,136.91,155.86,158.4,161.15.
Above-mentioned detected result confirms that the compound of preparation is 6 '-hydroxynaphenyl-2-Tisuacryl.
Embodiment 6
6 '-hydroxynaphenyl-2-alpha-cyanoacrylate (2-N, N-dimethylamino) ethyl ester
The preparation of 1.6 '-hydroxynaphenyl-2-alpha-cyanoacrylate (2-N, N-dimethylamino) ethyl ester
In 100ml flask, add 3.44g 6-hydroxyl-2-naphthaldehyde, 3.12g 2-Malonic mononitrile (2-N, N-dimethylamino) ethyl ester and 0.5g N, N-dimethyl-4-aminopyridine, then add 30ml anhydrous tetrahydro furan.React under room temperature after 24 hours, underpressure distillation is except desolventizing, and residual solids silicagel column consists of methylene dichloride at elutriant: under methyl alcohol=10:0.5 (v/v), purifying obtains yellow solid 3.47g.Productive rate 56%.
2. the sign of compound
1H NMR(400MHz,DMSO-d
6):δ3.04～3.07(m,6H),3.44～3.46(m,2H),4.21～4.23(m,2H),5.33～5.35(m,1H),7.09(s,2H),7.62～7.66(dd,2H),7.72～7.74(dd,1H),8.11～8.14(d,2H),10.22(s,1H).
13C NMR(100MHz,DMSO-d
6):δ46.67,58.11,63.22,102.91，110.03,117.22,121.53,124.01,132.01,136.75,137.10,154.46,158.14,162.77.
Above-mentioned detected result confirms that the compound of preparation is 6 '-hydroxynaphenyl-2-alpha-cyanoacrylate (2-N, N-dimethylamino) ethyl ester.
3. detect fluorion in the aqueous solution
6 '-hydroxynaphenyl-2-cyanacrylate is dissolved in THF, make 6 '-hydroxynaphenyl-2-Methyl 2-cyanoacrylate THF solution that concentration is 30mM, then the method that embodiment 2 is same is adopted, fluorion in the aqueous solution is detected with 6 '-hydroxynaphenyl-2-alpha-cyanoacrylate (2-N, N-dimethylamino) ethyl ester.Result shows, after adding sodium fluoride aqueous solution, 6 '-hydroxynaphenyl-2-alpha-cyanoacrylate (2-N, N-dimethylamino) fluorescence color of the ethyl ester aqueous solution becomes blue by green, and after adding the aqueous solution of Sodium Bromide, SODIUMNITRATE, sodium-chlor, sodium pyrosulfate, sodium carbonate, sodium azide, Sodium Thiocyanate 99, sodium disulfide and sodium-acetate, the fluorescence color of 6 '-hydroxynaphenyl-2-alpha-cyanoacrylate (2-N, N-dimethylamino) the ethyl ester aqueous solution all remains unchanged.This result shows, 6 '-hydroxynaphenyl-2-alpha-cyanoacrylate (2-N, N-dimethylamino) ethyl ester demonstrates selectivity and fluorescence identifying ability to fluorion.
Claims (4)
1. 6 '-hydroxynaphenyl-2-cyanoacrylate, its structural formula is for shown in following formula (I):
In formula (I), R is methyl, ethyl, propyl group, butyl, 2-(2-(2-methoxy ethoxy) oxyethyl group) ethyl or 2-(N, N-dimethyl) amido ethyl.
2. 6 '-hydroxynaphenyl-2 cyanoacrylate according to claim 1, is characterized in that in formula (I), and R is 2-(2-(2-methoxy ethoxy) oxyethyl group) ethyl.
3. described in claim 1 or 26 '-hydroxynaphenyl-2-cyanoacrylate is detecting the application of fluorion in the aqueous solution.
4. application according to claim 3, is characterized in that, in the described detection aqueous solution, the method for fluorion is made up of following steps:
(1) 6 '-hydroxynaphenyl-2-cyanoacrylate is dissolved in hydrophilic organic solvent, then in gained solution, the water that volume multiple is 99 is added, prepare the aqueous solution of 6 '-hydroxynaphenyl-2-cyanoacrylate, wherein said hydrophilic organic solvent is acetonitrile, THF, DMF or DMSO;
(2) then, sample aqueous solution is dripped in the aqueous solution prepared by step (1), be under the optical excitation of 365nm at wavelength, observe the change of the fluorescence color of the aqueous solution before and after dropping sample aqueous solution prepared by step (1), if described fluorescence color becomes blue by green, then contain fluorion in the interpret sample aqueous solution.
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| CN114207064B (en) * | 2019-08-08 | 2023-03-14 | 东亚合成株式会社 | Adhesive composition easily decomposable in water |
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| CN103483223B (en) * | 2013-09-12 | 2015-12-09 | 吉林大学 | Alpha-cyano-4-hydroxycinnamic acid n-propyl, preparation method and application |
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