CN103709069A - 6'-hydroxyl naphthyl-2-cyanoacrylate and application thereof - Google Patents
6'-hydroxyl naphthyl-2-cyanoacrylate and application thereof Download PDFInfo
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- JOYIFSZOVYXRLW-CPNJWEJPSA-N COCCOCCOCCOC(/C(/C#N)=C/c1ccc(cc(cc2)O)c2c1)=O Chemical compound COCCOCCOCCOC(/C(/C#N)=C/c1ccc(cc(cc2)O)c2c1)=O JOYIFSZOVYXRLW-CPNJWEJPSA-N 0.000 description 1
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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 is being played the part of key player in life science and chemical process, in fields such as biology, pathology and environmental monitorings, all plays an important role.Wherein fluorion is conducive to dental health and treatment osteoporosis, and meanwhile, it also can cause the diseases such as urinary calculi.Therefore good, highly sensitive fluorion probe has been a great concern in recent years to design synthesis of selective.
The Imaging-PAM that development in recent years is got up has quick nondestructive, and directly perceived, the features such as sensitivity height, have been widely used in detection fluorion.For example, it is a series of 1 that the designs such as Wang Ping Xiang have been synthesized, 5-diaryl-3-(2-hydroxyl-4; 6-Dimethoxyphenyl)-2-pyrazoline compounds; find that this compounds optionally identifies fluorion in DMSO, can be used as fluorescent probe (Wu Jing, the Xu Zhuxiong of identification 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, while causing most of fluorion fluorescent probe to detect fluorion in aqueous solution, exists 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 poor performance 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 detection of the report of the fluorion in the aqueous solution and intracellular fluorion.
Summary of the invention
The object of this invention is to provide a kind of 6 '-hydroxyl naphthyl-2 cyanoacrylate, this 6 '-hydroxyl naphthyl-2-cyanoacrylate can detect fluorion in the aqueous solution, especially can detect intracellular fluorion.
The technical scheme that the present invention addresses the above problem is:
6 '-hydroxyl naphthyl-2-cyanoacrylate, its structural formula is shown in (I):
In formula (I), R is methyl, ethyl, propyl group, butyl, 2-(2-methoxy ethoxy) oxyethyl group or 2-(N, N-dimethyl) amido ethyl.
In the cyanoacrylate compound of 6 '-hydroxyl of the present invention naphthyl-2, R is preferably 2-(2-methoxy ethoxy) oxyethyl group.
6 '-hydroxyl of the present invention naphthyl-2 cyanoacrylate adopts this area common method synthetic, as, as adopt the method as shown in lower formula II that 6-hydroxyl naphthalene 2-formaldehyde is reacted and obtained with 2-cyan-acetic ester:
In formula (II), R is methyl, ethyl, propyl group, butyl, 2-(2-methoxy ethoxy) oxyethyl group 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 following formula (III) by 2-Malonic mononitrile and corresponding alcohol and obtain:
In formula (III), R is methyl, ethyl, propyl group, butyl, 2-(2-methoxy ethoxy) oxyethyl group or 2-(N, N-dimethyl) amido ethyl.
6 '-hydroxyl of the present invention naphthyl-2 cyanoacrylate is combined with fluorion, can make the fluorescence color of the aqueous solution of 6 '-hydroxyl naphthyl-2-cyanoacrylate change.
The method that 6 '-hydroxyl naphthyl-2-cyanoacrylate of the present invention detects fluorion in the aqueous solution is comprised of following steps:
(1) 6 '-hydroxyl naphthyl-2-cyanoacrylate is dissolved in hydrophilic organic solvent, then adding volume multiple is 99 water, prepare the aqueous solution containing 6 '-hydroxyl naphthyl-2-cyanoacrylate, wherein said hydrophilic organic solvent is acetonitrile, THF, DMF or DMSO;
(2) whether dripping detected sample, is under 365nm optical excitation at wavelength, observe aqueous solution fluorescence color and change, if aqueous solution fluorescence color becomes blueness by green, in interpret sample, contains fluorion.
The fluorescence spectrum of 6 '-hydroxyl naphthyl-2-cyanoacrylate of the present invention demonstrates an absorption peak at 490nm place, and fluorescence color is green; Add after fluorion, its fluorescent absorption peak is displaced to 450nm, and fluorescence color is blue.Its principle is, fluorion can with 6 '-hydroxyl naphthyl-2-cyanoacrylate on phenolic hydroxyl group generation deprotonation, affect the conjugation effect of 6 '-hydroxyl naphthyl-2-cyanoacrylate, cause fluorescence color to change.
The present invention has the following advantages with respect to prior art: 6 '-hydroxyl naphthyl-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 '-hydroxyl naphthyl-2-alpha-cyanoacrylate 2-(2-methoxy ethoxy) ethoxy 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 '-hydroxyl naphthyl-2-alpha-cyanoacrylate 2-(2-methoxy ethoxy) ethoxy ester
In 100ml flask, add 3.44g6-hydroxyl-2-naphthaldehyde, 4.62g2-(2-(2-methoxy ethoxy) oxyethyl group) 2-cyan-acetic ester and 0.5g N, N-dimethyl-4-aminopyridine, then adds 30ml anhydrous tetrahydro furan.Under room temperature, react after 24 hours, underpressure distillation is except desolventizing, and residual solids is ethyl acetate with silicagel column at eluent components: normal hexane=1:1(v/v) lower purifying obtains yellow solid 7.24g.Productive rate 94%.
2. the sign of compound
Mp137.0～138.5℃.
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=13.53Hz2H),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 '-hydroxyl naphthyl-2-alpha-cyanoacrylate 2-(2-methoxy ethoxy) ethoxy ester, and its chemical structure is as shown in the formula shown in (IV):
3. compliance test result
3.1. detect fluorion in the aqueous solution
(1) 6 '-hydroxyl naphthyl-2-alpha-cyanoacrylate 2-(2-methoxy ethoxy) ethoxy ester DMSO solution that compound concentration is 30mM, get respectively 10 μ l 6 '-hydroxyl naphthyl-2-alpha-cyanoacrylate 2-(2-methoxy ethoxy) ethoxy ester DMSO solution, adding distil water is rare to 10ml, obtains 10 parts of 6 '-hydroxyl naphthyl-2-alpha-cyanoacrylate 2-(2-methoxy ethoxy) ethoxy aqueous solution of ester;
(2) aqueous solution of compound concentration is 30mM respectively Sodium Fluoride, Sodium Bromide, SODIUMNITRATE, sodium-chlor, sodium pyrosulfate, sodium carbonate, sodium azide, Sodium Thiocyanate 99, sodium disulfide and sodium-acetate;
(3) in every a 6 '-hydroxyl naphthyl-2-alpha-cyanoacrylate 2-(2-methoxy ethoxy) ethoxy aqueous solution of ester, drip respectively a kind of aqueous solution 0.1ml that step (2) is prepared, after mixing, the fluorescence color of observing 6 '-hydroxyl naphthyl-2-alpha-cyanoacrylate 2-(2-methoxy ethoxy) ethoxy aqueous solution of ester under 365nm optical excitation changes.
Result shows, add after sodium fluoride aqueous solution, the fluorescence color of 6 '-hydroxyl naphthyl-2-alpha-cyanoacrylate 2-(2-methoxy ethoxy) ethoxy aqueous solution of ester becomes blueness by green, and add after 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 '-hydroxyl naphthyl-2-alpha-cyanoacrylate 2-(2-methoxy ethoxy) ethoxy aqueous solution of ester all remains unchanged.This result shows, 6 '-hydroxyl naphthyl-2-alpha-cyanoacrylate 2-(2-methoxy ethoxy) ethoxy ester can be at fluoroscopic examination fluorion under aqueous conditions.
Fluorescence spectrum before and after the aqueous solution that the inventor also prepares 6 '-hydroxyl naphthyl-2-alpha-cyanoacrylate 2-(2-methoxy ethoxy) ethoxy aqueous solution of ester dropping step (2) is studied.Found that, in dripping the process of sodium fluoride aqueous solution, the fluorescence spectrum of solution is by 490nm blue shift to 450nm, and in dripping the process of other aqueous solution, the variation of the fluorescence spectrum of solution is less.This result of study explanation, 6 '-hydroxyl naphthyl-2-alpha-cyanoacrylate 2-(2-methoxy ethoxy) ethoxy 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 that contains 6 '-hydroxyl naphthyl-2-alpha-cyanoacrylate 2-(2-methoxy ethoxy) ethoxy ester of 10,15,20 μ mol/ml, continue to cultivate after 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, U.S. Bao Te Instrument Ltd.) in excitation wavelength, be under 490nm condition, measure each hole absorbance, nutrient solution and the MTT that contains cell of take is control group, and nutrient solution and the MTT that only adds equivalent of take is blank well.Calculate according to the following equation cell survival rate: 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 '-hydroxyl naphthyl-2-alpha-cyanoacrylate 2-(2-methoxy ethoxy) ethoxy ester concentration is the cytotoxicity bar graph that X-coordinate is drawn 6 '-hydroxyl naphthyl-2-alpha-cyanoacrylate 2-(2-methoxy ethoxy) ethoxy ester, and result as shown in Figure 1.Fig. 1 shows that the cytotoxicity of 6 '-hydroxyl naphthyl-2-alpha-cyanoacrylate 2-(2-methoxy ethoxy) ethoxy 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, using the RPMI-1640 that contains 10 μ mol/ml6 '-hydroxyl naphthyl-2-alpha-cyanoacrylate 2-(2-methoxy ethoxy) ethoxy ester instead continues to cultivate after 30min, with phosphate buffered saline buffer, clean 6 orifice plate 3 times, remove excessive 6 '-hydroxyl naphthyl-2-alpha-cyanoacrylate 2-(2-methoxy ethoxy) ethoxy ester.Continue to add the RPMI-1640 of propidium iodide (10 μ g/ml) to continue to cultivate after 30min, with phosphate buffered saline buffer, clean 6 orifice plate 3 times, remove excessive propidium iodide.Cell is placed under laser confocal microscope and is observed, and there is green fluorescence in the cell after 6 '-hydroxyl naphthyl-2-alpha-cyanoacrylate 2-(2-methoxy ethoxy) ethoxy ester is processed in tenuigenin.Result shows that 6 '-hydroxyl naphthyl-2-alpha-cyanoacrylate 2-(2-methoxy ethoxy) ethoxy ester has good cell-penetrating, can be for the preparation of the fluorescent probe that detects 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, using the RPMI-1640 that contains 10 μ mol/ml6 '-hydroxyl naphthyl-2-alpha-cyanoacrylate 2-(2-methoxy ethoxy) ethoxy ester instead continues to cultivate after 30min, with phosphate buffered saline buffer, clean 6 orifice plate 3 times, remove excessive 6 '-hydroxyl naphthyl-2-alpha-cyanoacrylate 2-(2-methoxy ethoxy) ethoxy ester.Use the DMEM nutrient solution that contains 100 μ mol/mlNaF instead and continue to cultivate after 30min, with phosphate buffered saline buffer, clean 6 orifice plate 3 times, remove excessive fluorion.The RPMI-1640 of using instead containing propidium iodide (10 μ g/ml) continues to cultivate after 30min, with phosphate buffered saline buffer, cleans 6 orifice plate 3 times, removes excessive propidium iodide.Cell is placed under laser confocal microscope and is observed.Result demonstration, fluorion enters after cell, and the fluorescence color that the cell after 6 '-hydroxyl naphthyl-2-alpha-cyanoacrylate 2-(2-methoxy ethoxy) ethoxy ester is processed shows in tenuigenin changes blueness into.Result shows that 6 '-hydroxyl naphthyl-2-alpha-cyanoacrylate 2-(2-methoxy ethoxy) ethoxy ester can detect intracellular fluorion.
Embodiment 2
The preparation of 1.6 '-hydroxyl naphthyl-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 adds 30ml anhydrous tetrahydro furan.Under room temperature, react after 24 hours, underpressure distillation is except desolventizing, and residual solids is ethyl acetate with silicagel column at eluent components: normal hexane=1:4(v/v) lower 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 '-hydroxyl naphthyl-2-Methyl 2-cyanoacrylate.
3. detect fluorion in the aqueous solution
(1) 6 '-hydroxyl naphthyl-2-Methyl 2-cyanoacrylate acetonitrile solution that compound concentration is 30mM, get respectively 10 μ l6 '-hydroxyl naphthyl-2-Methyl 2-cyanoacrylate acetonitrile solution, add distilled water rare to 10ml, obtain 10 parts of 6 '-hydroxyl naphthyl-2-alpha-cyanoacrylate aqueous solution of ester;
(2) aqueous solution of compound concentration is 30mM respectively Sodium Fluoride, Sodium Bromide, SODIUMNITRATE, sodium-chlor, sodium pyrosulfate, sodium carbonate, sodium azide, Sodium Thiocyanate 99, sodium disulfide and sodium-acetate;
(3) in every a 10ml6 '-hydroxyl naphthyl-2-Methyl 2-cyanoacrylate aqueous solution, drip respectively a kind of aqueous solution 0.1ml that step (2) is prepared, after mixing, the fluorescence color of observing 6 '-hydroxyl naphthyl-2-Methyl 2-cyanoacrylate aqueous solution under 365nm optical excitation changes.
Result shows, add after sodium fluoride aqueous solution, the fluorescence color of 6 '-hydroxyl naphthyl-2-Methyl 2-cyanoacrylate aqueous solution becomes blueness by green, and add after 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 '-hydroxyl naphthyl-2-Methyl 2-cyanoacrylate aqueous solution all remains unchanged.This result shows, 6 '-hydroxyl naphthyl-2-Methyl 2-cyanoacrylate demonstrates selectivity and fluorescence recognition capability to fluorion.
Embodiment 3
The preparation of 1.6 '-hydroxyl naphthyl-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 adds 30ml anhydrous tetrahydro furan.Under room temperature, react after 24 hours, underpressure distillation is except desolventizing, and residual solids is ethyl acetate with silicagel column at eluent components: normal hexane=1:4(v/v) lower 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 '-hydroxyl naphthyl-2-cyanacrylate.
3. detect fluorion in the aqueous solution
6 '-hydroxyl naphthyl-2-cyanacrylate is dissolved in DMF, making concentration is 6 '-hydroxyl naphthyl-2-Methyl 2-cyanoacrylate DMF solution of 30 mM, then adopts the same method of embodiment 2 to detect fluorion in the aqueous solution by 6 '-hydroxyl naphthyl-2-cyanacrylate.Result shows, add after sodium fluoride aqueous solution, the fluorescence color of 6 '-hydroxyl naphthyl-2-cyanacrylate aqueous solution becomes blueness by green, and add after 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 '-hydroxyl naphthyl-2-cyanacrylate aqueous solution all remains unchanged.This result shows, 6 '-hydroxyl naphthyl-2-cyanacrylate demonstrates selectivity and fluorescence recognition capability to fluorion.
Embodiment 4
6 '-hydroxyl naphthyl-2-alpha-cyanoacrylate propyl ester
The preparation of 1.6 '-hydroxyl naphthyl-2-alpha-cyanoacrylate propyl ester
In 100ml flask, add 3.44g6-hydroxyl-2-naphthaldehyde, 2.54g 2-Malonic mononitrile propyl ester and 0.5g N, N-dimethyl-4-aminopyridine, then adds 30ml anhydrous tetrahydro furan.Under room temperature, react after 24 hours, underpressure distillation is except desolventizing, and residual solids is ethyl acetate with silicagel column at eluent components: normal hexane=1:4(v/v) lower 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 '-hydroxyl naphthyl-2-alpha-cyanoacrylate propyl ester.
3. detect fluorion in the aqueous solution
6 '-hydroxyl naphthyl-2-cyanacrylate is dissolved in DMSO, making concentration is 6 '-hydroxyl naphthyl-2-Methyl 2-cyanoacrylate DMSO solution of 30 mM, then adopts the same method of embodiment 2 to detect fluorion in the aqueous solution by 6 '-hydroxyl naphthyl-2-cyanacrylate.Result shows, add after sodium fluoride aqueous solution, the fluorescence color of 6 '-hydroxyl naphthyl-2-cyanacrylate aqueous solution becomes blueness by green, and add after 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 '-hydroxyl naphthyl-2-cyanacrylate aqueous solution all remains unchanged.This result shows, 6 '-hydroxyl naphthyl-2-cyanacrylate demonstrates selectivity and fluorescence recognition capability to fluorion.
6 '-hydroxyl naphthyl-2-Tisuacryl
The preparation of 1.6 '-hydroxyl naphthyl-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 adds 30ml anhydrous tetrahydro furan.Under room temperature, react after 24 hours, underpressure distillation is except desolventizing, and residual solids is ethyl acetate with silicagel column at eluent components: normal hexane=1:4(v/v) lower 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(100?MHz,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 '-hydroxyl naphthyl-2-Tisuacryl.
Embodiment 6
6 '-hydroxyl naphthyl-2-alpha-cyanoacrylate (2-N, N-dimethylamino) ethyl ester
The preparation of 1.6 '-hydroxyl naphthyl-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 adds 30ml anhydrous tetrahydro furan.Under room temperature, react after 24 hours, underpressure distillation is except desolventizing, and residual solids is methylene dichloride with silicagel column at eluent components: methyl alcohol=10:0.5(v/v) lower 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 '-hydroxyl naphthyl-2-alpha-cyanoacrylate (2-N, N-dimethylamino) ethyl ester.
3. detect fluorion in the aqueous solution
6 '-hydroxyl naphthyl-2-cyanacrylate is dissolved in THF, making concentration is 6 '-hydroxyl naphthyl-2-Methyl 2-cyanoacrylate THF solution of 30 mM, then adopt the same method of embodiment 2, with 6 '-hydroxyl naphthyl-2-alpha-cyanoacrylate (2-N, N-dimethylamino) ethyl ester, detect fluorion in the aqueous solution.Result shows, add after sodium fluoride aqueous solution, 6 '-hydroxyl naphthyl-2-alpha-cyanoacrylate (2-N, N-dimethylamino) fluorescence color of the ethyl ester aqueous solution becomes blueness by green, and add after 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 '-hydroxyl naphthyl-2-alpha-cyanoacrylate (2-N, N-dimethylamino) ethyl ester aqueous solution all remains unchanged.This result shows, 6 '-hydroxyl naphthyl-2-alpha-cyanoacrylate (2-N, N-dimethylamino) ethyl ester demonstrates selectivity and fluorescence recognition capability to fluorion.
Claims (5)
1. 6 '-hydroxyl naphthyl-2-cyanoacrylate, its structural formula is shown in following formula (I):
In formula (I), R is methyl, ethyl, propyl group, butyl, 2-(2-methoxy ethoxy) oxyethyl group or 2-(N, N-dimethyl) amido ethyl.
2. 6 '-hydroxyl according to claim 1 naphthyl-2 cyanoacrylate, is characterized in that in formula (I), and R is 2-(2-methoxy ethoxy) oxyethyl group.
3. the application of the naphthyl-2-of 6 '-hydroxyl described in claim 1 or 2 cyanoacrylate fluorion in detecting the aqueous solution.
4. application according to claim 3, is characterized in that, in the described detection aqueous solution, the method for fluorion is comprised of following steps:
(1) 6 '-hydroxyl naphthyl-2-cyanoacrylate is dissolved in hydrophilic organic solvent, then toward adding volume multiple in gained solution, be 99 water, prepare the aqueous solution of 6 '-hydroxyl naphthyl-2-cyanoacrylate, wherein said hydrophilic organic solvent is acetonitrile, THF, DMF or DMSO;
(2) then, in the prepared aqueous solution of step (1), drip sample aqueous solution, under the optical excitation that is 365nm at wavelength, observe the prepared aqueous solution of step (1) in the variation that drips the fluorescence color of sample aqueous solution front and back, if described fluorescence color becomes blueness by green, in the interpret sample aqueous solution, contain fluorion.
5. naphthyl-the 2-of 6 '-hydroxyl described in claim 1 or 2 cyanoacrylate application in fluorion in detecting cell.
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|---|---|---|---|---|
| CN106431986A (en) * | 2016-09-29 | 2017-02-22 | 济南大学 | Fluorescent probe for detecting hydrazine and application thereof |
| CN106632138A (en) * | 2016-09-23 | 2017-05-10 | 济南大学 | Micromolecular fluorescent probe for hydrazine identification and application of micromolecular fluorescent probe |
| CN114207064A (en) * | 2019-08-08 | 2022-03-18 | 东亚合成株式会社 | Adhesive composition easily decomposable in water |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106632138A (en) * | 2016-09-23 | 2017-05-10 | 济南大学 | Micromolecular fluorescent probe for hydrazine identification and application of micromolecular fluorescent probe |
| CN106632138B (en) * | 2016-09-23 | 2018-11-30 | 济南大学 | It is a kind of identify hydrazine small-molecule fluorescent probe and its application |
| CN106431986A (en) * | 2016-09-29 | 2017-02-22 | 济南大学 | Fluorescent probe for detecting hydrazine and application thereof |
| CN106431986B (en) * | 2016-09-29 | 2017-12-26 | 济南大学 | A kind of fluorescence probe for detecting hydrazine and its application |
| CN114207064A (en) * | 2019-08-08 | 2022-03-18 | 东亚合成株式会社 | Adhesive composition easily decomposable in water |
| 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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| CN103709069B (en) | 2015-03-18 |
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