CN101602745A - A kind of N, the synthetic method and the application of N '-two-[3-hydroxyl-4-(2-[4-morpholinodithio) phenyl] urea - Google Patents
A kind of N, the synthetic method and the application of N '-two-[3-hydroxyl-4-(2-[4-morpholinodithio) phenyl] urea Download PDFInfo
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- CN101602745A CN101602745A CNA2009100125186A CN200910012518A CN101602745A CN 101602745 A CN101602745 A CN 101602745A CN A2009100125186 A CNA2009100125186 A CN A2009100125186A CN 200910012518 A CN200910012518 A CN 200910012518A CN 101602745 A CN101602745 A CN 101602745A
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Abstract
The present invention relates to chemical field, be specifically related to a kind of N, the synthetic method and the application of N '-two-[3-hydroxyl-4-(2-[4-morpholinodithio) phenyl] urea.A kind of N, N '-two-[3-hydroxyl-4-(2-[4-morpholinodithio) phenyl] urea, its molecular structural formula such as the right side: its synthetic method is with 2-(4-amino-2-hydroxy phenyl) benzothiazole, be called for short 4-AHBA and carbonylic imidazole, abbreviation CDI is a raw material, reaction obtains N in toluene, benzene or xylene solvent, and N '-two-[3-hydroxyl-4-(2-[4-morpholinodithio) phenyl] urea is called for short 4-DHBTU.Reaction equation such as upper right: reaction raw materials of the present invention is easy to get, reaction conditions gentleness, productive rate height; And need not in the reaction process to add any other catalyzer and (or) reaction promoter, safety simple to operate need not the phenolic hydroxyl group of 4-AHBA is protected, the by product imidazoles reclaims convenient; 4-DHBTU is used for Zn as fluorescent probe
2+Detection, measure Zn
2+Concentration limit can reach 1 * 10
-10Mol/L, and Fe
2+, Fe
3+, Cd
2+, Co
2+, Mn
2+, Cu
2+, Ni
2+, Ag
+, Sn
2+, La
3+, Pb
2+All do not disturb Zn
2+The mensuration of concentration.
Description
Technical field
The present invention relates to chemical field, be specifically related to a kind of excited state molecule inner proton transfer-urea derivatives N, the new synthetic method of N ' two-[3-hydroxyl-4-(2-[4-morpholinodithio) phenyl] urea (4-DHBTU); And this compound as fluorescent probe at Zn
2+Application in the detection.
Background technology
The excited state molecule inner proton shifts (ESIPT)-urea derivatives and is widely used in chemical sensor, laser dyes and UV light stabilizing agent etc.Synthetic urea derivatives typical method has the addition of amine and isocyanic ester and the reaction of amine and carbamyl halogen.But these methods are because of the difficult preparation of raw material, instability, and reaction yield is low, and shortcoming such as aftertreatment difficulty, makes its range of application be subjected to certain restriction.
Summary of the invention
The excited state molecule inner proton transfer-urea derivatives N that the purpose of this invention is to provide a kind of novelty, the simple synthetic method of N '-two-[3-hydroxyl-4-(2-[4-morpholinodithio) phenyl] urea (be called for short 4-DHBTU), and this compound is used for Zn as fluorescent probe
2+Detection, improve to detect Zn
2+Sensitivity.
Technical scheme of the present invention: a kind of N, N '-two-[3-hydroxyl-4-(2-[4-morpholinodithio) phenyl] urea, its molecular structural formula is as follows:
Above-mentioned N, the synthetic method of N '-two-[3-hydroxyl-4-(2-[4-morpholinodithio) phenyl] urea: with 2-(4-amino-2-hydroxy phenyl) benzothiazole, be called for short 4-AHBA and carbonylic imidazole, abbreviation CDI is a raw material, reaction obtains N in toluene, benzene or xylene solvent, N '-two-[3-hydroxyl-4-(2-[4-morpholinodithio) phenyl] urea is called for short 4-DHBTU.Reaction equation is as follows:
Concrete reactions steps is as follows: with 4-AHBA and CDI 4-AHBA: CDI=1 in molar ratio: 0.5～20 ratio joins in the solvent to material dissolution; stirring and refluxing is to a large amount of faint yellow solids occurring, stopped reaction under the condition of dry and protection of inert gas such as logical nitrogen or helium.The evaporated under reduced pressure solvent is used volume ratio CH
2Cl
2: CH
3OH=20～5: 1 carries out silica gel column chromatography with product purification as eluent, obtains yellow solid matter, and the productive rate of 4-DHBTU is 40-90%.Described solvent is toluene, benzene or dimethylbenzene.
Aforesaid method synthetic N, the application of N '-two-[3-hydroxyl-4-(2-[4-morpholinodithio) phenyl] urea: 4-DHBTU detects Zn as fluorescent probe
2+Method: accurately prepare 1 * 10
-6-1 * 10
-5Mol/L 4-DHBTU acetonitrile solution, and in this solution, add Zn
2+The aqueous standard sample is mixed with and contains Zn
2+Concentration is 10
-10-10
-4The standard model 5-10 of mol/L, measure fluorescence spectrum.The bigger new peak of intensity has appearred in the 445nm place on the fluorescence spectrum, is ordinate zou with the fluorescence peak area at 445nm place, lg (c/10
-11) as the X-coordinate curve of working, c is Zn
2+Volumetric molar concentration.This method is measured Zn
2+Concentration limit can reach 1 * 10
-10Mol/L, and Fe
2+, Fe
3+, Cd
2+, Co
2+, Mn
2+, Cu
2+, Ni
2+, Ag
+, Sn
2+, La
3+, Pb
2+All do not disturb Zn
2+The mensuration of concentration, actual sample and working curve contrast, its recovery of standard addition is all within desired scope.
The beneficial effect that the present invention reached is: reaction raw materials is easy to get, stablizes reaction conditions gentleness, productive rate height; And need not in the reaction process to add any other catalyzer and (or) reaction promoter, safety simple to operate need not the phenolic hydroxyl group of 4-AHBA is protected, the by product imidazoles can obtain reclaiming very easily; Compound 4-DHBTU is as detecting Zn
2+Fluorescent probe, the detection sensitivity height detects lower limit and can reach 1 * 10
-10Mol/L.
Description of drawings
Fig. 1 is 4-DHBTU acetonitrile solution 445nm place's fluorescent emission peak area and Zn among the embodiment 2
2+The working curve of concentration relationship.
Embodiment
Embodiment 1
With 0.242g 2-(4-amino-2-hydroxy phenyl) benzothiazole (4-AHBA; 1mmol) (CDI 1.2mmol) joins in the 20mL toluene, stirring and refluxing 8h under the condition of dry and logical nitrogen protection with the 0.198g carbonylic imidazole; a large amount of faint yellow solids appears, stopped reaction.The evaporated under reduced pressure solvent is used volume ratio CH
2Cl
2: CH
3OH=10: 1 carries out silica gel column chromatography with product purification as eluent, obtains a yellow solid matter, productive rate 90%.
Embodiment 2
Be mixed with 5 * 10 with the 100mL volumetric flask
-6Mol/L 4-DHBTU acetonitrile solution is got this solution of 10mL then respectively and is joined in 7 10mL volumetric flasks, prepares 2 * 10 respectively
-8Mol/L, 2 * 10
-7Mol/L, 2 * 10
-6Mol/L, 2 * 10
-5Mol/L, 2 * 10
-4Mol/L, 2 * 10
-3Mol/L, 2 * 10
-2The Zn of mol/L
2+The aqueous solution is respectively got 50 μ L and is joined in 7 10mL 4-DHBTU acetonitrile solutions, so approximately thinks Zn
2+Concentration is respectively 1 * 10
-10Mol/L, 1 * 10
-9Mol/L, 1 * 10
-8Mol/L, 1 * 10
-7Mol/L, 1 * 10
-6Mol/L, 1 * 10
-5Mol/L, 1 * 10
-4Mol/L shakes up the back and measures fluorescence spectrum.Fluorescence peak area with the 445nm place is an ordinate zou, lg (c/10
-11) being the X-coordinate curve of working, c is Zn
2+Volumetric molar concentration.Working curve is seen Fig. 1, and the two presents exponential relationship, fluorescence peak area (A) and Zn
2+The Trendline equation of concentration c is:
A＝2.1015×10
6c
0.2481(R
2＝0.9213)
Recovery of standard addition calculated example: treat test sample fluorescence peak integral area A
1=33475, calculating concentration c
1=5.6120 * 10
-8, add standard Zn
2+Concentration be 5 * 10
-9Mol/L measures fluorescence peak integral area A
2=34153, calculating recovery of standard addition is 104%.
Claims (3)
1, a kind of N, N '-two-[3-hydroxyl-4-(2-[4-morpholinodithio) phenyl] urea is characterized in that molecular structural formula is as follows:
2, the described a kind of N of claim 1, the synthetic method of N '-two-[3-hydroxyl-4-(2-[4-morpholinodithio) phenyl] urea, it is characterized in that, this method is called for short 4-AHBA and carbonylic imidazole with 2-(4-amino-2-hydroxy phenyl) benzothiazole, and abbreviation CDI is a raw material, reaction obtains N in toluene, benzene or xylene solvent, N '-two-[3-hydroxyl-4-(2-[4-morpholinodithio) phenyl] urea is called for short 4-DHBTU, and reaction equation is as follows:
Reactions steps is: with 4-AHBA and CDI 4-AHBA: CDI=1 in molar ratio: 0.5～20 ratio joins in the solvent to material dissolution; stirring and refluxing is to a large amount of faint yellow solids occurring under the condition of dry and protection of inert gas such as logical nitrogen or helium; stopped reaction; the evaporated under reduced pressure solvent is used volume ratio CH
2Cl
2: CH
3OH=20～5: 1 carries out silica gel column chromatography with product purification as eluent, obtains yellow solid matter, and described solvent is toluene, benzene or dimethylbenzene.
3, the described a kind of N of claim 1, the application of N '-two-[3-hydroxyl-4-(2-[4-morpholinodithio) phenyl] urea is characterized in that 4-DHBTU detects Zn as fluorescent probe
2+Method: accurately prepare 1 * 10
-6-1 * 10
5Mol/L 4-DHBTU acetonitrile solution, and in this solution, add Zn
2+The aqueous standard sample is mixed with and contains Zn
2+Concentration is 10
-10-10
-4The standard model 5-10 of mol/L measures fluorescence spectrum, and the bigger new peak of intensity has appearred in the 445nm place on the fluorescence spectrum, is ordinate zou with the fluorescence peak area at 445nm place, lg (c/10
-11) as the X-coordinate curve of working, c is Zn
2+Volumetric molar concentration detects lower limit and can reach 1 * 10
-10Mol/L.
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|---|---|---|---|
| CN2009100125186A CN101602745B (en) | 2009-07-10 | 2009-07-10 | Synthetic method and application of N, N'-bis-[3-hydroxy-4-(2-benzothiazole)phenyl] carbamide |
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|---|---|---|---|
| CN2009100125186A CN101602745B (en) | 2009-07-10 | 2009-07-10 | Synthetic method and application of N, N'-bis-[3-hydroxy-4-(2-benzothiazole)phenyl] carbamide |
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|---|---|
| CN101602745A true CN101602745A (en) | 2009-12-16 |
| CN101602745B CN101602745B (en) | 2011-05-25 |
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| CN102703441A (en) * | 2012-04-28 | 2012-10-03 | 陕西师范大学 | Hairpin type nucleic acid fluorescent probe and application of probe in lead ion detection |
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| CN102735663B (en) * | 2012-07-19 | 2014-07-09 | 贵州大学 | High sensitivity and high selectivity fluorescence quenching spectrum analysis method for cobalt ions |
| CN102735663A (en) * | 2012-07-19 | 2012-10-17 | 贵州大学 | High sensitivity and high selectivity fluorescence quenching spectrum analysis method for cobalt ions |
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| CN103896874A (en) * | 2014-04-03 | 2014-07-02 | 河北工业大学 | Open chain crown ether type compound as well as preparation method and application thereof |
| CN103896874B (en) * | 2014-04-03 | 2015-08-19 | 河北工业大学 | A kind of open chain crown ether type compound and its preparation method and application |
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| CN113330093A (en) * | 2018-11-29 | 2021-08-31 | 霍尼韦尔国际公司 | Luminescent materials comprising luminescent benzothiazole, articles including security features, and methods of forming luminescent particles comprising luminescent benzothiazole |
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| CN101602745B (en) | 2011-05-25 |
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Granted publication date: 20110525 Termination date: 20120710 |