CN101602745B - Synthetic method and application of N, N'-bis-[3-hydroxy-4-(2-benzothiazole)phenyl] carbamide - Google Patents
Synthetic method and application of N, N'-bis-[3-hydroxy-4-(2-benzothiazole)phenyl] carbamide Download PDFInfo
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- CN101602745B CN101602745B CN2009100125186A CN200910012518A CN101602745B CN 101602745 B CN101602745 B CN 101602745B CN 2009100125186 A CN2009100125186 A CN 2009100125186A CN 200910012518 A CN200910012518 A CN 200910012518A CN 101602745 B CN101602745 B CN 101602745B
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Abstract
The invention relates to the field of chemistry, in particular to a synthetic method and application of N, N'-bis-[3-hydroxy-4-(2-benzothiazole)phenyl] carbamide. The molecular structural formula of the N,N'-2-[3-hydroxy-4-(2-benzothiazole)phenyl] carbamide is shown at below; and the synthetic method of the N, N'-bis-[3-hydroxy-4-(2-benzothiazole)phenyl] carbamide comprises the step that 2-(4-amido-2-hydroxybenzene radical) benzothiazole, 4-AHBA for short, and carbonyl imidazole, CDI for short, are used as raw materials, the raw materials are reacted in toluene, benzene or xylene solvents to obtain the N, N'-bis-[3-hydroxy-4-(2-benzothiazole)phenyl] carbamide, for short 4-DHBTU. The reaction equation is shown at below. The invention has available reaction raw materials, mild reaction conditions and high yield; any other catalysts and (or) reaction auxiliary agents do not need to be added in the reaction process, the operation is simple and safe, the phenolic hydroxyl radical of the 4-AHBA does not need to be protected, and the recovery of a byproduct of the imidazole is convenient; and the 4-DHBTU is used as a fluorescent probe and used for the detection of Zn<2+>, the measured concentration lower limit of the Zn<2+> can reach 1*10<-10>mol/L, and Fe<2+>, Fe<3+>, Cd<2+>, Co<2+>, Mn<2+>, Cu<2+>, Ni<2+>, Ag<+>, Sn<2+>, La<3+> and Pb<2+> all do not interfere the measurement of the concentration of the Zn<2+>.
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%.
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. 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 with 2-(4-amino-2-hydroxy phenyl) benzothiazole and carbonylic imidazole, reaction obtains N, N '-two-[3-hydroxyl-4-(2-[4-morpholinodithio) phenyl] urea in toluene, benzene or xylene solvent;
Reactions steps is: with 2-(4-amino-2-hydroxy phenyl) benzothiazole and carbonylic imidazole 2-(4-amino-2-hydroxy phenyl) benzothiazole in molar ratio: the ratio of carbonylic imidazole=1: 0.5～20 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 logical nitrogen or helium protection; 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, N '-two-[3-hydroxyl-4-(2-[4-morpholinodithio) phenyl] urea detects Zn as fluorescent probe
2+Application, it is characterized in that, accurately prepare 1 * 10
-6-1 * 10
-5Mol/L N, N '-two-[3-hydroxyl-4-(2-[4-morpholinodithio) phenyl] urea 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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| CN101602745B true CN101602745B (en) | 2011-05-25 |
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| CN101914063B (en) * | 2010-08-05 | 2011-11-23 | 大连大学 | N, N'-di-[3- hydroxyl-4-(2- benzimidazole) phenyl] urea and application thereof as zinc ion fluorescent probe |
| CN102703441B (en) * | 2012-04-28 | 2013-09-25 | 陕西师范大学 | Hairpin type nucleic acid fluorescent probe and application of probe in lead ion detection |
| 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 |
| CN103265539B (en) * | 2013-04-19 | 2015-09-02 | 浙江大学 | For distinguishing fluorescent probe benzothiazole-terpyridyl compounds and the methods for making and using same thereof of detection zine ion and cadmium ion |
| 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 |
| CN105985289B (en) * | 2015-02-15 | 2018-12-21 | 正大天晴药业集团股份有限公司 | A kind of pleasure cuts down the preparation method for Buddhist nun |
| CN106831642B (en) * | 2017-04-05 | 2019-02-26 | 南京工业大学 | For detecting zinc ion or pyrophosphate fluorescence probe, preparation method and application |
| US11873432B2 (en) * | 2018-11-29 | 2024-01-16 | Honeywell International Inc. | Luminescent materials including a luminescent benzothiazole, articles including a security feature, and methods of forming luminescent particles including a luminescent benzothiazole |
| CN112812075B (en) * | 2020-12-30 | 2022-05-31 | 山西大学 | Preparation method and application of benzothiazole Schiff base-based fluorescent probe |
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