CN101602745A

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Publication number: CN101602745A
Application number: CNA2009100125186A
Authority: CN
Inventors: 尹静梅; 阳强; 贾颖萍; 崔颖娜; 周广运; 高大彬
Original assignee: Dalian University
Current assignee: Dalian University
Priority date: 2009-07-10
Filing date: 2009-07-10
Publication date: 2009-12-16
Anticipated expiration: 2029-07-10
Also published as: CN101602745B

Abstract

本发明涉及化学领域，具体涉及一种N，N’－二－[3－羟基－4－(2－苯并噻唑)苯基]脲的合成方法及应用。一种N，N’－二－[3－羟基－4－(2－苯并噻唑)苯基]脲，其分子结构式如右：其合成方法是以2－(4－氨基－2－羟基苯基)苯并噻唑，简称4－AHBA和羰基咪唑，简称CDI为原料，在甲苯、苯或二甲苯溶剂中反应得到N，N’－二－[3－羟基－4－(2－苯并噻唑)苯基]脲，简称4－DHBTU。反应方程式如右上：本发明反应原料易得，反应条件温和，产率高；且反应过程中无需添加任何其它的催化剂和(或)反应助剂，操作简单安全，无需对4－AHBA的酚羟基进行保护，副产物咪唑回收方便；4－DHBTU作为荧光探针用于Zn²⁺的检测，测定Zn²⁺浓度下限可达到1×10^－10mol/L，且Fe²⁺，Fe³⁺，Cd²⁺，Co²⁺，Mn²⁺，Cu²⁺，Ni²⁺，Ag⁺，Sn²⁺，La³⁺，Pb²⁺均不干扰Zn²⁺浓度的测定。

The invention relates to the field of chemistry, in particular to a synthesis method and application of N,N'-bis-[3-hydroxy-4-(2-benzothiazole)phenyl]urea. A kind of N,N'-bis-[3-hydroxyl-4-(2-benzothiazole)phenyl]urea, its molecular structure is as follows: its synthesis method is based on 2-(4-amino-2-hydroxybenzene Base) benzothiazole, referred to as 4-AHBA and carbonylimidazole, referred to as CDI as raw materials, react in toluene, benzene or xylene solvent to obtain N, N'-di-[3-hydroxyl-4-(2-benzothiazole ) phenyl] urea, referred to as 4-DHBTU. The reaction equation is shown on the upper right: the reaction raw materials of the present invention are easy to obtain, the reaction conditions are mild, and the yield is high; and there is no need to add any other catalysts and (or) reaction aids during the reaction process, the operation is simple and safe, and there is no need to modify the phenolic hydroxyl group of 4-AHBA. protection, the by-product imidazole is convenient to recover; 4-DHBTU is used as a fluorescent probe for the detection of Zn²⁺ , and the lower limit of the concentration of Zn²⁺ can reach 1×10^-10 mol/L, and Fe²⁺ , Fe³⁺ , Cd²⁺ , Co²⁺ , Mn²⁺ , Cu²⁺ , Ni²⁺ , Ag⁺ , Sn²⁺ , La³⁺ , and Pb²⁺ did not interfere with the determination of Zn²⁺ concentration.

Description

Translated fromChinese

一种N，N’-二-[3-羟基-4-(2-苯并噻唑)苯基]脲的合成方法及应用A kind of synthetic method and application of N, N'-di-[3-hydroxyl-4-(2-benzothiazole) phenyl]urea

技术领域technical field

本发明涉及化学领域，具体涉及一种激发态分子内质子转移-脲衍生物N，N’二-[3-羟基-4-(2-苯并噻唑)苯基]脲(4-DHBTU)的新的合成方法；以及该化合物作为荧光探针在Zn²⁺检测中的应用。The invention relates to the field of chemistry, in particular to a kind of excited state intramolecular proton transfer-urea derivative N, N'di-[3-hydroxyl-4-(2-benzothiazole)phenyl]urea (4-DHBTU) A new synthesis method; and the application of the compound as a fluorescent probe in the detection of Zn²⁺ .

背景技术Background technique

激发态分子内质子转移(ESIPT)-脲衍生物广泛用于化学传感器、激光染料以及紫外光稳定剂等。合成脲衍生物典型的方法有胺和异氰酸酯的加成以及胺与氨基甲酰卤的反应。但这些方法因原料较难制备，不稳定，反应产率低，且后处理困难等缺点，使其应用范围受到了一定的限制。Excited-state intramolecular proton transfer (ESIPT)-urea derivatives are widely used in chemical sensors, laser dyes, and UV light stabilizers. Typical methods for the synthesis of urea derivatives include the addition of amines to isocyanates and the reaction of amines with carbamoyl halides. However, due to the disadvantages of difficult preparation of raw materials, instability, low reaction yield, and difficult post-processing, the application range of these methods is limited to a certain extent.

发明内容Contents of the invention

本发明的目的是提供一种新颖的激发态分子内质子转移-脲衍生物N，N’-二-[3-羟基-4-(2-苯并噻唑)苯基]脲(简称4-DHBTU)的简单的合成方法，并将该化合物作为荧光探针用于Zn²⁺的检测，提高检测Zn²⁺的灵敏度。The object of the present invention is to provide a novel excited state intramolecular proton transfer-urea derivative N, N'-two-[3-hydroxyl-4-(2-benzothiazole) phenyl]urea (abbreviated 4-DHBTU ), and the compound is used as a fluorescent probe for the detection of Zn²⁺ to improve the sensitivity of detecting Zn²⁺ .

本发明的技术方案：一种N，N’-二-[3-羟基-4-(2-苯并噻唑)苯基]脲，其分子结构式如下：Technical scheme of the present invention: a kind of N, N'-two-[3-hydroxyl-4-(2-benzothiazole) phenyl] urea, its molecular structural formula is as follows:

上述N，N’-二-[3-羟基-4-(2-苯并噻唑)苯基]脲的合成方法：以2-(4-氨基-2-羟基苯基)苯并噻唑，简称4-AHBA和羰基咪唑，简称CDI为原料，在甲苯、苯或二甲苯溶剂中反应得到N，N’-二-[3-羟基-4-(2-苯并噻唑)苯基]脲，简称4-DHBTU。反应方程式如下：The above-mentioned N, N'-di-[3-hydroxyl-4-(2-benzothiazole) phenyl] urea synthesis method: 2-(4-amino-2-hydroxyphenyl) benzothiazole, referred to as 4 -AHBA and carbonyl imidazole, referred to as CDI as raw materials, react in toluene, benzene or xylene solvent to obtain N, N'-di-[3-hydroxy-4-(2-benzothiazole)phenyl]urea, referred to as 4 -DHBTU. The reaction equation is as follows:

具体反应步骤如下：将4-AHBA和CDI按摩尔比4-AHBA∶CDI＝1∶0.5～20的比例加入到溶剂中至原料溶解，在干燥和通氮气或氦气等惰性气体保护的条件下搅拌回流至出现大量的淡黄色固体，停止反应。减压蒸干溶剂，用体积比CH₂Cl₂∶CH₃OH＝20～5∶1作为洗脱剂进行硅胶柱层析将产物纯化，得到黄色固体物质，4-DHBTU的产率为40-90％。所述溶剂为甲苯、苯或二甲苯。The specific reaction steps are as follows: 4-AHBA and CDI are added to the solvent in a molar ratio of 4-AHBA:CDI=1:0.5～20 until the raw materials are dissolved, and under the conditions of drying and inert gas protection such as nitrogen or helium Stir and reflux until a large amount of light yellow solid appears, and stop the reaction. The solvent was evaporated to dryness under reduced pressure, and the product was purified by silica gel column chromatography with a volume ratio of CH₂ Cl₂ :_{CH 3} OH=20～5:1 as the eluent to obtain a yellow solid substance, and the yield of 4-DHBTU was 40- 90%. The solvent is toluene, benzene or xylene.

上述方法合成的N，N’-二-[3-羟基-4-(2-苯并噻唑)苯基]脲的应用：4-DHBTU作为荧光探针检测Zn²⁺的方法：准确配制1×10^-6-1×10^-5mol/L 4-DHBTU乙腈溶液，并向该溶液中加入Zn²⁺水溶液标准样品，配制成含Zn²⁺浓度为10^-10-10^-4mol/L的标准样品5-10个，测定荧光光谱。荧光光谱上445nm处出现了强度较大的新峰，以445nm处的荧光峰面积为纵坐标，lg(c/10^-11)作为横坐标做工作曲线，c为Zn²⁺摩尔浓度。此方法测定Zn²⁺浓度下限可达到1×10^-10mol/L，且Fe²⁺，Fe³⁺，Cd²⁺，Co²⁺，Mn²⁺，Cu²⁺，Ni²⁺，Ag⁺，Sn²⁺，La³⁺，Pb²⁺均不干扰Zn²⁺浓度的测定，实际样品与工作曲线对照，其加标回收率均在所要求的范围之内。The application of N, N'-bis-[3-hydroxyl-4-(2-benzothiazole)phenyl]urea synthesized by the above method: 4-DHBTU is used as a fluorescent probe to detect Zn²⁺ : accurate preparation of 1× 10^-6 -1×10^-5 mol/L 4-DHBTU acetonitrile solution, and Zn²⁺ aqueous solution standard sample was added to the solution to prepare a Zn²⁺ containing concentration of 10^-10 -10^-4 mol/L For 5-10 standard samples, measure the fluorescence spectrum. A new peak with higher intensity appeared at 445nm in the fluorescence spectrum. Take the area of the fluorescence peak at 445nm as the ordinate, lg(c/10^-11 ) as the abscissa to draw the working curve, and c is the molar concentration of Zn²⁺ . The lower limit of the concentration of Zn²⁺ determined by this method can reach 1×10^-10 mol/L, and Fe²⁺ , Fe³⁺ , Cd²⁺ , Co²⁺ , Mn²⁺ , Cu²⁺ , Ni²⁺ , Ag⁺ , Sn²⁺ , La³⁺ , and Pb²⁺ do not interfere with the determination of Zn²⁺ concentration. Compared with the actual sample and the working curve, the recoveries of the standard addition are all within the required range.

本发明所达到的有益效果是：反应原料易得、稳定，反应条件温和，产率高；且反应过程中无需添加任何其它的催化剂和(或)反应助剂，操作简单安全，无需对4-AHBA的酚羟基进行保护，副产物咪唑可以很方便的得到回收；化合物4-DHBTU作为检测Zn²⁺的荧光探针，检测灵敏度高，检测下限可以达到1×10^-10mol/L。The beneficial effects achieved by the present invention are: the reaction raw materials are easy to obtain and stable, the reaction conditions are mild, and the yield is high; and there is no need to add any other catalysts and (or) reaction aids in the reaction process, the operation is simple and safe, and no need for 4- The phenolic hydroxyl group of AHBA is protected, and the by-product imidazole can be easily recovered; the compound 4-DHBTU is used as a fluorescent probe for detecting Zn²⁺ , with high detection sensitivity, and the detection limit can reach 1×10^-10 mol/L.

附图说明Description of drawings

图1是实施例2中4-DHBTU乙腈溶液445nm处荧光发射峰面积与Zn²⁺浓度关系的工作曲线。Fig. 1 is the working curve of the relationship between the fluorescence emission peak area at 445nm of 4-DHBTU acetonitrile solution and the^{concentration} of Zn in Example 2.

具体实施方式Detailed ways

实施例1Example 1

将0.242g 2-(4-氨基-2-羟基苯基)苯并噻唑(4-AHBA，1mmol)和0.198g羰基咪唑(CDI，1.2mmol)加入到20mL甲苯中，在干燥和通氮气保护的条件下搅拌回流8h，出现大量的淡黄色固体，停止反应。减压蒸干溶剂，用体积比CH₂Cl₂∶CH₃OH＝10∶1作为洗脱剂进行硅胶柱层析将产物纯化，得到一黄色固体物质，产率90％。0.242g 2-(4-amino-2-hydroxyphenyl)benzothiazole (4-AHBA, 1mmol) and 0.198g carbonylimidazole (CDI, 1.2mmol) were added to 20mL toluene, in a dry and nitrogen-protected Stirring and reflux under the conditions for 8h, a large amount of light yellow solid appeared, and the reaction was stopped. The solvent was evaporated to dryness under reduced pressure, and the product was purified by silica gel column chromatography using a volume ratio of CH₂ Cl₂ :_{CH 3} OH=10:1 as the eluent to obtain a yellow solid substance with a yield of 90%.

实施例2Example 2

用100mL容量瓶配制成5×10^-6mol/L 4-DHBTU乙腈溶液，然后分别取10mL此溶液加入到7个10mL容量瓶中，分别配制2×10^-8mol/L，2×10^-7mol/L，2×10^-6mol/L，2×10^-5mol/L，2×10^-4mol/L，2×10^-3mol/L，2×10^-2mol/L的Zn²⁺水溶液，各取50μL加入到7个10mL 4-DHBTU乙腈溶液中，这样就近似认为Zn²⁺浓度分别为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，摇匀后测定荧光光谱。以445nm处的荧光峰面积为纵坐标，lg(c/10^-11)为横坐标做工作曲线，c为Zn²⁺摩尔浓度。工作曲线见图1，二者呈现指数关系，荧光峰面积(A)与Zn²⁺浓度c的趋势线方程是：Use a 100mL volumetric flask to prepare 5×10^-6 mol/L 4-DHBTU acetonitrile solution, then add 10mL of this solution to seven 10mL volumetric flasks to prepare 2×10^-8 mol/L, 2×10^{- 7} mol/L, 2×10^-6 mol/L, 2×10^-5 mol/L, 2×10^-4 mol/L, 2×10^-3 mol/L, 2×10^-2 mol/L Add 50 μL of Zn²⁺ aqueous solution to seven 10mL 4-DHBTU acetonitrile solutions, so that the Zn²⁺ concentration is approximately 1×10^-10 mol/L, 1×10^-9 mol/L, 1× 10^-8 mol/L, 1×10^-7 mol/L, 1×10^-6 mol/L, 1×10^-5 mol/L, 1×10^-4 mol/L, shake well and measure the fluorescence spectrum. The working curve was drawn with the fluorescence peak area at 445nm as the ordinate and lg(c/10^-11 ) as the abscissa, and c was the molar concentration of Zn²⁺ . The working curve is shown in Figure 1, and the two show an exponential relationship, and the trend line equation of the fluorescence peak area (A) and the Zn2⁺ concentration c is:

A＝2.1015×10⁶c^0.2481(R²＝0.9213)A=2.1015×10⁶ c^0.2481 (R² =0.9213)

加标回收率计算举例：待测样荧光峰积分面积A₁＝33475，计算浓度c₁＝5.6120×10^-8，加入标准Zn²⁺的浓度为5×10^-9mol/L，测定荧光峰积分面积A₂＝34153，计算加标回收率为104％。Example of standard recovery calculation: the integrated area of the fluorescence peak of the sample to be tested is A₁ =33475, the calculated concentration c₁ =5.6120×10^-8 , the concentration of the standard Zn²⁺ added is 5×10^-9 mol/L, and the fluorescence peak is measured The integral area A₂ =34153, and the calculated recovery rate of standard addition was 104%.

Claims

Translated fromChinese

1、一种N，N’-二-[3-羟基-4-(2-苯并噻唑)苯基]脲，其特征在于，分子结构式如下：1, a kind of N, N'-two-[3-hydroxyl-4-(2-benzothiazole) phenyl] urea, it is characterized in that, molecular structural formula is as follows:

2、权利要求1所述的一种N，N’-二-[3-羟基-4-(2-苯并噻唑)苯基]脲的合成方法，其特征在于，该方法以2-(4-氨基-2-羟基苯基)苯并噻唑，简称4-AHBA和羰基咪唑，简称CDI为原料，在甲苯、苯或二甲苯溶剂中反应得到N，N’-二-[3-羟基-4-(2-苯并噻唑)苯基]脲，简称4-DHBTU，反应方程式如下：2. The synthetic method of a kind of N, N'-bis-[3-hydroxyl-4-(2-benzothiazole)phenyl]urea according to claim 1, characterized in that, the method uses 2-(4 -Amino-2-hydroxyphenyl) benzothiazole, referred to as 4-AHBA and carbonylimidazole, referred to as CDI as raw materials, reacted in toluene, benzene or xylene solvent to obtain N, N'-di-[3-hydroxyl-4 -(2-benzothiazole)phenyl]urea, referred to as 4-DHBTU, the reaction equation is as follows:

反应步骤是：将4-AHBA和CDI按摩尔比4-AHBA∶CDI＝1∶0.5～20的比例加入到溶剂中至原料溶解，在干燥和通氮气或氦气等惰性气体保护的条件下搅拌回流至出现大量的淡黄色固体，停止反应，减压蒸干溶剂，用体积比CH₂Cl₂∶CH₃OH＝20～5∶1作为洗脱剂进行硅胶柱层析将产物纯化，得到黄色固体物质，所述溶剂为甲苯、苯或二甲苯。The reaction steps are: add 4-AHBA and CDI to the solvent in a molar ratio of 4-AHBA:CDI=1:0.5～20 until the raw materials are dissolved, and stir under the conditions of drying and inert gas protection such as nitrogen or helium Reflux until a large amount of light yellow solid appears, stop the reaction, evaporate the solvent to dryness under reduced pressure, and use the volume ratio_CH2Cl2_:_CH3OH =20～5:1 as the eluent to perform silica gel column chromatography to purify the product to obtain a yellow Solid matter, the solvent is toluene, benzene or xylene.

3、权利要求1所述的一种N，N’-二-[3-羟基-4-(2-苯并噻唑)苯基]脲的应用，其特征在于，4-DHBTU作为荧光探针检测Zn²⁺的方法：准确配制1×10^-6-1×10⁵mol/L 4-DHBTU乙腈溶液，并向该溶液中加入Zn²⁺水溶液标准样品，配制成含Zn²⁺浓度为10^-10-10^-4mol/L的标准样品5-10个，测定荧光光谱，荧光光谱上445nm处出现了强度较大的新峰，以445nm处的荧光峰面积为纵坐标，lg(c/10^-11)作为横坐标做工作曲线，c为Zn²⁺摩尔浓度，检测下限能够达到1×10^-10mol/L。3. The application of a kind of N,N'-di-[3-hydroxyl-4-(2-benzothiazole)phenyl]urea according to claim 1, characterized in that 4-DHBTU is used as a fluorescent probe for detection Zn²⁺ method: accurately prepare 1×10^-6 -1×10⁵ mol/L 4-DHBTU acetonitrile solution, and add Zn²⁺ aqueous solution standard sample to the solution to prepare a Zn²⁺ concentration of 10^- 5-10 standard samples of¹⁰ -10^-4 mol/L, measure the fluorescence spectrum, a new peak with higher intensity appears at the 445nm place on the fluorescence spectrum, take the fluorescence peak area at the 445nm place as the ordinate, lg(c/10^-11 ) is used as the abscissa to make the working curve, c is the molar concentration of Zn²⁺ , and the detection limit can reach 1×10^-10 mol/L.