阅读说明：本技术 一种喹啉类溶致变色荧光染料及其制备方法和其在有机溶剂水含量测定中的应用 (Quinoline type lyotropic color-changing fluorescent dye, preparation method thereof and application thereof in organic solvent water content measurement ) 是由 杜奎 席眉扬 沈润溥 刘伊琳 陈嘉伟 骆翔 于 2020-06-04 设计创作，主要内容包括：本发明公开了一种喹啉类溶致变色荧光染料及其制备方法和其在有机溶剂水含量测定中的应用。该喹啉类溶致变色荧光染料其结构式如式II所示：<Image he="173" wi="674" file="DDA0002525140300000011.GIF" imgContent="drawing" imgFormat="GIF" orientation="portrait" inline="no"></Image>式II中取代基位置为喹啉3号位,5号位或7号位；R为氨基或者氮氮二甲基。该种喹啉类溶致变色荧光染料具有斯托克位移变化大,荧光量子产率高,有机溶剂水含量检测灵敏等优点。该荧光探针被成功应用于有机溶剂中微量水的高效检测,并取得了较好的检测效果。(The invention discloses a quinoline lyotropic color-changing fluorescent dye, a preparation method thereof and application thereof in organic solvent water content measurement. The structural formula of the quinoline type lyotropic color-changing fluorescent dye is shown as a formula II: in the formula II, the substituent position is quinoline No. 3, No. 5 or No. 7; r is amino or nitrogen-dimethyl. The quinoline type lyotropic color-changing fluorescent dye has the advantages of large Stokes shift change, high fluorescence quantum yield, sensitive detection of the water content of an organic solvent and the like. The fluorescent probe is successfully applied to organic materialsThe trace water in the solvent is detected efficiently, and a better detection effect is obtained.)

1. A quinoline type lyotropic color-changing fluorescent dye is characterized in that the structural formula is shown as formula II:

in the formula II, the substituent position is quinoline No. 3, No. 5 or No. 7; r is amino or nitrogen-dimethyl.

2. A preparation method of quinoline type lyotropic color-changing fluorescent dye is characterized by comprising the following steps:

reacting a compound of formula I, 4-ethynylaniline or 4-azadimethylacetylene, potassium phosphate, Pd (Ph)₃)₂Cl₂Adding the mixture into DMF according to the molar ratio of 1:2:2:0.02, stirring and reacting for 24 hours at the temperature of 100 ℃, and purifying reaction liquid to obtain a compound II;

wherein R in the formula I₁The position of (a) is quinoline 3, 5 or 7; in the formula II, the substituent position is quinoline No. 3, No. 5 or No. 7; r is amino or nitrogen-dimethyl.

3. The method of claim 2, wherein the reaction solution purification process comprises: filtering the reaction solution, pouring the filtrate into 300mL of water, adding 300mL of dichloromethane into the filtrate under the stirring condition, extracting for three times, combining organic phases, adding anhydrous sodium sulfate into the organic phases, drying, performing spin drying, performing column chromatography, and using ethyl acetate as a developing agent: petroleum ether 1:30 to give compound II.

4. The method of preparing a quinoline lyotropic color-changing fluorescent dye according to claim 2, wherein said R is₁Is halogen.

5. The method of preparing a quinoline lyotropic color-changing fluorescent dye according to claim 4, wherein said R is₁Is Br.

6. Use of a quinoline-based lyotropic fluorescent dye as claimed in claim 1 for the detection of water content in organic solvents.

7. The use of a quinoline-based lyotropic fluorescent dye in the detection of water content in an organic solvent according to claim 6, comprising the steps of: adding a proper amount of organic solvent to be detected into a colorimetric tube, adding the quinoline type lyotropic color-changing fluorescent dye, adjusting the concentration to be 1 mu M, shaking and standing for 5 minutes, observing the fluorescence emission color of the organic solvent under the irradiation of a 365nm ultraviolet lamp, and referring to fluorescence spectrum change data of the quinoline type lyotropic color-changing fluorescent dye in the organic solvents with different water contents according to the change of the emission color and the brightness to obtain the water content in the organic solvent to be detected.

8. The use of a quinoline-based lyotropic fluorescent dye for detecting water content in an organic solvent according to claim 6 or 7, wherein the organic solvent is acetone, ethyl acetate, toluene, dichloromethane, chloroform, DMF, DMSO, NMP, toluene or tetrahydrofuran.

Technical Field

The invention relates to the technical field of application of a lyotropic chromotropic fluorescent dye, in particular to a novel quinoline lyotropic chromotropic fluorescent dye based on quinoline groups, a preparation method thereof and application thereof in measurement of water content of an organic solvent.

Background

The lyotropic chromogen (solvatochromic) phenomenon is a phenomenon in which an organic solvent interacts with a fluorescent molecule, resulting in a change in the color of the fluorescence spectrum. In organic solvents with different polarities, absorption or emission spectra of fluorescent dye molecules generate different responsivities, and obvious color development capability differences are shown. The lyotropic chromotropic fluorescent dye has important research value in the aspects of chemical reaction rate, physical and chemical balance and the like, and is widely applied to the fields of fluorescent probes, indicators, color developing agents and molecular recognition. Therefore, the development of new fluorescent dyes with better lyotropic discoloration performance has become an important research hotspot in recent years.

A large number of lyotropic chromophoric fluorescent dyes are designed based on a D-Pi-A strategy, and the main ring structure of the lyotropic chromophoric fluorescent dyes mainly comprises benzoxazole, triphenylamine star-shaped conjugated molecules, anthracene, benzofuran, dicyanoethylene, phenyl dicyanoethylene, benzothiazine part cyanine and the like, but the lyotropic chromophoric fluorescent dyes based on a quinoline main ring structure are rarely seen. Because quinoline has good fluorescence properties, it is one of the research directions of those skilled in the art how to design a quinoline-based lyotropic fluorescent dye.

Disclosure of Invention

In view of the above, the present invention provides a quinoline type lyotropic color-changing fluorescent dye.

The invention also provides a preparation method of the quinoline lyotropic color-changing fluorescent dye.

The invention also provides application of the quinoline lyotropic color-changing fluorescent dye in the measurement of the water content of the organic solvent.

The technical scheme of the invention is as follows:

the invention provides a quinoline type lyotropic color-changing fluorescent dye shown in a formula II:

in the formula II, the substituent position is quinoline No. 3, No. 5 or No. 7; r is amino or nitrogen-dimethyl.

Further, the quinoline type lyotropic color-changing fluorescent dye is one of the following:

the invention also provides a preparation method of the quinoline lyotropic color-changing fluorescent dye, which comprises the following steps:

reacting a compound of formula I, 4-ethynylaniline or 4-azadimethylacetylene, potassium phosphate, Pd (Ph)₃)₂Cl₂Adding the mixture into DMF according to the molar ratio of 1:2:2:0.02, stirring and reacting for 24 hours at the temperature of 100 ℃, and purifying reaction liquid to obtain a compound II;

wherein R in the formula I₁The position of (a) is quinoline 3, 5 or 7, for example one of the following:

in the formula II, the substituent position is quinoline No. 3, No. 5 or No. 7; r is amino or nitrogen-dimethyl.

Preferably, the reaction liquid purification process comprises: filtering the reaction solution, pouring the filtrate into 300mL of water, adding 300mL of dichloromethane into the filtrate under the stirring condition, extracting for three times, combining organic phases, adding anhydrous sodium sulfate into the organic phases, drying, performing spin drying, performing column chromatography, and using ethyl acetate as a developing agent: petroleum ether 1:30 to give compound II.

The invention also provides an application of the quinoline lyotropic color-changing fluorescent dye in the determination of the water content of the organic solvent, which comprises the following steps: adding a proper amount of organic solvent to be detected into a colorimetric tube, adding quinoline type lyotropic color-changing fluorescent dye, adjusting the concentration to be 1 mu M, shaking and standing for 5 minutes, observing the fluorescence luminescent color of the organic solvent under the irradiation of a 365nm ultraviolet lamp, and referring to fluorescence spectrum change data of the quinoline type lyotropic color-changing fluorescent dye in the organic solvent with different water contents according to the change of the luminescent color and the brightness to obtain the water content in the organic solvent to be detected.

Preferably, the organic solvent to be detected is acetone, ethyl acetate, toluene, dichloromethane, chloroform, DMF, DMSO, NMP, toluene or tetrahydrofuran.

Compared with the prior art, the quinoline type lyotropic color-changing fluorescent dye provided by the invention has the following advantages:

the quinoline lyotropic color-changing fluorescent dye has the advantages of simple synthesis method, high fluorescence quantum yield, large Stokes shift change, high fluorescence quantum yield, sensitive detection of the water content of an organic solvent and the like. And the quinoline type lyotropic color-changing fluorescent dye is successfully applied to the high-efficiency detection of trace water in an organic solvent, and obtains better detection effect.

Drawings

FIG. 1 is a reaction scheme of the quinoline type lyotropic color-changing fluorescent dye of the present invention.

FIG. 2 is a graph showing the change of fluorescence color of formula II-1 of the present invention in acetone with water content of various concentrations.

Detailed Description

For a better understanding of the present invention, reference is made to the following description taken in conjunction with the accompanying drawings and examples, but the scope of the invention as claimed should not be limited to the scope of the examples.

Referring to FIG. 1, FIG. 1 is a reaction scheme of quinoline type lyotropic fluorescent dyes, wherein R in formula I₁The position is quinoline No. 3, No. 5 or No. 7, R₁Is halogen, e.g. Br, I, F, etc., R in the examples shown₁Is embodied as Br. General ring of quinoline in formula IIThe substituent position is quinoline No. 3, No. 5 or No. 7; r is amino or nitrogen-dimethyl.