Preparation and application of beta-diketone boron fluoride fluorescent dye adopting first-class coumarin as framework

A technology of diketone boron fluoride and fluorescent dyes, which is applied in the field of β-diketone boron fluoride fluorescent dyes and its preparation and application, can solve the problems of small Stocks shift and limit the better application of coumarin, and achieve optical Stable properties, easy derivatization, and good application prospects

Active Publication Date: 2019-08-09
QINGDAO UNIV OF SCI & TECH
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  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

[0005] Coumarin dyes have the characteristics of high fluorescence quantum yield, good biocompatibility, relatively stable photochemical properties, and adjustable photophysical and phot

Method used

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  • Preparation and application of beta-diketone boron fluoride fluorescent dye adopting first-class coumarin as framework
  • Preparation and application of beta-diketone boron fluoride fluorescent dye adopting first-class coumarin as framework
  • Preparation and application of beta-diketone boron fluoride fluorescent dye adopting first-class coumarin as framework

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 2

[0041] [Example 2] Synthesis of a fluorescent dye formula I compound (i.e. I1) of a β-diketone boron fluoride with coumarin as a skeleton, wherein R1=R2=R3=R4=diethylamino, and the reaction The formula is as follows:

[0042]

[0043] Preparation I1: Dissolve 0.3g (0.597mmol) of intermediate V1 in anhydrous dichloromethane, add 0.18g (1.791mmol) of triethylamine and stir at room temperature for 30min, then add 0.252g (1.791mmol) of boron trifluoride diethyl ether, stirred the reaction mixture and heated to reflux for 4 hours, extracted three times with water and dichloromethane, separated the organic layer with a separating funnel, collected the organic layer, dried over anhydrous sodium sulfate, evaporated the solvent in a rotary evaporator, and washed with dichloromethane After recrystallization and suction filtration, 0.1 g of solid was obtained, namely product I1, with a yield of 56%.

[0044] figure 1 It is the H NMR spectrum of the compound prepared in Example 2. S...

Embodiment 4

[0050] [Example 4] A kind of synthesis of fluorescent dye compound II of β-diketone boron fluorides with coumarin as the skeleton, the reaction formula is as follows:

[0051]

[0052] Take 0.3g (0.545mmol) of compound VIII and dissolve it in anhydrous dichloromethane, then add 0.165g (1.64mmol) of triethylamine and stir at room temperature for 30min, then add 0.165g (1.64mmol) of boron trifluoride ether, and stir the reaction The mixture was extracted three times with water and dichloromethane for 4 hours, and the organic layer was separated with a separating funnel. After the organic layer was collected and dried on anhydrous sodium sulfate, the solvent was evaporated in a rotary evaporator, recrystallized with dichloromethane, and 0.12g was obtained by suction filtration. The solid is the product II, and the yield is 60%.

[0053] Figure 4 It is the H NMR spectrum of the compound prepared in Example 4. Structure: 1 H NMR (500MHz, TFA) δ7.68(s, 2H), 6.25(s, 2H), 2.43(...

Embodiment 5

[0055] [Example 5] Compound I1 is formulated with toluene, dichloromethane, tetrahydrofuran, and ethyl acetate to form a molar concentration of 10 -5 mol / L solution, the UV absorption spectrum and fluorescence emission spectrum were measured, and the basic photophysical related data are shown in Table 1.

[0056] Compound II was formulated with toluene, dichloromethane, tetrahydrofuran, and ethyl acetate to make a molar concentration of 10 -5 mol / L solution, the UV absorption spectrum and fluorescence emission spectrum were measured, and the basic photophysical related data are shown in Table 2.

[0057] Table 1 compound formula I1 relevant photophysical data in each solvent

[0058]

[0059] The results in Table 1 show that the maximum absorption wavelengths of dye I1 in toluene, dichloromethane, tetrahydrofuran, and ethyl acetate are 579, 597, 589, and 584, and the maximum emission wavelengths are 600, 630, 615, and 613, respectively. There are better fluorescence quant...

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Abstract

The invention discloses synthesis of a beta-diketone boron fluoride fluorescent dye adopting dicoumarin as a framework. The structural general formula of the beta-diketone boron fluoride fluorescent dye is shown as a formula I or a formula II. Through the design, a series of coumarin with substituents introduced from three positions is prepared, then Claisen condensation is conducted on coumarin-containing ester and a corresponding carbonyl compound to obtain a series of compounds of beta-diketo acid ligands, the length of conjugated chains is increased, and the emission wavelength of the conjugated chains is improved. Finally, the beta-diketo acid ligands are subjected to a coordination reaction with boron under the action of boron trifluoride diethyl ether to form a series of the beta-diketone boron fluoride fluorescent dye based on coumarin. The method has the advantages that the synthesis steps of raw materials are simple, the yield is high, and the method is simple and easy to implement. The fluorescent dye has a narrow ultraviolet absorption visible spectrum, a narrow fluorescence emission spectrum and long absorption emission waves and is stable in optical property; the dyecan be used for cell imaging, fluorescent probes and the like and has a broad application prospect in the fields of chemical sensing, biological labeling, biological imaging, organic light emitting diodes (OLED), photoelectric materials, fluorescent probes and the like. In the formula I, R1, R2, R3 and R4 refer to alkyl groups with the carbon number smaller than 20.

Description

[0001] 【Technical field】 [0002] The invention relates to the preparation and application of novel fluorescent dyes of β-diketone boron fluorides, in particular to a β-diketone boron fluoride fluorescent dye with coumarin as the skeleton and its preparation and application. [0003] 【Background technique】 [0004] Organic light-emitting compounds have important applications in the fields of chemical sensing, biolabeling, bioimaging and organic light-emitting diodes (OLEDs). In recent decades, people have continuously devoted themselves to the development of new organic light-emitting materials. β-diketone boron fluoride dyes are a class of highly fluorescent organic boron complexes with rich photophysical properties. Clausen condensations between esters and carbonyl compounds endow β-diketone fluorinated dyes with enormous structural diversity. Due to their rich photophysical properties, β-diketone boron fluoride dyes have been widely used in various fields. Therefore, desi...

Claims

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Application Information

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IPC IPC(8): C07F5/02C09B57/00C09K11/06
CPCC07F5/022C09B57/00C09K11/06C09K2211/1029C09K2211/1088C09K2211/1096
Inventor 王鲲鹏胡志强谷幸豪陈绍晋张琦
Owner QINGDAO UNIV OF SCI & TECH
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